BOOK OF ABSTRACTS
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Sponsored by Welcome to NyNa 2017
The aim of NyNA 2017 is to bring together scientists working in the field of analytical nanoscience and nanotechnology to show their recent findings with interest for various applications. The Organising Committee wants to thank you for being part of this exciting event.
The Institut Català de Nanociència i Nanotecnologia is a Severo Ochoa Centre of Excellence committed to bringing nanotechnology closer to industrial applications and society. This event is a unique opportunity to create enduring links and work together to bring benefit to society as a whole.
Diagnostics, safety and security, environmental monitoring and other industrial applications are just some of the many fields that could benefit from our joint efforts. Let’s make it happen!
Organising committee
ICREA Prof. CSIC Research Prof. ICREA Prof. Arben Merkoçi Laura Lechuga Jordi Arbiol Chair Co-Chair Co-Chair Catalan Institute of Catalan Institute of Catalan Institute of Nanoscience and Nanoscience and Nanoscience and Nanotechnology (ICN2) Nanotechnology (ICN2) Nanotechnology (ICN2) Scientific programme committee
Dr. Agustín Costa Dr. Alberto Escarpa Dr. Alfredo Sanz-Medel University of Oviedo University of Alcalá University of Oviedo
Dr. Ángel Ríos Dr. Arben Merkoci Dr. Cristina González University of Castilla-La Mancha Institute of Nanoscience and University of Alcalá Nanotechnology (ICN2)
Dr. Encarnación Dr. F. Xavier Rius Dr. José Manuel Lorenzo Universidad Rovira i Virgili Pingarrón Autonomous University of Complutense University of Madrid Madrid
Dr. Juan Ramón Castillo Dr. María Cruz Moreno Dr. María Jesús University of Zaragoza Complutense University of Almendral Madrid University of Salamanca
Dr. Miguel Ángel López Dr. Miguel Valcárcel University of Alcalá University of Córdoba
ICN2 organising team
Àlex Argemí
Alfredo de la Escosura
Ana de la Osa
Anna Puig
Dámaso Torres Scientific programme
Click on each talk to view the abstract
MONDAY 3 JULY Session I 10:30-11:30 Registration and poster set-up Electrochemistry 11:30-12:00 Opening Ceremony and LOC/LF (I) PLENARY 1 12:00-12:40 Yoshinobu Baba (Nagoya University, Chair: Arben Merkoçi Japan): “Nanobiodevices for society 5.0”
KEYNOTE 1 Anna Laromaine (Institut de Ciència 12:40-13:10 de Materials de Barcelona, Spain): “Multiresponsive bacterial cellulose nanocomposites”
Oral 1 Oliver Henry (Harvard University, USA): 13:10-13:25 “Integrating multifunctional sensors into human organs-on-chips”
13:25-15:00 Lunch Session II PLENARY 2 Anja Boisen (Technical University of Electrochemistry 15:00-15:40 Denmark): “Nanostructures for sensing - and LOC/LF (II) Applications in health”
Chair: Víctor Puntes KEYNOTE 2 Neus Sabaté (Institut de Microelectronica 15:40-16:10 de Barcelona, Spain): “Paper-based fuel cells for autonomous screening tests”
Oral 2 Juan Pablo Esquivel (Institut de Microelectronica de Barcelona, Spain): 16:10-16:25 “Development and commercialization of paper-based batteries for environmental and point-of-care diagnostics applications”
Oral 3 Andrea González (Univ. Oviedo, Spain): 16:25-16:40 “Paper-based device for electrochemical quantification of lateral flow immunoassays”
Oral 4 Alfredo de la Escosura-Muñiz (Institut Català de Nanociència i Nanotecnologia, 16:40-16:55 Spain) :”Nanoparticle/nanochannel based sensing systems for neuroblastoma biomarkers detection on plastic and paper platforms” 16:55-17:25 Coffee break and poster session 3 Scientific programme
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MONDAY 3 JULY Session III KEYNOTE 3 Carmen Blanco (Univ. Oviedo, Spain): Electrochemistry 17:25-17:55 “Magnetic biosensor based on lateral flow and LOC/LF (III) immunoassays”
Chair: Agustín Costa KEYNOTE 4 Mar Puyol (Univ. Autònoma de Barcelona, 17:55-18:25 Spain): “Microfabrication techniques based on multilamination for lab-on-a-chip devoted to nanotechnology”
Oral 5 Andrzej Chalupniak (Institut Català de Nanociència i Nanotecnologia, Spain): 18:25-18:40 “Toward integrated detection and graphene-based removal of contaminants in a lab-on-a-chip platform”
Oral 6 Khaled Murtada (Univ. Castilla-La Mancha, Spain): “Fabrication of nano-aluminum/ 18:40-18:55 titanium dioxide modified screen-printed carbon electrode for electrochemical detection of vanillin in food samples”
Oral 7 Tania García (Univ. Autónoma Madrid, 18:55-19:10 Spain): “Gene mutation detection by carbon nanodots nanostructured biosensors”
Oral 8 Isabel Álvarez-Martos (Aarhus University, 19:10-19:25 Denmark): “Highly biospecific self- assembled aptasensor for dopamine analysis in human body fluids”
4 Scientific programme
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TUESDAY 4 JULY Session IV PLENARY 3 Aydogan Ozcan (University of California, Optical sensing (I) 09:00-09:40 USA): “Mobile microscopy, sensing and diagnostics through computational Chair: J.M. Costa photonics”
KEYNOTE 5 Miguel Holgado (Univ. Politécnica Madrid, 09:40-10:10 Spain): “Towards the development of reliable optical label-free point-of-care (PoC) biosensing devices”
Oral 9 Hasan Ertas (Ege University, Turkey): “Computational study on the SPME 10:10-10:25 fiber selectivity for head space gas chromatographic determination of commonly used pesticides”
Oral 10 Blanca Chocarro (Institut Català de Nanociència i Nanotecnologia, Spain): 10:25-10:40 “Novel interferometric nanosensor for CO2 detection using nanoZIF-8 MOFs as specific receptors”
Oral 11 Vaclav Ranc (Palacký University, Czech Republic): “Magnetically assisted surface 10:40-10:55 enhanced raman spectroscopy (MA-SERS) as a promising tool in a fast screening of biomarkers” 10:55-11:25 Coffee break and poster session
5 Scientific programme
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TUESDAY 4 JULY Session V KEYNOTE 6 Francisco Blanco (Microliquid, Spain): Optical sensing (II) 11:25-11:55 “Microfluidic full solutions for POC-IVD and Drug Delivery “ Chair: Encarna Lorenzo KEYNOTE 7 J.M. Costa (Univ. Oviedo, Spain): “Synthesis 11:55-12:25 and use of isotopically enriched quantum dots for the assessment of nanoparticles- biomolecule interactions”
Oral 12 Holger Eickhoff (Scienion AG, Germany): 12:25-12:40 “Biofunctionalization as key step in biosensor applications – from R&D to highthroughput manufacturing”
Oral 13 Diego Bouzas-Ramos (Univ. Oviedo, Spain): “Determination of the stoichiometry 12:40-12:55 quantum dot to antibody in bioconjugates by AF4 coupled on-line to elemental mass spectroscopy”
Oral 14 Patricia Abasolo Linares (Univ. Oviedo, Spain):”Element-tagged immunoassay 12:55-13:10 with (LA)ICP-MS for the determination/ distribution of MMP-11 in breast cancer patients”
Oral 15 Pablo Llano-Suárez (Univ. Oviedo, Spain): 13:10-13:25 “Synthesis and characterization of water- soluble NIR-Emitting quantum dots: bioanalytical applications”
13:25-15:00 Lunch
6 Scientific programme
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TUESDAY 4 JULY Session VI PLENARY 4 Anna Fontcuberta (Institute of Materials, Optical sensing 15:00-15:40 EPFL, Switzerland ): “Semiconductor (III) nanowires for sensing”
Chair: Aydogan Ozcan KEYNOTE 8 Victor Puntes (Institut Català de 15:40-16:10 Nanociència i Nanotecnologia, Spain): “Enhancing plasmonic detection with hollow nanocrystals”
Oral 16 Gerardo A. López-Muñoz (Institut Català de Nanociència i Nanotecnologia, Spain): 16:10-16:25 “Metallic nanostructures based on blu- ray discs for multiplexed plasmonic biodetection”
Oral 17 Sara López-Sanz (Univ. Castilla-La Mancha, 16:25-16:40 Spain): “Complementary techniques to study gold nanoparticles transdformation in cell culture medium”
Oral 18 Elena Benito-Peña (Univ. Complutense, 16:40-16:55 Spain): “Gold-core, MIP-Shell (Au@MIP) surface-enhanced raman scattering (SERS) nanosensor for antibiotic detection” 16:55-17:25 Coffee break and poster session
7 Scientific programme
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TUESDAY 4 JULY Session VII KEYNOTE 9 Ramon Eritja (Institute for Advanced Optical sensing Chemistry of Catalonia, Spain): “Novel 17:25-17:55 (IV) and versatile approaches for DNA-based nanosensing based on nucleic acid triplex Chair: Alberto Escarpa formation”
KEYNOTE 10 Encarna Lorenzo (Univ. Autónoma Madrid, 17:55-18:25 Spain): “Nanoparticles based label-free DNA biosensors”
Oral 19 Alba Martín Barreiro (Univ. Zaragoza, Spain): “Fluorescence-enzymatic 18:25-18:40 nanobiosensors: interference free choline determination based on energy transfer phenomena between chlonie oxidase and gold nanoclusters”
Oral 20 Sara Martí-Sánchez (Institut Català de Nanociència i Nanotecnologia, Spain): 18:40-18:55 “Strain relaxation mechanisms in ZnSe@ ZnTe core-shell nanowires grown horizontallly from a guided growth approach”
21:00 Gala dinner
8 Scientific programme
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WEDNESDAY 5 JULY Session VIII PLENARY 5 Hatice Altug (École Polytechnique Graphene and 09:00-09:40 Fédérale de Lausanne, Switzerland): nanomaterials (I) “Nanophotonics and metasurfaces for next-generation biosensors” Chair: Francisco Andrade KEYNOTE 11 Jesús Martínez de la Fuente (Instituto de Ciencia de Materiales de Aragón, 09:40-10:10 Spain): “Hybrid nanoparticles for therapy and diagnosis: Au nano prisms for gastrointestinal cancer”
KEYNOTE 12 Alberto Escarpa (Univ. Alcalá, Spain): 10:10-10:40 “Magneto-catalytic graphene quantum dots Janus micromotors for bacterial endotoxin detection”
Oral 21 Gema M. Duran (Univ. Castilla-La Mancha, Spain): “Modification of gold nanoparticles- 10:40-10:55 screen printed carbon electrodes with graphene quantum dots: voltammetric determination of vanillin in food samples” 10:55-11:25 Coffee break and poster session
9 Scientific programme
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WEDNESDAY 5 JULY Session IX KEYNOTE 13 Francisco Andrade (Univ. Rovira i Virgili, Graphene and 11:25-11:55 Spain): “Nanostructured materials for nanomaterials (II) the development of paradigm-shifting analytical platforms” Chair: Hatice Altug KEYNOTE 14 Valerio Pruneri (Institut de Ciencies Fotoniques, Spain): “Large-field-of-view 11:55-12:25 cytometer and differential interference contrast microscope using CMOS image sensor arrays”
Oral 22 Filiz Kuralay (Ordu University, Turkey): 12:25-12:40 “Stimuli-responsive conducting surfaces for controlled drug release”
Oral 23 Carina S.Gondim (Federal University of Minas Gerais, Brazil): “Graphene quantum 12:40-12:55 dots@nafion modified glassy carbon electrode as an electrochemical sensor for detection of sulphonamide residues in milk”
Oral 24 Irem Aydin (Ege University, Turkey): “Polypirrole-carbon nanotube composite 12:55-13:10 solid-phase microextraction fiber: preparation, characterization and application to the analysis of fungicides in vineyards”
Oral 25 K. Volkan (Ege University, Turkey): “Simultaneous determination of 13:10-13:25 levodopa and carbidopa at a polypirrole- carbon nanotube composite electrode preparaed by ultrasound assisted pulsed electropolymerization”
13:25-13:55 Closing session and awards
Lunch
10 Abstracts
11 MONDAY 3 JULY Session I: Electrochemistry and LOC/LF (I) 12:00-12:40 PLENARY 1
NANOBIODEVICES FOR SOCIETY 5.0 Yoshinobu Baba Department of Chemistry and Biotechnology, School of Engineering, ImPACT Research Center for Advanced Nanobiodevices, Department of Advanced Medical Science, School of Medicine, Nagoya University, Nagoya, 464-8603, Japan
Nanobiodevice is a piece of contrivance, equipment, machine, or component, which is created by the overlapping multidisciplinary activities associated with nanotechnology and biotechnology. In this lecture, I will describe the development of nanobiodevices for society 5.0; super smart society [1-23], including immuno-wall devices for healthcare and point-of-care testing, nanopillar-nanopore devices for single DNA and microRNA sequencing, nanowire devices for exosome analysis, AI-powerd IoT nanosensors, and quantum switching in vivo imaging of iPS cells. Immuno-wall devices realized the fast and low invasive “from blood to analysis” type biomarker detection of cancer with fM detection sensitivity within 2 min. Additionally, nanopillar devices give us ultrafast electophoretic separation of DNA and microRNA within 60 µs and nanopillar-nanopore integrated nanobiodevice enables us ultarafast single molecular DNA sequencing. Nanowire devices coupled with super-resolution optical microscopy are extremely useful to analyze exosomes from cancer cells and exosomal microRNA analysis. Nanowire-nanopore devices combined with machine learning technique enable us to develop mobile sensors for PM2.5, bacteria, and virus in the environment. Quantum dots are applied to develop quantum-biodevices for single cancer cell diagnosis, single molecular epigenetic analysis, quantum switching in vivo imaging for iPS cell (induced pluripotent stem cells) based regenerative medicine, and theranostic devices for cancer diagnosis/therapy.
References
[1] N. Kaji, Y. Baba, et al., Chem. Soc. Rev., 39, 948 (2010). [2] D. Onoshima, H. Yukawa, Y. Baba, Advanced Drug Delivery Reviews, 95, 2-14(2015). [3] S. Rahong, T. Yasui, N. Kaji, Y. Baba, Lab on a Chip,16, 1126-1138 (2016). [4] H. Yukawa, Y. Baba, Anal. Chem., 89, 2671-2681 (2017). [5] N. Kaji, Y. Baba, et al., Nanopillars, Nanowires and Nanoballs for DNA and Protein Analysis, Nanofluidics, RSC, 2017. [6] D. Onoshima, Y. Baba, Microfluidic DNA Stretching Device, Methods in Molecular Biology, Springer, 2017 [7] M. Tabuchi, Y. Baba, et al., Nature Biotech., 22, 337 (2004). [8] R. Bakalova, Y. Baba, et al., Nature Biotech., 22, 1360 (2004). [9] M. F. Serag, Y. Baba, et al., ACS Nano., 5, 493, (2011). [10] T. Yasui, Y. Baba, et al., ACS Nano, 5, 7775 (2011). [11] M.F. Serag, Y. Baba, et al., ACS Nano, 5, 9264 (2011). [12] M.F. Serag, Y. Baba, et al., Nano Lett., 12, 6145 (2012). [13] T. Yasui, Y. Baba, et al., ACS Nano, 7, 3029 (2013). [14] K. Hirano, Y. Baba, et al., Nano Lett., 13, 1877 (2013). [15] S. Rahong, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 4, 5252 (2014). [16] S. Rahong, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 5, 10584(2015). [17] T. Yasui, Y. Baba, et al., Nano Lett., 15, 3445 (2015). [18] T. Kameyama, Y. Baba, et al., Nanoscale, 8, 5435 (2016). [19] S. Fukushima, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 6, 25950(2016). [20] T. Yamamoto, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 6, 30136(2016). [21] T. Yasui, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 6, 31642(2016). [22] Y. Ogihara, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 7, 40047 (2017). [23] Q. Wu, Y. Baba, et al., Sci. Rep. (Nature Pub. Group), 7, 43877 (2017).
< Back to Programme 12 MONDAY 3 JULY Session I: Electrochemistry and LOC/LF (I) 12:40-13:10 KEYNOTE 1
MULTIRESPONSIVE BACTERIAL CELLULOSE NANOCOMPOSITES Soledad Roig, Irene Anton, Muling Zeng, Maria Milla, Deyaa Youseff, Sebastià Parets, Judit Fuentes, Jordi Floriach-Clark, Anna May, Anna Roig, Anna Laromaine Nanoparticles and Nanocomposites Group (www.icmab.es/nn) Institut Ciencia de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra, Spain Email [email protected]
Cellulose constitutes an almost inexhaustible biopolymer, being the most abundant renewable polysaccharide produced in the biosphere. Cellulose is predominantly obtained from plants; however it can also be synthesized by bacteria, algae and fungi. In particular, cellulose obtained by bacteria has the same molecular formula as vegetal cellulose but exhibits a high degree of polymerization, crystallinity and, importantly, does not contain lignin and hemicelluloses, increasing its biocompatibility. We can obtain bacterial cellulose (BC) films characterized by a three-dimensional architecture of cellulose fibers forming an interconnected open pore network. BC films also have high porosity, transparency in the UV-NIR and a high water holding capacity. The bacterial synthesis of BC allows us to control the micro(nano)structuration, 3D structure and shape of the BC materials. We will present the production and characterization of cellulose films and the impact that different physical and chemical parameters such as the bacterial culture properties, drying method and chemical modification have on its microstructure, porosity, wettability, transparency and mechanical properties. We will present multilayered and multicomposite BC structures which can respond to different stimuli. In order to exploit its biocompatibility we will present additionally some results of the use of BC films and its nanocomposites for applications in biology. These innovative BC structures will provide the proof of concept for devices or products.
References
[1] Zeng et al. Journal of Materials Chemistry C 2 (2014) 6312-6318 DOI: 10.1039/c4tc00787e [2] Zeng et al. Cellulose (2014) 21 4455–4469 DOI 10.1007/s10570-014-0408-y
< Back to Programme 13 MONDAY 3 JULY Session I: Electrochemistry and LOC/LF (I) 13:10-13:25 ORAL 1
INTEGRATING MULTIFUNCTIONAL SENSORS INTO HUMAN ORGANS-ON-CHIPS O.Y.F. Henry a, W. Leineweber a, M. Cronce a, R. Villenave a, J. Sabate del Rio a, M. Benz a, B. Maoz a, b, A. Herland a, K. K. Parkera, b, D. E. Ingber a, b, c a The Wyss Instiute at Harvard University, 3 Blackfan Circle, Boston, USA b Harvard John A. Paulson School of Engineering and Applied Sciences, Cambridge, USA; c Vascular Biology Program and Department of Surgery, Boston Children’s Hospital and Harvard Medical School, Boston, USA. [email protected]
Microfluidic organs-on-chip (OOC) provides an elegant in vitro platform to culture cells under controlled conditions. In addition to supplying fresh nutrients and controlling cells differentiation chemically, mechanical forces such as strain and shear forces can be applied to result in more physiologically relevant in vitro models. However, these closed systems pose a new set of analytical challenges to assess organ viability and functionality. Here we present a number of solution we implemented to address these challenges. We developed a range of micro- and nano-fabrication techniques to integrate semi-transparent electrodes and measure trans-epithelial electrical resistance (TEER) to monitor the establishment of robust barrier function in situ and in real time via impedance spectroscopy. This allowed us to follow the differentiation of a small airway at air-liquid interface, as well the formation and disruption of 3D villi-like structure in a human gut-chip lined by intestinal epithelial cells. We further integrated microelectrode arrays to assess drug diffusion and its effect in a vascularized myocardium model. We followed the formation of the endothelium and its disruption under chemical stress via TEER while at the same time measure field potential of cardiomyocytes to assess drug pharmacodynamics and kinetics. Finally, we developed a micro-electrochemical sensor array platform that enables the simultaneous detection of several pro- inflammatory markers in small sample volumes taken from our chips with high sensitivity. While the tools we developed permit the direct assessment of OOC and provide valuable information on the organs biology and physiology, several challenges still lie ahead to achieve full integration and long term operation of multiple organs simultaneously.
< Back to Programme 14 MONDAY 3 JULY Session II: Electrochemistry and LOC/LF (II) 15:00-15:40 PLENARY 2
NANOSTRUCTURES FOR SENSING - APPLICATIONS IN HEALTH Anja Boisen Technical University of Denmark
Structures such as nanopillar substrates, nanomechanical resonators, nanometer sized magnetic beads and microfabricated electrodes can all be applied in in a variety of sensing scenarios. They all have their cons and pros and sometimes a combination of sensors is feasible - for example when different components such as small molecules and whole cells need to be detected simultaneously in the same sample. We have specifically applied our developed sensors in the field of human health, addressing issues such as patient monitoring, diagnostics and material characterization in relation to oral drug delivery (active pharmaceutical ingredients and biodegradable polymers). Integration of microfluidic handling with one or more sensors is achieved using optics and mechanics from a simple DVD player.
< Back to Programme 15 MONDAY 3 JULY Session II: Electrochemistry and LOC/LF (II) 15:40-16:10 KEYNOTE 2
PAPER-BASED FUEL CELLS FOR AUTONOMOUS SCREENING TESTS Neus Sabaté Institució Catalana de Recerca i Estudis Avançats (ICREA) and Institut de Microelectronica de Barcelona (IMB-CNM-CSIC), Campus UAB, 08193 Bellaterra-Barcelona (Spain)
The advances in paper microfluidics have brought a new generation of devices that promise more accurate and specific test results at affordable prices, enabling earlier disease diagnostics, patient stratification and prognosis of diseases and making a significant impact to the sustainability of health care systems. However, test quantification requires the use of handheld or benchtop readers. These readers are only cost-effective when used in hospitals or consultation rooms and eventually, to perform home-test monitoring of chronic diseases (e.g. glucometer). It is becoming clear that the huge potential of this new technology may be restricted due to the lack of affordable readout solutions. In the search of simpler approaches, smartphones have opened up a low-cost route to quantification of colorimetric paper-based assays through its built-in camera. However, this approach is limited to colorimetric tests and still has some unresolved questions like the influence of ambient lighting and the condition of dry and wet paper on the test results. On-chip approaches are a more promising alternative; the Clearblue Digital Pregnancy Test - conceived as a fully disposable system able to yield semi-quantitative results- is a very good example. However, it is surprising that despite the huge expected impact behind paper-based assays, the search for effective on-chip readout solutions is still in its infancy. A key aspect to accomplish this vision is sufficient and available electrical power on board. Ideally, the power source has to be affordable, paper-based and environmentally friendly when disposed of. In this sense, research in printed batteries – also in paper substrates - has been very active in the recent years. The Self-Powered Engineered Devices Group (SPEED) aims to develop a new generation of disposable and low environmental impact fuel cells ready to integrate in paper platforms. The fuel cell is conceived to deliver the power required by the application for a limited period of time - until paper gets saturated - and to be disposed of afterwards. In fact, the materials used in these devices (paper, carbon-based inks and ultra-low contents of metallic nanoparticles or enzymes) make them more environmentally friendly than batteries.
< Back to Programme 16 MONDAY 3 JULY Session II: Electrochemistry and LOC/LF (II) 16:10-16:25 ORAL 2
DEVELOPMENT AND COMMERCIALIZATION OF PAPER-BASED BATTERIES FOR ENVIRONMENTAL AND POINT-OF-CARE DIAGNOSTICS APPLICATIONS Juan Pablo Esquivel a,b, Neus Sabaté a,b,c a Instituto de Microelectrónica de Barcelona, IMB-CNM (CSIC), C/ del Til·lers, Campus UAB, Barcelona, Spain b Fuelium S.L., Av. De Can Domenech – Edifici Eureka, Campus UAB, Barcelona, Spain c Catalan Institution for Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, Barcelona, Spain [email protected]
The use of electronic devices has experienced a tremendous rise and consequently, the rate of waste electrical and electronic equipment (WEEE or e-waste) generated after their disposal. Due to their content of heavy metals, batteries are one of the most hazardous components of e-waste. Therefore, an alternative to supplement or substitute metals, such as lithium, is urgently needed for satisfying the growing need of electric energy for portable electronic applications. It is mandatory that the alternatives are not only energy dense but also environmentally sustainable. The Self-Powered Engineered Devices Group (SPEED) works on several paper-based battery technologies to achieve those goals, following the sustainability principles of circular economy theory, in which waste has to be minimized from the very conception of the device. Here, two of their developed technologies will be presented. Firstly, the development of metal-free organic redox flow batteries, designed and fabricated using exclusively organic materials such as cellulose, carbon and wax and featuring an integrated quinone-based redox chemistry to generate electricity within a compact form factor. These primary capillary flow batteries can run an electronic portable water analyzer and once depleted, they can be disposed of without the need of any recycling facility, as their components are non-toxic and shown to be biotically degradable in a standardized test. Secondly, the non-toxic disposable paper-based batteries in a lateral flow test format, which will be commercialized by the spinoff company Fuelium. These batteries provide an environmentally friendly alternative to substitute Li-ion coin cell batteries in disposable point-of-care applications, such as digital pregnancy and ovulation tests already in the market. The paper-based batteries can be fabricated in the same materials and cost-effective manufacturing technology currently used by lateral flow test industry, reducing integration costs and allowing the battery to follow the same disposal pathway as the biological assay. The batteries are activated upon the addition of a liquid sample and are able to work with water as well as with most relevant biological matrices in point-of-care applications (blood, urine and saliva). This innovative approach would enable the digitalization of lateral flow assays for markets beyond women’s health sector.
< Back to Programme 17 MONDAY 3 JULY Session II: Electrochemistry and LOC/LF (II) 16:25-16:40 ORAL 3
PAPER-BASED DEVICE FOR ELECTROCHEMICAL QUANTIFICATION OF LATERAL FLOW IMMUNOASSAYS Andrea González-López, M. Carmen Blanco-López*, M. Teresa Fernández-Abedul* Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Asturias, Spain * email corresponding authors: [email protected]; [email protected]
Lateral flow immunoassays (LFIA) represent a well-established technology and are powerful tools for rapid and low-cost on-site detection of different analytes [1]. However, a device which allows the final signal quantification is highly demanded. If, in addition, a low-cost and portable device is achieved, we will be closer to the complete POC (point-of-care) concept. On the other hand, paper has demonstrated to be very adequate as substrate for fabricating quantitative electrochemical platforms with foldability as one of the specific and useful advantages [2]. In this work, a folded paper-based platform for electrochemical measurements was developed, with three integrated channels for hosting the electrodes. The central channel is filled with carbon ink to operate as working electrode (WE). The device is connected to the potentiostat by a gold-plated connector header, that includes also the other two electrodes [3]. The LFIA strip is placed in the middle of this folded paper device, with the test line in contact with the channel that contains the WE. In the preliminary trials, the reduction of the previously oxidized 3,3’,5,5’ tetramethylbenzidine (TMB) by the peroxidase enzyme (HRP) deposited on the strip, was measured.
