DOCSLIB.ORG

From Supramolecular Self-Assemblies to On-Surface Synthesis Monitored by Scanning Probe Microscopies Irma Čustovic

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
From Supramolecular Self-Assemblies to On-Surface Synthesis Monitored by Scanning Probe Microscopies Irma Čustovic From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies Irma Čustovic To cite this version: Irma Čustovic. From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies. Micro and nanotechnologies/Microelectronics. Université Bourgogne Franche- Comté, 2020. English. NNT : 2020UBFCD044. tel-03128924 HAL Id: tel-03128924 https://tel.archives-ouvertes.fr/tel-03128924 Submitted on 2 Feb 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THESE DE DOCTORAT DE L’ETABLISSEMENT UNIVERSITE BOURGOGNE FRANCHE-COMTE PREPAREE A l’UNIVERSITE DE FRANCHE-COMTE Ecole doctorale : n°37 ED SPIM Doctorat de Sciences pour l'ingénieur Par Irma Custovic De l’auto-assemblage supramoléculaire à la synthèse sur surface : études par microscopie à champ proche From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies Soutenue à Montbéliard, le 9/11/2020 devant le jury composé de Rapporteur MASSON, Laurence Pr., Aix-Marseille Université, Marseille, France Rapporteur TEJEDA, Antonio Dr. CNRS, Laboratoire de Physique des Solides, Orsay, France PIRRI, Carmelo Pr., Université de Haute Alsace, Mulhouse, France Président De WOLF, Peter Dr. AD, Bruker Nano Surfaces and Metrology, Nimes, France Examinateur BRIOIS, Pascal Dr. Maitre de Conférences, Univérsite Technologique Belfort-Montbéliard Examinateur CHERIOUX, Fréderic Dr. CNRS, FEMTO-ST, Besançon, France Directeur PALMINO, Frank Pr., Univeristé de Franche-Comté, France Co-directeur THESIS TO OBTAIN THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY BOURGOGNE FRANCHE-COMTE PREPARED AT University of Bourgogne Franche-Comte Doctoral School n°37 ED SPIM Engineering sciences and Microtechnology Thesis in 2020 By Irma Custovic Thesis title: From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies Defended in Montbéliard, the 9th November, 2020 Defence committee: Chairman Pr. Carmelo Pirri MASSON, Laurence Pr., Aix-Marseille Université, Marseille, France Reviewer TEJEDA, Antonio Dr. CNRS, Laboratoire de Physique des Solides, Orsay, France Reviewer PIRRI, Carmelo Pr., Université de Haute Alsace, Mulhouse, France Jury member De WOLF, Peter Dr. AD, Bruker Nano Surfaces and Metrology, Nimes, France Jury member BRIOIS, Pascal Dr. Maitre de Conférences, Univérsite Technologique Belfort-Montbéliard Jury member CHERIOUX, Fréderic Dr. CNRS, FEMTO-ST, Besançon, France Supervisor PALMINO, Frank Pr., Univeristé de Franche-Comté, France Co-supervisor Acknowledgements I would like to express my appreciation to the director and co-director of my thesis, Dr. Frédéric Chérioux and Professor Frank Palmino, for providing me this opportunity to join their research group and for their enthusiastic, cooperative and indispensable guidance and supervision. I would like to thank them for enrolling me in the world of science and research and for sharing their experience, knowledge and scientific discussion that I will carry with myself in a long- term life pathway. I owe my deep sense of gratitude to the members of jury for devoting their time and assessment to this thesis. I would also extend my special thanks to Professor Laurence Masson and Dr. Antonio Tejeda, for accepting to be the reviewers of my thesis and to Professor Carmelo Pirri and Dr. Peter de Wolf for their acceptation to be the examiners of my thesis. A great thanks are devoted to the collaborators which were enrolled in my work, Professor Christian Loppacher, Professor Alain Rochefort, Hamed Abbasian, as well as members of our group, Judicael Jeannoutot, Katia Verbeke and Guillaume Levasseur. Following part of Acknowledgements are dedicated to the intimate appreciation that I own to the people who were encouraged support during three years of my thesis. First, my personal thanks are dedicated to Dr. Muamer Kadic, for his enormous help, advise and support since the beginning of my thesis. I am grateful that I met you and have you as my friend. Thank you for pushing me forward towards this important part of my life. In addition, I would thank to Myriam Carrillat for her companion, friendship and for giving me opportunity to collaborate with her as a teaching assistant. My deep gratitude