scholarly journals Concentration-dependent supramolecular self-assembly of A1/A2-asymmetric-difunctionalized pillar[5]arene

RSC Advances ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 2995-3002
Author(s):  
Talal F. Al-Azemi ◽  
Mickey Vinodh

Concentration-dependent supramolecular self-assembly of A1/A2-asymmetric-difunctionalized pillar[5]arene was synthesized by co-cyclization strategy. This approach enables wide range of structural manipulations to regulate the supramolecular assembly.

Research ◽  
2019 ◽  
Vol 2019 ◽  
pp. 1-10 ◽  
Author(s):  
Xu Wang ◽  
Xin-Yue Lou ◽  
Xiao-Yu Jin ◽  
Feng Liang ◽  
Ying-Wei Yang

We construct a fluorescent supramolecular system (TPE-Q4⊂ DSP5) of excellent tolerance to a wide range of pH by the facile self-assembly of a new pillar[5]arene bearing disulfonated arms (DSP5) with an AIE-active tetraphenylethene-based tetratopic guest bearing four quaternary ammonium binding sites (TPE-Q4), which exhibits strong blue emission even in dilute aqueous solutions along with much higher quantum yield and longer fluorescence lifetime than TPE-Q4 itself. This appreciable property can be attributed to the supramolecular assembly-induced emission (SAIE) mechanism endowed by the host-guest inclusion complexation based on synthetic macrocycles. Remarkably, the enhanced fluorescence of the supramolecular assembly is quenched efficiently and exclusively by ferric ions in water with a high Stern–Volmer formula constant of 1.3 × 105  mol-1, demonstrating the excellent cation selectivity and visualized responsiveness in ion sensing and detection.


2012 ◽  
Vol 9 (1) ◽  
pp. 43 ◽  
Author(s):  
Hueyling Tan

Molecular self-assembly is ubiquitous in nature and has emerged as a new approach to produce new materials in chemistry, engineering, nanotechnology, polymer science and materials. Molecular self-assembly has been attracting increasing interest from the scientific community in recent years due to its importance in understanding biology and a variety of diseases at the molecular level. In the last few years, considerable advances have been made in the use ofpeptides as building blocks to produce biological materials for wide range of applications, including fabricating novel supra-molecular structures and scaffolding for tissue repair. The study ofbiological self-assembly systems represents a significant advancement in molecular engineering and is a rapidly growing scientific and engineering field that crosses the boundaries ofexisting disciplines. Many self-assembling systems are rangefrom bi- andtri-block copolymers to DNA structures as well as simple and complex proteins andpeptides. The ultimate goal is to harness molecular self-assembly such that design andcontrol ofbottom-up processes is achieved thereby enabling exploitation of structures developed at the meso- and macro-scopic scale for the purposes oflife and non-life science applications. Such aspirations can be achievedthrough understanding thefundamental principles behind the selforganisation and self-synthesis processes exhibited by biological systems.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Chaojian Chen ◽  
Manjesh Kumar Singh ◽  
Katrin Wunderlich ◽  
Sean Harvey ◽  
Colette J. Whitfield ◽  
...  

AbstractThe creation of synthetic polymer nanoobjects with well-defined hierarchical structures is important for a wide range of applications such as nanomaterial synthesis, catalysis, and therapeutics. Inspired by the programmability and precise three-dimensional architectures of biomolecules, here we demonstrate the strategy of fabricating controlled hierarchical structures through self-assembly of folded synthetic polymers. Linear poly(2-hydroxyethyl methacrylate) of different lengths are folded into cyclic polymers and their self-assembly into hierarchical structures is elucidated by various experimental techniques and molecular dynamics simulations. Based on their structural similarity, macrocyclic brush polymers with amphiphilic block side chains are synthesized, which can self-assemble into wormlike and higher-ordered structures. Our work points out the vital role of polymer folding in macromolecular self-assembly and establishes a versatile approach for constructing biomimetic hierarchical assemblies.


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.