This work has been supported by CTQ2014-58826-R project from the Spanish Ministry of Economy and Competitiveness (MINECO) and by the Consejería de Economía y Empleo del Principado de Asturias, under the Grant GRUPIN14-021 and GRUPIN14-022.
References
[1] M. Oliveira-Rodríguez et al., Biosens. Bioelectron., 87, (2017), 38-45 [2] O. Amor-Gutiérrez et al., Biosens. Bioelectron., 93, (2017), 40-45 [3] A. C. Glavan et al., Anal. Chem., 86, (2014), 11999-12007
< Back to Programme 18 MONDAY 3 JULY Session II: Electrochemistry and LOC/LF (II) 16:40-16:55 ORAL 4
NANOPARTICLE/NANOCHANNEL BASED SENSING SYSTEMS FOR NEUROBLASTOMA BIOMARKERS DETECTION ON PLASTIC AND PAPER PLATFORMS Alfredo de la Escosura-Muñiz1, Marisol Espinoza-Castañeda1, Alejandro Chamorro-García1, Carlos J. Rodríguez-Hernández2, Carmen de Torres2, Arben Merkoçi 1,3 1. Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain. 2. Hospital Sant Joan de Déu and Fundació Sant Joan de Déu, 08950 Barcelona, Spain 3. ICREA, Institució Catalana de Recerca i Estudis Avançats, Barcelona, Spain. Email: [email protected]
Neuroblastoma (NB) is a childhood cancer of the peripheral nervous system. It affects 10.2 per million children under 15 years of age, and it is the most frequent type of cancer in the first year of life. Despite all the efforts in new therapies, overall survival rates remaining below 40% [1]. Besides, long term survivors suffer from secondary effects inflicted by current multimodal therapies on their normal, developing organs. In this context, there is an important medical need to develop devices for rapid quantification of circulating markers that allow for the precise evaluation of tumor evolution either spontaneous and/or in response to treatments. Parathyroid Hormone-like Hormone (PTHLH) is a cytokine that exerts relevant roles in normal tissues as well as in the initiation, progression and dissemination of several tumors. PTHLH is identified as a factor responsible for neuroblastoma- induced hypercalcemia [2,3] and it is known that circulating PTHLH is a useful marker to monitor the state of malignant-associated hypercalcemia and the effectiveness of treatment in cancer patients. However, there is a lack of specific, sensitive and widely available techniques to detect and quantify this protein. Methods used in hospitals are based on radioimmunoassays (RIAs), involving time consuming hazardous procedures which require sophisticated and expensive equipment and facilities. So point-of-care biosensors for PTHLH detection are strongly demanded by oncologists. In this context, we present here two different nanobiosensing approaches for the rapid and sensitive determination of PTHLH in physiological samples. The first approach is based on the use of solid-state nanoporous platforms in combination with electrochemical detection on screen-printed electrodes. Immunocomplex formation inside the nanoporous platforms leads to nanochannel blockage, which is electrochemically monitored and related to PTHLH concentration [4]. The second methodology relies in a lateral-flow immunoassay (LFIA) using gold nanoparticle (AuNP) tags [5]. Cell culture medium and cell lysates are evaluated with these systems, giving relevant information for understanding the factors that regulate the production and secretion of this protein by tumor cells, with potential interest for new therapies. PTHLH is also determined in human serum, being this data of great interest for diagnostics and for monitoring the effectiveness of therapies. Acknowledgements: ICN2 acknowledges support of the Spanish MINECO under projects MAT2014-52485-P and PCIN-2016-066 (“NACANCELL”) and through the Severo Ochoa Centers of Excellence Program under Grant SEV-2013-0295. The Secretaria d’Universitats i Recerca del Departament d’Economia i Coneixement de la Generalitat de Catalunya (Grant 2014 SGR 260) is also acknowledged. The authors also wish to acknowledge funding from the Spanish Ministry of Health (FIS PI14/ 00040 to CdT) and Fundació Privada Cellex. References
[1] J.M. Maris. N Engl J Med, 362 (2010) 2202-2211. [2] L.J. Suva et al. Science 237 (1987) 893-896. [3] C. de Torres, H. Beleta , R. Diaz, N. Toran, E. Rodriguez et al. Cancer 115 (2009) 2792-2803. [4] M. Espinoza-Castañeda, A. de la Escosura-Muñiz, A. Chamorro-García, C. de Torres, A. Merkoçi. Biosens. Bioelectron., 67 (2015) 107-114. [5] A. Chamorro-Garcia, A. de la Escosura-Muñiz, M. Espinosa-Castañeda, C.J. Rodríguez-Hernández, C. de Torres, A. Merkoçi. Nanomedicine, 12(1) (2016) 53-61. < Back to Programme 19 MONDAY 3 JULY Session III: Electrochemistry and LOC/LF (III) 17:25-17:55 KEYNOTE 3
MAGNETIC BIOSENSOR BASED ON LATERAL FLOW IMMUNOASSAYS D. Lago-Cachóna, M. Oliveira-Rodríguezb, M.C. Blanco-Lópezb, M. Rivasa, J. C. Martínez-Garcíaa, A. Moyanoa,b, M. Salvadora, J.A. Garcíaa a. Dpto. de Física, Universidad de Oviedo, Edificio Departamental Este, Campus de Viesques, 33204 Gijón, Spain b. Departamento de Química Física y Analítica, University of Oviedo, 33006, Oviedo, Asturias, Spain * email corresponding author: [email protected]
Lateral flow immunoassays are widely used at the biomedical, environmental and food control fields. Their current limitation is the need to provide quantitative results. These can be achieved by using as label different nature of nanoparticles. In this work we have developed a lateral flow immunoassay for Prostate Specific Antigen (PSA), biomarker of prostate cancer, using superparamagnetic iron oxide nanoparticles as labels. The test was coupled to a scanning magnetic sensor, which allowed quantification. The measurement is based on the electromagnetic induction produced bythe superparamagnetic nanoparticles [1] . This is the first time that this principle is applied to a lateral flow immunoassay. In contrast with other magnetic sensors, the one proposed here does not require the application of an external magnetic field, which reduces its complexity. The ability of the system has been proved by successfully measuring prostate specific antigen levels in the clinically interesting interval.
Acknowledgements: This work was supported by the Consejería de Economía y Empleo del Principado de Asturias under the Grants GRUPIN14-022 and GRUPIN14-037.
References
[1] LAGO-CACHON, D., RIVAS, M., MARTINEZ-GARCIA, J. C. & GARCIA, J. A. 2013. Cu impedance-based detection of superparamagnetic nanoparticles. Nanotechnology, 24, 245501.
< Back to Programme 20 MONDAY 3 JULY Session III: Electrochemistry and LOC/LF (III) 17:55-18:25 KEYNOTE 4
MICROFABRICATION TECHNIQUES BASED ON MULTILAMINATION FOR LAB-ON-A-CHIP DEVOTED TO NANOTECHNOLOGY Mar Puyol, OriolYmbern , Pedro Couceiro, Antonio Calvo, Miguel Berenguel and Julian Alonso-Chamarro Group of Sensors and Biosensors, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain [email protected]
Microfluidics have been a key element for the exponential growth observed in the development of miniaturized devices, capable of integrating all the required steps for a chemical analysis procedure (MicroTotal Analysis Systems or Lab on a Chip). Even though different materials and techniques have been employed to obtain these structures, the ideal fabrication technology would be the one that could combine the versatility of a multilayer fabrication, a rapid prototyping and the possibility of mass production at low cost without the need of special fabrication conditions as clean rooms. Additionally, the most common employed technologies for microfabrication (Silicon and PDMS) provide mainly 2D-microfluidic structures and, the integration of the different components related to each specific step of the analytical procedure is not feasible. The use of thermoplastic materials such as COC or Low Temperature Co-Fired Ceramics has demonstrated to overcome such drawbacks due to the multilayer approach of the fabrication procedure. It allows the monolithic integration of 3D microfluidic structures in substrates with a high level of compatibility with other materials (polymers, conductive pastes, etc.) and therefore fulfils the previously mentioned requirements. Some applications of both technologies will be detailed in this talk, which lay in the field of the nanomaterials synthesis process intensification by means of microreactors, for instance for the synthesis of metallic nanoparticles (mNPs), Quantum dots (QDs) and Carbon Dots (CDots), and in the field of the separation of nanoparticles (size-purification) by microfluidic Free Flow Electrophoresis devices.
< Back to Programme 21 MONDAY 3 JULY Session III: Electrochemistry and LOC/LF (III) 18:25-18:40 ORAL 5
TOWARD INTEGRATED DETECTION AND GRAPHENE-BASED REMOVAL OF CONTAMINANTS IN A LAB-ON-A-CHIP PLATFORM
Andrzej Chałupniaka, Arben Merkoçiab a. Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, Barcelona, Spain b. ICREA, Pg. Lluís Companys 23, Barcelona, Spain [email protected]
In this work a miniaturized microfluidic platform for the simultaneous detection and removal of polybrominated diphenyl ethers (PBDEs) is developed. This device consists of a polydimethylsiloxane (PDMS) microfluidic chip for an immunoreaction step, a PDMS chip with an integrated screen-printed electrode (SPCE) for detection and a PDMS-reduced graphene oxide (rGO) chip for physical adsorption and subsequent removal of PBDE residues. The detection was based on competitive immunoassay (PBDE vs. HRP-PBDE) followed by the monitoring of enzymatic oxidation of o-aminophenol (o-AP) using square wave anodic stripping voltammetry (SW-ASV). PBDE was detected with the limit of detection similar to that obtained with a commercial colorimetric test (0.018 ppb), but with the advantage of using lower reagent volumes and a reduced analysis time. The use of microfluidic chips also provides improved linearity and a better reproducibility in comparison to those obtained with batch-based measurements using screen-printed electrodes. In order to design a detection system suitable for hazardous compounds such as PBDEs, a reduced graphene oxide–PDMS composite was developed and optimized to obtain increased adsorption (based on both the hydrophobicity and π–π stacking between rGO and PBDE molecules) compared to those of non-modified PDMS. To the best of our knowledge, this is the first demonstration of electrochemical detection of flame retardants and a novel application of the rGO-PDMS composite in a biosensing system. This system can be easily adjusted to detect any analyte using the appropriate immunoassay and it supports operation in complex matrices such as seawater.
References
[1] Chałupniak, A. & Merkoçi, A. Nano Res. (2017). doi:10.1007/s12274-016-1420-3
< Back to Programme 22 MONDAY 3 JULY Session III: Electrochemistry and LOC/LF (III) 18:40-18:55 ORAL 6
FABRICATION OF NANO-ALUMINUM/TITANIUM DIOXIDE MODIFIED SCREEN PRINTED CARBON ELECTRODE FOR ELECTROCHEMICAL DETECTION OF VANILLIN IN FOOD SAMPLES Khaled Murtadaa,b, Sehdeh Jodehc, Mohammed Zougaghb,d, Angel Ríosa,b,* a. Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha Ciudad Real, Spain b. Regional Institute for Applied Chemistry Research (IRICA), 13004 Ciudad Real, Spain c. Department of Chemistry, An-Najah National University, P.O. Box 7, Nablus, Palestine d. Castilla-La Mancha Science and Technology Park., 20006 Albacete, Spain * Corresponding author at: Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha, Ciudad Real 13071, Spain. E-mail address: [email protected] (A. Ríos)
A new chemically modified electrode based on aluminium nanoparticles (Al-NPs) has been constructed. Titanium was incorporated into the Al-NPs to prepare titanium oxide doped nano-aluminium. Titanium
oxide/nano-aluminium screen printed carbon electrode (TiO2/Al-NPs-SPCE) was employed as simple, efficient and rapid sensor for electrochemical detection of vanillin in various types of food samples.
TiO2/Al-NPs were characterized by X-ray diffraction (XRD) and transmission electron microscopy
(TEM) analyses showing that the average particle sizes varied for the Al-NPs (7.63 nm) and TiO2/Al-NPs (7.47 nm) with spherical crystal. The liner sweep voltammetry (LSV) and cyclic voltammetry (CV) were used to optimize the analytical procedure and a detection limit of 0.985 µM for vanillin was found. A relative standard deviation of 2.09 % was calculated for a 250 µM concentration of vanillin. The electrochemical behaviour of other compounds (vanillic acid, vanillic alcohol, p-hydroxybenzaldehyde and p-hydroxybenzoic, etc.), generally present in natural samples, were also studied, to check the interferences with respect to vanillin voltammetric signal. To validate the methodology and efficacy of proposed sensor, detection of vanillin was also examined in food samples. The obtained results were compared with those povided by a reference method based on liquid chromatography.
Acknowledgements: The Spanish Ministry of Economy and Competitiveness (MINECO) and JJCC Castilla-La Mancha are gratefully acknowledged for funding this work with Grants CTQ2016-78793-P and JCCM PEIC-2014-001-P, respectively.
< Back to Programme 23 MONDAY 3 JULY Session III: Electrochemistry and LOC/LF (III) 18:55-19:10 ORAL 7
GENE MUTATION DETECTION BY CARBON NANODOTS NANOSTRUCTURED BIOSENSORS
Tania García-Mendiolaa,b,c, José María López Morenoa, Iria Bravoa,b, Félix Parientea,c, Reinhold Wannemacherb, Dana Cialla-Mayd,e, Jürgen Poppd,e and Encarnación Lorenzoa,b,c a. Departamento Química Analítica y Análisis Instrumental, b. Institute for Advanced Re-search in Chemical Sciences (IAdChem) of Universidad Autónoma de Madrid. c. Instituto Madrileño de Estudios Avanzados (IMDEA), d. Leibniz Institute of Photonic Technology (IPHT), Institute for Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-University Jena, Germany. [email protected]
Carbon dots (CDs) are defined as nanoparticles mainly composed of carbon, with a size below 10 nm [1]. Nanomaterial-modified detection systems represent a chief driver towards the adoption of electrochemical methods for sensing applications [2,3]. In this work, a nanostructured DNA biosensor constructed by using a carbon nanodots (CDs) modified screen-printed gold electrode is reported. CDs were synthesized by thermal carbonization of ethylene glycol bis-(2-aminoethyl ether)-N,N,N’,N’- tetraacetic acid and characterized by different techniques. The electrode surface modification was accomplished by drop-casting a suspension of CDs. Synthetic 25-mer or 100-mer DNA capture probes from the pathogen Helicobacter pylori or the cystic fibrosis transmembrane regulator (CFTR) gen were attached to the CDs-gold surface. A 25 bases synthetic sequence or a 373 bases PCR amplicons of exon 11 of CFTR containing a sequence complementary to the capture probe, were employed as target sequences. The hybridization event was electrochemically monitored by using Safranine as redox indicator. The biosensor has been applied to the detection of F508del mutation in the CFTR gen.
References
[1] Baker, S.N.; Baker, G.A. Angew. Chem., Int. Ed., 49, (2010), 6726–6744, 10.1002/anie.200906623. [2] Milosavljevic, V.; Nguyen, H.V.; Michalek, P.; Moulick, A.; Kopel, P.; Kizek, R.; Adam, V. Chem. Pap., 69, (2015), 192-201, 10.2478/s11696-014-0590-2. [3] Shen, J.; Zhu,Y.; Yang, X.; Li, C. Chem. Commun., 48, (2012), 3686–3699, 10.1039/c2cc00110a.
< Back to Programme 24 MONDAY 3 JULY Session III: Electrochemistry and LOC/LF (III) 19:10-19:25 ORAL 8
HIGHLY BIOSPECIFIC SELF-ASSEMBLED APTASENSOR FOR DOPAMINE ANALYSIS IN HUMAN BODY FLUIDS Isabel Álvarez-Martos and Elena E. Ferapontova Interdisciplinary Nanoscience Center (iNANO) Aarhus University, Gustav Wieds Vej, 14, 8000 Aarhus C, Denmark. [email protected]
Understand the function of small molecule neurotransmitters, such as dopamine (DA) in the complex landscape of brain is critical to prevent or treat neurological disorders. However, the presence of other coexisting molecules whose oxidation potential overlaps with dopamine hinders its direct electroanalysis. The use of high specific biorecognition elements, such as aptamers offer a fast and simple, and still sensitive and selective approach to tackle this problem. Here, we show that absolute discrimination of DA over other catecholamines is possible through a specific RNA aptamer sequence [1] immobilized on cysteamine-modified gold electrodes via the alkanethiol linker [2, 3]. On the contrary to the DNA sequence obtained by replacement of the RNA bases by their DNA analogues, which did not show any specificity of binding and therefore is not suitable for specific analysis of DA. One of our main goals was to probe that even though RNA aptamer stability can be compromised in biological fluids by the ribonuclease digestion or chemical cleavage [4], binding to electrodes stabilize their structure, so that measurements can be performed in undiluted biological fluids i.e.( , human serum). Given the simplicity of the design and demonstrated operation in serum, the developed aptasensor can undoubtedly contribute to the development of more complex in vivo electroanalytical platforms for diagnosis.
References
[1] C. Mannironi, A. Di Nardo, P. Fruscoloni, G.P. Tocchini-Valentini, Biochemistry, 36 (1997) 9726-9734. [2] I. Álvarez-Martos, E.E. Ferapontova, Anal. Chem., 88 (2016) 3608-3616. [3] I. Álvarez-Martos, R. Campos, E.E. Ferapontova, Analyst, 140 (2015) 4089-4096. [4] E.E. Ferapontova, K.V. Gothelf, Langmuir, 25 (2009) 4279-4283.
< Back to Programme 25 TUESDAY 4 JULY Session IV: Optical sensing (I) 9:00-9:40 PLENARY 3
MOBILE MICROSCOPY, SENSING AND DIAGNOSTICS THROUGH COMPUTATIONAL PHOTONICS
Aydogan Ozcan, Ph.D. Electrical Engineering Department, Bioengineering Department, California NanoSystems Institute University of California, Los Angeles, CA [email protected] ; http://innovate.ee.ucla.edu/ ; http://org.ee.ucla.edu/
My research focuses on the use of computation/algorithms to create new optical microscopy, sensing, and diagnostic techniques, significantly improving existing tools for probing micro- and nano-objects while also simplifying the designs of these analysis tools. In this presentation, I will introduce a new set of computational microscopes which use lens-free on-chip imaging to replace traditional lenses with holographic reconstruction algorithms. Basically, 3D images of specimens are reconstructed from their “shadows” providing considerably improved field-of-view (FOV) and depth-of-field, thus enabling large sample volumes to be rapidly imaged, even at nanoscale. These new computational microscopes routinely generate >1–2 billion pixels (giga-pixels), where even single viruses can be detected with a FOV that is >100 fold wider than other techniques. At the heart of this leapfrog performance lie self- assembled liquid nano-lenses that are computationally imaged on a chip. These self-assembled nano- lenses are stable for >1 hour at room temperature, and are composed of a biocompatible buffer that prevents nano-particle aggregation while also acting as a spatial “phase mask.” The field-of-view of these computational microscopes is equal to the active-area of the sensor-array, easily reaching, for example, >20 mm2 or >10 cm2 by employing state-of-the-art CMOS or CCD imaging chips, respectively. In addition to this remarkable increase in throughput, another major benefit of this technology is that it lends itself to field-portable and cost-effective designs which easily integrate with smartphones to conduct giga-pixel tele-pathology and microscopy even in resource-poor and remote settings where traditional techniques are difficult to implement and sustain, thus opening the door to various telemedicine applications in global health. Some other examples of these smartphone-based biomedical tools that I will describe include imaging flow cytometers, immunochromatographic diagnostic test readers, bacteria/pathogen sensors, blood analyzers for complete blood count, and allergen detectors. Through the development of similar computational imagers, I will also report the discovery of new 3D swimming patterns observed in human and animal sperm. One of this newly discovered and extremely rare motion is in the form of “chiral ribbons” where the planar swings of the sperm head occur on an osculating plane creating in some cases a helical ribbon and in some others a twisted ribbon. Shedding light onto the statistics and biophysics of various micro-swimmers’ 3D motion, these results provide an important example of how biomedical imaging significantly benefits from emerging computational algorithms/theories, revolutionizing existing tools for observing various micro- and nano-scale phenomena in innovative, high-throughput, and yet cost-effective ways.
< Back to Programme 26 TUESDAY 4 JULY Session IV: Optical sensing (I) 9:40-10:10 KEYNOTE 5
TOWARDS THE DEVELOPMENT OF RELIABLE OPTICAL LABEL-FREE POINT-OF-CARE (POC) BIOSENSING DEVICES M. Holgado1,2,3, María V. Maigler1,2, Beatriz Santamaría1,2, S. Quintero1, Y. Ramírez1,3, Rocío L. Espinosa1, Francisco J. Sanza1,3, A.L. Hernández1, David López-Romero3, R. Casquel1,2, Álvaro Lavín1,2, M. Domimngo3, M. Vicente3, María F. Laguna1,2,3 1.- Centro de Tecnología Biomédica, Universidad Politécnica de Madrid. 2.- Depto. de Física Aplicada, Escuela Técnica Superior de Ingenieros Industriales, Universidad Politécnica de Madrid 3.- Bio Optical detection S.L.
In-Vitro Diagnostics (IVDs) technology is of a highly relevant for many sectors. Among many of them can be mentioned: healthcare, clinical, agro-food, environmental, pharmaceutical research or drug discovery. Most of the IVD systems are based on labeled technologies such as ELISA tests or lateral flow devices. Significant advantages are being described for label-free biosensing technology. However, still a limited number of label-free-based biosensing PoCs are adopted for the IVD marked, although further developments, efforts and improvements are continuously reported in the literature. Modern ELISA-based tests offer undoubtedly a competitive LoD and can be considered the as a goal standard for immunoassay technology. Thus, the challenge for label-free PoC devices is to achieve a competitive LoD avoiding this chemical amplification and working with simple drops of samples in an easy-to- use manner. Thus, being the LoD the main figure of merit to compare PoCs, it is worthy to mention that this figure can be improved mainly by enhancing the transducer sensitivity or by reducing the uncertainty of the PoC readout systems. In this paper we attempt to discuss how can be improved the LoD of optical label-free biosensing systems considering both: the transducers and the optical readers to offer a better performance in optical label-free PoCs.
< Back to Programme 27 TUESDAY 4 JULY Session IV: Optical sensing (I) 10:10-10:25 ORAL 9
COMPUTATIONAL STUDY ON THE SPME FIBER SELECTIVITY FOR HEAD SPACE GAS CHROMATOGRAPHIC DETERMINATION OF COMMONLY USED PESTICIDES Hasan Ertaş, Tuğberk N. Dizdaş, Armağan Kınal, Levent Pelit, Fusun. Pelit, F.Nil Ertaş Ege University, Science Faculty, Chemistry Department, Bornova İzmir TURKEY [email protected]
As a green extraction method, solid phase microextraction (SPME) is becoming more popular due to its efficiency for attaining low detection limits and to extract analyte compounds having a wide range of polarities [1]. To reduce the cost and improve the selectivity, a number of studies have been published in the last decade on the fabrication of novel fiber coatings by electrochemical deposition from a variety of monomers [2]. Present study describes the use of lab-made fibers for the HS-SPME determination of selected pesticides having different polarities namely; chlorpyrifos (CP), Penconazole (PNZ), Procymidone (PRC), bromopropylate (BRP) and lambda cyhalothrin (LMD). The performances of the fibers prepared by electropolymerization of pyrrole, thiophene and their mixture, aniline and 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl) benzenamine were evaluated by comparing the GC- ECD chromatograms. It was revealed that the type of fibers significantly affect the actual response. In addition, gas phase adsorptions of the pesticides on the modelled polymer surfaces were computationally investigated with recently developed semi empirical PM6-D3H4X method that can account for the weak nonbonding interactions, and their surface binding enthalpies were determined. MOPAC 2016 semi empirical program suite has been used throughout the study. Theoretical surface binding enthalpies and the experimental findings agree well with each other for the pesticides with different polymer surfaces. It can be concluded that the more tightly bound pesticides to surface, the higher the signal was observed.
Acknowledgements: Authors thank to TUBITAK (114Z394) for financial support.
References
[1] J. Pawliszyn, Solid Phase Microextraction: Theory and Practice, Wiley, 1997. [2] K. Korba, L. Pelit, F. Pelit,K. V. Özdokur, H. Ertaş, A. E. Eroğlu, F. N. Ertaş, J. Chrom. B, 929 (2013) 90– 96
< Back to Programme 28 TUESDAY 4 JULY Session IV: Optical sensing (I) 10:25-10:40 ORAL 10
NOVEL INTERFEROMETRIC NANOSENSOR FOR CO2 DETECTION USING NANOZIF-8 MOFS AS SPECIFIC RECEPTORS B. Chocarro-Ruiz, J. Pérez, D. Maspoch, L. M. Lechuga Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, The Barcelona Institute of Science and Technology, Campus UAB, Ed-ICN2, 08193 Bellaterra, Barcelona, Spain. [email protected]
Despite the strong advances in the field of sensing and analytical techniques, the specific and fast control of a large number of environmental pollutants is still challenging. This is mainly due to the lack of analytical tools which, in addition to being fast, accurate and reliable, have an affordable cost and, more importantly, bare selective. For this reason, we have developed a novel photonic nanosensor, using a new class of nanoporous materials, the so-called Metal-Organic Frameworks (MOFs)1, as receptors for the rapid and selective detection of carbon dioxide as a control parameter for environmental monitoring. The nanosensor transducer is based on highly sensitive heteromodal waveguides2 and the receptors are transparent nanoZIF-8, made by zinc ions clusters coordinated by four imidazolate rings. The MOF layer is deposited by spin-coating and permanently attached to the sensor surface through a PDMS layer (Figure 1). Preliminary results show a limit of detection around 1% of CO2 and selectivity
for CO2 versus N2. Each measure-regeneration cycle takes less than a minute. The process is reversible and the sensor surface is stable for more than one month.
References
[1] Lehn, J.-M., “Toward complex matter: supramolecular chemistry and self-organization.” Proc. Natl. Acad. Sci. U. S. A. 99(8), 4763–4768, National Academy of Sciences (2002). [2] Zinoviev, K. E., González-Guerrero, A. B., Domínguez, C.., Lechuga, L. M., “Integrated bimodal waveguide interferometric biosensor for label-free analysis” J. Light. Technol. 29(13), 1926–1930, IEEE (2011).
