XIV

International

Workshop on

Sensors and

Molecular

Recognition

th July, 8 and 9 2021

BOOK OF ABSTRACTS

ORGANIZING COMMITTEE

CHAIR: Pablo Gaviña Costero

Salvador Gil Grau Silvia Rodriguez Nuévalos María Manconi Daniel Ferri Angulo Carmen Ferriol Eva Mª Brun Sánchez

SCIENTIFIC COMITTEE

Ana Mª Costero Ramón Martínez-Mañez Angel Maquieira Catalá Miguel Alcañiz Fillol Rurack Knut Gustavo Fernandez Carla Caddeo Matilde Merino Sanjuan

INDEX

Page

Scientific Program 7 Full Lectures 11 Oral Communications 21 Poster Communications 47 List of participants 147

SCIENTIFIC PROGRAM

Thursday, July 8, 2021

MORNING SESSION

9.00 – 9.15h Opening ceremony

Chaired by Vicerrector de Investigación de la Universitat de Valencia, Carlos Hermenegildo Caudevilla

9.15 – 10.15h Full Lecture

Interfacing Self-Assembly and External Stimuli: from responsive to adaptive behaviour Gustavo Fernández

10.15 – 11.00h First Session of Oral Communications:

Chairman: Ana María Costero Nieto

O-01 Gold nanoclusters for ratiometric sensing of pH in extremely acidic media Irene Pérez-Herráez, Adele Bonanno, Elena Zaballos-García, Julia Pérez- Prieto O-02 Non-invasive and renal clearable cy7gal probe for the fluorescence senescence detection by direct urine measurement Juan F. Blandez, Beatriz Lozano-Torres, Alba García-Fernández, Félix Sancenón and Ramón Martínez-Máñez O-03 Host-guest chemistry of fullerene derivatives with polyamide macrocycle-based metal-organic frameworks Adrian Saura-Sanmartin, Alberto Martinez-Cuezva, Marta Marin-Luna, Jose Berna

11.00 – 11.30h Coffee break

11.30 – 12.30h Second Session of Oral Communications:

Chairman: Salvador Gil Grau

O-04 Molecular encapsulagion using molecular cages Vicente Martí-Centelles, Giovanni Montà González, Félix Sancenón, Ramón Martínez-Máñez

O-05 An off-on fluorescent probe for the sensitive detection of Alanine Aminopeptidase (APN) in real urine samples Marcia Domínguez, Juan F. Blandeza, Félix Sancenóna, Ramón Martínez-Máñez O-06 Bodipy's derivatives for cathinone detection Jordi H. Contreras, P. Rodrigo Martínez, Ana M. Costero, Salvador Gil O-07 Chromogenic chemodosimeter based on capped silica particles to detect spermine and spermidine Mariana Barros, Alejandro López-Carrasco, Pedro Amorós, Salvador Gil, Pablo Gaviña, Margarita Parra, Jamal El Haskouri, M. Carmen Terencio, Ana M. Costero

12.30 – 13.30h Full Lecture

Consequences of the mechanical bond of amide-based rotaxanes in organocatalysis José Berná

13.30 – 15.30h Lunch

AFTERNOON SESSION

15.30 – 17.15h Third Session of Oral Communications

Chairman: Miguel Alcañiz Fillol

O-08 Sensor for food analysis applying impedance spectroscopy and artificial neural networks Josef Peter Gessler, Laura Contat Rodrigo, Nicolás Laguarda Miró, Miguel Alcañiz Fillol y Rafael Masot Peris O-09 The development of photothermal therapy devices in the idm José Manuel Terrés-Haro, Javier Ibañez, Rafael Masot-Peris, Eduardo García-Breijo O-10 System for monitoring deformation in reinforced concrete structures with wireless connection Luis Chapa Chordá, Vicente Beltrán Morte, Cristina Bastida Molina, Roberto Vengut Tro, José Manuel Gandía Romero, Miguel Alcañiz Fillol O-11 Development and perspectives of optochemogenetic devices at idm Javier Monreal-Trigo, José Manuel Terrés-Haro, Esther Giraldo, Victoria Moreno-Manzano O-12 Low cost measurement system for biosensors based on organic electrochemical transistors (oefts) and field effect transistors (fets) Vicente Beltrán Morte, Javier Monreal Trigo, Jakob Sabbe, Flor Boydens, Miguel Alcañiz Fillol, Liv K. Heidenreich O-13 Wirelessly powered reinforced concrete corrosion monitoring system based on potential step voltammetry Cristina Bastida-Molina, Roberto Vengut-Tro, Vicente Beltrán Morte, Josep Ramon Lliso-Ferrando, Ana Martínez-Ibernón, Ignasi Cairó

O-14 Wirelessly powered reinforced concrete chloride penetration measurement system based on cyclic voltammetry Roberto Vengut-Tro, Cristina Bastida-Molina, Vicente Beltrán-Morte, Ana Martínez-Ibernón, Josep Ramon Lliso-Ferrando, Román Bataller- Prats

17.15 – 18.30h Poster Session: Everyone who presents a poster must be available by email for any consultation.

Friday, July 9, 2021

MORNING SESSION

9.00 – 10.00h Full Lecture

Stimuli-Responsive Porphyrin Receptors for Controlled Molecular Recognition Valerié Heitz

10.00 – 11.00h Fourth Session of Oral Communications:

Chairman: Pablo Gaviña Costero

O-15 Asymptotic modeling of signaling in biomedical analysis Antonio Doménech-Carbó, José Luís Pontones, Clara Doménech- Casasús, David Ramos O-16 New interferometric in-vitro food allergy diagnostic system based on molecular allergens and nanoparticles Rocio L. Espinosa, María Garrido-Arandia, Alejandro Romero-Sahagun, Pedro Herreros, Luca Tramarin, Mª Fe Laguna, Araceli Díaz-Perales , Miguel Holgado O-17 Towards a competitive immunoassay with gold nanoparticles for mmp9 inflamatory biomarker detection in tear sample Beatriz Santamaría, Yolanda Ramírez, Ana María M. Murillo, Luis Vallez, Miguel Holgado O-18 Nanosystem based on mesoporous silica nanoparticles for dual delivery of doxorubicin and mir-99a-5p to treat breast cáncer Iris Garrido-Cano, Anna Adam-Artigues, Ana Catarina Trigo Lameirinhas, Juan F. Blandez, Ana Llucha, Juan Miguel Cejalvo, Pilar Eroles, Ramón Martínez-Máñez

11.00 – 11.30h Coffee break

11.30 – 12.30h Fifth Session of Oral Communications:

Chairman: Angel Maquieira Catalá

O-19 Exploring the synergy of paper-based electrophoresis and lateral flow assay: towards improved point-of-care biosensing Amadeo Sena-Torralba, Sergi Morais and Ángel Maquieira O-20 Gratings of responsive hydrogels for label free-biosensing María Isabel Lucío, Andy Hernández Montoto, Estrella Fernández, Kheloud Berramdane, Manuel G. Ramírez, Inmaculada Pascual, María- José Bañuls, Ángel Maquieira O-21 Bio bragg gratings: diffractive molecular networks for on-fiber label-free biosensing Augusto Juste-Dolz, Martina Delgado-Pinar, Miquel Avella-Oliver, Estrella Fernández, Daniel Pastor, Miguel V. Andrés, Ángel Maquieira O-22 Nanoscale pillar arrays for vapor detection Sergio Quintero, Rafel Casquel, Maria Fe Laguna, Miguel Holgado

12.30 – 13.30h Full Lecture

Tailoring bodipys for (bio)photonic applications Beatriz Lora Maroto

13.30 – 13.45h Closing ceremony

POSTER SESSION The posters will be on the website: http://www.iwosmor.com/ from July 5th

BOOK OF ARTICLES The deadline for submitting the articles of the communications for the edition of the book will end on September 17, all those that are not received on date we will assume that they are not interested. The format should be like the abstracts but with an extension of 4 or 5 sheets.

FULL LECTURES

Interfacing Self-Assembly and External Stimuli: from responsive to adaptive behaviour

Gustavo Fernández Organisch-Chemisches Institut, Universität Münster, Corrensstraße 36, 48151 Münster, Germany. E-mail: [email protected]

Understanding the relationship between external stimuli and self-assembly is key to achieve adaptive behaviour, one of the core elements of intelligent matter.1 However, given that the energy landscape of supramolecular assemblies is extremely sensitive to minor changes in the environment,2 controlling and predicting the influence of external stimuli on self-assembly phenomena remains a major challenge. In this presentation, different strategies to control the self-assembly behaviour of stimuli-responsive - conjugated systems will be discussed. For instance, the hierarchical self-assembly of pyridine-based ligand L1 as well as its responsiveness towards light, trifluoacetic acid II II (TFA) addition (L1:TFA) and complexation of metal ions (Pd and Pt ) will be discussed. Target ligand L1 undergoes complex time-, temperature- and concentration- dependent self-assembly pathways driven by H-bonding leading to fiber-like associates.3 Irradiation with UV light (365 nm) leads to a reversible transition from long to short fibers. On other hand, addition of TFA causes the transformation of the anti- parallel H-bonded fibrillar assembly of L1 in MCH into superhelical fibers stabilized by H-bonding of parallel-stacks of L1:TFA.4 Light irradiation causes a strain-driven disassembly and subsequent aggregate reconstruction that ultimately leads to short II II fibers. In contrast, complexation of Pd and Pt ions (complexes C1 and C3) leads to a slight attenuation of the supramolecular growth into short thin fibers.5 Ultimately, the rational choice of “good” vs. “poor” solvents allows precise control over the photochemical behaviour of light-responsive systems (E/Z isomerization vs. [2 + 2] photocycloaddition).6 Detailed mechanistic insights into the self-assembly and photo responsive behavior of all species have been provided using a combination of spectroscopic and microscopic techniques.

. Scheme 1. Summary of stimuli-responsive systems described in this presentation

1 Zeng, H.; Wasylczyk, P.; Wiersma, D. S.; Priimagi, A. Adv. Mater., 2018, 30, e1703554. 2 Matern, J.; Dorca, Y.; Sanchez, L; Fernández, G. Angew. Chem. Int. Ed. 2019, 58, 16730. 3 Kartha, K. K.; Allampally, N. K.; Politi, A. T.; Prabhu, D. D.; Ouchi, H.; Albuquerque, R. Q.; Yagai, S.; Fernández, G. Chem. Sci. 2019, 10, 752. 4 Kartha, K. K.; Allampally, N. K.; Yagai, S.; Albuquerque, R. Q.; Fernández, G., Chem. Eur. J. 2019, 25, 9230. 5 Bäumer, N.; Kartha, K. K.; Allampally, N. K.; Yagai, S.; Albuquerque, R. Q.; Fernández, G. Angew. Chem. Int. Ed. 2019, 58, 15626. 6 Dünnebacke, T.; Kartha, K. K.; Wiest, J. M.; Albuquerque, R. Q.; Fernández, G. Chem. Sci. 2020, 11, 10405.

CONSEQUENCES OF THE MECHANICAL BOND OF AMIDE-BASED ROTAXANES IN ORGANOCATALYSIS

José Berná Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, E-30100, Murcia, Spain. E- mail: [email protected]

Keywords: rotaxane ● organocatalysis ● hydrogen bond ● catalysis ● selectivity During last years, the use of mechanically interlocked compounds in catalysis has importantly increased. The steric protection of the structural moieties included in the threads caused by the macrocycle has been used for the development of switchable catalysts with rotaxane structures.[1] The catalytic activity of these systems and their selectivity can be dictated by the application of an external stimulus. In this presentation I will talk about the building of a photo-commutable molecular shuttle, having a fumaramide as a photoconvertible template, and a thiodiglycolamide as the second binding site and the catalytic active site, for a Morita-Baylis-Hillman reaction.[2] More recently, the use of chiral rotaxanes as organocatalysts is receiving an important attention, thanks to the properties of the mechanical bond.[3] In this regard, we have developed an enantiodivergent protocol for carrying out Michael reactions between different ketones and trans-nitrostyrene.[4] The use of a prolinamide-based thread or its corresponding interlocked surrogate in this enamine-type transformation yielded both possible enantiomers.

Finally, I will describe our experience in the use of the di(acylamino)pyridine as a template for the building of prolinamide-based organocatalysts.[5] These systems catalyzed various enamine-type reactions between acetone and different electrophiles. Also, the use of N-hexylthymine as a co-factor enhanced the yield and enantioselectivity of the reaction between acetone and nitrostyrene. References 1 [1] Blanco, V.; Leigh, D. A.; Marcos, V. Chem. Soc. Rev. 2015, 44, 5341. 2 [2] Martinez-Cuezva, A.; Saura-Sanmartin, A.; Nicolas, T.; Navarro, C.; Orenes, R.-A.; Alajarin, M.; Berna, J. Chem. Sci., 2017, 8, 3775. 3 [3] Martinez-Cuezva, A.; Saura-Sanmartin, A.; Alajarin, M.; Berna, J. ACS Catal. 2020, 10, 7719. 4 [4] Martinez-Cuezva, A.; Marin-Luna, M.; Alonso, D. A.; Ros-Ñiguez, D.; Alajarin, M.; Berna, J. Org. Lett. 2019, 21, 5192. 5 [5] Calles, M.; Puigcerver, J.; Alonso, D. A.; Alajarin, M.; Martinez-Cuezva, A.; Berna, J. Chem. Sci., 2020, 11, 3629. Acknowledgments These works were supported by the MINECO (CTQ2017-87231-P) with joint financing by FEDER Funds, and Fundación Seneca-CARM (Project 20811/PI/18).

Stimuli-Responsive Porphyrin Receptors for Controlled Molecular Recognition

Valérie Heitz

Laboratoire de Synthèse des Assemblages Moléculaires Multifonctionnels, Institut de Chimie de Strasbourg CNRS/UMR 7177, Université de Strasbourg E-mail: [email protected]

Porphyrins have been incorporated in many multicomponent systems for various applications due to their appealing coordination, electronic and photophysical properties. The synthesis of three-dimensional architectures with metalloporphyrins as active components gave rise to attractive structures for molecular recognition or chemical transformation.1 By analogy with biological processes, molecular cages that incorporate both binding and regulation sites are appealing systems for an allosteric control of their properties as receptor, catalyst or drug carrier.2 Our group has developed flexible porphyrin cages with peripheral binding sites able to modulate to a large extent their cavity size with a chemical stimulus.3 We will discuss the ability of these molecular cages to behave as allosteric receptors and as bimetallic catalysts.4,5

1. a) S. Durot, J. Taesch, V. Heitz, Chem. Rev., 2014, 114, 8542. b) S. H. A. M. Leenders, R. Gramage- Doria, B. de Bruin, J. N. H. Reek, Chem. Soc. Rev., 2015, 44, 433 2. a) A. J. McConnell, C. S. Wood, P. P. Neelakandan, J. R. Nitschke, Chem. Rev. 2015, 115, 7729. b) C. Kremer, A. Lützen, Chem. Eur. J., 2013, 19, 6162. 3. a) J. Taesch, V. Heitz, F. Topic, K. Rissanen, Chem. Commun., 2012, 48, 5118. b) L. Kocher, S. Durot, V. Heitz, Chem. Commun. 2015, 51,13181. c) L. Schoepff, L. Kocher, S. Durot, V. Heitz, J. Org. Chem., 2017, 82, 5845. 4. a) R. Djemili, L. Kocher, S. Durot, A. Peuronen, K. Rissanen, V. Heitz, Chem. Eur. J. 2019, 25, 1481. b) L. Zanetti-Polzi, R. Djemili, S. Durot, V. Heitz, I. Daidone, B. Ventura, Chem. Eur. J. 2020, 26, 17514. 5. L. Schoepff, L. Monnereau, S. Durot, S. Jenni, C. Gourlaouen, V. Heitz, ChemCatChem, 2020, 12, 5826.

TAILORING BODIPYS FOR (BIO)PHOTONIC APPLICATIONS

Beatriz Lora Maroto Departamento de Química Orgánica, Universidad Complutense de Madrid [email protected]

The excellent photophysical properties of BODIPYs (BOron DIPYrromethenes) have thrown them into the limelight and the scientific articles published on these organic dyes has growth exponentially in the last 15 years. BODIPYs show strong absorption and emission of visible light (with high molar absorption coefficients, high fluorescence quantum yields and long fluorescence lifetimes) and are stable and relatively insensitive to the polarity or pH of the medium. They are easy to obtain, and this makes them low-cost dyes, which is an essential quality for their use in technological applications. Thus, BODIPYs have found application in many different fields: as laser dyes, fluorescence sensors, switches and probes, light harvesting arrays for antenna systems, optoelectronic devices, biological labels for bioimaging, photosensitizers for photodynamic therapy and phototheranosis, or dyes for applications based on circularly polarized luminescence (CPL), such as 3D hologram projection, spintronics based telecommunication, or OLED technology, to name just a few. A remarkable characteristic of BODIPYs is the fact that it is possible to fine-tune their properties by chemical manipulation to design BODIPYs ad hoc for a particular photonic application. Thus, not only photophysical properties (e.g. absorption and emission wavelengths, photosensitizing capability, or CPL emission) can be finely modulated, but also physical (e.g. water solubility, aggregation, etc.), chemical (e.g. specific reactivity towards the ulterior functionalization of materials or biomolecules) or biological (e.g. specific organelle recognition). The research we carry out in the group Organic Dyes for Photonic Materials, at UCM, is focused to the development of organic dyes based on BODIPY and other related boron chelates, designed towards advanced photonic applications in the fields of Energy and Health. In this line, we do research directed towards the establishment of the basis for the modulation of the properties of these dyes through chemical manipulation, and towards the development of new methodologies for the unconventional functionalization of BODIPYs.

ORAL COMMUNICATIONS

O-01

GOLD NANOCLUSTERS FOR RATIOMETRIC SENSING OF pH IN EXTREMELY ACIDIC MEDIA Irene Pérez-Herráez,a Adele Bonanno,b Elena Zaballos-García,b Julia Pérez-Prieto.a aInstituto de Ciencia Molecular (ICMol), Universitat de Valencia, Catedrático José Beltrán 2, 46980, Paterna, Valencia, Spain, registered autor e-mail: [email protected] bDepartamento de Química Orgánica, Universitat de Valencia, Av. Vicent Andrés Estellés s/n, 46100, Burjassot, Valencia, Spain Keywords: Gold nanoclusters ● NADP ● pH ● Photoluminescence ● Sensing Gold nanoclusters (AuNCs) are under the spotlight for chemical sensing on account of their photoluminescence (PL), low toxicity, biocompatibility, chemical and photochemical stability. The nature of the ligand determines the PL properties of the AuNCs [1]. A novel and powerful strategy to enable absolute measurement of the pH of the sample with high reproducibility is ratiometric imaging, in which the emission shift is imaged [2a]. There are few examples of ratiometric fluorescence molecular probes for pH imaging, among them are single organic fluorophores [2b]. With regard to nanomaterial-based ratiometric pH sensors, most of them rely on the attachment of molecular fluorophores to the nanomaterial surface. An exception are AuNCs capped with nicotinamide adenine dinucleotide (AuNC@NAD+) [2c]. The detection of pH values in extremely acidic media is of particular interest. We report here that water-dispersible AuNC capped with β-nicotinamide adenine dinucleotide phosphate (AuNC@NADP) exhibit strong ratiometric fluorescence response to [H+] in extremely acidic media. AuNC@NADP were prepared by a top-down strategy based on the reduction of Au ions to AuNPs, which were then treated with HCl to produce AuNCs. The PL spectrum of the as-synthesized NCs show two maximums at 417 and 470 nm. The pH response can be monitored by measuring the ratio between the emissions (I470/I417). The PL fluctuation (Fig. 1) can be attributed to the change in the chelation degree of the phosphates to the NC surface with the pH [3].

O O H2N H2N + N N+ O O OH O N P O OH O N O O O N N O O P O P OH H N OH O P 2 N O O H N N OH 2 N O O HO N O O OH P - O O O P HO O Au O O Au

pH BASIC

Figure1. Pictorial representation and emission spectra of AuNC@NADP at acid (blue) and basic (green) pHs.

References [1] Landoño-Larrea, P. et al. Chem. Eur. J. 2017, 23, 8137-8141. [2] (a) Bencina, M. Sensors 2013, 13, 16736-16758. (b) Richardson, D. S. et al. Nat. Commun. 2017, 8, 577-585. (c) Cuaran-Acosta, D. et al. Chem. Commun. 2019, 55, 1604-1606. [3] Bonanno, A. et al. Chem. Commun. 2020, 56, 587-590. Acknowledgments The work was supported by Ministerio de Economía, Industria y Competitividad (CTQ2017-82711-P, co-financed by FEDER; PRE2018-084460 (IPH), Ministerio de Ciencia e Innovación (Unit of Excellence “Maria de Maeztu” CEX2019- 000919-M, MDM-2015-0538-18-1), and Generalitat Valenciana (IDIFEDER/2018/064 and PROMETEO/2019/080), co- financed by FEDER.

O-02

NON-INVASIVE AND RENAL CLEARABLE CY7GAL PROBE FOR THE FLUORESCENCE SENESCENCE DETECTION BY DIRECT URINE MEASUREMENT

Juan F. Blandez,a,b,c,d, Beatriz Lozano-Torres, a,b,c Alba García-Fernández, a,b,c Félix Sancenón a,b,c,d and Ramón Martínez-Máñez a,b,c,d a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València. Spain, [email protected] b Unidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, Valencia, Spain c CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) d Unidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, IIS La Fe, Valencia, Spain Keywords: Cellular senescence ● diagnosis ● non-invasive ● urine ● NIR fluorophore

Nowadays, the development of diagnostic techniques for the detection of different diseases by the use of non-invasive, cheap, versatile and easily measurable systems is a matter of concern [1-4]. One of these methods can be the use of urine to carry out the monitoring of diseases [5-7]. Here we present the use of a molecular probe with intrinsic diuretic activity which allowed the urine excretion of a highly emissive molecule which can be monitored in a fluorimeter. This probe, based in a Cyanine-7 dye was namely Cy7Gal. Probe was used for the detection of senescent cells in three different mice models. Cy7Gal was selectively hydrolysed by SaβGal enzyme, overexpressed in senescent cells, generating the highly emissive Cy7 fluorophore [8]. Both, probe and fluorophore, contained sulfonic acid moieties that enhance water solubility and generated the diuretic activity related with the excretion by the urinary system of both compounds [9, 10]. Furthermore, to the ability of Cy7Gal for the detection of senescence cells, the probe can quantify the senescence degree by direct fluorescence measurement in urine. The proper working of the probe was assessed in three mice models of senescence (with different senescence burden). In the first case, 4T1 breast cancer mice were treated with palbociclib in different doses in order to obtain different degree of senescence. In a second experiment, the probe was tested with untreated young (2 months) and old (14 months) BALB/CBYJ mice in order to determine the natural senescence degree. In a final experiment, we compared the senescence degree between SAMR1 (senescence accelerated mice resistant) and SAMP8 (senescence accelerated mice prone). SAMP8 mice are often used to study age- related diseases while SAMR1 are used as control. Physical differences between both groups start when mice are 6 months old. Cy7gal is a sensitive and specific probe for senescent burden evaluation regardless of the murine model. The probe successfully classifies animals with low senescence burden and differentiates them to animals with high senescence burden. Ex vivo IVIS images corroborated the presence and localization of senescent cells. Cy7Gal probe is the first example of non-invasive detection of senescent cells by direct urine fluorescence measure, this probe has a high expectative for the rapid diagnosis of different diseases and the monitoring patients of therapeutic treatment.

Figure1. a) IVIS image of BALB/cByJ female mice carrying orthotopical 4T1 breast tumors were treated daily with different doses of palbociclib (oral gavage, 10, 50 or 100 mg/Kg). Different burden of senescence in mice was confirmed after treated with cy7gal probe, showing higher fluorescent signal in bladder as a function of palbociclib dosis. b) IVIS image from bladder from 2 or 14 month old BALB/CBYJ mice showed no auto-fluorescent signal. In sharp contrast, mice injected with Cy7gal probe showed a strong fluorescence signal in blader. c) Quantification of average radiance efficiency from urine ascribed to the renal clearance of Cy7 fluorophore in young (2 months) and aged (14 months) SAMP8 and SAMR1 mice. Values are expressed as mean ± SEM. d) Receiver operating characteristic curve by moles of excreted fluorophore discriminated healthy from diseased mice with an area under the curve of 0.97 (N = 3 independent experiments, n = 3 or 4 mice per group as in Figures 3, 4 and 5, P = 0.0001 from a random classifier shown by the dashed line). References [1] Jute, A. Sociol. Health Illn. 2009, 31, 278-299. [2] Schito, M. Peter et al., J. Infect. Dis. 2012, 205, S169-S180. [3] Palamountain, K. M. Baker. et al. J. Infect. Dis. 2012, 205, S181-S190. [4] Shikha, S. Zapatero-Rodríguez. et al. Biosensors. 2015, 5, 577-601. [5] Hay Burgess, et al. Nature. 2006, 444, 1-2. [6] Kwo ng, G. A. et al. Nat. Biotech. 2013, 31, 63-71. [7] Lin, K. Y. et al. ACS Nano. 2013, 7, 9001-9009. [8] Karton-Lifshin, N. et al. J. Am. Chem. Soc. 2011, 133, 10960-10965. [9] Husain A, et al. J Enzyme Inhib Med Chem, 2012; 27, 773–783. [10]. Supuran CT. Nat Rev Drug Discov. 2008, 7,168–181 Acknowledgments R.M. laboratory members thank the financial support from the Spanish Government (project RTI2018-100910-B- C41) and the Generalitat Valenciana (project PROMETEO 2018/024). B.L-T. is grateful to the Spanish Ministry of Economy for their PhD grants (FPU15/02707). A. G.-F. thanks her contract from CIBER-BBN.. J. F.-B. thanks to his postdoctoral fellowship (PAID-10-17).

O-03

HOST-GUEST CHEMISTRY OF FULLERENE DERIVATIVES WITH POLYAMIDE MACROCYCLE-BASED METAL-ORGANIC FRAMEWORKS Adrian Saura-Sanmartin,a Alberto Martinez-Cuezva,a Marta Marin-Luna, a Jose Berna.a a Departamento de Química Orgánica, Facultad de Química, Regional Campus of International Excellence “Campus Mare Nostrum”, Universidad de Murcia, 30100 Murcia, Spain, e-mail: [email protected]

Keywords: host-guest chemistry ● macrocycles ● selective recognition ● metal-organic frameworks ● fullerene The use of macrocyclic organic linkers in the preparation of metal-organic frameworks (MOFs) provides flexible materials with huge cavities (large pore sizes) in comparison with small and rigid organic ligands [1]. These macrocycle-based MOFs can be employed for the recognition of large molecules, such as fullerene derivatives [2]. Herein, the preparation of flexible metal-organic frameworks using polyamide macrocyclic linkers functionalized with carboxylic acids groups is described [3]. These materials crystallizes forming 1D-periodic linear polymers with bent macrocycles coordinated through the carboxylate moieties to dimeric copper(II) clusters. The incorporation of fullerene C60 inside the cavities of these MOFs was performed (Figure 1), uptaking a remarkable 34% w/w. These metallopolymers show greater selectivity for the smaller fullerene derivative (C60) in comparison with the larger one (C70), allowing the complete elimination of C60 from different mixtures of C60:C70.

Figure1. Computed model of C60 encapsulated inside the cavity delimited by two macrocycles. References

[1] Zhang, H. et al. Coordination Chemistry Reviews. 2015, 292, 74-90. [2] (a) Chae, H. K. et al. Nature. 2004, 427, 523-527; (b) Inokuma, Y. et al. Nature Chemistry 2010, 2, 780-783; (c) Feng, Y. et al. Journal of the American Chemical Society. 2015, 137, 15055-15060; (d) Martinez, V. et al. Chemistry of Materials. 2020, 32, 10628-10640. [3] Saura-Sanmartin, A. et al. Angewandte Chemie International Edition. 2021, 60, 10814-10819. Hot Paper. Acknowledgments This research was supported by the MINECO and MICINN (CTQ2017‐87231‐ P, PID2020‐ 113686GB‐ I00 and RYC‐2017‐ 22700) and Fundacion Seneca‐CARM (Project 20811/PI/18). A.S.‐ S. thanks to the Fundación Séneca‐CARM for his Ph.D. fellowship (20259/FPI/17). The authors also thank the computer resources at Cibeles and the technical support provided by the Centro de Computacion Cientifica‐UAM (RES‐ QSB‐ 2019‐ 3‐ 0012).

O-04

MOLECULAR ENCAPSULAGION USING MOLECULAR CAGES

Vicente Martí-Centelles,a Giovanni Montà González, Félix Sancenón, Ramón Martínez-Máñez a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM) Universitat Politècnica de València, Universitat de València. Camino de Vera, s/n. 46022, Valencia, Spain. e-mail: [email protected]

Keywords: Molecular Cages ● Supramolecular Chemistry ● Encapsulation ● Host-Guest Chemistry ● Sensing

Tailored cage cavities have attracted attention to supramolecular chemists, who have developed numerous molecular cages for encapsulation of guest molecules. The interest is constantly growing, with the work developed focused on the development of structures with tailored cavities for numerous applications including catalysis, molecular recognition, gas separation, catalysis, materials chemistry and emerging biomedical applications.[1,2] The large structural variety and the synthetic facility of the molecular cages have allowed the development of the field in the last decade. Cage synthesis involves the self-assembly of building blocks with precise shape and geometry under equilibrium control to yield the most stable cage structure, and therefore it is required a labile nature of the bonds formed in the self-assembly process to drive cage formation. In this communication the different structural parameters in the building blocks that define the cage geometry will be presented. Cage design is key to define the host- guest properties of the cage that depend on its volume and chemical nature of the groups that form the cavity, just changing one single atom can have dramatic effects in their properties.[3,4]

Figure1. Generic structure of a molecular cage that is self-assembled from the corresponding building blocks and the encapsulation of a guest molecule. References [1] Adriaenssens, L.; Ballester, P. Hydrogen Bonded Supramolecular Capsules with Functionalized Interiors: The Controlled Orientation of Included Guests. Chem. Soc. Rev. 2013, 42, 3261–3277. [2] Biros, S. M.; Rebek, J. Structure and Binding Properties of Water-Soluble Cavitands and Capsules. Chem. Soc. Rev. 2007, 36, 93–104. [3] Martí-Centelles, V.; Spicer, R. L.; Lusby, P. J. Non-covalent allosteric regulation of capsule catalysis Chem. Sci. 2020, 11, 3236-3240. [4] Martí-Centelles, V.; Lawrence, A. L.; Lusby, P. J. High Activity and Efficient Turnover by a Simple, Self- Assembled Artificial "Diels-Alderase" J. Am. Chem. Soc. 2018, 140, 2862-2868.

Acknowledgments V.M.-C thanks the financial support from Generalitat Valenciana (CIDEGENT/2020/031).

O-05

An off-on fluorescent probe for the sensitive detection of Alanine Aminopeptidase (APN) in real urine samples

Marcia Domíngueza, Juan F. Blandeza,b,c, Félix Sancenóna,b,c,d, and Ramón Martínez-Máñeza,b,c,d

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Spain, [email protected] bUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, Spain. cUnidad Mixta de Investigación en Nanomedicina y Sensores, Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, Spain. dCIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Spain.

Keywords: Kidney ● Nile blue ● Alanine aminopeptidase ● Drug-induced kidney injury ● Human urine Kidneys are in charge to regulating body fluid homeostasis, filtration of blood as well as in the maintenance of the balance of electrolytes. Furthermore, in this organ is carried out the metabolism and excretion of drugs, contrast agents, or other environmental hazards. Due to their functions, the kidneys can be strongly affected in presence of toxic substances as can be certain drugs such as cisplatin or doxorubicin.1-3 In particular, drug-induced kidney injury (DIKI) is a common complication in intensive care unit (ICU) patients with a high risk of morbidity and mortality.4,5 The overexpression of alanine aminopeptidase (APN) enzyme in urine can be related with renal damage overexpressed that suffer patient treated with doxorubicin or cisplatin used in chemotherapy treatment. Until now, several methods have been developed to evaluate APN activity. However, the direct detection of enzymatic activity by fluorescence in urine is a particularly attractive method, due to its cost effectiveness, simplicity, high sensitivity and selectivity.6,7 In this work, we describe the design and development of a fluorogenic probe based on Nile Blue (NB) fluorophore (NB-ALA) to detect the presence of APN in real urine sample. To investigate detection sensitivity and specificity of NB-ALA, fluorescence spectra were measured in the absence or presence of the enzyme. Solutions of NB-ALA (in the absence of APN are weakly emissive in contrast with the fluorescent emission enhancement observed in the presence of enzyme. This fluorescence emission enhancement was ascribed to the APN induced hydrolysis of NB-ALA probe which yielded the highly emissive NB fluorophore (Figure 1). Probe solution in the presence of other enzymes and chemical reagents demonstrated the selectivity of NB-ALA. Effectiveness probe was also evaluated in real urine samples, obtaining excellent performance in the detection of APN activity in human urine. This work provide the development of NB-ALA as a NIR ultrasensitive fluorescent probe for specific detection of APN in urine sample with a detection limit of 5 ng/mL.

a-) b-)

Water/DMSO or Urine + APN

Figure1. a) The fluorescence signalling mechanism. b) Fluorescence emission spectra (λexc = 530 nm) of NB-ALA + APN (2 µg/ml) (red curve); and NB-ALA (black curve) in water/DMSO 99:1 v/v mixtures at pH 7.4. References [1] Choudhury, D.; Ahmed, Z. Nat. Clin. Pract. Nephrol. 2006, 2, 80−91. [2] Abuelo, J. G. N. Engl. J. Med. 2007, 357, 797–805. [3] Alobaidi R., Basu R. K., Goldstein S. L. & Bagshaw, S. M. Semin. Nephrol. 2015, 35, 2–11. [4] Network, V. N. A. R. F. T. N. Engl. J. Med. 2008, 359, 7−20. [5] Kellum, J. A.; Prowle, J. R. Nat. Rev. Nephrol. 2018, 14, 217−230 [6] Yan, F.; Tian, X.; Luan, Z.; Feng, L.; Ma, X.; James, T. D. Chem. Commun. 2019, 55, 1955−1958. [7] Huang, J.; Lyu, Y.; Li, J.; Cheng, P.; Jiang, Y.; Pu, K. Angew. Chem. 2019, 131, 17960−17968. Acknowledgments The authors thank the Spanish Government (RTI2018-100910-B-C41) and the Generalitat Valenciana (PROMETEO 2018/024) for support.

O-06

BODIPY'S DERIVATIVES FOR CATHINONE DETECTION

Jordi H. Contreras, P. Rodrigo Martínez, Ana M. Costero, Salvador Gil

Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat de Valencia, Doctor Moliner 50, Burjassot, 46100 Valencia, Spain

[email protected], [email protected], [email protected], [email protected]

Keywords: BODIPY • NPS • chemodosimeter • click chemistry • fluorescence

Synthetic cathinones belong to a wide group of compounds known as New Psychoactive Substances (NPS). These substances, also known as "salt bath" or "designer drugs", were isolated for the first time in 2005. Their use causes similar stimulating effects that these produced by other common drugs such as amphetamine, methamphetamine or MDMA [1]. Methylendioxypyrovalerone (MDPV), mephedrone and methylone are the only derivatives that are under international control since 2015. The aim of this work is to develop a chemodosimeter based on the BODIPY structure in order to achieve a generic detection of cathinones. The 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene, also known as BODIPY (boron- dipyrromethene), can be easily modified to obtain derivatives with photophysical properties different to the parent compound. This fact allows the use of BODIPY derivatives to design sensors for many analytes. [2]. Cathinones are known to be capable of reducing Cu2+ to Cu+. That property led us to think about Click Chemistry. In this sort of reaction, Cu+ acts as a catalyst between an azide and a terminal alkyne, giving rise to an 1,2,3-triazole derivative [3]. In the development of this work, an alkyl group was added to the core structure of the BODIPY, and after triazole formation, a fluorescence change occurs. This study was carried out using two BODIPY modified at 2 and 8 positions. It is concluded that Click reaction product showed more fluorescence quantum yield than the starter material. Nevertheless, a quenching effect appeared when low concentration of cathinone was used.

+ + N - N N - N B B F F F F Figure 1. BODIPY derivatives

References [1] Philp, M. et al. Development and validation of a presumptive color spot test method for the detection of synthetic cathinones in seized illicit materials. Forensic Chemistry, 2016, 1, 39-50 http://dx.doi.org/10.1016/j.forc.2016.06.001 [2] Li, l. et al. Syntheses and spectral properties of functionalized, water-soluble BODIPY derivatives. Journal of Organic Chemistry, 2008, 1963-1970, 73(5) https://doi.org/10.1021/jo702463f [3] Agalave, S. et al. Click chemistry: 1,2,3-triazoles as pharmacophores. Chemistry - An Asian Journal, 2011, 2696- 2718, 6(10) https://doi.org/10.1002/asia.201100432 Acknowledgements This research was funded by Spanish Government, MICINN funds (RTL2018- 100910-B-C42 and RTI2018-100910- B-C41), MSC (Plan Nacional de drogas) 2020I040 and the Generalitat Valenciana (PROMETEO 2018/024) for financial support.

O-07

CHROMOGENIC CHEMODOSIMETER BASED ON CAPPED SILICA PARTICLES TO DETECT SPERMINE AND SPERMIDINE

Mariana Barros,a Alejandro López-Carrasco,a Pedro Amorósc, Salvador Gil a,b, Pablo Gaviñaa,b, Margarita Parraa,b, Jamal El Haskouric, M. Carmen Terencioa,d, Ana M. Costeroa,b a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM). Universitad Politècnica de València, Universitat de València, Doctor Moliner 50, Burjassot, 46100, Valencia, Spain. [email protected] b CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) (Spain) c Instituto de Ciencia de Materiales (ICMUV), Universitat de València, P.O. Box 2085, 46071, Valencia, Spain. d Departamento de Farmacología, Universitat de València. Vicente Andrés Estellés S/n, Burjassot, 46100, Valencia, Spain

Keywords: Detection ● Spermidine ● Spermine● Silica particles Detection of polyamines like spermine (Spm) and spermidine (Spd) is a field of research since these amines have evidence to be interesting biomarkers in the detection of various pathological situations [1- 3]. Recently, the studies are focused to get new probes because they can be used to detect the presence of these polyamines in biological fluids and tissues with no need of expensive instruments [4-5]. Therefore, a new hybrid organic–inorganic material based on MCM-41 functionalized with an N- hydroxysuccinimide derivative and loaded with rhodamine 6G has been developed for the sensing of Spm and Spd. A covalent bound is formed between silica nanoparticles and the inner layer. In addition, hydrogen and hydrophobic interactions occur to create an external coverage of organic matter that causes the dye to be kept inside the porous. In the presence of amine groups this coverage is removed and, consequently, the pores open, and the dye is released. Fluorimetric titrations were performed to release studies, obtaining limits of detection of 27 µM for Spm and 45 µM for Spd. The sensor remains silent in the presence of other biologically important amines and can be used to detect Spm and Spd in aqueous solution and in cells.

Figure1. Sensing protocol for detecting Spm and Spd. References [1] Gerner, E.W. et al. Nature Reviews Cancer. 2004, 4, 781–792. [2] Gupta, S. et al. Cancer Research. 2000, 60, 5125–5133. [3] Gilmour, SK. et al. Toxicology and applied pharmacology. 2007, 224, 249–256. [4] Jiang, G. et al. Sensors and Actuators B. 2018, 261, 602-607. [5] Sancenón, F. et al. ChemistryOpen. 2015, 4, 418-437.

Acknowledgments We thank the SCSIE (Universitat de València) for all the equipment employed. NMR was registered at the U26 facility of ICTS “NANBIOSIS” at the Universitat of València. M.B. thanks the Generalitat Valenciana for her Grisolia Grant.

O-08

SENSOR FOR FOOD ANALYSIS APPLYING IMPEDANCE SPECTROSCOPY AND ARTIFICIAL NEURAL NETWORKS

Josef Peter Gessler,a Laura Contat Rodrigo,b Nicolás Laguarda Miró,b Miguel Alcañiz Fillol,b y Rafael Masot Peris,b aDpto.de Ingeniería Electronica, UPV, Camí de Vera s/n, Valencia 46022, Spain, [email protected] bInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universitat Politècnica de València (UPV)-Universitat de València (UV), Camí de Vera s/n, 46022, Valencia, Spain Keywords: Electrical impedance spectroscopy ● Artificial neural network ● ESP32 ● Salt content The objective of the thesis was to design a portable low-cost measurement device for saline solutions applying electrical impedance spectroscopy (EIS) and artificial neural networks (ANN). In food analysis, EIS is an effective method to measure chemical concentrations or to determine certain physical properties [1]. At a basic level, the method consists of the acquisition of electrical impedances at various frequencies and subsequently the evaluation of the resulting series of complex values.

The first step was to investigate the feasibility of measuring with a frequency up to 30 kHz with the microcontroller ESP32. The ESP32 is a family of low-cost dual-core System-on-Chip-Controllers developed by Espressif Systems and designed for the Internet-of-Things.

The following step was to program embedded software in C++ for digital signal processing. Multitasking was realized with FreeRTOS which is included in the Arduino framework. Its main tasks were the stimulation signal generation on the internal DAC, to sample the resulting signals with the ADC in a DMA-accelerated mode and to calculate the complex impedance values.

Several solutions for an adjustable transimpedance amplifier were examined. To enable precise and accurate measurement a PCB was designed with Proteus Design Suite carrying the ESP32-module and containing the analogue amplifier circuit.

A graphical user interface was programmed in Python which communicates with the microcontroller via UART through a virtual serial port, facilitating the acquisition of sensor data, to configure the device and visualizing spectra.

Finally, an ANN was implemented [2]. Spectroscopy data had to be acquired in order to determine the exact architecture and to train the ANN to classify given samples. The applicability of the prototype was proven by determining the salinity of aqueous solutions.

References [1] Masot Peris, Desarrollo de un sistema de medida basado en espectroscopía de impedancia para la determinación de parámetros fisicoquímicos en alimentos, Valencia,Spain, 2010 [2] Goodfellow,Bengio,Courville,Deep Learning (Adaptive Computation and Machine Learning series), The MIT Press ,2016

Acknowledgments The presented work was carried out at the “Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM)” in Valencia, Spain, 2021

O-09

THE DEVELOPMENT OF PHOTOTHERMAL THERAPY DEVICES IN THE IDM

José Manuel Terrés-Haro a,b, Javier Ibañez a,b, Rafael Masot-Peris a,b, Eduardo García-Breijo a,b a Instituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València - Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain: [email protected] b Departamento de Ingeniería Electrónica (UPV, C/ Vera s/n, 46022, València, España).