goes to my best friend, Elie Geagea, in a way that words are not sufficient to describe my appreciation for your unconditional support and help in one of the most difficult periods I had been through. Knowing you is the evidence that still good people exist and thank you for being by my side. Thank you for sharing with me the eternal life lectures and thank you for being my true friend. Finally, a deep gratitude goes to my family, my mother Edina, my father Edhem and my brother Irfan. Without your love, comprehension and support I would never achieve my dreams and my goals. I am happy to be daughter and sister to the most amazing persons I have ever known. Dedication of the thesis I dedicate this thesis to my grandmother “Sika”, my eternal support and inspiration. The joy of my life! General introduction General introduction “There’s Plenty of Room at the Bottom: An Invitation to Enter a New field of Physics” was a famous lecture given by Richard P. Feynman at the annual American Physical Society meeting at Caltech, 1959 [1] . In his lecture, Feynman settled the inception for the field which was based on his vision of computer and machine miniaturization to the atomic scale where a huge amount of information could be storage and encoded onto increasingly small spaces. His speech significantly influenced the commencement of the nanotechnology and nanoscience which aim refers to the study and manipulation of a matter and particles on nanometer scale for a development of new nanomaterials and nanocomponents. The development of molecular electronics involves study and implementation of molecules as primary building blocks for the fabrication of the nanoscale devices. One of the fascinating examples regarding the given opportunity to the molecular integration into an electronic circuit was reported in work of Nongjian Tao and Bingqian Xu in 2003, who addressed electrode–molecule–electrode junctions presented by the conductance peaks for the set of organic molecules [2]. In this issue, an efficient current junction method which studies the conductivity of various organic molecules, quested to be deeply understood and controlled, not by using any another technique but by basic principle of chemistry: understanding the relationship between molecular structure and function which will enable the synthesis of molecules with improved properties. Therefore, the organic nanostructures with desired properties could be studied by “bottom-up” approach which is inspired by “nature autonomous order phenomena” and refers to the fabrication of ordered nanostructures by using chemical or physical bonds operating at the nanoscale to the molecular building blocks which results into self-organized supramolecular growth or so-called self-assembled nanostructures [3]. The major advantage of the investigation of supramolecular self-assembly relays on efficient tuning of the resulting self-assembled properties (structural, electrical, photophysical etc.) just by shifting the structure-specific part of utilised molecular building blocks. In such a way, the variations in supramolecular self- assembled properties are contemplated by existence of different interactions between the building blocks. The breakthrough example of the development of 3D organic nanostructures based on self-assembly which are influenced by intermolecular interactions is presented by Jean-Marie Lehn, Donald Cram and Charles Pedersen, awarded by the Nobel prize in chemistry in 1987 for development and use of “molecules with structure-specific interactions of high selectivity” [4]. General introduction a) b) c) d) Figure 1.1 a) Atomic scale view of nanostructure growth on surfaces. Atoms and molecules are deposited from vapor phase. The type of growth depends of ratio between diffusion D and deposition flux F. b) When F is larger than D (blue arrow) the growth is determined by kinetics individual processes mostly recognized in formation of metallic islands onto metal surfaces upper image presents Cu chains on anisotropic Pd(110) surface and down image presents Ag dendrites on Pt(111) surface). c) When D is equal to F, complex interplay between kinetics and thermodynamics affects nanostructure growth. This condition is recognized for semiconductor nanostructures: upper right and upper left panels show pyramidal and dome-shaped Ge semiconductor quantum dots grown on Si(100). Lower panel of figure 1.1 c) presents boron- nitride nanomesh on Rh(111). d) If the D is higher than F (red arrow), it allows thermodynamic conditions to be set at equilibrium state which is recognized at self-assembly of organic molecules on metal surfaces and shows self-assembly in formation of rod-like benzoic acid molecules on Ag(111) surface. Images adapted from [5]. The idea of supramolecular self-assembly was extended in