< Back to Programme 29 TUESDAY 4 JULY Session IV: Optical sensing (I) 10:40-10:55 ORAL 11
MAGNETICALLY ASSISTED SURFACE ENHANCED RAMAN SPECTROSCOPY (MA-SERS) AS A PROMISING TOOL IN A FAST SCREENING OF BIOMARKERS Vaclav Ranc, Anna Balzerova, Ariana Fargasova, Zuzana Chaloupkova, Radek Zboril Regional Centre of Advanced Technologies and Materials, Department of Experimental Physics and Physical Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, 771 46 Olomouc, Czech Republic. [email protected]
Nowadays tendencies in medicine accompanied by an extensive development on the fields of molecular biology and physiology lead to increased demands for fast and reliable analytical procedures aimed at the screening of compounds frequently present in complex matrixes at ultra-trace concentration levels. Magnetically assisted surface enhanced Raman spectroscopy (MA-SERS) belongs between interesting alternatives to already established techniques.1,2 MA-SERS technique utilizes surface functionalized nanostructures, composed of noble metal nanocrystals and magnetic nanoparticles. This combination allows a simple magnetic separation of targeted compounds, and their follow-up analysis by surface enhanced Raman spectroscopy with limits of detection often lower than units of ng/L. We have developed MA-SERS based analytical protocols for the analysis of physiologically active compounds, including dopamine in brain tissue and cerebrospinal fluid, immunoglobulin G in a single drop of whole human blood and prostate-specific membrane antigen (PSMA) in human plasma.3,4 In this work, case studies covering MA-SERS based multiplex analysis of nucleic acids and cancer biomarkers will be demonstrated. Analysis of a total content of DNA and RNA in cancerous tissues was performed using magnetic Fe3O4@Ag@chlorambucil nanocomposite. Similarly, EpCAM and Her2 cancer biomarkers were analyzed in whole human blood using Fe3O4@anti-EpCAM and Fe3O4@Anti- Her2 nano-structures.
References
[1] Shi, Z.; Wang, T.; Lin, H.; Wang, X.; Ding, J.; Shao, M. Nanoscale, 20, (2013) 10029. [2] Song, J.; Duan, B.; Wang, C.; Zhou, J.; Pu, L.; Fang, Z.; Wang, P.; Lim, T. T.; Duan, H. J. Am. Chem. Soc., 19, (2014), 6838. [3] Ranc, V.; Markova, Z.; Hajduch, M.; Prucek, R.; Kvitek, L.; Kaslik, J.; Safarova, K.; Zboril, R. Anal. Chem.,6, (2014), 2939. [4] Balzerova, A.; Fargasova, A.; Markova, Z.; Ranc, V.; Zboril, R. Anal. Chem., 22, (2014), 11107.
< Back to Programme 30 TUESDAY 4 JULY Session V: Optical sensing (II) 11:25-11:55 KEYNOTE 6
MICROFLUIDIC FULL SOLUTIONS FOR POC-IVD AND DRUG DELIVERY Francisco Blanco CBDO & Co-Founder - MICROLIQUID
The volume of point-of-care testing (PoCT) has steadily increased over the 40 or so years since its widespread introduction. That growth is likely to continue, driven by changes in healthcare delivery which are aimed at delivering less costly care closer to the patient’s home. In the developing world there is the challenge of more effective care for infectious diseases and PoCT may play a much greater role here in the future. Microfluidic devices are entering in this huge market, include those that are utilising in biosensor or molecular techniques (such as PCR ) to provide infectious disease testing in a sufficiently small device to be used at the point of care. These areas are likely togrowwith many devices being developed and likely to reach the commercial market in the next few years. In this presentation, microLIQUID will introduce how is working with IVD companies in order to reduce time-to-market of these new approaches and/or manufacturing these novel products under the high quality standards that this sector demands.
< Back to Programme 31 TUESDAY 4 JULY Session V: Optical sensing (II) 11:55-12:25 KEYNOTE 7
SYNTHESIS AND USE OF ISOTOPICALLY ENRICHED QUANTUM DOTS FOR THE ASSESSMENT OF NANOPARTICLES-BIOMOLECULE INTERACTIONS José M. Costa-Fernández*, Mario Menéndez Miranda, Jorge Ruiz, Alfredo Sanz-Medel. Department of Physical and Analytical Chemistry, University of Oviedo, Oviedo (Asturias), Spain * [email protected]
Life science applications of functionalized inorganic nanoparticles (NPs) involve dispersions of such materials in biological fluids, which typically contain high amounts of ions and biomolecules. Such conditions may lead to the formation of a protein adsorption layer (known as “protein corona”) on the surface of colloidal nanoparticles, which plays an important role in their interaction with living matter. The assessment of the interactions between engineered NPs and biomolecules that can be present in biological fluids is of utmost importance for understanding how exposure to nanoparticles affects the biological responses of cells and organisms. On the other hand, the increasing useof NPs in imaging studies and in the design of platforms for controlled drug delivery typically requires the bioconjugation of nanoparticles to antibodies (against specific biomarkers) for active targeting. Though many approaches have been reported in this direction, the controlled bioconjugation of NPs, a key issue to achieve a success in such applications, is still a challenge [1]. In this context, here we present the results on synthesis of isotopically enriched (aprox. 95%, 34S) CdSe/ ZnS quantum dots (QDs) and its application in the investigation of protein-nanoparticle association and in the study of the bioconjugation efficiency of the QDs to a model biomolecule. For such purpose, in a first experiment, a known concentration of QDs were incubated with different concentrations of Bovine Serum Albumin protein (BSA). After separation of the unbounded BSA by ultrafiltration, the amount of protein associated to the nanoparticles (in terms of number of protein per nanoparticle) were estimated just by measuring, with high accuracy, the molar ratio between the 32S and 34S in the colloidal sample. Such approach also allowed the characterization of the bioconjugation product after chemical reaction of a “model” biomolecule (biotin) with the QDs.
References
[1] J. M. Montenegro, V. Grazu, A. Sukhanova, S. Agarwal, J. M. de la Fuente, I. Nabiev, A. Greiner and W. J. Parak, Adv. Drug Deliv. Rev., 65 (2013) 677 – 688.
< Back to Programme 32 TUESDAY 4 JULY Session V: Optical sensing (II) 12:25-12:40 ORAL 12
BIOFUNCTIONALIZATION AS KEY STEP IN BIOSENSOR APPLICATIONS FROM R&D TO HIGHTHROUGHPUT MANUFACTURING Wilfried Weigel, Alba Simon Munoz and Holger Eickhoff Scienion AG, Volmerstrasse 7b, Berlin, Germany [email protected]
Array based analytics have evolved into powerful tools for high-throughput multiplex analysis of a variety of classes of substrates as DNA, proteins, peptides, glycans, the detection of small molecule and screening of polymer properties. Further development of this technology focuses on new components and methods as surface functionalized substrates, probe deposition techniques, strategies of probe immobilization, target preparation and incubation as well as label and label free detection methods to im-prove sensitivity, reproducibility and to minimize material consumption. The transfer of these systems from open R&D platforms using e.g. microscopic slides to cartridge systems using fully integrated microfluidic chips or biosensors is another goal to enable fully automated diagnostics in the clinical laboratory and Point of Care applications. A key step in the development of such systems is the biofunctionalization that consists of chemical functionalization of the supports to introduce reactive moieties, deposition of the probes and the subsequent immobilization reaction. All steps of this workflow widely depend on the design of the biosensors as the material and requirements related to the detection technology. Printing of probes on biosensors requires highly exactly spotting at predefined sensor elements based on optical detection of fiducials. The sensors are imbedded in microfluidic chips made of special polymer materials and of complex geometries. They can carry regions of different wettabilities and surface func-tionality designed for fluidic function, reagent storage and capture probe immobiliza-tion. We will present recent results of our picoliter printing technology for reagent deposi-tion on biosensors and into microfluidic cartridges. The presentation will also focus on a new hydrogel immobilization technology that allows immobilization of capture probes on the sensor elements without prior surface functionalization. Application ex-amples for detection of microRNAs using CMOS and microfluidic chips will be pre-sented.
References
[1] Cancer-Cells on Chip for Label-Free Detection of Secreted Molecules, Ophélie I. Berthuy, Loic J. Blum, and Christophe A. Marquette, biosensors 2016; 6 [2] Inkjet printing for biosensor fabrication: combining chemistry and technology for advanced manufacturing, Jia Li, Fabrice Rossignol, and Joanne Macdonald, The Royal Society of Chemistry 2015, Lab Chip, DOI:10.1039/c5lc00235d [3] Autoassembly Protein Arrays for Analyzing Antibody Cross-Reactivity, Richard S. Gaster, Drew A. Hall, and Shan X. Wang, Nano Lett. 2011 July 13; 11(7): 2579–2583. Published online 2010 August 30. doi: 10.1021/nl1026056 [4] Quantification of Protein Interactions and Solution Transport Using High-Density GMR Sensor Arrays, Richard S. Gaster, Liang Xu, Shu-Jen Han, Robert J. Wilson, Drew A. Hall, Sebastian J. Osterfeld, Heng Yu, and Shan X. Wang, Nat Nanotechnol. 2011 May; 6(5): 314–320. Published online 2011 April 10. doi: 10.1038/nnano.2011.45 [5] Analysis of Inflammatory Biomarkers by Arrayed Imaging Reflectometry, Jared A. Carter, Sourabh D. Mehta, Michael V. Mungillo, Christopher C. Striemer, and Benjamin L. Miller Jared A. Carter, Sourabh D. Mehta, Michael V. Mungillo, Christopher C. Striemer, and Benjamin L. Miller, Biosens Bioelectron. Published online 2011 February 24. doi: 10.1016/j.bios.2011.02.025 [6] Polysaccharide microarrays with a CMOS based signal detection unit, Baader J, Klapproth H, Bednar S, Brandstetter T, Rühe J, Lehmann M, Freund I., Biosens Bioelectron. 2011 Jan 15;26(5):1839-46. Epub 2010 Jan 28. [7] CMOS-Integrated Film Bulk Acoustic Resonators for Label-Free Biosensing, Martin Nirschl, Arto Rantala, Kari Tukkiniemi, Sanna Auer, Ann-Charlotte Hellgren, Dana Pitzer, Matthias Schreiter, and Inger Vikholm-Lundin, Sensors 2010, 10, 4180-4193; doi:10.3390/ s100504180 [8] Mass-transport limitations in spot-based microarrays, Ming Zhao, Xuefeng Wang, and David Nolte, Biomed Opt Express. 2010 October 1; 1(3): 983–997. [9] Quantification of DNA and Protein Adsorption by Optical Phase Shift, Emre Özkumur, Ayça Yalçýn, Marina Cretich, Carlos A. Lopez, David A. Bergstein, Bennett B. Goldberg, Marcella Chia-ri, and M. Selim Ünlü, Biosens Bioelectron. Author manuscript; available in PMC 2010 September 15. [10] Dosieren im Pikoliterbereich: Was heute machbar ist, Holger Eickhoff, Mikrofluidik. 2010 September: 34-36 < Back to Programme 33 TUESDAY 4 JULY Session V: Optical sensing (II) 12:40-12:55 ORAL 13
DETERMINATION OF THE STOICHIOMETRY QUANTUM DOT TO ANTIBODY IN BIOCONJUGATES BY AF4 COUPLED ON-LINE TO ELEMENTAL MASS SPECTROMETRY Diego Bouzas-Ramos, Jorge Ruiz Encinar, José M. Costa-Fernández, Alfredo Sanz-Medel Department of Physical and Analytical Chemistry, University of Oviedo, Julián Clavería 8, Oviedo, Spain [email protected]
A key issue in development of analytical and bioanalytical photoluminescent quantum dots (QDs) applications is the appropriate control of the bioconjugation reaction. Particularly, the analytical potential of QDs to be used as labels for the quantitative analysis of biomolecules will require for the determination of the number of antibodies or recognition units attached per nanoparticle. In this context, the hybridation of the asymmetric flow field-flow fractionation (AF4), which is one of the most promising separation techniques able to achieve size-dependent separation of nanoparticles and biomolecules, with an inductively coupled plasma-mass spectrometry (ICP-MS) could provide invaluable capabilities and information to achieve the intended purpose. In this work, the AF4 coupled on-line to ICP-MS is proposed as a powerful diagnostic tool for QDs bioconjugation studies. In particular, the determination of QDs stoichiometry in bioconjugates (between a monoclonal IgG antibody (Ab) and CdSe/ZnS core-shell QDs, which are surface-coated with an amphiphilic polymer) has been monitored by such hyphenated technique. Experimental conditions have been optimized searching for an appropriate separation between the sought bioconjugates from the eventual free QDs and antibodies excesses employed during the bioconjugation reaction. Moreover, ICP-MS was selected as elemental detector to enable sensitive and reliable simultaneous quantification of the elemental constituents of the QD-Ab bioconjugates, and the free QDs and Ab. The hybrid AF4-ICP-MS technique used provided nanoparticle size-based separation and elemental detection analysis that turned out not only to investigate in depth the bioconjugation process but also to determine and quantify the stoichiometry QD:Ab in different bioconjugates assessed (including a commercially available sample of QD conjugates).
< Back to Programme 34 TUESDAY 4 JULY Session V: Optical sensing (II) 12:55-13:10 ORAL 14
ELEMENT-TAGGED IMMUNOASSAY WITH (LA)ICP-MS FOR THE DETERMINATION/DISTRIBUTION OF MMP-11 IN BREAST CANCER PATIENTS Patricia Abásolo Linares*a, Mª Luisa Fernández Sáncheza, Marcos García Ocañac, Raquel González de Vegaa, Noemí Eirób, Francisco J. Vizosob, Alfredo Sanz Medela a. Department of Physical and Analytical Chemistry, University of Oviedo, Spain b. Research Unit, Hospital de Jove Foundation, Gijón, Spain c. Unit of Biotechnological and Biomedical Tests, University of Oviedo, Spain [email protected]
The extracellular matrix metalloproteinases (MMPs) are a family of 28 zinc-dependent endopeptidases, which are involved in physiological processes such as embryonic development, reproduction and tissue remodeling, as well as in disease processes such as arthritis and metastasis [1]. The main functions of these MMPs are the degradation of the stromal connective tissue and basement membrane components which are key elements in tumor growth, invasion, metastasis and angiogenesis [1]. In healthy individual tissues the activity of the MMPs is regulated by specific endogenous tissue inhibitors (TIMPs). However, in cancerous tissues the MMPs are overexpressed. Moreover, accumulating evidence indicates that diverse inflammatory cells could exert pro-tumor functions, as they secrete metalloproteinases that stimulate angiogenesis as well as the proliferation, migration and invasive potential of cancer cells [2]. Therefore, MMPs can be candidates as diagnostic biomarkers and functional analysis has to be designed and carried out in order to confirm their actual role in breast cancer (BC) patients. In particular, MMP-11 is expressed in stromal compartment of malignant tumors, and high levels of this MMP are associated with tumor progression and poor prognosis of BC [2]. Thus, MMP-11 levels in tissues or blood could be a prognostic biomarker of BC. Accordingly, the aims of this work are firstly the development of new strategies, based on an immunoassay with ICP-MS, for highly sensitive determination of the MMP-11 levels in serum and inflammatory cells from breast cancer patients. In this vein, an ELISA sandwich immunoassay with Au-labeled secondary antibody has been developed. Secondly, this immunoassay has been applied to study the distribution of MMP-11 in breast cancer tissues by LA-ICP-MS
References
[1] Cascales Angosto, M. et al., An. R. Acad. Nac.Farm., 76 (1): (2010), 59-84. [2] Eiró, N. et al., OncoImmunology, 2:5 e24010 (2013).
< Back to Programme 35 TUESDAY 4 JULY Session V: Optical sensing (II) 13:10-13:25 ORAL 15
SYNTHESIS AND CHARACTERIZATION OF WATER-SOLUBLE NIR-EMITTING QUANTUM DOTS: BIOANALYTICAL APPLICATIONS Pablo Llano-Suárez*a, Diego Bouzas-Ramosa, José M. Costa-Fernándeza, Ana Belén Soldadob, Alfredo Sanz-Medela a. Department of Physical and Analytical Chemistry, University of Oviedo, Oviedo (Asturias), Spain b. Department of Animal Nutrition, Grassland and Forages, Regional Institute for Research and Agro-Food Development (SERIDA), Villaviciosa (Asturias), Spain *[email protected]
Photoluminescence can be considered nowadays a routine technique in bioanalysis. Traditionally, organic fluorophore markers have been used for fluorescence analysis, but in recent times Quantum Dots (QDs) have been of increasing interest, as they present several important advantages such as long luminescence lifetimes, improved photostability and high sensitivity. However, most work done with QDs make use of nanoparticles emitting in the UV-Vis spectral range. Thus, applicability of such QDs for biological applications is hindered by self-fluorescence of biological media, increasing the luminescence background and affecting the sensitivity. In this work, Near-Infrared Emitting Quantum Dots (NIR QDs) were synthesized and extensively characterized. Using the NIR window (700-900 nm) allows us to bypass the quenching effect that water, and therefore biological samples, presents in the visible region (400–700 nm). Ag2S NIR QDs were selected due to their reported low band gap and potential for cytocompatibility. Synthesized using a one-pot approach in aqueous solution and optimized to obtain maximum quantum yield at
λem≈800 nm when excited at λex=530 nm, Ag2S QDs present lifetime upwards of 6 months, and were characterized using Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD), Asymmetric Flow Field Flow Fractionation (AF4) and Inductively-Coupled Plasma Mass Spectrometry (ICP-MS). Due to their simple synthesis, long lifetime, appropriate photoluminescent properties and high cytocompatibility, Ag2S QDs show a promising future for the development of immunosensing and direct analysis. Here we present the development of a sensing material for control of dissolved cyanide and heavy metals by immobilizing the synthesized Ag2S QDs in a sol-gel matrix.
< Back to Programme 36 TUESDAY 4 JULY Session VI: Optical sensing (III) 15:00-15:40 PLENARY 4
SEMICONDUCTOR NANOWIRES FOR SENSING Anna Fontcuberta i Morral Laboratory of Semiconductor Materials, Institute of Materials, EPFL, Lausanne, Switzerland [email protected]
Nanowires are filamentary crystals with a tailored diameter in the few to 100 nm range. Their special morphology and shape renders them especially suited for photonic and opto-mechanical applications. In this presentation we will show how the photonic properties of nanowires renders them ideal to capture light very efficiently [1], which allows us to elaborate on their use in solar cells and biosensors [2,3]. Finally we will address how these nanowires can be used as atomic force microscopy tips and how their hexagonal cross-section can be used to sense and map electrical fields at the nanoscale [4].
References
[1] P. Krogstrup et al, Nature Photonics, 7, (2013) 306. [2] R. S. Frederiksen, E. Alarcon-Llado et al. ACS Photonics, 3, (2016) 1208. [3] R. S. Frederiksen, E. Alarcon-Llado et al. Nano Letters, 15, (2015) 176. [4] N. Rossi, et al. Nature Nanotechnology, 12, (2017) 150.
< Back to Programme 37 TUESDAY 4 JULY Session VI: Optical sensing (III) 15:40-16:10 KEYNOTE 8
ENHANCING PLASMONIC DETECTION WITH HOLLOW NANOCRYSTALS Victor Puntes Catalan Institute de Nanotechnology, Barcelona, Spain, Vall d Hebron Institute of Recerca, Barcelona, Spain, Institut Català de Recerca i Estudis Avançats, Barcelona, Spain. [email protected]
Metallic nanostructures have received great attention due to their ability to generate surface plasmon resonances, which are collective oscillations of conduction electrons of a material excited by an electromagnetic wave. Plasmonic metal nanostructures are able to localize and manipulate the light at the nanoscale and, therefore, are attractive building blocks for various emerging applications. In particular, hollow nanostructures are promising plasmonic materials as cavities are known to have better plasmonic properties than their solid counterparts thanks to the plasmon hybridization mechanism [1,2]. The hybridization of the plasmons results in the enhancement of the plasmon fields along with more homogeneous distribution as well as the reduction of LSPR quenching due to absorption. Examples of the applications, i.e. sensing, surface enhanced Raman spectroscopy, photothermal ablation therapy of cancer, drug delivery or catalysis among others, where hollow nanostructures perform better than their solid counterparts, are also of importance.
References
[1] A Genç, J Patarroyo, J Sancho-Parramon, NG Bastús, V Puntes, J Arbiol Hollow metal nanostructures for enhanced plasmonics: synthesis, local plasmonic properties and applications Nanophotonics 6 (1), 2017, 193. [2] A Genc, J Patarroyo, J Sancho-Parramon, R Arenal, M Duchamp et al. Tuning the plasmonic response up: Hollow cuboid metal nanostructures ACS Photonics 3 (5), 2016, 770
< Back to Programme 38 TUESDAY 4 JULY Session VI: Optical sensing (III) 16:10-16:25 ORAL 16
METALLIC NANOSTRUCTURES BASED ON BLU-RAY DISCS FOR MULTIPLEXED PLASMONIC BIODETECTION Gerardo A. López-Muñoza,b, M. Carmen Estevezb,a, Antoni Homs-Corberaa, M. Berenguel-Alonsoc, J. Alonso-Chamarroc and Laura M. Lechugaa,b a. Nanobiosensors and Bioanalytical Applications Group (NanoB2A), Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of Science and Technology, 08193 Bellaterra (Barcelona), Spain b. CIBER-BBN Networking Center on Bioengineering, Biomaterials and Nanomedicine, Spain c. Sensors & Biosensors Group, Department of Chemistry, Autonomous University of Barcelona, Edifici Cn, 08193 Bellaterra, (Barcelona), Spain [email protected]
Nanostructure-based plasmonic biosensors have quickly positioned themselves as interesting candidates for the design of portable optical biosensor platforms considering the potential benefits they can offer in miniaturization, multiplexing, real-time and label-free detection [1]. Wehave developed a simple integrated nanoplasmonic sensor taking advantage of the periodic nanostructured array of commercial Blu-ray discs [2]. Sensors with different metallic film layers (50 and 100 nm) were fabricated and optically characterized by varying the oblique-angle of the incident light in optical reflectance measurements. We observed an enhancement in sensitivity and a narrowing of the resonant linewidths as the light incidence angle was increased, which could be related to the generation of Fano resonant modes. The new sensors achieve a figure of merit (FOM) up to 35 RIU-1 and a competitive bulk limit of detection (LOD) of 6.34×10-6 RIU. Based on these structures, a single- channel sensor in a 1cm2 integrated chip has been designed an incorporated in a compact biosensor prototype. The label-free biosensing capability of the new sensor has been assessed by evaluating the presence of specific antibodies against the GTF2b protein, a tumor-associate antigen (TAA) related to colorectal cancer. We have achieved a LOD in the pM order and have evaluated the feasibility of directly measuring biological samples such as human serum. The design has been transferred and adapted to a multiplexed prototype incorporating a sensor chip with four integrated channels. The optical and the sensing performance have been evaluated. We have assessed bulk sensitivity and attempted real-time biosensing measurements, obtaining good reproducibility between the channels.
References
[1] Lopez, G.A., Estevez, M.-C., Soler, M., Lechuga, L.M. Nanophotonics. 6, (2017), 123-136. [2] Guner, H., Ozgur, E., Kokturk, G., Celik, M., Esen, E., Topal, A.E., Ayas, S., Uludag, Y., Elbuken, C., Dana, A. Sensors & Actuators B: Chemical. 239, (2017), 571-577.
< Back to Programme 39 TUESDAY 4 JULY Session VI: Optical sensing (III) 16:25-16:40 ORAL 17
COMPLEMENTARY TECHNIQUES TO STUDY GOLD NANOPARTICLES TRANSFORMATIONS IN CELL CULTURE MEDIUM Sara López-Sanza, Nuria Rodríguez Fariñasa, Rosa del Carmen Rodríguez Martín-Doimeadiosa, Ángel Ríos Castrob a. Faculty of Environmental Sciences and Biochemistry, University of Castilla-La Mancha, Avda. Carlos III s/n, 45071 Toledo, Spain. b. Faculty of Chemical Sciences and Technologies, University of Castilla-La Mancha, Avda. Camilo José Cela s/n, 13071 Ciudad Real, Spain. [email protected]
Gold nanoparticles (AuNPs) are used for biomedical applications but their impacts on human health and the environment are not fully known. The study of the AuNPs toxicity addresses these concerns, but special attention should be paid during these studies to the AuNPs transformations and interactions with the matrix components. Therefore, it is necessary the characterization of AuNPs in complex matrices such as the cell culture medium used in toxicological studies. For this purpose, the coupling of hydrodynamic separation techniques with elemental specific detectors begin to play a decisive role but they are still under development. In the present work, an analytical strategy based on asymmetric flow field flow fractionation (AF4) hyphenated to inductively coupled plasma mass spectrometry (ICP-MS) have been used to study the AuNPs transformation in a cell culture medium widely used (Dulbecco’s Modified Eagle Medium, DMEM). The selection of the dimensions ofthe channel, the characteristics of the membrane, and the optimization of the carrier composition and the perpendicular rate flow (cross flow) were fundamental to obtain reproducible results and high recoveries. The oxidation of AuNPs and the increase in the hydrodynamic volume were observed by AF4-ICP-MS. The change in the size suggests that AuNPs and gold ion (Au3+) could be coated by biomolecules present in the cell culture medium. These results were validated using complementary techniques. Transmission electron microscopy (TEM) confirmed the increase of AuNPs size and the change in size distribution. The centrifugal ultrafiltration allowed to distinguish between the species of Au3+ and AuNPs. Moreover, Au3+ release from AuNPs was observed by HPLC-ICP-MS.
Acknowledgements: Project MINECO CTQ-2016-78793-P and pre-doctoral contract MINECO BES-2014-069095.
< Back to Programme 40 TUESDAY 4 JULY Session VI: Optical sensing (III) 16:40-16:55 ORAL 18
GOLD-CORE, MIP-SHELL (AU@MIP) SURFACE-ENHACED RAMAN SCATTERING (SERS) NANOSENSORS FOR ANTIBI-OTIC DETECTION Sergio Carrascoa, Elena Benito-Peñaa, Marta N. Sanz-Ortizb, Javier Reguerab, Fernando Navarro-Villosladaa, Luis M. Liz-Marzánb,*, María Cruz Moreno-Bondia,* a. Dpt. Analytical Chemistry, Universidad Complutense de Madrid, Madrid (Spain) b. Bionanoplasmonics Laboratory, CIC biomaGUNE, Donostia-San Sebastián (Spain) [email protected]; [email protected]
Herein we describe the development of enrofloxacine (ENRO) responsive gold-core, molecularly imprinted polymer (MIP) shell (Au@MIP) nanoparticles and their application as label free nanosensors for the specific detection of the fluoroquinolone by surface-enhanced Raman scattering (SERS). The design of SERS sensing platforms requires a careful control of both electronic and chemical effects. The intensity of the SERS signal will be strongly affected by the composition, size and shape of the optical substrates, but also by the distance between the target molecules and the metallic nanoparticles. In order to evaluate the effect of the morphology of the gold nanostructure on the optical and spectroscopic response of the hybrid nanosensors, Gold nanstructures with different shapes, namely gold nanostars (GNSs), gold nanorods (GNRs) and multi-branched gold nanospheres (bGNSs) were prepared to investigate the effect of their morphology on the optical and spectroscopic response of the hybrid nanosensors.1 The metallic cores were then covered with a nanometric sol-gel layer and
with a thin MIP shell (Au@SiO2@MIP) in a second step, to facilitate the selective retention of the target antimicrobial onto the optical enhancer. The use of bGNSs cores resulted in a dramatic enhancement of the SERS signal upon ENRO rebinding thas was attibuted to the presence of hot spots2 in close proximity to the MIP binding sites. The
optimized nanostructures (bGNS@ SiO2@MIPs) yielded detection limits of 1.5 nM for ENRO, two orders of magnitude lower than other previously reported plasmonic nanosensors based on MIPs.3
Acknowledgements: S. Carrasco thanks the Ministry of Education, Culture and Sport for a doctoral grant (FPU). Financial support from CTQ2015-69278-C2-1-R MINECO/FEDER.