Keywords: Photothermal therapy ● Hyperthermia ● Drug release ● Electronic devices ● Lab automation Photothermal therapies started to become a relevant topic at the first decade of the XXI century [1]. They consist in using an electromagnetic radiation to treat various diseases, in this case, cancer [2]. The Instituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico (IDM) has proposed different methods to apply this treatment mediated by nanoparticles, both by the production of heat and the localized release of drugs when the sample is irradiated by a laser [3, 4]. As the ideas evolved from a proof- of-concept state, the need for robust and adaptive electronic devices to test the treatment viability became evident. This paper is a review of the progress of hyperthermia and photothermal therapy electronic devices in the IDM from the start of this line of investigation. It will discuss the design and alternatives presented to solve the various challenges during development. a b c

Figure1. a) First irradiation device prototype b) In-vitro system c) In-vivo equipment The first sample irradiation device, shown in Figure 1.a, was developed by Montes- Robles in 2016, using an 808 nm and 500 mW laser in a thermostatic chamber to keep the samples in the human body average temperature [5]. Then it was followed by the in- vitro system in Figure 1.b, with automatic sample positioning, allowing to reduce the manipulation of the samples to the least possible and with much more robust electronics. The next development is called the in-vivo equipment, shown in Figure 1.c, which has a laser header sustained by a flexible arm, allowing to irradiate one individual sample at a time but with different distance and angle to it. References [1] Jaque, D. et al. Nanoscale, 2014, 6, 9494-9530 [2] Mendes, R. et al. Sci Rep, 2017, 7, 10872 [3] Hernandez, A. et al. ACS Appl. Mater. Interfaces, 2018, 10(33), 27644-27656 [4] Hernandez, A. et al. Chemistry Europe, 2019, 25(36), 8471-8478 [5] Montes, R. et al. Sensors and Actuators A: Physical, 2017, 255, 61-70 Acknowledgments This research is funded by MINECO/FEDER RTI2018-100910-B-C43 and FPU17/03800

O-10

System for monitoring deformation in reinforced concrete structures with wireless connection

Luis Chapa Chordá,a Vicente Beltrán Morte,a Cristina Bastida Molina,a Roberto Vengut Tro,a José Manuel Gandía Romero,b Miguel Alcañiz Fillol.b aSchool of Design Engineering, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain, registered author e-mail : [email protected] bInteruniversity Research Institute for Molecular Recognition and Technological Development, Universitat Politècnica de València - Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain Keywords: Reinforced concrete ● Deformation measurement ● Stain gauges ● Remote monitoring ● Mussel raft Deformation is a critical issue in reinforced concrete structures in marine environment. Cracks produced by expansion stress allow aggressive ions to penetrate to the inner of concrete and accelerate the corrosion of steel bars [1]. A low-cost deformation monitoring system for reinforced concrete has been designed. The system will be used to monitor the mechanical stress suffered by reinforced concrete mussel rafts manufactured by the company Research and Development Concretes, S.L. [2]. As the mussel rafts are installed in the sea the system will include a wireless communication interface (3G/4G) and will be powered by means of a solar panel and a battery. The system also includes a single board computer (Raspberry Pi) connected through a RS- 485 bus to the measurement boards. Each measurement board can measure the deformation in up to 4 points of the structure by means of strain gauges that can be configured in different modes (quarter bridge, half bridge or full bridge). The measurement board is based on an ARM 32-bit microcontroller that digitizes the analog signals coming from the instrumentation amplifiers connected to the strain gauges bridges. To allow an initial calibration of the system (zeroing of the Wheatstone bridge), a quad analog-to-digital converter is used. The Raspberry Pi collects the deformation data from the measurement board and store them in text files for further processing. This information will be used to analyse the relation between the intensity of sea waves and the stress suffered by the reinforced concrete mussel raft.

RS-48 5 Bus Measurement Measurement board board

Central Unit Deformation Raspberry Pi measurement So la r P an e l p oi nt Battery 4 G M o de m Measurement board Measurement board

Figure1. Deformation measurement system block diagram. References [1] Wang, X. et al. Construction and Building Materials. 2021, 266, 121018. [2] Kolver, K. et al. (Eds.) ConcreteLife 2020. 2020, 26, 121-125. Acknowledgments This project has been carried out thanks to the funding of the company Research and Development Concretes, S.L.

O-11

DEVELOPMENT AND PERSPECTIVES OF OPTOCHEMOGENETIC DEVICES AT IDM Javier Monreal-Trigoa,b, José Manuel Terrés-Haroa,b, Esther Giraldoc,d, Victoria Moreno-Manzanoc; *: [email protected] a Departamento de Ingeniería Electrónica (UPV, C/ Vera s/n, 46022, València, España). b I.I.I. en Recon. Molecular y Desarrollo Tecnológico (idm UPV-UV) (UPV, C/ Vera s/n, 46022, València, España) c Neuronal and Tissue Regeneration Lab (C. de Investigación Príncipe Felipe, C/ Eduardo Primo de Yúfera 3, 46012, Valencia, España). d Departamento de Biotecnología (Universitat Politècnica de València, C/Vera s/n, 46022, València, España). Keywords: Optochemogenetics ● High Irradiance ● Stimulation Device ● Measurement System ● Biomedical Device Following the emergence of protein-coding opsin genes that respond to illumination at certain optical wavelengths, optochemogenetic techniques have seen increasing development and interest. The response of these biosystems is mainly characterized by triggering events after stimulus and hyperpolarizing and depolarizing currents [1]. Hand in hand with the development of the field, electronic equipment has been emerging to perform the various experiments, generally with highly specific characteristics in terms of light power density, temporal parameters or applied wavelength [2,3,4,5]. There are some devices available that are more flexible in terms of wavelength and configuration of the stimulus sequences, but with real shortcomings in terms of their power density limits (<0.04 mW/mm2), space occupied and high economic cost [5,6]. At the IDM we are developing configurable devices for optochemogenetic stimulation (and measurement) at a more competitive price than state-of-the-art alternatives (see Fig. 1): • OSIVE, operating at 470 nm and 590 nm (and implementable in either) with up to 0.2 mW/mm2 configurable in real time from a personal computer. • OSIVE IMS, real-time measurement system in the full visible and near-infrared spectrum with a 27 mW/mm2 full scale and six additional scales with lower full scale. • OSIVE Slim, a slim version of OSIVE that fits the dimensions of the confocal microscope, thus being able to observe fast transients after stimulation. • OSIVE High Irradiance, a version under development with a maximum irradiance of 10 mW/mm2.

Figure 1. Optochemogenetic Stimulation for In-Vitro Experimentation (OSIVE) device family tree. References Acknowledgments [1] Mattis, J. et al. Nat Methods. 2012, 9(2): 159–172. This research was supported by the Spanish Ministry of [2] Bugak, L., et al. Nature Protocols. 2019, 14: 2205– Science, Innovation and Universities via a doctoral grant 2228. to J. Monreal-Trigo (FPU17/03239) and J. M. Terrés- [3] Yu, S. et al. The J. of Neuroscience. 2019, 39(33): Haro (FPU17/03800), and by the Spanish 6571–6594. Government/FEDER funds (RTI2018-100910-B-C43) [4] Weick, J., et al. Stem Cells. 2010, 28(11): 2008– (MINECO/FEDER) and RTI2018-095872-B-C21/ERDF. 2016. [5] Park, S. et al. Scientific Reports. 2015, 5: 9669. [6] Gerhardt, K. et al. Scientific Reports. 2016, 6: 35363. [7] Bugaj, L. et al. Nature Protocols. 2019, 14: 2205- 2228.

O-12

LOW COST MEASUREMENT SYSTEM FOR BIOSENSORS BASED ON ORGANIC ELECTROCHEMICAL TRANSISTORS (OEFTS) AND FIELD EFFECT TRANSISTORS (FETS)

Vicente Beltrán Morte,a Javier Monreal Trigo,b Jakob Sabbe,c Flor Boydens,c Miguel Alcañiz Fillol,b Liv K. Heidenreich.d e aSchool of Design Engineering, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain, registered author e-mail : [email protected] bInteruniversity Research Institute for Molecular Recognition and Technological Development, Universitat Politècnica de València - Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain cElectronics ICT, Odisee University College, 9000 Ghent, Belgium dCalifornia NanoSystems Institute, University of California, Los Angeles, CA 90095 eDepartment of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095

Keywords: Low-cost measurement system ● Field Effect Transistor ● Low noise ● Low current ● Organic Electrochemical Transistor

In recent years an important number of sensing devices have been developed, which take advantage of the transistor effect for improving the sensitivity, the signal-to-noise ratio and the detection threshold. For example, Organic Electrochemical Transistors (OECT) are based on the modulation of the channel current by electrochemical doping or de-doping from the electrolyte when gate voltages are applied. Our research group has recently developed OECTs based on PEDOT:PSS for the measurement of ascorbic acid in orange juice [1]. Moreover, the binding of aptamers to the surface of the channel present in a Field Effect Transistor (FET) translates in a high specificity sensor, which drain-source current changes depending on the concentration of the target molecule. The group of Dr. Anne M. Andrews (University of California Los Angeles) has developed a functionalized FET able to measure serotonin and other neurotransmitters in a low concentration level and with a very good selectivity [2]. The present work consists of the development of a low-cost electronic measurement system for FETs and OECTs. This measurement system has the following characteristics: low noise, high precision for low-current measurements and high temporal resolution. This system is also battery-powered and will have a microcontroller with ARM Cortex M0+ core and firmware programmed in low-level C as main logic element. Moreover, a Matlab software that receives and plots the data sent by the electronic system and stores it for posterior analyses has been developed. A basic validation of the system will be carried out with the functionalized FETs developed by Anne Andrews’ group and the OECTs developed by our research group. References [1] Contat-Rodrigo, L. et al. Organic electronics. 2017, 47., 89-96. [2] Nakatsuka, N. et al. Science. 2018, 362., 319-324.

O-13

WIRELESSLY POWERED REINFORCED CONCRETE CORROSION MONITORING SYSTEM BASED ON POTENTIAL STEP VOLTAMMETRY

Cristina Bastida-Molina a, Roberto Vengut-Tro a, Vicente Beltrán Morte a, Josep Ramon Lliso- Ferrando b,c, Ana Martínez-Ibernón b,c, Ignasi Cairó d. a Escuela Técnica Superior de Ingeniería del Diseño (ETSID). Universitat Politècnica de València, Camino de Vera s/n, 46022 València, España, registered author e-mail: [email protected] bInteruniversity Research Institute for Molecular Recognition and Technological Development (IDM). Escuela Técnica Superior de Ingeniería de Edificación (ETSIE). Universitat Politècnica de València, Camino de Vera s/n, 46022 València, España. cEscuela Técnica Superior de Ingeniería de Edificación (ETSIE). Universitat Politècnica de València, Camino de Vera s/n, 46022 València, Spain. dWiteklab, C. Albinyana 109, 08223 Terrassa, Spain

Keywords: Wirelessly powered ● Supercapacitor ● Potencial step voltammetry ● Corrosion ● Reinforced concrete

Reinforced concrete deteriorates progressively due to corrosion of the embedded steel rebars. [1] Many conditions affect to the evolution of corrosion, so it is not possible to accurately predict when the maximum acceptable degree of corrosion beyond which repairs are required will be reached. This is a dangerous situation, since degradation causes the concrete to detach from the steel and the structures fall apart. Typically, an on-site destructive analysis is carried out by a technician via a wall perforation to quantify corrosion. The topic of this work is the design of a system for corrosion monitoring that is embedded in the structure before concrete pouring. It allows to quantify corrosion with the desired periodicity without impacting the structure nor requiring specialized technicians. The device employs potential step voltammetry as the measuring technique [2]. The system is powered by a supercapacitor [3], which is charged wirelessly by an external device with the energy to perform one measurement cycle. The data communications are performed wirelessly as well. In order to allow completely wireless operation, an electronic circuit with low consumption components is designed, and an ARM Cortex M0+ microcontroller is programmed to work in ultralow consumption mode, making use of advanced power management techniques. The system has been experimentally validated by measuring the corrosion of different samples of reinforced concrete submerged in water and comparing the results with the reference measurements obtained with different commercial laboratory equipment. The corrosion monitoring technique that is used is based on the European patent 3293509 of the UPV that is currently exploited by the company Witeklab, expert in wireless technology, in collaboration with which the project is developed. References [1] Luca, B. et al. Maintenance, Management, Life-Cycle Design and Performance. 2008, vol. 4., 123-137. [2] Ramón, J.E. et al. Cement and Concrete Composites. 2020, vol. 110, 103590 [3] Agbaeze, A. et al. Renewable and Sustainable Energy Reviews. 2017, vol .77, 486-505

Acknowledgments This project has been carried out thanks to the funding of the company Witeklab. The authors would like to express their gratitude to the Spanish Ministry of Science and Innovation for the pre- doctoral scholarship granted to Ana Martínez Ibernón (FPU16/00723). Also for the pre-doctoral scholarship granted to Josep Ramon Lliso Ferrando (FPI-UPV-2018).

O-14

WIRELESSLY POWERED REINFORCED CONCRETE CHLORIDE PENETRATION MEASUREMENT SYSTEM BASED ON CYCLIC VOLTAMMETRY

Roberto Vengut-Tro a, Cristina Bastida-Molina a, Vicente Beltrán-Morte a, Ana Martínez-Ibernón b,c, Josep Ramon Lliso-Ferrando b,c, Román Bataller-Prats b,d. aEscuela Técnica Superior de Ingeniería del Diseño (ETSID). Universitat Politècnica de València, Camino de Vera s/n, 46022 València, Spain, registered author e-mail : [email protected] bInteruniversity Research Institute for Molecular Recognition and Technological Development (IDM). Universitat Politècnica de València, Camino de Vera s/n, 46022 València, Spain. cEscuela Técnica Superior de Ingeniería de Edificación (ETSIE). Universitat Politècnica de València, Camino de Vera s/n, 46022 València, Spain. dWiteklab, C. Albinyana 109, 08223 Terrassa, Spain

Keywords: Wirelessly powered ● Supercapacitor ● Cyclic voltammetry ● Chloride penetration ● Reinforced concrete

Chlorides are one of the main causes of corrosion in reinforced concrete structures, especially those near the sea or in areas where salt is used to melt ice on roads [1]. They reach the concrete surface via salt spray (fog) caused by breaking waves and wind, underground water intrusion into the structure's foundation and direct contact with substances such as salt. There, chlorides spread towards the inside of the construction and reach the steel rebars embedded in the concrete in less than a year, dramatically increasing the rate of corrosion. Reinforced concrete eventually reaches a maximum acceptable degree of deterioration, beyond which repairs are required to prevent detaching of concrete from the rebars. As the occurrence of this point cannot be predicted, on-site destructive analysis are performed to assess the current state of the structure. In this work, the design of a system for measuring the penetration of chlorides which is embedded in the structure before concrete pouring is presented. It allows to quantify chloride ingress with the desired periodicity without impacting the structure nor requiring specialized technicians applying a cyclic voltammetry technique [2]. Energy for the operation is provided by a supercapacitor, charged wirelessly before each measurement cycle by an external device [3]. Results are transmitted wirelessly as well. To permit completely wireless operation, an electronic circuit with low consumption components has been designed, controlled by an ARM Cortex M0+ microcontroller programmed to achieve ultralow power consumption by means of sophisticated power management techniques. The system has been validated by measuring the evolution of three test pieces exposed to different chloride concentrations and comparing the results with reference measurements obtained with commercial laboratory equipment.

References [1] Neville, A. et al. Materials and Structures. 1995, 28, 63-70 [2] Correia, M. J. et al. Cement and Concrete Composites. 2006, 28, 226-32 [3] Agbaeze, A. et al. Renewable and Sustainable Energy Reviews. 2017, 77, 486-505 Acknowledgments This project has been carried out thanks to the funding of the company Witeklab. The authors would like to express their gratitude to the Spanish Ministry of Science and Innovation for the pre- doctoral scholarship granted to Ana Martínez Ibernón (FPU16/00723). Also for the pre-doctoral scholarship granted to Josep Ramon Lliso Ferrando (FPI-UPV-2018).

O-15

Asymptotic modeling of signaling in biomedical analysis

Antonio Doménech-Carbóa, José Luís Pontonesb, Clara Doménech-Casasúsc, David Ramosd

a Departament of Analytical Chemistry, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain.Registered author, e-mail: [email protected] bUrology Department, Hospital Universitari i Politècnic La Fe, Valencia, Spain. cHospital General de Requena, Valencia, Spain. dPathology Department, Hospital Universitari i Politècnic La Fe, Valencia, Spain.

Keywords: Theory ● Sensing ● Biomedical ● Electrochemistry ● Bladder cáncer

A theoretical modeling on disease diagnosis in biological fluids based on chemical signaling combining signals for marker and metabolites is described. Using different ratios between the intensities of optical, electrochemical, etc. signals, assumed to be linearly responsive to the concentration of metabolites, asymptotic relationships can be obtained usable for diagnostic purposes. This approach, who extends previous analysis of the general problem of the determination of an analyte in the presence of unknown interferents [1], is addressed to compensate concentration fluctuations in biological fluids due to water uptake, circadian cycles, etc. The proposed formulation is satisfactorily applied to the voltammetric diagnosis of bladder cancer in urine based on the sensing of Zn(II) and uric acid and other urine metabolites extending prior results [2]. a) b)

I(Y)* I(Y)*

Metabolic Signaling Malignant cell cycle

I(X)*

Healthy cell

d) c)

I(Y)* I(Y)*

I(X)* I(X)*

Figure1. Schematic representation of the relation between metabolites and signaling in the case of: a) unique marker metabolite solely produced by malignant cells; b) marker metabolite exclusively produced by malignant cells accompanied by the separate signal of other independent metabolite; c) separate signals of marker metabolite and inert metabolite both produced by healthy and malignant cells; d) the above case with the metabolites displaying overlapping signals.

References [1] Doménech-Carbó, A. et al. Sensors and Actuators B 2018, 265, 346-354. [1] Doménech-Carbó, A. et al. Spectrochimica Acta A 2020, 238, artic. 118432.

O-16

NEW INTERFEROMETRIC IN-VITRO FOOD ALLERGY DIAGNOSTIC SYSTEM BASED ON MOLECULAR ALLERGENS AND NANOPARTICLES

Rocio L. Espinosa a, c, María Garrido-Arandia b, Alejandro Romero-Sahagun b, Pedro Herreros a, c, Luca Tramarin a, c, Mª Fe Laguna a, c, Araceli Díaz-Perales b, Miguel Holgado a, c aCenter for Biomedical Technology (CTB), Universidad Politécnica de Madrid, Carretera M40, km 38, 28223 Pozuelo de Alarcón, Madrid, [email protected] bCenter for Plant Biotechnology and Genomics (CBGP), Universidad Politécnica de Madrid, Carretera M40, km 38, 28223 Pozuelo de Alarcón, Madrid cDepartment of Applied Physics and Materials Engineering, Escuela Técnica Superior de Ingenieros Industriales, Universidad Politécnica de Madrid, Calle de José Gutiérrez Abascal, 2, 28006 Madrid.

Keywords: Optical biosensor ● Interferometer ● Food allergy diagnosis ● Molecular allergens ● SiO2 nanoparticles Food allergy is a common disease worldwide with an important increase in children and young people. Component-resolved diagnostics (CRD) and the introduction of purified natural and recombinant allergenic molecules are promising tools to improve diagnosis efficiency and to clinically determine appropriate cut-off values. In this scientific work we developed a high-performance in vitro detection system for food allergy in a multiplex serologic IgE format which improves the specificity and selectivity of our biosensors, reducing the cross-reactivity and the matrix-effect in real serum assays. We demonstrated the effectivity of the system for one molecular allergen, with promising results to become a real alternative to existing CRD diagnostic tests based on specific IgE detection. The bio-transducers used are based on the patented and reported label-free Biophotonic Sensing Cells (BICELLs) in the configuration of Fabry-Perot multilayer interferometer (see [1] and [2]). Such BICELLs can be vertically interrogated and measured by the Interferometric Optical Detection Method (IODM) [3] through the read-out platform developed by BiOD s.l. We accomplished a novel assay framework inspired by the chemical and optical properties of SiO2 NPs and by the flexibility of the interferometric Fabry-Perot transducer used which helped us to solve the unspecific adsorption problem in diagnostic test based on specific IgE detection by separating the objective molecule, IgE, from the rest of the serum out of the sensor. The novelty of the methodology (already published [4] and patented [5]) lies on the use of a given size of SiO2 nanoparticles as filtering and signal amplification system to separate IgE from IgG and to improve the interferometric optical signal, respectively. Based on our findings, the successful implementation and outcome of the immobilization of different biomolecules supported the workability and feasibility of the system to become as an alternative for the existing food allergy diagnostic systems.

References [1] Sanza, F.J. et al. Biosensors and bioelectronics. 2011, 26, 4842–484 [2] Holgado, M. et al. Optical Detection System for Labelling-free High Sensitivity Bioassays, 2010 (patent). [3] Holgado, M. et al. Interferometric detection method, 2012 (patent). [4] Espinosa, R.L., et al. Biosensors and bioelectronics. 2020, 169. [5] Holgado, M. et al. Optical method of detection of a targeted molecule through amplification in the response of interference by index of refraction and dispersion, 2020 (patent). Acknowledgments This work has been developed by means of the funding received by the European project Allerscreening (H2020- NMBP-13-2017, project ID: 768641).

O-17

TOWARDS A COMPETITIVE IMMUNOASSAY WITH GOLD NANOPARTICLES FOR MMP9 INFLAMATORY BIOMARKER DETECTION IN TEAR SAMPLE

Beatriz Santamaría,a,b Yolanda Ramírez, b Ana María M. Murillo,b Luis Vallez,b Miguel Holgado,b,c a Dep. Ing. Mecánica, Química y Diseño Industrial, ETSIDI, UPM, Ronda de Valencia 3, Madrid 28012, Spain e-mail : [email protected] bGroup of Optics, Photonics and Biophotonics, Centre of Biomedical Technology, UPM, M40 km 38, Pozuelo de Alarcón 28223, Spain cDep. Física Aplicada e Ing. de Materiales, ESTII, UPM, C/ José Gutiérrez Abascal, 2, Madrid 28006, Spain

Keywords: Biosensor ● IODM ● Diagnosis ● Nanoparticles ● Optical transducer

Transducer based biosensors are widely used for proteins detection and their efficiency and advantages have been reported several times in the literature. In this work an optical biosensor based in the Interferometrical Optical Detection Method has been used for MMP9 biomarker detection into a tear sample [1]–[3]. The recognition of proteins within the tear matrix has not been possible with these sensors since all matrix components mask the detection signal. To overcome this challenge, for the first time, a competitive immunoassay with gold nanoparticles (NPs) is proposed in combination with a Point-of-Care device based on the Interferometric Optical Detection Method (IODM) [4]. NPs have been biofunctionalized with specific antibodies against the MMP9 and biosensor with a recombinant MMP9 protein. Thus, nanoparticles that have not recognized biomarkers within the tear will compete with the ones that have. Hence, a reference signal of 100 % will be achieved with nanoparticles that have not been mixed with the tear and the signal will decrease as the nanoparticles (in tear) detect the proteins.

Figure1. On the left a layout of the competitive immunoassay. On the right a simulated signal of the MMP9 recognition by using NPs. References [1] A. Acera, G. Rocha, E. Vecino, I. Lema, and J. A. Durán, Ophthalmic Res., 2008, vol. 40, 315–321. [2] R. Casquel et al., Anal. Bioanal. Chem., 2020, vol. 412, 3285–3297. [3] M. Holgado et al., Sensors Actuators B Chem., 2016, vol. 236, 765–772. [4] M. Holgado Bolaños et al., Patente, 2020, 2 750 374.

O-18

NANOSYSTEM BASED ON MESOPOROUS SILICA NANOPARTICLES FOR DUAL DELIVERY OF DOXORUBICIN AND miR-99a-5p TO TREAT BREAST CANCER Iris Garrido-Canoa,b, Anna Adam-Artiguesa, Ana Catarina Trigo Lameirinhasa, Juan F. Blandezb,c,d,e, Ana Llucha,f,g,h, Juan Miguel Cejalvoa,f,g, Pilar Erolesa,g,h, Ramón Martínez-Máñezb,c,d,e aBiomedical Research Institute INCLIVA, Valencia, Spain. [email protected] bCIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Madrid, Spain, cInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Valencia, Spain. dUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, , Valencia, Spain. eUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, IIS La Fe, Valencia, Spain fClinical Oncology Department, Hospital Clínico Universitario de Valencia, Valencia, Spain. gCentro de Investigación Biomédica en Red de Cáncer (CIBERONC), Valencia, Spain. Universitat de València, Valencia, Spain. h Universitat de València, Valencia, Spain Keywords: Mesoporous silica nanoparticles ● Breast cancer ● miRNA ● Therapy Breast cancer is one of the leading causes of cancer-related death among women worldwide [1]. Due to this fact, numerous researchers are focused on improving the efficacy of actual therapies for breast cancer treatment. In this context, microRNAs have been widely described to have an important role in modulating drug sensitivity [2]. Among them, the microRNA miR-99a-5p has been described by our group to increase the sensitivity to doxorubicin, which is a chemotherapy drug used for the treatment of breast cancer patients. This work aimed to develop nanodevices to deliver a combination of miR-99a-5p and doxorubicin into breast tumors. Therefore, mesoporous silica nanoparticles (MSNs) were employed. Besides, to improve therapeutic efficacy, MSNs were targeted to breast cancer stem cells (BCSCs), which are a tumoural subpopulation with a critical role in drug resistance [3]. Nanodevices were synthesized and characterized, and the effective delivery of the cargos and targeting ability were assessed in vitro. Next, the nanosystem was tested in an in vivo xenograft tumor model of breast cancer. Orthotopic tumors were generated in mice, and MSNs loaded with doxorubicin and miR-99a-5p (MSNs- miR99a-dox) were intravenously administered twice a week. Empty MSNs, MSNs loaded with doxorubicin (MSNs-dox) and MSNs loaded with miR-99a-5p (MSNs- miR99a) were employed as controls. Tumor growth was evaluated for one month. When compared to control mice, empty nanoparticles showed no effect, MSNs-miR- 99a and MSNs-dox showed an intermediate effect, and the MSNs-miR99a-dox efficiently inhibited tumor growth. Tumors were further analyzed by quantitative real- time PCR, thereby demonstrating that nanoparticles containing miRNA inhibited the expression of the miR-99a-5p target genes. Moreover, our nanodevices showed no adverse effect on body weight or hematological parameters. Herein, a new approach based on the delivery of miR-99a-5p and doxorubicin demonstrated to be an effective strategy to sensitize breast cancer to doxorubicin. Moreover, our results suggest that MSNs are effective and safe nanocarriers that can be employed to deliver microRNAs in vivo. References [1] Bray, F. et al. CA: A Cancer Journal for Clinicians. 2018, 68, 394–424, doi:10.3322/caac.21492. [2] Loh, H.Y. et al. International Journal of Molecular Sciences. 2019, 20, 1–27. [3] Bai, X. et al. Cancer Treatment Reviews. 2018, pp. 152–163 Acknowledgments We thank the Spanish Government (RTI2018-100910-B-C41), Generalitat Valenciana (PROMETEO/2018/024), CIBERBBN (CB06/01/2012), CIBERONC (CB16/12/00481), and ISCII/FEDER (PI18/01219) for support.

O-19

EXPLORING THE SYNERGY OF PAPER-BASED ELECTROPHORESIS AND LATERAL FLOW ASSAY: TOWARDS IMPROVED POINT-OF-CARE BIOSENSING.

Amadeo Sena-Torralba,a Sergi Morais, a,b and Ángel Maquieira a,b a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain bDepartamento de Química, Universitat Politècnica de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain

Keywords: ● Lateral flow assay ● Point-of-Care ● Sensitivity Enhancement ● Multiplexing ● Matrix Effect

Lateral flow assays (LFA) are currently the most used point-of-care sensors for both diagnostic (e.g. pregnancy test, COVID-19 monitoring) and environmental (e.g. pesticides and bacterial monitoring) applications. Although the technology at the base of LFAs is several decades old, in more recent years the integration of novel nanomaterials as signal transducers has brought novel analytical capabilities. Now we are at the verge of a new healthcare revolution: personalized medicine.1 In this communication we will present how the enhancements in LFAs can address the inherent challenges of personalized medicine such as signal amplification, multiplexing and quantification at the point-of-care. In particular, we are going to present a case study aimed at improving the analytical properties of lateral flow assay. We will show how the combination of electrophoresis and lateral flow assay can provide enhanced sample treatment capabilities to the latter, when evaluating complex biological samples such as un-diluted whole blood.2 The application of electrophoresis in lateral flow assay opens the doors to the development of multiple strategies, such as sample pre-concentration, flow rate modulation,3 signal amplification and enhanced multiplexing. Regarding the latter, we will also comment on the current need to develop a lateral flow assay for the simultaneous determination of the major food allergens in commercial products.4 We will discuss the key aspects that should be considered when developing multiplex detection strategies.

References

[1] Parolo C. et.al., Nature Protocol, 2020, 15, 3788–3816. [2] Sena A. et.al., Analytical Chemistry, 2021, 93, 6, 3112–3121. [3] Sena A. et.al., Biosensors and Bioelectronics, 2020, 168, 112559. [4] Sena A. et. al., Trends in Analytical Chemistry, 2020, 132, 116050.

Acknowledgements We acknowledge financial support from PROMETEO/2020/094. Part of the work exposed in this presentation has been performed during the PhD thesis of Dr. Amadeo Sena-Torralba, under the supervision of Prof. Arben Merkoçi at the Catalan Institute of Nanoscience and Nanotechnology (ICN2).

O-20

GRATINGS OF RESPONSIVE HYDROGELS FOR LABEL FREE- BIOSENSING María Isabel Lucío,a Andy Hernández Montoto,a Estrella Fernández,a Kheloud Berramdane,b Manuel G. Ramírez,b,c Inmaculada Pascual,b María-José Bañuls,a,d Ángel Maquieiraa,d

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, España. bDepartamento de Óptica, Farmacología y Anatomía, Universidad de Alicante, Apartado de correos 99, Alicante E- 03080, España. cInstituto Universitario de Física Aplicada a las Ciencias y las Tecnologías, Universidad de Alicante, Carretera San Vicente del Raspeig s/n, 03690 San Vicente del Raspeig, España. dDepartamento de Química, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, España.

Key words: Hydrogel ● Holography ● Diffraction gratings ● Label-free ● Optical Biosensor

Hydrogel-based diffraction gratings have shown great performance as transducers in the label-free sensing of pH, metal ions and glucose [1] and in the analysis of IgGs by competitive assays [2]. The analytical signal is generated after the illumination of the hydrogel-based gratings with a laser beam or a white light and it depends on their periodicity and refractive index. As the hydrogels are responsive, i. e. they incorporate molecules able to recognise specific targets [3], their response depends on this interaction [4]. However, despite the potential application of this systems, their use in biosensing is still not extensive as new appropriate design of materials is needed for this purpose.

In this communication, our latest results on the fabrication of hydrogel-based gratings, both as holograms and surface relief gratings, will be shown. Special emphasis on the optimization of the responsive hydrogels will be placed. In addition, the selective and successful detection of C-Reactive Protein with the most promising material will be addressed.

References [1] Yetisen, A. K. et al. Chem. Rev. 2014, 114 (20), 10654–10696. [2] Zhao, J. J. et al. Ind. Eng. Chem. Res. 2020, 59 (22), 10469–10475. [3] Koetting, M. C. et al. Mater. Sci. Eng. R Reports 2015, 93, 1–49. [4] Yetisen, A. K. et al. Biotechnol. Adv. 2016, 34 (3), 250–271. Acknowledgements This work was financially supported by the E.U. FEDER, the Spanish MINECO (PID2019-106601RB-I00 and AdBiHol-PID2019-110713RB-I00) and Generalitat Valenciana (PROMETEO/2020/094 and CDEIGENT/2018/024). M. I. Lucío acknowledges MINECO for her Juan de la Cierva Formación and Incorporación grants (FJCI-2016-29593 and IJC2018-035355-I).

O-21

BIO BRAGG GRATINGS: DIFFRACTIVE MOLECULAR NETWORKS FOR ON-FIBER LABEL-FREE BIOSENSING

Augusto Juste-Dolz,a Martina Delgado-Pinar,b Miquel Avella-Oliver,a,c Estrella Fernández,a Daniel Pastor,d Miguel V. Andrés,b Ángel Maquieira,a,c

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, 46022 Valencia, Spain. e-mail : [email protected] b Department of Applied Physics and Electromagnetism-ICMUV, Universitat de València, Burjassot 46100, Spain. c Departamento de Química, Universitat Politècnica de València, 46022 Valencia, Spain. d Photonics Research Labs, Universitat Politècnica de València, 46021 Valencia, Spain.

Keywords: Biosensor ● Optical microfiber ● Immunoassay ● Non-specific binding ● Label-free Discovering new nanoscale phenomena to transduce biorecognition events into quantitative signals promote new insights to exploit nanotechnology for bioanalytical purposes [1]. In this work, we present Bio Bragg Gratings (BBGs), a novel biosensing approach that consists of diffractive structures of protein bioreceptors patterned on the surface of optical waveguides [2]. As shown in Figure 1A, BBGs transduce the magnitude of biorecognition assays into the intensity of reflected signals. We assessed the design, fabrication, and optimization of this system by both theoretical and experimental studies, and explored the fundamental physicochemical parameters involved. The transduction principle was experimentally demonstrated by generating BBGs onto tapered optical microfibers and the bioanalytical prospects were assessed by a representative immunoassay based on protein probes and IgG targets. The results displayed well-correlated quantitative dose response curves in label-free conditions and presented appealing perspectives to avoid the signal contribution of non-specific bindings, herein investigated in human serum samples. Finally, the optical response of the system can be easily tuned, providing an interesting solution to conceive multiplexed BBG systems capable to perform multiple label-free biorecognition assays in a single device.

Figure1. Scheme of a BBG on a microfiber, its interaction with guided light and the optical response in the reflection spectra. References [1] Wong, X.Y. et al. ACS nano, 2020, 14, 2585-2627. [2] Juste-Dolz, A. et al. Biosens. Bioelectron. 2021, 176, 112916. Acknowledgments MINECO (CTQ2016-75749-R and TEC2016-80385-P), FEDER (PID2019-110877 GB-I00 and PDI2019- 104276RB-I00) and PROMETEO (PROMETEO/2019/048 and PROMETEO/2017/103). A.J.-D. acknowledges the FPI-UPV 2017 grant program, M.A.-O acknowledges the APSOSTD/2019 program of the GVA.

O-22

NANOSCALE PILLAR ARRAYS FOR VAPOR DETECTION

Sergio Quinteroa,b, Rafel Casquela,b , Maria Fe Lagunaa,b, Miguel Holgadoa,b aCenter for Biomedical Technology, Campus de Montegancedo, Universidad Politécnica de Madrid: [email protected] b Dep. de física aplicada e ingeniería de materiales, Escuela Técnica de Ingenieros Industriales, Universidad Politécnica de Madrid

Keywords: Optical Sensors ● Vapor sensing ● Photonic structures ● Optical inteferometers

Electronic and photonic noses are devices whose primary function is detecting volatile chemical compounds dissolved in the air. This sensing can be very useful in various fields, such as factory quality control, environmental monitoring, or even clinical tests [1,2]. Porous materials or nanostructured surfaces are beneficial for vapor detection since these topologies can promote condensation of the vapor molecules within the transducer and hence a magnification of the sensing signal. It is possible to find this type of structure in the novel transducer developed GOFB research group of the UPM, the Resonant nanopillars arrays (RNPs)[3]. The RNPs are optical interferometric sensors that can detect changes in the sample's refractive index with high precision. The array distribution of this type of sensor not only helps for the vapor detection but also improves the sensing signal's quality and robustness. However, the application of the RNPs for vapor sensing has been explored recently [4]. For this vapor detection proof of concept, several samples of volatile liquid solvents were placed in a chemical beaker close to the sensor in room pressure and temperature, see Fig. 1A. In particular, it was analyzed the following chemical samples: propionic acid (PAD), acetic acid (AAD), Toluene (TOL), Isopropanol (IPA), Ethanol (ETH), and methanol (MTH). For these samples, it was registered the sensor signal produced close to them at different working distances that range from 15.7 to 65.7 mm. It can be appreciated in Fig 1B the sensor had a distinguish response that depends on the distances to the sample liquid surface and the solvent vapor pressure. In particular, the sensor signal is higher the lower the sample vapor pressure is. These results point out that the RNPs transducers are suitable for vapor identification. However, further studies are required to understand the sensor behavior to species in vapor state deeply.

Figure1. (A) Scheme of the experimental setup. (B) Sensing signal obtained with the RNPs to the solvents at the different working distances. The plotted shift is calculated in respect of the no-vapor sensor baseline. References [1] Azzouz, A. et al. Trends in Analytical Chemistry. 2019, 118, 502-516. [2] Fitzgerald, J. et al. Trends in Biotechnology. 2017, 35, 33-42. [3] Hernández, A. et al. Sensors and Actuators B: chemical. 2017, vol., 956-962. [4] Quintero, S. et al. ACS Omega. 2020, 5, 25913-25918. Acknowledgments This work was supported in part by the Spanish Ministry (Ministerio de Economía y Competitividad) under project HERON under Grant TEC2017-84846-R. The work of S.Q. was supported by the predoctoral contract by the Universidad Politécnica de Madrid, Madrid, sponsored by Banco de Santander under grant RR24/2017.

POSTERS

P-01

MEDICAL IMAGING, VISUALISATION, MOLECULAR INFOGRAPHY AND PERCEPTION Francisco Torrens,a Gloria Castellano.b aInstitut Universitari de Ciència Molecular, Universitat de València, Edifici d’Instituts de Paterna, P. O. Box 22085, E-46071 València, Spain, registered author e-mail : [email protected] bCentro de Investigación Traslacional San Alberto Magno (CITSAM), Universidad Católica de Valencia San Vicente Mártir, Guillem de Castro 94, E-46001 València, Spain Keywords: Expertise ● Explicit knowledge ● Medical diagnosis ● Tacit knowledge ● Pain

Investigations are concentrated in facets related to visual evidence and shows, and the dynamics of comprehending and building expert knowledge in fields, e.g., medical diagnosis, visualisation of scientific data, molecular infography, perception and authentication of works of art [1]. What do persons understand by digital health [2]? How will future hospitals be [3]? What technologies will permit persons to make the transformation [4]? Which technologies are persons going to find in the hospital environment [5]? The present study helps coalesce a long-standing interest in visualisation of scientific data among historians, philosophers and sociologists of science, and remains a touchstone for current research in science and technology studies [6]. This work reviews the topic, taking into account the changing conceptual scenery of science and technology studies, and the emergence of imaging technologies in scientific practice. This work offers cutting-edge research on a broad array of fields, which study information and short reflections on the evolution of the subject. This work results a fresh approach to data visualisation practices in science, which considers new forms of imaging technology and draws on recent theoretical perspectives on representation and perception. Connecting the how, the what and the who in the matter of visualisation of scientific data. Persons are taught to expect close resemblance and invited to put their trust in a number of experts, but the emphasis on visual confirmation generates a reinforcing loop for the cultural trope of seeing for oneself and individual mystical connection via art. As sociologists and performances, the accounts of visualisation of scientific data are constitutive of epistemologies of seeing and knowing, and of art itself. References [1] Torrens, F., Ortí, E., Sánchez-Marín, J. Representación de propiedades moleculares en la didáctica de la Química, in: Colloquy University Pedagogy. Horsori, Barcelone, Spain, 1991, pp. 375-379. [2] Torrens, F., Castellano, G. A tool for interrogation of macromolecular structure, J. Mater. Sci. Eng. B 2014, 4(2), 55-63. [3] Torrens, F., Castellano, G. Pain and pleasure, in: Molecular Chemistry and Biomolecular Engineering: Integrating Theory and Research with Practice. Pogliani, L., Torrens, F., Haghi, A.K., (Eds.), Apple Academic– CRC, Waretown, NJ, 2020, pp. 173-190. [4] Torrens, F.; Castellano, G. Precision personalized medicine from theory to practice: Cancer, in: Green Chemistry and Biodiversity: Principles, Techniques, and Correlations. Aguilar, C.N., Ameta, S.C., Haghi, A.K., (Eds.), Apple Academic–CRC: Waretown, NJ, 2020, pp. 209-242. [5] Torrens, F., Castellano, G. From medical diagnosis to data visualization to works of art, in: Sensors and Molecular Recognition, Martínez Máñez, R., Aznar Gimeno, E., Bañuls Polo, M.J.; Bernardos Bau, A., Brun Sánchez, E.M., Díaz Betancour, Z., Garrido García, E.M., González Martínez, M.Á., González Pedro, M.V., Gorbe Moya, M., Lucio Benito, M.I., Martínez Bisbal, M.C., Pardo Vicente, T., Pérez Esteve, É., Tortajada Genaro, L.A., Eds., Universidad Politécnica de Valencia, València, Spain, 2020, Vol. 13, pp. 54-57. [6] Torrens, F., Castellano, G. Particle physics, show, and innovation: Industry, medicine, and big data, in: Chemistry and Chemical Engineering for Sustainable Development: Best Practices and Research Directions. Esteso, M.A., Ribeiro, A.C.F., Haghi, A.K., (Eds.), Apple Academic–CRC, Waretown, NJ, in press. Acknowledgments The authors acknowledge financial support from an internal aid from Universidad Católica de Valencia San Vicente Mártir.

P-02

DEVELOPMENT OF A FIBER-LOOP REFRACTOMETER BASED ON RESONANT MODAL COUPLINGS FOR BIO-SENSING APPLICATIONS Carolina Londero,a Martina Delgado-Pinar,b Christian Cuadrado-Laborde,a Miguel V. Andrés.c a Optics and Photonics Group, IFIR, UNR – CONICET, Bv. 27 de Febrero, S2000EKF Rosario, Argentina. [email protected] b Department of Applied Physics, University of Barcelona, c/ Martí I Franqués 1, 08080 Barcelona. c Laboratory of Fiber Optics, Department of Applied Physics, ICMUV, University of Valencia, c/ Dr. Moliner 50, 46100 Burjassot. Keywords: fiber-loop ● RI sensing ● resonant coupling ● sensor characterization ● photonic sensor In this work, we present a robust refractive index (RI) sensing device easily fabricated with a loop of optical fiber with prospects of its functionalization to perform as a biosensor. A section of curved single-mode fiber couples the light from the core-mode to the cladding modes in a resonant manner [1], resulting in a series of attenuation notches whose central wavelengths (λr) depends on different parameters, in particular the external refractive index [2]. This provides an enhanced evanescent tail of the optical cladding mode that makes this device sensitive to variations of the external medium, in particular the presence of a biological target. In this work, as a preliminary study, a wavelength-coded refractometer is developed. The dependence of λr with the loop radius (R) was analysed (Figure 1a), as well as the effect of temperature and the refractive index of the medium. The performance of the optical response in solutions with refractive indices between [1.33 , 1.37] of two particular devices (R= 5.25 mm and 6 mm) was measured (Figure 1b). Moreover, the resonant wavelength of one attenuation notch was monitored through time as the loop was immersed in and out of different EtOH-H2O solutions (Figure 1c). The sensitivity and limit of detection of these refractometers were determined (Table 1), and show good prospects for biosensing applications.