Load more

Recommended publications
  • Supramolecular Chemistry
    Supramolecular Chemistry Rohit Kanagal Introduction Supramolecular Chemistry is one of the most rapidly growing areas of chemistry. This branch of chemistry emphasises on ‘chemistry beyond the molecule’ and ‘chemistry of molecular assemblies and the intermolecular bond’. Supramolecular Chemistry lends the idea of how molecules interact with one another. It aims to understand the structural and functional properties of systems that contain more than one molecular assembly. Phenomena such as molecular self-assembly, protein folding, molecular recognition, host-guest chemistry, mechanically-interlocked molecular architectures, and dynamic covalent chemistry are all integral parts of Supramolecular chemistry. These phenomena are controlled by certain non- covalent interactions between molecules such as ion-dipole, dipole-dipole interactions, van der Waals forces, hydrogen bonding, metal coordination, hydrophobic forces, pi-pi interactions, and various electrostatic effects. Over the last few decades, the ideas and studies of supramolecular chemistry have entered multiple fields such as chemical science, biological science, physical science, and material science. (Hasenknopf) An example of a supramolecular assembly Superamolecule A supramolecule or supramolecular assembly is a well-defined system of molecules that are held together with non-covalent intermolecular forces to form a bigger unit having its own organization, stability and tendency to associate or isolate. These are formed through the interactions between a molecule having convergent binding sites (such as hydrogen bond donor atoms and a large cavity) and another molecule having divergent binding sites (such as hydrogen bond acceptor atoms). The molecule having convergent binding sites is called host or receptor molecule while the molecule having divergent binding sites is called a guest or analyte molecule.
    [Show full text]
  • From Supramolecular Chemistry to Nanotechnology: Assembly of 3D Nanostructures*
    Pure Appl. Chem.,Vol. 81, No. 12, pp. 2225–2233, 2009. doi:10.1351/PAC-CON-09-07-04 © 2009 IUPAC, Publication date (Web): 3 November 2009 From supramolecular chemistry to nanotechnology: Assembly of 3D nanostructures* Xing Yi Ling‡, David N. Reinhoudt, and Jurriaan Huskens Molecular Nanofabrication Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede, The Netherlands Abstract: Fabricating well-defined and stable nanoparticle crystals in a controlled fashion re- ceives growing attention in nanotechnology. The order and packing symmetry within a nanoparticle crystal is of utmost importance for the development of materials with unique op- tical and electronic properties. To generate stable and ordered 3D nanoparticle structures, nanotechnology is combined with supramolecular chemistry to control the self-assembly of 2D and 3D receptor-functionalized nanoparticles. This review focuses on the use of molecu- lar recognition chemistry to establish stable, ordered, and functional nanoparticle structures. The host–guest complexation of β-cyclodextrin (CD) and its guest molecules (e.g., adaman- tane and ferrocene) are applied to assist the nanoparticle assembly. Direct adsorption of supramolecular guest- and host-functionalized nanoparticles onto (patterned) CD self-as- sembled monolayers (SAMs) occurs via multivalent host–guest interactions and layer-by- layer (LbL) assembly. The reversibility and fine-tuning of the nanoparticle-surface binding strength in this supramolecular assembly scheme are the control parameters in the process. Furthermore, the supramolecular nanoparticle assembly has been integrated with top- down nanofabrication schemes to generate stable and ordered 3D nanoparticle structures, with con- trolled geometries and sizes, on surfaces, other interfaces, and as free-standing structures. Keywords: nanoparticles; nanoparticle arrays; self-assembly; self-assembled monolayer; supramolecular chemistry.
