Fabrication of pH- and temperature-directed supramolecular materials from 1D fibers to exclusively 2D planar structures using an ionic self-assembly approach

2015 ◽  
Vol 3 (14) ◽  
pp. 3273-3279 ◽  
Author(s):  
Yanjun Gong ◽  
Qiongzheng Hu ◽  
Ni Cheng ◽  
Tao Wang ◽  
Wenwen Xu ◽  
...  

Constructing multiple-response smart materials is a very interesting and challenging task in materials science.

2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>


2020 ◽  
Vol 05 ◽  
Author(s):  
Silas Santos ◽  
Orlando Rodrigues ◽  
Letícia Campos

Background: Innovation mission in materials science requires new approaches to form functional materials, wherein the concept of its formation begins in nano/micro scale. Rare earth oxides with general form (RE2O3; RE from La to Lu, including Sc and Y) exhibit particular proprieties, being used in a vast field of applications with high technological content since agriculture to astronomy. Despite of their applicability, there is a lack of studies on surface chemistry of rare earth oxides. Zeta potential determination provides key parameters to form smart materials by controlling interparticle forces, as well as their evolution during processing. This paper reports a study on zeta potential with emphasis for rare earth oxide nanoparticles. A brief overview on rare earths, as well as zeta potential, including sample preparation, measurement parameters, and the most common mistakes during this evaluation are reported. Methods: A brief overview on rare earths, including zeta potential, and interparticle forces are presented. A practical study on zeta potential of rare earth oxides - RE2O3 (RE as Y, Dy, Tm, Eu, and Ce) in aqueous media is reported. Moreover, sample preparation, measurement parameters, and common mistakes during this evaluation are discussed. Results: Potential zeta values depend on particle characteristics such as size, shape, density, and surface area. Besides, preparation of samples which involves electrolyte concentration and time for homogenization of suspensions are extremely valuable to get suitable results. Conclusion: Zeta potential evaluation provides key parameters to produce smart materials seeing that interparticle forces can be controlled. Even though zeta potential characterization is mature, investigations on rare earth oxides are very scarce. Therefore, this innovative paper is a valuable contribution on this field.


2019 ◽  
pp. 128-138
Author(s):  
V. S. Yagubov ◽  
A. V. Shchegolkov ◽  
A. V. Shchegolkov ◽  
N. R. Memetov

Developing "smart" materials with improved both structural and functional characteristics is one of the promising areas of materials science. Measuring the electrical resistance of CNTs-modified (various mass contents) polymers and in particular, elastomers during performing several tests (compression, stretching, and torsion) at a constant current is relevant in electrical engineering, mechanical engineering, aviation, and space industry. Changes in the elastomer shape under different types of testing lead to the destruction of macromolecules and the structuring of the material as a whole. Therefore, it is important to study the effect of CNTsbased modifying fillers on the elastomer. When compressing, stretching or twisting the nano-modified elastomer, along with the mutual movement of its macromolecular fragments and aggregates, the modifier particles also move, which generally determines the transport of electrons in the resulting structure and affects the physical and mechanical parameters of the composite material. To conduct studies, elastomers containing different amounts of a CNTs-based modifying filler were prepared. To investigate and elucidate relevant dependencies, a measuring system (MS) was constructed, which makes it possible to determine electrical resistance values of the composite material with different CNTs contents in the polymer matrix composition exposed to various mechanical loads. Basing the research results, it was established that the electrical resistance of the elastomer composites modified with 1.0–2.5 wt.% CNTs decreases when compressing from 0 to 100 N, whereas when the compression force ranges from 100 to 350 N, the electrical resistance remains unchanged. When the elastomer composites modified with 2–2.5 wt.% CNTs were stretched by 30–40 %, the electrical resistance was found to increase from 5·103 to 1.9·107 Ω.


2020 ◽  
Vol 2020 ◽  
pp. 1-24 ◽  
Author(s):  
Carmen Cretu ◽  
Loredana Maiuolo ◽  
Domenico Lombardo ◽  
Elisabeta I. Szerb ◽  
Pietro Calandra

The involvement of metal ions within the self-assembly spontaneously occurring in surfactant-based systems gives additional and interesting features. The electronic states of the metal, together with the bonds that can be established with the organic amphiphilic counterpart, are the factors triggering new photophysical properties. Moreover, the availability of stimuli-responsive supramolecular amphiphile assemblies, able to disassemble in a back-process, provides reversible switching particularly useful in novel approaches and applications giving rise to truly smart materials. In particular, small amphiphiles with an inner distribution, within their molecular architecture, of various polar and apolar functional groups, can give a wide variety of interactions and therefore enriched self-assemblies. If it is joined with the opportune presence and localization of noble metals, whose chemical and photophysical properties are undiscussed, then very interesting materials can be obtained. In this minireview, the basic concepts on self-assembly of small amphiphilic molecules with noble metals are shown with particular reference to the photophysical properties aiming at furnishing to the reader a panoramic view of these exciting problematics. In this respect, the following will be shown: (i) the principles of self-assembly of amphiphiles that involve noble metals, (ii) examples of amphiphiles and amphiphile-noble metal systems as representatives of systems with enhanced photophysical properties, and (iii) final comments and perspectives with some examples of modern applications.