References
[1] M.N. Sanz-Ortiz, K. Sentosun, S. Bals, L.M. Liz-Marzán, ACS Nano 9 (2015) 10489. [2] L. Brus, Accounts Chem. Res. 41 (2008) 1742. [3] S. Carrasco, E. Benito-Peña, M.N. Sanz-Ortiz, J. Reguero, F. Navarro-Villoslada, L.M. Liz-Marzán, M.C. Moreno-Bondi, Chem. Mat, 28 (2016) 7947.
< Back to Programme 41 TUESDAY 4 JULY Session VII: Optical sensing (IV) 17:25-17:55 KEYNOTE 9
NOVEL AND VERSATILE APPROACHES FOR DNA-BASED NANOSENSING BASED ON NUCLEIC ACID TRIPLEX FORMATION Ramon Eritja1,2, Laura Lechuga2,3, César S. Huertas2,3 and Anna Aviñó1,2 1. Institute for Advanced Chemistry of Catalonia (IQAC), CSIC, Jordi Girona 18-26, 08034 Barcelona. Spain 2. Networking Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN) 3. Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, ICN2 Building, Campus UAB 08193 Bellaterra, Barcelona, Spain Email: [email protected]
DNA is an ideal molecule for sensing not only because of its specificity but also because they can be prepared and modified with high efficiency and selectivity. DNA nanostructure-based sensors may provide highly specific detection based on the molecular recognition properties of DNA as well as the possibility of developing specific aptamers for biologically relevant molecules [1]. Some time ago, our group reported the triplex-stabilizing properties of 8-aminopurines [2] and the use of parallel and antiparallel tail clamps to increase the efficiency of triplex formation with structured DNA and RNA targets [3,4]. This knowledge has been recently applied to develop novel DNA detection techniques based on the stability of triplex by using tail-clamps carrying 8-aminopurines as bioreceptor. In the present communication we will describe the optimization of these methods for the detection of bacterial mRNA [5] as well as miRNAs [6].
References
[1] Chandrasekaran, A.R., Wady, H., Subramanian, H.K. Small, 2016, 12, 2689-2700. [2] Soliva, R., Güimil García, R., Blas, J.R., Eritja, R., Asensio, J.L., González, C., Luque, F.J., Orozco, M. Nucleic Acids Res., 2000, 28, 4531-4539. [3] Aviñó, A., Cubero, E., González, C., Eritja, R., Orozco, M. J. Am. Chem. Soc., 2003, 125, 16127-16138. [4] Nadal, A., Coll, A., Aviñó, A. Esteve, T., Eritja, R., Pla, M. ChemBioChem, 2006, 7, 1039-1047. [5] Carrascosa, L.G., Gómez-Montes, S., Aviñó, A., Nadal, A., Pla, M., Eritja, R., Lechuga, L.M. Nucleic Acids Res., 2012, 40, e56. [6] Aviñó, A., Huertas, C. S., Lechuga, L. M., Eritja, R. Anal. Bioanal. Chem., 2016, 408, 885-893.
< Back to Programme 42 TUESDAY 4 JULY Session VII: Optical sensing (IV) 17:55-18:25 KEYNOTE 10
NANOPARTICLES BASED LABEL-FREE DNA BIOSENSORS T. García-Mendiolaa,b,c, Iría Bravoa,c, Cristina García Eloseguia, J. M. López Morenoa,c, F. Parientea,b,c and E. Lorenzoa,b,c a. Departamento Química Analítica y Análisis Instrumental b. Institute for Advanced Re-search in Chemical Sciences (IAdChem) of Universidad Autónoma de Madrid. c. Instituto Madrileño de Estudios Avanzados (IMDEA), [email protected]
The interaction of DNA with nanomaterials not only opens new opportunities for specific molecular recognition, but it also expands the promising applications of nanomaterials from material science to biotechnology and biomedicine. In the present work, we focus on the interaction of two nanomaterials, gold nanoparticles (AuNPs) and carbon nanodots (CDs), and DNA, in which we have explored their promising applications in sensing. For both nanomaterials the basic principles, binding mode and applications to DNA biosensor development are studied. CDs were synthesized by thermal carbonization of ethylene glycol bis-(2-aminoethyl ether)-N,N,N’,N’- tetraacetic acid (EGTA) and characterized by different techniques. AuNPs were synthetized from
HAuCl4 and sodium citrate. CDs bind stronger to dsDNA than ssDNA, and from the melting point experiments we can conclude that CDs intercalate to dsDNA. ssDNA bounded to CDs shows a fluorescence band at 450 nm. Hybridization resulted in the quenching of emission. Based on these results, specific DNA sequence recognition is explored. AuNPs strongly interacts with DNA, increasing the absorption band at 520 nm. From these results, the binding constant to ds and ssDNA have been estimated, indicating that AuNPs bind stronger to dsDNA than ssDNA. This property has been exploited for DNA sensing applications.
< Back to Programme 43 TUESDAY 4 JULY Session VII: Optical sensing (IV) 18:25-18:40 ORAL 19
FLUORESCENCE-ENZYMATIC NANOBIOSENSORS: INTERFERENCE FREE CHOLINE DETERMINATION BASED ON ENERGY TRANSFER PHENOMENA BETWEEN CHOLINE OXIDASE AND GOLD NANOCLUSTERS Martín-Barreiro, A.a,b, de Marcos, S.a, Grazú, V.b, Galbán, J.a a. Analytical Biosensors Group. University of Zaragoza, Pedro Cerbuna, 12, Zaragoza, Spain. b. Nanotechnology and Apoptosis Group. Institute of Nanoscience of Aragón, Zaragoza, Spain [email protected]
The variation of the intrinsic fluorescence of Choline Oxisade (ChOx) due to its flavin adenine dinucleotide (FAD) cofactor (Fig.1a) has allowed the determination of Choline in synthetic samples [1], but may present problems of spectral interference when applied in biological samples. In this work, it has been developed the basis of an enzymatic-nanobiosensor based on gold nanoclusters (AuNC’s), a luminescent marker in the near infrared region (NIR). The NC’s have been biofunctionalized using carbodiimide chemistry to obtain oriented-covalent binding of AuNC in the proximities of the active site of the enzyme, where the FAD cofactor is located (Figure 1b). In these conditions, the fluorescence of AuNC-ChOx (λem= 700 nm) varies during the enzymatic reaction of ChOx with Ch, proportionally to the concentration of analyte (Fig.2). The origin of this analytical signal has been studied and demonstrated to be due to two phenomena: fluorescence energy transfer (FRET) between AuNC- ChOx and NC’s fluorescence quenching. The methodology shows a linear response for choline ranging 1,3·10-6 from to 1,6·10-5 M and a RSD of about 3,6%. The nanoplatform it is now being coupled to the determination of neurotransmitters.
Acknowledgements: This work has been supported by the MINECO of Spain (project CTQ2016-76846-R) and by the founding to research group of the DGA-FEDER (E74).
References
[1] E. Ortega, S. de Marcos, I. Sanz-Vicente, et al. Talanta, 147, (2016), 253-260.
< Back to Programme 44 TUESDAY 4 JULY Session VII: Optical sensing (IV) 18:40-18:55 ORAL 20
STRAIN RELAXATION MECHANISMS IN ZNSE@ZNTE CORE-SHELL NANOWIRES GROWN HORIZONTALLY FROM A GUIDED GROWTH APPROACH Sara Martí-Sáncheza, Eitan Oksenberg2, Ernesto Joselevich2, Jordi Arbiol1,3 1. Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology (BIST), Campus UAB, Bellaterra, 08193 Barcelona, Catalonia, Spain. 2. Department of Materials and Interfaces and Chemical Research Support, Weizmann Institute of Science, Rehovt, 76100, Israel. 3. ICREA, Passeig Lluís Companys 23, 08010 Barcelona, Catalonia, Spain. [email protected]
The organization of nanowires on surfaces remains a major obstacle towards their large scale integration into functional devices. In order to overcome these issues, aligned arrays of heterostructured horizontal planar core-shell ZnSe@ZnTe nanowires were grown exploiting the epitaxial relations with the substrate in a guided growth approach to form well organized assemblies. We exploit the directional control of the guided growth for the parallel production of multiple radial p-n heterojunctions. The formed arrays exhibit great optoelectronic properties, with dark currents below the detection limit and upon illumination a rectifying behavior with photovoltaic characteristics. By the use of atomic resolution (S)TEM together with Geometric Phase Analysis (GPA), a deep understanding of the strain fields on the different nanostructures can be obtained. In that framework, we perform a study of the relaxation mechanisms taking place in the structure and how are they affected by the core morphology and substrate orientation with the aim of being able to exploit the strain on them to optimize the electronic behavior of the nanostructures.
References
[1] M. de la Mata et al., Nano Lett, 14(11), (2014), pp 6614-6620. [2] M. de la Mata et al., Nano Lett. 16(2), (2016), pp 825-833. [3] E. Oksenberg, S. Martí-Sánchez et al., ACS Nano, DOI: 10.1021/acsnano.7b02199 (2017).
< Back to Programme 45 WEDNESDAY 5 JULY Session VIII: Graphene and nanomaterials (I) 9:00-9:40 PLENARY 5
NANOPHOTONICS AND METASURFACES FOR NEXT-GENERATION BIOSENSORS Hatice Altug Bionanophotonic systems laboratory, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne 1015, Switzerland
New healthcare initiatives including personalized medicine, global health, point-of-care and early disease diagnostics require breakthrough developments in biosensing technologies. Current technologies are limited as they are time consuming, costly, bulky, require a relatively advanced infrastructure and trained laboratory professional. To address these shortcomings we exploit nano- photonics and engineering toolboxes, such as optical resonators, metamaterials, microfluidics [1]. Among various different nanophotonic phenomena, plasmonics is of particular interest for biosensor development. Plasmons can confine the light below the fundamental diffraction limit and create extremely intense electromagnetic fields in volumes much smaller than the wavelength of light. These features are especially promising for device applications. In this talk we will cover how to utilize nano-scale photonics interfaced with biology and chemistry for ultra-sensitive, real-time, label-free and high-throughput biosensors. We develop lab-on-a-chip systems for investigation of live cells by directly detecting secreted protein biomarkers in real-time [2]. We are developing multiplexed nanoplasmonic biosensor arrays for one-step simultaneous detection of bacteria directly from body fluids for an efficient population screening [3]. We are introducing novel sensing methodologies for in-vivo analysis of lipids and protein conformations under biological conditions [4-5]. In parallel, we also explore graphene as a new platform for biosensing due to its exceptional opto-electronic properties [6].
References
[1] H. Altug et al. Nature Nanotechnology, Vol 10, 11-15 (2015). [2] X. Li et al. “Plasmonic nanohole array biosensor for label-free and real-time analysis of live cell secretion” Lab on a Chip, accepted May (2017). [2] M. Soler et al. “Multiplexed Nanoplasmonic Biosensor for One-step Detection of Major STD Bacteria in Urine” Biosensors and Bioelectronics (2017). [4] D. Etezadi et al. “Nanoplasmonic mid-infrared biosensor for in vitro protein secondary structure detection” Light Science and Applications, (2017). [5] O. Limaj et al. “Infrared Plasmonic Biosensor for Real-Time and Label-Free Monitoring of Lipid Membranes” Nano Letters, Vol 16, 1502–1508 (2016). [6] D. Rodrigo et al. “Mid-infrared Plasmonic Biosensing with Graphene”, Science, Vol 349, 165-168 (2015).
< Back to Programme 46 WEDNESDAY 5 JULY Session VIII: Graphene and nanomaterials (I) 9:40-10:10 KEYNOTE 11
HYBRID NANOPARTICLES FOR THERAPY AND DIAGNOSIS: AU NANO PRISMS FOR GASTROINTESTINAL CANCER J.M. de la Fuente Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, Spain. & Shanghai Jiao Tong University, P.R. China. *[email protected]
In the last decades, inorganic nanoparticles have been steadily gaining more attention from scientists from a wide variety of fields such as material science, engineering, physics or chemistry. The very different properties compared to that of the respective bulk, and thus intriguing characteristics of materials in the nanometre scale, have driven nanoscience to be the centre of many basic and applied research topics. Moreover, a wide variety of recently developed methodologies for their surface functionalization provide these materials with very specific properties such as drug delivery and circulating cancer biomarkers detection. In this talk we describe the synthesis and functionalization of magnetic and gold nanoparticles as therapeutic and diagnosis tools against cancer. Gold nanoprisms (NPRs) have been functionalized with PEG, glucose, cell penetrating peptides, antibodies and/or fluorescent dyes, aiming to enhance NPRs stability, cellular uptake and imaging capabilities, respectively.3,4 Cellular uptake and impact was assayed by a multiparametric investigation on the impact of surface modified NPRs on mice and human primary and transform cell lines. Under NIR illumination, these nanoprobes can cause apoptosis. Moreover, these nanoparticles have also been used for optoacoustic imaging,5 as well as for tumoral marker detection using a novel type of thermal ELISA nanobiosensor using a thermosensitive support.6
References
[1] J. Conde, A. Ambrosone, V. Sanz, Y. Hernandez, F. Tian, P. V. Baptista, M. R. Ibarra, C. Tortiglione, J. M. de la Fuente, ACS Nano 6, 8316 (2012) [2] J. Conde, F. Tian, Y. Hernández, C. Bao, D. Cui, M. R. Ibarra, P. V. Baptista, J. M. de la Fuente. Biomaterials 34, 7744 (2013) [3] B. Pelaz, V. Grazú, A. Ibarra, C. Magén, P. del Pino, J. M. de la Fuente. Langmuir 28, 8965 (2012). [4] M. Pérez-Hernández, P. del Pino, S.G. Mitchell, M. Moros, G. Stepien, B. Pelaz, W.J. Parak, E. M. Gálvez, J. Pardo, J. M. de la Fuente. ACS Nano 9, 52 (2015). [5] C. Bao, N. Beziere, P. del Pino, B. Pelaz, G. Estrada, F. Tian, V. Ntziachristos, J. M. de la Fuente, D. Cui. Small 9, 68 (2013). [6] E. Polo, P. del Pino, B. Pelaz, V. Grazu, J.M. de la Fuente. Chemical Communications 49, 3676 (2013).
< Back to Programme 47 WEDNESDAY 5 JULY Session VIII: Graphene and nanomaterials (I) 10:10-10:40 KEYNOTE 12
MAGNETO-CATALYTIC GRAPHENE QUANTUM DOTS JANUS MICROMOTORS FOR BACTERIAL ENDOTOXIN DETECTION M. Pacheco, J. Rojo, B. Jurado-Sánchez and A. Escarpa Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Madrid, Spain. Email: [email protected]
Magneto-catalytic hybrid Janus micromotors encapsulating phenylboronic acid (PABA) graphene quantum dots (GQDs) are used here as ultrafast sensors for detection of deadly bacteria endotoxins. A bottom-up approach is adopted to synthetize an oil-in-water emulsion containing the GQDs along with a high loading of platinum and iron oxide nanoparticles on one side of the Janus micromotor body. The two different “active regions” allow for highly efficient propulsion in the presence of peroxide solutions or magnetic actuation. Fluorescence quenching is observed upon GQDs interaction with the target endotoxin (LPS), with the PABA tags acting as highly specific recognition receptors of the LPS-core polysaccharide region. Such adaptive hybrid operation and highly specific detection hold considerable promise towards diverse clinical, agro-food and biological applications with clear promising to integrate in future lab-on-chip technology.
References
[1] B. Jurado-Sánchez*, M. Pacheco, J. Rojo, A. Escarpa*. Angewandte Chemie International Edition, (2017). DOI:10.1002/anie.201701396R2
< Back to Programme 48 WEDNESDAY 5 JULY Session VIII: Graphene and nanomaterials (I) 10:40-10:55 ORAL 21
MODIFICATION OF GOLD NANOPARTICLES-SCREEN PRINTED CARBON ELECTRODES WITH GRAPHENE QUANTUM DOTS: VOLTAMMETRIC DETERMINATION OF VANILLIN IN FOOD SAMPLES
Gema M. Durána,b, Eulogio J. Llorent-Martínezb, Ana M. Contentoa, and Ángel Ríosa a. Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha, Camilo José Cela Av., Ciudad Real E-13071, Spain b. Regional Institute for Applied Chemistry Research (IRICA), Camilo José Cela Av., Ciudad Real E-13071, Spain [email protected]
An electrochemical sensor for selective detection and quantification of vanillin in food samples was developed based on the modification of gold nanoparticles-modified screen printed carbon electrode (AuNPs-modified SPCE) with G-QDs and Nafion nanocomposite. Their assembly onto AuNPs-modified SPCE surface resulted in an enhancement of 30% the electrochemical response of vanillin. After the optimization of experimental conditions a linear relationship of 0.1 - 5 mg L-1 and a detection limit of 0.05 mg L-1 was obtained using differential pulse voltammetry (DPV). Thus, the proposed electrochemical G-QDs-based sensor also demonstrated good selectivity, an improvement in sensitivity and accurate stability. The analytical performance of the developed electrochemical sensor was demonstrated for the determination of vanillin in food samples with satisfactory results. This study provides new opportunities for the development of simple and selective electrochemical detection methods for quality food control by simple modification of commercial low-cost electrochemical devices.
Acknowledgements: Projects CTQ2016-78793-P (MINECO) and PEIC-2014-001-P (JCCM). E. J. Llorent-Martínez also thanks the financial support from UCLM Research Plan.
< Back to Programme 49 WEDNESDAY 5 JULY Session IX: Graphene and nanomaterials (II) 11:25-11:55 KEYNOTE 13
NANOSTRUCTURED MATERIALS FOR THE DEVELOPMENT OF PARADIGM- SHIFTING ANALYTICAL PLATFORMS Francisco Javier Andrade, F. Xavier Rius, Jordi Riu, Pascal Blondeau, Santiago Macho, Rafael Hoekstra, Rocio Cánovas, Marta Borrull, Marta Borras Nanosensors Group, Universitat Rovira i Virgili, Tarragona, Spain [email protected]
Telemedicine, point of care and chemical sensing networks are some of the novel social and technological trends that are creating a rising demand for systems that can generate chemical information everywhere, in real time. Indeed, the traditional lab-centred approaches cannot cope with the scale and speed required today by many of these new approaches. For this reason, devices that can generate information without the need of a laboratory infrastructure, in real time, with minimal or no human intervention and at affordable costs are increasingly required. Thus, while traditional approaches were focused mostly on the analytical performance, today’s paradigm-shifting challenges are geared towards the development of systems that can simultaneously offer analytical robustness, speed, affordability, simplicity of operation and scalable manufacturing. Nanostructured materials are becoming an essential tool to tackle these complex challenges. In this presentation we will present recent developments in the field of electrochemical sensing approaches using nanostructured materials to build simple, compact and ultra-low-cost analytical platforms. Either as structural components of conductive substrates or as ion-to-electron transduction devices, the use of carbon nanomaterials, metal nanoparticles and nanoporous polymeric membranes are opening new ways to produce chemical sensors with an outstanding combination of sensitivity, selectivity, cost and simplicity. This work will present recent advances in the development of wearable electrochemical sensors and ultra-low-cost (under 0.10€) chemical sensors with ability to measure ions, organic and biological molecules in different settings outside the lab. Examples of paper-based electrochemical sensors and sensing textiles with wireless connectivity will be shown. The ability of these novel tools become a widespread platform to tackle emerging social challenges will be discussed, and their use in real scenarios will be presented.
< Back to Programme 50 WEDNESDAY 5 JULY Session IX: Graphene and nanomaterials (II) 11:55-12:25 KEYNOTE 14
LARGE-FIELD-OF-VIEW CYTOMETER AND DIFFERENTIAL INTERFERENCE CONTRAST MICROSCOPE USING CMOS IMAGE SENSOR ARRAYS J.M. Pérez1, R.A. Terborg1, T. Coll1, P. Martínez1, W. Amaya1, C. Hurth1, J. Pello1, M. Jofre1, and V. Pruneri1,2 1. ICFO-Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, 08860 Castelldefels, Barcelona, Spain 2. ICREA-Institució Catalana de Recerca i Estudis Avançats, 08010 Barcelona, Spain [email protected]
Many sensing applications, including ballast water or remote areas drinking water testing and point-of- care medical diagnosis, would vastly benefit from low-cost compact sensing equipment. By exploiting the full field-of-view of CMOS or CCD image sensor arrays (ISA), coupled with a computation unit and off-the-shelf optical and electrical components, one can bring down the cost and complexity of sensing devices while maintaining excellent performance. In this paper, we present two such portable devices for detecting and counting microorganisms in water, and for reading biomarker protein microarrays, respectively.
< Back to Programme 51 WEDNESDAY 5 JULY Session IX: Graphene and nanomaterials (II) 12:25-12:40 ORAL 22
STIMULI-RESPONSIVE CONDUCTING SURFACES FOR CONTROLLED DRUG RELEASE Filiz Kuralay Department of Chemistry, Faculty of Arts and Sciences, Ordu University, Ordu, Turkey. [email protected]
Utilization of conducting polymers (CPs) has been widely increased since CPs exhibit similar properties to natural biological systems. These polymers can be effectively used in many areas due to their distinct responses to external changes. They are highly sensitive to environmental effects such as pH and electrical field [1-3]. As a result, they exhibit changes in their shapes, charges, mechanical motion and degradation behaviors. Because of being permeable to electroactive species, easily being modified with various methods, being able to be coated to many surfaces and being biocompatible, CPs have many advantageous with respect to the other responsive polymeric materials. These polymers have high conductivities, porous structures and high surface areas. According to their oxidation states and doped/undoped forms, their volumes change and owing to the occurring current, they can convert electrical energy to mechanical work [4,5]. Thus, they have found great interest in biotechnology and nanotechnology. In the scope of this talk, development of nanostructured conducting polymer-based controlled drug release/delivery systems will be outlined.
Acknowledgements: F. Kuralay acknowledges Turkish Academy of Sciences (TÜBA) as an associate member and TÜBA- GEBİP program.
References
[1] F. Kuralay, H. Özyörük, A. Yıldız, Sens. Actuat. B: Chem., 109, (2005), 194. [2] C.L. Weaver, J.M. LaRosa, X. Luo, X.T. Cui, ACS Nano, 8, (2014), 1834. [3] N. Kamaly, B. Yameen, J. Wu, O.C. Farokhzad, Chem. Rev., 116, (2016), 2602. [4] M.R. Abidian, D.H. Kim, D.C. Martin, Adv. Mater., 18, (2006), 405. [5] F. Kuralay, S. Sattayasamitsathit, W. Gao, A. Katzenberg, J. Wang, J. Am. Chem. Soc., 134, (2012), 15217.
< Back to Programme 52 WEDNESDAY 5 JULY Session IX: Graphene and nanomaterials (II) 12:40-12:55 ORAL 23
GRAPHENE QUANTUM DOTS@NAFION MODIFIED GLASSY CARBON ELECTRODE AS AN ELECTROCHEMICAL SENSOR FOR DETECTION OF SULPHONAMIDE RESIDUES IN MILK Carina S. Gondima, Gema M. Duránb,c, Ana M. Contentob, Angel Ríosb a. Department of Food Science, Faculty of Pharmacy, Federal University of Minas Gerais, Presidente Antônio Carlos Av., 6627, 31270-010, Belo Horizonte, Brazil. b. Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha, Camilo José Cela Av., Ciudad Real E-13071, Spain c. Regional Institute for Applied Chemistry Research (IRICA), Camilo José Cela Av., Ciudad Real E-13071, Spain [email protected]
A rapid and simple electrochemical method based on the assembly of graphene quantum dots and Nafion onto glassy carbon electrode (G-QDs@Nafion/GCE) was developed to detect sulphonamide residues in milk. The electrochemical technique employed was differential pulse voltammetry. G-QDs@Nafion/GCE demonstrated repeatability, reproducibility and stability (RSD ≤ 10%, for all parameters); with a significant increase on the sensitivity comparing with the glassy carbon electrode. After optimization, the method was validated according to a specific protocol for qualitative methods [1]. Six sulfonamides were evaluated: sulfadimethoxine, sulfadiazine, sulfamethazine (SMZ), sulfamethoxypyridazine, sulfapyridine and sulfathiazole. Milk samples spiked with sulphonamides at concentrations between 25 and 150 µg L-1 were analyzed. Sulphonamides were detected at the maximum residue limit (MRL) recommended by the Codex Alimentarius for SMZ (25 µg L-1) and at the MRL established by the European Union for the sum of sulphonamides in milk (100 µg L-1) [2,3]. In addition, a great performance related to the false-positive results and precision was observed. The proposed methodology demonstrated the applicability of G-QDs@Nafion/GCE in the monitoring of antimicrobial residues in milk samples.
References
[1] CS Gondim, OAM Coelho, RL Alvarenga, RG Junqueira, SVC Souza. Analytica Chimica Acta, 830, (2014), 11-22. [2] Codex Alimentarius, Available in http://www.fao.org/fao-who-codexalimentarius/standards/vetdrugs/veterinary-drug- detail/en/?d_id=57 Acessed on May 2017. [3] Commission Regulation (EU) 37/2010, Official Journal of the European Communities, L15, (2010) 1–72.