    [Show full text]
  • Supramolecular Assembly of DNA-Phenanthrene Conjugates Into Vesicles with Light-Harvesting Properties Caroline D
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Bern Open Repository and Information System (BORIS) Supramolecular Assembly of DNA-Phenanthrene Conjugates into Vesicles with Light-Harvesting Properties Caroline D. Bösch, Jovana Jevric, Nutcha Bürki, Markus Probst, Simon M. Langenegger, and Robert Häner* Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland Supporting Information Placeholder ABSTRACT : Vesicle-shaped supramolecular polymers are formed by self-assembly of a DNA duplex containing phenanthrene overhangs at both ends. In presence of spermine, the phenanthrene overhangs act as sticky ends linking the DNA duplexes together. In aqueous solution, the assembly leads to vesicles in the range of 50 – 200 nm, as shown by electron microscopy and dynamic light scattering. Fluorescence measurements show that the assembled phenanthrene units act as light-harvesting antennae and transfer absorbed energy to an acceptor, such as pyrene or Cy3, which can either be directly added to the polymer or attached via a complementary DNA strand. The presence of DNA in the nanostructures allows the con- struction of light-harvesting vesicles that are amenable to functionalization with different chemical groups. DNA is used to create one-, two-, or three-dimensional assemblies phodiester groups. Hybridization leads to the formation of DNA du- due to its unique molecular recognition properties which opens oppor- plex 1*2 containing three phenanthrenes at each end. Oligonucleotides tunities to precisely organize functional groups within space.1-9 Func- 3 and 4 serve as unmodified control sequences. tional supramolecular assemblies of DNA object have a potential for biomedical, biomimetic and electronic applications.10-18 DNA Table 1.
    [Show full text]
  • Supramolecular Assemblies of Cucurbiturils with Photoactive, Π
    Review 1 DOI: 10.1002/ijch.201700114 2 3 4 Supramolecular Assemblies of Cucurbiturils with 5 Photoactive, -conjugated Chromophores 6 p 7 [a] [a, b] 8 Ahmet Koc and Do¨nu¨s Tuncel* 9 10 11 Abstract: Supramolecular assemblies of cucurbituril (CBn) polymers. How supramolecular complexes of p-conjugated 12 homologues with p-conjugated chromophores will be over- chromophores including porphyrin derivatives, conjugated 13 viewed. Special emphasis will be given to the effect of CBn oligomers and polymers with CBn could be utilized in the 14 on the optical properties of conjugated oligomers and theranostic and photonic applications will also be discussed. 15 Keywords: Cucurbiturils · supramolecular assemblies · p-conjugated chromophores · porphyrins · conjugated polymers 16 17 18 1. Introduction 10 glycoluril units, respectively.[9] The new members of CB 19 family that shows remarkable differences in their cavity sizes, 20 In this review, we are going to discuss the supramolecular guest binding affinities, size selectivity and water-solubility 21 assemblies of cucurbituril (CBn) homologues with photo- attracted huge interest by the supramolecular chemists.[10] 22 active, conjugated chromophores. Photoactive, p-conjugated Among them, CB7, with good water solubility, appropriate 23 chromophores have many important applications in the areas guest size selectivity and binding affinity, have been the most 24 of sensing, catalysis, lasers, imaging, theranostics and pho- in demand up to now. 25 tonics.[1–6] However, there are some drawbacks that should be Compared to other well-known macrocyclic host mole- 26 overcome in order to utilize them in a wider context including cules such as cyclodextrins, calixarenes and crown ethers, CBs 27 stability (chemical, thermal, photo), solubility, poor optical not only exhibit the similar low-toxic nature, but they also 28 performance (low quantum yields, low lifetime) due to offer much higher chemical stability and far better guest 29 aggregation.