Figure1. a) Radius dependence of one resonant wavelength in air and water. b) Wavelength shift vs. refractive index change for two different resonances. c) Temporal evolution of the resonant wavelength shift subjected to different EtOH-H2O solutions. Table 1. Optical features of several resonant notches and the experimental sensitivities and detection limits.

R λr air ∆λ3 dB Minimum Transmittance Sensitivity Detection Limit [mm] [nm] [nm] [dB] [nm/RIU] [RIU] 5.25 1527.53 17.8 -16.1 261.32 8 · 10-4 6 1506.97 22.5 -19.3 327.69 6 · 10-4 6 1535.29 26.8 -14.8 378.38 5 · 10-4 References [1] Wang P. et al. Applied Optics 2009, 48, 31, 6044–6049. [2] Reyes M. et al. Sensors 2013, 13, 9, 11260–11270. Acknowledgments This work has been funded by the European Commission H2020-MSCA-RISE-872049 (IPN-Bio) project.

P-03

APPLICATION OF SILICA PARTICLES COATED WITH ESSENTIAL OIL COMPONENTS AS FILTERING AIDS FOR THE REMOVAL OF BACILLUS SUBTILIS SPORES

María Ruiz-Rico,a Susana Ribes,a José M. Barat.a aGrupo de Investigación e Innovación Alimentaria. Departamento de Tecnología de Alimentos, Universitat Politècnica de València. Camino de Vera s/n, 46022, Valencia, Spain. [email protected]

Keywords: Covalent immobilization ● Filtration ● Natural antimicrobial ● Bacillus subtilis ● Spores

The surface modification of materials to improve their functional properties can be adopted to develop novel filtering materials with great antimicrobial properties, overcoming the limitations of conventional filtration methodologies in water treatment and microbial stabilization of drinks [1]. Among microbial contaminants, bacterial spores are of great concern to the food industry due to their high resistance to physicochemical preservation treatments, which can result in spore germination and, therefore, food spoilage or potential foodborne diseases [2]. The aim of this work was to evaluate the applicability of natural antimicrobial-coated filtering materials for the removal of Bacillus subtilis spores from two liquid matrices (water and nutrient broth). The essential oil components (EOCs) thymol and vanillin were covalently immobilized on the surface of silica microparticles and the removal properties of the supports used as filtering materials were assessed against spores of B. subtilis by plate count and fluorescent viability staining. Filtering through the EOC-coated silica supports resulted in effective removal of the B. subtilis spores obtaining logarithmic reduction values between 4-5. The removal capacity observed could be produced by a combined effect of physical adsorption of the spores on the bed of particles and spores’ inactivation after coming into contact with the immobilized natural antimicrobials in accordance with the plate count and fluorescent viability results. Therefore, the antimicrobial-coated filtering aids have proven suitable for eliminating spore-forming microorganisms, confirming their use as a potential sterilization technique for preservation of different beverages alone or in combination with other mild-thermal or non-thermal techniques.

References [1] Ruiz-Rico, M. & Barat, J.M. LWT 2021, 111634. [2] Fan, L. et al. Food Res Int. 2019, 116, 1094-1102.

Acknowledgments The authors gratefully acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades, the Agencia Estatal de Investigación and FEDER-EU (Project RTI2018-101599-B-C21). M.R.R. acknowledges the Generalitat Valenciana for her postdoctoral fellowship (APOSTD/2019/118).

P-04

REMOVAL OF Zn(II) IONS FROM AQUEOUS SOLUTIONS WITH ORANGE WASTE-BASED ADSORBENT

Nelly Ma. Rosas-Laverde a*, David Castro a, Victor H. Guerreroa, Alina Prunab aDepartment of Materials, Escuela Politécnica Nacional, Quito 170524, Ecuador; *[email protected] bInstitute of Materials Technology, Universitat Politècnica de València, 46022 Valencia, Spain

Keywords: agro-industrial waste ● orange peel ● adsorbent ● zinc(II) ions ● adsorption kinetics

This work presents the removal of Zn(II) ions from 50 mg L−1 synthetic aqueous solutions with novel bio-adsorbent obtained from agro-industrial waste based adsorbents, namely from orange peels. The adsorbent particles were specifically modified with varying concentration of sodium hydroxide and calcium acetate solutions to improve the adsorption properties. The obtained particle adsorbent was characterized in terms of contents of the raw material (in agreement with ASTM standards), microstructure by scanning electron microscopy (SEM), composition and structure by Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). The results showed the adsorbent improved its performance towards Zn(II) removal with the increase in concentration of the modifier solutions, the particles modified using 0.8 M NaOH and Ca(CH3COO)2 solutions reaching 97% removal and a maximum adsorption capacity of 27.5 mg Zn per gram of bio-adsorbent. The fitting results indicated the kinetics of adsorption process follow a pseudo-second order model. The fitting results of non-linear models of Langmuir and Freundlich isotherms indicated Freundlich isotherm as best fit. The results obtained in this study indicates the approach of chemical modification of agro-industrial wastes represents a viable alternative for the synthesis of adsorbents for wastewater treatment technologies.

Table 1. Effect of modifier concentration on Zn removal performance of orange waste-based adsorbent Adsorbent Zn Removal (%) 0 91.9 ± 0.1 0.2 93.4 ± 0.1 0.5 96.2 ± 0.3 0.8 97.1 ± 0.2

References [1] Klara, P. et al. Materials 2020, 13, 1338 [2] Hoang, H.G. et al. Environ. Technol. Innov. 2020, 20, 101043. [3] Okereafor, U. et al. Environ. Res. Public Health 2020, 17, 2204.

Acknowledgments Authors would like to thank to Cristina Almeida and Belén Aldás for their useful advices.

P-05

IMPROVED ADSORPTION PERFORMANCE OF LAUREL LIGNOCELLULOSIC WASTE-BASED ADSORBENT UPON MODIFICATION WITH MAGNETITE NANOPARTICLES

Nelly Ma. Rosas-Laverde a*, Christopher Asimbayaa, Victor H. Guerreroa, Alina Prunab

aDepartment of Materials, Escuela Politécnica Nacional, Quito 170524, Ecuador; *[email protected] bInstitute of Materials Technology, Universitat Politècnica de València, 46022 Valencia, Spain; [email protected]

Keywords: magnetite ● lignocellulosic waste ● adsorbent ● zinc(II) ions ● laurel

This work presents an approach to improve the zinc removal from synthetic solutions with novel adsorbents obtained from lignocellulosic waste-based adsorbents, namely from laurel residues. The laurel residue particles were employed as support for the impregnation in a 1:1 wt ratio with magnetite nanoparticles obtained by co- precipitation. The adsorbents were characterized structurally and morphologically by X- ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The results confirmed the successful impregnation with magnetite nanoparticles of 20 nm in diameter. The adsorbent improved its performance towards Zn(II) removal upon modification with magnetite nanoparticles from 60% to 98.9% removal for 7 g/L adsorbent dose. The fitting results indicated the kinetics of adsorption process follow a pseudo-second order model. The isotherm fitting results indicated Freundlich isotherm as best fit. The results obtained in this study indicates the modification with magnetite nanoparticles of waste-based adsorbents is an attractive alternative for the synthesis of adsorbents for wastewater treatment technologies.

a b

Fig. 1. SEM image of laurel-based adsorbent before and after magnetite impregnation.

References [1] Ali, A. et al. Alexandria Eng. J. 2016, 55, 2933–2942. [2] Setyono, D. et al. ACS Sustain. Chem. Eng. 2014, 2, 2722–2729. [3] Azzaz, A. et al. Water Treat. 2016, 57, 22107–22119. [4] Chompu-Inwai, R. et al. J. Clean. Prod. 2015, 108, 1352–1364.

Acknowledgments Authors would like to thank to Salome Galeas and Alexis Debut for their useful advices.

P-06

EFFECT OF REDUCED GRAPHENE OXIDE BUFFER ON ELECTROCHEMICAL PROPERTIES OF POLYPYRROLE COATINGS Alina Prunaa*, Nelly Ma. Rosas-Laverde b, D. Busquets-Mataixa

aInstitute of Materials Technology, Universitat Politècnica de València, 46022 Valencia, Spain; [email protected] bDepartment of Materials, Escuela Politécnica Nacional, Quito 170524, Ecuador;

Keywords: electrodeposition ● reduced graphene oxide ● coatings ● polypyrrole ● electrochemical properties

This work presents the electrosynthesis of polypyrrole (PPy) coatings by cyclic voltammetry and their electrochemical properties with the presence of a chemically reduced graphene oxide (rGOC) layer as buffer. Fourier Transform Infrared Spectroscopy, Field-Emission Scanning Electron Microscopy, Raman spectroscopy and cyclic voltammetry were employed to characterize the properties of the coatings. It is shown that the use of rGO affects the electrodeposition and morphology of the PPy coating by forming complex networks and, consequently, both its bulk and surface contribution to the total stored charge. The effect on the contribution distribution to the total charge from the inner and outer charge was analyzed according to Trasatti, Dunn and Conway. The results showed higher dominance on the charge storage mechanism from the surface capacitive process. This work shows the modification of conducting polymers with rGO layer as buffer could represent an alternative approach to improve their electrochemical charge storage properties.

Fig. 1. Evolution of contributions to the current response with the scan rate for PPy electrodeposited onto GO and rGO C

P-07

ELECTROCHEMICAL PROPERTIES OF TERNARY GRAPHENE OXIDE-CARBON NANOTUBES-POLYPYRROLE COATINGS

Alina Prunaa*, Nelly Ma. Rosas-Laverde b, D. Busquets-Mataixa

aInstitute of Materials Technology, Universitat Politècnica de València, 46022 Valencia, Spain; [email protected] bDepartment of Materials, Escuela Politécnica Nacional, Quito 170524, Ecuador;

Keywords: coatings ● reduced graphene oxide ● carbon nanotubes ● polypyrrole ● electrochemical properties

Ternary nanocoatings based on polypyrrole (PPy) conducting polymer were electrosynthesized by cyclic voltammetry. Graphene oxide (GO) and multi-walled carbon nanotubes (CNTs) were employed in a hybrid buffer layer prior to the deposition of PPy coatings. The electrochemical properties of the ternary coatings were studied with the amount of GO:CNTs from a 1:1 wt. ratio to 1:2.5. Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Raman spectroscopy and cyclic voltammetry were employed to characterize the properties of the coatings. It is shown that electrochemical performance of ternary nanocoating improved with increasing the addition of CNTs and that inner charge had major contribution to total charge. The results obtained in this study indicates the formation of an electrode with high potential for electrochemical capacitors.

Fig. 1. Cyclic voltammograms of ternary PPY-rGO:CNT (1:2.5) nanocoatings with scan rate.

P-08

DESARROLLO DE NANOANTICUERPOS PARA EL DIAGNÓSTICO IN VITRO DE ALERGIA

Pedro Quintero-Camposa, Sergi Moraisa,b,c, Ángel Maquieiraa,bc

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València-Universitat de València, Camino de Vera s/n, E46022 Valencia, Spain. e- mail: [email protected] bDepartamento de Química, Universitat Politècnica de València, Camino de Vera s/n, E46022 Valencia, Spain. cUnidad Mixta UPV-La Fe, Nanomedicine and Sensors, IIS La Fe, Av. Fernando Abril Martorell, (46026), Valencia, Spain

Keywords: Hipersensibilidad ● Inmunoglobulina E ● Phage Display ●

La disponibilidad de sueros control humanos positivos es esencial para el desarrollo, producción, y evaluación de las pruebas in vitro de alergia. El uso de sueros humanos positivos es un paso necesario para llevar a cabo pruebas interlaboratorio “round robin” realizadas de forma independiente, utilizando muestras idénticas para la determinación de la precisión (repetibilidad y reproducibilidad) de los métodos in vitro de alergia. Sin embargo, este tipo de suero no existe para todos los alérgenos. Las muestras de suero de los biobancos muestran a menudo variabilidad en la concentración de IgE específica y normalmente para algunos alérgenos los niveles son muy bajos. Además, la cantidad de estas muestras es limitada, la accesibilidad difícil y éstas son muy caras. Así pues, actualmente no se dispone de material de referencia certificado específico con el que validar los métodos para la determinación de inmunoglobulina E específica. En este trabajo se presenta una solución científicamente interesante para superar estas limitaciones basada en el desarrollo de nanoanticuerpos mediante ingeniería de proteínas y tecnología Phage Display. Estos han mostrado una alta solubilidad, resistencia a altas temperaturas, buen rendimiento en su expresión en E. coli, y una elevada selectividad, con los que poder llevar a cabo ensayos in vitro de modo más preciso y normalizado.

Referencias [1] Rodríguez-Herrera, R., et al. Enzymes in Food Biotechnology. 2018, 627− 643. [2] Doña, I., et al. Allergy, Asthma Immunol Res. 2017, 9, 288−298.

Agradecimientos P. Q-C agradece a la GVA por la Beca Doctoral GVA ACIF/2018/173 para la realización de sus estudios de doctorado.

P-09

MULTIPLEXED QUANTITATIVE DETERMINATION OF ALLERGENS IN FOOD COMMODITIES BY LATERAL FLOW IMMUNOASSAY. Javier Gabaldón Atienza,a Amadeo Sena-Torralba,a Sergi Morais, a,b and Ángel Maquieira a,b a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain bDepartamento de Química, Universitat Politècnica de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain

Keywords: ● Allergens ● Nanoparticles ● Extraction ● Internal calibration ● Smartphone

Introduction In recent years, the food industry has experienced a real technological revolution that has led to the development of improved detection kits for the determination of food allergens. Special emphasis has been given to the design of simpler and faster tests based on lateral flow assay, more powerful sample extractors and more user-friendly quantification readers (smartphone-based). However, the multiplexed determination of the major food allergens, which has been one of the greatest challenges during the last decade, still remains to be fully addressed. The fact that the commercial kits are currently designed for individualized allergen identification represents a real bottleneck for the end user who is advocated to not only buy different detection kits, but to apply several sample extraction protocols, which cause high assay variability and low reliability.1 In this sense, we present a novel all-in-one multiplexed biosensing platform based on lateral flow assay, that includes an internal calibration approach for direct quantification. Methods We propose a grinder-based portable device that includes an attached lateral flow assay strip.2 The former, enables a power-free extraction of the allergenic substances present in the food sample, while the latter provides a fast, single-step and multiplexed detection of food allergens. Polyclonal antibodies were raised in rabbits against almond, hazelnut, peanut. 20 nm sized gold nanoparticles were used as labels and serial dilutions of anti-rabbit IgG antibodies were immobilized in the detection zone and used as internal signal calibrators. Results Here we show the characterization of the food extracts by electrophoresis and the characterization of the antibodies by western blot and ELISA. We also show the design and fabrication of the biosensing platform, as well as the assay characterization and optimization. We prove no cross-reactivity between the detection antibodies, high sensitivity (LoD < 100 ppb), reproducibility (CV < 15%) and good recoveries (> 80%) when evaluating the biosensor system with commercial cookies. Conclusion The proposed all-in-one biosensing platform represents a valid tool for the reliable and fast quantification of most of the major food allergens, proving direct applicability in real scenarios. References [1] Sena-Torralba, A. et al. Trends in Analytical Chemistry. 2020, vol.132, 116050. [2] Parolo, C. et al. Nature Protocols. 2020, vol. 15, 3788–3816. Acknowledgements We acknowledge financial support from PROMETEO/2020/094.

P-10

Novel (poly)rotaxane-based hydrogel for biomolecular sensing

Paola Zezza1, María Isabel Lucío1,2, María-José Bañuls 1,2, Ángel Maquieira1,2

1 Instituto Interuniversitario de Investigación de Reconoscimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politécnica de Valéncia, Universitat de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain. E-mail: [email protected] 2 Departamento de Quimica, Universitat Politécnica de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain.

Keywords: hydrogels ● biosensor ● polyrotaxane ● crosslinking ● analyte

Bioresponsive hydrogels are getting increased interest in biosensing applications. Recently, in our group, an acrylamide-based hydrogel biosensor for C-reactive protein (CRP) has been developed. This label-free system is based on diffractive gratings that have shown changes in its diffraction efficiency, proportionally to the CRP concentration. Herein, we prepared a series of poly(2-hydroxyethyl methacrylate) [p(HEMA)] hydrogels, employing simple free-radical polymerization reaction. As a bioreceptor, 2- methacryloyloxyethyl phosphorylcholine (MPC) was incorporated, to specifically recognize CRP [1]. A novelty of this work, for enhancing the mechanical performance of the designed biosensor, is the addition of (poly)rotaxanes. This supramolecule has great potential in smart materials due to the unique supramolecular structures, that supply freely movable macrocycles mechanically linked to polymer chains [2]. Polyrotaxane was included to get a freely movable crosslink, and so for expecting larger volume change in response to the analyte detection. Polyrotaxane-based hydrogel composition was optimized to record diffraction gratings within the hydrogel matrix, by replica molding (REM), towards label-free optical recognition. Hydrogel morphological and structural modifications given by the polyrotaxane addition were studied by means of scanning electron microscopy (SEM) and swelling degree. The specific recognition of CRP by the synthesized hydrogels was demonstrated by fluorescence-based detection. Typically, hydrogel grating sensors transduce the analyte signals via analyte-induced structural changes into diffracted optical signals, including the distance between the zero-order and first-order diffraction spots, refractive index (RI) and diffraction efficiency (DE). In these new systems, a recognition event between CRP and phosphorylcholine group (MPC) will be coupled to a macroscopically observable change in hydrogel grating properties.

References [1] J. Watanabe, K. Ishihara, Colloids Surfaces B Biointerfaces 2008, 65, 155. [2] L. Jiang, C. Liu, K. Mayumi, K. Kato, H. Yokoyama, K. Ito, Chem. Mater. 2018, 30, 5013.

Acknowledgments This work was supported by ADBIHOL (PID2019-110713RB-I00) from MINECO and PROMETEO/2020/094 from Generalitat Valenciana.

P-11

Nucleic acid-functionalized hydrogels for diffraction-based label-free biosensing Paola Zezza1, María Isabel Lucío1,2, María-José Bañuls 1,2, Ángel Maquieira 1,2 1 Instituto Interuniversitario de Investigación de Reconoscimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politécnica de Valéncia, Universitat de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain. E-mail: [email protected] 2 Departamento de Quimica, Universitat Politécnica de Valéncia, Camino de Vera s/n, 46022, Valencia, Spain. Keywords: hydrogel ● acrydite-probe ● biosensor ● analyte ● label-free Hydrogels are promising materials, consisting of 3D-crosslinked polymeric network, characterized by the ability of retaining a large amount of water, being permeable to analytes. Furthermore, this family of materials is applied in biosensing either to increase the loading capacity, compared to two-dimensional surfaces, or to support biospecific hydrogel swelling occurring due to the specific recognition of an analyte [1]. Acrylamide-based hydrogels have been prepared for analytes detection as point-of-care devices for various diagnostic applications[2]. Here, we propose an approach based on hydrogel functionalization, during the polymerization, with an acrydite-probe as sensitive group to introduce the analyte response. These acrylamide-based hydrogels have been prepared by free radical polymerization, via photochemical and/or thermal activation. Results obtained of target hybridization, by fluorescence detection, demonstrated that the acrydite-probe has been covalently immobilized into the 3D hydrogel network. For future applications as label-free system, diffraction grating has been employed as optical transducer and recorded within the hydrogel matrix by replica molding (REM). Different optical patterns have been replicated easily thanks to hydrogel suitable physical properties, such as flexibility, transparency, and photosensitivity. Under exposure to analyte, holographic-based gratings will change the diffraction efficiency and/or the grating period. These novel biosensors, based on interference patterns, can be used as easily interpretable indicators through an optical set-up. Therefrom, this work will have significant impact on the fabrication of diffractive optical structures of hydrogels, highly promising for biomolecular sensing in disease diagnosis and healthcare monitoring.

References [1] K. Gawel, D. Barriet, M. Sletmoen, B. T. Stokke, Sensors 2010, 10, 4381. [2] I. Y. Jung, J. S. Kim, B. R. Choi, K. Lee, H. Lee, Adv. Healthc. Mater. 2017, 6, 1.

Acknowledgments This work was supported by ADBIHOL (PID2019-110713RB-I00) from MINECO and PROMETEO/2020/094 from Generalitat Valenciana.

P-12

FEATURE ANALYSIS OF GOLD NANOPARTICLES FOR DNA- BASED OPTICAL BIOSENSING María Isabel Lucío,a Luis A. Tortajada-Genaro,a,b,c Ángel Maquieiraa,b,c a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain. e-mail: [email protected] b Departamento de Química, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain c Unidad Mixta UPV-La Fe, Nanomedicine and Sensors, Valencia, Spain Keywords: gold nanoparticles ● biosensing ● salt-mediated aggregation ● surface plasmon ● DNA- based method Gold nanoparticles (AuNPs) as transductors of biosensing processes have attracted tremendous interest due to their unique optical properties [1]. These nanomaterials exhibit distinct colours and strong absorbance peaks in the UV–vis spectrum, as the result of localized surface plasmon resonance or the collective electrons oscillation [2]. The interest for biosensing is based on salt-mediated modification of their optical properties. The addition of salt triggers their aggregation and, thus, produces dramatic variation on their optical response, offering a suitable platform for colorimetric detection of DNA based on non-cross-linking mechanism [3]. Specific single strand DNA (ssDNA) can be adsorbed onto AuNPs because this molecule is sufficiently flexible and uncoiled its bases. This adsorption stabilizes them against salt-induced aggregation by enhancing their electrostatic repulsion. In this work, we explore the changes in the optical properties of synthesized AuNPs in the presence of ssDNA. AuNPs were prepared by reducing gold (III) chloride trihydrate with trisodium citrate. The produced gold nanoparticles were homogeneous with a 15 nm diameter, showing a detectable absorption peak at λ = 520 nm in colloidal state (wine-red), and at λ = 650 nm in aggregated stated (purple). The assay was performed with model oligonucleotides and offered an excellent sensitivity (10 pmol), selectivity (absence of unspecific response) and reproducibility (standard deviation 2-11 %). The major advantage is that analyte concentration can be directly estimated through the naked eye based on changes in colour, which could be useful for point-of-care testing prior to instrumental analysers.

Figure 1. (left) Size distribution of synthetized nanoparticles. (right) Registered UV-vis spectrum of AuNPs in the presence/absence of target DNA. References [1] Li, H. et al. Proceedings of the National Academy of Sciences. 2004, 101(39), 14036-14039. [2] Chang, C. C. et al. Chemical Communications. 2016, 52(22), 4167-4170. [3] Srimongkol, G. et al. Scientific reports, 2020, 10(1), 1-11. Acknowledgments MINECO Project PID2019-110713RB-I00 and GVA PROMETEO/2020/094.

P-13

THEORETICAL STUDY OF SURFACE RELIEF GRATINGS FOR BIOSENSING

Estrella Fernándeza, María-José Bañulsa, b, Rosa Puchadesa, b, Ángel Maquieiraa, b a Instituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València. Camino de Vera, s/n 46022 Valencia. e-mail: [email protected] b Departamento de Química. Universitat Politècnica de València. Camino de Vera, s/n 46022 Valencia

Keywords: Holographic surface relief grating ● Direct laser interference patterning ● Diffraction efficiency ● Diffractive biosensor

One of the major challenges in the fields of biomedicine and healthcare is the development of low-cost, non-complex, and easily integrated portable biosensors to analyse biological samples such as blood and urine for detection and diagnostics of diseases [1]. In the last two decades, surface relief gratings (SRGs) have generated wide interest in biosensing as they can respond to an analyte with an easily identifiable change in their optical properties [2, 3, 4, 5] and can be mass-produced at low cost by UV direct laser interference patterning (UV DLIP) [6]. Our work is built upon two approaches: the immobilization of bioreceptors on a polycarbonate SRGs fabricated by UV DLIP; and the creation of SRGs made of bioreceptors by micro-contact printing, using the polycarbonate SRGs as stamps [3]. In both applications, the recognition event generates a measurable change in the diffraction efficiency of the diffraction grating, due to a change of the index modulation or thickness, that enables to confirm the presence of the analyte in the sample, or even quantify its concentration [2, 3, 4, 5, 7, 8]. This contribution describes the fabrication and characterisation of customized SRGs in polycarbonate for biosensing and the theoretical modelling of the sensor behaviour. The SRGs were manufactured under the two-beam configuration. A Q-Switched Nd:YAG laser emitting 10 ns pulses at a wavelength of 266 nm with a repetition rate of 10 Hz (Quanta Ray, Spectra Physics) was used as the laser source. The interference period was controlled by the angle between the two laser beams and the laser wavelength. The influence of the SRG geometry, thickness, period, reconstruction wavelength and refractive index of the bioreceptors on the sensor response has been simulated using the open-source EMUstack [9] package. Finally, the theoretical studies have been confirmed employing a model immunoassay based on bovine serum albumin (BSA) as a probe and anti-BSA antibody as a target. References [1] Mohankumar, P. et al. Measurement 2021, 167, 108293. [2] Yetisen, A. et al. Chemical Reviews. 2014, 114, 10654-10696. [3] Avella-Oliver, M. et al. Analytica Chimica Acta. 2018, 1033, 173-179. [4] Juste-Dolz, A. et al. Sensors. 2018, 18, 3163. [5] Chen, J. et al. Adv. Mater. Interfaces. 2014, 1, 1300074. [6] Lasagni, A.F. et al. Proc. of SPIE. 2017, 10092, 1009211. [7] Yasui, T. et al. Scientific Reports. 2016, 6, 31642. [8] Zhao, J. et al. Ind. Eng. Chem. Res. 2020, 59, 10469−10475. [9] Sturmberg, B. et al. Comput. Phys. Commun. 2016, 202. 276-28. Acknowledgments This work was supported byADBIHOL (PID2019-110713RB-I00) from MINECO and PROMETEO/2020/094) from Generalitat Valenciana.

P-14

Monodispersed CsPb2Br5@SiO2 Core−Shell Nanoparticles as Luminescent Labels for Biosensing

Cynthia Collantes, a Victoria González-Pedro, a María-José Bañuls, a,b Ángel Maquieira a,b. aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València-Universitat de València, Camino de Vera s/n, E46022 València, Spain. Email: [email protected] bDepartamento de Química, Universitat Politècnica de València, Camino de Vera s/n, E46022 València, Spain.

Keywords: cesium lead bromide nanocrystals ● CsPb2Br5@SiO2 core−shell nanoparticles ● monodisperse nanoparticles● water stability● luminescent label One of the major challenges toward the implementation of metal halide perovskite (MHP) nanocrystals (NCs) in biosensing applications is to produce monodispersed nanoparticles with desired surface characteristics and stable in aqueous environments [1]. Silica (SiO2) is an interesting coating for such materials as is chemically stable, biocompatible, shows optical transparency, offers protection against moisture and is easy to functionalize [2]. The synthesis of silica core-shell nanoparticles via sol-gel process consists in the basic hydrolysis of a silicon alkoxide precursor (tetramethylorthosilicate (TMOS) or tetraethylorthosilicate (TEOS)), followed by room- temperature condensation into a silica network. However, given the ionic nature of MHP NCs, these are prone to degradation under the required conditions for the silica- shell growth [3]. Here, we report an adaptation of the sol-gel process for the synthesis of monodispersed CsPb2Br5@SiO2 core−shell nanoparticles consisting in a post-synthetic chemical transformation of pre-synthesized CsPbBr3 NCs in the presence of tetraethyl orthosilicate and a critical water/ammonia ratio. The resulting nanoparticles exhibit narrow size distribution (36.1 ± 4.5 nm), compatibility with aqueous environments (as they preserve their blue emission in water), and ease to functionalize with amine and vinyl-functional groups by an additional post-synthetic treatment with alkoxysilanes. Finally, as a proof of concept, we demonstrated their potential as luminescent probes in a direct model immunoassay.

(a) (b)

Figure 1. a) TEM image and b) blue emission under UV light (254 nm) of the monodispersed core−shell CsPb2Br5@SiO2 nanoparticles References [1] Zhang, F. et al. Nanoscale. 2018, 10(43), 20131–20139. [2] Navarro-Palomares E. et al. Nanoescale. 2020, 12(10), 6164–6175 [3] Boyd, C. et al. Chem. Rev. 2019, 119(5), 3418–3451 Acknowledgments This work was financially supported by the E.U FEDER projects ADBIHOL (PID2019--110713RB-I00) from MINECO and PROMETEO/2020/094 from Generalitat Valenciana. C.C. thanks the Spanish MINECO for her predoctoral contract (FPI/17 Scholarship). V.G-P. thanks Universitat Politècnica de València for financial support from the project PAID/16/18 (VIITUPV).

P-15

CsPbBr3 NCs encapsulation into a polystyrene-based polymer by electrospraying

Cynthia Collantes, a Victoria González-Pedro, a Mª José Fabra,b Amparo López,b Vicenta Devesa,b María- José Bañuls, a,c Ángel Maquieira a,c. aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València-Universitat de València, Camino de Vera s/n, E46022 València, Spain. Email: [email protected] bInstituto de Agroquímica y Tecnología de Alimentos-CSIC, Calle catedrático Agustín Escardino, 7, 46980 Paterna, València, Spain cDepartamento de Química, Universitat Politècnica de València, Camino de Vera s/n, E46022 València, Spain.

Keywords: cesium lead bromide nanocrystals ● electrospraying ● water stability ● cell culture

Metal halide perovskites nanoparticles exhibit interesting optoelectronic properties, such as: tunable emission wavelengths (410-760 nm), narrow full width at half maximum (fwhm), high photoluminescence quantum yield (PLQY) and long PL lifetime (10–100 ns) [1]. However, its poor stability in polar media hinders their potential in biological applications. Electrospraying (ES), also known as Electro Hydrodynamic Atomization (EHDA), is a bottom-up encapsulating method which produces very fine droplets from a liquid solution by applying high voltage. The influence of this electric field leads to fast solvent evaporation, generating dried nano- or micro-particles with a narrow size distribution [2]. In this work we used this approach to encapsulate CsPbBr3 nanocrystals into poly(styrene-alt-maleic anhydride) (PSMA), a hydrophobic polymer that enhances the stability in water of the resulting particles (~1 µm). We also exposed macrophage cells to these particles to assess their potential as fluorescent labels in cell cultures with phagocytic activity.

Figure 1. Schematic representation of CsPbBr3@PSMA encapsulation by electrospraying References [1] Zhang, M. et al. New J Chem. 2018, 42, 9496-9500. [2] Boda S. et al. J. Aerosol Sci. 2018, 125, 164-181.

Acknowledgments This work was financially supported by the E.U FEDER projects ADBIHOL (PID2019--110713RB-I00) from MINECO and PROMETEO/2020/094 from Generalitat Valenciana. C.C. thanks the Spanish MINECO for her predoctoral contract (FPI/17 Scholarship). V.G-P. thanks Universitat Politècnica de València for financial support from the project PAID/16/18 (VIITUPV).

P-16

HYBRIDIZATION CHAIN REACTION FOR THE OPTICAL DETECTION OF ONCOGENE VARIANTS

Luis A. Tortajada-Genaroa,b, Ána Lázaroa, Ángel Maquieiraa,b

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain b Unidad Mixta UPV-La Fe, Nanomedicine and Sensors, Valencia, Spain. author e-mail: [email protected]

Keywords: DNA origami ● enzyme-free biorecognition ● genotyping ● oncogene ● optical sensing

Genotyping of single-point mutations holds a crucial role for disease diagnosis and prognosis of cancer. In this communication, we report a multiplexing and highly sensitive strategy based on the formation of DNA origami. The specific probes immobilized on the chip surface recognized the products obtained by an isothermal amplification technique called recombinase polymerase amplification (RPA). Later, allele-specific hybridization chain reaction (AS-HCR) was induced. The RPA products initiated the cross-opening of two DNA hairpins, yielding nicked double helices that are analogous to alternating copolymers. The resulting products enabled the optosensing detection using a smartphone. Having demonstrated the assay principle, the variables for the adequate integration of the AS-HCR process were studied and compared to conventional approaches. The proposed method discriminated multiple targets with low limit of detection (0.7 % mutant copies) and good reproducibility (inter-assay error lower than 17%) from genomic DNA. As a proof of concept, single-point mutations in KRAS gen (codon 12-13) and NRAS gene (codon 61) were identified in biopsied tissues from cancer patients. The results agreed with those obtained by next generation sequencing. In conclusion, AS-HCR is a rapid, simple, accurate and low-cost method and it shows a great potential to point-of-care demands for supporting personalized healthcare.

Figure 1. Assay scheme: detection of single-point-mutation applied to samples from cancer patients. References [1] Yang, D. et al. Trends in Analytical Chemistry, 2017, 94, 1. [2] Bi, S. et al. Chemical Society Reviews, 2017, 46, 4281. [3] Tortajada-Genaro, L.A. et al. Talanta, 2019, 198, 424. [4] Zhang, C. et al. ACS sensors, 2020, 5(10), 2977-3000. Acknowledgments MINECO Project PID2019-110713RB-I00 and GVA PROMETEO/2020/094.

P-17

MASSIVE SCREENING OF FOOD EXTRACTS FOR QUALITY ASSESSMENT AND STANDARDIZATION OF ALLERGENIC ACTIVITY

Aaron Boughbinaa, Luis A. Tortajada-Genaroa,b, Sergi Moraisa,b, Ángel Maquieiraa,b

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain. author e- mail: [email protected] b Unidad Mixta UPV-La Fe, Nanomedicine and Sensors, Valencia, Spain.

Keywords: food-induced-allergy ● allergen extracts ● biotech and pharmaceutical industry ● optical sensing Worldwide, over 220 million people suffer from some form of food allergy. A reliable diagnosis is important to prevent adverse reactions related with allergens. In vivo (skin testing) and in vitro (serum) tests are essential tools in assessing patients with a suggestive clinical history of food allergy. In both approaches, food extracts are employed as reagents for the selective recognition of the most important allergic biomarker, i.e. specific IgEs. However, the preparation of protein extracts from raw food and the standardization of the resulting products are not easy, considering the applicable regulatory requirements. Major challenges in the quality assessment of allergenic extracts include the choice of source material and manufacturing condition. In this context, high-throughput methods for the comparison of extracts are required to predict their diagnostic efficacy and to control the manufacturing steps. In this communication, we demonstrated that optical disc technology is an efficient massive screening platform for testing food extracts. The studied methodology involves a phase reverse protein array. Briefly, extracts from different manufacturers are spotted on disc surface in array format (40 nL per spot). Later, representative serum samples from allergic patients are dispensed, enabling the biosensing of food-specific IgEs. The data analysis revealed a clear discrimination pattern depending on the extract quality. The method was applied to the study of several commercial pharmaceutical products for the diagnosis of the most common food allergies. Results were inconsistent between manufacturers or unreliable, confirming its potential use for the improvement of industrial practices.

Figure 1. (left) Reverse-phase protein array. (right) Registered signal from serum sample (patient: allergy to prawn). Reference method: ImmunoCAP [specific IgEs] = 6.8 kUA/L. References [1] Sicherer, S. H., et al. Journal of Allergy and Clinical Immunology, 2018, 141(1), 41-58. [2] David, N. A. et al. Annals of Allergy, Asthma & Immunology, 2017, 119(2), 101-107. [3] Bonertz, A. et al. Current opinion in allergy and clinical immunology, 2019, 19(6), 640-645. [4] Morais, S. et al. TrAC Trends in Analytical Chemistry, 2020, 115904. Acknowledgments MINECO Project PID2019-110713RB-I00 and GVA PROMETEO/2020/094.

P-18

SMARTPHONE-BASED METHOD FOR DNA BIOSENSING APPLIED TO FOOD CONTROL

Germán Báez-Morillasa, Luis A. Tortajada-Genaroa,b, Ángel Maquieiraa,b

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain. author e- mail: [email protected] b Unidad Mixta UPV-La Fe, Nanomedicine and Sensors, Valencia, Spain.

Keywords: nanomaterials ● DNA methods ● food analysis ● optical sensing ● consumer devices

Analytical methods are demanded for the protection of consumer against food hazards. The development of novel fast-response methods requires improvements regarding to selectivity, portability and analysis cost. This communication reports an optical DNA- based method for the specific detection of food allergies and ingredients associated with illegal practices. After the selective amplification of the specific DNA regions, a reproducible optical detection is performed. The interest arises from the formation of a hybrid complex between non-functionalized gold nanoparticles and purified amplification products, featuring short incubation time, simplicity and low sample and reagent volumes compared to conventional methods. The assay mainly relies on the stronger electrostatic repulsion between negative charge surfaces of hybrid complexes, stabilizing against salt-induced aggregation. The target presence can be directly observed (naked-eye detection) and quantified using a smartphone. The result is directly obtained after the automated imagen decomposition in red-green-blue channels. The method was successfully applied for detecting specific regions of cereal genomes in a set of commercial foods. In fact, an accurate discrimination of gluten-free foods was achieved. The advantages of platform, such as suitable analytical performances, low- cost assay and easy interpretation system, demonstrated the capability to be implemented in the food industry.

Figure 1. Smartphone based-quantification of complexes between unmodified gold nanoparticles and selective DNA products. References [1] Lo, Y.T. et al. Food Chemistry, 2017, 240, 767-774. [2] Chang, C.C. et al. Nanomaterials, 2019, 9(6), 861. [3] Tortajada-Genaro, L.A. et al. Talanta, 2019, 198, 424-431. Acknowledgments MINECO Project PID2019-110713RB-I00 and GVA PROMETEO/2020/094.

P-19

DENDRON-MEDIATED CHIP FOR INTEGRATED GENOSENSING

Sara Martorella, Luis A. Tortajada-Genaroa,b, Ángel Maquieiraa,b

a Unidad Mixta UPV-La Fe, Nanomedicine and Sensors, Valencia, Spain. author e-mail : [email protected] b Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain

Keywords: DNA chip ● probe coupling ● allele-specific hybridization assay ● single-point mutation ● oncogene

In DNA chips, highly branched linkers (3D immobilization) provides better assay sensitivity than brush-like structures of single-site approaches (2D immobilization). Based on this principle, an integrated genosensor was developed for the optical detection of specific DNA targets on high-density dendron polymer chips. The probes were DNA-dendron conjugates prepared by fast clean click-chemistry (thiol-yne reaction) and coupled onto photo-activated surface of polycarbonate substrates (carbodiimide reaction). The amplification products were hybridized to complementary and no-complementary probes immobilized in array format for colorimetric readout. These forest-array chips with multipoint-sites exhibited sensitive recognition in comparison with linear surfaces (10-100 folds). Excellent analytical performances were obtained for non-fluidic (planar chips) and fluidic (µL-chamber) formats. The method was successfully applied to detection of H1047R mutation (c.3140A>G PIK3CA human gene) from clinical samples of cancer tissues. The colorimetric genosensor was versatile, low cost, sensitive (detection limit genomic DNA: 0.02 ng/µL) and specific (accuracy 95%).

Figure 1. (left) Scheme of dendron-mediated immobilization of DNA probes onto polycarbonate chip. (right, top) Scheme of micro-chamber chip. (right, bottom) Scanned images of chips obtained applying the assay to samples from cancer patients. References [1] Warner, C.N. et al. Langmuir. 2020, 36, 5428. [2] Liu, H. et al. Journal of the American Chemical Society. 2010, 132, 18054. [3] Martorell, S., et al. Analytical Biochemistry. 2018, 544, 49. Acknowledgments MINECO Project PID2019-110713RB-I00, GVA PROMETEO/2020/094 and GVA PTA-2016.

P-20

Naked-eye GHB detection in beverages through napthoxazole derivatives

Silvia Rodríguez-Nuévalos,a Ana M. Costero, a,b,c Pau Arroyo,a,b José A. Sáez,a,b Margarita Parra a,b,c

a IDM, Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico, Universitat de València-Universitat Politècnica de València,, Dr. Moliner, 50, 46100 Burjassot (València). [email protected] b Departamento de Química Orgánica, Universitat de València, Dr. Moliner, 50, 46100 Burjassot (València) c CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) (Spain)

Keywords: submission ● GHB ● naphtozaxole ● naked-eye ● time

Chemical submission has become a great concern in the last years, due to the increase of ‘Drug Facilited Sexual Assaults’ (DFSA). During these assaults, Central Nervous System (CNS) depressant compounds such as: alcohol, ketamine, benzodiazepines and γ-hydrixybutyric acid (GHB), are used [1]. GHB, also known as ‘liquid ectasy’, is a well-known product used in medicine due to its sedative effects. However, its use as a rape drug has been demonstrated. This compound is commonly chosen between other drugs due to its properties, as it is an odorness, colourness and tasteless compound, which means it is ingested by the victim without realizing it. On the other hand, its quick metabolism promotes a huge challenge in order to detect it in biological fluids, such as urine or blood. [2,3] For all these reasons, it is required tests which allows potential victim to identify if their beverages are spiked or not. In order to do that, it has been developed a family of compounds which includes a naphtoxazole core as recognition unit [4]. These sensors have been tested in real samples and they provide a reliable, immediate and naked-eye answer, both colour and fluorescent changes have been observed. N R NH

O A B C

O

R = O

NO 2 HO O OH 1 2

Figure1. Left) Naphtoxazole derivatives synthesized. Right) Real time changes observed with both, proves 1 and 2.

References (Calibri 9 pt, justified) [1] Olszewski, D. Drugs: education, prevention, policy. 2019, 16, 39-52. [2] Nemeth, Z.; Kun, B.; Demetrovics, Z. J. Psychopharmacol. 2010, 24, 1281-1287. [3] Busardò F.P.; Jones, A.W. Current Neuropharmacology. 2015, 13, 47-70. [4] Rodríguez-Nuévalos, S.; Costero, A.M.; Arroyo, P.; Sáez, J.A.; Parra, M.; Sancenón F.; Martínez- Máñez, R. Chem. Commun. 2020, 56, 12600-12603.