< Back to Programme 53 WEDNESDAY 5 JULY Session IX: Graphene and nanomaterials (II) 12:55-13:10 ORAL 24
POLYPYRROLE–CARBON NANOTUBE COMPOSITE SOLID-PHASE MICROEXTRACTION FIBER: PREPARATION, CHARACTERIZATION, AND APPLICATION TO THE ANALYSIS OF FUNGICIDES USED IN VINEYARDS İrem Aydın, İmran Güney, Levent Pelit, Hasan Ertaş, F. Nil Ertaş Ege University, Science Faculty, Chemistry Dep., İzmir, TURKEY [email protected]
UGrape production is widespread in the Mediterranean area and the grapevine is subject to attack of numerous plant and animal parasites and several types of pesticides are widely used. However, their residues in food are harmful to human health and hence accurate and reliable analytical methods are required for their analysis [1,2]. Present study describes a headspace (HS) Solid phase micro extraction (SPME) method for the gas chromatographic analysis of some selected fungicides used in vineyards namely; pyrimethanil, cyprodinil, kresoxim-methyl and trifloxystrobin. Operational parameters effecting the extraction, namely; the sample pH and volume, stirring rate and salt amount adsorption time and temperature have been optimized by using a commercial PA fiber in grape juice samples. Then, the results have been compared with those lab-made SPME fibers produced by electropolymerization of pyrrole monomer onto the surface of a stainless steel wire and further modified with carbon nanotubes. Fiber surfaces have been characterized by SEM measurements and the analyses have been performed with GC-MS system in SIM mode. Analytical characteristics of the method have been investigated and it was revealed that these fungicides can be determined in ppb level with a high recovery percentages. The PPy-CNT-SPME fiber developed has provided more sensitive results than the commercial fibers.
Acknowledgements: Authors would like to thank TUBITAK (114Z394) for support.
References
[1] K. Korba et al., J of Chrom. B, 929 (2013) 90–96 [2] L. Pelit, T.N. Dizdas, J. Sep. Sci. 36 (2013) 3234–3241
< Back to Programme 54 WEDNESDAY 5 JULY Session IX: Graphene and nanomaterials (II) 13:10-13:25 ORAL 25
SIMULTANEOUS DETERMINATION OF LEVODOPA AND CARBIDOPA AT A POLYPYRROLE-CARBON NANOTUBE COMPOSITE ELECTRODE PREPARED BY ULTRASOUND ASSISTED PULSED ELECTROPOLYMERIZATION K. Volkan Özdokura,b, F. Nil Ertaşa a. Ege University, Science Faculty, Chemistry Dep., İzmir, TURKEY b. Erzincan University, Science&Letter Faculty, Chemistry Dep., Erzincan, TURKEY [email protected]
Parkinson’s disease is one of a larger group of neurological conditions where the dopamine precursor levodopa is employed for the treatment. For better therapeutic effect and lower toxicity, carbidopa is administered with levodopa in pharmaceutical formulation as an inhibitor on the decarboxylase activity. Therefore, the development of a method for the simultaneous determination of levodopa and carbidopa is of great importance because of their coexistence in pharmaceutical preparations. In this study, ultrasonic assisted pulsed electropolymerization was utilized for preparation of polypyrrole-carbon nanotube composite electrode (UA-PPy-CNT/GCE) for the first time. The proposed film was characterized by SEM, FTIR, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Then, the electrochemical behavior of carbidopa and levodopa was in investigated on the electrode. The oxidation peak of the analytes coincided at the same potential and therefore, multivariable calibration technique was used for their analysis along with droxidopa. The influence of pH, monomer concentration along with the amount of CNT and applied pulse number was investigated by aid of cyclic voltammetry. The method developed was applied to the trade formulation of carbidopa and levodopa and obtained results were found in good agreement with label value.
Acknowledgements: Authors thank to TUBITAK (114Z153) for financial support.
References
[1] Zapata-Urzúa C., Pérez-Ortiza M., Bravo M., Olivieri A.C., Álvarez-Lueje A., Talanta 82 (2010) 962–968 [2] Özdokur, K.V., Engin, E., Yengin, Ç., Ertaş, H., Ertaş, F.N., Anal. Lett., in press
< Back to Programme 55 Index of authors
Abasolo Linares, Patricia 35 García, Tania 24 Altug, Hatice 46 Gondim, Carina S. 53 Álvarez-Martos, Isabel 25 González, Andrea 18 Andrade, Francisco 50 Henry, Oliver 14 Aydin, Irem 54 Holgado, Miguel 27 Baba, Yoshinobu 12 Kuralay, Filiz 52 Benito-Peña, Elena 41 Laromaine, Anna 13 Blanco, Carmen 20 Llano-Suárez, Pablo 36 Blanco, Francisco 31 López-Muñoz, Gerardo A. 39 Boisen, Anja 15 López-Sanz, Sara 40 Bouzas-Ramos, Diego 34 Lorenzo, Encarna 43 Chalupniak, Andrzej 22 Martín Barreiro, Alba 44 Chocarro, Blanca 29 Martínez de la Fuente, Jesús 47 Costa, J.M. 32 Martí-Sánchez, Sara 45 de la Escosura-Muñiz, Alfredo 19 Murtada, Khaled 23 Duran, Gema M. 49 Ozcan, Aydogan 26 Eickhoff, Holger 33 Pruneri, Valerio 51 Eritja, Ramon 42 Puntes, Victor 38 Ertas, Hasan 28 Puyol, Mar 21 Escarpa, Alberto 48 Ranc, Vaclav 30 Esquivel, Juan Pablo 17 Sabaté, Neus 16 Fontcuberta, Anna 37 Volkan, K. 55
56 Posters
DEVELOPMENT OF AN AUTOMATED SYSTEM FOR THE ANALYSIS OF CELL-FREE FETAL DNA FROM MATERNAL PLASMA FOR NON-INVASIVE PRE-NATAL DIAGNOSTICS (62) Josep Lluís Acero, Carmen Bermudo, Teresa Mairal, Ciara K. O’Sullivan, Ian Riley, Ioanis Katakis
INTEGRATED ELECTROCHEMICAL MICROFLUIDIC SYSTEM FOR MOLECULAR DIAGNOSTICS (63) Nihad K.I. Ahmed and Ioanis Katakis
BOVINE SERUM ALBUMIN CAPPED CADMIUM SULPHIDE NANOPARTICLES. SYNTHESIS IN AQUEOUS SOLUTION AND INTERACTION WITH alpha-GST (64) Víctor Barba Vicente, María Jesús Almendral Parra, Juan Francisco Boyero Benito, and Manuel Fuentes
PAPER STRIP-EMBEDDED GRAPHENE QUANTUM DOTS: A SCREENING DEVICE WITH A SMARTPHONE READOUT (65) Ruslan Álvarez-Diduk, Jahir Orozco, Arben Merkoçi
ELECTROCHEMICAL BEHAVIOUR OF BISMUTH IN RELATION TO THE ADSORPTION OF METAL NANOPARTICLES ON THE SURFACE OF THE ELECTRODE (66) Olaya Amor-Gutiérrez, Alba Iglesias-Mayor, Agustín Costa-García
NUCLEIC ACIDS FOR BIOSENSING APPLICATIONS (67) Anna Aviñó , César Sánchez, Angela Ribes, Sara Santiago-Felipe, Mar Oroval,Elena Aznar , Ramón Martínez-Máñez, Laura Lechuga, and Ramon Eritja
AG NANOPARTICLES DROP-CASTING MODIFICATION OF SCREEN-PRINTED ELECTRODES FOR THE SIMULTANEOUS VOLTAMMETRIC DETERMINATION of Cu(II) and Pb(II) (68) Julio Bastos-Arrieta Clara Pérez-Ràfols, Núria Serrano, José Manuel Díaz-Cruz, Cristina Ariño, Joan de Pablo and Miquel Esteban
REAL-TIME IMAGING BIODETECTION WITH AU-NHA ENHANCED BY MICROFLUIDICS (69) Alexander Belushkin, Filiz Yesilkoy, Maria Soler, Andreas Tittl, Li Xiaokang, Hatice Altug
BIOLUMINESCENT NANOPAPER FOR THE FAST SCREENING OF TOXIC SUBSTANCES (70) Jie Liu, José Francisco Bergua, Eden Morales-Narváez, Jahir Orozco, Ruslan Álvarez-Diduk, Teresa Vincent, Guohua Zhong, Arben Merkoçi
57 IMPEDIMETRIC ELECTROCHEMICAL SENSOR FOR ALBUMIN DETERMINATION BASED ON POLY(BCP) FILM MODIFIED ELECTRODES (71) Bermudo Redondo M.Carmen, Ortiz Mayreli, Fragoso Alex and O’Sullivan C. K.
NANOSTRUCTURED ENZYMATIC BIOSENSOR FOR BIOGENIC AMINES USING PAPER-BASED ELECTRODES (72) Carla Cristina Rubio González-Valle, Olaya Amor-Gutiérrez, María Fernández, M. Carmen Blanco-López
A STAPLE-BASED ELECTROCHEMICAL LATERAL FLOW PLATFORM FOR PNEUMOLYSIN QUANTIFICATION (73) L. Blanco-Covián, M.C. Blanco-López, M.T. Fernández-Abedul
A NEW LATERAL FLOW STRIP ASSAY (LFSA) USING A PAIR OF APTAMERS FOR THE DETECTION OF VASPIN (74) Nurul Hanun, Vanthuan Mguyen, and Man Bock Gu
PEDOT:PSS PAPER-BASED CHEMIRESISTOR TOWARDS HYDROGEN PEROXIDE DETECTION (75) Marta Borràs-Brull, Rocío Cánovas, Pascal. J. C. L. Blondeau, Francisco J. Andrade and Jordi Riu
NOVEL APPROACHES TO BUILD POTENTIOMETRIC BIOSENSORS FOR DECENTRALIZED CHEMICAL ANALYSIS (76) Rocío Cánovas, Pascal Blondeau, Francisco J. Andrade
MULTIPLEXED DETECTION OF SINGLE NUCLEOTIDE POLYMORPHISMS USING ELECTROCHEMICAL MELTING CURVE ANALYSIS (77) Nassif Chahin, Mayreli Ortiz, Ahmed M. Debela, Serge Thorimbert , Bernold Hasenknopf , Ciara O’Sullivan
SCREEN-PRINTED CARBON ELECTRODES NANOESTRUCTURED FOR THE DETERMINATION OF CARBOHYDRATES (78) Beatriz Pérez-Fernández, Agustín Costa-García
TERBIUM-SENSITIZED LUMINESCENCE: A NOVEL TOOL FOR THE DETERMINATION OF GRAPHENE QUANTUM DOTS (79) Gema M. Durán, Eulogio J. Llorent-Martínez, Lucía Molina-García, Antonio-Ruiz-Medina and Ángel Ríos
THE USE OF POLYPYRROLE–CARBON NANOTUBE COMPOSITE SOLID-PHASE MICROEXTRACTION FIBER FOR THE ANALYSIS OF PESTICIDES USED IN APPLE PRODUCTION (80) Imran Güney, Irem Aydin, Levent Pelit, Hasan Ertas, F. Nil Ertas
58 PREPARATION OF VANADIUM - RUTHENIUM OXIDE / GOLD COMPOSITE ELECTRODES AND THEIR USE IN HYDRAZINE OXIDATION (81) Sibel Karacaa, Süleyman Koçaka, K. Volkan Özdokurb,c, F. Nil Ertasc
TAILORED MAGNETIC CARBON ALLOTROPE CATALYTIC MICROMOTORS FOR ‘ON-CHIP’ OPERATIONS (82) Roberto Maria-Hormigosa, Beatriz Jurado-Sáncheza, Alberto Escarpa
RAPID DETECTION OF SEPSIS WITH A POINT-OF CARE AND LABEL FREE MICROARRAY PLATFORM (83) Nuria Fabri-Faja, Olalla Calvo, M.- Carmen Estévez, Josselin Pello, Roland A. Terborg, Alexander Belushkin , Filiz Yesilköy , Pieterjan Soetaert, Mathieu Rabaey, Hatice Altug, Valerio Pruneri, Laura M. Lechuga
VERTICALLY-ORIENTED AND SHAPE-TAILORED ELECTROCATALYTIC NICKEL NANOWIRES FOR ENZYME-FREE GALACTOSEMIA RAPID DIAGNOSIS (84) Laura García-Carmona, María Cristina González and Alberto Escarpa
MULTIPLEXED DETECTION OF ALTERNATIVE SPLICED mRNA ISOFORMS FOR CANCER DETECTION USING A BIMODAL WAVEGUIDE INTERFEROMETER BIOSENSOR (85) Daniel Grajales, César S. Huertas, Laura M. Lechuga
STUDY OF MERCURY SIGNAL AMPLIFICATION EMPLOYING SPCEs MODIFIED WITH NANOPARTICLES, AND ITS APPLICATION AS LABEL IN IMMUNOLOGICAL REACTIONS (86) Alba Iglesias-Mayor, Olaya Amor-Gutiérrez, Agustín Costa-García
DEVELOPMENT OF NANOFIBER FUNCTIONALIZED APTASENSOR FOR ELECTROCHEMICAL DETECTION OF CANCER CELL (87) E. Kivrak, A. Ince, R. Ilhan, P. Ballar, S. Yilmaz, P. Kara
A ELECTROCHEMICAL SENSOR BASED ON ULTRATHIN NANOSTRUCTURAL COATING FOR PERFLUOROOCTANE SULFONATE ANALYSIS (88) Najmeh Karimian, Angela M. Stortini, Ligia M. Moretto, Paolo Ugo
PREPARATION, CHARACTERIZATION AND BIOSENSING APPLICATIONS OF GRAPHENE/POLY- L-LYSINE COATED ELECTRODES (89) Nilgün Dükara, Filiz Kuralay
ABSTRACT TITLE ISOTHERMAL MULTIPLEXED BRIDGE AMPLIFICATION AND ELECTROCHEMICAL DETECTION FOR RELIABLE AND COST EFFECTIVE MOLECULAR DIAGNOSTICS (90) Ivan Magriñá , Mayreli Ortiz , Ciara K. O’Sullivan
59 BIOSENSING STRATEGY FOR SIMULTANEOUS AND ACCURATE QUANTITATIVE ANALYSIS OF MYCOTOXINS IN FOOD SAMPLES USING NON-FUNCIONALIZATED GRAPHENE MICROMOTORS (91) Águeda Molinero-Fernández, María Moreno-Guzmán, Miguel Ángel López, Alberto Escarpa
CLASS ENZYME-BASED MOTORS FOR “ON THE FLY” ENANTIOMER ANALYSIS OF AMINO ACIDS (92) Laura García-Carmona, María Moreno-Guzmán, María Cristina González, Alberto Escarpa
GOLD NANOPARTICLES FORMATION AS AN INDICATOR OF ENZYMATIC METHODS: TIRAMINE DETERMINATION (93) Navarro Domínguez J., de Marcos Ruiz S., Galbán Bernal J.
LOCALISED SURFACE PLASMON RESONANCE BIOSENSOR FOR THE MONITORING OF SINTROM® THERAPEUTIC DRUG IN PLASMA (94) E-Cristina Peláez, M-Carmen Estevez, J-Pablo Salvador, M-Pilar Marco, and Laura M. Lechuga
IMPLEMENTATION OF GOLD NANOPARTICLES IN LIQUID-PHASE MICROEXTRACTION FOR MICROVOLUME COLORIMETRIC DETECTION OF IODIDE IN WATERS (95) F. Pena-Pereira, V. Romero, A. Garcia-Figueroa, I. Lavilla, C. Bendicho
MODIFICATION OF ELECTRODE SURFACE FOR CORTISOL DETECTION (96) Briza Pérez-López, Ruta Grinyte, Judith Arboledas, Jordi Ricart, Marc Masa, Chantal Vilà, Robert Pous, Gregorio Azcarate, Xavier Ventura
3D-PRINTED MICROFLUIDIC PLATFORM FOR S2- MONITORING IN BIOTECHNOLOGICAL PROCESSES (97) Roberto Pol, Yasmine Alonso, Raquel Montes, David Gabriel, Francisco Céspedes, Mireia Baeza
DEVELOPMENT OF A LOW-COST POINT-OF-CARE TEST FOR TUBERCULOSIS DETECTION (98) Patricia Ramírez, Daan Martens, Peter Bienstman, Mahavir Singh, Ayssar A. Elamin, Wim Van Roy, Rita Vos, Pieterjan Soetaert, Birgit Anton, Holger Becker, and Laura M. Lechuga
GRAPHENE MEMBRANE THIN-FILM MICROEXTRACTION FOR CR SPECIATION IN WATERS BY TOTAL REFLECTION X-RAY FLUORESCENCE (99) Vanesa Romero, Isabel Costas, Francisco Pena, Isela Lavilla, Carlos Bendicho
HEAVY METAL DETERMINATION BY PAPER-BASED ELECTRODES MODIFIED WITH MERCURY AND BISMUTH FILMS (100) A.Sánchez Calvo, M.T. Fernández-Abedul, M.C. Blanco López, A. Costa García
MULTIPLEXED NANOPLASMONIC BIOSENSOR FOR RAPID PATHOGEN DETECTION AT THE POINT OF CARE (101) Maria Soler, Alexander Belushkin, Xiaokang Li, Hatice Altug
60 PREPARATION OF COBALT OXIDE AND PLATINUM NANOPARTICLE MODIFIED ELECTRODES AND THEIR ELECTROCATALYTIC ACTIVITY FOR ORR (102) K. Volkan Özdokura, Ceren Kusci, Süleyman Koçak, F. Nil Ertas
TUNGSTEN OXIDE MODIFIED ELECTRODES: A PROMISING PLATFORM FOR BIOSENSORS (103) Irem Çakar Davaslioglu, K. Volkan Özdokura, Süleyman Koçak, F. Nil Ertas
MOLECULAR IMPRINTED POLYMER FOR HAZARD COMPOUNDS DETECTION (104) Alejandro Zamora-Gálvez, Arben Merkoçi
61 DEVELOPMENT OF AN AUTOMATED SYSTEM FOR THE ANALYSIS OF CELL-FREE FETAL DNA FROM MATERNAL PLASMA FOR NON-INVASIVE PRE-NATAL DIAGNOSTICS
Josep Lluís Aceroa, Carmen Bermudoa, Teresa Mairala, Ciara K. O’Sullivana,b, Ian Rileyc, Ioanis Katakisa
aUniversitat Rovira i Virgili, Av. Països Catalans 26, Tarragona, Spain. bInstitució Catalana de Recerca i Estudis Avançats, .Pg Lluís Companys 23, Barcelona, Spain. c Labman Automation Ltd., Seamer Hill, Seamer, Stokesley, North Yorkshire TS9 5NQ, UK
The analysis of circulating cell-free (cf) DNA from plasma, serum or urine, has the potential to serve as non-invasive approach to detect and monitor targets associated with certain diseases. In 1997 the presence of fetal DNA in the plasma and serum of pregnant women was demonstrated1. This opened new perspectives in field of non-invasive pre- natal diagnostics since the analysis of cell-free fetal (cff) DNA can provide information about pregnancy related disorders (pre-eclampsia, pre-term labour), chromosomal aberrations (e.g. aneuploidies), and genetic disorders (e.g. cystic fibrosis, thalassaemia, Huntington’s disease)2. We report on the development of an automated and integrated modular system for the isolation, amplification and detection of cffDNA from maternal plasma for non-invasive pre-natal diagnostics. The system consists of a first module for the cfDNA isolation from plasma based on silica-coated magnetic beads technology. Subsequently, the cfDNA obtained is introduced to a second module which is based on a polymeric microsystem containing a capillary electrophoresis step for the size separation of the fetal DNA from maternal DNA. Finally, the cffDNA is transferred to the amplification/detection module. This module consists of PCB (Printed Circuit Board) electrode arrays functionalized with surface immobilised primers for the multiplexed isothermal recombinase polymerase DNA amplification (RPA) and electrochemical quantitative detection of specific genetic sequences. The developed technology is of generic and flexible nature allowing its' facile modification to other targets of interest in clinical diagnostics and thus the developed platforms can also be exploited for analysis of circulating nucleic acids in oncology and multiple other disorders.
References: [1] Lo Y.M., Corbetta N., Chamberlain P.F., Rai V., Sargent I.L., Redman C.W., Wainscoat J.S. Lancet, 9076, (1997), 485-7. [2] Daley R., Hill M., Chitty L.S. Arch Dis Child Fetal Neonatal, 5, (2014), 426-30.
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Integrated Electrochemical Microfluidic System for Molecular Diagnostics
Nihad K.I. Ahmed and Ioanis Katakis
Interfibio Research Group, Department of Chemical Engineering, Universitat Rovira i Virgili ,Avinguda Països Catalans 26, 43007 Tarragona, Spain.
Abstract
We are demonstrating a new electrochemical microfluidic device as a molecular diagnostics tool; the system facilitates a rapid and inexpensive detection of nucleic acids. The objective is to achieve a low cost, integrated device for use at the point-of-need. The system is low cost (less than 1€ bill of materials) and the time to results is less than 45 min with minimal user intervention, and total integration, truly achieving “sample in-result out”. The power requirement should permit the system to operate with the battery of a mobile device such as a smartphone.
The availability of such a device can be transformational for health care not only in resource- limited environments but also for the rationalisation of health costs in advanced economies. Food safety and quality assurance from farm to fork and the disruptive innovation of HACCP implementation could be another beneficiary of the proposed technological innovation. Finally, environmental monitoring can be improved. The model system used for development is centred on the environmental monitoring field proposing the field detection of toxic algae.
Sketch for design and components of the proposed microfluidic system
This work has been carried out with the financial support from the Ministry of Economy and Competitiveness, (Seasensing Project, ref.BIO2014-56024-C2-1-R) )):“Seasensing: Microsystems for rapid, reliable and cost effective detection of toxic microalgae on-site and in real-time”
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BOVINE SERUM ALBUMIN CAPPED CADMIUM SULPHIDE NANOPARTICLES. SYNTHESIS IN AQUEOUS SOLUTION AND INTERACTION WITH -GST.
Víctor Barba Vicentea, María Jesús Almendral Parraa, Juan Francisco Boyero Benitoa, and Manuel Fuentesb
aDepartment of Analytical Chemistry, Nutrition and Food Science, Faculty of Chemistry, University of Salamanca, 37008 Salamanca, Spain. bProteomics Unit. Cancer Research Centre (IBMCC/CSIC/USAL/IBSAL), Salamanca, Spain.
Email corresponding author: [email protected]
For the last 20 years, there has been an increasing interest in hybrid materials between inorganic nanoparticles and biomolecules [1]. Today it is simple to control and modify the properties of nanostructures in order to achieve their integration with biological systems.
The CdS QDs functionalised with BSA in a colloidal aqueous solution, which are stable over a long period, have been synthesised. The conditions of synthesis, at a homogeneous phase and at low temperature, allow the limiting of the concentration of S2- in solution during the synthesis, which significantly restricts the consequent growth of the NPs. This allows the binding with the BSA in the most favourable manner for the molecule. The existence of Cd2+ ions on the surface of the CdS nanoparticle is counteracted by the negative charge domains of the BSA, the result being the formation of small NPs with a low aggregation tendency.
The pH (Fig 1) and the temperature variables have a great influence on the fluorescent characteristics of the nanoparticles synthesised. The best results are obtained by working at low temperatures (4oC) and at pH values between 10 and 11. Under these conditions the kinetic control of the hydrolysis of the thioacetamide precursor (Fig. 2) has allowed the obtaining of nanoparticles which attain high fluorescence sustained over time and a stability of over 3 months.
The BSA bound to the CdS QD (CdS-BSA) maintains its biological activity to allow subsequent bioconjugation with other biological entities such as peptides, proteins, enzymes, or antibodies. Their interaction with the -GST antibody produces a strong quenching of fluorescence that proves the possibilities of its use in biological labeling.
References:
1. [1] S. Kango, S. Kalia, A. Celli, J. Njuguna, Y. Habibi, R. Kumar. Surface Mod- ification of Inorganic Nanoparticles for Development of Organic-Inorganic Nanocomposites – A Review. Progress in Polymer Science 38 (2013) 1232-1261.
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Paper strip-embedded graphene quantum dots: a screening device with a smartphone readout Ruslan Álvarez-Diduka, Jahir Orozcoa, Arben Merkoçia,b *.
a Nanobioelectronics and Biosensor Group, Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC. The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193, Barcelona, Spain. b ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain.
E-mail: [email protected]
Simple, inexpensive and rapid sensing systems are very demanded for a myriad of uses. Intrinsic properties of emerging paper-based analytical devices have demonstrated considerable potential to fulfill such demand.[1] This work reports an easy-to-use, low cost, and disposable paper-based sensing device for rapid chemical screening with smartphone readout. The device comprises luminescent graphene quantum dots (GQDs) sensing probes embedded into a nitrocellulose matrix where the resonance energy transfer phenomenon seems to be the sensing mechanism. The GQDs probes were synthesized from citric acid by a pyrolysis procedure, further physisorbed and confined into small wax-traced spots on the nitrocellulose substrate. The GQDs were excited by an UV LED, this, is powered by a smartphone used as both; energy source and imaging capture. The LED was contained within a 3D-printed dark chamber that isolates the paper platform from external light fluctuations leading to highly reproducible data. The cellulose-based device was proven as a promising screening tool for phenols and polyphenols in environmental and food samples, respectively. It opens new opportunities up for simple and fast screening of organic compounds and offers numerous possibilities having versatile applications. It can be especially useful in remote settings where sophisticated instrumentation is not always available. [2]
[1] Morales‐Narváez, E., Baptista‐Pires, L., Zamora‐Gálvez, A., & Merkoçi, A. (2016). Advanced Materials.
[2] Álvarez-Diduk, R., Orozco, J., & Merkoçi, A. (2017). Scientific Reports, 7(1), 976.
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ELECTROCHEMICAL BEHAVIOUR OF BISMUTH IN RELATION TO THE ADSORPTION OF METAL NANOPARTICLES ON THE SURFACE OF THE ELECTRODE
Olaya Amor-Gutiérrez, Alba Iglesias-Mayor, Agustín Costa-García
Departamento de Química Física y Analítica, Universidad de Oviedo, 33006 Oviedo, Spain
email address of the corresponding author: [email protected]
In recent years, nanotechnology has received increasing attention because of their unique properties, both physical and chemical, that allow distinguish them from bulk materials. In fact, materials have novel effects when their size is at the scale of nanometers, being one of the most important ones its high surface area, that makes them very sensitive in surface processes. In particular, in the field of electroanalysis, metal nanoparticles have become one of the most used to modify electrodic surfaces because of the advantages they have in comparison with bare electrodes [1][2]. In this work, we are studying the behaviour of the bismuth towards the modification of the working electrode of a Screen-Printed Carbon Electrode (SPCE) with different types of nanoparticles, either silver or gold nanoparticles, by adsorption. The effect of the metal nanoparticles on the signal of the bismuth was studied by Cyclic Voltammetry (CV). As can be seen in Figure 1, it is clear that the presence of gold nanoparticles (AuNPs, 15 nm) makes the process of bismuth much more reversible and also enhances the underpotential deposition (UPD).
Figure 1. Cyclic Voltammograms of Bi3+ 10-4 M in acetate buffer solution (NaAc 0.1 M pH = 4.5) on bare and nanostructured electrodes. References: [1] Editorial. Trends Anal. Chem., 58, (2014), 8-9. [2] S.E.F. Kleijn, S.C.S. Lai, M.T.M. Koper, P.R. Unwin. Angew. Chem. Int. Ed., 53, (2014), 3558-3586. Acknowledgements: This work has been supported by the FC-15-GRUPIN14-021 project from the Asturias Regional Government and the CTQ2014-58826-R project from the Spanish Ministry of Economy and Competitiveness (MINECO). Alba Iglesias-Mayor thanks the Spanish Ministry of Education, Culture and Sports (MECD) for the award of a FPU Grant (FPU2014/04686).