    [Show full text]
  • Synthesis and Characterization of Supramolecular Cucurbituril, Molybdenum 2,2'-Bipyridyl Complex
    International Journal of Scientific & Engineering Research Volume 8, Issue 10, October-2017 140 ISSN 2229-5518 SYNTHESIS AND CHARACTERIZATION OF SUPRAMOLECULAR CUCURBITURIL, MOLYBDENUM 2,2’-BIPYRIDYL COMPLEX Ms. Anitha. V1 , Dr. Nandagopal. J2, Ms. Ramanachiar.R3, Ms. Sasikala.S4, Ms. Ariyamala .R5 Department of chemistry, Velammal Engineering college, Chennai, Tamilnadu. Abstract Supra molecular Cucurbituril, Molybdenum2,2’-bipyridyl complex has been synthesized by precipitation followed by slow evaporation techniques. Changes in the physical properties of the ligand and the complex were characterized by melting point and solubility test . The absorption spectrum of the Cucurbituril, Molybdenum2,2’-bipyridyl complex were studied by decreasing and increasing concentrations by using UV – Visible spectrophotometer and IR spectrophotometer. The interaction between the metal and ligands were studied by UV- visible spectral analysis. The functional groups and modes of vibration were identified by IR spectral analysis. Key words: Cucurbituril, evaporation, precipitation, absorption, ligand, spectrophotometer. INTRODUCTION complex of Cucurbit[6]uril which incorporates the p-Xylene diammonium cation into the macrocyclic A Supramolecular assembly or “supramolecule” is a cavity. Researchers have shown that Cucurbit[6]uril well defined complex of molecules held together by acts as a catalyst in cyclo-addition reactions. noncovalent bonds. Cucurbiturils are macrocyclic Detailed examination has been done on the molecules consisting of glycouril repeating units. construction of supramolecular organic, inorganic These supramolecular compounds are particularly compounds from macrocyclic cavitand interesting to chemists because they are molecular cucurbit[6]Uril and mono and polynuclear aqua containers that are capable of binding other complexes. Cucurbit[6]uril is used in the molecules within their cavities.
    [Show full text]
  • Nanoparticle As Supramolecular Platform for Delivery and Bioorthogonal Catalysis
    University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations Dissertations and Theses November 2017 NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS Gulen Yesilbag Tonga University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_2 Part of the Materials Chemistry Commons, Medicinal-Pharmaceutical Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Yesilbag Tonga, Gulen, "NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS" (2017). Doctoral Dissertations. 1141. https://doi.org/10.7275/10521708.0 https://scholarworks.umass.edu/dissertations_2/1141 This Open Access Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS A Dissertation Presented by GULEN YESILBAG TONGA Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY September 2017 Department of Chemistry i © Copyright by Gulen Yesilbag Tonga 2017 All Rights Reserved ii NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS A Dissertation Presented by GULEN YESILBAG
    [Show full text]
  • Supramolecular Structures and Self-Association Processes in Polymer Systems
    Physiol. Res. 65 (Suppl. 2): S165-S178, 2016 https://doi.org/10.33549/physiolres.933419 REVIEW Supramolecular Structures and Self-Association Processes in Polymer Systems M. HRUBÝ1, S. K. FILIPPOV1, P. ŠTĚPÁNEK1 1Institute of Macromolecular Chemistry of the Czech Academy of Sciences, Prague, Czech Republic Received July 14, 2016 Accepted July 14, 2016 Summary synthesize macromolecules (Hadjichristidis et al. 2002) Self-organization in a polymer system appears when a balance is with more complex and controlled composition, along achieved between long-range repulsive and short-range with a better understanding of the physical-chemical attractive forces between the chemically different building blocks. processes interactions have provided the basis not only Block copolymers forming supramolecular assemblies in aqueous for a rational design and fabrication of sophisticated self- media represent materials which are extremely useful for the assembled nanostructures but, more generally, the basis construction of drug delivery systems especially for cancer for a new and powerful nanotechnology (Forster and applications. Such formulations suppress unwanted physico- Konrad 2003). In particular, the development of self- chemical properties of the encapsulated drugs, modify assembling block copolymers with different blocks being biodistribution of the drugs towards targeted delivery into tissue able to segregate in immiscible phases under appropriate of interest and allow triggered release of the active cargo. In this conditions, have proven their enormous potential to review, we focus on general principles of polymer self- obtain different nanostructures of interest, both in 2 and organization in solution, phase separation in polymer systems 3 dimensions (Hamley 1999). This naturally leads to (driven by external stimuli, especially by changes in temperature, investigation of physical (Strobl 2007) and biophysical pH, solvent change and light) and on effects of copolymer aspects of self-assembled polymer materials since self- architecture on the self-assembly process.