P-21

HYBRID LEAD HALIDE PEROVSKITE NANOPLATELETS: SYNTHESIS AND STUDY OF STABILITY

Rita Belén Cevallos-Toledo, a Ignacio Rosa-Pardo, a Raquel E. Galian. a Julia Pérez-Prieto a a Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, C/Catedrático José Beltrán 2, 46980, Paterna, Valencia, Spain, [email protected]

Keywords: Hybrid Perovskite ● Nanoplatelets ● Stability ● Optical properties ● Organic ligands

Hybrid lead halide perovskites nanoparticles with CH3NH3PbBr3 formula exhibit outstanding optoelectronic properties; among them, few-layer 2D perovskites are attracting a great interest, since they are materials with blue emission, which offers them plenty of applications in the field of photovoltaics, catalysis, and sensing. [1,2] Surface chemistry can play an important role in the preparation of these materials. The right combination of ligands can play a key role in their stability, confinement degree, their optical properties, and lateral dimensions. [3] We report here the preparation of two-layer lead bromide perovskites with deep-blue emission (λem= 439 nm) by using a combination of a long chain amine and a sulfonic acid pair and the ligand-assisted reprecipitation method. Square-shaped nanoplatelets (NPLs) with a lateral size in the µm scale and with a 2.5 nm in height were obtained. However, they slowly evolved to other stoichiometries, as shown by the appearance of additional emission peaks at 456 nm and 520 nm (Fig. 1), ascribed to the formation of three-layer NPLs and three- dimensional nanoparticles. The tendency of two-layer lead halide perovskites to evolved into a material with a considerable broad emission has already reported in the literature. [4]

Figure 1: Evolution in time of the emission spectrum of a two-layer hybrid lead halide perovskite nanoplatelet inset: Transmission Electron Microscope image of the perovskite nanoplatelets (Scale bar: 4µm) References [1] a) A. K. Jena, A. Kulkarni, T. Miyasaka, Chemical Reviews 2019, 119, 3036-3103; b) V. Blay, R. E. Galian, L. M. Muresan, D. Pankratov, P. Pinyou, G. Zampardi, Advanced Sustainable Systems 2020, 4, 1900145. [2] a) M. C. Weidman, A. J. Goodman, W. A. Tisdale, Chemistry of Materials 2017, 29, 5019-5030; b) G. Xing, B. Wu, X. Wu, M. Li, B. Du, Q. Wei, J. Guo, E. K. L. Yeow, T. C. Sum, W. Huang, Nature Communications 2017, 8, 14558 [3] Pan, A.; He, B.; Fan, X.; Liu, Z.; Urban, J.; Alvisatos, A.; He, L. and Liu, Y. ACS Nano 2016, 10, 7943−7954. [4] a) S. Kumar, J. Jagielski, S. Yakunin, P. Rice, Y.-C. Chiu, M. Wang, G. Nedelcu, Y. Kim, S. Lin, E. J. G. Santos, M. V. Kovalenko, C.-J. Shih, ACS Nano 2016, 10, 9720-9729; b) H. Fang, W. Deng, X. Zhang, X. Xu, M. Zhang, J. Jie, X. Zhang, Nano Research 2019, 12, 171-176

Acknowledgments.The work was supported by Ministerio de Economía, Industria y Competitividad (CTQ2017- 82711-P, co-financed by FEDER; FPU17/ 05564 (IRP), Ministerio de Ciencia e Innovación (Unit of Excellence “Maria de Maeztu” CEX2019-000919-M), and Generalitat Valenciana (IDIFEDER/2018/064 and PROMETEO/2019/080, GRISOLIAP/2019/041, RCT),c o-financed by FEDER.

P-22

NON-INVASIVE Gd-DTPA-GALACTOSE COMPLEX FOR THE DIRECT DETECTION BY MIR OF SENESCENT CELLS

Guillermo Hernández-Sigüenza,a Juan F. Blandez,a,b,c,d, Jose-Alberto Lopez-Dominguez,d Manuel Serrano, d,e Félix Sancenón a,b,c,d and Ramón Martínez-Máñez a,b,c,d a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València. Spain, [email protected] b Unidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, Valencia, Spain c CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) d Unidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, IIS La Fe, Valencia, Spain e Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (BIST), Carrer de Baldiri Reixac, 10, Barcelona 08028, Spain. e Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluís Companys 23, 08010 Barcelona, Spain.

Keywords: MIR ● Gd-galactose complex ● senescent cells ● renal fibrosis ● CYTOF

The use of proton NMR tomography techniques shows great interest for the visualization and identification of suspicious abnormalities in tissues since it is a fast and non-invasive technique that allows the detection of damaged areas [1-3]. However, this technique does not allow direct differentiation because there is no difference between the spin-lattice (T1) and / or spin-spin (T2) relaxation times of the protons found in these tissues, as well as their relative density [4]. For that, the direct MIR exhibits the overlap of signals between healthy and damaged tissues. Current studies are centred on the use of contrast agents based on rare earth metals, which allow to increase the contrast between magnetically similar areas but that present histological differentiation as can be damaged tissues [4,5]. The high paramagnetic power of Gd reduces the hydrogen-proton relaxation time even at low concentrations (less than 0.01 mmol / L). This achieves to differentiate the relaxation times of protons close to Gd compared to the rest. The use of Gd chelates with different polyamine acid chains results in the formation of stable complexes in in vivo conditions. This has allowed its administration in animals, being viable a concentration of Gd-DTPA complex of 10 mmol / kg in rats [6]. In recent years, the detection of senescent cells has been of great interest, since the chronical accumulation of this type of cells in tissue can be related with different diseases such as Alzheimer's, renal fibrosis, neurodegenerative diseases, osteoporosis, or age-related diseases [7]. Here we show the synthesis of a modified Gd- DTPA complex with a galactose unit (Gd-Gal) that preferentially accumulated in senescent cells. Gd-Gal was incubated with Sk-Mel-103 cells treated or untreated with doxorubicin to generate senescence. CYTOF measurements showed a preferential probe accumulation (5-fold) in senescent cells when compared to control cells. Ex vivo studies of Gd-Gal in tissue sections of fibrotic kidney corroborated a Gd concentration of 0.66% in damaged tissue versus the 0.13% obtained from control kidney tissues. The present work is the first example where a Gd complex was used for the detection of senescent cells accumulation in tissue.

Figure1. a) CYTOF of untreated control cells. b) CYTOF of control cells incubated with Gd-Gal probe after 6h. c) CYTOF of senescent cells incubated with 0.1 mM of Gd-Gal after 6h. d) Quantification of CYTOF results.

References [1] Grover, V.P.B et al., J. Clin. Exp. Hepatol. 2015, 5, 246-255. [2] Salerno, M. et al., AHA. 2017, 10, E003951. [3] Meyer, H-J. et al. Magnetic Resonance Imaging. 2021, 80, 127-131. [4] Kahakachchi, C. L. and Moore D. A., J. Anal. At. Spectrom. 2009, 24, 1389-1396. [5] Younis, S. A. et al. Coord. Chem. Rev. 2021, 429, 213620. [6] Weinmann, H. J. et al. AJR, Am. J. Roentgenol. 1984, 142, 619-624. [7] Lozano-Torres, B. et al. Nat Rev Chem, 2019; 3, 426–441.

Acknowledgments R.M laboratory members thank the financial support from the Spanish Government (project RTI2018-100910-B- C41). G. H. S thanks from the Generalitat Valenciana (project BIOMEDCOM 2018/024). J. F.-B thanks to his postdoctoral fellowship from Carlos III research institute (CD19/00038).

P-23

GOLD NANOCLUSTERS AS LUMINESCENT SENSORS

Martina Di Maggio a, Miguel Justo-Tirado b, Irene Pérez-Herráez b, Elena Zaballos-García a and Julia Pérez-Prieto b a. Departamento de Química Orgánica, Universidad de Valencia, Av. Vicent Andres Estelles s/n, 46100, Burjassot, Spain b. Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, Catedrático José Beltrán 2, 46980, Paterna, Valencia, Spain Keydwords: ● gold nanoclusters ● photoluminescence ● amino acids ● neurotransmitters

Luminescent nanomaterials have emerged as candidates for sensing applications in recent years [1]. An attractive property of gold nanoclusters (AuNCs) is their photoluminescence and chemical stability. In addition, AuNCs exhibit high photostability and biocompatibility and are nontoxic [2]. We report here the preparation and characterization of luminescent AuNCs (Figure 1) capped with the cysteine (Cys): They have been prepared by reduction of HAuCl4 in the presence of a weak reductant and the ligand (Cys).

Figure 2. Photographs of an aqueous solution of Cys and AuNC under UV light (left) and visible (right).

These AuNCs were tested as sensors of different analytes [3], such as amino acids and neurotransmitters, by following the changes of their optical properties using absorption and emission UV-Vis spectroscopy. The results will be presented and discussed in the poster.

References [1] a) Mako, T. L. et al.Chem. Rev.2019, 119, 322-477; b) Nonappa Beilstein J. Nanotechnol. 2020, 11, 533-546. [2] Peng, C. et al. Nano Lett. 2020, 20, 1378-1382. [3] Shui, Z. et al. Anal. Methods 2019, 11, 5691-5698. Acknowledgments We thank Ministerio de Economía, Industria y Competitividad (CTQ2017-82711-P, co-financed by FEDER), Ministerio de Ciencia e Innovación (Unit of Excellence “Maria de Maeztu” CEX2019-000919-M), and Generalitat Valenciana (IDIFEDER/2018/064 and PROMETEO/2019/080, co-financed by FEDER.

P-24

Gold nanocluster-based fluorescent sensors for detection of several analytes

Miguel Justo-Tirado a, Elena Zaballos-García b and Julia Pérez-Prieto a a. Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, Catedrático José Beltrán 2, 46980, Paterna, Valencia, Spain b. Departamento de Química Orgánica, Universidad de Valencia, Av. Vicent Andres Estelles s/n, 46100, Burjassot, Spain

Keywords: Chemical sensing ● gold nanoclusters ● photoluminescence ● phenylethylamine derivatives

Noble metal nanoclusters (NCs), such as gold and silver, have sizes smaller than 2-3 nm [1]. The small dimension of the material causes these materials to present quantized energy levels and, consequently, their optical, electrical and chemical properties are drastically modified compared to those of the macroscopic material [2]. Its most outstanding characteristics are photoluminescence, a considerable Stokes shift and photostability [1]. Gold nanoclusters (AuNCs) find applications in multiple fields, such as chemical sensing, energy conversion, catalysis, as well as in biological labeling and imaging, detection, drug administration and photodynamic therapy [1-6].

We report here the preparation of AuNCs decorated with a phenylethylamine derivative, specifically norephedrine (Nore). The AuNC@Nore was tested as sensor of several inorganic salts, such as chlorides (KCl, CaCl2, and FeCl3) and sulfates (Na2SO4 and MgSO4), see Figure 1.

A B C D E F A B C D E F

Figure 3. Photograhs of AuNC@Nore (A) and AuNC@Nore plus Na2SO4 (B), KCl (C), CaCl2 (D), MgSO4 (E) and FeCl3 (F) under visible (right) and UV light (left).

This preliminary analysis showed that Fe3+ quenched the emission of AuNC@Nore and might be detected in the presence of a series of salts.

References [1] Cuaran-Acosta, D. et al. Chem Commun, 2019, 55, 1604–1606 [2] Abbas-Muhammad, A. et al ACS Energy Letters., 2018, 3, 840-854 [3] Govindaraju, S. et al. Sci Rep., 2017, 7, 1–12 [4] Nasaruddin-Ricca. R. et al. Coord. Chem. Rev., 2018, 368, 60–79 [5] Li-Yi, C. et al. Anal. Chem., 2015, 87, 216–229 [6] Bonanno, A. et al. Chemical Communications., 2020, 56, 587-590

Acknowledgments We thank MINECO (CTQ2017-82711-P co-financed by FEDER) and GVA (PROMETEO/2019/080, IDIFEDER/2018/064 co-financed by FEDER).

P-25

NOVEL EMISSIVE AGGREGATES OF XANTHENE DYES

Delia Bellezza,a Rita Belén Cevallos-Toledo,a María González-Béjar,a Julia Pérez-Prieto.a a Instituto de Ciencia Molecular, Catedrático José Beltrán Martínez nº 2, 46980 Paterna, Spain

Keywords: xanthene dyes ● Fluorescence emission ● H-aggregates

Many improvements in dye chemistry have mainly focused on mechanisms that control the fluorescence efficiency. Emission output of xanthene dyes is regulated through chemical modification, concentration, pH and solvent environment. [1] In particular, it is necessary to take into account the geometry of the dye molecules, and charge and steric hindrance effects of the substituents introduced in the new target derivatives. These factors can change the molecular configuration and stacking pattern of the dyes, leading to the formation of non-emissive H-aggregates (aggregate in co-facial stacks) or J-aggregates (aggregate in a head-to-tail configuration) with unique optical properties. [2] Aggregation of xanthene dyes at high concentrations usually causes quenching of their fluorescence. [3] Here, we have introduced a study on the influence of the molecular structure and packing arrangement on the emission properties of eosin Y in a molecular yttrium complex, in which the aggregation-caused quenching was reduced (Fig.1). The reduced mobility of the phenyl group of eosin Y may be responsible for this behavior. Eosin Y- Yttrium complex was synthesized and characterized by using 1H NMR, 13C NMR, UV– vis, PL, XPS spectra and ICP-MS analysis.

Eosin Y-Yttrium complex Eosin Y 3000000

2000000 PL intensity u.) (a. 1000000

0 500 600 700 Wavelength (nm) Figure 1. (left) Photograph of a solution of Eosin Y-Yttrium complex under lab light. (right) Comparison between -2 the PL spectra of Eosin Y-Yttrium complex (red line) and Eosin Y (blue line) at the same concentration (1.45x10 M); excitation wavelength: 530 nm.

References [1] De, S. et al. Spectrochim Acta A 2005, 61, 1821–1833; b) Zhang, X.-F. et al. J. Photochem. Photobiol. A Chem 2008, 200, 307–313; c) Panda, A.K. et al. Spectrochim Acta A 2011, 81, 458– 465; d) Estevão, B.M. et al. J. Photochem. Photobiol. A Chem 2014, 287, 30–39; e) Hioka, N. et al. RSC Adv. 2016, 6, 110312–110328. [2] Das, S. et al. J Photochem Photobiol A Chem 2008, 197, 402–414. [3] a) López Arbeloa, I. Dyes and Pigments 1983, 4, 211-220; b) Valdes-Aguilera, O. et al. Acc. Chem. Res. 1989, 22, 171-177; c) Katoh, R. et al. Photochem. Photobiol. Sci. 2018, 17, 793–799.

Acknowledgments The work was supported by Ministerio de Economía, Industria y Competitividad (CTQ2017-82711-P, co-financed by FEDER; FPU17/ 05564 (IRP), Ministerio de Ciencia e Innovación (Unit of Excellence “Maria de Maeztu” CEX2019-000919-M), and Generalitat Valenciana (IDIFEDER/2018/064 and PROMETEO/2019/080), co-financed by FEDER.

P-26

WATER-SOLUBLE ORGANIC MOLECULAR CAGES

Giovanni Montà-González,a Vicente Martí-Centelles, Félix Sancenón, Ramón Martínez-Máñez a Instituto de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022, Valencia, Spain, e-mail: [email protected]

Keywords: Molecular Cages ● Supramolecular Chemistry ● Encapsulation ● Host-Guest Chemistry ● Sensing● Self-assembly● Water-solubility

In the last few decades there has been a growing interest on molecular hosts such as molecular cages that possess large cavities able to accommodate different kinds of molecules. In this sense, this type of structures has been used in a wide range of different applications such as catalysis, sensing, host-guest studies, recognition of proteins or drug delivery. Lately, their use as drug delivery systems has increasingly gained interest as they can host drug molecules inside of their cavities.[1,2,3] In order to use molecular cages in biological applications it is critical to solubilize in water these host molecules which are mainly organic compounds and, consequently, not soluble enough. To achieve that purpose, host molecules have to contain functional groups that lead to a complete solubility of the structure. Therefore, the water-solubility can be increased by adding charged groups (e.g., carboxylates, sulfonates, etc.) or neutral polar groups (i.e., polyethylene glycol chains, sugars, etc.). A wide range of methods has been described in the scientific literature to synthesise these kind of water-soluble host molecules.[4,5] This communication has as an objective to describe different approximations to synthesise different water-soluble host molecules from its basic building blocks. The final structure can be obtained by the self-assembly of an amine and an aldehyde building block in which the last one possesses the water solubilizing groups.[6,7]

Figure1. Examples of designed building blocks for cage formation and cages with different cavity volumes. Water solubilizing groups omitted for clarity.

References [1] Giri, A.; Patra, A. et al. ACS Omega. 2020, 5, 44, 28413-28424. [2] De, M. et al. ChemBioChem. 2021, 22, 1-7. [3] Lu, Z.R. et al. Mol. Pharmaceutics. 2018, 15, 3603-3616. [4] Reinhoudt, D.N.; Verboom, W. et al. Eur. J. Org. Chem. 2002, 15, 2587-2597. [5] Berthault, P. et al. Chem. Eur. J. 2010, 16, 12941-12946. [6] Albrecht, M. Natturwissenschaften 2007, 94, 951-966. [7] Warmuth, R. et al. Angew. Chem. Int. Ed. 2006, 45, 901-904. Acknowledgments V.M.-C thanks the financial support from Generalitat Valenciana (CIDEGENT/2020/031).

P-27

CARBON NANOPARTICLE-BASED LATERAL FLOW IMMUNOASSAY FOR SENSITIVE DETECTION OF LACTATE DEHYDROGENASE

Yulieth Bangueraa, Amadeo Sena-Torralbaa, Sergi Moraisa,b, Patricia Nogueraa,b, Ángel Maquieiraa,b.

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico, Universitat Politécnica de Valéncia-Universitat de Valéncia, Camino de vera s/n, 46022, Valencia, Spain, e-mail: [email protected] b Departamento de Química, Universitat Politécnica de València, Camino de Vera s/n, 46022, Valencia, Spain.

Keydwords: Biosensor ● Lactate Dehydrogenase ● Lateral Flow ● Carbon nanoparticle ● Inmunoassay

Lactate dehydrogenase (LDH) is a very important enzyme protein, which is used for diagnostic of different types of diseases like cancers, anemia, myocardial infarction, respiratory failure, tissue hypoxia and sepsis [1] [2]. Optical or electrochemical-based biosensors are usually used for the regular analysis of LDH in the clinical practice, reaching micromolar detection limit. However, most of these methods are based on macro-sized probes that require a large sample volume [3].

Currently there is no method based on lateral flow immunoassays (LFIA) to detect the level of LDH in serum. Here in, we present a rapid and sensitive method for the detection of LDH based on a LFIA that uses carbon nanoparticles as label to improve visual detection limit due to the contrast they have in nitrocellulose unlike other colored nanoparticles (Figure 1, inlet). The developed assay has revealed that the concentration of lactate dehydrogenase can be detected in 3-5 minutes. The assay has yielded good sensitivity and shows a limit of detection and quantification of 0.50 mg/L and 0.64 mg/L, corresponding to 62 and 48.4 IU/L, respectively. The linear working range goes from 0.6 to 6.0 mg/L (62 - 580 IU/L) (Figure 1) which encompasses the normal range of basal level of lactate dehydrogenase concentration in blood (105-333 IU/L), allowing the detection of LDH in real blood samples in a reliable way.

Figure 2. Results of the immunoassay lateral flow for detection LDH. inlet: i) 0 mg/L ii) 3 mg/L iii) 6 mg/L of LDH

References [1] Kaplan, A. et al. Química Clínica. Lea y Febiger, Filadelfia, Estados Unidos, 1988. [2] Rathee, K. et al. Biochemistry and Biophysics Reports. 2016, 5, 35-54. [3] Zheng, X. et al. Analytical Chemistry. 2010, 82, 12, 5082–5087.

Acknowledgments The authors thank the financial support from the Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico of Universitat Politécnica de Valencia.

P-28

LATERAL FLOW IMMUNOASSAY USING CARBON NANOPARTICLES FOR THE DETECTION OF CHLORPYRIFOS

Yulieth Bangueraa, Sergi Moraisa,b, Patricia Nogueraa,b, Angel Maquieiraa,b.

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico, Universitat Politècnica de València-Universitat de València, Camino de vera s/n, 46022, Valencia, Spain, e-mail: [email protected] b Departamento de Química, Universitat Politècnica de València, Camino de Vera s/n, 46022, Valencia, Spain.

Keydwords: Sensor ● Chlorpyrifos ● Lateral Flow ● Carbon nanoparticle ●Inmunoassay

Chlorpyrifos is widely used as a plant protection measurement to control pests of economically important crops and for a reduced amount of indoor use. Chlorpyrifos and its metabolites cause harmful effects in the long and short term, including abnormalities in the immune system, birth defects, endocrine disturbances and disorders of the nervous system, even affecting a large number of beneficial and non-target species such as silkworms, bees and earthworms in the environment [1][2][3]. The methodologies used for monitoring chlorpyrifos residues such as chromatography and mass spectrometry have a high cost, require sample preparation, qualified professionals, making the analysis time very long and expensive.

A few decades ago the Immunochemical techniques began to gain acceptance as rapid and profitable tools to detect traces of chemical substances such as pesticides, which is why today enzyme-linked immunosorbent kits (ELISA) can be found for the detection of some pesticides. These require a multi-step procedure to develop. In contrast to lateral flow immunoassays (LFIA) require a single step and have the advantage that they do not need technical knowledge to operate, which makes them easy and convenient to use because the detection can be observed with the naked eye.

We present a lateral flow immunoassay (LFIA) strip, which uses carbon nanoparticles as a label that improves visual detection, compared to other assays that use colloidal gold nanoparticles. The LFIA works in a competitive format and takes 5 min to perform. A limit of detection of 50 ng/mL was achieved, using 100 µL of aqueous spiked samples. The results revealed that the LFIA could aid in the continuous and efficient monitoring of pesticide residues in water for screening purposes, saving laboratory costs. However, further studies must be done before implementing the technology in the routine analysis.

References [1] Vidair, C.A. et al. Toxicol. Appl. Pharmacol. 2004, 196, 2, 287-302. [2] Uniyal, S. et al. Environmental Research. 2021, 194,110660. [3] Chishti, Z. et al. Applied Soil Ecology. 2021, 166, 103990.

Acknowledgments The authors thank the financial support from the Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico of Universitat Politécnica de Valencia.

P-29

Método del patrón interno para la detección in vitro de alergia a fármacos.

Mª José Juáreza, Sergi Moraisa,b,c, Ángel Maquieiraa,b,c

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politécnica de Valencia, Universitat de Valencia, Camino de Vera s/n, 46022, Valencia, España. E-mail: [email protected] b Departamento Química, Universitat Politècnica de València, Camino de Vera s/n 46022 Valencia, España. cUnidad Mixta UPV-La Fe, Nanomedicine and Sensors, IIS La Fe, Av. Fernando Abril Martorell, (46026), Valencia, España

Keywords: Sensibilidad ● cuantificación ● precisión ● exactitud ● multiplexado ● ß-lactámicos

La hipersensibilidad a fármacos más común es la provocada por los antibióticos ß-lactámicos. Este tipo de hipersensibilidad es mediada, principalmente, por inmunoglobulinas E (IgE). Diversos estudios han establecido una relación entre la concentración de IgE especifica en sangre y la gravedad de los síntomas que presentan los pacientes, por lo que la cuantificación de este biomarcador es clave. A pesar de su necesidad, son pocos los sistemas analíticos que cuantifican IgE específica de modo reproducible [1]. Actualmente, la cuantificación de IgE específica se realiza mediante una calibración heteróloga. Aunque este tipo de practica es muy común, la ausencia de materiales certificados, formatos de trabajo normalizados y la variabilidad de reactivos utilizados hacen que la correlación entre métodos sea baja [2], [3]. Otra de las limitaciones de los test in vitro que existen actualmente. es que no permiten la determinación simultanea de IgE originarias de varios fármacos. Aunque los ensayos de carácter multiplex, presentan muchas ventajas, a menudo, muestran problemas de reactividad cruzada con otros anticuerpos, bajo rango lineal, y altos coeficientes de variación[4]. En este trabajo, se ha evaluado el método del patrón interno para la determinación de IgE específica mediante un inmunoensayo en formato de micromatriz. Los resultados han revelado que el método de patrón interno mejora las prestaciones analíticas del ensayo multiplex, aumentando la precisión y la sensibilidad. Los valores de RSD obtenidos varían entre 15 y 20 % en el intervalo de concentraciones correspondiente al límite de detección (0,06 IU/mL; 0,14 ng/mL). En estudios comparativos se ha alcanzado una correlación con el sistema de referencia de 0.99 tras analizar una cohorte de 40 muestras de suero, y una sensibilidad diagnóstica del 42 y 95 % para penicilina G y amoxicilina, respectivamente, superior a la del método de referencia.

Referencias [1] Decuyper, I. et al. Drugs in R and D. 2017, 17(2), 265-278. [2] Espinosa, R. L. et al. Sensors. 2018, 18(8), 2686. [3] Jeon, H. al. Ann. Lab. Med. 2018, 38(4), 338-347. [4] Van Hage, M. al. J. Allergy Clin. Immunol. 2017, 140(4), 974-977. Agradecimientos M.J. Juárez agradece a la UPV la concesión de una beca de formación del personal investigador (FPI).Este trabajo ha sido financiado por el programa H2020 (proyecto COBIOPHAD, grant agreement No. 688448), siendo una iniciativa de Photonics Public Private Partnership (www.photonics21.org), por la Agencia Estatal de Investigación (PID2019- 110713RB-I00, FEDER), y el programa de ayudas UPV-La FE 2019 (P105 VALBIOAL).

P-30

IMMUNOARRAY FOR THE ALZHEIMER MARKERS β- AMILOID PROTEINS ON INDIUM AND TIN OXIDE SURFACE Iván Carreroa, Antonio Juradob, María José Bañulsc,d, Miguel Ángel González-Martínezc,d, Ángel Maquieirac,d a Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Valencia, [email protected] b cDepartamento de Biotecnología, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia cInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM),Universitat Politècnica de València-Universitat de València. Camino de vera s/n, 46022 Valencia dDepartamento de Química, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia

Keywords: Indium and Tin Oxide ● Thiol-ene click photocoupling ● Immunoarray ● β-Amiloid proteins ● Alzheimer Alzheimer’s disease is a progressive neurodegenerative disease with insidious onset. The continuous increase in this population has made Alzheimer a major public health problem [1]. Amyloid-β (Aβ), which abnormally accumulates in the brain and forms extracellular amyloid plaques that induce synaptic dysfunction and disrupt neuronal function, is a fundamental hallmark of Alzheimer. This work aims to develop a method for Aβ-40 and 42 detection applying a sandwich immunoarray on Indium and Tin Oxide support, as part of a multidisciplinary project (HERON) devoted to the development of opotoelectrochemical biosensors. The devices developed through this project are innovative micro-nano metric structures scalable to mass production. These advanced transducers employ different arrays of base structures with photonic functionality, which will allow the development of unique equipment with improved performance. Some of the issues included in this project to develop these technologies are modulation of support wettability and conjugation of gold nanoparticles to antibodies. In our contribution, Indium and Tin Oxide surface was alkene-functionalized using vinyltrietoxysilane, wettability being controlled by water contact angle measures. Anti- Aβ capture antibodies were further arrayed and irradiated at 254 nm for the covalent attachement by the thiol-ene photochemical click reaction [2]. After a BSA blocking for removing unspecific adsorption, the sandwich was built with Aβ-40 and 42 analyte proteins and a common secondary anti-Aβ antibody conjugated to gold nanoparticles. Signal was displayed with silver enhancer solution. Figure 1 shows immunoarray results for the recognition of Aβ-40, displaying clear spots when the whole sandwich is formed (chips 2,3 and 4) but only control ones in absence of analyte (chip 1). Analyte concentrations of 0,5 ng/mL give rise to naked-eye detectable spots. Results prove that photochemical reaction takes place properly. Besides, BSA addition to arrayed capture antibodies improves the spot quallity.

Figure 1. Immunoarray results for Aβ-40. Chip number one is a blank assay in absence of analyte, and only control rows on the top are observed References [1] Yu. H, Wu. J. Amyloid-β: A double agent in Alzheimer’s disease? Biomed Pharmacother [Internet]. 2021,139,111575. [2] Bañuls. MJ, González-Martínez. MÁ, Sabek. J, García-Rupérez. J, Maquieira. Á. Thiol-click photochemistry for surface functionalization applied to optical biosensing. Anal Chim Acta. 2019, 1060, 103–113. Acknowledgments Financial support from European Union FEDER and the Spanish MINECO (HERON project TEC2017-84846-R) is acknowledged.

P-31

CORRELATION BETWEEN HEPG2 CELLS AND CAENORHABDITIS ELEGANS EXPOSED TO ESSENTIAL OIL COMPONENTS

Cristina Fuentesa, Samuel Verdúa, Ana Fuentesa, José Manuel Barata, María José Ruizb

aDepartment of Food Technology, Universitat Politècnica de València. Camino de Vera s/n, 46022, Valencia, Spain, [email protected] b Laboratory of Toxicology, Faculty of Pharmacy, University of Valencia, Av. Vicent Andrés Estellés s/n, 46100 Burjassot, Valencia, Spain

Keywords: essential oil components ● cell culture ● nematode ● toxicity ● prediction

The search for rapid and inexpensive alternative methods that reduce the use of mammals in toxicity assessment has become a priority in the last years. The nematode Caenorhabditis elegans has become a relevant biological model due to important attributes such as small size, short life cycle, ease and inexpensive culture, and in vitro handling techniques [1, 2]. Moreover, C. elegans presents a conserved and metabolically active digestive system comparable to that of mammals, making this nematode a good oral toxicity model [3]. In this study, the acute toxicity of four essential oil components (carvacrol, eugenol, thymol, and vanillin) was compared using in vitro human hepatocarcinoma cells and the in vivo model C. elegans. The viability of HepG2 cells after 24 h of essential oil components exposure was studied by the MTT assay, while toxicity on nematodes was evaluated by a 24 h lethality test. Results showed that the IC50 ranking in HepG2 cells correlated with LC50 ranking in the worm. From the different compounds studied, the most toxic components were carvacrol and thymol, with similar IC50 and LC50 values, followed by eugenol and lastly, vanillin. All the LC50 values were in the range between 1.6 and 2.9 times higher than the IC50 values found for HepG2 cells, finding the highest differences for the most toxic compounds. These results suggest that C. elegans is a sensitive model for predicting acute toxicity of chemicals. In this sense, this model organism can provide a bridge between in vitro assays and mammalian toxicity tests for the study of different exposure routes and toxicokinetic responses.

References

[1] Leung, C. K. et al. Toxicological Sciences. 2008, 106(1):5-28. [2] Tejeda-Benitez, L., Olivero-Verbel, J. Reviews of Environmental Contamination and Toxicology. 2016, 237, 1-35. [3] Hunt, P. R. Journal of Applied Toxicology. 2017, 37(1), 50-59.

Acknowledgments Authors gratefully acknowledge the financial support from the Spanish government (Project RTI2018-101599-B-C21 (MCUI/AEI/FEDER, EU)).

P-32

SYNTHESIS AND STABILIZATION OF FLUORESCENT LABELS BASED ON METAL HALIDE PEROVSKITE NANOCRYSTALS EMBEDDED IN MESOPOROUS SILICA NANOPARTICLES

William Teixeira,a María Victoria González,a,b María-José Bañuls,a,b Ángel Maquieiraa,b

aInteruniversity Research Institute for Molecular Recognition and Technological Development (IDM), Polytechnic University of Valencia (UPV), Camino de Vera s/n, 5M, 46022 Valencia, Spain. E- mail: [email protected] bDepartment of Chemistry, Polytechnic University of Valencia, Camino de Vera s/n, 5M, 46022 Valencia, Spain.

Keywords: Metal halide perovskites ● Mesoporous silica ● Fluorescent labels ● Packed column

Metal halide perovskites nanocrystals (MHP NCs), with general formula ABX3 (A = + + + + 2+ 2+ – – – Cs , Rb , CH3NH3 , CH(NH2) ; B = Pb , Sn ; X = Cl , Br , I ), exhibit very appealing optical properties [1], such as high photoluminescence quantum yield (PLQY), narrow emission bands, tunable emission spectra through their size and/or composition, and simplicity of synthetic processes, which make them very cost- effective fluorescent labelling agents for biosensing and bioimaging. However, spontaneous nanocrystals coalescence or its high instability against humidity limit its utility in water medium [2]. Therefore, in this work, a systematic route for its synthesis and stabilization is presented, based on the intercalation and growth of MHP NCs in mesoporous silica (MS) [3], using high pressure packed columns, followed by a heat treatment at high temperature. Different green- to blue-emitting nanostructured composites MHP@MS (CH3NH3PbBr3 or CsPbBr3 grown in MCM-41 and SBA-15) have been obtained (Figure 1). Optical and structural characterization confirm the improvement of the growth of cubic MHP NCs inside the mesopores, with a higher PLQY than the one obtained through the reference methodologies [3, 4]. By means of post-synthetic heat treatment, it was achieved the stability of single MHP@MS nanoparticles in aqueous medium, maintaining its photoluminescent properties for several weeks. Preliminary results indicate that the stabilized materials have great potential as fluorescent contrast agent for bioimaging in cell cultures, and pave the way for the development of highly sensitive fluorescence-based biosensing systems. MS template AX · APbX @MS (a) (b) 3 PbX @MS 2 A PbXX 2 (c) (d) High pressure Drying and UV light (100 – 200 bar) heat treatment (254-365 nm) (120 – 700 °C)

Figure 1. Scheme of synthesis and stabilization of different MHP@MS fluorescent nanoparticles, and the aspect of some representative obtained materials under UV light (254 nm): (a) CH3NH3PbBr3@SBA-15, (b) CsPbBr3@SBA-15 and (c,d) two types CsPbBr3@MCM-41. References [1] Protesescu, L. et al. Nano Lett. 2015, 15 (6), 3692-3696. [2] Wang, C. et al. J. Phys. Chem. Lett. 2018. 9 (16), 4657-4666. [3] Malgras, V. et al. J. Am. Chem. Soc., 2016. 138 (42), 13874-13881. [4] Malgras, V. et al. Angew. Chem. Int. Ed., 2018. 57 (29), 8881-8885. Acknowledgments This work was supported by the projects ADBIHOL (PID2019-110713RB-I00) from MINECO, PROMETEO/2020/094 from Generalitat Valenciana, Nueva generación de biomarcadores luminiscentes de alta eficiencia basados en nanocristales de tipo perovskita (PAID-06-18/SP20180121) from UPV and PhD grant (PAID- 01-19-06) from UPV.

P-33

NANOVESICLES FOR CORTICOSTEROIDS SKIN ADMINISTRATION

Taléns-Visconti R.a, Ferrandis-Romero I.a, Muñoz-Alfonso C.a, Díez-Sales O. a,b, Nácher A.a,b

aDept. Pharmacy and Pharmaceutical Technology and Parasitology, Faculty of Pharmacy, University of Valencia, Spain bInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Av. Vicent Andrés Estellés s/n, 46100, Burjassot, Valencia, Spain.

Keywords: liposomes ● corticoids ● skin diseases ● ecoscalable process

Introduction: Corticosteroid effects are not the single component involved in the pharmacological response but additional factors such as formulation and adjuvant compounds play a relevant role. Several strategies based on the use of emulsions and lotions are currently being used in skin diseases treated with corticosteroids [1]. Their physicochemical characteristics (molecular weight and/or lipophilia) are major handicaps for transdermal administration. Objectives: The aim of the present work was the design, preparation and characterization of a pharmaceutical vehicle able to improve these limitations. Materials and Methods: The proposed new formulation is based in vesicles using mometasone furoate as a corticosteroid model. From the know-how [2] liposomes were designed and proposed as optimal formulation. Vesicles have been prepared by direct sonication, avoiding the use of organic solvents and were deeply characterized from a physico-chemical point of view. Results and Discussion: The liposomes obtained were small in size (< 200 nm), homogeneously dispersed (PI< 0.22) negatively charged (around – 30 mV), with acceptable drug loading capacity (> 60%) and were stable as their physico-chemical properties remained almost unchanged during 3 months of storage at cold temperature (∼ 5°C).

Conclusions: A new formulation has been proposed to treat skin diseases with corticosteroids. The applied processes could be easily ecoscalable for industrial liposomes production.

References:

[1] Gual A.,et al.,J Dermatolog Treat. 2016,27(3):228-34. [2] Pleguezuelos-Villa M. et al., Int J Pharm.2020, 5;573:118844.

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MICROFLUIDIC INTEGRATED BIOSENSOR FOR THE MULTIPLEX DETERMINATION OF VIRAL ANTIGENS William Teixeira,a Yeray Pallás-Tamarit,a Augusto Juste-Dolz,a David Giménez-Romero,b Sergi Morais,a,c,d Ángel Maquieiraa,c,d aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain, e- mail: [email protected] bDepartamento de Química-Física, Facultad de Química, Universitat de Valencia, Av. Dr. Moliner 50, 46100 Burjassot, Valencia, Spain. cDepartamento Química, Universitat Politècnica de València, Camino de Vera s/n 46022 Valencia, Spain. dfUnidad Mixta UPV-La Fe, Nanomedicine and Sensors, IIS La Fe, Av. Fernando Abril Martorell, (46026), Valencia, Spain. Keywords: SARS-CoV-2 ● COVID-19 ● Respiratory virus ● Microfluidic platform ● Multiplex immunoassay Coronavirus disease 2019 (COVID-19) pandemic, with almost 170 million infected people [1], has reinforced the need for rapid, reliable, and inexpensive diagnostic tests, that allow massive screening for patients triage and management [2]. Although huge efforts focused on the sensitivity of point-of-care biosensors have been made, it is still necessary and urgent to identify and discriminate several respiratory viruses simultaneously [2, 3]. In this work, a fast and robust microfluidic integrated biosensor is presented. The system not only is able to quantity the antigen load of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) in human nasopharyngeal swab samples, but also differentiate it from influenza A or B, adenovirus and/or respiratory syncytial virus (RSV). The multiplex assay is performed on a transparent disc-shaped polycarbonate surface with microfluidic structures (Figure 1), where immobilized specific antibodies selectively recognize viral antigens. A portable optical-centrifugal analyser is used as detector, which can process simultaneously 6 samples in 30 min, needing just 25 µL of extracted specimen. For SARS-Cov-2 antigen, a limit of detection as low as 20 ng mL–1 was achieved. From approximately 150 COVID-19 suspicious samples, 29 % of them have tested positive for SARS-CoV-2 and 2 % for influenza A or B. In comparison with the well stablished commercial PANBIO™ COVID-19 Ag rapid test device (Abbot, USA), it was found a 100 % of coincidence for positive results, with a specificity of 98 % for negative tested samples. These results pave the way for the potential use of the herein described system as a good and cost-effective tool for sanitary screening rapid test. 1) 2) Sample 3) Specific biorecognition and 4) Data acquisition and Microfluidic Colorimetric signal in SARS CoV 2 disc presence of a developer Labelle d Influenza A Virus specific Immobilized antigen specific Respiratory viruses Nasopharynge tib d Polycarbonate surface al swab Portable Figure 1. Scheme of multiplex determination of viral antigens in a microfluidic integrated biosensor. References [1] World Health Organization. COVID-19 weekly epidemiological update – 25 May 2021, ed. 41, 2021. [2] Afzal, A. J. Adv. Res. 2020, 26, 149–159. [3] Vandenberg, O. et al. Nat. Rev. Microbiol. 2021, 19, 171–183. Acknowledgments This work was supported by Generalitat Valenciana (DOGV no. 8815, 18 May 2020, 16712-1676).

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Combination of PD-L1 and TGF-β suppression to overcome immune evasion in malignant melanoma using mesoporous silica nanoparticles

Lucena-Sánchez, Elena a c, García-Fernández, Alba a b c, Díez, Paula a c d, Martínez-Mañez, Ramón a b c d a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM) Universitat de València–Universitat Politècnica de València, Camino de Vera s/n, 46022, Valencia, Spain. [email protected] b CIBER de Bioingeniería Biomateriales y Nanomedicina (CIBER-BBN), Spain c Unidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Valencia, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, Valencia Spain d Instituto de Investigación Sanitaria La Fe (IIS La Fe), Valencia Spain.

Keywords: MCM-41 ● Melanoma ● Immunotherapy ● PD-L1 ● TGF-β Melanoma is one of the most common type of skin cancer and it is frequently associated with poor clinical outcomes [1]. Patients presenting the most disseminated form of this disease have very low survival rates and highly restricted therapeutic alternatives. Recently, a potential therapeutic strategy has gained tremendous attention, it is cancer immunotherapy. Cancer cells are able to develop mechanisms to escape immunosurveillance barriers which impairs anti-tumor function of T cells [2]. Recent advances in this area have provided exciting outcomes in the clinical treatment of melanoma, wherein the PD-1/PD-L1 immune checkpoint blockade reactivated immune killing melanoma cells [1]. Despite the improvements, only a small percentage of patients respond to these treatments, so combination therapies are usually required [2]. Besides, depending on the environmental conditions, T cells can display different phenotypes with distinct functions. For example, their exposure to inhibitory cytokines as TGF-β drives their polarization to T regulatory subtypes which contributes to cancer immunosuppression [3]. Taking everything into account, inhibition of the TGF- β production and the PD-1/PD-L1 checkpoint is a feasible strategy to increase T cell infiltration and cytotoxicity and overcome tumor immune escape. In this work, mesoporous silica nanoparticles (MCM-41) have been developed to combine two therapeutic agents. These nanoparticles are composed by a mesoporous silica phase, acting as PD-L1 inhibitor (JQ-1) carrier and functionalized with polyethylenimine (PEI) to control the drug release and to attach a siRNA targeting TGF-β (siTGF-β) to the nanoparticle. The polymer allows the system to carry out endosomal escape necessary for the siRNA release and its proper functionality. This system pretends to be a specific and innovative therapeutic approach for the treatment of melanoma.

Figure1. Design of mesoporous silica nanoparticle as JQ-1 carrier and PEI and siTGF-β attached to control the drug release. References [1] Xu et al. Journal of Experimental & Clinical Cancer Research. 2018, 37, 261. [2] Carreira et al. Adv. Therap. 2020, 2000147 [3] Wang et al. Biomater. Sci. 2020, 8, 5121-5132. Acknowledgments We thank the Spanish Government for RTI2018-100910-B-C41 (MCIU/AEI/FEDER, UE) and CTQ2017-87954-P projects and the Generalitat Valenciana for support by project PROMETEO/2018/024. E.L-S thanks also MINECO for her FPU fellowship.

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Proton conductivity of Polybenzimidazole (PBI)/Zeolitic Imidazolate Framework Composite Membranes doped with phytic acid for high temperature fuel cells applications

Abel Garcia-Bernabéa, Dimas Cuerda a, Jorge Escorihuelab, Vicente Compaña

a Departamento de Termodinámica Aplicada, Escuela Técnica Superior de Ingeniería Industrial, Universitat Politècnica de València camino de Vera s/n 46022 Valencia (Spain), [email protected] b Departamento de Química Orgánica, Universitat de València, Av. Vicent Andrés Estellés s/n, 46100 Burjassot, Valencia (Spain).