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NUCLEIC ACIDS FOR BIOSENSING APPLICATIONS
Anna Aviñó a, César Sánchez b, Angela Ribes c, Sara Santiago-Felipe c, Mar Oroval c Elena Aznar c , Ramón Martínez-Máñez c, Laura Lechuga b, and Ramon Eritja a
a Networking Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), Institute for Advanced Chemistry of Catalonia (IQAC), CSIC, Jordi Girona 18-26 08034 Barcelona, Spain b Catalan Institute of Nanoscience and Nanotechnology (ICN2), CIBER-BBN, CSIC, UAB Campus, Bellaterra, Barcelona, 08193, Spain c Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta UPV - UV, Camino de Vera, s/n 46022 Valencia, Spain [email protected] DNA biosensors are small devices which intimately couple biological recognition element interacting with the target with a physical transducer that translates the biorecognition event into a useful electrical signal. DNA biosensors, based on nucleic acid recognition processes, are being developed towards the goal of rapid, simple and inexpensive testing of genetic or infectious diseases. In one hand, we present a biosensing approach for the label-free detection of nucleic acid sequences with special emphasis on targeting RNA sequences with secondary structures or microRNAs that are involved in several diseases [1]. The approach is based on selecting 8-aminopurine- modified parallel-stranded DNA tail-clamps as affinity bioreceptors. These receptors have the ability of creating stable triple-stranded helices at neutral pH upon hybridization with the nucleic acid target. A surface plasmon resonance biosensor has been used for the detection. On the other hand, the design of stimuli-responsive nanoscopic gated systems involving biomolecules has recently attracted great attention. Capped materials have been mainly used in drug delivery applications. However in sensing are less common. Nucleic acids aptamers are especially attractive for the design of gated nanosensors for sensing applications. Specifically, we have prepared an aptamer-gated delivery system for the fluorogenic detection of thrombin [2]. Similarly, tail-clamps gated system was used for the detection of miRNA.
[1] Aviñó, A., Huertas, C. S., Lechuga, L. M., & Eritja, R. Anal. Bioanal. Chem. 408, (2016), 885-893.
[2] Oroval, M. Climent, E. Coll, C. Eritja R. Aviñó A. Marcos M.D. Sancenón F. Martínez-Máñez R. and Amorós P, Chem. Commun. 49 (2013), 5480-5482.
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Ag nanoparticles drop-casting modification of screen-printed electrodes for the simultaneous voltammetric determination of Cu(II) and Pb(II)
Julio Bastos-Arrietaa,b, Clara Pérez-Ràfolsc, Núria Serranoc, José Manuel Díaz-Cruzc, Cristina Ariñoc, Joan de Pabloa,b,d and Miquel Estebanc
a Departament d’Enginyeria Química, Universitat Politècnica de Catalunya (UPC), Campus Diagonal Besòs, Edificio I (EEBE). Carrer Eduard Maristany, 10-14. 08019, Barcelona, Spain. b Barcelona Research Center for Multiscale Science and Engineering, 08019 Barcelona, Spain c Departament d’Enginyeria Química i Química Analítica, Facultat de Química, Universitat de Barcelona. Martí i Franquès 1-11, E-08028 Barcelona, Spain d Fundació CTM Centre Tecnològic, Plaça de la Ciència 2, 08240 Manresa, Spain
Voltammetric stripping techniques have been widely applied to trace metal ions determination. These techniques were traditionally associated to hanging mercury drop electrode (HMDE) although its toxicity has led to the development of new working electrodes. In this sense, the incorporation of nanomaterials can lead to improved electrochemical sensors since they increase the electrode surface area and the mass- transport rate, and they also fasten the electron transfer. Particularly, silver nanoparticles present a wide anodic range which allows the determination of more easily oxidizable metals like Cu(II) and have the advantage of being inexpensive.
In this work, two different types of silver nanoparticles with different shapes and sizes, Ag nanoseeds and Ag nanoprisms, were synthesized and microscopically characterized. Then, they were drop-casted to screen-printed electrodes with three different carbon substrates (graphite, graphene and carbon nanofibers) and the resulting electrodes were tested for the simultaneous determination of Cu(II) and Pb(II). The best analytical performance was achieved for the combination of Ag nanoseeds with a carbon nanofiber modified screen-printed electrode. The resulting sensor allowed the simultaneous determination of Pb(II) and Cu(II) at trace levels and its applicability to natural samples was successfully tested with a groundwater certified reference material, presenting high reproducibility and trueness.
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Real-time imaging biodetection with Au-NHA enhanced by microfluidics Alexander Belushkin, Filiz Yesilkoy, Maria Soler, Andreas Tittl, Li Xiaokang, Hatice Altug. Bionanophotonic systems laboratory, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne 1015, Switzerland
Corresponding author: [email protected]
Nanoplasmonic biosensors hold great potential for lab-on-a-chip and point-of-care ap- plications due to their ability for ultra-sensitive label-free and real-time detection. Gold nanohole arrays (Au-NHAs) are prominent nanoplasmonic biosensors due to their tuna- ble and sharp transmission resonance peak, which is highly sensitive to refractometric changes induced by the biomolecular binding events on the surface. [1]. Compared to conventional SPR biosensing, collinear light coupling ability of Au-NHAs enables tre- mendous multiplexing and high-throughput screening capability, making Au-NHAs especially suited for point-of-care (POC) applications and field settings [1]. The highly sensitive and multiplexed detection with Au-NHAs was shown in biological applica- tions ranging from the screening of small molecules to pathogenic bacteria [2]. These studies, however, relied upon spectral monitoring of the plasmonic resonance peak, which requires bulky spectroscopic equipment, not suitable for field settings. To fully exploit the potential of Au-NHA platform, it is crucial to adapt the system for its poten- tial implementation in a compact footprint essential for POC instruments, without sacri- ficing sensing performance. In this work, we investigate the integration of a multiplexed Au-NHA plasmonic biosensor with microfluidics and show that under optimized flow conditions the limit of detection is improved by one order of magnitude. We also pre- sent real-time imaging biodetection by tuning a narrow band LED source to the flank of the plasmonic resonance that enables tracking of the plasmonic response through inten- sity monitoring with a CCD camera. Eliminating the need for spectrometer and enabling ultimate multiplexing capability, such imaging approach paves the way towards high- throughput cost-effective biosensing applications.
References:
[1] Chang, Tsung-Yao, et al. "Large-scale plasmonic microarrays for label-free high- throughput screening." Lab on a Chip 11.21 (2011): 3596-3602. [2] Soler, Maria, et al. "Multiplexed nanoplasmonic biosensor for one-step simultaneous detection of Chlamydia trachomatis and Neisseria gonorrhoeae in urine." Biosensors and Bioelectronics 94 (2017): 560-567.
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Bioluminescent Nanopaper for the Fast Screening of Toxic Substances
Jie Liu1,2, José Francisco Bergua1, Eden Morales-Narváez1, Jahir Orozco1, Ruslan Álvarez-Diduk, Teresa Vincent3, Guohua Zhong2, Arben Merkoçi1,4 1 Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain 2 Laboratory of Insect Toxicology, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, South China Agricultural University, Guangzhou 510642, P. R. China 3 Departament d’Enginyeria Química, Universitat Autònoma de Barcelona, Bellaterra, Barcelona 08193, Spain 4 ICREA, Institució Catalana de Recerca i Estudis Avançats, Barcelona, Spain E-mail: [email protected]
Chemical pollution is widely spread in environment nowadays. Particularly, the uncontrolled use of pesticides in agriculture leads to high-levels of these chemical compounds in water resources. INTCATCH H2020 European project aims to monitor and manage water quality in EU countries through the use of biosensors [1].
In this context, a biosensor for pesticides monitoring has been developed using the luminiscent bacteria Aliivibrio fischeri in combination with a nanopaper-based platform [2]. A. fischeri had previously been used in the ready-to-use kit Microtox ® since 1978 as a bioindicator of toxicity of water samples [3]. However, this methodology requires high-trained personal and expensive laboratory equipment. The use of nanopaper offers several advantages such as biocompatibility, low cost and simple procedure, increasing the sensitivity of the biosensor at the same time [4]. To study its applicability three common-used pesticides were chosen as model analytes: diuron, tributyltin (TBT) and polybrominated diphenyl ethers (PBDE). Results obtained so far as well as some future plans in applying such nanopaper platform combined with mobile phone for simple in- field pesticides monitoring will be presented.
References:
[1] http://intcatch.eu/index.php/the-project [2] J. Liu, E. Morales-Narváez, J. Orozco, T. Vincent, G. Zhong, A. Merkoçi. NanoResearch. (2017). DOI: 10.1007/s12274-017.1610-7 [3] E. Argese, C. Bettiol, A. V. Ghirardini, M. Fasolo, G. Giurin, P. F. Ghetti, Environ. Toxicol. Chem. 17, (1998), 1005. [4] E. Morales-Narváez, H. Golmohammadi, T. Naghdi, H. Yousefi, U. Kostiv, D. Horák, N. Pourreza, A. Merkoçi. ACS Nano. 9, 7, (2015), 7296-7305.
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IMPEDIMETRIC ELECTROCHEMICAL SENSOR FOR ALBUMIN DETERMINATION BASED ON POLY(BCP) FILM MODIFIED ELECTRODES
Bermudo Redondo M.Carmena, Ortiz Mayrelia, Fragoso Alexa and O’Sullivan C. K.a,b aDepartment of Chemical Engineering, Universitat Rovira i Virgili, Països Catalans 26, 43007 Tarragona, Spain bInstitució Catalana de Recerca i Estudis Avançats, Passeig Lluís Companys 23, 08010 Barcelona, Spain. [email protected]
Human serum albumin (HSA) is the major protein in plasma synthetized principally in the liver and playing significant rules after is released in the circulation. Albumin is a very important factor of regulation in the exchange of water between the plasma and the interstitial compartment being largely responsible of the colloidal osmotic pressure of blood[1]. Moreover, it is a protein with a notable ability to bind an extensive range of other small molecules helping in the transport of important substances in the human body such as hormones, fatty acids and drugs[2]. A decrease of albumin level in serum is associated with severe illnesses of the kidney as well as other conditions such as liver disease, malnutrition and extensive burns. Therefore, HSA determination is extremely useful in the diagnosis and treatment of many clinical entities. This research work reports on the development and integration of a novel label-free impedimetric sensor based on a poly(bromocresol purple) surface for the specific detection of HSA. The fabricated sensor was incubated with serum albumin, and electrochemical impedance spectroscopy (EIS) was employed to measure the changes in the conductance of the electrode of bromocresol purple (BCP) by reacting with the albumin. In addition, we validated the specificity of the designed sensor to only albumin. Clinical applicability of the sensor was also demonstrated utilizing real serum sample from patients obtaining excellent agreement with the commercial available colorimetric kit. It is expected that the new poly(BCP) sensor will become a successful diagnostic platform for HSA detection in clinical diseases.
References:
[1] Theodore Peters, Jr. Book All about albumin. Biochemistry, Genetics and Medical Applications. Elsevier Science, (Edition 1995). [2] Patricia A Zunszain, Jamie Ghuman, Teruyuki Komatsu, Eishun Tsuchida and Stephen Curry. Crystal structural analysis of human serum albumin complexed with hemin and fatty acid. BCM Structural Biology, Volume 3:6, (2003).
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NANOSTRUCTURED ENZYMATIC BIOSENSOR FOR BIOGENIC AMINES USING PAPER-BASED ELECTRODES
Carla Cristina Rubio González-Vallea, Olaya Amor-Gutiérreza, María Fernándezb, M. Carmen Blanco-Lópeza
a Departamento de Química Física y Analítica, Universidad de Oviedo, 33006 Oviedo, Spain b Instituto de Productos Lácteos, IPLA-CSIC, 33300 Villaviciosa, Asturias, Spain. email: [email protected]
Biogenic amines (BAs) are low molecular weight nitrogen compounds found in foods and fermented beverages (such as wine), that are produced through decarboxylation of amino acids by different microorganisms, and they can have a broad range of toxicological effects. Therefore, their control and monitorization in products for human consumption is becoming increasingly important.1 On the other hand, miniaturization, simplification and reduction of costs are among the most important trends for Analytical Chemistry. For this reason, paper-based analytical devices are one of the most demanding fields to develop (bio)sensors able to quantify compounds of interest. In this work, we have developed a bi-enzymatic electrochemical biosensor on paper- based electrodes and using low-cost gold-plated connections, with a design previously developed in our research group.2 The mixture of enzymes, monoamine oxidase (MAO) and horseradish peroxidase (HRP), together with ferrocyanide as mediator, was able to quantify biogenic amines like putrescine or histamine by chronoamperometry. With the aim of improving analytical characteristics, we have explored the nanostructuration of the working electrode with nanomaterials, such as colloidal gold, reduced graphene oxide and carbon black, as seen in Figure 1.
BA O2 MAO Ferrocyanide Bare electrode Graphene oxide BAox H2O2 - HRP e
H2O Ferricyanide
Colloidal Gold NPs Carbon Black
Fig. 1. Scheme of the catalytic cycle of the biosensor and the nanostructured electrodes. Acknowledgements: This work has been supported by the project FUO-148-16.
References: [1] J. L. Ordóñez, A. M. Troncoso, M. C. García-Parrilla, R. M. Callejón. Anal. Chim. Acta, 939, (2016), 10-25. [2] O. Amor-Gutiérrez, E.C. Rama, A. Costa-García, M.T. Fernández-Abedul. Bios. Bioelectron, 93, (2017), 40-45.
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A STAPLE-BASED ELECTROCHEMICAL LATERAL FLOW PLATFORM FOR PNEUMOLYSIN QUANTIFICATION
L. Blanco-Covián, M.C. Blanco-López, M.T. Fernández-Abedul*
Departamento de Química Física y Analítica, Universidad de Oviedo, 33006 Oviedo, Spain
email corresponding author: [email protected]
A lateral flow immunoassay (LFIA) with electrochemical detection was developed for the rapid detection and quantification of pneumolysin (PLY), an antigenic marker of pneumonia. The principle of the determination involved the flow of the fluid containing the analyte through the membrane, towards an absorbent pad. The analyte was captured by anti-PLY-4 on the surface of the membrane in the test line, and sandwiched with another antibody (anti-PLY-7) labeled with silver nanoparticles (AgNPs) [1]. In order to increase the sensitivity, a silver enhancement procedure was followed, generating a silver shell over AgNPs. The detection system was composed by three stainless-steel staples, with a design previously developed in our research group [2]. One of the staples was covered with conductive carbon ink, and was used as working electrode (WE). The other two acted as reference electrode (RE) and counter electrode (CE). In order to achieve good precision, the staples were inserted in an in-house designed PDMS platform. Cyclic voltammetric measurements were carried out using 80 µL of 0.1 M nitric acid as background electrolyte. The analytical signal was the anodic peak current at ca. +0.08 V, corresponding to silver oxidation, which was proportional to the concentration of PLY. The detection limit was 5 ng/mL.
Staple-based electrochemical LFIA
This work has been supported by the Spanish Ministry of Economy and Competitiveness through the project MINECO CTQ2014-58826-R and the Asturias Regional Government under projects GRUPIN14-021 and GRUPIN14-022.
[1] L. Blanco-Covián et al., Nanoscale, 9 (2017) 2051–2058 [2] P. Nanni et al., Application patent: P201600860; Filed: 07/10/2016
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A NEW LATERAL FLOW STRIP ASSAY (LFSA) USING A PAIR OF APTAMERS FOR THE DETECTION OF VASPIN
Nurul Hanun, Vanthuan Mguyen, and Man Bock Gu
Department of Biotechnology, Korea University, Anam-dong, Seongbuk-Gu, Seoul 136-713, Rep. of Korea.
Email: [email protected]
A new lateral flow strip assay (LFSA) using a pair of aptamers has been designed and successfully developed using a pair of aptamers-functionalized with gold nanoparticles (AuNPs). This new LFSA biosensor system utilizes a cognate aptamer duo binding to vaspin, a target protein, at the two different binding sites, and exhibited a sensitive and highly selective response to vaspin. A sandwich-type format in LFSA was developed based on biotin-labeled primary V1 aptamer immobilized on streptavidin coated membrane as a capturing probe and secondary V49 aptamer conjugated with AuNPs as a signaling probe. Using this LFSA, vaspin could be visibly observed within the detectable concentrations of vaspin up to 5 nM in both buffer and serum conditions. The sensitivity of this LFSA developed in this study was ranged from 0.137 to 25 nM in buffer and from 0.105 to 25 nM in spiked human serum, respectively. The limit of detection (LOD) of this LFSA was found to be 0.137 nM and 0.105 nM in buffer and spiked human serum condition, respectively. Therefore, this study has shown successful development of a simple yet effective LFSA for vaspin detection, and this development is not only limited to this target, but also other targets with a pair of aptamers available, without any special and laborious instrumentations. This system will be particularly useful as a screening tool for rapid on-site detection of any targets with a pair of aptamers generated.
References:
[1] Nurul Hanun Ahmad Raston, Van-Thuan Nguyen, Man Bock Gu. Biosensors Bioelectronics, 93, (2017), 21-25.
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PEDOT:PSS paper-based chemiresistor towards hydrogen peroxide detection
Marta Borràs-Brull, Rocío Cánovas, Pascal. J. C. L. Blondeau, Francisco J. Andrade and Jordi Riu Analytical and Organic Chemistry Department, Universistat Rovira i Virgili Marcel·lí Domingo, 1 - 43007 Tarragona [email protected]
Hydrogen peroxide (H2O2) is a common byproduct of many biochemical reactions involving oxidase enzymes such as glucose oxidase, cholesterol oxidase or lactate oxi- dase. Although many methods have been developed for its determination, electrochemi- cal methods provide considerable advantages since they are considered to be simple, inexpensive and high sensitive sensing tools [1]. Among them, chemiresistors are the simplest ones since they are only based on the change in their electrical resistance due to a chemical change in the nearby environment of the sensing material. Conducting polymers (CPs) are highly sensitive to redox and pH changes and can be molecularly doped to tune their conductivity across a range of about fifteen orders of magnitude. The ease of miniaturization and their ability to tailor their characteristics, make CPs good candidates as sensing materials for new (bio)sensor platforms [2]. Thus, poly(3,4- ethylenedioxythiophene-poly(styrene-sulfonate) (PEDOT:PSS) has recently attracted more attention as a charge-transfer media due to its electrochemical stability and relia- bility [3].
In the present study we aim at developing a sensor to detect H2O2 with a PE- DOT:PSS paper-based chemiresistor. The electrodes are hand-drawn using carbon ink on paper substrate, and PEDOT:PSS is drop-casted in the gap between the two elec- trodes to electrically connect them. Previous modification of the CP ink is needed to improve its stability in aqueous media. Preliminary results show that we have construct- ed a redox sensitive paper-based substrate to detect H2O2 at different concentrations. Further studies need to be done to optimize the sensor. Thus, we will finally reach a simple, low-cost and fast platform for H2O2 detection able to carry out a wide variety of biomolecule detections for medical applications.
References:
[1] W. Chen, S. Cai, Q-Q. Ren, W. Wen and Y-D. Zhao. Analyst, 137, (2012), 49-58. [2] H. Bai and G. Shi. Sensors, 7, (2007), 267-307. [3] J. Liu, M. Agarwal and K. Varahramyan. Sensors and Actuators B: Chemical, 135, (2008), 195-199.
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Novel approaches to build potentiometric biosensors for decentralized chemical analysis.
Rocío Cánovas, Pascal Blondeau, Francisco J. Andrade*
Department of Organic and Analytical Chemistry, Group of Chemometrics, Qualimetry and Nanosensors, Universitat Rovira i Virgili, Tarragona, Spain.
The growing demand for tools to generate chemical information in decentralized settings is creating a vast range of opportunities for potentiometric sensors, since their combination of robustness, simplicity of operation and cost can be hardly rivalled by any other technique. The recent progress in the development of ultra-low cost paper based potentiometric cells has opened new avenues for the determination of inorganic ions in biological fluids [1]. Thus, there is a significant interest on the extension of this progress to the detection of organic and biological substances. Unfortunately, traditional approaches where an enzymatic reaction generates a substance that can be detected potentiometrically cannot be easily implemented in decentralized settings. In this work, a novel platform for the development of ultra-low-cost potentiometric biosensors is presented. A platinum surface coated with a suitable polyelectrolyte is used to monitor the changes in the redox potential produced by the generation of hydrogen peroxide during an enzymatic reaction [2]. This approach allows for the highly sensitive and selective detection of different types of substances. For example, a fully integrated paper-based potentiometric cell for the detection of glucose in whole blood has been developed, optimized and validated against standard techniques. Factors affecting the generation of the signal and the principle of detection of this approach are discussed. The integration of this platform to build a whole paper- based potentiometric cell and its extension to different types of substances is presented. Approaches to improve detection scheme and applications to the development of ultra- low-cost sensors for blood and urine are presented. Future prospects expanding this platform to different types of enzymatic reactions are discussed.
References:
[1] J. Hu, S. Wang, L. Wang, F. Li, B. Pingguan-Murphy, T. J. Lu, F. Xu. Advances in paper-based point-of-care diagnostics. Biosensors and Bioelectronics 2014, 54, 585- 597. [2] M. Parrilla, R. Cánovas, F. J. Andrade. Paper-based enzymatic electrode with enhanced potentiometric response for monitoring glucose in biological fluids. Biosensors and Bioelectronics 2017, 90, 110-116.
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Multiplexed detection of single nucleotide polymorphisms using electrochemical melting curve analysis
Nassif Chahina, Mayreli Ortiza, Ahmed M. Debelab, Serge Thorimbert b, Bernold Hasenknopf b, Ciara O’Sullivana,c a Interfibio Research Group, Department of Chemical Engineering, Universitat Rovira i Virgili, Avinguda Països Catalans 26, 43007 Tarragona b Institut Parisien de Chimie Moléculaire UMR 8232 Sorbonne Universités, UPMC, Univ. Paris 06, 4 place Jussieu, 75005 Paris, France c ICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain [email protected]
The detection of single nucleotide polymorphisms (SNPs) is of great importance in life sciences. SNPs can provide information regarding the susceptibility of humans to diseases, with identified SNPs being associated with predisposition to diseases and response to drugs. Fluorescent melting curve analysis has been widely reported for the detection of mutations and high resolution melting curve analysis (HRMCA) has been exploited for the detection of SNPs, In the work reported here, we use electrochemical detection of polyoxometalate labels, (primers/dNTPs), with an in- house developed peltier heating set-up for HRMCA. Gold electrodes were fabricated using photolithography and sputtering, housed within laser-patterned polymeric microsystems and packaged between temperature controlled plates. The gold electrodes were functionalised with DNA probes for hybridisation to single stranded DNA containing the SNP(s) to be interrogated, produced using asymmetric PCR. Following hybridisation, temperature ramping was applied and the signal decrease due to denaturation measured using differential pulse voltammetry.
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SCREEN-PRINTED CARBON ELECTRODES NANOESTRUCTURED FOR THE DETERMINATION OF CARBOHYDRATES
Beatriz Pérez-Fernándeza, Agustín Costa-Garcíaa a Department of Physical and Analytical Chemistry, University of Oviedo, Julian Clavería 8, 33006 Oviedo, Asturias (Spain)
Abstract
Nanostructured electrodes exhibit several advantages over conventional ones, such as higher surface area, catalytic effects and an improved electron transference. Electrodeposition is a widely-used method to prepare nanomaterials over analytic surfaces due to its simplicity, low-cost requirements and versatility. Moreover, screen-printed carbon electrodes (SPCEs) are mass-produced, low cost, disposable, and portable devices that allow in situ analyses, that is, true point-of-care tests [1].
Copper nanospheres (CuNSs) and nickel nanoflowers (NiNFs) [2] were synthesized by chronoamperometry over the working electrode in a SPECs. Then, the nanostructured surface was activated using cyclic voltammetry in 0.1M NaOH to generate copper oxide (II) or nickel oxide (II), which are the catalytic elements. The electrode surface was then characterized by SEM, XPS and electrochemically. Under optimum conditions, we employed the sensors to quantify several carbohydrates (see figure 1), obtaining working linear ranges between 1-10.000µM and 25-1000µM and limits of detection between 3 to 12µM and 8 to 25µM respectively. These sensors show a high reproducibility and an acceptable stability. Furthermore, the sensors were employed for the determination of sugar concentration in real samples (honey, commercial fruit juice and soft drinks) with high grade of accuracy.
Figure 1. Oxidation reaction of carbohydrates about CuNSs-SPCEs and
NiNFs-SPCEs.
References:
[1] Fanjul-Bolado P, Hernández-Santos D, Lamas-Ardisana PJ, Martín-Pernía A, Costa- García A. Electrochim Acta., 53(10), (2008), 3635-3642. [2] Perez-Fernandez. B, Martin-Yerga. D, Costa-Garcia. A. RSC Advances, 6, (2016), 83748-83757.
Acknowledgements: This work has been supported by the FC-15-GRUPIN-021 project from the Asturias Regional Government and the MINECO-15-CTQ2014-58826-R project from the Spanish Ministry Economy and Competitiveness (MEC).
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TERBIUM-SENSITIZED LUMINESCENCE: A NOVEL TOOL FOR THE DETERMINATION OF GRAPHENE QUANTUM DOTS
Gema M. Durána,b, Eulogio J. Llorent-Martínez a,b, Lucía Molina-Garcíac, Antonio- Ruiz-Medinac and Ángel Ríosa
a Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha, Camilo José Cela Av., Ciudad Real E-13071, Spain. b Regional Institute for Applied Chemistry Research (IRICA), Camilo José Cela Av., Ciudad Real E-13071, Spain cDepartment of Physical and Analytical Chemistry, Faculty of Experimental Sciences, University of Jaén, Campus Las Lagunillas, E-23071, Jaén, Spain.