    [Show full text]
  • Fabrication of Two-Dimensional Materials from Zero-Dimensional Fullerene
    molecules Review Zero-to-Two Nanoarchitectonics: Fabrication of Two-Dimensional Materials from Zero-Dimensional Fullerene Guoping Chen 1 , Lok Kumar Shrestha 2 and Katsuhiko Ariga 1,2,* 1 Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan; [email protected] 2 WPI Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Ibaraki, Tsukuba 305-0044, Japan; [email protected] * Correspondence: [email protected] Abstract: Nanoarchitectonics of two-dimensional materials from zero-dimensional fullerenes is mainly introduced in this short review. Fullerenes are simple objects with mono-elemental (carbon) composition and zero-dimensional structure. However, fullerenes and their derivatives can create various types of two-dimensional materials. The exemplified approaches demonstrated fabrications of various two-dimensional materials including size-tunable hexagonal fullerene nanosheet, two- dimensional fullerene nano-mesh, van der Waals two-dimensional fullerene solid, fullerene/ferrocene hybrid hexagonal nanosheet, fullerene/cobalt porphyrin hybrid nanosheet, two-dimensional fullerene array in the supramolecular template, two-dimensional van der Waals supramolecular framework, supramolecular fullerene liquid crystal, frustrated layered self-assembly from two-dimensional nanosheet, and hierarchical zero-to-one-to-two dimensional fullerene assembly for cell culture. Keywords: fullerene; interface; nanoarchitectonics; nanosheet; self-assembly; two-dimensional Citation: Chen, G.; Shrestha, L.K.; Ariga, K. Zero-to-Two material Nanoarchitectonics: Fabrication of Two-Dimensional Materials from Zero-Dimensional Fullerene. Molecules 2021, 26, 4636. https:// 1. Introduction doi.org/10.3390/molecules26154636 As a game-changer of science and technology in the late 20th to 21st century, nanotech- nology has great contributions in explorations on nanoscale materials and their phenomena.
    [Show full text]
  • Ph-Responsive Supramolecular Assemblies of Hoechst-33258 with Cucurbiturils: Modulation in the Photophysical Properties
    Indian Journal of Chemistry Vol. 57B, February 2018, pp. 241-253 pH-Responsive supramolecular assemblies of Hoechst-33258 with cucurbiturils: Modulation in the photophysical properties Nilotpal Barooaha, Achikanath C Bhasikuttana,b & Jyotirmayee Mohanty*a,b a Radiation & Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India b Homi Bhabha National Institute, Training School Complex, Anushaktinagar, Mumbai 400 094, India E-mail: [email protected] Received 24 December 2016 Stimuli-responsive molecular assemblies of potential drug/guest molecules through non-covalent host-guest interaction have been found very attractive in transporting and releasing the desired form on demand. In this review article, the supramolecular interaction of a biologically important dye Hoechst-33258 (H33258) has been investigated in aqueous solutions at two different pHs (~4.5 and ~7), in the presence of macrocyclic hosts, namely, cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8). The pH-dependent emission behaviour of H33258 is inherently connected with its protolytic equilibria which allows the dye to exist in different geometrical conformations. This pH-dependent structural orientation is greatly affected by the complexation with cucurbiturils. The strong ion-dipole interactions provided by the carbonyl portals of the CB7 host adequately stabilizes the CB7-H33258 complex, both in 1:1 and 2:1 stoichiometries at both the pH conditions. The non-covalently stabilized assembly brings out large enhancement in the fluorescence emission due to the unique structural orientation attained by H33258 partly within the CB7 cavity, which reduces the non-radiative relaxation pathways. The pH-dependent structural conformations of H33258 are found to be decisive in determining the stoichiometry and geometry of the supramolecular assembly.
    [Show full text]
  • Molecular Motions in Functional Self-Assembled Nanostructures
    Int. J. Mol. Sci. 2013, 14, 2303-2333; doi:10.3390/ijms14022303 OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Review Molecular Motions in Functional Self-Assembled Nanostructures Alexandre Dhotel 1,2, Ziguang Chen 2, Laurent Delbreilh 1, Boulos Youssef 1, Jean-Marc Saiter 1 and Li Tan 2,* 1 AMME–LECAP, EA4528, International Laboratory, Institut des Matériaux de Rouen, Université et INSA de Rouen, BP12, 76801 Saint Etienne du Rouvray Cedex, France; E-Mails: [email protected] (A.D.); [email protected] (L.D.); [email protected] (B.Y.); [email protected] (J.-M.S.) 2 AMME–A-TEAM, Department of Mechanical and Materials Engineering, University of Nebraska, Lincoln, NE 68588, USA; E-Mail: [email protected] * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-402-472-4018. Received: 11 December 2012; in revised form: 11 January 2013 / Accepted: 11 January 2013 / Published: 24 January 2013 Abstract: The construction of “smart” materials able to perform specific functions at the molecular scale through the application of various stimuli is highly attractive but still challenging. The most recent applications indicate that the outstanding flexibility of self-assembled architectures can be employed as a powerful tool for the development of innovative molecular devices, functional surfaces and smart nanomaterials. Structural flexibility of these materials is known to be conferred by weak intermolecular forces involved in self-assembly strategies. However, some fundamental mechanisms responsible for conformational lability remain unexplored. Furthermore, the role played by stronger bonds, such as coordination, ionic and covalent bonding, is sometimes neglected while they can be employed readily to produce mechanically robust but also chemically reversible structures.