Keywords: Proton conductivity ● PBI ● ZIFs ● phytic acid ● high temperature fuel cells

Polybenzimidazole (PBI) membranes doped with phosphoric acid have been extensively as proton exchange membranes in fuel cell applications at high temperature [1]. Phosphoric acid is coordinated by electrostatic forces with imidazole groups, and this acid can provide a network of protons that communicate between the cathode and anode in a fuel cell. Generally, protonic conductivity increases with temperature, and usually provides competitive values to other types of acidic membranes such as Nafion®. This is because the proton conductivity of PBI membranes doped with phosphoric acid depends less on membrane moisture than in the case of Nafion® membranes. The addiction of some type of organic-inorganic compounds improves the performance of membranes. Zeolitic Imidazolate Frameworks (ZIFs) are one subclass of these compounds [2]. The ZIFs have a high microporosity, which is a factor of interest for the inclusion of guest molecules to favour proton conductivity though the framework structure. Two kind of ZIFs are ZIF-8 and ZIF-67, where ZIF-8 is a zinc imidazolate and ZIF-67 is a cobalt imidazolate. These ZIFs have been used in the preparation of phosphoric acid doped-PBI composite membranes [3] Phytic acid is a phosphorus‐containing organic acid w ith great molecul ar that is present in plants, especially in seeds and fibers. Phytic acid is a prominent candidate to replace phosphoric acid in PBI membranes, and under low acid doping, membranes doped with phytic acid displayed a better proton conductivity than phosphoric acid doped-PBI membranes. [4] In this communication, we have prepared some PBI/ZIF composites membranes doped with phytic acid by casting, and its proton conductivity has been determined by electrochemical impedance spectroscopy in different temperature ramps. We note that the conductivity membranes with ZIFs retain values greater conductivity than their ZIF- free homologue (phytic acid-doped PBI membranes), and this is indicative that the durability of these membranes in high-temperature fuel cells may be greater than PBI membranes doped with phosphoric acid. References [1] Araya, S.S. Zhou, F. Liso, V. Sahlin, S.L. Vang, J.R. Thomas, S. Gao, X. Jeppesen, C. Kaer, S.K. Inter J. Hydrogen Energy 2016, 41, 21310-21344. [2] Erkartal, M.; Erkilic, U.; Tam, B.; Usta, H.; Yazaydin, O.; Hupp, J.T.; Farha, O.K.; Sen, U. Chem. Commun. 2017, 53, 2028–2031. [3] Escorihuela, J. Sahuquillo, Ó. García-Bernabé, A. Giménez, E. Compañ, V. Nanomaterials. 2018, 8, 775. [4] Escorihuela, J.; Garcia‐Bernabé, A.; Compañ, V. Polymers 2020, 12, 1374.

Acknowledgments This work was presented as Bachelor’s Thesis of Degree in Energy Engineering (Dimas Cuerda).

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Proton conductivity of sulfonated Poly(Ether Ether Ketone) with Metal-Organic Frameworks for applications in humidity sensor

Rafael Rubio Sáncheza, Abel Garcia-Bernabéa, Jorge Escorihuelab, Vicente Compaña a Departamento de Termodinámica Aplicada, Escuela Técnica Superior de Ingeniería Industrial, Universitat Politècnica de València camino de Vera s/n 46022 Valencia (Spain), [email protected] b Departamento de Química Orgánica, Facultad de Farmacia, Universitat de València, Av. Vicent Andrés Estellés s/n, 46100 Burjassot, Valencia (Spain).

Keywords: Proton conductivity ● sPEEK ● MOF ● electrochemical impedance spectroscopy ● humidity sensor

Some recent research papers have been reported on the applications in humidity sensor of sulfonated Poly(Ether Ether Ketone) (sPEEK) [1][2][3][4]. The conductivity of the membrane depends directly on relative humidity, increasing the conductivity with the humidity. This property can be used as humidity sensor applications. In our laboratory, we have proton conductivity characterized some sPEEK-MOF composite membranes by electrochemical impedance spectroscopy. Metal-Organic Frameworks (MOF) are a subclass of coordination polymers consisting of transition metal ions coordinated to multidentate organic ligands to form three-dimensional crystalline structures [5] [6]. MOF used in this study was Basolite® F300 (iron 1,3,5-benzenetricarboxylate). Composite membrane was prepared by casting in dimetylacetamide, with different percentage of MOF: 0, 1, 2, 3, 5, 7 and 10%. Water uptake was realized by immersion of dry membranes in distilled water for 120 hours. The results of proton conductivity of wet and dry composite membranes can be observed in figure 1.

35,1 σ DC wet 35 -4 σ 10 DC dry Water uptake (120 h) 30

10-5 24,4 25 21,1 -6 10 18,5 20

(S/cm) 15 -7 14 15

DC 10 12,7 σ 10 10-8

5 Water uptake (120 h) (%)

10-9 0 0 1 2 3 4 5 6 7 8 9 10 % MOF

Figure 1. Proton conductivity of composite membranes in wet and dry conditions, and water uptake (columns). Proton conductivity is increasing from dry to wet conditions, where can be observed biggest increase with 2% of MOF in the composite, 105 times. These results indicate that these membranes can be used as humidity sensors by conductivity measurements.

References [1] Zhuang, Z. Qi, D. Zhao, C. Hui, N. Sensor and Actuators B. 2016, 236, 701-711. [2] Zhuang, Z. Qi, D. Ru, C. Pan, J. Zhao, C. Hui, N. Sensor and Actuators B. 2017, 253, 666-676. [3] Choi, J. Chen, Y. Abbel, R. Visague, I. Parker, K. Sensor and Actuators B. 2020, 324, 128704 [4] Zhuang, Z. Li, Y. Li, X. Zhao C. IEEE sensors Journal, 2021, 21, 8886-8895. [5] Furukawa, H. Cordova, K.E., O’Keele, M., Yaghi, O.M. Science, 2013, 341, 1230444. [6] James, S.L. Chem. Soc. Rev. 2003, 32, 276-288. Acknowledgments This work has been presented as Bachelor’s Thesis of Degree in Industrial Engineering (Rafael Rubio Sánchez).

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DEVELOPMENT OF OPTICAL BIOSENSORS FOR CLINICAL APPLICATIONS

Aitor Cubells-Gómez,a María Isabel Lucío,a María-José Bañuls,a,b Ángel Maquieira.a,b aInstituto interuniversitario de investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain. [email protected]. bDepartamento de Química, Universitat politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain.

Keywords: Hydrogel ● Bovine Serum Albumin ● Optical Biosensor ● Label free ● Diffraction grating

In the field of label-free biosensors, diffraction grating sensors provide an efficient and versatile approach for biomarker detection because of their advantages such as low cost, easy operation, and flexibility. [1] Concretely, diffraction gratings of smart hydrogels have been developed for selective and sensitive detection of human IgG via sandwich immunoassay. [2] Typically, hydrogel grating sensors can transduce the analyte presence into a diffraction signal change due to an analyte-induced polymer structural modification. The diffraction signal change may involve the distance between the zero- order and first-order diffraction spots and/or the diffraction efficiency (DE). [3] This communication describes the development of a label free (LF) biosensing platform based on the use of hydrogels biofunctionalized with Bovine Serum Albumin (BSA). Optical biosensing of the antibody anti-BSA is performed by direct immunoassay. Hydrogels with different crosslinking degrees were synthesized to find the optimal conditions for the suitable fabrication of surface relief gratings. After the full characterization, the specific target interaction of the most promising hydrogels was firstly verified by fluorescence detection. Finally, diffraction techniques were used for the successful and selective direct label free detection of anti-BSA with the optimized surface relief grating based on BSA-functionalized hydrogel.

Figure 1. Scanning electron microscopy (SEM) image of a lyophilized hydrogel biofunctionalized with BSA. References [1] Lee, J. et al. Anal. Chem. 2009, 82, 197−202. [2] Zhao, J. J. et al. Eng. Chem. 2020, 59 (22), 10469-10475. [3] Peng, H.-Y. et al. J. Mater. Chem. C 2018, 6, 11356−11367.

Acknowledgments This work was supported by ADBIHOL (PID2019-110713RB-I00) from MINECO and PROMETEO/2020/094 from Generalitat Valenciana.

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OSIVE PROTOTYPE FOR OPTOCHEMOGENETIC STIMULATION

José Manuel Terrés-Haroa,b, Javier Monreal-Trigoa,b, Esther Giraldoc,d, Victoria Moreno-Manzanoc

a Departamento de Ingeniería Electrónica (UPV, C/ Vera s/n, 46022, València, España): [email protected] b I.I.I. en Recon. Molecular y Desarrollo Tecnológico (idm UPV-UV) (UPV, C/ Vera s/n, 46022, València, España) c Neuronal and Tissue Regeneration Lab (C. de Investigación Príncipe Felipe, C/ Eduardo Primo de Yúfera 3, 46012, Valencia, España). d Departamento de Biotecnología (Universitat Politècnica de València, C/Vera s/n, 46022, València, España).

Keywords: Optochemogenetics ● Neural growth ● Electronic devices ● Optical stimulation ● Software development

Optochemogenetics are a newly developed set of strategies to excite or inhibit nervous tissue by the modification of its cells to include light-gated ion channels or other light sensitive proteins [1]. We recently showed that blue-light stimulation of neural precursor cells (NPC) engineered to ectopically express the excitatory light-sensitive protein channelrhodopsin-2 (ChR2-NPCs) prompted an influx of cations and a subsequent increase in proliferation and differentiation into oligodendrocytes and neurons and the polarization of astrocytes from a pro-inflammatory phenotype to a pro-regenerative/anti-inflammatory phenotype [2], therefore, prompting a more pro-regenerative profile for further NPC therapeutic applications such as spinal cord injury or stroke [3, 4]. Following with this line of research at the Centro de Investigación Príncipe Felipe (CIPF) we have developed a more accurate electronic system adapted to the in vitro experimentation to precisely irradiate the light-sensitive cells as shown in Figure 1.

a b

Figure1. a) Prototype OSIVE b) Graphical user interface for OSIVE control.

Two prototype devices as the one shown in Figure 1.a were developed to provide two different wavelengths making use of 24 LEDs at 470 and 590 nm, for active stimulation and control non- active stimulation, respectively. Both devices were calibrated to irradiate the monolayer cell culture at each well with irradiance of 0 to 20 mW/cm2, a pulse width modulation of 1 µHz to 1 kHz in frequency and adding a resting period from milliseconds to days. The variables were applied to groups of 3 LEDs. The devices are connected to a computer, controlled by a graphical user interface as seen in Figure 1.b specifically developed for this purpose. References [1] Park, S. et al. Sci Rep, 2015, 5, 9669. [2] Giraldo el at. IJMS, 2020, 22(1):365 [3] Yu, S.P. et al. The Journal of Neuroscience, 2019, 39(33), 6571-6594. [4] Habibey, R. et al. Biochemical and Biophysical Research Communications, 2020, 527(2), 343-349. Acknowledgments This research is funded by MINECO/FEDER RTI2018-100910-B-C43 and RTI2018-095872-B-C21/ERDF

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IMPEDANCE SPECTROSCOPY PROCESS RE-DESIGN

María Pilar Hernández Colomera, Jose Antonio Pérez Balasteguia, Luis Edgar Menesesa, Rafael Masot Perisb, Cristian Ariel Olguin Pinattib, Nicolás Laguarda Mirób aEscuela Técnica Superior de Ingeniería del Diseño, Universitat Politècnica de València, Camí de Vera S/N, 46022 Valencia (Spain), [email protected]. bCentro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universitat Politècnica de València – Universitat de València, Camí de Vera S/N, 46022 Valencia (Spain).

Keywords: Impedance Spectroscopy ● Quality Control ● Cold ● User Experience ● Design

One of the main stages in Impedance Spectroscopy is acquisition, writing down and interpretation of the obtained data. In this stage, the human factor must be taken into particular account for a holistic consideration of the problem. The process of taking data requires the users to be focused and keeping a responsible attitude. Besides, after taking the data, the users must write it down and keep a record of previous information so that they can turn it into meaningful information and transform numbers into conclusions and fruitful knowledge. So that, an appropriate design of this stage in terms of an efficient acquisition and data organization might contribute a research line to succeed. To do so, valuing the working conditions of the researchers when working with data becomes essential thus these conditions must be included in a holistic redesign of the working place [1].

This work has been developed in the laboratories of the Group of Electronic Development and Printed Sensors belonging to the Interuniversity Research Institute for Molecular Recognition and Technological Development located at the Design Engineering School at the Universitat Politècnica de València. There, a group of researchers are applying Electrochemical Impedance Spectroscopy for quality control in the agri-food sector showing the above-mentioned data treatment problems.

The aim of this work is designing a proper User Experience and User Interface for the software used by the GEDPS researchers called FruitesFRA [2] leading to an improved user’s performance. As a result, Fig.1: New Isotype designed for the user’s satisfaction while working on Impedance Spectroscopy has FruitesFRA, representing the freezing process, the most iconic kind of fruits increased as well as a better data communication between the team in the Comunitat Valenciana (citrus) members has been allowed. Additionally, this study will help the group as well as FruitesFRA’s sensor. to gain consistency by being involved in the creation of their own brand, with new naming, new brand identity and other aspects bringing up their values [3] and increasing team’s engagement with the investigation.

References [1] Stull, E. UX Fundamentals for Non-UX Professionals: User Experience Principles for Managers, Writers, Designers, and Developers. Apress, Upper Arlington, Ohio, USA, 2018. [2] Masot, R.; Alcañiz, M.; Fuentes, A.; Schmidt, F.C.; Barat, J.M.; Gil, L.; Baigts, D.; Martínez-Máñez, R.; Soto, J. Design of a low-cost non-destructive system for punctual measurements of salt levels in food products using impedance spectroscopy. Sens. Actuators A Phys. 2010, 158, 217–223. [3] Schultz, M; Hatch, M. Taking Brand Initiative: How Companies Can Align Strategy, Culture, and Identity Through Corporate Branding. Jossey-Bass, San Francisco, CA, USA, 2008.

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DISPERSIVE MICRO-SOLID PHASE EXTRACTION USING POLYDOPAMINE COATED MAGNETITE NANOPARTICLES FOR PRECONCENTRATION OF ANTIDEPRESSANTS

Ángela Recuenco Cavaa, Mireia Pérez-Baezaa, María José Medina-Hernándeza, Laura Escuder-Gilaberta, Yolanda Martín-Bioscaa, Salvador Sagradoa,b, Francisco F. Pérez Plac. aDepartamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain. Avd. Vicente A. Estellés s/n, 46100 Burjassot, Valencia, Spain. [email protected] bInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM). Universitat Politècnica de València, Universitat de València. cInstituto de Ciencias de los Materiales (ICMUV). Universitat de València. c/Catedrático José Beltrán, 2. Paterna 46980, Valencia, Spain.

Keywords: solid phase extraction ● magnetite nanoparticles ● polydopamine ● antidepressants

The need to determine analyte’s trace amounts has become one of the main reasons of the development of analytical techniques such as magnetic dispersive micro-solid phase extraction (MD-µSPE). The SPE is based on the distribution (partition coefficient) of the analyte between the liquid phase and the sorbent. The use of magnetic nanoparticles as solid support offers several advantages such as high extraction capacity, large breakthrough volumes, simple analyte desorption and easy regeneration of sorbents [1]. A MD-µSPE method using magnetite nanoparticles coated with polydopamine is developed for extraction and preconcentration of antidepressants. The extraordinary properties of Fe3O4 nanoparticles, such as strong magnetism, low toxicity, high surface area, easy surface modification and low cost [2], are used to obtain suitable preconcentration factors (20) and satisfactory extraction recoveries (70-104 %), with short extraction times (about 10 min). A comprehensive study about the parameters that affect to the extraction recovery such as the amount of Fe3O4 nanoparticles, the polydopamine coating percentage, extraction pH value, extraction time, and desorption conditions is performed.

References [1] Wierucka, M. Biziuk, M. TrAC Trends in Analytical Chemistry, 2014, 59, 50- 58. http://dx.doi.org/10.1016/j.trac.2014.04.007 [2] Vasconcelos, I. Fernandes, C. TrAC Trends in Analytical Chemistry, 2017, 89, 41-52. Acknowledgments Mireia Pérez Baeza acknowledges to Generalitat Valenciana and European Social Fund for the contribution to the contract ACIF/2019/158.

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MODELLING THE ENANTIORESOLUTION OF BASIC AND NEUTRAL COMPOUNDS USING CELLULOSE CHIRAL STATIONARY PHASES BY HPLC

Mireia Pérez-Baezaa, María José Medina-Hernándeza, Laura Escuder-Gilaberta, Yolanda Martín-Bioscaa, Salvador Sagradoa,b.

aDepartamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain. Avd. Vicente A. Estellés s/n, 46100 Burjassot, Valencia, Spain. [email protected] bInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM). Universitat Politècnica de València, Universitat de València.

Keywords: chiral separation ● cellulose CSPs ● basic and neutral compounds ● modelling

Due to its simplicity and accuracy, high performance liquid chromatography (HPLC) with chiral stationary phases (CSPs) is the most used analytical technique for separation of enantiomers [1]. Among the large number of CSPs commercially available, the polysaccharide-based chiral stationary phases are one of most used due to their broad applicability. A systematic study on the chiral separation of several drugs and pesticides using five cellulose based CSPs [Lux® Cellulose-1 (cellulose tris(3,5-dimethylphenylcarbamate)); Lux® Cellulose-2 (cellulose tris(3-chloro-4-methylphenylcarbamate)); Lux® Cellulose- 3 (cellulose tris(4-methylbenzoate)); Lux® Cellulose-4 (cellulose tris(4-chloro-3- methylphenylcarbamate)); and immobilized Lux® Cellulose-5 (cellulose tris (3,5- dichlorophenylcarbamate))] under reversed phase conditions, using acetonitrile as organic modifier is performed. Structural information of 57 neutral and basic compounds, not related structurally, is used to model their enantioresolution levels obtained by HPLC. A large data set of topological parameters and molecular descriptors (totalling 55 variables) were evaluated. Up to 22 predictor variables were selected after a discriminant partial least squares refinement process (DPLS1). Categorical enantioresolution levels (RsC: 0 = no baseline enantioresolution, 1 = baseline enantioresolution) can be discriminated using the refined models based on 1-6 latent variables (LV). A brief comparison on the retention behaviour and enantioselectivity between the CSPs used in this study is performed. It is observed that the interaction by hydrogen bonding (hydrophilic interactions residing with carbamate or ester moieties), hydrophobic interactions (associated with phenyl moieties) and steric hindrances (molecular size, shape, branching, presence of heteroatoms and multiple bonds) play an important role in the chiral recognition.

References [1] Lämmerhofer, M. J. Chromatogr. A. 2010, 1217, 814–856. Acknowledgments Mireia Pérez Baeza acknowledges to Generalitat Valenciana and European Social Fund for the contribution to the contract ACIF/2019/158.

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SOLID PHASE EXTRACTION USING POLYDOPAMINE COATED MAGNETITE NANOPARTICLES FOR DIRECTLY ANALYSIS OF FOOD ADDITIVES

Sara Ballester Gómeza, Mireia Pérez-Baezaa, Yolanda Martín-Bioscaa, María José Medina-Hernándeza, Laura Escuder-Gilaberta, Salvador Sagradoa,b, Rafael Muñoz Espíc.

aDepartamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain. Avd. Vicente A. Estellés s/n, 46100 Burjassot, Valencia, Spain. [email protected] bInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM). Universitat Politècnica de València, Universitat de València. cInstituto de Ciencias de los Materiales (ICMUV). Universitat de València. c/Catedrático José Beltrán, 2. Paterna 46980, Valencia, Spain.

Keywords: solid phase extraction ● magnetite nanoparticles ● polydopamine ● food colorants ● directly analysis

Solid phase extraction (SPE) has become the most used extraction and preconcentration technique. In SPE the extraction is based on the distribution (partition coefficient) of the analyte between the liquid phase and the sorbent. There are many variations of this technique related to different extraction methodologies, the shape and size of the sorbent bed, and the type of absorbent material [1]. The use of magnetic nanoparticles as solid support in SPE offers several advantages such as high extraction capacity, large breakthrough volumes, simple analyte desorption and easy regeneration of sorbents [1]. Among them, magnetite nanoparticles show great benefits due to their strong magnetism, low toxicity, high surface area, easy surface modification and low cost [2]. The objective of this communication is to study the potential of polydopamine coated magnetite nanoparticles for preconcentration of low amounts of food colorants. A SPE method using magnetite nanoparticles coated with polydopamine is developed for extraction and preconcentration of food colorants. The extraordinary properties of magnetite nanoparticles are used to obtain suitable preconcentration factors (20) and satisfactory extraction recoveries (75-105 %), with short extraction times (about 5 min). In addition, the magnetic properties of nanoparticles simplify the extraction process. A comprehensive study on the parameters that affect the extraction recovery, such as the amount of Fe3O4 nanoparticles, extraction time, pH value, and desorption conditions is performed. Finally, the possibility of using the recommended procedure for real food samples is also evaluated.

References [1] Wierucka, M. Biziuk, M. TrAC Trends in Analytical Chemistry, 2014, 59, 50- 58. http://dx.doi.org/10.1016/j.trac.2014.04.007 [2] Vasconcelos, I. Fernandes, C. TrAC Trends in Analytical Chemistry, 2017, 89, 41-52. Acknowledgments Mireia Pérez Baeza acknowledges to Generalitat Valenciana and European Social Fund for the contribution to the contract ACIF/2019/158.

P-44

RETENTION BEHAVIOUR OF NEUTRAL AND BASIC COMPOUNDS USING CELLULOSE CHIRAL STATIONARY PHASES AND AQUEOUS-ORGANIC MOBILE PHASES

Sofía Rodrigo Bustosa, Mireia Pérez-Baezaa, María José Medina-Hernándeza, Laura Escuder-Gilaberta, Yolanda Martín-Bioscaa, Salvador Sagradoa,b.

aDepartamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain. Avd. Vicente A. Estellés s/n, 46100 Burjassot, Valencia, Spain. [email protected] bInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM). Universitat Politècnica de València, Universitat de València.

Keywords: chiral separation ● cellulose CSPs ● aqueous-organic mobile phases ● basic compounds

Chiral molecules play an important role in all aspects of life sciences [1]. The most used analytical technique for separation of enantiomers is high-performance liquid chromatography (HPLC) with chiral stationary phases (CSPs) due to its simplicity and accuracy [1]. Among the large number of CSPs commercially available, the polysaccharide-based chiral stationary phases are one of most used due to their broad applicability. Separations with polysaccharide based CSPs are normally carry out in normal and polar organic conditions. When polysaccharide-based chiral columns are used in combination with aqueous-organic mobile phases for the separation of enantiomers in HPLC, the separation mode is commonly called “reversed-phase” in analogy to achiral separations. In several recent studies on neutral and basic chiral analytes, it was shown that due to multiple type of interactions involved in selector-selectand binding and enantioselective recognition with polysaccharide derivatives, the above-mentioned separation system may show behave like a HILIC–system. Thus, polysaccharide-based CSPs may behave either as RP-like or HILIC-like stationary phases based on analyte characteristics and separation conditions, especially when using ACN mobile phases with low water contents (<30%). In order to understand better the reasons of this dual behaviour of polysaccharide-based CSPs, and the role of hydrogen-bonding (hydrophilic interactions residing with carbamate or ester moieties) and hydrophobic interactions (associated with phenyl moieties) in analyte retention and chiral recognition, the gradual transition from polar- organic to aqueous-organic mobile phases was investigated. The retention behaviour of 57 neutral and basic compounds, not related structurally, is studied using two cellulose based CSPs [cellulose tris(3,5-dimethylphenylcarbamate), Lux® Cellulose 1, and immobilised cellulose tris(3,5-dichlorophenylcarbamate), Lux® Cellulose 5] and mobile phases containing acetonitrile with small percentages of aqueous phase (2-20 %). A brief comparison on the retention behaviour and enantioselectivity between both CSPs, showing the effect of the donating methyl versus withdrawing chlorine substituent in cellulose derivatives, is performed.

References [1] Lämmerhofer, M. J. Chromatogr. A. 2010, 1217, 814–856. Acknowledgments Mireia Pérez Baeza acknowledges to Generalitat Valenciana and European Social Fund for the contribution to the contract ACIF/2019/158.

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TETRAPHENYLETENES AS SENSORS OF ALIPHATIC POLYAMINE METABOLITE FOR THE EARLY CANCER DETECTION IN URINE

Andrea Reche,a Mariana Barros,a Pau Arroyo,a Pablo Gaviña,a Ana Costero.a

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM). Universitat Politècnica de València, Universitat de València, Doctor Moliner 50, Burjassot, 46100, Valencia, Spain. [email protected]

Keywords: AIE effect ● Biogenic amines ● Urine sample ● Early cancer detection Biogenic amines are basic nitrogen compounds formed mainly by decarboxylation of amino acids or by amination and transamination of aldehydes and ketones. Polyamines are involved in multiple biological functions as well as pathological processes. Their dysregulation affects the epigenetic processes of cell proliferation and apoptosis, which is why they are related to cancer and neurodegenerative diseases [1]. In situations of disease and infection these amines can be found at high levels. For this reason, with their detection it is possible to make an early diagnosis of certain types of cancer, that is the best chance of more successful treatments. Spermidine (SPMD) and spermine (SPM) (Figure 1) are examples of these amines. Aggregation-induced emission (AIE) is a phenomenon that some compounds undergo where restriction of intramolecular rotations promotes light emission [1]. An example of this behaviour is tetraphenylethene (TPE) derived compounds (Figure 1), whose chromophore core is activated when aromatic-rings rotation is restrained inducing fluorescent emission. C6 is a TPE-derivative cable to binding to SPMD and SPM, selectively promoting an increase in the fluorescence of the system. In this work, we have systematically assayed several aliphatic mono- and polyamines with different chain length, as well as some biogenic amine neurotransmitters that could be act as interference because of their presence in urine samples. Spectroscopic results of buffered single mixtures in equimolar concentrations of these amines with the C6 sensor show to be very selective and sensitive in SPMD and SPM recognition. In the presence of these amines, after irradiating the mixture with a 340 nm light, an intense fluorescence emission centred at 480 nm was observed. In addition, a complete computer simulation study has been performed, which has allowed us to propose a way of binding that is able to explain the observed selectivity.

Figure1. The C6 polyamine sensor (the TPE core in red) and selective analytes spermidine (SPMD) and spermine (SPM).

References [1] Casero Jr, R.A. et al. Nat Rev Cancer. 2018, 18(11), 681-695. [2] Luo, J et al. Chem. Commun., 2001, 1740-1741.

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GLUCOSE POWERED NANOMOTORS MADE BY GLUCOSE OXIDASE- JANUS PT-MESOPOROUS SILICA NANOPARTICLES FOR ACTIVE ANTICANCER DRUG DELIVERY Andrea Escudero Nogueraa,b,c ,Paula Díez Sáncheza,b,c,d , Elena Lucena Sáncheza,b,c, Alba García Fernándeza,b,c and Ramón Martínez-Máñeza,b,c,d aInstituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Spain. [email protected]. bDepartamento de Química, Universitat Politècnica de València, Cami de Vera s/n, 46022, València, Spain. 3CIBER de Bioingeniería, biomateriales y nanomedicina (CIBER-BBN), 28029 Madrid, Spain. cUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, València, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, 46012 València, Spain. dUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, 46026, València, Spain. Keywords: Janus nanomotors ● Self-propulsion ● Biocompatible fuel ● Anti-cancer therapy ● Controlled drug delivery The design of self-propelled and bio-inspired nano- and micromotors for anti-cancer therapy is promising field that has recently achieved a great deal of interest due to their ability to improve tumour reach, tumour infiltration, and tumour cells internalization. However, that devices still present several disadvantages that limit their real application. The main problem relies on the use of toxic and exogenous fuels for living beings, commonly high concentrations of hydrogen peroxide to achieve elevated levels of diffusion or velocity [1,2]. Therefore, usually nano-micromotors reported until now present a dichotomy between velocity and biocompatibility. Herein, we have developed a new versatile nanomotor capable of both self-propulsion and drug delivery for “smart” anti-cancer therapy. It is composed by two different faces: a platinum nanoparticle (Pt NP) and a mesoporous silica nanoparticle (MSN), unified in a unique anisotropic nanodevice named as Janus Pt-MSN. The MSN face acts as a container for the anticancer drug Doxorubicin (DOXO), which is loaded inside their pores. Moreover, the MSN external surface is decorated with the Figure 1. Representation of Janus Pt- high active enzyme Glucose Oxidase DOXO-GOx (GOx) attached by amide bonds. GOx enzyme acts as “molecular gate” controlling the specific intracellular delivery of the DOXO and as trigger to start the propelling reaction, converting the abundant glucose present in the tumour microenvironment into gluconic acid and hydrogen peroxide (H2O2). The platinum face is responsible of the autonomous movement, through the catalytic decomposition of the H2O2 produced by the GOx into water and oxygen (gas) (Figure 1). The advantages of Janus Pt-MSN- Doxo-GOx nanomotor reside in the bio-availability and non-toxicity of the fuel glucose in tumours and in its geometry, that guide their spatial trajectories in a directional manner at high speed. References [1] Peng, F. et al. Self-Guided Supramolecular Cargo-Loaded Nanomotors with Chemotactic Behavior towards Cells. Angew. Chem. 2015, 127, 11828–11831. [2] Sun, J. et al. Enzyme-Powered Nanomotors with Controlled Size for Biomedical Applications. ACS Nano 2019, 13, 10191–10200. Acknowledgments Authors want to thank the Spanish Government for RTI2018-100910-B-C41 (MCIU/AEI/FEDER, UE) and CTQ2017-87954-P projects and the Generalitat Valenciana for support by project PROMETEO/2018/024.

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REVERSIBLE JANUS-TYPE NANOSYSTEM WITH DUAL CAPABILITY: SELF-PROPULSION AND LIGHT-MEDIATED DRUG DELIVERY Francisco Javier Hicke Garcíaa,b,c , Paula Díez Sáncheza,b,c,d , Andrea Escudero Noqueraa,b,c, Vicente Martí Centellesa,b,c and Ramón Martínez-Máñeza,b,c,d aInstituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Spain. [email protected]. bDepartamento de Química, Universitat Politècnica de València, Cami de Vera s/n, 46022, València, Spain. 3CIBER de Bioingeniería, biomateriales y nanomedicina (CIBER-BBN), 28029 Madrid, Spain. cUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, València, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, 46012 València, Spain. dUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, 46026, València, Spain. Keywords: Janus nanoparticles ● Chemical communication ● Host-Guest Interaction ● Self-propulsion ● Drug delivery Chemical communication is a process which allows two or more systems to exchange information, cooperate and orchestrate collective behaviours. There are different models of communication, but all involve a flow of information from a sender to a receiver [1]. The use of Janus type metal-mesoporous silica nanoparticles to develop communication systems is a barely unexplored field, with interesting future applications as the possibility to treat diseases. In previous works, interactive models of communication composed by independent Janus nanodevices have been designed, based on enzymatic processes and the interchange of delivered chemical messengers [2,3]. Herein, an innovative and reversible communication system capable of self-propelling and delivering payloads to a target site has been designed. This system is based on two different Janus, with platinum (Pt) and gold (Au) faces, Janus Pt-MSN and Janus Au- MSN. Both are coupled through the formation of a host-guest interaction between the β- cyclodextrin and a trans azobenzene (Az) form moiety. The first Janus Pt-MSN (S1Azt) employs the silica face for drug loading and its surface is functionalized with an azobenzene-polyethylene glycol (Azt-PEG) derivative. In the second Janus Au-MSN nanoparticle (S2Inv-GOx), the MSN is decorated with the enzymes invertase (Inv) and glucose oxidase (GOx) and the Au face with a β-cyclodextrin moiety. The combination of S1Azt, S2Inv-GOx and sucrose (Figure 1) activates the communication process by the catalytic reaction between the two enzymes producing hydrogen peroxide (H2O2) which is catalytically decomposed on the Pt face producing the self-propel movement to the target area. Then, cargo release is induced by the irradiation with UV-light at ca. 365 nm for the isomerization to the cis form of Az, which is unable to form inclusion complexes with β-CD [4]. References [1] Akyildiz, I. F. et al. Nanonetworks: A new communication paradigm, Comput. Networks, 2008, 52, 2260–2279. [2] Llopis-Lorente, A. et al. Interactive models of communication at the nanoscale using nanoparticles that talk to one another, Nat. Commun., 2017, 8, 15511. [3] de Luis, B. et al. A chemical circular communication network at the nanoscale, Chem. Sci., 2021, 12, 1551– 1559. [4] Ferris, D. P. et al. Light-Operated Mechanized Nanoparticles. J. Am. Chem. Soc., 2009, 131, 1686−1688. Acknowledgments Authors want to thank the Spanish Government for RTI2018-100910-B-C41 (MCIU/AEI/FEDER, UE) and CTQ2017-87954-P projects and the Generalitat Valenciana for support by project PROMETEO/2018/024. Figure 1. Illustration of the interactive nanosystem.

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DETECTION OF FREEZE DAMAGE IN CONFERENCE PEARS USING IMPEDANCE SPECTROSCOPY

Luis Edgar Meneses Menesesa, María Pilar Hernández Colomera, Jose Antonio Pérez Balasteguia, Cristian Ariel Olguín Pinattib, Clara Pérez Fusterb, Nicolás Laguarda Mirób aEscuela Técnica Superior de Ingeniería del Diseño, Universitat Politècnica de València, Camí de Vera S/N, 46022 Valencia (Spain), [email protected] bCentro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universitat Politècnica de València – Universitat de València, Camí de Vera S/N, 46022 Valencia (Spain).

Keywords: Freeze damage ● Detection ● Analysis ● Conference pear ● Electrochemical Impedance Spectroscopy

The aim of this study is the detection of freeze-damage in Conference Pear (Pyrus communis L. ‘Conference’). These damages are due to abrupt weather changes, causing frost phenomenon. Every year, the agri-food sector is economically affected by this phenomenon [1]. Therefore, several analyses are used to find a response able to identify fruits affected by frost. In this study, Electrochemical Impedance Spectroscopy (EIS) is applied since this technique has yielded great results in other research lines related to food technology, especially in quality control parameters in vegetables and fruits [2]. In addition, EIS has been successfully used with agri-food by-products and their wastes [3-4]. Measurements were conducted in different places of the fruits to have contrasted data and determine the electrochemical behavior of the pears before and after freezing. Data acquisition was obtained by a double-needle sensor connected to a frequency and voltammetry response analyzer. The analyzer was connected to a CPU with a user interface called FRA, which graphically and numerically displays the results of the performed EIS tests. Further statistical data-treatment has been carried out to reliably detect differences between fresh and frozen fruits. These differences are manifested in phase and module of the impedance. Thus, the obtained results allows this technique to be presented as a new alternative for the early detection of freeze-damage in pears as it is fast, low-cost and easy to use and implement.

References

[1] Strang, J. G. Frost hardiness of buds, flowers and fruit of pear (Pyrus communis L.). OSU Scholars Archive. 1979, p-2. [2] Masot, R.; Alcañiz, M.; Fuentes, A.; Schmidt, F.C.; Barat, J.M.; Gil, L.; Baigts, D.; Martínez-Máñez, R.; Soto, J. Design of a low-cost non-destructive system for punctual measurements of salt levels in food products using impedance spectroscopy. Sens. Actuators A Phys. 2010, 158, 217–223. [3] Conesa, C.; Ibáñez, J.; Seguí, L.; Fito, P.; Laguarda-Miro, N. An Electrochemical Impedance Spectroscopy System for Monitoring Pineapple Waste Saccharification. Sensors 2016, 16, 188. [4] Serrano-Pallicer, E.; Muñoz-Albero, M.; Pérez-Fuster, C.; Masot Peris, R.; Laguarda-Miró, N. Early Detection of Freeze Damage in Navelate Oranges with Electrochemical Impedance Spectroscopy. Sensors 2018, 18, 4503; doi:10.3390/s18124503

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DETECCIÓN DE ANTÍGENOS DE SARS-COV-2 EN MUESTRAS DE SALIVA MEDIANTE MICROBALANZA DE CRISTAL DE CUARZO

Noemí Farinós-Navajas,a Augusto Juste-Dolz,a Yeray Pallás-Tamarit.a, William Teixeira,a Ismael Mingarro,b Luís Martínez-Gil,b María Jesús García-Murria,b David Giménez-Romero,c Sergi Morais,a,d Angel Maquieira,a,d

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, 46022 Valencia, Spain. e-mail : [email protected] b Departamento de Bioquímica y Biología Molecular (Instituto BIOTECMED) C/ Dr. Moliner, 46100 Burjassot, Spain. c Department of Physical–Chemistry, Universitat de València, C/ Dr. Moliner, 46100 Burjassot, Spain. d Departamento de Química, Universitat Politècnica de València, 46022 Valencia, Spain.

Palabras clave: SARS-CoV-2 ● QCM-D ● Inmunosensor ● Saliva

La aparición la pandemia de COVID-19 ha puesto de manifiesto la creciente demanda de técnicas de biosensado rápidas y sensibles para la evaluación y control de epidemias. En este sentido la micro balanza de cristal de cuarzo con factor de disipación (QCM-D) ha demostrado una excelente capacidad para detectar cambios de masa por debajo del nanogramo a tiempo real y sin necesidad de marcaje [1]. Además, permite monitorizar conjuntamente los efectos viscoelásticos de las biomoléculas adheridas sobre la superficie del sensor, los cuales están asociados a cambios estructurales [2], aportando así una perspectiva innovadora y atractiva dentro del campo del biosensado. En este trabajo se presenta un inmunosensor basado en la tecnología QCM-D para la detección de antígeno N procedente de partículas víricas de SARS-CoV-2 en muestras de saliva. Para ello, en primer lugar se ha puesto a punto el sistema utilizando partículas de virus no infectivas como referencia, llamadas Virus-like particles (VLPs). Se ha comparado la señal obtenida antes y después de liberar las partículas de antígeno N mediante lisis (Figura 1) y se ha demostrado también la selectividad del método evaluando la respuesta del biosensor llevando a cabo el mismo proceso con VLPs de otro virus que no poseen dichos antígenos, como es el caso del virus Nipah. Por último, una vez caracterizado el biosensor y realizado la prueba de concepto, se ha estudiado su comportamiento con muestras reales de saliva de pacientes de COVID-19.

Figura1. Comparación de las señales de QCM-D obtenidas antes (izquierda) y después de realizar la lisis de las VLPs de SARS-CoV-2 (derecha). Referencias [1] Do Nascimento, N. et al. Biosens. Bioelectron. 2017, 90., 166-173. [2] Juste-Dolz, A et al. Anal. Bioanal. Chem., 2018, 411., 4709-4720. Agradecimientos Proyecto financiado por la Generalitat Valenciana (DOGV nº 8815, 18 de Mayo de 2020)

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Two new gated mesoporous hybrid materials for detecting hypoxia environment

Antonio Valero1, Margarita Parra1,2, Salvador Gil 1,2, Pablo Gaviña1,2, Ana M. Costero1,2

1 instituto Interuniversitario de Investigación de Reconocimiento Moleculary Desarrollo Tecnológico (IDM). Universitad Politècnica de València, Universitat de València, Doctor Moliner 50, Burjassot, 46100, Valencia, Spain. [email protected] 2 CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) (Spain)

Keywords: Cancer release ● Hypoxia ● Azo reduction ● Nitro reduction ● mesoporous silica nanoparticles

Solid tumours are the most common kind of human malignant tumour. Cell masses grow rapidly and wildly, leading to an incorrect vascularization and in consequence, hypoxia. They are also found to be resistant to conventional treatments forcing to increase the dose over damaging all other tissues. Hypoxia means a low oxygen pressure which is responsible for the tumour’s aggressive nature. The presence of numerous reducing enzymes, such as azo and nitro reductases, makes those hypoxic zones characteristically reductant. There is a need to designing novel strategies to improve cancer treatments reducing the general damage beyond the tumour cells. Hence, two novel hybrid materials based on MCM-41 functionalised with azo and nitro self-inmolative aromatic chains as gated organic molecules and loaded with Sulphorodamine B have been developed. By capping the mesoporous particles with the self-inmolative molecules the dye is kept inside. The self-immolative process will come about due to a change in the electron density distribution caused by the reduction of an azo or nitro group in an amine. This molecular fragmentation releases the cargo occluded inside the pores; as a result, the self-inmolative process could be controlled.

reduccion

References [1] Brown, J. et al. Molec. Med. Tod. 2000, 6, 157-162 [2] Thomlinson, R.H. et al. Brit. J Cancer, 1995, 9, 539-549 [3] Fraga, A. et al. Act. Urol. Esp., 2009, 33, 941-951 [4] Li, Z. et al. Chem. Comm., 2018, 54, 13127-13100 [5] Juárez, L. A., et al. Chem. Eur. J., 2016, 22, 14126-14132

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IN-VITRO CULTURE WELL FOR THE COMBINED APPLICATION OF ELECTROSTIMULATION AND ELECTRICALLY-CONTROLLED DRUG RELEASE

Luis Alamán-Escolano a, Javier Monreal-Trigo* b,c, Juan Francisco Blandez-Barradas c, Eduardo García- Breijo b,c, Esther Giraldod,e, Mª del Mar Sánchez-Martínd, Victoria Moreno-Manzanod; * e-mail: [email protected] a Escuela Técnica Superior de Ingeniería del Diseño (UPV, C/ Vera s/n, 46022, València, España). b Departamento de Ingeniería Electrónica (UPV, C/ Vera s/n, 46022, València, España). c I.I.I. en Recon. Molecular y Desarrollo Tecnológico (idm UPV-UV) (UPV, C/ Vera s/n, 46022, València, España) d Neuronal and Tissue Regeneration Lab (C. de Investigación Príncipe Felipe, C/ Eduardo Primo de Yúfera 3, 46012, Valencia, España). e Departamento de Biotecnología (Universitat Politècnica de València, C/Vera s/n, 46022, València, España).

Keywords: Biomaterials ● Conductive Polymer ● Electrostimulation ● Electrically-Controlled Drug Release ● Electrodes

In the research line of nerve tissue regeneration through the combination of electrostimulation techniques and electrically controlled release of drugs, the disposal of a stimulation device is not enough [1], one of the sinequanon conditions to perform the necessary in-vitro electrostimulation of monolayer cell cultures is to have a biocompatible, watertight, substrate-conductive uniform culture well system within the necessary electrodes connection to perform the stimuli in the necessary spatial distribution. For this purpose, a system of pairs of wells has been developed, which facilitates pairwise control. Each well has two silver screen-printed electrodes at its edges, accessible for direct connection through the stimulation terminals, as well as a lid that allows breathing inside the well and the introduction of two thin cylindrical electrodes whose ends contact the medium to act as a reference electrode and counter electrode for controlled drug release. This well system has a PMMA surface for mechanical stiffness, a medical grade PET substrate on which the silver electrodes and the conductive polymer PEDOT that constitutes the substrate of the wells are screen printed [2], the containing structure has been 3D printed in PLA, and the necessary bonding has been performed with PDMS elastomer (see Fig. 1). Its temporal degradation of conductivity, its biocompatibility and the release of a dye loaded on mesoporous silica nanoparticles [3] anchored to the PEDOT have been evaluated, demonstrating its suitability for the application in primary cultures of neural precursor cells, with the final goal to promote functional neuronal features.

Figure 1. PEDOT Well-Duo, part of the SCIR (Spinal Cord Injury Repair In-Vitro Experimentation) system. References Acknowledgments [1] Monreal-Trigo, J. et al., IWOSMOR XIII, 2019, 76- This research was supported by the Spanish Ministry of 79, València. Science, Innovation and Universities via a doctoral grant [2] Wang, S. et al., Biomat. Sci., 2017, 5, 2024-2034 to J. Monreal-Trigo (FPU17/03239), and by the Spanish [3] Cheng, C., American Chem. Soc., 2019, 11, 17, Government/FEDER funds (RTI2018-100910-B-C43; 15322-31 RTI2018-095872-B-C21/ERDF).