Graphene quantum dots (GQDs) are carbon-based nanomaterials that share characteristics from both graphene and carbon dots. They have excellent mechanical, thermal, optical and electrical properties. In addition, they present low toxicity when compared to other nanomaterials, and they are soluble in water. For all these reasons, the use of GQDs has increased in the last years in diverse research fields. However, although novel uses and future trends for the applications of GQDs are constantly reported, the development of analytical methods for their determination is not evolving at the same pace – a similar trend is observed for other nanomaterials. Therefore, the aim of this work was to propose a novel analytical method for the analysis of GQDs. Terbium-sensitized luminescence (TSL) presents inherent advantages over other luminescence techniques. The most interesting features of TSL are a large Stokes shift, a narrow-band emission, and a long luminescence lifetime, which makes possible to carry out the analytical measurements in phosphorescence mode. These characteristics make TSL a high sensitive and selective detection technique. Considering the ability of Tb(III) to form complexes with GQDs, TSL was selected for further experiments. In Tb(III)-GQDs complexes, the energy absorbed by GQDs at their characteristic excitation wavelength is transferred to terbium, which emits at its particular emission wavelength. Under optimum conditions, a quantification limit of 50 µg L-1 was obtained. The proposed method was satisfactorily applied to the analysis of GQDs in water samples, and interference studies demonstrated its selectivity to other nanomaterials of similar size.
Acknowledgments: Projects CTQ2016-78793-P and CTQ2016-7511-R (MINECO); and PEIC-2014-001-P (JCCM). E. J. Llorent-Martínez also thanks the financial support from UCLM Research Plan.
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THE USE OF POLYPYRROLE–CARBON NANOTUBE COMPOSITE SOLID-PHASE MICROEXTRACTION FIBER FOR THE ANALYSIS OF PESTICIDES USED IN APPLE PRODUCTION
İmran Güney, İrem Aydın, Levent Pelit, Hasan Ertaş, F. Nil Ertaş
a Ege University, Science Faculty, Chemistry Dep., İzmir, TURKEY
e mail address: [email protected]
Pesticides are widely used in agricultural production against fungus and insects that may cause plant damage. However, their residues can accumulate in the plant during the growing stage or from post-harvest treatment. Due to their harmful effect to human health and environment, accurate and reliable analytical methods are required for their analysis [1,2]. Present study deals with the analysis of selected pesticides used in apple production namely; bifentrin, propargite and tebufenpyrad by direct injection solid phase micro extraction technique prior to the GC-MS analysis.
Operational parameters effecting the extraction, namely; the sample pH, adsorption and desorption time have been optimized by using a commercial PDMS/DVB fiber in apple juice samples. Then, the results have been compared with those lab-made polypyrrole coated fibers produced by electropolymerization of the monomer onto the surface of a stainless steel wire and further modified with carbon nanotubes. Fiber surfaces have been characterized by SEM measurements and the analyses have been performed with GC-MS system in SIM mode. Analytical characteristics of the method have been investigated and it was revealed that these pesticides can be determined in ppb level with a high recovery percentages.
Acknowledgement: Authors thank to TUBITAK (114Z394) for financial support.
References: [1] K. Korba et al., J of Chrom. B, 929 (2013) 90–96 [2] L. Pelit, T.N. Dizdas, J. Sep. Sci. 36 (2013) 3234–3241
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PREPARATION OF VANADIUM - RUTHENIUM OXIDE / GOLD COMPOSITE ELECTRODES AND THEIR USE IN HYDRAZINE OXIDATION
Sibel Karacaa, Süleyman Koçaka, K. Volkan Özdokurb,c, F. Nil Ertaşc
a Manisa Celal Bayar University, Science&Letter Faculty, Chemistry Dep., Manisa, TURKEY b Erzincan University, Science&Letter Faculty, Chemistry Dep., Erzincan, TURKEY c Ege University, Science Faculty, Chemistry Dep., İzmir, TURKEY
email address: [email protected]
Vanadium and ruthenium oxides have received a special attention owing to their remarkable electronic and catalytic, properties. The synergistic enhancement effect in two mixed metal oxides or could possess better electrochemical activity than that of single metal oxides owing to higher electron conductivities1. Electrochemical Pulsed Deposition (PD) technique is used as determines the composition and morphology of MeOx. A recent study has shown that PD deposited VOx-RuOx film on multi walled carbon nanotubes (CNT) modified GCE and further decorated with Au nanoparticles can be used for oxidation of hydrazine2. Hydrazine is a small inorganic molecule and used in certain rockets and spacecraft. Hydrazine is also an ideal fuel for a direct fuel cell system since its fuel electro-oxidation process does not suffer any poisoning effects.
In this study, the oxidation of hydrazine at bare GCE, AuNPs and VOx-RuOx was investigated with cyclic voltammetry. In comparison to the bare GCE (20 µA at 1011 mV), CNT/GCE (39 µA at 906 mV), and AuNPs/CNT/VOx-RuOx/GCE (104 µA at 247 mV) results have been obtained for oxidation of hydrazine. Experimental parameters such as vanadium and ruthenium concentration, pulse number and time have been optimized. The gold modified VOx-RuOx electrodes not only exhibit high electrocatalytic activity for hydrazine oxidation, but they also show remarkable stability, which is important for practical applications.
References: [1]. E. Yavuz, K.V. Özdokur, I. Çakar, S. Koçak, F.N. Ertaş, Electrochim. Acta 151 (2015) 72 [2]. S. Koçak, B. Aslışen, Sens. Actuat. B, 196 (2014) 610–618
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TAILORED MAGNETIC CARBON ALLOTROPE CATALYTIC MICROMOTORS FOR ‘ON-CHIP’ OPERATIONS
Roberto Maria-Hormigosa, Beatriz Jurado-Sáncheza, Alberto Escarpaa
a Department of Analytical Chemistry, Physical Chemistry and Engineering Chemistry, University of Alcalá de Henares, Alcalá de Henares, Spain.
Man-made micromotors are at the forefront of nanotechnology research due to their great potential in biomedicine.1 Autonomous propulsion of such microscale objects can be achieved by providing an external energy input from a power source or by means of a chemical reaction occurring at the interface of the device and the liquid environment.2 Micromotors could provide improvements in the analytical performance in lab-on-a chip technology (LOCs) because they can solve limitations in sample preparation and introduction in LOCs and replace electrophoretic flow.3,4 Moreover, micromotors could incorporated receptors for capture/detection of a myriad of analytes.
In this communication, we described the templated electrosynthesis of multiwalled carbon nanotubes (MWCNTs)/Ni/PtNP micromotors. The inner layer of PtNP provides catalytic activity to produce oxygen bubbles that propelled the devices in presence of hydrogen peroxide in the media. The intermediate Ni layer provides magnetic control of the devices to LOCs operation and support the devices tubular structure. Selected examples on the use of highly rough carbon back tubular for fluorescence detection operations will be presented. The potential of ultrafast lectin carbon nanonotubes micromotors with an inner antibiofouling layer for selective transport of sugar modified particles (as cell mimics) in human plasma is also illustrated.
References:
[1] G. A. Ozin, I. Manners, S. Fournier-Bidoz, A. Arsenault, A. Adv. Mater., 17, (2005), 3011-3018. [2] J. Wang, J. Wiley-VCH, ISBN: 978-3-527-33120-8, (2013). [3] R. Maria-Hormigos, B. Jurado-Sanchez, A. Escarpa. Lab Chip, 16, (2016), 2397- 2407. [4] R. Maria-Hormigos, B. Jurado-Sanchez, A. Escarpa. Nanoscale, doi: 10.1039/C6NR09750B
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RAPID DETECTION OF SEPSIS WITH A POINT-OF CARE AND LABEL FREE MICROARRAY PLATFORM
Nuria Fabri-Fajaa, Olalla Calvoa, M.- Carmen Estéveza, Josselin Pellob, Roland A. Terborgb, Alexander Belushkin c, Filiz Yesilköy c, Pieterjan Soetaertd, Mathieu Rabaeyd, Hatice Altug c, Valerio Prunerib, Laura M. Lechugaa a Nanobiosensors and Bioanalytical Applications Group, Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, CIBER-BBN and The Barcelona Institute of Science and Technology, Campus UAB, 08193 Bellaterra (Barcelona), Spain b ICFO-Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology, 08860 Castelldefels (Barcelona), Spain c Institute of Bioengineering, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne 1015, Switzerland d Trinean NV, Dulle Grietlaan 17/3 9050 Gentbrugge, Belgium Corresponding author: [email protected]
Sepsis is a potentially fatal whole-body inflammatory reaction caused by severe infection. It reaches a 35% mortality rate and accounts for more than 7 million deaths/year. The early diagnosis and subsequent stratification of its severity is very important and helps start timely and specific treatments. More than 170 biomarkers are described for sepsis but not all of them have a sufficient specificity or sensitivity to be routinely used in clinical practice. Within the frame of a Horizon 2020 European project (RAIS, www.rais-project.eu) a point-of care device for the early diagnosis of sepsis has been developed. The portable device is an optical microarray reader based on a novel design combining interferometric lens-free microscopy and CMOS image sensing [1]. Gold nanostructures designed to increase the sensitivity of the device are used as sensing chips. Accurate surface modification and biofunctionalization protocols have been developed for the optimal immobilization of specific receptors (both antibodies and DNA probes) for a panel of selected biomarkers (Several proteins, miRNAs and bacteria). Individual detection assays in a label-free microarray format have been developed and sensitivity levels established, to further integrate them in a unique chip that will allow the analysis of several biomarkers at the same time (multiplexed measurement).
References: [1] R.A. Terborg, J. Pello, I. Mannelli, J.P. Torres and V. Pruneri, Science Advances 2, e1600077 (2016)
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VERTICALLY-ORIENTED AND SHAPE-TAILORED ELECTROCATALYTIC NICKEL NANOWIRES FOR ENZYME- FREE GALACTOSEMIA RAPID DIAGNOSIS Laura García-Carmona, María Cristina González and Alberto Escarpa* Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering Faculty of Biology, Environmental Sciences and Chemistry. University of Alcalá E-28871 Alcalá de Henares. Madrid (Spain)
*Email address of the corresponding author: [email protected]
Vertically nickel nanowires (v-NWs), as exclusive flexible electrochemical transducers cut at tailored shape and size without extra conductive support for detection of carbohydrates in metabolic diseases, have been reported for the first time in miniaturized flow injection analysis (FIA) [1]. v-NWs were electrosynthesized using a polycarbonate membrane template, which was cut with the desired shape, stuck in double-sided adhesive tape, pasted into a non-conductive substrate and in situ removed. Then, they were were morphologically characterized using scanning electron microscopy (Figure 1).
Figure 1. Left: Scheme of v-NWs electrodes construction. A) Synthesis of NWs in a polycarbonate membrane, B) electrode shape and size design, C) final arrangement. ( ) Polycarbonate membrane, ( ) gold sputtering layer, ( ) NWs. Right: SEM image of v- NWS (Scale bar 1 μm).
The proposed strategy was very simple and highly versatile allowing a forest of v-NWs with a high analytical performance because of the transduction was supported exclusively by the nanomaterial.The analytical potency of this new approach was clearly demonstrated towards the fast and reliable diagnosis of galactosemia using precious newborn urine samples clinically diagnosed. A very good agreement was obtained between the values obtained by our method using galactose as standard and those diagnosed values (Er ≤3%).
References:
[1] L. García-Carmona, M.C. González, A. Escarpa, Chem. Eur. J. 2017. DOI: 10.1002/chem.201701213
84
MULTIPLEXED DETECTION OF ALTERNATIVE SPLICED mRNA ISOFORMS FOR CANCER DETECTION USING A BIMODAL WAVEGUIDE INTERFEROMETER BIOSENSOR
Daniel Grajales, César S. Huertas, Laura M. Lechuga Nanobiosensors and Bioanalytical Applications Group. Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of Science and Technology, and CIBER-BBN. Campus UAB, Barcelona, Spain. [email protected] Personalized medicine keeps progressing as discoveries in the field of Epigenetics demonstrate the environmental and hereditary components of many diseases, including cancer. Understanding the epigenetics gene regulation pathways provides more information about the molecular insight of cancer cells and help in tailoring more individualized therapies. Alternative splicing of mRNA precursors is one of these gene regulation pathways and enables cells to generate different protein outputs from the same gene depending on their developmental or homeostatic status. For example, the alternative splicing of Fas gene produces two isoforms, one that includes exon 6 and is associated with pro-apoptotic pathways and another that skips exon 6, producing an anti-apoptotic protein. Their misbalance expression is linked to the output of tumors, constituting an innovative class of biomarker that provides more information on early stages of the cancer development and subsequent treatment. Current methods for monitoring alternative splicing events rely on time consuming and lab-based procedures, which require trained personal. Therefore, there is an unmet need for new technologies with simplified protocols and capable of providing sensitive and real-time analyses of multiple alternative splicing events for routine clinical diagnosis. Herein we report a highly selective and sensitive nanophotonic biosensor based on bimodal waveguide interferometers [1] for the direct monitoring of the aberrant alternative splicing of Fas gene. Due to its miniaturized size each sensor chip contains 20 nanointerferometers, constituting an ideal platform for multiplexed analyses. In order to avoid sensitivity fading and signal ambiguity that impede the prediction of the phase change [2], a modulation system for the direct read-out of the signals was implemented, enhancing the resolution and sensitivity of the device by 12% and highly improving its reproducibility. In addition, we have designed S-shape beam splitters in arrays of 1x4 and 1x8 for the simultaneous analysis of multiple alternative splicing events. The sensor performs a real-time detection of the specific mRNA isoforms in the fM-pM range without any cDNA synthesis or PCR amplification requirements [3]. This biosensor represents an innovation in the field of epigenetics, facilitating and accelerating the analysis of gene regulation processes for cancer prognosis, diagnosis and patient’s follow-up.
[1] K. E. Zinoviev et al. J. Light. Technol., vol. 29, no. 13, (2011), pp. 1926–1930. [2] S. Dante et al. Optics Express, vol. 20, no. 7. (2012), p. 7195. [3] C. S. Huertas et al. Sci. Rep., vol. 7, no. July 2016, (2017), p. 41368.
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STUDY OF MERCURY SIGNAL AMPLIFICATION EMPLOYING SPCEs MODIFIED WITH NANOPARTICLES, AND ITS APPLICATION AS LABEL IN IMMUNOLOGICAL REACTIONS
Alba Iglesias-Mayor, Olaya Amor-Gutiérrez, Agustín Costa-García
Departamento de Química Física y Analítica, Universidad de Oviedo, 33006 Oviedo, Spain
email address of the corresponding author: [email protected]
The study of nanoscale materials in recent years has been extensive, particularly with respect to metallic nanoparticles (NPs) which have received great attention because of their specific properties [1]. Those characteristics make nanomaterials ideally suited for electroanalytical applications, due to the advantages that they offer compared to unmodified electrodes. Nowadays the progress of nanotechnology and biosensing integrates the design of materials with the exquisite specifity of biological molecules [2]. In this work, the electrochemical behaviour of mercury using different nanostructured screen-printed transducers has been studied. The effect of gold nanoparticles, adsorbed on Screen-Printed Carbon Electrodes (SPCEs), on the underpotential deposition (UPD) processes of mercury was studied by Cyclic Voltammetry (CV), as shown in Figure 1. Figure 1. Cyclic voltammograms for Hg2+ 10-3 M (in HCl 0.1 M) in different transducers. References: [1] S.E.F. Kleijn, Stanley C.S. Lai, Marc T.M. Koper, Patrick R. Unwin, Angew. Chem. Int. Ed, 53 (2014), 3558-3586. [2] Daniel Martín-Yerga, María Begoña González-García, Agustín Costa-García, Talanta, 116 (2013), 1091-1104. Acknowledgements: This work has been supported by the FC-15-GRUPIN14-021 project from the
Asturias Regional Government and the CTQ2014-58826-R project from the Spanish Ministry of Economy and Competitiveness (MINECO). Alba Iglesias-Mayor thanks the Spanish Ministry of Education, Culture and Sports (MECD) for the award of a FPU Grant (FPU2014/04686).
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Development of Nanofiber Functionalized Aptasensor for Electrochemical Detection of Cancer Cell
E. Kıvraka, A. Inceb, R. Ilhanc, P. Ballarc, S. Yılmazb, P. Karaa, a Ege University Faculty of Pharmacy, Analytical Chemistry Dept., 35100, Bornova, Izmir, TURKEY b Izmir Institue of Technology Chemical Engineering Department, Urla, Izmir c Ege University Faculty of Pharmacy, Biochemistry Dept., 35100, Bornova, Izmir
email [email protected]
Cancer is still one of the major public health problem worldwide. It is the second leading reason of death following cardiovascular diseases. Studies focusing on cancer prevention, early detection, and treatment aim to decline the cancer death rate. Therefore, early detection is especially important for survival of patients. [1]. There has been a growing interest for rapid, reliable and ultrasensitive cancer detection methods devoted to clinical analysis. Among the available techniques, aptamer based biosensing techniques have great promise in biosensing due to their high sensitivity and selectivity to their target biomolecules [2]. The development of aptasensors for proteins, cells and other biomolecules has the potential to impact life sciences as well as screening in medical applications [3]. In this work polyacrylonitrile nanofibers (PANnf’s) modified sensor surfaces for label free detection of cancer cell were developed. As a model case non-small cell type lung cancer cells were used. PANnf’s were electrospun directly onto disposable graphite electrode (DGE) surfaces for the first time. The PANnf/DGE electrode was partially hydrolyzed with an NaOH aqueous solution to convert the nitrile groups of the PANnf’s into carboxyl groups [4]. Aptamer sequence was immobilized onto PANnf’s modified electrode surface via carbodiimide chemistry. The binding of cancer cells onto Aptamer/ PANnfs /DGE surfaces at 37.5 oC were monitored by electrochemical impedance spectrometric (EIS) transduction of the Rct in the presence of 5mM [Fe(CN)6]3-/4-. The designed aptasensor’s selectivity were performed by using HeLa cells [5]. Our label free electrochemical aptasensor is applicable to the design of aptasensors for other type of cancer cells with a massively detection capability in clinical analysis. REFERENCES [1] R. L.Siegel, K.D. Miller, A. Jemal, Cancer statistics, Cancer J. Clin., 65, (2015), 5. [2] S. Raichlin, E. Sharon, R. Freeman, Y. Tzfati, I. Willner, Biosensors & Bioelectronics, 26, (2011), 4681. [3] X. Zhang, J. Zhang, Y. Ma, X. Pei, Q. Liu, B.Lu, L. Jin, J. Wang, J. Liu, The International Journal of Biochemistry & Cell Biology, 46, (2014), 1. [4] P.K. Gupta, A. Gupta, S. R. Dhakate, Z. H. Khan, P. R. Solanki, J. Of Applied Polymer Science, 44170, (2016), 1-9. [5] P. Kara, Y. Erzurumlu, P. Ballar, M. Ozsoz, J. Electroana. Chem., 775, (2016), 337.
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A Electrochemical Sensor Based on Ultrathin Nanostructural Coating for Perfluorooctane Sulfonate Analysis
Najmeh Karimian, Angela M. Stortini, Ligia M. Moretto, Paolo Ugo
Department of Molecular Sciences and Nanosystems, University Ca’Foscari of Venice, via Torino 155, 30172 Venezia Mestre, Italy
Perfluorooctane sulfonate (PFOS) pollution in aqueous environment is a problem of global concern1. Smart recognition systems using synthetic analogues offer improved stability, cost effectiveness and a means of rapid fabrication. Molecularly-imprinted electrodes can provide a promising alternative and direct approach to determine a template. Molecular imprinting of polymers (MIPs) is a technique used to create mimetic receptors by the formation of a polymer network around a template. The electrosynthetic approach simply and rapidly creates an adherent and compact polymeric film with controllable thickness, which could be very helpful both in improving the molecular imprinting polymerisation procedure and in extending the application of MIPs2,3. In this study, the fabrication and characterization of novel sensor for PFOS based on a molecularly-imprinted electrosynthesised polymer is reported. A PFOS sensitive layer was prepared by electropolymerization of o-phenylenediamine (o- PD) on a gold electrode in the presence of PFOS as a template so producing an ultrathin film with molecular recognition capibilities. To develop the molecularly imprinted polymer (MIP), the template molecules were removed from the modified electrode surface by suitable procedure. Electrochemical methods were used to monitor the processes of electropolymerization, template removal and binding in the presence of a redox probe. The imprinted layer was characterized by cyclic voltammetry (CV), differential pulse voltammetry (DPV), quartz crystal microbalance (QCM), profilometry and scanning electron microscopy (SEM). The incubation of the MIP-modified electrode with respect to PFOS concentration resulted in a suppression of the signal of the probe. The sensor was successfully tested for analysing PFOS in water at 0.1 nM- 1.5 µM concentration levels, giving results comparable with those obtained by HPLC/MS/MS analysis.
References:
[1] J.P. Giesy, K. Kannan. Sci. Technol., 35, (2001), 1339. [2] K. Haupt, K. Mosbach. TIBTECH, 16, (1998), 468. [3] N. Karimian, A.P.F. Turner, A. Tiwari. Biosens. Bioelectron. 59, (2014), 160.
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PREPARATION, CHARACTERIZATION AND BIOSENSING APPLICATIONS OF GRAPHENE/POLY-L-LYSINE COATED ELECTRODES
Nilgün Dükara, Filiz Kuralaya
aDepartment of Chemistry, Faculty of Arts and Sciences, Ordu University, Ordu, Turkey.
Electroactive polymer films are commonly used for biosensing applications since they facilitate the immobilization of biomolecules. These polymers can be easily formed from their monomers [1,2]. In addition, nanocomposites of the electroactive polymers with nanomaterials have attracted great attention. Nanomaterials can increase the sensitivity of these polymers [3]. In this study, we detail the preparation, characterization and biosensing applications of graphene/poly-L-lysine coated electrodes for DNA-anticancer drug interaction. The electropolymerization of L-lysine was performed by cyclic voltammetry (CV) and constant potential electrolysis in the presence of graphene onto the graphite electrodes. Then, double-stranded DNA (dsDNA) immobilized nanocomposite coated electrodes were used for DNA-Mitomycin C (MC) interaction. The prepared electrodes were characterized by cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (EIS).
References:
[1] D. Zhang, Y. Zhang, L. Zheng, Y. Zhan, L. He, Biosens. Bioelectron., 42, (2013), 112. [2] C. Jiang, T. Yang, K. Jiao, H. Gao, Electrochim. Acta, 53, (2008), 2917. [3] F. Kuralay, A. Erdem, Analyst, 140, (2015), 2876.
Acknowledgments
F. Kuralay acknowledges Turkish Academy of Sciences (TÜBA) as an associate member and TÜBA-GEBİP program.
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ABSTRACT TITLE ISOTHERMAL MULTIPLEXED BRIDGE AMPLIFICATION AND ELECTROCHEMICAL DETECTION FOR RELIABLE AND COST EFFECTIVE MOLECULAR DIAGNOSTICS
Ivan Magriñá a, Mayreli Ortiz , Ciara K. O’Sullivan
Interfibio Research Group, Universitat Rovira i Virgili
Av. Països Catalans, 26. 43007 Tarragona
ae-mail: [email protected]
We aim to develop a generic electrochemical platform for rapid DNA amplification, detection and quantification combining 3 different technologies: a) Recombinase polymerase amplification (RPA) b) Bridge amplification c) Electrochemical detection
RPA is a novel isothermal DNA amplification technology with outstanding features: it works at a low constant temperature (37-42ºC), has high sensitivity and selectivity, is the fastest amplification technology available and allows to incorporate modified nucleotides to the amplified DNA. To amplify multiple targets in a single reaction we will use solid phase bridge amplification. For that purpose, a 9-electrode array will be used and each electrode will be immobilised with primers for only one target. This primer configuration avoids primer-dimer problems and produce spatially amplified DNA products on the electrode surface. The DNA amplification will be done in presence of ferrocene labelled nucleotides, and the ferrocene incorporated in the DNA will be measured electrochemically by differential pulse voltammetry.
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BIOSENSING STRATEGY FOR SIMULTANEOUS AND ACCURATE QUANTITATIVE ANALYSIS OF MYCOTOXINS IN FOOD SAMPLES USING NON-FUNCIONALIZATED GRAPHENE MICROMOTORS Águeda Molinero-Fernándeza, María Moreno-Guzmána, Miguel Ángel Lópeza, Alberto Escarpaa a Department of Analytical Chemistry, Physical Chemistry and Engineering Chemistry, University of Alcalá de Henares, Alcalá de Henares, Spain.
An unique analytical application of graphene oxide (GO)/Pt microtubular engines as a powerful fluorescent aptamer-based “On-Off” strategy for the simultaneous detection of two food significance mycotoxins (Fumonisin B1(FB) and Ocratoxin A(OTA)) was developed. The assay principle is based on the selective recognition from aptamers to the target mycotoxins and further fluorescence quenching of the free aptamer in the outer layer of unmodified graphene micromotors simplifying the overall approach. (See Figure 1.)
The new approach offers, using just 1 µL of sample, a simultaneous and rapid “on-the- fly” detection (2 min) with high sensitivity (LODs of 7 and 0.4 pg/mL for OTA and FB, respectively), and high selectivity. In real samples, a remarkable accuracy (Er<5%) for the mycotoxin determination in certified reference material (CRM) and an excellent quantitative recoveries (96-98%) for the analysis of food samples were also obtained. The excellent results demonstrate an exciting future for the catalytic micromotors in a very important research area such as food safety diagnosis.
Figure 1. Biosensing strategy for myco- toxins detection using non-funcionalizated graphene-based micromotors. (A) In ab- sence of mycotoxin; (B) in excess of my- cotoxin; (C) intermediate mycotoxin con- centration.
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CLASS ENZYME-BASED MOTORS FOR “ON THE FLY” ENANTIOMER ANALYSIS OF AMINO ACIDS Laura García-Carmona, María Moreno-Guzmán, María Cristina González, Alberto Escarpa* Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, Faculty of Biology, Environmental Sciences and Chemistry, University of Alcalá, 28871 Alcalá de Henares, Madrid, Spain. *Email address of the corresponding author: [email protected]
Two class-enzyme motors have been properly designed allowing the rapid dispersion of the class-enzyme D-amino acid oxidase (DAO) and L-amino acid oxidase (LAO) for selective “on the fly” detection of D and L-amino acids (AAs), respectively [1]. The efficient movement together with the continuous release of fresh class-enzyme leads to a greatly accelerated enzymatic reaction process, without the need of external stirring or chemical physical attachment of the enzyme (see figure 1).
L-AAs D-AAs + + SDS + LAO LAO DAO DAO + SDS
H2O2 H2O2
Figure 1. Class-enzyme motors for enantiomer analysis.
Ultrafast detection “on-the-fly” (<2 min) and quantification of enantiomer biomarkers (L-Phe and D-AAs) as relevant examples of Phenylketonuria disease and Vibrio cholera cultures, respectively, were carried out using minimum sample amounts (less than 50 µL). This approach was applied for the first time for detection and quantification of L- Phe in plasma and whole blood from newborn samples diagnosed with Phenylketonuria and for total D-AAs in cultures of Vibrio cholera, obtaining in both cases a very good agreement between the values obtained using our approach and those diagnosed values (Er≤3%). The results obtained open novel avenues in biosensing for fast diagnosis monitoring and design of future point of care.
References:
[1] L. García-Carmona, M. Moreno-Guzmán, M. C. González, A. Escarpa. Biosens. Bioelectron (aceppted, may 2017).