    [Show full text]
  • Supramolecular Architectures of Nucleic Acid/Peptide Hybrids
    International Journal of Molecular Sciences Review Supramolecular Architectures of Nucleic Acid/Peptide Hybrids Sayuri L. Higashi 1, Normazida Rozi 2, Sharina Abu Hanifah 2 and Masato Ikeda 1,3,4,5,* 1 United Graduate School of Drug Discovery and Medical Information Sciences, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan; [email protected] 2 Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor, Malaysia; [email protected] (N.R.); [email protected] (S.A.H.) 3 Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan 4 Center for Highly Advanced Integration of Nano and Life Sciences, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan 5 Institute for Glyco-Core Research (iGCORE), Gifu University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan * Correspondence: [email protected]; Tel.: +81-58-293-2639 Received: 16 November 2020; Accepted: 9 December 2020; Published: 12 December 2020 Abstract: Supramolecular architectures that are built artificially from biomolecules, such as nucleic acids or peptides, with structural hierarchical orders ranging from the molecular to nano-scales have attracted increased attention in molecular science research fields. The engineering of nanostructures with such biomolecule-based supramolecular architectures could offer an opportunity for the development of biocompatible supramolecular (nano)materials. In this review, we highlighted a variety of supramolecular architectures that were assembled from both nucleic acids and peptides through the non-covalent interactions between them or the covalently conjugated molecular hybrids between them. Keywords: supramolecular architectures; self-assembly; nanostructures; nucleic acids; peptides; molecular hybrid 1.
    [Show full text]
  • Supramolecular Nanostamping (Suns) Fabricating Nano/Bio Devices Using DNA As Movable Type
    Supramolecular NanoStamping (SuNS) fabricating nano/bio devices using DNA as movable type by Arum Amy Yu B.S Materials Science and Engineering, and Chemistry KAIST, South Korea, 2001 SUBMITTED TO THE DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING IN PARTIAL FULFILLMENT OF REQUIREMENT FOR DEGREE OF DOCTOR OF PHILOSOPHY IN MATERIALS SCIENCE AND ENGINEERING at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY June 2007 © 2007 Massachusetts Institute of Technology All rights reserved Signature of Author: - L Department of Mate 'hcience and Engineering rpar 19, 2007 Certified by: - , y - .- Francesco Stellacci Assistant Professor of Materials Science and Engineering Thesis Supervisor Aceepted by: , ,, JL,' I V Samuel M. Allen POSCO Professor of Physical Metallurgy Chair, Department Committee on Graduate Students MASSACHUSETTS INSTITUTF. OF TECHNOLOCY JUL 0 5 2007 LIBRARIES ARCHNES Supramolecular Nano-Stamping (SuNS): using DNA as movable type for fabricating multi-component devices by Arum Amy Yu Submitted to the Department of Materials Science and Engineering on Mar 19, 2007 in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science and Engineering ABSTRACT When a useful device is developed, it always requires a mass-production technique to industrialize it. In the era of nano/biotechnology, the development of printing techniques has not followed the speed of the inventions of novel devices. One of the main challenges is handling at the same time the resolution and the chemical complexity of these nano/bio- devices. Here a new stamping technique, Supramolecular Nano-Stamping, SuNS, capable of reproducing surfaces containing DNA-features is presented and discussed. SuNS is based on the combination of contact and supramolecular interaction between complementary DNA strands.
    [Show full text]