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CROWN ETHER AMINO ACIDS AS COORDINATING AND FLUORESCENT REPORTING UNITS FOR METAL ION COMPLEXATION

Cátia Martins,a Patrícia Batista, a Manuela Raposo, a Susana Costa a

a Centre of Chemistry, University of Minho, Campus of Gualtar, 4710-057 Braga, Portugal [email protected]

Keywords: Crown ethers ● Unnatural amino acids ● Fluorimetric chemosensors ● Metal cations

Crown ethers occupy a special position among supramolecular host molecules in the design of new chemosensors. They possess the unique ability to complex with alkali metals cations, with very high selectivity, as well as alkali-earth metals and, when nitrogen and sulfur atoms are inserted into their structure, they also interact with transition metal cations [1]. Also, the chemistry of metal-peptide and metal-protein interactions is of the utmost importance in many crucial physiological mechanisms, as amino acids can complex metal ion through nitrogen, oxygen and sulphur donor atoms at their main and side chains. Therefore, unnatural amino acids with increased complexing ability and improved optical properties, acting simultaneously as the coordinating and reporting unit, via fluorescence changes, are highly attractive as building blocks for bioinspired frameworks, i.e. probes for biomolecule dynamics, environmentally sensitive fluorescent sensors, peptides for molecular imaging, peptidomimetics biological activity and protein engineering [2-3]. Following our research interests in the synthesis and evaluation of fluorimetric chemosensors for ions based on heterocycles and amino acids [3-7], a series of unnatural alanines 1a-c substituted with different (hetero)aromatic π-bridges (phenyl, furyl or thienyl) linked to a benzocrown ether moiety (Figure 1) were evaluated as chemosensors for the recognition of several metal cations, with biological relevance. Chemosensing studies showed that these benzoxazolyl-alanines displayed a highly sensitive fluorimetric response for Fe3+.

Figure 1. Structure of benzoxazolyl-alanines 1a-c.

References [1] Liu, Z. et al. Chem. Soc. Rev. 2017, 46, 2459-2478. [2] Laxman P. et al. Front. Chem. 2021, 9, 641355. [3] Ferreira, R. C. M. et al. New J.Chem. 2018, 42, 3483-3492. [4] Esteves, C. I. C. et al. Dyes Pigments 2018, 151, 211-218. [5] Ferreira, R. C. M. et al. Amino Acids 2018, 50, 671-684. [6] Esteves, C. I. C. et al. Amino Acids 2017, 49, 921-930. [7] Esteves, C. I. C. et al. Dyes Pigments 2016, 134, 358-68.

Acknowledgments The authors acknowledge Fundação para a Ciência e Tecnologia – FCT (Portugal) for funding through CQUM (UID/QUI/00686/2020) and a PhD grant to C. D. F. Martins (SFRH/BD/05277/2020).

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NOU PROTOCOL PER A LA IMPLANTACIÓ DEL IOT EN ENTORNS DE XARXES DE SENSORS SUBAQUATIQUES

Jose Navarro,a Jose C. Campelo,a Alberto Bonastre,a Rafael Ors,a Juan V. Capella,a

a Universitat Politècnica de València, registered author e-mail : [email protected]

Keywords: modelo ns-3 ● enrutamiento ● redes de sensors ● IoT ● redes subacuáticas

En este articulo se presenta un nuevo modelo de protocolo de enrutamiento que facilita la implantación del IoT (Internet of Things) en entornos de redes subacuáticas. Este protocolo también integra un mecanismo de machine learning, que le permite encaminar los mensajes hacia los nodos receptores con mayores garantías de entrega y mejor rendimiento -como puede apreciarse en la figura 1- que otras técnicas de encaminamiento de referencia [1,2]. Para ello, se ha entrenado una red neuronal, que es la que toma las decisiones para encaminar dichos paquetes de datos. Se comparará el protocolo con una implementación basada en un sistema basado en reglas del tipo de lógica difusa [3]. Este protocolo esta implementado sobre el conocido simulador de redes basado en eventos, ns-3 [4]. La información necesaria para la toma de decisiones de cual es el mejor vecino para retransmitir el paquete de datos se analiza la calidad de la señal, y dentro del rango de cobertura del nodo cual tiene una localización geografica apropiada para optimizar consumos de energía de los nodos, entre otros parámetros [4], facilitando todo ello la implementación de nodos con las capacidades IoT necesarias en entornos subacuáticos.

Figure1. Resultados del impacto de la variación del LNS en el consumo de red

References [1] Brad Karp and H. T. Kung. “GPSR: greedy perimeter stateless routing for wireless networks” In Proceedings of the 6th annual international conference on Mobile compu-ting and networking (MobiCom '00). ACM, New York, NY, USA, 243-254. Year 2000 [2] Kayhan Zrar Ghafoor, Kamalrulnizam Abu Bakar, Shaharuddin Salleh, Kevin C. Lee, Mohd Murtadha Mo- hamad, Maznah Kamat, and Marina Md Arshad. “Fuzzy logic-assisted geographical routing over vehicular ad hoc networks”. International Journal of Innovative Computing, Information and Control, 8(7(B)):5095–5120, 2012. [3] J. Navarro, J.V. Capella. Nou ecosistema per al desenvolupament de xarxes de sensors mòbils i robus-tes. X International Workshop on Sensors and Molecular Recognition, 2016. [4] Ns-3 team. https://www.nsnam.org/

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DFT REACTIVITY INDICES AND pKa CALCULATIONS IN BODYPY-BASED SENSORS

Jose A. Sáez,a,b Ana M. Costero,a,b Pau Arroyo,a,b Silvia Rodríguez-Nuévalosa, Margarita Parraa,b

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Spain., [email protected] bDepartamento de Química Orgánica, Universitat de València, Doctor Moliner 50, 46100, Burjassot, Valencia, Spain.

Keywords: BODIPY ● DFT calculations ● Reactivity indices ● Fukiu ● pKa determination

Locating the reactivity sites of a molecular sensor is a challenging task since several interactions between the analyte and the chemosensor may take place in both the signalling moiety and recognition moiety. In this way, our group has focused lately in the ability of some BODIPY-based sensors of displaying UV-Vis and fluorescence changes in presence of small molecules, as γ-hydroxybutyric acid (GHB)[1]. In this way, molecular sensors 1 to 6 (see Figure 1) synthesized in our group, show different responses towards some nucleophilic/basic species, ranging from monoatomic anions (fluoride, iodide anions), polyatomic anions (thiocyanate, methanethiol and bisulfide anions) and even tertiary amines (triethylamine, DABCO). In addition, some of the changes reported are not fully reversible or take some time to complete. To disclose which mechanisms are operating in these recognition processes, computational chemistry can be of great help since it allows to find out the electrophilic/nucleophilic sites of an organic moiety and the acidity/basicity of a functional groups attached to the BODIPY moiety. This task can be accomplished by means of simple Density Functional Theory calculations that will allow the determination of reactivity indices as Fukui[2] ones and the calculation of pKa of the species through a computing scheme different from classical thermodynamic cycles[3].

Figure 1. BODIPY-based sensors studied.

References [1] Costero, A. M. et al. Chem. Commun. 2020, 56., 12600-12603. [2] Parr, R. G. et al. Density Functional Theory of Atoms and Molecules. Oxford University Press, New York, USA, 1989. [3] Ho, J. Phys. Chem. Chem. Phys. 2015, 17., 2859-2868.

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NOVEL SYNTHETIC APPROACH TO PREPRARE COLLOIDAL PEROVSKITE NANOCRYSTALS WITH POSSIBLE SENSING APPLICATION

Ignacio Rosa-Pardo,[a] Manuel Rando-Brotons,[a] Salvador Pocoví-Martinez,[a] Raquel E. Galian[a], Julia Pérez Prieto[a]

a Institute of Molecular Science, University of Valencia,C/ Cat. José Beltrán 2, Paterna, 46980. Spain; [email protected]

Keywords: Perovskites ● Top-down approach ● Laser ablation ● Sensing ● Photoluminiscence Lead halide perovskites of general formula APbX3, and specially CH3NH3PbX3, are materials that generate great interest due to their exceptional electronic and optical properties and, consequently, they have been widely studied in optoelectronic applications. Their easy synthesis and solution procesability are crucial for the manufacture of low-cost devices.[1] Since our first report on the preparation of colloidal CH3NH3PbBr3 (photoluminescence quantum yield, ΦPL, of 20%)[2] via a hot-injection method, the vast majority of scientific publications have focused on bottom-up synthetic methodologies. In the present work, a novel top-down synthetic procedure of colloidal hybrid perovskites nanocrystals, using a nanosecond pulsed laser ablation strategy, is presented. To achieve this objective, we have developed a simple strategy consisting of i) the synthesis of perovskite bulks, ii) irradiation of the bulk in the presence of adamantylammonium halides (ADAX, X = Br, I), by using a Nd-YAG laser, and iii) stabilization of the sample for 30 minutes. The optical properties of the perovskites were tuned by changing the CH3NH3PbX3:ADAX molar ratio. Remarkably, ADAX acted as the ligand and as the source of iodine or bromine. (figure 1a).[3]

From Bulk MAPbBr MAPbBrI MAPbI 1 3 2 3

0.8

0.6

0.4

Intensity (a.u.) 0.2

0 480 520 560 600 640 680 720 760 800 Wavelength, nm

Figure 1. a) Photoluminescence spectra of the array of the colloidal hybrid lead halide perovskites prepared with this methodology, b) The effect of different metal ions on the PL intensity in perovskite QDs.

There are few examples of CH3NH3PbX3 perovskites as sensors. Among them, it has been demonstrated their capacity to detect small amounts of metal cations (Cu2+), toxic ions (UO2+ and Hg2+) and gases (HCl and NH3), reactive compounds (ozone and picric acid), humidity levels. To highlight their sensing potential, as shown in figure 1b, the photoluminescence of metal halide perovskites can be drastically quenched in the presence of Cu2+, exhibiting a remarkable linear response in the 0–100 nM concentration range, with a limit of detection (LOD) of 0.1 nM. [4] References [1] Lee, M. M. et al. Science. 2012, 338, 643-647 [2] Schmidt, L. et al. J Am Chem Soc. 2014, 136, 850-853 [3] Rosa-Pardo, I. et al. ChemNanoMat. 2019, 5, 328-333 [4] Shellaiah, M. et al. Chemosensors. 2020, 8, 55 Acknowledgments We thank to MINECO (CTQ2017-82711-P), partially co-financed with FEDER (IDIFEDER/2018/064) and PROMETEO (PROMETEO/2019/080) funds and I.R.P. FPU grant (FPU17/05564).

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EVALUACIÓN DE LA VARIABILIDAD DE PARÁMETROS CANDIDATOS PARA ESTABLECER BIOEQUIVALENCIA DE FORMULACIONES SEMISÓLIDAS

Andreu Máñez Asensia, Mª Jesús Hernándezc, Matilde Merino Sanjuána, b, Virginia Merino Sanjuána, b.

a Dpto. de Farmacia y Tecnología Farmacéutica y Parasitología, Universidad de Valencia, Avda.Vicent Andrés Estellés s/n 46100 Burjasot ,Valencia, Spain. Registered author e-mail: [email protected] b Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València. Avd. Vicente A. Estellés s/n, 46100, Burjassot,Valencia, Spain c Dept de Fisica de la Terra i Termodinàmica, Universitat de València, Vicente Andrés Estelles s/n. Burjassot. Valencia. Spain

Palabras clave: formulaciones semisólidas ● Propiedades reológicas● Bioequivalencia tópica ● Absorción tansdérmica El desarrollo de medicamentos genéricos de administración tópica está en auge, aunque no se han descrito completamente los criterios para determinar la bioequivalencia entre formulaciones [1]. La European Medicines Agency (EMA) publicó en 2018 un documento donde señala que se podrá valorar la equivalencia terapéutica entre dos formulaciones tópicas cuando la composición cualitativa, cuantitativa y la microestructura entre la formulación de referencia y problema sean equivalentes [2]. Este trabajo tiene como objetivo cuantificar la variabilidad de los parámetros seleccionados por la EMA, en cinco lotes de una única formulación. Se realizaron ensayos de liberación y de absorción en celdas de tipo Franz, empleando filtros de polietersulfona de 0.45 µm y piel porcina, respectivamente. Por otro lado, se determinó el tamaño de gota de la fase interna de la emulsión y se efectuó un análisis -1 reológico para determinar viscosidad en reposo (η0), viscosidad a 100 s (η100), esfuerzo umbral (σ0) y módulo viscoso (G”) y elástico (G’). Los resultados obtenidos muestran que la variabilidad, tanto intralote como interlote, difiere entre los parámetros. Respecto a la liberación, el flujo presentó una variabilidad intralote expresada por coeficiente de variación (CV), entre el 4% y el 9% y la variabilidad interlote fue de 8,83%. En los ensayos de absorción, el flujo mostró variabilidades intralote entre el 38-78% y una variabilidad interlote de 39.36%. El tamaño de partícula presentó una variabilidad intralote en torno al 21-30% e interlote de 9.27%. Respecto a los parámetros reológicos, los CV intra e interlote de η100, G´ y G” fueron menores del 10%. El CV intralote del σ0 osciló entre el 10-20% con un CV interlote de 12,88%. Por último, el CV intralote de η0 oscila entre 13-30% y el interlote es de 23,53%. Los resultados indican que la variabilidad intra e interlote de los parámetros cuantificados puede llegar a ser elevada y no homogénea para todos los parámetros, lo cual compromete los criterios de la EMA.

References [1] Miranda, M. et al. Pharm Res. 2020, 18. [2] EMA. Draft guideline on quality and equivalence of topical products. 2018.

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SYNTHESIS AND CHARACTERIZATION OF A PHENANTHROIMIDAZOLE DERIVATIVE FOR METAL IONS DETECTION

Nuna Ramos,a Mariana Barros,a,b Susana Costa,a Manuela Raposoa

aCentre of Chemistry, University of Minho, Campus de Gualtar, 4710-057, Braga, Portugal, [email protected] bPresently at Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM),Universitat Politècnica de València, Universitat de València, Doctor Moliner 50, Burjassot, 46100 Valencia, Spain Keywords: Imidazole ● Phenanthrene ● Fluorescent chemosensor ● Metal ions 2,4,5-Tri(hetero)arylimidazole derivatives have been explored over the past few years as optical chemosensors due to their ability to coordinate with analytes, especially with ions. In addition, the replacement of aryl groups at positions 2, 4 and 5 of the imidazole ring with heterocyclic groups allows the tuning of its optical properties and the improvement of its recognition abilities [1-4]. The recognition and signaling of metal ions in biological, medicinal and environmental samples is important since they are involved in several biological processes. However, a high concentration of ions in the cells of living organisms, or even in watercourses, can be harmful to human health and to the organisms that inhabit ecosystems [5]. In order to continue the work developed by the research group [1-4], we report the synthesis of the new phenanthroimidazole 1 (figure 1A) and its characterization by the usual spectroscopic techniques (NMR, IR, UV-Vis absorption and emission spectroscopies). As a complement to the characterization of the synthesized imidazole derivative, a preliminary study as a fluorimetric chemosensor was carried out in acetonitrile in the presence of relevant ions with biological, medicinal and environmental relevance. Through spectrofluorimetric titrations, it was confirmed that the synthesized compound could have potential application as a fluorescent chemosensor for palladium(II) (figure 1B) and lead(II).

Figure 1. A) Structure of phenanthroimidazole 1. B) Fluorimetric titration of phenanthroimidazole 1 with Pd2+ in -5 acetonitrile [λexc 1 = 331 nm, [1] = 1x10 M]. Inset: normalised emission at 394 nm as a function of added palladium equivalents. References [1] Oliveira, E. et al. Inorg. Chem. 2010, 49, 10847-10857. [2] Ferreira, R. C. M. et al. New J. Chem. 2017, 41, 12866. [3] Okda, H. E. et al. Dyes Pigments. 2018, 159, 45-48. [4] Okda, H. E. et al. Dyes Pigments. 2019, 162, 303-308. [5] Liu, Z. et al. Chem. Soc. Rev. 2013, 42, 1568. Acknowledgments This research was funded by the Foundation for Science and Technology (FCT) through CQ/UM (UIDB/00686/2020). Thanks are also due to FCT for financial support to the Portuguese NMR Network (PTNMR, Bruker Avance III 400-Univ. Minho).

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PHENANTHROIMIDAZOLE DERIVATIVE: SYNTHESIS, CHARACTERIZATION AND CHEMOSENSORY ABILITY FOR ANIONS

Nuna Ramos,a Susana Costa,a Manuela Raposoa

aCentre of Chemistry, University of Minho, Campus de Gualtar, 4710-057, Braga, Portugal, [email protected]

Keywords: Phenanthromidazole ● Fluorimetric chemosensor ● fluoride ● cyanide

The development of new selective chemosensors for anions is a very active research topic in supramolecular chemistry, since these analytes are of biological, clinical and environmental interest. Fluoride is of particular importance due to its regular use in orthodontics and in the treatment of osteoporosis. In addition, cyanide is a very toxic ion, both in terms of health and the environment [1]. 2,4,5-Triarylimidazoles are versatile compounds and have applications in areas such as medicine, materials and biomedical sciences. An interesting feature of these derivatives is their optical properties, which can be optimized through a careful selection of substituents at positions 2, 4 and 5. However, heterocyclic substituents are preferable to aryl groups due to a larger π-conjugation of the system, culminating in improved optical properties for various applications in materials and medicinal chemistry such as two-photon absorption fluorophores (TPA) for bioimaging, DNA intercalators, optical chemosensors, among others [2-3]. In this communication, we report the synthesis of a new phenanthroimidazole 1, substituted at position 2 with a carbazolyl group (figure 1) using a simple synthetic methodology and an easy purification procedure. The new compound was characterized by the usual techniques and a detailed photophysical study was undertaken. The evaluation of the imidazole derivative as a fluorimetric chemosensor was carried out in acetonitrile in the presence of relevant anions with biological, medicinal and environmental relevance. The results from spectrofluorimetric titrations confirmed that the new compound constitutes a fluorimetric chemosensor for fluoride and cyanide.

Figure1. Structure of phenanthroimidazole 1. References [1] Batista, R. M. F. et al. Sensors Act. B Chem. 2014, 191, 791. [2] Ferreira, R. C. M. et al. New J. Chem. 2017, 41, 12866. [3] Hazem E. O. et al. Dyes Pigments. 2019, 162, 303. Acknowledgments This research was funded by the Foundation for Science and Technology (FCT) through CQ/UM (UIDB/00686/2020) Thanks are also due to FCT for financial support to the Portuguese NMR Network (PTNMR, Bruker Avance III 400-Univ. Minho).

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SULPHATED-POLYSACCHARIDE FUCOIDAN AS NATURAL ANTIMICROBIAL AGENT FROM ALGAE: ALIMENTARY AND PHARMACEUTICAL APPLICATIONS Alejandro Rivasa, Héctor Gómez-Llorentea, Édgar Pérez-Estevea, José Manuel Barata, Maria Consuelo Pina-Pérezb aUniversitat Politècnica de València, Dept Tecnología de Alimentos, Camino de Vera s/n, 46022, Valencia (SPAIN) [email protected] bAUniversitat de València, Dept Microbiologia y Ecología, C/Dr. Moliner, 50, 46100 Burjassot, Valencia (SPAIN)

Keywords: Fucoidan ● Phaeophyceae algae ● natural antimicrobials ● Clostridioides difficile ● bactericidal capacity Nowadays, algae represents a valuable sustainable source of bioactives with pharmaceutical, alimentary and technological applications. Fucoidan, a sulphated – heteropolysaccharide molecule extracted from brown Phaeophyceae algae, has been recently associated to potential health benefits, such as antioxidant, antimicrobial, anti- inflammatory, anticancerigen, and immunomodulatory effects, among others [1,2]. The present study aims to evaluate the potential antimicrobial capacity of fucoidan from Undaria pinnatifida and Macrocystis pyrifera, against the highly resistance - gastrointestinal pathogen Clostridioides difficile (CECT 531 T). An in vitro assay was carried out in sterile Brain Heart Infusion Broth (BHIB) supplemented/not supplemented with fucoidan at concentrations in the range [500-3000] µg/mL. Artificially inoculated substrates (initial bacterial load of ≈104 CFU/mL) were incubated at 37°C, 48h, under anaerobic conditions; and microbial load was registered at 8h intervals (by plate count methodology). Microbial growth/death curves were obtained and both, minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) were estimated. Chemical fucoidan structure, concentration (µg/mL), and contact time (h), were influential factors (p-value< 0.05) determining fucoidan in vitro antimicrobial capacity. According to obtained results, fucoidan from Undaria pinnatifida showed the most effective antimicrobial capacity against C. difficile (Figure 1). MIC values for fucoidan against C. difficile were in the range 1000- 3000 µg/mL, depending on the fucoidan structure and origin. Fucoidan from Undaria pinnatifida showed a MBC value of 3000 µg/mL (≈3 log10 cycles reduction after 24h contact time). These results are promising as baseline for future pharmaceutical and functional food products development.

Figure1. Bactericidal and bacteriostatic effect of fucoidan against Clostridioides difficile References [1] Pina-Pérez et al. Microalgae as healthy ingredients for functional food. Elsevier ed., Amsterdam, Netherlands, 2019, pp:103-137. [2] Marco-Castro et al. Fermentation, 2019, 5(28), 1-16. Acknowledgments The present study has been developed by funds provided by the Conselleria de Innovación, Universidades, CIencia y Sociedad Digital (GVA), reference: GV2020/031

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SHELF-LIFE OF MICROPARTICLES WITH INMOBILIZED VANILLIN FOR MICROBIAL WATER QUALITY IMPROVEMENT AT DIFFERENT pHs

Héctor Gómez-Llorentea, Édgar Pérez-Estevea, María Ruiz-Rico, Isabel Fernández-Segoviaa, Jose Manuel Barata

aDepartamento de Tecnología de Alimentos, Grupo de Investigación e Innovación Alimentaria, Universitat Politècnica de València, Camino de Vera s/n, 46022, Spain, email: [email protected]

Keywords: ● Vanillin ● Filter shelf-life ● pH ● Water ● Immobilization

Access to safe water is crucial to avoid health risks caused by the presence of pathogenic microorganisms. For this purpose, chemical compounds such as chloramine or chlorine are commonly used. However, despite their effectiveness, harmful disinfection by-products are formed [1]. To avoid this problem, new alternatives, such as the use of natural antimicrobials anchored to surfaces, are emerging as a novel approach. In this context, silica particles functionalized with vanillin have been shown to be capable of removing E. coli from water [2]. To use this system for the purification of real samples, the shelf-life of this particles should be evaluated, which is understood as the number of litres of water that can be filtered until they lose their antimicrobial activity. The objective of this study was to determine the shelf life of silica microparticles with immobilized vanillin in the filtration process of water adjusted to different pHs (3.5, 5, 7.5 and 8.5). To achieve this goal, silica microparticles (50-110 µm) were functionalized with vanillin. Then, water filtration tests were carried out. For each pH tested, first, 100 mL of inoculated water (105 UFC/100 mL of Escherichia coli) were filtered through a bed of the vanillin-functionalized supports to assess the initial removal capability. Next, 10 L of non-inoculated water were filtered. Finally, 100 mL of inoculated water was filtered, and the new removal capability was evaluated. This process was repeated until the particles lost their antimicrobial effect. The results showed that using a 2 cm bed of particles (25 g), up to 60 L of water can be filtered until the filtration system is no longer effective to remove E. coli present in the waters. This value decreased to 40 L when the filtered water had a pH of 8.5. However, when acidic waters were filtered, the number of liters increased to 250 L (pH 5) or 520 L (pH 3.5). These results show the importance of the pH of the water in the shelf-life of the filtration system.

References [1] Richardson, S. D. et al. Mutation Research/Reviews in Mutation Research. 2007, vol. 636(1-3)., 178-242. [2] Peña-Gómez, N. et al. Innovative Food Science & Emerging Technologies. 2019, vol 58., 102228. Acknowledgments Authors gratefully acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades, the Agencia Estatal de Investigación and FEDER-EU (Project RTC-2017-6100-2-AR). H. G. gratefully acknowledge the Univeristat Politècnica de València for his Pre-doctoral Scholarship (FPI).

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OPTIMIZATION OF THE REACTION OF INMOBILIZATION OF VANILLIN IN SILICA MICROPARTICLES FOR E. Coli REMOVAL IN WATER

Héctor Gómez-Llorente,a Alessandro Dallamanoa, Alejandro Rivasa, Édgar Pérez-Estevea, Isabel Fernández-Segoviaa, José Manuel Barata

aDepartamento de Tecnología de Alimentos, Grupo de Investigación e Innovación Alimentaria, Universitat Politècnica de València, Camino de Vera s/n, 46022, Spain, email: [email protected]

Keywords: Vanillin ● Antimicrobial ● Natural compounds ● Water ● Immobilization

Development of filtration technologies to purify and microbiologically stabilize water and other liquid food products has experienced an increase in recent years [1]. In this context, the design of filtering materials based on silica microparticles in which natural antimicrobial compounds, such as essential vanillin, have been anchored to its surface, has been demonstrated to be a good alternative for water, juice, wine, or beer microbial stabilization, without modifying their colour, flavour, consistency… [2]. Once the efficacy of this technology has been proven in different applications, a scaling process should be carried out, the first step being the optimization of the synthesis conditions, and the evaluation of different reactions parameters to maximize the microbial removal capacity of the particles. The aim of this work was to optimize the main parameters of the vanillin anchoring reaction in the silica microparticles (50-110 µm) to develop a suitable antimicrobial filter material, which is effective against Escherichia coli. In this context, firstly, different amounts of vanillin (8 g or 4 g) were tested. Next, two types of reducing agents used for the stabilization of the imide bond (formic acid/formate or sodium borohydride), and two solvents in which this reaction is carried out (isopropanol or methanol) were evaluated. Once the different supports were prepared, their capacity to remove E. coli from inoculated water adjusted at different pHs were assessed. For this purpose, 100 mL of inoculated water were filtered through the different particles. After the filtering process, the collected water was plated in TBX and plates were incubated at 37 °C for 24 h. This process was repeated until the particles lost their antimicrobial effect. The results showed that sodium borohydride as reducing agent, methanol as solvent, 8 g of vanillin, and neutral pH were the best parameters to achieve the maximum effectiveness of the antimicrobial filter.

References [1] Ribes, S. et al. Environmental Technology & Innovation. 2021, vol 21., 101219. [2] Peña-Gómez, N. et al. Innovative Food Science & Emerging Technologies. 2019, vol 58., 102228.

Acknowledgments Authors gratefully acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades, the Agencia Estatal de Investigación and FEDER-EU (Project RTC-2017-6100-2-AR). H. G. gratefully acknowledge the Univeristat Politècnica de València for his Pre-doctoral Scholarship (FPI).

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FORMYL-THIENO[3,2-b]THIOPHENE DERIVATIVE: PRELIMINARY CHEMOSENSORY STUDIES AND SPECTROPHOTOMETRIC TITRATIONS

Rui Sousa,a Raquel Gonçalves,a Susana Costa,a Rita Figueira,a,b Manuela Raposoa aCentre of Chemistry, University of Minho, Campus of Gualtar, 4710-057 Braga, Portugal, registered author e-mail : [email protected] bPresently at Vasco da Gama CoLAB, Rua Roberto Frias, 4200-465 Porto, Portugal

Keywords: Heterocyclic aldehydes ● Thieno[3,2-b]thiophene ● Optical chemosensors ● Cations

The versatility of heterocyclic aldehydes allows them to act as “building blocks” in the synthesis of more complex compounds, with applications in medicinal, materials and supramolecular chemistry. The conjugation with thienothiophene π-bridges can yield highly conjugated push-pull systems with a wide variety of optical applications. For instance, heterocyclic aldehydes have already been reported as ion chemosensors [1-4]. Following the research carried on in the our group [3-4], this work reports the preliminary chemosensory tests and spectrophotometric titrations of a heterocyclic aldehyde based on a thieno[3,2-b]thiophene core, previously synthesized by Suzuki coupling [4]. Preliminary chemosensory studies of compound 1 in the presence of 50 eq. of different anions and cations showed fluorescence quenching in the presence of Hg2+, Fe2+, Cu2+, Pd2+, Fe3+, and Al3+ cations. Spectrophotometric titrations were performed to assess the interaction between the compound and the six cations, of which Al3+, Fe3+ and Cu2+ required a low number of equivalents in order to induce total quenching of the compound’s fluorescence.

0 eq. Al3+

S O N 6 eq. Al3+ S 1

Figure 1. Structure of compound 1 and spectrofluorimetric titration with Al3+ in acetonitrile.

References [1] Chebrolu, L. D. et al. Sens. Actuators, B Chem. 2014, 204, 480–488. [2] Chakraborty, N. et al. J. Photochem. Photobiol. A Chem. 2018, 359, 53–63. [3] Okda, H. E. et al. New J. Chem. 2019, 43, 7393–7402. [4] Sousa, R. P. C. L. et al. Chem. Proc. 2021, 3, 88. Acknowledgments Thanks are due to Fundação para a Ciência e Tecnologia (FCT) and FEDER (European Fund for Regional Development)-COMPETE-QRENEU for financial support through the Chemistry Research Centre of the University of Minho (Ref. CQ/UM (UIDB/QUI/00686/2019 and UIDB/QUI/00686/2020), and a PhD grant to R. P. C. L. Sousa (SFRH/BD/145639/2019).

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JANUS PT- MESOPOROUS SILICA NANOMOTORS FOR BACTERIAL BIOFILM ERADICATION

Paula Díez a,b,c,d, Andrea Escudero a,b,c, Miglė Žiemytė e, María D. Ferrer e,f, Jose R. Murguía a,b,c, Alex Mira e,f and Ramón Martínez-Máñez a,b,c,d

aInstituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Spain. [email protected]. bDepartamento de Química, Universitat Politècnica de València, Cami de Vera s/n, 46022, València, Spain. 3CIBER de Bioingeniería, biomateriales y nanomedicina (CIBER-BBN), 28029 Madrid, Spain. cUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, València, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, 46012 València, Spain. dUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, 46026, València, Spain. e Genomics & Health Department, FISABIO Foundation, Valencia, Spain. f CIBER of Epidemiology and Public Health, Madrid, Spain.

Keywords: Janus nanomotors ● Self-propulsion ● Controlled drug delivery ● Antimicrobial therapy Treatment of microbial diseases supposes a major public health challenge as the emergence of biofilm-related antibiotic resistances invalidates many conventional therapies. Biofilms are extremely arduous to eliminate as bacteria employs an own extracellular polymeric matrix (EPS) as “protective clothing” for external attacks [1,2]. Regarding this, nano- and micromotors could serve as useful tools for the EPS mechanical disassembling due to their movement [3]. Here, we describe the development of multitasking platinum (PtNP)-mesoporous silica (MSN) Janus nanomotors for the treatment of Staphylococcus aureus infections. These nanosystems employ the PtNPs face as a propulsive element and the MSN face as nanocarrier for vancomycin antibiotic drug, locked in the pores by a pH-sensitive inclusion complex formed between the benzimidazole groups that decorating mesoporous surface and the β-cyclodextrin-modified ficin protease. Nanodevices showed remarkable self-propelled movement due to catalytic transformation of hydrogen peroxide (H2O2), as well as an enhanced protease activity, achieving more than 75% EPS disruption. In addition, A) Biofilm disruption due to nanomotor self- B) Vancomycin release mediated by the acidic vancomycin propulsion and enhanced Ficin activity biofilm environment. delivery triggered by an acidic pH present within the biofilm core led to

H2O2 a 90% reduction in the number of H2O + ½ O2 viable S. aureus

S. aureus biofilm S. aureus plaktonic form cell elimination, far superior to any conventional treatment, figure 1. Figure 1. Janus Pt-MSNs nanomotor for the treatment of bacterial biofilms.

References [1] Smith, K.F. et al. J. R. Soc. Interface 2014, 11, 20140950. [2] Sadekuzzaman, M.; Yang, S.; Mizan, M.; Ha, S. Compr. Rev. Food Sci. Food Saf. 2015, 14, 491–509. [3] Yuan,K.; Jurado-Sánchez, B.; Escarpa, A. Angew. Chem. Int. Ed. 2021, 60, 4915– 4924 Acknowledgments Authors want to thank the Spanish Government for RTI2018-100910-B-C41 (MCIU/AEI/FEDER, UE) and CTQ2017-87954-P projects and the Generalitat Valenciana for support by project PROMETEO/2018/024.

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COMPUTATIONAL INSIGHTS ON THE STABILITY AND FORMATION OF DIFUNCTIONALIZED PILLAR-[N]-ARENE COMPOUNDS

Jorge Escorihuela,a Andrew C.-H. Sue,b Han Zuilhof,b,c a Departamento de Química Orgánica, Universitat de València, Avda. Vicent Andrés Estellés s/n, 46100 Burjassot, València, Spain, E-mail : [email protected] b Institute for Molecular Design and Synthesis, School of Pharma-ceutical Science & Technology, Tianjin Uni- versity, 92 Weijin Road, Nankai District, Tianjin, 300072, P. R. China c Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6703 WE Wageningen, The Netherlands

Keywords: pillar[n]arene ● supramolecular chemistry ● quantum chemistry ● formation ● stability

The rapid rise in supramolecular chemistry has invoked a wide range of macrocyclic compounds, which make increasingly use of precisely balanced covalent and non- covalent forces. A particular class of these supramolecular compounds are pillar[n]arenes, particularly, pillar[5]arene [P5], which has gained special attention in the last years. With this size, the para-substituted aryl rings are all oriented in the same direction (see Figure 1), giving rise to the unique hollow pillar shape and has recently come to full fruition by the development of synthetic methods that allow a functionalization at will of rim-differentiated Ps. More recently increasing use has also been made of P6-based materials. The yield of P6s is characteristically only a few percent in this Friedel-Crafts-based cyclization reaction. In contrast, no P4 has been described, and the syntheses of larger Ps (P7-P10) have been marred by very low yields. The questions we aim to answer in this poster are: a) to which degree are the thermodynamics of the products determining the outcome of this ring-forming reaction, and b) do the differently sized Pns display significant differences in their formation, and c) what is the role of the solvent.

RO RO Pillar[5]arene RO OR OR OR OR OR OR K RO RO CH2OH OR k Other pillar-[n]-arenes K or (Lewis) acid conditions / solvent RO (templating?) RO K OR RO OR OR + CH2O OR OR OR OR OR RO RO RO Pillar[6]arene Figure 1. Aim of this study: a) study of thermodynamics of differently sized pillararenes (n=4-8); b) study of kinetics of pillar[5]arene and pillar[6]arene formation, and the role of templating solvents References [1] Demay-Drouhard, P. et al. Org. Lett. 2019, 21, 3976–3980. [2] Guo, M. et al. J. Am. Chem. Soc. 2018, 140, 74–77. [3] Yang, W. et al. Angew. Chem. Int. Ed. 2020, 59, 3994–3999. Acknowledgments Financial support of the National Science Foundation of China (grant #21871208) and Wageningen University is greatly acknowledged.

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A FLUORESCENT PROBE BASED ON A BODIPY- BENZIMIDAZOLE DERIVATIVE TO DETECT INTRACELLULAR pH CHANGES IN LIVING CELLS

Raquel Gonçalves,a Milene Silva,b Juan Gallo,b Susana Costa,a Manuela Raposoa aCentre of Chemistry, University of Minho, Campus of Gualtar, 4710-057 Braga, Portugal, registered author e-mail : [email protected] b Nanomedicine Research Group, International Iberian Nanotechnology Laboratory, Av. Mestre José Veiga s/n, 4715-330, Braga, Portugal

Keywords: BODIPY ● Intracellular pH ● Fluorescent probe ● Bioimaging ● Living cells

The function of cellular organelles in living cells, such as lysosome and mitochondria, depends on the establishment and maintenance of a distinct intracellular pH, thus influencing processes of cell cycle and apoptosis [1]. Several small molecules have been reported as fluorimetric pH sensors, however only few demonstrate biocompatibility. Therefore, the development of novel fluorescent probes to monitor the dynamic changes of intracellular pH is highly important and, if combined with fluorescence microscopy, these probes become a powerful tool for bioimaging [2]. Due to their outstanding photophysical features, BODIPY derivatives have been studied as fluorescent probes for many applications in the biological and bioimaging research field [3]. Here, in continuation of the investigation developed in our research group concerning BODIPYs for several applications [4-6], we report the synthesis and characterization of a BODIPY with potential application as fluorescent probe to detect cellular cytosolic pH variations through confocal microscopy analysis.

N

H N

N N B N F F

1

Figure1. Structure of BODIPY derivative and confocal fluorescence images of HeLa cells pre-treated with buffer with nigericin at different pH values (pH=4.5 or 7) and stained with probe 1. The fluorescence of probe 1 was detected in the green channel (λex= 488 nm, λem= 530 nm) and red channel (λex= 561 nm, λem= 620 nm).

References [1] Casey, J. et al. Nature Reviews Molecular Cell Biology. 2009, 11, 50–61. [2] Hou, J. et al. Chemical Society Reviews. 2017, 46, 2076–2090. [3] Kaur, P. et al. Journal of Materials Chemistry C. 2019, 7, 11361–11405. [4] Collado, D. et al. Chemistry European Journal. 2011, 17, 498-507. [5] Lo Presti, M. et al. New Journal of Chemistry. 2018, 42, 7863–7868. [6] Gonçalves, R. et al. Chemistry Proceedings. 2020, 3, 65.

Acknowledgments The authors acknowledge Fundação para a Ciência e Tecnologia - FCT (Portugal) for funding through CQUM (UID/QUI/00686/2020) and project PTDC/QUI-COL/28052/2017 and a PhD grant to R. C. R. Gonçalves (SFRH/BD/05278/2020). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased within the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT.

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A FLUORIMETRIC CHEMOSENSOR FOR FLUORIDE BASED ON A BODIPY FLUOROPHORE

Sónia Pinto,a Raquel Gonçalves,a Susana Costa,a Manuela Raposoa

a Centre of Chemistry, University of Minho, Campus of Gualtar, 4710-057 Braga, Portugal [email protected]

Keywords: BODIPY ● Carbazole ● Fluorimetric chemosensor ● Fluoride

Fluoride is an anion extremely harmful to human health since its high intake can lead to chronic diseases such as dental and skeleton fluorosis, and metabolic dysfunctions. Thus, monitoring fluoride levels in the body is of great importance. Among the several classic analytical techniques, optical chemosensors have been highlighted for their simplicity, non-destructive character, low-cost technique and for allowing high sensitivity and fast analysis [1-4]. Boron-dipyrromethene (BODIPY) derivatives have received great attention for chemosensory applications due to their remarkable physical- chemical properties, such as high molar absorption coefficients, high quantum fluorescence yields, intense and narrow absorption/emission bands in the visible region of the electromagnetic spectrum, and good photochemical stability. Additionally, the optical properties can be optimized through functionalization of the BODIPY core, considering its application as chromofluorogenic chemosensors [5-7]. In continuation of the work developed in our research group [8-10], we report the synthesis, spectroscopic characterization, and evaluation of the chemosensory ability of BODIPY derivative 1 functionalized with a carbazolyl and a formyl group at the meso and 2-position, respectively, as a fluorimetric chemosensor for the selective detection of fluoride.

N

CHO N N B F F 1 Figure1. Structure of BODIPY derivative 1 and selective fluorimetric detection of fluoride with BODIPY 1, in acetonitrile solution.

References [1] Jiao, Y. et al. Theranostics 2015, 5, 173–187. [2] Wang, L. et al. Dyes Pigments 2020, 172, 107857. [3] Suganya, S. et al. ChemistrySelect 2018, 3, 7231–7268. [4] Ullah, N. et al. TrAC - Trends Anal. Chem. 2018, 100, 155–166. [5] Zlatić, K. et al. Photochem. Photobiol. A Chem. 2020, 388, 112206. [6] Lakshmi, V. et al. Reports Org. Chem. 2016, 6, 1–24. [7] Bañuelos, J. Chem. Rec. 2016, 16, 335–348. [8] Lo Presti, M. et al. New J. Chem. 2018, 42, 7863–7868. [9] Collado, D. et al. Chem. Eur. J. 2011, 17, 498-507. [10] Pinto, S. C. S. et al. Chem. Proc. 2021, 3, 79.

Acknowledgments The authors acknowledge Fundação para a Ciência e Tecnologia - FCT (Portugal) for funding through CQUM (UID/QUI/00686/2020). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased within the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT.

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BODIPY CHEMISTRY TOWARDS THE RATIONAL DESIGN OF PROPERTIES

Carolina Díaz,b,§ Fernando García-Garrido,a,§ Josué Jiménez,a,§ Alejandro Prieto- Castañeda,a,§ César Ray,a,§ Christopher Schad,a,§ Sergio Serrano,a,§ Beatriz L. Maroto.a aDepartamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, 28040, Madrid, Spain. [email protected] bDepartamento de Química Física, Universidad del Pais Vasco-EHU, Apartado 644, 48080, Bilbao, Spain. §These authors contributed equally.

Keywords: BODIPY ● organic dyes ● Photonics ● properties modulation

BODIPYs (boron dipyrromethenes) are outstanding dyes due to their excellent photophysical properties (strong absorption molar coefficients and high fluorescence quantum yields) and their low sensibility towards media changes (polarity, pH, temperature). Their exceptional properties, together with their straightforward synthesis from available starting materials, make them top low-cost dyes, as demonstrated in the large range of photonic applications where these leading dyes have found use (as fluorescent sensors and switches, as labels for bioimaging and/or biotherapy, for the development of materials for optoelectronic devices, etc.) [1]. In addition to this, what has furthered their utility in the development of photonic tools, is the possibility of modulating their photophysical properties by chemical modifications of the chromophore. Thus, there is a wide variety of chemical transformations that can be carried out over the BODIPY (BODIPY Chemistry) directed towards the achievement of a particular property. For example, the extension of the π-conjugation of the chromophore to bathochromically shift the emission towards the red/NIR, or the attachment of iodine atoms to populate triplet excited states and make singlet oxygen photosensitizers [2]. In this communication, we present the latest results achieved by our research group in chemical transformations in BODIPYs directed to obtaining and modulating specific properties [3]. For example, the attachment of recognition sites for specific accumulation of the dye in a particular organelle for biomedicine or the construction of BODIPYs with a tuneable fluorescence response for sensing of pH or cations. We have also established the guidelines to modulate important properties such as fluorescence efficiency, emission of circularly polarized light or photosensitizing capability in BINOL-derived O-BODIPYs by properly choosing the substitution pattern in BODIPY and BINOL moieties.