Author(s):  
Joshua D. Carter ◽  
Chenxiang Lin ◽  
Yan Liu ◽  
Hao Yan ◽  
Thomas H. LaBean

This article examines the DNA-based self-assembly of nanostructures. It first reviews the development of DNA self-assembly and DNA-directed assembly, focusing on the main strategies and building blocks available in the modern molecular construction toolbox, including the design, construction, and analysis of nanostructures composed entirely of synthetic DNA, as well as origami nanostructures formed from a mixture of synthetic and biological DNA. In particular, it considers the stepwise covalent synthesis of DNA nanomaterials, unmediated assembly of DNA nanomaterials, hierarchical assembly, nucleated assembly, and algorithmic assembly. It then discusses DNA-directed assembly of heteromaterials such as proteins and peptides, gold nanoparticles, and multicomponent nanostructures. It also describes the use of complementary DNA cohesion as 'smart glue' for bringing together covalently linked functional groups, biomolecules, and nanomaterials. Finally, it evaluates the potential future of DNA-based self-assembly for nanoscale manufacturing for applications in medicine, electronics, photonics, and materials science.


2006 ◽  
Vol 33 (10) ◽  
pp. 893 ◽  
Author(s):  
Hendrik Bargel ◽  
Kerstin Koch ◽  
Zdenek Cerman ◽  
Christoph Neinhuis

The cuticle is the main interface between plants and their environment. It covers the epidermis of all aerial primary parts of plant organs as a continuous extracellular matrix. This hydrophobic natural composite consists mainly of the biopolymer, cutin, and cuticular lipids collectively called waxes, with a high degree of variability in composition and structure. The cuticle and cuticular waxes exhibit a multitude of functions that enable plant life in many different terrestrial habitats and play important roles in interfacial interactions. This review highlights structure–function relationships that are the subjects of current research activities. The surface waxes often form complex crystalline microstructures that originate from self-assembly processes. The concepts and results of the analysis of model structures and the influence of template effects are critically discussed. Recent investigations of surface waxes by electron and X-ray diffraction revealed that these could be assigned to three crystal symmetry classes, while the background layer is not amorphous, but has an orthorhombic order. In addition, advantages of the characterisation of formation of model wax types on a molecular scale are presented. Epicuticular wax crystals may cause extreme water repellency and, in addition, a striking self-cleaning property. The principles of wetting and up-to-date concepts of the transfer of plant surface properties to biomimetic technical applications are reviewed. Finally, biomechanical studies have demonstrated that the cuticle is a mechanically important structure, whose properties are dynamically modified by the plant in response to internal and external stimuli. Thus, the cuticle combines many aspects attributed to smart materials.


1992 ◽  
Vol 277 ◽  
Author(s):  
Geoffrey A. Ozin ◽  
Carol L. Bowes ◽  
Mark R. Steele

ABSTRACTVarious MOCVD (metal-organic chemical vapour deposition) type precursors and their self-assembled semiconductor nanocluster products [1] have been investigated in zeolite Y hosts. From analysis of in situ observations (FTIR, UV-vis reflectance, Mössbauer, MAS-NMR) of the reaction sequences and structural features of the precursors and products (EXAFS and Rietveld refinement of powder XRD data) the zeolite is viewed as providing a macrospheroidal, multidendate coordination environment towards encapsulated guests. By thinking about the α- and β-cages of the zeolite Y host effectively as a zeolate ligand composed of interconnected aluminosilicate “crown ether-like” building blocks, the materials chemist is able to better understand and exploit the reactivity and coordination properties of the zeolite internal surface for the anchoring and self-assembly of a wide range of encapsulated guests. This approach helps with the design of synthetic strategies for creating novel guest-host inclusion compounds having possible applications in areas of materials science such as nonlinear optics, quantum electronics, and size/shape selective catalysis.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Takahiro Itami ◽  
Akihito Hashidzume ◽  
Yuri Kamon ◽  
Hiroyasu Yamaguchi ◽  
Akira Harada

AbstractBiological macroscopic assemblies have inspired researchers to utilize molecular recognition to develop smart materials in these decades. Recently, macroscopic self-assemblies based on molecular recognition have been realized using millimeter-scale hydrogel pieces possessing molecular recognition moieties. During the study on macroscopic self-assembly based on molecular recognition, we noticed that the shape of assemblies might be dependent on the host–guest pair. In this study, we were thus motivated to study the macroscopic shape of assemblies formed through host–guest interaction. We modified crosslinked poly(sodium acrylate) microparticles, i.e., superabsorbent polymer (SAP) microparticles, with β-cyclodextrin (βCD) and adamantyl (Ad) residues (βCD(x)-SAP and Ad(y)-SAP microparticles, respectively, where x and y denote the mol% contents of βCD and Ad residues). Then, we studied the self-assembly behavior of βCD(x)-SAP and Ad(y)-SAP microparticles through the complexation of βCD with Ad residues. There was a threshold of the βCD content in βCD(x)-SAP microparticles for assembly formation between x = 22.3 and 26.7. On the other hand, the shape of assemblies was dependent on the Ad content, y; More elongated assemblies were formed at a higher y. This may be because, at a higher y, small clusters formed in an early stage can stick together even upon collisions at a single contact point to form elongated aggregates, whereas, at a smaller y, small clusters stick together only upon collisions at multiple contact points to give rather circular assemblies. On the basis of these observations, the shape of assembly formed from microparticles can be controlled by varying y.


Science ◽  
2008 ◽  
Vol 321 (5891) ◽  
pp. 919-920 ◽  
Author(s):  
R. A. Segalman

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