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GOLD NANOPARTICLES FORMATION AS AN INDICATOR OF ENZYMATIC METHODS: TIRAMINE DETERMINATION
Navarro Domínguez J.a, de Marcos Ruiz S.a, Galbán Bernal Ja. a University of Zaragoza, Institute of Nanoscience of Aragón. Analytical Chemistry Department. C/ Pedro Cerbuna 12, Zaragoza, Spain.
Tyramine is a biogenic amine which can be found in certain foods like chocolate, beer, wine and cheese [1]. Intake of large quantity of tyramine is associated with migraines, hypertension and hyperthyroidism. These is because, analytical methods have been developed for quantification, but they all have disadvantages regarding sample preparation, cost and time consuming.
It is therefore that, in this work, an enzymatic-colorimetric method has been developed based on the reaction between tyramine oxidase (TAO) and tyramine (tyr) in presence of Au (III), which lead to the formation of gold nanoparticles (figure 1) that can be related to the concentration of tyramine in the sample. These nanoparticles show molecular absorption around 540 nm (figure 2).
Since dissolved O2 regenerate the enzyme and modify the mechanism of the kinetic reaction, there are two lineal ranges, one for [tyr]<[O2]dissolved (0.01 mM–0.2 mM) and other for [tyr]>[O2] dissolved (0.2 mM –1 mM). Besides, the fluorescence properties of these nanomaterials are being evaluated.
Figure 1: Scheme of the enzymatic reaction Figure 2: Absorption spectra before and after in presence of Au (III). enzymatic reaction TAO-tyr in presence of Au (III). This work has been supported by the MINECO of Spain (project CTQ2016-76846-R) and by the founding to research group of the DGA-FEDER (E74). J. Navarro thanks to the Government of Aragón for a grant.
References: [1] Lata, S., Yadav, S., Bhardwaj, R., & Pundir, C. S. Sensing and Instrumentation for Food Quality and Safety, 5(3-4), (2011) 104-110.
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LOCALISED SURFACE PLASMON RESONANCE BIOSENSOR FOR THE MONITORING OF SINTROM® THERAPEUTIC DRUG IN PLASMA
E-Cristina Peláeza,b, M-Carmen Estevezb,a, J-Pablo Salvadorb,c, M-Pilar Marcoc,b and Laura M. Lechugaa,b a Nanobiosensors and Bioanalytical Applications Group, Catalan Institute of Nanoscience and Nanotechnology (ICN2) and The Barcelona Institute of Science and Technology, 08193Campus UAB Bellaterra, (Barcelona), Spain. b CIBER-BBN Networking Center on Bioengineering, Biomaterials and Nanomedicine, Spain. c Nanobiotechnology for Diagnostics Group, Institute for Advanced Chemistry of Catalonia (IQAC), CSIC, 08034 Jordi Girona 18-26, Barcelona, Spain [email protected]
Acenocoumarol (Sintrom®) is an oral anticoagulant prescribed for the treatment of a variety of thromboembolic disorders. It inhibits fibrin production preventing clot formation. Sintrom has a narrow therapeutic range, and its effects depend on many factors, such as body weight, age, metabolism, or diet, among others. A higher dose would result in the risk of bleeding, while if it is too low, the risk of blood clot would increase. Complementary tools that allow the therapeutic drug monitoring (TDM) of Sintrom plasmatic levels from the beginning of the treatment would be of paramount importance. Point-of-care devices would have an added value to facilitate on-site monitoring (i.e. hospitals or primary care doctor) aiding in dosage management. According to this, we have developed a nanoplasmonic biosensor based on the Localised Surface Plasmon Resonance (LSPR) of gold nanodisks for the rapid monitoring of Sintrom, using highly specific polyclonal antibodies produced against this drug. The nanoplasmonic sensor was first modified with a thiolated self-assembled monolayer (SAM) containing carboxylic groups to further allow the covalent attachment of the Sintrom antigen conjugate. In order to assess the viability of performing the measurements in 50 % of plasma and reduce non-specific adsorptions on the sensor surface, a blocking agent (gelatin 3 %) was used and a specific buffer was tailored. Several experimental conditions have been optimised to show a Limit of Detection (LOD) and an IC50 of 0.66 nM and 50.1 nM respectively, and a working range between 3.24 nM and 777 nM, which are relevant for the diagnostic application of Sintrom monitoring.
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Implementation of gold nanoparticles in liquid-phase microextraction for microvolume colorimetric detection of iodide in waters
F. Pena-Pereira, V. Romero, A. Garcia-Figueroa, I. Lavilla, C. Bendicho
Analytical and Food Analytical Chemistry Department, Faculty of Chemistry, University of Vigo, Campus As Lagoas-Marcosende s/n, 36310 Vigo, Spain.
A wide number of plasmonic sensing approaches have been exploited for the development of analytical methods in recent years. From them, gold nanoparticles (AuNPs) are probably the most typical colloidal systems used with this aim. However, certain limitations arise when dealing with their analytical application in real samples. In fact, AuNPs can be affected under relatively harsh pH, temperature or ionic strength conditions. Besides, functionalization of AuNPs is commonly performed to achieve appropriate selectivity toward target compounds. In this work we have explored the possibility of implementing non-functionalized gold nanoparticles in headspace single- drop microextraction for the colorimetric determination of iodide. The method was based on the in situ generation of molecular iodine and exposure of a microdrop of gold colloidal solution to the headspace above the sample. The presence of water miscible organic solvents such as N,N-dimethylformamide in the microdrop yielded a significant enhancement of the sensitivity. Under optimal experimental conditions, a log-log correlation was observed between the red-shift of the plasmonic band and the concentration of iodide with both pristine and DMF-containing AuNPs. The limits of detection and quantification were 2.3 and 7.6 µM with pristine AuNPs, and 0.3 and 1.0 µM with DMF-containing AuNPs, respectively. The method was successfully validated against a certified reference material (QC-1047) and recovery studies were carried out in different water samples, with satisfactory recoveries in the range 91-105%.
Acknowledgements: Financial support from the Spanish Ministry of Economy and Competitiveness (Project CTQ2015-68146-P) (MINECO/FEDER) is gratefully acknowledged.
References: [1] F. Pena-Pereira, I. Lavilla, C. Bendicho. Sensors Actuat. B, 242, (2017), 940. [2] J. Zhang, X. Xu, C. Yang, F. Yang, X. Yang. Anal. Chem., 83, (2011), 3911. [3] C. Bendicho, I. Costas-Mora, V. Romero, I. Lavilla. TrAC, Trends Anal. Chem., 68, (2015), 78.
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MODIFICATION OF ELECTRODE SURFACE FOR CORTISOL DETECTION Briza Pérez-Lópeza, Ruta Grinytea, Judith Arboledas, Jordi Ricarta, Marc Masaa, Chantal Vilàb, Robert Pousb, Gregorio Azcarateb, Xavier Venturab,
a Technological Center LEITAT C/ de la Innovació, 2 • 08225 Terrassa (Barcelona), Spain b PROMAX Electrónica, c/ Francesc Moragas, 71 • 08907 L’Hospitalet de Llobregat (Barcelona), Spain
Cortisol is often called the “stress hormone”, but it also plays an important role in the homeostasis of physiological processes e.g., adrenal, immune, circulatory, metabolic etc. Many different techniques were used for detection of this “stress hormone”, like HPLC, radioimmunoassay, flow immunoassay and ELISA. However, these approaches are laborious, time-consuming, require large sample volume or radioisotopes. In this context, the use of electrochemical immunosensors, because of their excellent analytical capabilities such as sensitivity, reproducibility, simplicity of construction and use, and feasible miniaturization, can be envisaged as a promising alternative for detection of cortisol. These important advantages become more evident insofar as the immunorea- gent immobilization and the transduction event are more efficient. Therefore, the prepa- ration of bioelectrodes combining immobilization methods capable of improving stabil- ity with no significant loss of the biological activity of biomolecules, with electrochem- ical transducers able to enhance the electron transfer, constitutes a challenge in modern bioanalytical chemistry. For this reason, in this work has been studied an electrochemi- cal immunosensor and an ELISA system which could allow a rapid and sensitive detec- tion of cortisol using a label-free biosystem of detection. The main interest has been focused on the optimization of each one of the phases of immobilization achieving a very simple and label-free square-wave voltammetry (SWV) immunosensor to detect cortisol, in which anti-cortisol antibodies was used as a molecular recognition element, and the couple ferro/ferricyanide as a redox probe.
References:
[1] A. Kumar, S. Aravamudhan, M. Gordic, S. Bhansali and S. S. Mohapatra. Biosensors& Bioelectronics, 22, (2007), 2138–2144. [2] C. Seoyeon, H. Jung, C. Jong-Soon,J. Hyo-Il Anal. Methods, 2015, 7, 1834–1842. [3] L. Manenschijn, J. W. Koper, S. W. J. Lamberts, E. F. C. van Rossum Steroids, 76, 1032 (2011).
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3D-Printed microfluidic platform for S2- monitoring in biotechnological processes
Roberto Pola,b, Yasmine Alonsoa, Raquel Montesb, David Gabrielb, Francisco Céspedesa, Mireia Baezaa a Grup de Sensors I Biosensors, Departament de Química, Facultat de Ciències, Edifici C-Nord, Universitat Autònoma de Barcelona, 08193 Bellaterra (Spain) bGENOCOV, Departament d’Enginyeria Química, EE, Universitat Autònoma de Barcelona, 08193 Bellaterra (Spain)
A crucial challenge to address in biotechnological processes is the development of automated devices for real-time monitoring of chemicals involved. Since traditional analysis methods consist on multiple steps and are rather costly and time consuming, the emphasis nowadays is shifted towards the use of remote autonomous systems in a miniaturised fashion. Three-dimensional (3-D) printing technology has emerged as one of the cheapest alternatives to manufacture highly reproducible and durable scaffolds. Herein, the production of a 3D-printed platform with integrated potentiometric detection is described. The device contains integrated therein a second kind sulfide-selective electrode (Ag/Ag2S) and a pseudo-reference electrode (Ag/AgCl), both produced by electrochemical deposition onto a silver wire using their respective anions solutions. The electrodes were morphologically characterized while the device was characterized in terms of its analytical response. Furthermore, river/sea-spiked environmental samples and wastewater from a biotechnological process were measured and compared against a commercial available sensor giving no significance differences. Considering all the current challenges in biotechnological screening this appealing technology could open a new point of view for mass production of low-cost electrochemical-based detection microfluidic platforms.
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Development of a low-cost point-of-care test for Tuberculosis detection
Patricia Ramíreza, Daan Martensb,c, Peter Bienstmanb,c, Mahavir Singhd, Ayssar A. Elamind, Wim Van Roye, Rita Vose, Pieterjan Soetaertf, Birgit Antong, Holger Beckerg, and Laura M. Lechugaa a Nanobiosensors and Bioanalytical Applications Group, Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, The Barcelona Institute of Science and Technology, and CIBER-BBN, Campus UAB, 08193 Barcelona, Spain b Photonics Research Group, Ghent University-IMEC, c Center for Nano- and Biophotonics, Ghent University, Technologiepark-Zwijnaarde 15, 9052 Ghent, Belgium d LIONEX GmbH, Salzdahlumer Str. 196, Building 1A, 38126 Braunschweig, Germany e IMEC, Kapeldreef 75, 3001 Leuven, Belgium f Trinean NV, Dulle Grietlaan 17/3, 9050 Gentrbrugge, Belgium g Microfluidic ChipShop GmbH, Stockholmer Str. 20, 07747 Jena, Germany
Tuberculosis (TB), caused by Mycobacterium tuberculosis, is a re-emerging disease impacting global health and affecting around 10.4 million people annually, with 1.8 million deaths. Registered incidence rates are low due to the lack of rapid and accurate diagnostic tools, especially in low-resource countries, posing serious hurdles for TB control. Since several years ago, a major effort is directed to develop a point-of-care (PoC) platform to facilitate the prompt and reliable TB diagnostics at low cost. In the frame of the European FP7 Pocket project, we have developed a novel PoC platform for the non-invasive technique detection of TB in human urine, accomplishing the above requirements.
The new tuberculosis PoC is based on the combination of highly sensitive Mach- Zehnder integrated interferometers with an on-chip spectral filter, combined with a polymer microfluidic cartridge (disposable part), a SLED light source, a CCD camera for read-out and a graphical user interface for data processing. All the elements are incorporated in a PoC platform (see Figure 1). The TB detection is achieved directly in the urine samples by an immunoassay employing high quality and selective antibodies against M. tuberculosis cell wall lipopolysaccharide lipoarabinomannan (LAM) and Ag85 complex. A preliminary Limit of Detection (LoD) of 956 pg/mL and 8.496 ng/mL for LAM and Ag85, respectively, have been achieved.
Figure 1. Pocket instrument and the disposible cartridge.
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Graphene membrane thin-film microextraction for Cr speciation in waters by total reflection X-ray fluorescence
Vanesa Romero, Isabel Costas, Francisco Pena, Isela Lavilla, Carlos Bendicho Department of Analytical and Food Chemistry, Analytical Chemistry Area, Chemistry Faculty, University of Vigo, As Lagoas-Marcosende s/n 36310, Vigo, Spain.
Email: [email protected]
Graphene is a planar sheet of sp2-bonded carbon atoms packed in a honeycomb crystal lattice, which has attracted much attention in the field of material science due to its unique properties. One of the most used methods for its production is the Hummers’ method based on the oxidation of graphite [1]. In the last few years, graphene oxide (GO) and graphene nanosheets have been reported as promising sorptive materials for extraction and preconcentration of trace metal ions [2]. Most reported applications use dispersive micro-solid phase extraction. After sorption, nanosheets have to be isolated, which could lead to losses of the nanomaterial. Therefore, new formats of carbon nanomaterials for microextraction such as easy-to-handle graphene membranes would avoid separation steps thus simplifying sorption procedures. In this work fabrication of unmodified circular-shaped multilayer graphene membranes (Ø 10 mm) by means of drop-casting of GO onto glass substrates followed mild thermal reduction for Cr speciation in water by total reflection X-ray fluorescence (TXRF) is described for the first time [3]. Synthesized graphene membranes are 122 nm height with a surface nanoroughness of 22.14 nm containing non-reduced functional groups (e.g. hydroxyl, carboxy and epoxy). Highly flexible graphene membranes become conical-shaped in the vortex occurring upon sample stirring. When stirring is stopped, graphene membranes return to its initial flat shape being transferred to a quartz substrate for TXRF measurement. Experimental results for sorption of Cr(VI) fit well with the Langmuir isotherm model, assuming that the adsorption sites on graphene membranes are uniformly distributed and Cr(VI) can be retained both by electrostatic interactions with positively charged functional groups and by chemisorption upon reaction with hydroxyl groups. Adsorption capacity is 22 µg Cr(VI) per mg of graphene membrane. The detection limit is 0.08 µg L-1 Cr(VI). Repeatability expressed as relative standard deviation is 3% (N=5). Two reference materials, i.e. CASS-4 seawater and NWTM-27.2 lake water are used for testing accuracy and recovery studies obtaining results in the range 99-102%. The proposed method is sensitive, simple and solvent-free, being suitable for Cr speciation in waters including high salinity samples. Acknowledgements: Financial support from the Spanish Ministry of Economy and Competitiveness (Project CTQ2015-68146-P) (MINECO/FEDER) is gratefully acknowledged.
References: [1] W.S. Hummers, R.E. Offeman. J. Am. Chem. Soc., 80, (1958), 1339. [2] R. Sitko, B. Zawisza, E. Malicka, TrAC Trends Anal. Chem, 51, (2013), 33. [3] V. Romero, I. Costas-Mora, I. Lavilla, C. Bendicho, RSC Adv., 6, (2016), 669.
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HEAVY METAL DETERMINATION BY PAPER-BASED ELECTRODES MODIFIED WITH MERCURY AND BISMUTH FILMS
A. Sánchez Calvo, M.T. Fernández-Abedul, M.C. Blanco López, A. Costa García* Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006 Oviedo, Spain. [email protected] Materials based on cellulose such as paper can be modified with carbon conductive inks to generate working electrodes with different applications [1-2]. As a step forward to the development of competitive chemical sensors, these cellulose-based materials can also be modified by the formation of new surfaces to develop different transducers. In this work, the in-situ formation of mercury or bismuth films on paper-based electrodes was tested towards the determination of heavy metals (Pb, Cu, Cd, In). Paper-based carbon working electrodes (PCWEs) were made with chromatographic paper (Whatman Grade 1). Hydrophobic barriers were created by wax printing and curing, to yield hydrophilic areas with a diameter of 4 mm. Then, 2 µL of a suspension of carbon ink (30% w/w in DMF) were added and dried at room temperature. The PCWE was overlaid at the surface of the working electrode of a screen-printed platform with an adhesive. The cellulose fibers were modified by the electrodeposition of mercury from mercury acetate by applying a potential of -0.75 V for 240 s. A film was formed and it was used for the electrodeposition of heavy metals such as lead, cupper, cadmium and indium. Bismuth was also tested as a film, prepared following the same modification procedure. The formation of films were made by chronoamperometry and the determination of heavy metals by anodic stripping voltammetry. In conclusion, a paper-based working electrode was used as a platform for determination of heavy metals. The substrate was modified by the in-situ formation of different mercury and bismuth films, acting as transducers. The mercury film yielded the best results. Future objectives are the simultaneous determination of heavy metals and the alternative film formation investigation.
Acknowledgements: This study was financed by the Consejería de Economía y Empleo del Principado de Asturias (Plan de Ciencia, Tecnología e Innovación 2013-2017), under the Grant GRUPIN14-021 and GRUPIN14-022 and the project CTQ2014-58826-R. Alberto Sánchez Calvo thanks the Ministry of Economy and Competitiveness for the award of a FPI Grant (BES-2015-072220)
[1] E. Nunez-Bajo, M.C. Blanco-Lopez, A. Costa-Garcia, M. T. Fernández-Abedul, Biosens. Bioelectron. 91 (2017) 824
[2] Y. Wu, P. Xue, Y. Kang, K. M.Hui, Anal. Chem., 85 (2013) 8661-8668
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MULTIPLEXED NANOPLASMONIC BIOSENSOR FOR RAPID PATHOGEN DETECTION AT THE POINT OF CARE
Maria Solera, Alexander Belushkina, Xiaokang Lia, Hatice Altuga* aInstitute of Bioengineering, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland.
*corresponding author : [email protected]
The implementation of multiplexed point-of-care biosensors is a top priority to address the current epidemic problems originated by widespread pathogenic infections, like those caused by viruses or bacteria. A rapid and accurate detection, identification, and quantification of the infectious pathogens is essential not only to facilitate a prompt treatment but also to prevent onward transmission, reduce economic expenses, and significantly promote healthcare in resource-constrained environments. Photonic and nanoplasmonic biosensors have shown unique capabilities, as the high sensitivity and robustness, the label-free analysis, and the exceptional potential for miniaturization and integration in lab-on-a-chip devices. Our group has developed a lens-free handheld biosensor device based on plasmonic nanohole arrays for fast and highly sensitive analysis in a simple and direct configuration [1]. The arrays of plasmonic nanoholes support the extraordinary optical transmission (EOT), offering label-free imaging and detection of biointeractions in real time. Our nanoplasmonic microarray is integrated in a microfluidic system to allow for high- throughput detection of multiple targets in a few minutes, without the need of sample pretreatment or amplification steps. We have demonstrated the utility of the biosensor for the detection of hazardous live viruses, such as the Ebola or Vaccinia viruses, measured directly in biological media. We also have proved the truly multiplexing capability of our plasmonic microarray with the simultaneous identification and quantification of Chlamydia trachomatis and Neisseria gonorrhoeae in urine samples [2]. We are able to detect and distinguish the two different bacteria with detection limits in the range of 102-103 bacteria/mL. Most recent advances in plasmonics nanotechnology, an optimized surface chemistry, and microfluidics integration are combined to bring about an innovative biosensor for simple, efficient, and accurate detection of whole-cell pathogens, which could definitely provide a non-invasive and rapid diagnosis at the point of care.
References:
[1] Cetin, A.E., Coskun, A.F., Galarreta, B.C., Huang, M., Herman, D., Ozcan, A., Altug, H., Light: Science & Applications, 3 (2014), 1, e122. [2] Soler, M., Belushkin, A., Cavallini, A., Kebbi-Beghdadib, C., Greub, G., Altug, H., Biosensors and Bioelectronics, 94 (2017), 560-567.
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PREPARATION OF COBALT OXIDE AND PLATINUM NANOPARTICLE MODIFIED ELECTRODES AND THEIR ELECTROCATALYTIC ACTIVITY FOR ORR
K. Volkan Özdokura,b, Ceren Kuşcia, Süleyman Koçakc, F. Nil Ertaşa
a Ege University, Science Faculty, Chemistry Dep., İzmir, TURKEY b Erzincan University, Science&Letter Faculty, Chemistry Dep., Erzincan, TURKEY c Manisa Celal Bayar University, Science&Letter Faculty, Chemistry Dep., Manisa, TURKEY
email address: [email protected]
Nowadays, cobalt oxide has received a great deal of attention owing to their remarkable electronic and catalytic properties depending on the synthesis procedure1. Electrochemical techniques is more practical and inexpensive techniques for uniform oxide film formation and recently, electrochemical pulsed deposition (PD) technique is becoming popular since the pattern of applied potential during deposition step has a strong effect on the surface morphologies. This technique allows the formation of nucleation sites and contributes to a high dispersion of the deposits compared to other methods. The activity can be enhanced by decorating with metallic nanoparticles1.
In this study, electrochemical deposition of CoOx and its further decoration with Pt nanoparticles in pursue of any synergetic effect for electrocatalytic activity was investigated. The electrode surface has been characterized by using SEM and XPS measurements. In comparison to the bare GCE (15 µA at -0.8 V) and platinum nanoparticle modified GCE (49 µA at 0.08 V), very satisfying results have been obtained for electrocatalytic reduction of dissolved oxygen in pH 5.0 Britton Robinson buffer solution giving a large peak about 59 µA at 0.21 V. Experimental parameters such as cobalt and platinum concentration, pulse number and time have been optimized. Therefore, the electrode prepared can be further utilized in biosensor development by monitoring the oxygen reduction reaction (ORR).
References: [1] A.D. Jagadale, V. S. Kumbhar, Ravindra N. Bulakhe, Chandrakant D. Lokhande, Energy 64 (2014) 234-241 [2] E. Yavuz, K.V. Özdokur, I. Çakar, S. Koçak, F.N. Ertaş, Electrochim. Acta 151 (2015) 72
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TUNGSTEN OXIDE MODIFIED ELECTRODES: A PROMISING PLATFORM FOR BIOSENSORS
İrem Çakar Davaslıoğlua, K. Volkan Özdokura,b, Süleyman Koçakc, F. Nil Ertaşa
a Ege University, Science Faculty, Chemistry Dep., İzmir, TURKEY b Erzincan University, Science&Letter Faculty, Chemistry Dep., Erzincan, TURKEY c Manisa Celal Bayar University, Science&Letter Faculty, Chemistry Dep., Manisa, TURKEY
email address: [email protected]
Among the transition metal oxides tungsten oxides have gained interest for several applications including photo catalysis, solar cells etc. Present study includes the preparation of tungsten oxide (WOx) modified glassy carbon electrode surfaces and their electrocatalytic activity towards oxygen reduction reaction (ORR).
On the other hand, it is known that the catalytic activity of transition metal oxides can be enhanced by decorating with noble metal particles due to the hypo-hyper interactions. Here, tungstate ions were deposited with platinum nanoparticles (WOx- Pt/GCE) via cyclic voltammetry from a 0.01 M sulfuric acid solution and obtained electrode surface has been characterized by using XPS and SEM measurements. In comparison to the bare GCE (15 µA at -0.8 V) and platinum nanoparticle modified GCE (49 µA at 0.08 V), very satisfying results have been obtained for electrocatalytic reduction of dissolved oxygen in pH 5.0 Britton Robinson buffer solution giving a large peak about 61 µA at 0.23 V. Molar ratio of platinum ion to tungstate ion has been 2- optimized as 1:50 mM (Pt : WO4 ) and the best peak formation was observed at a scan rate of 25 mV/s. The modified electrode has displayed a high catalytic activity towards ORR and therefore, it can be considered as a good candidate for biosensor studies in which oxygen signal is monitored.
References: [1] E. Yavuz, K.V. Özdokur, I. Çakar, S. Koçak, F.N. Ertaş, Electrochim. Acta 151 (2015) 72 [2] S.H. Lee, H. Lee, M.S. Cho, J.D. Nam, Y. Lee, J. Mater. Chem. A 2013, 1, 14606 [3] K.V. Ozdokur, B. Demir, E. Atman, A.Y. Tatlı, B. Yılmaz, D.O. Demirkol, S. Kocak, S. Timur, F. N.Ertas, Sensors and Actuators B: Chemical, 237 (2016) 291
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Molecular imprinted polymer for hazard compounds detection
Alejandro Zamora-Gálveza, Arben Merkoçib
a Nanobioelectronics & Biosensors Group, Catalan Institute of Nanoscience and Nanotechnology (ICN2),Campus UAB, Bellaterra, Barcelona, 08193, Spain.
b ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain.
Nowadays environmental monitoring of hazardous small molecules such as pesticides, drugs, toxics...etc at very low concentration levels remains a challenge for the scientific community. We will discuss an emerging approach that address this challenge based on magnetic nanoparticles (MNP) decorated with molecularly imprinted polymers (MIPs). MIPs are synthetic materials endowed with highly cross-linked three- dimensional network binding sites. These polymers facilitate high sensitivity targeting a specific analyte relying on functional monomers such as ethylene glycol dimethacrylate or pyrrole, in order to create a template molecule.
Composites made of MIPs build onto MNP bring several advantages as sensing platform since their synergy and properties allow manipulation of the analyte in a selective way as well as a label-free detection via electrochemical impedance spectroscopy. Furthermore, they offer a rapid and simple alternative as filtration or centrifugation processes are not required.
We will describe the synthesis and characterization of two proposed hybrid material. On the other hand, we will explore and report the application of both composites in chemical contaminants detection in environmental samples such as seawater.
References:
[1] Merkoçi, a.; Alegret, S. TrAC, Trends Anal. Chem. 21, (2002) 717−725. [2] Ligan Chen, Xiaopan Zhang, Lei Sun, Yang Xu , Qinglei Zeng, Hui Wang, Haoyan Xu, Aimin Yu, Hanqi Zhang and Lan Ding. J. Agric. Food Chem. 57 (2009) 10073–10080. [3] Zor, E.; Morales-Narváez, E.; Zamora-Gálvez, A.; Bingol, H.; Ersoz, M.; Merkoçi, A. ACS Appl. Mater. Interfaces, 7, (2015) 20272−20279.
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