References [1] (a) Loudet, A. et al. Chem. Rev. 2007, 107, 4891-4932; (b) Ulrich, G. et al. Angew. Chem. Int. Ed. 2008, 47, 1184-1201; (c) Boens, N. et al. Coord. Chem. Rev. 2019, 399, 213024. [2] (a) Kamkaew, A. et al. Chem. Soc. Rev. 2013, 42, 77-88; (b) Prieto-Montero, R. et al. Photochem. Photobiol. 2020, 96, 458-477. [3] For example see: (a) Jiménez, J. et al. Chem. Commun. 2021, DOI: 10.1039/D1CC01255J; (b) Ramos-Torres, A. et al. Chem. Commun. 2021, 57, 5318-5321; (c) Avellanal-Zaballa, E. et al. Phys. Chem. Chem. Phys. 2021, 23, 11191-11195; (c) Tabero, A. et al. Chem. Commun. 2020, 56, 940-943; (d) Ray, C. et al. J. Org. Chem. 2020, 85, 4594-1601. Acknowledgments Financial support from Ministerio de Ciencia e Innovación of Spain (MAT2017-83856-C3-2-P and -3-P and PID2020-114755GB-C3) and Gobierno Vasco (IT912-16) is gratefully acknowledged. C.S. and S.S thank Comunidad de Madrid - UCM for a research contract. C.D. thanks the from Ministerio de Ciencia e Innovación of Spain for a FPI predoctoral fellowship.

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PHOTONIC SENSORS BASED ON FIBER DEVICES: NARROW BANDWIDTH LONG PERIOD GRATINGS

Víctor González-Morote,a Martina Delgado-Pinar,b Jose Luis Cruz,a Antonio Díez,a Miguel V. Andrés.a

a Laboratory of Fiber Optics, Department of Applied Physics, ICMUV, University of Valencia, c/ Dr. Moliner 50, 46100 Burjassot, Valencia. b Department of Applied Physics, University of Barcelona, c/ Martí I Franqués 1, 08080 Barcelona

Keywords: fiber grating ● RI sensing ● evanescent wave sensor ● sensor characterization ● photonic sensor

In this work we present an example of the capabilities of the Laboratory of Fiber Optics to fabricate optical fiber-based devices suitable to be used as sensors and biosensors. Here, we focus on a special type of Long Period Grating (LPG) with an unusual narrow bandwidth, whose fabrication process has been designed and optimized in our facilities. This device consists on a length of photosensitive fiber, typically 10 cm, where a permanent, periodic modulation of the refractive index of the fiber core has been photoinscribed using UV radiation. The design of such modulation is optimized to produce a resonant coupling at a given wavelength (∼ 1550 nm in our example) with a narrow bandwidth of 1-2 nm, which is, at least, one order of magnitude lower than the bandwidths of other LPGs used for sensing and biosensing [1]. This feature leads to an improved detection limit and figure of merit of the sensor performance. Figure 1 (a) shows the spectrum of a LPG that shows a notch with a bandwidth of 1.7 nm. The notch in the spectrum corresponds to the optical power coupled from the fundamental mode, confined in the fiber core, to a cladding mode. Cladding modes show a significant evanescent optical wave that makes these devices sensible to external variations of index or, in practice, a specific target. As an example, the spectrum is shown when the device is surrounded by air and water. The wavelength shift of the notch would allow quantifying the concentration of the target after the device is properly functionalized. Fig 1 (b) shows the calibration of the LPG as a refractometer, that is, the wavelength shift as a function of the external refractive index. To do so, the device was immersed in different solutions of EtOH/water of known refractive indices [2]. The sensitivity of the device is 155±7 nm/RIU, and the calculated detection limit is 6×10-5 RIU. In conclusion, we present the characterization as a refractometer of a narrow bandwidth LPG that shows a good prospect to be used as a biosensor. Our experience includes other alternatives for fiber-based biosensors such as tapered fibers, fiber Bragg gratings, acousto-optic devices or photonic crystal fibers [3].

Figure 1 (a): spectrum of the LPG in air (black line) and water (blue line). (b) Wavelength shift as a function of the variation of the external refractive index, ∆next = next,solution – next,water. References [1] Ghoreyshi A. A. et al. J. Membr. Sci. 2003, 211, 193-214. [2] Chen X. et al. Biosensors and Bioelectron. 2015, 6, 2, 1000173. [3] Laboratory of Fiber Optics, Andrés M. V. et al. www.uv.es/lfo (27/05/2021) Acknowledgments This work has been funded by the European Commission H2020-MSCA-RISE-872049 (IPN-Bio) project, Spanish Government (MICINN) PID2019-104276RB-I00, and Generalitat Valenciana PROMETEO/2019/048

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CHLORIDES DETECTION IN HARDENED CONCRETE MATRIX BY MEANS OF VOLTAMMETRIC Ag SENSORS Ana Martínez Ibernón,a Isabel Gasch,a,b Juan Sotoa,c a IDM - Instituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico. ETSIE. Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, España. E-mail:[email protected] b Dpto. de Mecánica de los Medios Continuos y Teoría de Estructuras. Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, España. c Dpto. de Química. Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, España. Keywords: Chlorides ● Concrete ● Sensors ● Monitoring ● Voltammetric With the purpose to ensure the sustainable development of a country it is fundamental to enlarge its reinforcement concrete structures (RCS) service life. Therefore, will be necessary the implementation of monitoring systems in order to control in real-time the state of the RCS. Ones of the most promising monitoring systems is that formed by voltammetric sensors embedded in the concrete [1]. In this type of sensors is applied a potential sweep, in this way the reaction with different substances found in the concrete pore solution are promoted over the sensor surface. Through the processing of this signal we will be able to quantify the presences of these substances and develop forecasting models. The study was focused on testing the effectiveness of the silver voltammetric sensor to detect the chlorides presences inside the hardened concrete matrix. The chlorides are one of the mainly despassivation agents of the rebars [2,3], after the despassivation, in favourable thermodynamic conditions, the rebars begins to corrode actively. This fact is very relevant having account corrosion is the main lost durability cause in the RCS [4]. The capability of the sensor to detect the chlorides presences as well as different concentrations in the concrete was demonstrated in different samples of standard concrete (C30) submerged in different NaCl solutions concentration. By means of the sensors response analysis was defined a parameter correlated with the concentration of chlorides in the concrete pore solution. With this parameter were set up the foundations of simple models to quantify the chlorides concentration (Figure 1). Based in these models will be able to develop a forecasting models for the initiation period in the RCS (Tutti corrosion model [3]).

Figure1. Correlation between solution concentration were are submerged the concrete samples and the parameter to detect chlorides (P_Cl). References [1] Ramón JE, Gandía-Romero JM, Valcuende M, Bataller R. Integrated Sensor Network for Monitoring Steel Corrosion in Concrete Structures. Int J Archit Technol Sustain [Internet]. 1(1):64–79. Available from: http://dx.doi.org/10.4995/vitruvio- ijats.2016.5191 [2] Poursaee A, Hansson CM. Potential pitfalls in assessing chloride-induced corrosion of steel in concrete. Cem Concr Res [Internet]. 2009;39(5):391–400. Available from: http://dx.doi.org/10.1016/j.cemconres.2009.01.015 [3] Tutti K. Corrosion of steel in concrete. Stokholm: Swedish Cement and Concrete Institute; 1982. [4] Ramón Zamora JE. Sistema de Sensores Embebidos para Monitorizar la Corrosión en Estructuras de Hormigón Armado. Fundamentos , Metodología y Aplicaciones. PhD Thesis, Univ Politècnica València, València, Spain,. 2018; Acknowledgments The authors would like to express their gratitude to the Spanish Ministry of Science and Innovation for the pre-doctoral scholarship granted to Ana Martínez Ibernón (FPU16/00723). To the Universitat Politècnica de València for the financial support in the project “Ayudas a Primeros Proyectos de Investigación (PAID-06-18): Lengua Electrónica Voltamétrica para el control de durabilidad en hormigones, SP20180245”.

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CONCRETE RESISTIVITY INFLUENCE ON THE MACROCELL CORROSION INTENSITY IN REINFORCED CONCRETE STRUCTURES

J. R. Lliso-Ferrando,a M. Valcuende,b A. Martínez-Ibernón.a

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Camino de Vera, s/n 46022 Valencia, Spain. E-mail: [email protected] b Department of Architectural Constructions; Universitat Politècnica de València, Camino de Vera, s/n 46022 Valencia, Spain

Keywords: Reinforced Concrete Corrosion ● Macrocell Corrosion Currents ● Resistivity ●

In recent years, the durability of reinforced concrete structures has become a key factor during the designing process. Historical statements claiming concrete could keep a service life for hundreds of years or even infinity have been discredited by reality. Currently it is possible to find reinforced concrete structures showing signs of deterioration after 20-50 years after building. This may be due to the load they are subjected to, but most often it is because the damage caused by the environment where they are located. Reinforcement corrosion is one of the main damages causing premature failure of reinforced concrete structures [1], [2]. Corrosion is a natural phenomenon in which steel tends to its original state [3]. Due to corrosion is an unavoidable process, many designers have tried to slow down this process or reduce its impact. For example, some research groups have proposed improving concrete mix designs in order to avoid the aggressive agent’s penetration, as chlorides, which can onset the corrosion processes [4]. Other authors have proposed increasing the concrete resistivity trough less porous cementitious materials to reduce the impact of macrocell currents. The macrocell currents in reinforcements are one of the most important factors increasing the corrosion rates and damage in reinforced concrete structures. This phenomenon is produced by electrical connection of passive and actives steels [5]–[8]. This study summarizes a brief description of how macrocell currents work. Later, an experimental work is presented where macrocell currents and concrete resistivity were analysed.

References [1] J. M. Gandía Romero, Tesis Doctoral Universitat Politècnica de València. 2014. [2] M. de Fomento, Instrucción del hormigón estructural EHE-08. 2011. [3] J. E. Ramon Zamora, Tesis Doctoral Universitat Politècnica de València. 2018. [4] P. Garcés Terradillos, et al. 2008. [5] J. Warkus et al. Mater. Corros. 2010, vol. 61, no. 6, pp. 494–504. [6] K. Hornbostel, et al. Eval. Program Plann. 2016, vol. 110, pp. 46–56. [7] C. M. Hansson, et al. Cem. Concr. Compos. 2006, vol. 36, no. 6, pp. 2098–2102. [8] M. G. Sohail, et al. Materials and Structures. 2015, vol48, no 1-2, pp. 217–233.

Acknowledgments The authors would like to express their gratitude to the Universitat Politècnica de València for the pre-doctoral scholarship granted to Josep Ramon Lliso Ferrando (FPI-UPV-2018) and to the Spanish Ministry of Science and Innovation for the pre-doctoral scholarship granted to Ana Martínez Ibernón (FPU 16/00723).

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CORROSION MASUREMENT CELL IN REINFORCED CONCRETE STRUCTURES: 2 OR 3 ELECTRODES

J. R. Lliso-Ferrando,a I. Gasch,a J.M. Gandía-Romero.a

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Camino de Vera, s/n 46022 Valencia, Spain. E-mail: [email protected]

Keywords: Concrete Corrosion Monitoring ● Corrosion Measurement Cell ● Concrete ● Durability ● Corrosion of reinforcements is one of the main causes of premature failure in reinforced concrete structures (RCS). Because of this, analyzing the reinforcements condition is of crucial importance to ensure the correct functioning of these structures [1]. The early 1990s saw the emergence of the first embedded monitoring systems aimed at reducing the damage caused by corrosion or preventing costly repairs. These systems consisted of a measuring cell mounted on a frame [1]–[4]. The configuration for measurements was a 3-electrode cell configuration including a Working Electrode (WE), a Reference Electrode (RE) and a Counter Electrode (CE). The technology for monitoring corrosion in RCS continued to develop in subsequent years. The most modern systems use a 2- electrode cell configuration, where the RE and CE are replaced by a counter electrode which is also used as a pseudo-reference electrode [5]–[9]. The reliability of the 2-electrode cell measurement depends on the surface of the counter electrode used. Elements having a small surface area increase the polarization risk during the measurement, i.e. their equilibrium potential varies during the measurement. This can lead to wrong results and inadequate estimations of the reinforcements real state. This study demonstrated the influence of the counter electrode surface used in the 2 electrodes measurement, and the difference in monitoring results between 2 or 3- electrode cells. This study was carried out on reinforcements embedded in different types of concrete and with different levels of corrosion.

References [1] I. Martínez et al., Cem. Concr. Compos. 2009, vol. 31, no. 8, pp. 545–554, doi: 10.1016/j.cemconcomp.2009.05.007. [2] E. V. Pereira et al. Sensors. 2009, vol. 9, no. 11, pp. 8391–8398, doi: 10.3390/s91108391. [3] R. B. Figueira, et al. Appl. Sci. 2017, vol. 7, no. 11, doi: 10.3390/app7111157. [4] J. P. Broomfield, et al. Cem. Concr. Compos. 2002, vol. 24, no. 1, pp. 27–34, doi: 10.1016/S0958- 9465(01)00024-5. [5] M. Alcañiz, et al. 2015, Patente-ES2545669B2. [6] J. E. Ramón, et al. Vitr. - Int. J. Archit. Technol. Sustain. 2016, vol. 1, no. 1, p. 65, doi: 10.4995/vitruvio- ijats.2016.5191. [7] J. E. Ramón et al. Electrochim. Acta. 2019, vol. 323, doi: 10.1016/j.electacta.2019.134702. [8] A. Martínez-Ibernón et al. Electrochim. 2019, Acta, vol. 328, doi: 10.1016/j.electacta.2019.135111. [9] J. E. Ramón et al. Cem. Concr. Compos. 2020, vol. 110, no. 4, doi: 10.1016/j.cemconcomp.2020.103590.

Acknowledgments The authors would like to express their gratitude to the Universitat Politècnica de València for the pre-doctoral scholarship granted to Josep Ramon Lliso Ferrando (FPI-UPV-2018).

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MESOPOROUS SILICA NANOPARTICLES TARGETING TUMOUR MICROENVIRONMENT AS A TOOL FOR BREAST CANCER TREATMENT Ana Lameirinhasa, Iris Garrido-Canoa,b, Paula Díezb,c,d, Ana Llucha,e,f,h, Juan Miguel Cejalvoa,e,f, Ramón Martínez-Máñezb,c,d,g, Pilar Erolesa,f,h aBiomedical Research Institute INCLIVA, Valencia, Spain. analameirinhas @gmail.com bCIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Madrid, Spain. cInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Valencia, Spain. dUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Valencia, Spain. eClinical Oncology Department, Hospital Clínico Universitario de Valencia, Valencia, Spain. fCentro de Investigación Biomédica en Red de Cáncer (CIBERONC), Valencia, Spain. Universitat de València, Valencia, Spain. g Unidad Mixta de Investigación en Nanomedicina y Sensores, Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, Valencia, Spain. h Universitat de València, Valencia, Spain.

Keywords: Nanoparticles ● Breast cancer ● Treatment ● Tumour microenvironment Breast cancer (BC) is the most common cancer in women worldwide [1]. The majority of the BC therapies currently used are focused on targeting the tumour cells. However, new developments in immunology field uncover an important role of tumour microenvironment (TME) in tumour progression and therapy resistance [2]. The cancer- associated fibroblasts (CAFs) are the most abundant cells in tumour stroma and key regulators of the BC TME. They are implicated in tumour progression and metastasis, as well as in immunosuppression and therapy resistance [3]. Hence, we hypothesized that targeting CAFs can improve BC treatment. The goal of this work is the development of a mesoporous silica nanoparticle (MSN) loaded with doxorubicin, a cytotoxic drug widely used in BC treatment, which will target the breast TME cells, namely CAFs. CAFs are characterized by the high expression of fibroblast activation protein alpha (FAPα) in their cellular membranes [3]. FAPα is commonly overexpressed in several tumours, and associated with tumor progression and metastasis [4]. Furthermore, recent studies also reported an increased FAPα expression in tumor cells and tumor-associated macrophages [5]. Taking this into account, FAPα was chosen as the nanoparticles’ target. MSNs coated with a cleavable amphiphilic peptide specifically responsive to FAPα were synthesized. Simultaneously, MSNs coated with an uncleavable amphiphilic peptide with a similar structure and sequence were used as control [6]. Our first results demonstrated that MSNs can efficiently target FAPα positive cells. Moreover, the MSNs proved to have a good cytotoxic effect on the cells. Subsequently, the nanoparticles’ effect in tumor cells’ aggressiveness and in endothelial cells’ angiogenic capacity will be also evaluated to prove the nanoparticles’ efficacy for BC treatment. References [1] Sung, H., et al., CA Cancer J Clin, 2021. 71(3): p. 209-249. [2] Bahrami, A., et al., J Cell Biochem, 2018. 119(1): p. 111-122. [3] Houthuijzen, J.M., et al., Cancer Metastasis Rev, 2018. 37(4): p. 577-597. [4] Jia, J., et al., BMC Cell Biol, 2014. 15: p. 16. [5] Muliaditan, T., et al., Nat Commun, 2018. 9(1): p. 2951. [6] Ji, T., et al., Angew Chem Int Ed Engl, 2016. 55(3): p. 1050-5. Acknowledgments We thank the Spanish Government (RTI2018-100910-B-C41), Generalitat Valenciana (PROMETEO/2018/024), CIBERBBN (CB06/01/2012), CIBERONC (CB16/12/00481), and ISCII/FEDER (PI18/01219) for support.

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TUNNING THE OPTICAL PROPERTIES OF DONOR-ACCEPTOR SYSTEMS

Alejandro Cortés Villena,a Carolina Aliaga,b Raquel E. Galian,a Julia Pérez Prietoa Instituto de Ciencia Molecular, C/ Catedrátic José Beltrán Martínez, 2, 46980, Paterna, Valencia, Spain. [email protected]

bDepartamento de Ciencias del Ambiente, Facultad de Química y Biología, Av. Libertador B. O'Higgins 3363

Keywords: Fluorescence ● ICT ● Polarity ● Fluorosolvatochromism ● Sensing

The photophysical properties of some fluorescent organic molecules can be sensible to the surrounding environment, especially those which can suffer internal charge transfer (ICT) [1]. The ICT process occurs upon photoexcitation of the organic molecule acting as a donor-acceptor or push-pull fluorophore. They consist of a donor and acceptor group linked by a spacer by which an electron is promoted from the negatively charged part (donor) to the deficiently charged part (acceptor) with a significant change in the charge distribution in the molecule. The degree of charge transfer character in terms of an electronic transition can be modulated by the solvent polarity. In polar solvents, the ground and excited states are stabilized to different extent, thus resulting in fluorosolvatochromic shifts [2]. The spectral shift, intensity and shape are highly influenced by the environment and the solvent polarity and hence, they are potential candidates for solvent sensing. In the present work, the fluorosolvatochromism of a 2,4,6-triarylpyrimidine derivative was analysed experimentally by using steady-state and time-resolved fluorescence [3]. The shape and spectral position of the first absorption band are only weakly dependent on the solvent polarity. In contrast to absorption spectra, the fluorescence spectrum is strongly solvent-dependent.

Figure 1. Fluorescence spectra of 2-phenyl-4-[4-(4-N,N-diphenylaminophenyl)phenyl]-6-phenylpyrimidine in different solvents (from left to right: hexane, toluene, ethyl acetate, chloroform, tetrahydrofuran, dichloromethane, N- methyl-2-pyrrolidone, N,N-dimethylformamide, ethanol, acetonitrile and dimethyl sulfoxide). Molecular structure of this compound highlighting both the donor and acceptor part as well as the corresponding photograph of these solutions under a UV lamp. References [1] Sasaki, S. et al. J. Mater. Chem. C, 2016, 4, 2731-27-43. [2] Panja, S. K. et al. RCS Adv., 2016, 6, 105786-105794. [3] Rodríguez-Aguilar, J. et al. J. Photochem. Photobiol., 2018, 94, 1100-1108. Acknowledgments We thank MINECO (CTQ2017-82711-P), MICINN (MDM-2015-0538-18-1; A.C.V. PRE2018-084294) partially co- financed with FEDER and Generalitat Valenciana funds (PROMETEO/2019/080 and IDIFEDER/2018/064).

P-74

Design, synthesis and characterization of new Janus nanomotors with antimicrobial effect and self-propulsion capability

Lucía Marína, Ángela Morellá-Aucejoa,b,d, Serena Medagliaa,b,d, Andrea Escuderoa,b,d, Paula Díeza,b,c,d,e, Ramón Martínez-Máñeza,b,c,d,e, Pedro Amorosf, Andrea Bernardosa,b,d,e,* and María Dolores Marcosa,b,c,d,e,*

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València and Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain b CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), 46022 Valencia, Spain c Unidad Mixta de Investigación en Nanomedicina y Sensores, Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe (IISLAFE), Av. Fernando Abril Martorell 106, 46026 Valencia, Spain d Unidad Mixta UPV-CIPF de Investigación en Mecanismos Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, C/ Eduardo Primo Yúfera 3, 46012 Valencia, Spain e Departamento de Química, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain f Institut Universitari de Ciencia dels Materials (ICMUV)Universitat de Valencia, P.O. Box 2085, 46071 València, Spain E-mail: [email protected]

Keywords: Janus nanomotors ● self-propulsion ● directional motion ● nanoparticles ● bacteria resistance ● natural antimicrobial

Bacterial infections are the main cause of diseases and even mortality due to the resistance of certain pathogens to antibiotics. One of the promising treatment alternatives is the use of antimicrobial-hybrid nanomaterials that can act as nanomotors to increase their antibiotic activity against bacterial infections. An example of this type of nanomotors are the Janus particles based on platin and mesoporous silica nanoparticles (Janus-Pt-MSNs)[1], capable of exhibit a directional movement which drives the nanomotors toward biological targets (such as bacteria). In particular, Janus-Pt-MSNs nanodevices functionalized with a derivative of a natural antimicrobial (vanillin) have been developed. Those nanodevices combined the use of antimicrobial activity of vanillin with the autonomous self-propulsion, allowing the rupture of the biofilm formed by lactic acid bacteria Lactobacillus Plantarum.

References [1] Díez, P., Lucena-Sánchez, E., Escudero, A., Llopis-Lorente, A., Villalonga, R., & Martínez-Máñez, R. Ultrafast Directional Janus Pt-Mesoporous Silica Nanomotors for Smart Drug Delivery. ACS Nano. 2021, 15(3), 4467–4480.

Acknowledgment: This research was funded by the Ministerio de Ciencia, Innovación y Universidades (Spanish Government) (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22-AR (MCUI/FEDER, EU)) and the Generalitat Valenciana (project PROMETEO 2018/024). A.M., S.M., A.E. thank the Generalitat Valenciana for their Garantía Juvenil grant and PhD fellowships. A.B. thanks the Ministerio de Universidades (Spanish Government) for her Beatriz Galindo contract.

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SEROLOGY MICROFLUIDIC TEST FOR THE SIMULTANEOUS DETERMINATION OF SPECIFIC ANTI-VIRAL ANTIBODIES

Yeray Pallás-Tamarita, Roberto Gozalbo-Rovirab, William Teixeiraa, Augusto Juste-Dolza, Jesús Rodríguez-Díazb, David Giménezc, David Navarrob,d, Sergi Moraisa,e,f, Ángel Maquieiraa,e,f

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain. e- mail: [email protected] bDepartamento de Microbiología, Escuela de Medicina, Universitat de València, Valencia, Spain. cDepartamento de Química-Física, Facultad de Química, Universitat de Valencia, Avenida Dr. Moliner 50, 46100 Burjassot, Valencia. Spain. dServicio de Microbiología, Hospital Clínico Universitario de Valencia, INCLIVA Instituto de Investigación Sanitaria, Valencia, Spain. eDepartamento Química, Universitat Politècnica de València, Camino de Vera s/n 46022 Valencia, Spain. fUnidad Mixta UPV-La Fe, Nanomedicine and Sensors, IIS La Fe, Av. Fernando Abril Martorell, (46026), Valencia, Spain.

Keywords: SARS-CoV-2 ● Respiratory virus ● Multiplex ● bench-top rapid-diagnostics

A quantitative serology test for the multiplexed and semi-automatic determination of specific antibodies against respiratory viruses (SARS-CoV-2, influenza A and B, adenovirus and respiratory syncytial virus) is presented. It is based on a transparent disc-shaped polycarbonate microfluidic platform, which is functionalized with specific antigens as capture probes in microarray format (Figure 1) and a portable optical analyzer for the readouts. The test requires 25 µL of human serum and analyzes six samples in 50 min. The accuracy of the test has been evaluated, using a cohort of 87 serum samples from positive confirmed COVID-19 patients and 34 controls. The results were in good agreement with those obtained with an ELISA antibody test. A positive predictive value of 98.8% and a specificity of 85.7% for the N antigen was reached, correlating well with both the ELISA and the Abbott Panbio COVID-19 IgG/IgM Rapid Test. The features of the solution make the test a suitable bench-top rapid-diagnostic analytical system for testing in healthcare settings, communities, schools and workplaces.

TMB

1. Antigen immobilization 3. α-HIgG-HRP incubation 4. Results Figure 1. Scheme of the serology microfluidic test for the determination of specific anti-viral antibodies.

Acknowledgments This research was supported by the Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital under the research call to the Valencian innovation system to fight against covid 19 (https://dogv.gva.es/datos/2020/05/19/pdf/2020_3509.pdf).

P-76

SELECTIVE INACTIVATION OF PROTEINS BY UV-LASER TO CREATE FUNCTIONAL PATTERNS FOR BIOSENSING

Augusto Juste-Dolz,a Martina Delgado-Pinar,b Miquel Avella-Oliver,a,c Estrella Fernández,a Jose Luís Cruz,b Miguel V. Andrés,b Ángel Maquieira,a,c

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, 46022 Valencia, Spain. e-mail : [email protected] b Department of Applied Physics and Electromagnetism-ICMUV, Universitat de València, Burjassot 46100, Spain. c Departamento de Química, Universitat Politècnica de València, 46022 Valencia, Spain.

Keywords: Biosensor ● UV-induced denaturation ● Immunoassay ● Non-specific binding ● Label-free Protein nanopatterned substrates have emerged as an exciting tool to exploit nanoscale light-matter phenomena for transducing biointeractions. Contact printing and photolithographic techniques are typically employed to produce these structures of bioactive molecules and have proven to be appealing options [1, 2]. However, the advances in this direction are hindered by the complexity, expensiveness, and low scalability of these techniques. In this work, we present a novel patterning method that consists in the selective inactivation of surface-bound proteins by UV-laser irradiation (Figure 1A). When the UV-laser irradiates the photomask, an interference pattern is generated in the biofunctionalized surface. Proteins that are exposed to constructive interferences become deactivated but not removed from the substrate, thus producing protein patterns free of topographic contributions (Figure 1B). This is a significant advantage since deactivated proteins may act as backfilling agents that reduce the interaction of non- specific binders. Herein we report the introduction, optimization, and characterization of this approach, and explore its bioanalytical capabilities by diffraction-based sensing [3] (Figure 1C) using a representative immunoassay based on protein probes and IgG targets and discusses them.

Figure1. (A) Scheme of the UV-induced selective protein deactivation process. (B) AFM images before (left) and after (right) incubating IgG targets. (C) Diffraction pattern observed when irradiating with a 532 nm laser source. References [1] Juste-Dolz, A. et al. Sensors. 2018, 18, 3163. [2] Juste-Dolz, A. et al. Biosens.Bioelectron, 2021, 176, 112916. [3] Avella-Oliver, M. et al. ACA, 2018, 133 173-179. Acknowledgments MINECO (CTQ2016-75749-R and TEC2016-80385-P) and PROMETEO (PROMETEO/2019/048 and PROMETEO/2017/103).

P-77

NANOPARTICLES TO ENHANCE SENESCENT CELLS CLEARANCE BY THE IMMUNE SYSTEM

Blanca Escriche-Navarro, a,c,d Eva Garrido, a,b Alba García-Fernández, a,b,d Ramón Martínez-Máñez a,b,c,d and Félix Sancenón a,b,c,d aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València-Universitat de València. Camino de Vera s/n, 46022 Valencia, Spain [email protected] b CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN). cUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, Valencia, Spain. dUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Valencia, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, Valencia, Spain

Keywords: Senescent cells ● Nanoparticles ● CXCL12 ● Matrix metalloprotease-3 ● Immune System

Cellular senescence is an irreversible process of cell-cycle arrest as a consequence of various stress signals to prevent the propagation of damaged cells. Senescent cells (SCs) present a radically altered phenotype characterized by resistance to cell death or apoptosis, elevated senescence-associated β-galactosidase (SA-β-gal) activity and acquisition of senescence-associated secretory phenotype (SASP). Among the molecules composing SASP are pro-inflammatory cytokines, chemokines, interleukins and high amounts of matrix metalloproteases (MMPs), such as MMP-3 [1]. Although these signaling molecules activate the innate and adaptive immune system, numerous studies have identified mechanisms of immunoevasion in certain pathologies, related to age or cancer [2]. From this antecedent, the aim of this work is the development of an innovative therapeutic strategy, based on the use of mesoporous silica nanoparticles that allows the efficient elimination of SCs by immune cells. For this purpose, large-pore mesoporous silica nanoparticles (LPMSNs) are loaded with the CXCL12 chemokine, to induce migration for immune cells. In addition, the external surface of LPMSNs is functionalized with a peptide selectively cleavaged by MMP-3, acting as "molecular gate" (Figure 1). In the senescent environment, high levels of MMP-3 hydrolyze the “molecular gate” with the subsequent release of CXCL12 protein, which enhances the recruitment of immune cells, triggering the recognition and elimination of SCs.

Figure1. Large-pore mesoporous silica nanoparticle (LPMSNs) loaded with CXCL12 and functionalized with MMP- 3 substrate peptide. References [1] Campisi J. et al. Annu. Rev. Physiol. 2013, 75, 685-705 [2] Prata LGPL., et al., Semin. Immunol. 2019, 11:101275

Acknowledgments The authors thank the Spanish Government for RTI2018-100910-B-C41 (MCIU/AEI/FEDER, UE), CTQ2017- 87954-P projects and the Generalitat Valenciana for support by project PROMETEO/2018/024 and the company Senolytic Therapeutics S.L for support. B.E.N. is grateful to the Spanish Instituto de Salud Carlos III for the grant through the project “IFI19/00026” and co-funded by European Social Fund "Investing in your future“ and E. G. is grateful to the Spanish MECD for her FPU grant.

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BODIPY´S DERIVATES FOR GASES DETECTION

Paula García Moreno, Ana M. Costero, Salvador Gil, Jose V. Ros Lis

Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat de Valencia, Doctor Moliner 50, Burjassot, 46100 Valencia, Spain [email protected], [email protected], [email protected], [email protected]

Keywords: BODIPY ● Fluorescence ● Gas emission ● Chemosensor ● CO NO2 detection

Nowadays, gas emissions to nature are one of the oldest and main environmental problems. Specifically, we have been analyzed NO2, which is a reddish-brown gas with a strong odor, and CO, that is colorless and odorless. NO2 is produced as a consequence of road traffic and fuel-burning processes causing acid rain, while CO is generated when a fuel containing carbon is burned without sufficient oxygen, detrimental to the oxygenation of organs and tissues also contributes to the greenhouse effect.[1,2]

The aim of this work is to develop a chemosensor, based on 4,4-difluoro-4-bora-3a, 4a- diaza-s-indacene, also known as BODIPY core (boron-dipyrromethene) to simultaneously detect the gases CO and NO2. This is characterized by absorbing UV- Vis radiation and emitting fluorescence. In addition, its molecular structure is easily modifiable, thus offering great variations in its optical properties.[3]

To achieve simultaneous detection of both gases, using BODIPY as the main structure to which hydrazine and Ruthenium (II) complex (hydridocarbonyl-chlorotris (triphenylphosphine) ruthenium (II)) are added with the purpose that when both gases are present, the compound emits a relatively sharp fluorescence peak with high quantum yields.[4]

a) b)

Figure. a) BODIPY derivates b) Ruthenium complex

References

[1] Monóxido de carbono. (2021). Retrieved 31 May 2021, from https://www.miteco.gob.es/es/calidad-y-evaluacion- ambiental/temas/atmosfera-y-calidad-del-aire/calidad-del-aire/salud/monoxido-carbono.aspx [2] La Contaminación del Aire Dióxido de Nitrógeno. (2021). Retrieved 31 May 2021, from https://www.greenfacts.org/es/dioxido-nitrogeno-no2/index.htm [3] Zhu, S; Zhang, J; Vegensa, G; Luo, F. T; Green, S. A; and Lio, H. Highly Water-Soluble Neutral BODIPY DYES with Controllable Fluorescence Quantum Yields. Org Lett 2011, 13, 438-441. DOI: 10.1021/ol102758z.

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Antimicrobial bioactive molecules coupling on stainless steel surface

Serena Medaglia,a,b,c Maria Ruiz Rico, f Édgar Pérez-Esteve, f Ramón Martínez-Máñez, a,b,c,d,e María D. Marcos, a,b,c,d,e,* Andrea Bernardos, a,b,c,e,* and Félix Sancenón. a,b,c

a Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de Valencia, Universitat de València, Spain b CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBERBBN), Spain. c Departamento de Química, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022, Valencia, Spain d Unidad Mixta de Investigación en Nanomedicina y Sensores, Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe, Av Fernando Abril Martorell 106, 46026 Valencia, Spai e Unidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, C/ Eduardo Primo Yúfera 3, 46100 Valencia, Spain f Departamento de Tecnología de Alimentos, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain E-mail: [email protected]

Keywords: Stainless steel • Antimicrobial surface • Vanillin • Naturally-occurring antimicrobial compounds

Pathogenic microorganisms can be attached to a food surfaces, equipment and processing environments, giving rise to the formation of biofilms. This is a serious issue for food spoilage and safety, and for this purpose it is interesting to inhibit the formation of biofilm by naturally occurring antimicrobial compounds, avoiding the use of common disinfectants. [1] Focusing on that objective, in this study the antimicrobial bioactive molecule (Vanillin) was immobilized on stainless steel (SS) surface, on which a layer of silica was previously deposited to make the bond between antimicrobial molecule and surface (SS) more resistant. The untreated and modified surface were analyzed by HRFESEM, indicating that the antimicrobials was immobilized on the surfaces. Antimicrobial tests for the modified surface were performed against Escherichia Coli and Staphylococcus Epidermidis and the results showed that the functionalized SS surfaces reduced the bacteria viability and the biofilm formation on the stainless steel surface.

References [1] Orhan-Yanıkan, E. et al, Essential oils compounds as antimicrobial and antibiofilm agents against strains present in the meat industry. Food Control, 2019.

Acknowledgments This research was funded by the Ministerio de Ciencia, Innovación y Universidades (Spanish Government) (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22-AR (MCUI/FEDER, EU)) and the Generalitat Valenciana (project PROMETEO 2018/024). S.M. and M.R.-R. thank the Generalitat Valenciana for her Grisolía and Postdoctoral Val i+d grants. A.B. thanks the Ministerio de Universidades (Spanish Government) for her Beatriz Galindo contract.

P-80

IL-1β EFFECTS ON OSTEOARTHRITIC SYNOVIOCYTES IN EARLY PRIMARY CULTURES

Alvaro Compañ 1, María Isabel Guillén 1,2, María Luisa Ferrándiz 1, Antonio Silvestre 3 y María José Alcaraz 1

1Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, 46100 Burjassot, Valencia. 2Departemento de Farmacia, Universidad Cardenal Herrera-CEU, 46115 Alfara del Patriarca, Valencia. 3Hospital Clínic Universitari de València, 46010 Valencia, Valencia Registered author e-mail: [email protected]

Keywords: Osteoarthritis ● Synoviocites ● Articular Inflammation ● Proliferation ● Viability

Introduction. Osteoarthritis (OA) is a common problem in the elderly. Joint cells, chondrocytes and synoviocytes, are involved in the inflammatory mechanism mainly by cytokines such as IL-1β [1,2]. Articular synoviocytes are highly proliferative cells. Thus, most of the studies on their properties have been performed in advanced passage cell cultures. These experimental conditions lead to cell dedifferentiation that makes it difficult to extrapolate the results to the pathological conditions of osteoarthritis.

Objective. To study the effects IL-1β on the proliferation and cell viability of OA synoviocytes under different culture conditions.

Material and methods. Synoviocytes were isolated from the synovium of OA patients by enzymatic digestion and seeded in 25cm2 culture flasks with DMEM/F12 medium, 1% antibiotics and 10% FBS. When they reached confluence, cells were seeded in 6- well plates (2,5x105 cells/ml/well) or in 96-well plates (4x104 cells/ml/well), with the same culture conditions. Synoviocytes were stimulated with IL-1β (10ng/ml) at the indicated times. Cell viability was evaluated by the MTT method in different passages and cell proliferation by the BrdU Cell Proliferation ELISA Kit. In the cell supernatants, the levels of metalloproteinase-13 (MMP-13) were evaluated using the Human MMP- 13 ELISA Kit.

Results. Cell viability of synoviocytes was not modified in the different passages or in cells stimulated with IL-1β vs. naïve cells. The proliferation assay was performed in passage 1, at 24, 48 and 72h. The results obtained indicate a very significant increase in proliferation at 48h, with a higher effect in cells stimulated with IL-1β vs. naïve cells. The MMP-13 assay was performed at passage 1 and at 48H, because the proliferation assay showed the best results. The release of MMP-13 increased significantly in cells stimulated with IL-1β vs. naïve, as expected.

Conclusions. These results indicate that, in early passages, cell viability of OA synoviocytes is maintained, and proliferation is greater at 48h of culture. However, more studies of the culture conditions of synoviocytes are necessary to standardize the results.

References [1] Tofiño-Vian M, et al. Biochem Pharmacol. 2018;153:134-46. [2] Alcaraz MJ, et al. Cells. 2020;9(1):98. Acknowledgments Ministerio de Economía, Industria y Competitividad, MINECO SAF 2017 85806 R.

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REMOTE ELECTRONIC SYSTEM FOR LONG-DURATION IN- VITRO COMBINATION OF ELECTROSTIMULATION AND ELECTRICALLY CONTROLLED DRUG RELEASE Javier Monreal-Trigo* a,b, Cristina Bastida-Molinac, Roberto Vengut-Troc, Miguel Alcañiz-Fillol a,b;*e- mail: [email protected] a Departamento de Ingeniería Electrónica (UPV, C/ Vera s/n, 46022, València, España). b I.I.I. en Recon. Molecular y Desarrollo Tecnológico (idm UPV-UV) (UPV, C/ Vera s/n, 46022, València, España) c Escuela Técnica Superior de Ingeniería del Diseño (UPV, C/ Vera s/n, 46022, València, España). Keywords: Electrically-controlled drug release ● Electrostimulation ● Biomedical ● Long-Duration In- Vitro Both electrostimulation [1,2], the use of nanoparticles [3] and controlled drug release [4] are techniques with promising results in nerve tissue regeneration. That is why Z0IS [5] was developed, a device capable of performing the combination of electrostimulation and controlled release of drugs from mesoporous silica nanoparticles [6] for in-vitro application. However, in the execution of experiments, this device has demonstrated inadequacies that make it impossible to be used for obtaining an effective treatment for nerve tissue regeneration: the built-in wireless communications are a bottleneck for the data transmission measured in short sampling periods, the applied voltage ranges are insufficient, and its autonomy of few days is too short to meet the requirements of the laboratory routine, with experiments lasting up to 21 days. This last requirement also limits the use of a personal computer to control the device. For all these reasons, a new device has been developed that meets the requirements of the application: IVEEDRIS-SCIR (Fig. 1). The device has a slave subsystem based on a microcontroller for the application of stimuli between the ends of the substrate of the culture well or between the substrate and the cell medium with a voltage range of ±2.5V; and a second subsystem, based on the Raspberry Pi small-board computer, which allows remote control of the first one by the user through a Wi-Fi connection to the Internet. The master subsystem indicates the immediate action to be executed step by step to the slave, either commanded in real time by the user or following a configuration file that the user has previously implemented. Both subsystems are connected by wired communications based on 10 Mbps RS-485, which overcomes the bottleneck that the BLE meant in Z0IS. Both communications and power cables have been specifically selected to allow access to the cell culture chamber.

Slave Master

Figure1. In-Vitro Electrostimulation and Electrically-Controlled Drug Release Instrumentation System for Spinal Cord Injury Repair. References Acknowledgments [1] Kobelt L. J. et al,.Ann. Biomed. Eng. 2014, 42, 2164- This research was supported by the Spanish Ministry of 2176. Science, Innovation and Universities via a doctoral grant [2] Zhu W. et al. Nanomedicine: N., B & M., In Press, to J. Monreal-Trigo (FPU17/03239) and by the Spanish 2017. Government/FEDER funds (RTI2018-100910-B-C43) [3] Cho,Y. et al,.Nanotechnology, 2010, 21. (MINECO/FEDER). [4] Soumetz, F. C. et al., 4th IEEE Conf. Nanotechnology, 2004. [5] Monreal-Trigo, J. et al., IWOSMOR XIII, 2019, 76- 79, València. [6] Aznar, E. et al., Chem. Rev., 2016, 116, 561–718.

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ANALYSIS OF THE CELLULAR TISSUE IN APPLES USING IMPEDANCE SPECTROSCOPY.

Jose Antonio Pérez Balasteguia, María Pilar Hernández Colomer a, Luis Edgar Meneses a , Rafael Masot Peris b , Cristian Ariel Olguin Pinatti b , Nicolás Laguarda Miró b a Escuela Técnica Superior de Ingeniería del Diseño, Universitat Politècnica de València, Camí de Vera S/N, 46022 Valencia (Spain), [email protected]. b Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universitat Politècnica de València – Universitat de València, Camí de Vera S/N, 46022 Valencia (Spain)

Keywords: Physicochemical parameters ● Frost damage ● Electrochemical impedance spectroscopy ● cell tissue

Currently, freeze-damage in fruits and vegetables implies significant economic losses to the agri-food sector [1]. Sudden climatic changes cause frost, deteriorating the quality of the products, creating insecurity in the final consumer. The objective of this study is the detection of frost damage in Fuji Apples (Pyrus communis). In this study, electrochemical impedance spectroscopy (EIS) is applied to analyze the state of the cellular tissue before and after freezing. This technique is very promissory as it has been used in other research lines related to food technology, resulting in highly relevant results in terms of determining several physicochemical parameters for quality control and validity for consumption [2]. The present study consists of two stages. The first one is the data acquisition, making measurements in different parts of the fruits before and after freezing. Applying a double-needle sensor connected to an amperometry and voltammetry response analyzer, the system is able to provide impedance values as a function of frequency. An specific software (named FRA) allows the computer to display graphically and numerically the results on the screen using a user interface as well as the backup of the data for further analyses and data treatment. The second stage is the analysis of results. The differences in module and phase between fresh and frozen products are compared by carrying out an additional statistical study of the data. These differences show the behavior of the tissue when freezing, varying its electrical, chemical, and biological properties. Thus, frozen apples are able to be electrochemically identified. Finally, depending on the results of the analyses, the fruit may be sent to the market for direct consumption or used in other processes, reducing economic losses due to frost.

References [1] ARTÉS CALERO, Francisco, ARTÉS CALERO, Francisco de asís. Daños por frío en la postrecolección de frutas y hortalizas. En: Congreso Español de Ciencias y Técnicas del Frío (1º: 2002: Cartagena). Avances en Ciencias y Técnicas del Frío-1. Cartagena: Universidad Politécnica. Sociedad Española de Ciencias y Técnicas del Frío. 2002. pp.299-310 [2] Masot, R.; Alcañiz, M.; Fuentes, A.; Schmidt, F.C.; Barat, J.M.; Gil, L.; Baigts, D.; Martínez-Máñez, R.; Soto, J. Design of a low-cost non-destructive system for punctual measurements of salt levels in food products using impedance spectroscopy. Sens. Actuators A Phys. 2010, 158, 217–223.

P-83

INCREASING CANCER INMUNOGENICITY VIA THE DIRECTED EXPRESSION OF MEASLES VIRUS PROTEIN

Javier Martínez-Latorre ab, Alba García-Fernández abc, Elena Aznar abcd, Ramón Martínez-Máñez. abcde

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de Valencia, Spain. E mail: [email protected]. bUnidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Valencia, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, València, Spain. c CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) (Spain) dUnidad Mixta de Investigación en Nanomedicina y Sensores UPV-IIS La Fe, València, Spain. eDepartamento de Química, Universitat Politècnica de València, Spain.

Keywords: breast cancer ● measles virus ● mesoporous nanoparticles ● immunotherapy

This research aims to increase the immunogenicity of cancer cells enhancing the immune system response. One of the most immunogenic types of proteins are the viral proteins, in particular those proteins against which we have been vaccinated. Thanks to the vaccines our immune system has generated an immune memory against these proteins which translates into a quick response against the antigen. Specifically, measles virus protein H has been chosen because of the widely distribution and effectiveness of its vaccine [1]. A mesoporous nanoparticle loaded with the plasmid of interest will be targeted to the cancer cells (figure 1), inducing the expression of the H protein of the measles virus. To improve the specificity of the treatment the targeting will be directed by folic acid [2] and the expression of the H protein will be controlled by a cancer-specific promoter [3]. Cancer cells expressing the H protein in a previously vaccinated host are expected to be rejected by the host's immune system [4], leading to the destruction of the tumour. Concretely, the research plan will focus on the treatment of triple-negative breast cancer through its application to murine 4T1 cells.

Polyethylenimine pDNA Folic acid

Figure 1. Design of the nanoparticle.

References [1] Di Pietrantonj, C. et al. Cochrane Database of Systematic Reviews. 2020, 4. [2] Porta, F. et al. Advanced Healthcare Materials. 2013, 2(2), 281-286. [3] Kim, N. W et al. Science. 1994, 266(5193), 2011-2015. [4] Qi, Y. et al. Journal of cancer research and clinical oncology. 2018, 144(10), 1945-1957.

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New smart nanodevices to avoid antibiotic resistance

Ángela Morellá-Aucejo1,2,5, María Ruiz-Rico3, Ramón Martínez-Máñez,1,2,4,5,6 María Dolores Marcos1,2,4,5,6* and Andrea Bernardos1,2,5,6*

1 Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València and Universitat de València, Camino de Vera s/n, 46022 Valencia, Spain; 2 CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), 46022 Valencia, Spain 3 Departamento de Tecnología de Alimentos, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain 4 Unidad Mixta de Investigación en Nanomedicina y Sensores, Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe (IISLAFE), Av Fernando Abril Martorell 106, 46026 Valencia, Spain 5 Unidad Mixta UPV-CIPF de Investigación en Mecanismos Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, C/ Eduardo Primo Yúfera 3,46012 Valencia, Spain 6 Departamento de Química, Universitat Politècnica de València, Camino de Vera s/n, 46022 Valencia, Spain * Correspondence: [email protected] (M.D.M.); [email protected] (A.B.) Contact email: [email protected]

Abstract Due to the great problems that Antimicrobial Resistance (AMR) presents, the need arises to use new phytosanitary products for its agri-food application. This challenge could be approached with the application of natural products as antimicrobial agents encapsulated into gated-nanodevices. In the present work, a nanodevice consisting of mesoporous silica nanoparticles loaded with an essential oil component (cinnamaldehyde) and functionalized with the ε-polylysine antimicrobial peptide (AMP) as molecular gate is developed. In the presence of the corresponding stimuli (such as exogenous enzymes from the bacteria or fungi with proteolytic activity) the gate is “opened” and allows the release of cinnamaldehyde, effectively eliminating bacteria or fungi. It has been demonstrated that the new nanodevice presented is able to deliver cinnamaldehyde by a bio-controlled uncapping mechanism using exogenous enzymes from the E.Coli and Z.Bailii, improving the antimicrobial properties of the free compound by decreasing volatility and increasing local concentration.

Acknowledgment:

This research was funded by the Ministerio de Ciencia, Innovación y Universidades (Spanish Government) (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22-AR (MCUI/FEDER, EU)) and the Generalitat Valenciana (project PROMETEO 2018/024). A.B. thanks the Ministerio de Universidades (Spanish Government) for her Beatriz Galindo contract (BG20/00020). Á.M.A. thanks the Generalitat Valenciana for her Garantía Juvenil grant.

P-85

HIGH IRRADIANCE REAL-TIME MEASUREMENT SYSTEM FOR IN-VITRO OPTOCHEMOGENETIC STIMULATION

Vicente Beltrán-Monte a,c, Javier Monreal-Trigo* b,c, José Manuel Terrés-Haro b,c, Esther Giraldod,e, Beatriz Martínez-Rojasd, Victoria Moreno-Manzanod;*e-mail: [email protected]

a Escuela Técnica Superior de Ingeniería del Diseño (UPV, C/ Vera s/n, 46022, València, España). b Departamento de Ingeniería Electrónica (UPV, C/ Vera s/n, 46022, València, España). c I.I.I. en Recon. Molecular y Desarrollo Tecnológico (idm UPV-UV) (UPV, C/ Vera s/n, 46022, València, España) d Neuronal and Tissue Regeneration Lab (C. de Investigación Príncipe Felipe, C/ Eduardo Primo de Yúfera 3, 46012, Valencia, España). e Departamento de Biotecnología (Universitat Politècnica de València, C/Vera s/n, 46022, València, España). Keywords: Optochemogenetic Tool ● High Irradiance ● Real Time Graphic User Interface ● Measurement System Optochemogenetics is a field of growing interest and under active development, especially following the emergence of protein-coding opsin genes responsive to illumination at certain wavelengths of light. Their response to optical stimulation consist of depolarizing and hyperpolarizing currents, as well as transduction of signal- triggered events [1]. The main properties that concern the investigational equipment in optochemogenetic stimulation are stimulation time, illumination and non-illumination times (duty cycle), wavelength and light power density. The power density of optochemogenetics stimulation tools can vary from 0.04 mW/mm2 peak [2], 1 mW/mm2 [3,4] or even higher [5], which is why in the present work a real-time monochromatic irradiance measurement system commanded by a graphical user interface has been developed (Fig. 1). The device features seven simultaneous measurement scales, the largest having a full scale of 27 mW/mm2 and the one with highest resolution with a full scale of 0.04 mW/mm2. The scale in which the signal level fits better is selected automatically, counting with a resolution of 1024 points per scale. The system has been designed to be placed either at the distance of a standard cell multi-well plate for stimulation equipment calibration or under the transparent multi-well plate matrix to give real-time feedback of the applied irradiance after given the absorption measurement. As a proof of concept, the system has been tested in neural precursor cells which overexpressed an adenylate cyclase light-sensitive protein, resulting in the activation of calcium influx, measured at real time using a fluorescence calcium probe under confocal microscopy.

Figure1. Graphic User Interface (left) and OSIVE Irradiation Measurement System device with no-enclosure (right). References Acknowledgments [1] Mattis, J. et al. Nat Methods. 2012, 9(2): 159–172. This research was supported by the Spanish Ministry of [2] Bugak, L., et al. Nature Protocols. 2019, 14: 2205– Science, Innovation and Universities via a doctoral grant 2228. to J. Monreal-Trigo (FPU17/03239) and J. M. Terrés- [3] Yu, S. et al. The J. of Neuroscience. 2019, 39(33): Haro (FPU17/03800), and by the Spanish 6571–6594. Government/FEDER funds (RTI2018-100910-B-C43) [4] Weick, J., et al. Stem Cells. 2010, 28(11): 2008– (MINECO/FEDER). 2016. [5] Park, S. et al. Scientific Reports. 2015, 5: 9669.

P-86

SERUM BIOMARKERS FOR ALZHEIMER DISEASE

Marina Botello-Marabotto,a,b M.Carmen Martínez-Bisbal,a,b,c,d,e Miguel Calero Lara,f,g,h Ana Belén Pastor López,g Miguel Medina,e,f Ramón Martínez-Máñeza,b,d,e,i a Unidad Mixta de Investigación en Nanomedicina y Sensores. Instituto de Investigación Sanitaria La Fe, Universitat Politècnica de València. Valencia, Spain [email protected] b Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico, Universitat Politècnica de València, Universitat de València, Valencia, Spain c Departamento de Química-Física, Universitat de València, Valencia, Spain d CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Spain e Unidad Mixta UPV-CIPF de Investigación en Mecanismos de Enfermedades y Nanomedicina, Universitat Politècnica de València, Centro de Investigación Príncipe Felipe, Valencia, Spain f Network Center for Biomedical Research in Neurodegenerative Diseases (CIBERNED), Madrid, Spain g CIEN Foundation, Queen Sofia Foundation Alzheimer Research Center, Madrid, Spain h Instituto de Salud Carlos III, Madrid, Spain i Departamento de Química, Universitat Politècnica de València, Valencia, Spain

Keywords: Alzheimer Disease● Metabolomics ● 1H-NMR Spectroscopy ●Biomarkers

Alzheimer Disease (AD) is the most common type of dementia worldwide, with over 50 million of people suffering it in 2019, a figure expected to rise to 150 million by 2050 [1]. It is a progressive degenerative disorder characterized by the extracellular accumulation of β-amyloid plaques, the formation of neurofibrillary tangles and neuronal death [2]. This biological process starts up to 15 years prior to the apparition of clinic symptoms. The identification of early biomarkers of the disease is crucial to have a prompt diagnosis. In this work we conduct a metabolomics study by 1H-NMR spectroscopy in serum samples of patients with AD to search for metabolites that could be used as biomarkers. In this study 100 serum samples (50 from AD patients and 50 from controls) were studied by 1H-NMR spectroscopy. After acquisition, spectra underwent correction in the phase, baseline and chemical shift. The signals in the spectra were integrated and normalised to the total sum of integrals. Afterwards, the data were analysed by multivariate statistics, using PLS-DA to determine a model to discriminate between controls and AD patients. The model was first calculated with 70 samples (calibration) and then the model was applied to 30 samples (validation) to test the performance and the ability for disease discrimination. The calculated PLS-DA model showed a sensitivity of 100% and a specificity of 100% for both, cross validation and validation sets. Moreover, for validation set, a receiver operating characteristic curve AUROC = 1 was obtained. These results highlight the potential of metabolomics by 1H-NMR spectroscopy in biofluids as a non-invasive approach to support diagnosis in Alzheimer Disease.

References [1] Alzheimer’s Disease International. 2019. World Alzheimer Report 2019: [2] Lucey, B. P. It’s complicated: The relationship between sleep and Alzheimer’s disease in humans. Neurobiol. Dis. 144, 105031 (2020).

P-87

STUDIES towards THE APPLICATION OF A HYBRID BIOCIDE based on nanomaterials AGAINST THE WHITEFLY (BEMISIA TABACI)

Jose Vicente Ros-Lis, a Pedro Amorós,b Maria Dolores Garcerá,c Pablo Gaviña,d

a Departamento de Química Inorgánica, Universitat de València. Doctor Moliner 50, 46100 Burjassot. [email protected] bInstitut de Ciència dels Materials (ICMUV), Universitat de València, P. O. Box 22085, 46071-Valencia. cDepartamento de Biología Celular, Biología Funcional y Antropología Fisica, Universitat de València. Doctor Moliner 50, 46100 Burjassot. d Institute of Technological Development and Molecular Recognition, Universitat de Valencia. Doctor Moliner 50, 46100 Burjassot

Keywords: Nanomaterial ● Bacillus thuringiensis ● Whitefly

The study aims to evaluate the potential of the application of a new approach to the treatment of Bemisia tabaci based on the combination of nanomaterials with Bt protein. Three types of nanomaterials have been prepared and functionalized with amines. The materials obtained have been characterized and various strategies have been evaluated to maximize the loading of nanomaterials with protein. The three functionalized nanomaterials allow charges of around 10% when the materials are previously sonicated to disaggregate the particles. We have verified that the protein is capable of inducing the death of adults in significant percentages (greater than 50%) in a period of only 24 or 48 hours, which is promising for its application in agricultural fields. With amounts of only 0.025 mg / mL it induces mortality, but to achieve high mortality it is necessary to reach concentrations close to 0.5 mg / mL. The charged nanomaterials are also effective, inducing mortalities higher than 10% at 48h in adults, when applied at a concentration of 1mg / mL, mortalities higher than 10% at 48h in adults. These values may seem discrete, but they are those that correspond to the level of charge reached. In the case of eggs and nymphs, no relevant mortality was obtained. The effectiveness as a biocide depends on the topology of the materials (size, shape and type of pores), being stronger in nanoparticles than in mesoporous microparticulated materials. Field trials carried out with the collaboration of AVA-ASAJA in the Finca Sinyent (Valencia) on tomato show that both the protein and the NanoBt material, based in a combined application, are capable of inducing mortality at both 24 and 48 h, but that the nanomaterial gives a faster response, since the full and most intense effect is seen at 24 hours, reaching 65% of adult mortality in tomato.

Acknowledgments This project has been funded by the FEADER funds “Europe invests in rural areas”, the Generalitat Valenciana and the Spanish Ministry of Agriculture under the measurement 16.2 of the PDR-CV 2014-2020 (AGCOOP_A/2019/016).

P-88

DEVELOPMENT AND APPLICATION OF CHITOSAN- FUNCTIONALIZED SILICA MICROPARTICLES AS NOVEL ANTIMICROBIAL AGENTS

María Ruiz-Rico, a José M. Barat.a

aGrupo de Investigación e Innovación Alimentaria. Departamento de Tecnología de Alimentos, Universitat Politècnica de València. Camino de Vera s/n, 46022, Valencia, Spain. [email protected]

Keywords: Chitosan ● Covalent immobilization ● Food preservative ● Natural antimicrobial ● Silanization

Chitosan is a biodegradable and non-toxic biopolymer with antimicrobial properties [1]. However, its direct application to food is limited given its scarce solubility at neutral and alkaline pH values [2]. The covalent immobilization of other types of natural antimicrobials on the surface of inert supports has made possible to prevent the limitations of the use of these antimicrobials in their free form while preserving the bioactive properties of the immobilized molecules [3]. Therefore, the aim of this work was to develop and validate new antimicrobial agents based on the surface grafting of chitosan on silica microparticles. The chitosan was immobilized by silanization using two approaches: (i) by the urea covalent bonding between isocyanate groups on the surface of the supports and amino groups on chitosan, (ii) by the phosphoramidate covalent bonding between phosphonate groups on the surface of the supports and amino groups on chitosan. After the synthesis and characterization of the materials, the antimicrobial properties of chitosan-functionalized supports were studied through in vitro and in situ antimicrobial susceptibility assays using reference strains of pathogenic and food spoilage microorganisms, including Gram-positive and Gram-negative bacteria and yeast. The characterization results showed that both immobilization approaches allowed the covalent bonding of chitosan. The study of the antimicrobial activity of the chitosan-functionalized supports displayed the preservation of the bioactive properties of the immobilized chitosan after the functionalization process. According to the in vitro antimicrobial susceptibility results, the antimicrobial activity of the supports is significantly influenced by the material support, the particle concentration, and the target microorganism. In addition, the use of the chitosan- functionalized supports as food additives in apple juice resulted in the reduction of microbial contamination of the food matrix, increasing its shelf life. Therefore, the antimicrobial agents developed have proven suitable for inhibiting the growth of foodborne and spoilage microorganisms, confirming their potential use as food preservatives or food processing aids in the food industry.

References [1] Pisoschi, A.M. et al. Eur J Med Chem. 2018, 143, 922-935. [2] Ma, Z. et al. Carbohydr Polym. 2017, 176, 257-265. [3] Ruiz-Rico, M. et al. Food Chem. 2017, 233, 228-236.

Acknowledgments The authors gratefully acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades, the Agencia Estatal de Investigación and FEDER-EU (Project RTI2018-101599-B-C21). M.R.R. acknowledges the Generalitat Valenciana for her postdoctoral fellowship (APOSTD/2019/118).

P-89

TOWARDS NEW NANOMATERIALS FOR SARS-COV-2 DETECTION

M. Isabel Caballos-Gómeza,b,c, Guillermo Rodrigod, M. Carmen Marquésd, Alba Lópeza,b,c, Elena Aznara,b,c, Ramón Martínez-Máñez.a,b,c

aInstituto interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022, Valencia (Spain): [email protected] bCIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) cUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe de Valencia (IISLAFE), Spain. d Institute for Integrative Systems Biology (I2SysBio), CSIC – U. Valencia, Paterna, 46980, Spain

Keywords: Nanomaterials ● molecular gates ● oligonucleotides ● SARS-CoV-2

The recent emergence of the novel coronavirus (SARS-CoV-2) which caused the coronavirus disease 2019 (COVID-19) has brought serious threats to public health resulting in a global pandemic counting with 171 million laboratory-confirmed SARS- CoV-2-infected cases and more than 3500000 reported deaths all over the world until 31st of May 2021. [1] This virus is a positive stranded RNA virus and can cause mild to acute respiratory infections and has varied symptoms like fever, cough, difficulty breathing, loss of taste, and smell. Elderly people, infants, adolescent children, and people with compromised immune system are the ones at maximum risk of contracting the virus. [1] Additionally, asymptomatic and pre-asymptomatic SARS-CoV-2 infected patients are highly contagious and given the lack of appropriate detection assays, many SARS-CoV-2 infected patients have had contact with uninfected people before being identified for home isolation or hospitalization. [2] Nowadays, the reference method to detect the coronavirus is RT-PCR, which requires trained personnel, specific chemical supplies and expensive instruments that take hours to provide results and are often found only in labs and centralized services which are not always available. [2] That is the reason why sensible, selective and rapid, easy detection should be developed to meet the testing demands and overcome the drawbacks of the gold standard detection protocols. In this work, we have developed an innovative sensor system for the detection of the SARS-CoV-2 genetic material using a combination of a CRISPR-based system and a gated material. Optical signaling in response to the presence of the target pathogen is accomplished by monitoring the fluorescence of the released dye from the pore voids to an aqueous solution. Preliminary results have shown their potential use as sensing probe, demonstrating great sensitivity and selectivity.

References [1] Kumar, R., Nagpal, S., Kaushik, S. and Mendiratta, S. VirusDisease. 2020, 31(2), 97-105. [2] Yüce, M., Filiztekin, E. and Özkaya, KG. Biosensors and bioelectronics. 2021, 172, 112752.

P-90

NEW GATED MATERIAL FOR COVID-19 DIAGNOSIS

Alba López-Palacios, a,b María Nieves Aranda-Sobrino, a,b Eva Calabuig,d María Dolores Gómez,d Elena Aznar, a,b,c and Ramón Martínez-Máñez, a,b,c

aInstituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat Politècnica de València, Universitat de València, Camino de Vera s/n, 46022, Valencia (Spain): [email protected] bCIBER de Bioingeniera, Biomateriales y Nanomedicina (CIBER-BBN). cUnidad Mixta de Investigación en Nanomedicina y Sensores. Universitat Politècnica de València, Instituto de Investigación Sanitaria La Fe de Valencia (IISLAFE), Spain. dHospital Universitario y Politécnico La Fe, Spain.

Keywords: Nanomaterials ● Molecular gates ● COVID-19

COVID-19 from the Coronaviridae family is a virus which produces a respiratory disease with symptoms similar to influenza, manifesting as dry cough, fever, severe headache, and tiredness. Infected individuals show a wide range of symptoms from mild respiratory disease to severe respiratory disease, some critical cases may lead to death [1]. Currently, due to the global pandemic, health organizations and countries around the world are still struggling to control the spread of SARS-CoV-2 by developing tests for the rapid detection of individuals while a treatment for the infected ones and vaccines to immunization are being developed. As there are clinically reported cases of asymptomatic carriers of SARS-CoV-2, fast and accurate diagnosis plays an important role in the control and prevention of this disease. The proposed method for the routine confirmation is the reverse transcription polymerase chain reaction (RT-PCR) which amplifies the virus RNA [2] since this virus is a positive-sense single-strand RNA virus. In this work, we have developed a new method for the detection of COVID-19 RNA based on gated mesoporous materials. The material has demonstrated good performance in aqueous buffers and biological media. The system could proportionate faster results than RT-PCR with the same reliability. Preliminary results have shown high potential for its use as a diagnostic probe.

References [1] Kumar, S. Preprints. 2020. [2] Taleghami, N. and Taghipour, F. Elsevier. 2021. 174.

P-91

EFFECT OF WATER HARDNESS AND DIRT ON THE ANTIMICROBIAL EFFECTIVINESS OF SILICA MICROPARTICLES FUNCTIONALIZED WITH VANILLIN

Esra Karakasa, Édgar Pérez-Estevea, Héctor Gómez-Llorentea, Alejandro Rivasa, Isabel Fernández- Segoviaa, Jose Manuel Barata

aDepartamento de Tecnología de Alimentos, Grupo de Investigación e Innovación Alimentaria, Universitat Politècnica de València, Camino de Vera s/n, 46022, Spain, email: [email protected]

Keywords: ● Water purification ● Effectiveness ● Vanillin ● Escherichia coli

Development of water purification systems using silica particles functionalized with vanillin have been shown to be a promising alternative in those contexts in which chlorination is not an option or it is insufficient [1]. These particles exhibit bactericidal effect (capability to remove more than the 99.9% of the initial microbial charge) when the target microorganism (E. coli) is inoculated in distilled water. However, it is known that the antimicrobial effect of a biocide can be affected by the hardness and dirt of water [2]. The goal of this work was to compare the E. coli removal capacity of the filtration system using different types of water: distilled water, hard water and dirty water. To achieve this goal, silica microparticles (50-110 µm) were functionalized with vanillin. Then, water filtration tests were carried out. Hard water was prepared by mixing MgCl2, CaCl2 and NaHCO3. Dirty water was prepared by adding bovine serum albumin to the water. For each type of water, 100 mL of inoculated water (105 UFC/100 mL of Escherichia coli) were filtered through a bed of the vanillin-functionalized supports to assess the initial removal capability. After the filtering process, the collected water was plated in TBX and plates were incubated at 37 °C for 24 h. This process was repeated until the particles lost their antimicrobial effect. Results showed that while hardness of water does not affect the antimicrobial effectiveness, it is reduced under dirty water conditions.

References [1] Peña-Gómez, N. et al. Innovative Food Science & Emerging Technologies. 2019, vol 58., 102228. [2] UNE-EN 1276:2020. Chemical disinfectants and antiseptics - Quantitative suspension test for the evaluation of bactericidal activity of chemical disinfectants and antiseptics used in food, industrial, domestic and institutional areas - Test method and requirements (phase 2, step 1)

Acknowledgments Authors gratefully acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades, the Agencia Estatal de Investigación and FEDER-EU (Project RTC-2017-6100-2-AR). H. G. gratefully acknowledge the Univeristat Politècnica de València for his Pre-doctoral Scholarship (FPI).

P-92

SWITCHING-ON FLUORESCENCE BY COPPER (II) AND BASIC ANIONS

Jessica Milia1, Giacomo Picci 1, Claudia Caltagirone1

Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, Cagliari, Italy; [email protected] (J.M.)

Keywords: ● anion recognition ● DFT ● metal Sensing ● squaramides ● supramolecular chemistry

Squaramides represent an important class of cyclobutene ring derivatives that have stimulated the interest in the supramolecular chemistry area. The interest toward this class of compounds arises from their intrinsic features, such as the possibility to act as both H-bond donor and acceptor, the structural rigidity, aromaticity, as well as the ability to form strong bi-directional hydrogen bonds making them ideal candidates for the development of catalysts, self-complementary molecular recognition motifs and self-assembled materials. The new symmetric acyclic N,N’-bis(1-pyrenyl) squaramide (H2L) [1] functionalized with the pyrene moiety as a fluorogenic fragment has been designed and its ability to selectively detect specific anions and metals investigated. - H2L selectively binds Cl both in solution (DMSO 0.5% H2O and MeCN) and in the solid state and allows to selectively detect Cu2+ in MeCN with the formation of a 2:1 metal-receptor complex, with a green intense emission appreciable by naked eye under the UV lamp. The H2L copper complex preserves its emission properties in the presence of Cl-. The addition of basic anions (OH-, CN-, and F-) up to 10 equivalents caused the deprotonation of the squaramide NHs and a dramatic change of the emission properties of the H2L copper complex.

H2L

(b) (d)

(a) (c)

Figure1. a) fluorescent spectra for the spectrofluorimetric titration in MeCN of H2L in the presence of increasing amount of Cu(ClO4)2 hydrate ; b) colour change of H2L upon the addition of 2 equivalents of Cu(ClO4)2 hydrate; c) spectrofluorimetric changes of copper complex of H2L upon the addition of increasing amount of TBAOH; d) naked eye emission change of copper complex of H2L before (left) and after the addition of 2 equivalents (middle) and 6 equivalents (right) of TBAOH. References [1] G. Picci, J. Milia, M. C. Aragoni, M. Arca, S. J. Coles, A. Garau, V. Lippolis, R. Montis, J. B. Orton, C. Caltagirone, Molecules, 2021, 26, 1301

Acknowledgments Financial support from MIUR (PRIN 2017 project 2017EKCS35) is gratefully acknowledged as well as Università degli Studi di Cagliari (FIR 2016– 2019), Fondazione di Sardegna (FdS Progetti Biennali di Ateneo, annualità 2018).

P-93

Coordination chemistry and sensing properties of a simple fluorescent urea towards anions and metal ions

Giacomo Piccia, Jessica Miliaa, Claudia Caltagironea aDipartimento di Scienze Chimiche e Geologiche Università degli Studi di Cagliari SS 554 Bivio per Sestu, 09042 Monserrato (CA), IT E-mail: [email protected]

Keywords: Anion sensing ● DFT ● Metal ions sensing ● Supramolecular chemistry ●

Urea can be considered one of the most important molecule for the development of modern organic chemistry. Recently, urea has become a fundamental synthon in supramolecular chemistry used for the development of functional materials such as capsules, gels, and polymers. [1] Its versatility arises from multiple factors. It can act both as an efficient hydrogen bond donor (due to the presence of the NHs) and as hydrogen-bond acceptor via the carbonyl group. These features can be exploited in the development of receptors able to selectively bind, recognize (sense) and transport anions across membranes, and on the other hand, to bind metal ions as a monodentate ligand, especially useful for carboxylate one. [2] Herein, the coordination and sensing properties towards anions and transition metal ions of a simple novel fluorescent urea 1- (2-aminophenyl)3-(naphtalen-1)-yl)urea (L) (Figure 1) were investigated in solution, in the solid state. The presence of an electron donating amine group in the molecular skeleton of L decreased the acidity of the urea NHs that are normally deprotonated by basic anions and allowed for a good degree of affinity towards fluoride in DMSO-d6 - 0.5% H2O. Moreover, the amine moiety could be used as a binding group for metal ions. Indeed L was able to bind Zn2+ both in solution and in the solid state. Moreover, L was also able to respond to the presence of this metal ion in MeCN with an enhancement of the fluorescence emission. Although solution studies pointed out the formation of a 1:1 complex of L with Zn2+, complexes with 2:1 stoichiometry were isolated in the solid state. DFT calculations helped to clarify the energetic reasons behind these results.

2+ - 2+ - Figure 1. Structure of L; crystal structure of a) [L Zn(MeCN)2] (ClO4)2 and b) [L Zn(MeCN)2] (BF4)2 References [1] N. Volz et al., Angewandte Chemie - International Edition 2011, 50, 12148-12155; b M. Yokoya et al., Chemistry - A European Journal 2021, 27, 5601-5614. [2] A. Kadam et al., Journal of Organic Chemistry 2014, 79, 2501-2513; b S. A. Kadam et al., Chemistry - A European Journal 2015, 21, 5145-5160

P-94

DEVELOPMENT OF A GATED SISTEM TO ASSESS THE RISK OF CARDIOTOXICITY

M.Nieves Aranda Sobrino, a,b M.Isabel Caballos, a,b Elena Aznar,a,b,c,d Pilar Sepúlveda e and Ramón Martínez-Máñeza,b,c,d

a Unidad Mixta de Investigación en Nanomedicina y Sensores. Instituto de Investigación Sanitaria La Fe, Universidad Politécnica de Valencia. Valencia, Spain [email protected] b Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico, Universidad Politécnica de Valencia, Universidad de Valencia, Valencia, Spain c CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Spain d Departamento de Química, Universidad Politécnica de Valencia, Valencia, Spain e Regeneración y Trasplante Cardiaco, Instituto de Investigación Sanitaria La Fe, Valencia, Spain

Keywords: Cardiotoxicity ● Cancer prevention ● Molecular gate

Breast cancer mainly affects women and is highly prevalent in developed countries, with around 30,000 new cases in Spain and 400,000 in Europe each year. Of these, 90% are treated with anthracyclines. One of the main side effects of anthracyclines is the induction of chronic cardiotoxicity [1,2]. Thus, the identification of patients at risk of cardiotoxicity is a key point to optimize personalized treatments.

On the other hand, molecular gates can be defined as porous support devices functionalized with suitable molecules capable of blocking pore entrances and that only "open" in the presence of analyte. When this kind of systems are used for the recognition of species, the gating mechanism is designed in such a way that only the target analyte can trigger charge release [3]. Among the different biomolecules that could act as gates, nucleic acids have shown excellent applicability for the development of detection systems [4,5].

In this work, a system capable of detecting the presence of a miRNA related with the risk of cardiotoxicity in less than 60 minutes was prepared. The system works in biological media such as serum and will be validated with clinical samples in a near future. This new nanosystem would help to reduce cost associated with the health system and would represent an improvement in the quality of life of cancer patients by preventing the appearance of a serious and chronic disease such as cardiotoxicity.

References [1] Giordano, SH. et al. Journal of Clinical Oncology. 2012, 30, 18. [2] Byers JL. et al. Breast Cancer Res, 2011, 13, R64. [3] Pascual, Ll et al. Org. Lett, 2016, 18, 5548-5551. [4] Pla L. et al. ChemPlusChem, 2017, 2192-6506. [5] Ribes, A. et al. Sensors and Actuators B: Chemical, 2018, 277, 598-603.

Acknowledgments

The authors want to thank the help for the promotion of employment and the implantation of the youth guarantee in I + D + I (Ministry of Science, Innovation and Universities, Government of Spain) for support.

P-95

VIBRIO VULNIFICUS, AN EMERGING PATHOGEN ASSOCIATED WITH CLIMATE CHANGE

M.Nieves Aranda Sobrino,a,b Eva Sanjuan,c Elena Aznar,a,b,d,e Carmen Amaroc and Ramón Martínez-Máñeza,b,d,e

a Unidad Mixta de Investigación en Nanomedicina y Sensores. Instituto de Investigación Sanitaria La Fe, Universidad Politécnica de Valencia. Valencia, Spain [email protected] b Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico, Universidad Politécnica de Valencia, Universidad de Valencia, Valencia, Spain c Instituto de Biotecnología y Biomedicina, Universidad de Valencia, Valenica, Spain d CIBER de Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Spain e Departamento de Química, Universidad Politécnica de Valencia, Valencia, Spain

Keywords: Molecular gates ● Oligonucleotides ● Pathogens ● Detection

V. vulnificus is an emerging zoonotic pathogen known worldwide as a meat-eating marine bacteria. The set of diseases caused by this pathogen is known as vibriosis, regardless of the variant of the disease and the infected host. WHO considers that V. vulnificus is the only species of the genus Vibrio capable of crossing the epithelial barrier and causing death by septicemia in humans [1,2]. Traditional V. vulnificus detection methods are based on culture and identification of the pathogen by biochemical assays or by PCR [2,3]. Although this methodology is the gold standard, it is laborious and requires between 3 and 5 days to obtain the result. Taking into account that patients with vibriosis only survive 3 days if they are not administered the appropriate treatment, this traditional methodology does not meet the needs for clinical diagnosis. In the field of nanotechnology, gated inorganic mesoporous supports are container- shaped structures that can load numerous chemical substances, such as fluorophores, and can be functionalized with gating mechanisms [4] to achieve a selective pore opening in the presence of a pathogen of interest [5]. Within this work we intend to develop a new method for the rapid diagnosis of septicemia caused by V.vulnificus that will reduce the risk of death from this disease. In our case, we have designed a new nanomaterial-based probe for the detection of V. vulnificus. In our system, the pores of the support remain closed in the absence of the bacteria. In contrast, in the presence of V. vulnificus a massive reporter release was obtained. The obtained results are promising, and we expect to prepare a portable kit for V. vulnificus identification in a near future.

References [1] Fouz, B. et al. Journal of fish diseases, 2006, 29, 285-291. [2] Cañigral, I. et al. Investigación microbiológica, 2010, 165 (8), 657-664. [3] Panicker, G. et al. Appl Environ Microbiol, 2004, 70 (1): 498–507. [4] Aznar, E. et al. Chem. Rev, 2016, 2, 561-718. [5] Sancenón, F. et al. Chemistry Open, 2015, 4, 418–437.

Acknowledgments The authors want to thank the help for the promotion of employment and the implantation of the youth guarantee in I + D + I (Ministry of Science, Innovation and Universities, Government of Spain) for support.

P-96

ECOLOGICAL CONTROL OF FUNGAL GRAPEVINE TRUNK PATHOGENS IN NURSERY AND VINEYARD THROUGH THE USE OF THE AQUACTIVA SOLUTION

Ros-Lis, Jose Vicente;a Armengol, Josep b

aDepartamento de Química Inorgánica, Universitat de València. Doctor Moliner 50, 46100 Burjassot. [email protected] b Instituto Agroforestal del Mediterraneo. Universitat Politècnica de Valencia. Camino de Vera s/n. Valencia

Keywords: Electrolyzed water ● Grape vine ● fungus

This study focused on the application of the "Aquactiva" solutions in grapevine nursery and vineyard trials, to verify its potential to control infections caused by fungal trunk pathogens in grapevine plants. Firstly, five different electrolyzed water (EW) biocide solutions with different chemical properties were obtained and characterized and their stability and interaction with plant material studied. The influence of its properties on stability was also modeled. In vitro tests for the efficacy of these solutions were performed on mycelium for 8 different fungal species and on spores of 3 fungal species. It was observed that the effect of the EW depends on the type of product and the fungal species. For instance, the mycelium of Phaeomoniella chlamydospora, Phaeoacremonium minimum, Neofusicoccum parvum, Eutypa Iata and Dactylonectria torresensis showed sensitivity for concentrations of 500 ppm of product and 30 minutes of exposure. Spore tests showed that Pa. chlamydospora, Pm. minimum and Ilyonectria Iiriodendri spores were sensitive to the products tested. These results confirm that EW could be used in a nursery for its application in the production process of grafted plants. In a nursery experiment, treatment with EW achieved a reduction of more than 50% in the percentage of plants infected by Petri and black foot diseases. In contrast, a reduction in the percentage of plants infected with fungi associated with Botryosphaeria dieback was not achieved. In a vineyard experiment, the treatment with EW applied to the thumbs achieved a slight reduction in both the incidence and the severity of the fungi Diplodia seriata, N. parvum, Pa. chlamydospora and Pm. minimun. But, these reductions were very low, clearly insufficient to achieve statistically significant infection levels compared to the untreated vine plants in the trial. Acknowledgments This project has been funded by the FEADER funds “Europe invests in rural areas”, the Generalitat Valenciana and the Spanish Ministry of Agriculture (AGCOOP_A/2019/012).

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PARTICIPANTS

LIST OF PARTICIPANTS

PARTICIPANT TYPE OF PARTICIPATION Alamán Escolano, Luis P-51 Alcañiz Fillol, Miguel Angel Attendance Aranda Sobrino, María Nieves P-94, P-95 Arroyo Máñez, Pau Attendance Avella Oliver, Miquel Attendance Aznar Gimeno, Elena Attendance Báez Morillas, Germán P-18 Banguera Ordoñez, Yulieth Deifan P-27, P-28 Bañuls Polo, Mª José Attendance Barros Nogueira, Mariana O-07 Bastida Molina, Cristina O-13 Bellezza, Delia P-25 Beltrán Morte, Vicente O-12, P-85 Berna Canovas, Jose Full Lecture Bernardos Bau, Andrea Attendance Blández Barradas, Juan Francisco O-02 Botello Marabotto, Marina P-86 Bouhgbina Portoles, Aaron P-17 Brun Sánchez, Eva María Attendance Caballos Gómez, María Isabel P-89 Capella Hernández, Juan Vicente P-53 Carrascosa Rubio, Javier Attendance Carrero Ferrer, Iván P-30 Ceballos Fernández, Samuel Adrián Attendance Cevallos Toledo, Rita Belén P-21 Chapa Chordá, Luis Diego O-10 Collantes Pablo, Cynthia P-14, P-15 Compañ Bertomeu, Alvaro P-80 Cortes Villena, Alejandro P-73 Costa-Rainha Gonçalves, Raquel P-65 Costero Nieto, Ana Attendance Cruz Ortiz, Andrés Felipe Attendance Cubells Gómez, Aitor P-38 Dallamano, Alessandro Attendance Delgado Pinar, Martina Attendance Di Maggio, Martina P-23 Díaz Arellano, Ignacio Attendance Díaz Norambuena, Carolina P-67 Díez Sales, Octavio Attendance Díez Sanchez, Paula P-63 Doménech Carbó, Antonio O-15 Domínguez Rodríguez, Marcia O-05 Escorihuela Fuentes, Jorge P-64 Escriche Navarro, Blanca P-77 Escudero Noguera, Andrea P-46 Estepa Fernández, Alejandra Attendance Esteve Sanchez, Yoel Attendance Farinós Navajas, Noemi P-49 Fernández Huertas, Gustavo Full Lecture Fernández Sánchez, Estrella P-13 Ferrandis Romero, Irene P-33 Ferrándiz Manglano, María Luisa Attendance Ferriol Gabarda, María Carmen Attendance Figueiredo Martins, Catia P-52 Fuentes López, Cristina P-31 Gabaldón Atienza, Javier P-09 Galian Baca, Raquel Eugenia Attendance García Bernabé, Abel P-36 García Fernández, Alba Attendance García Moreno, Paula P-78 Garrido Cano, Iris O-18 Gasch Molina, Isabel Attendance Gaviña Costero, Pablo Attendance Gessler, Josef Peter O-08 Gil Grau, Salvador Attendance Giménez Romero, David Attendance Giraldo, Esther Attendance Godoy Reyes, Tania Mariel Attendance Gómez, Aidan Attendance Gómez Llorente, Hector P-60, P-61 González Martínez, Miguel Angel Attendance González Morote, Victor P-68 Heitz, Valerie Full Lecture Hernández Colomer, María Pilar P-40 Hernández Contreras, Jordi O-06 Hernández Sigüenza, Guillermo P-22 Hicke García, Javier P-47 Ibáñez Civera, Javier Attendance Jiménez González, Josue Attendance Juárez Rodríguez, María José P-29 Jurado García, Antonio Attendance Juste Dolz, Augusto O-21, P-76 Justo Tirado, Miguel Angel P-24 Laguarda Miró, Nicolás Attendance Lameirinhas, Ana P-72 Lérida Viso, Araceli Attendance Lliso Ferrando, Josep Ramón P-70, P-71 Londero, Carolina P-02 López Espinosa, Rocío O-16 López Palacios, Alba P-90 López Paz, Jose Luis Attendance Lora Maroto, Beatriz Full Lecture Lucena Sánchez, Elena P-35 Lucío Benito, María Isabel O-20, P-12 Máñez Asensi, Andreu P-56 Maquieira Catalá, Angel Attendance Marín Ferrándis, Lucia P-74 Martí Centelles, Vicente O-04 Martínez Bisbal, María Carmen Attendance Martínez Ibernón, Ana P-69 Martínez Latorre, Javier P-83 Martínez Máñez, Ramón Attendance Martínez Rojas, Beatriz Attendance Martorell Tejedor, Sara P-19 Masot Peris, Rafael Attendance Medaglia, Serena P-79 Meneses Meneses, Luis Edgar P-48 Merino Sanjuán, Matilde Attendance Merino Sanjuán, Virginia Attendance Milia, Jessica P-92 Mohr, Gerhard Attendance Monreal Trigo, Javier O-11, P-81 Montá González, Giovanni P-26 Morais Ezquerro, Sergi Attendance Morellá Aucejo, Angela P-84 Moreno Manzano, Victoria Attendance Muñoz Alfonso, Carles Attendance Murguía Ibáñez, José Ramón Attendance Nácher Alonso, Amparo Attendance Nicolás García, Tomás Attendance Noguera Murray, Patricia Attendance Olguin Pinatti, Cristian Ariel Attendance Otri, Ismael Attendance Pallás Tamarit, Yeray P-75 Parra Alvarez, Margarita Attendance Pereira Ramos, Nuna Liliana P-57, P-58 Pérez Baeza, Mireia P-41, P-42 Pérez Balastegui, Jose Antonio P-82 Pérez Esteve, Edgar P-91 Pérez Herráez, Irene O-01 Picci , Giacomo P-93 Pruna, Alina P-06, P-07 Puchades Pla, Rosa Attendance Quintero Campos, Pedro P-08 Quintero Moreno, Sergio Andrés O-22 Ray Leiva, César Attendance Reche Esteso, Andrea P-45 Ribes Llop, Susana P-03 Rivas Soler, Alejandro P-59 Rodrigo Martínez, Paula Attendance Rodríguez Nuévalos, Silvia P-20 Ros Lis, José Vicente P-87, P-96 Rosa Pardo, Ignacio P-55 Rosas Laverde, Nelly María P-04, P-05 Rubio Arráez, Susana Attendance Rubio Sánchez, Rafael P-37 Ruíz Rico, María P-88 Sáez Cases, José Antonio P-54 Sagrado Vives, Salvador P-43, P-44 Sancenón Galarza, Félix Attendance Sánchez Martín, María del Mar Attendance Santamaría Fernández, Beatriz O-17 Saura Sanmartín, Adrián O-03 Schad Alburquerque, Cristóbal Martín Attendance Sena Torralba, Amadeo O-19 Serrano Buitrago, Sergio Attendance Silva Pinto, Sonia Catarina P-66 Sousa, Rui P-62 Taléns Visconti, Raquel Attendance Teixeira Miranda, William P-32, P-34 Terencio Silvestre, María Carmen Attendance Terrés Haro, José Manuel O-09, P-39 Torrens Zaragozá, Francisco P-01 Tortajada Genaro, Luis Antonio P-16 Valero Martínez, Antonio P-50 Vengut Tro, Roberto O-14 Zaballos García, Elena Attendance Zezza, Paola P-10, P-11