2011 ◽  
Vol 2011 ◽  
pp. 1-9 ◽  
Author(s):  
David M. Smith ◽  
Verena Schüller ◽  
Carsten Forthmann ◽  
Robert Schreiber ◽  
Philip Tinnefeld ◽  
...  

Nanometer-sized polyhedral wire-frame objects hold a wide range of potential applications both as structural scaffolds as well as a basis for synthetic nanocontainers. The utilization of DNA as basic building blocks for such structures allows the exploitation of bottom-up self-assembly in order to achieve molecular programmability through the pairing of complementary bases. In this work, we report on a hollow but rigid tetrahedron framework of 75 nm strut length constructed with the DNA origami method. Flexible hinges at each of their four joints provide a means for structural variability of the object. Through the opening of gaps along the struts, four variants can be created as confirmed by both gel electrophoresis and direct imaging techniques. The intrinsic site addressability provided by this technique allows the unique targeted attachment of dye and/or linker molecules at any point on the structure's surface, which we prove through the superresolution fluorescence microscopy technique DNA PAINT.


RSC Advances ◽  
2016 ◽  
Vol 6 (48) ◽  
pp. 41761-41764 ◽  
Author(s):  
M. B. Bijesh ◽  
Rituraj Mishra ◽  
Narayanan D. Kurur ◽  
V. Haridas

Macrocycles containing serine self-assembled into fibres, while threonine induced vesicular self-assembly. Macrocycles with serine can be driven to form vesicular assembly by incorporating a non-planar spacer.


2008 ◽  
Vol 1087 ◽  
Author(s):  
Marco Palumbo ◽  
Simon J. Henley ◽  
Thierry Lutz ◽  
Vlad Stolojan ◽  
David Cox ◽  
...  

AbstractRecent results in the use of Zinc Oxide (ZnO) nano/submicron crystals in fields as diverse as sensors, UV lasers, solar cells, piezoelectric nanogenerators and light emitting devices have reinvigorated the interest of the scientific community in this material. To fully exploit the wide range of properties offered by ZnO, a good understanding of the crystal growth mechanism and related defects chemistry is necessary. However, a full picture of the interrelation between defects, processing and properties has not yet been completed, especially for the ZnO nanostructures that are now being synthesized. Furthermore, achieving good control in the shape of the crystal is also a very desirable feature based on the strong correlation there is between shape and properties in nanoscale materials. In this paper, the synthesis of ZnO nanostructures via two alternative aqueous solution methods - sonochemical and hydrothermal - will be presented, together with the influence that the addition of citric anions or variations in the concentration of the initial reactants have on the ZnO crystals shape. Foreseen applications might be in the field of sensors, transparent conductors and large area electronics possibly via ink-jet printing techniques or self-assembly methods.


2021 ◽  
Vol 22 (17) ◽  
pp. 9634
Author(s):  
Moran Aviv ◽  
Dana Cohen-Gerassi ◽  
Asuka A. Orr ◽  
Rajkumar Misra ◽  
Zohar A. Arnon ◽  
...  

Supramolecular hydrogels formed by the self-assembly of amino-acid based gelators are receiving increasing attention from the fields of biomedicine and material science. Self-assembled systems exhibit well-ordered functional architectures and unique physicochemical properties. However, the control over the kinetics and mechanical properties of the end-products remains puzzling. A minimal alteration of the chemical environment could cause a significant impact. In this context, we report the effects of modifying the position of a single atom on the properties and kinetics of the self-assembly process. A combination of experimental and computational methods, used to investigate double-fluorinated Fmoc-Phe derivatives, Fmoc-3,4F-Phe and Fmoc-3,5F-Phe, reveals the unique effects of modifying the position of a single fluorine on the self-assembly process, and the physical properties of the product. The presence of significant physical and morphological differences between the two derivatives was verified by molecular-dynamics simulations. Analysis of the spontaneous phase-transition of both building blocks, as well as crystal X-ray diffraction to determine the molecular structure of Fmoc-3,4F-Phe, are in good agreement with known changes in the Phe fluorination pattern and highlight the effect of a single atom position on the self-assembly process. These findings prove that fluorination is an effective strategy to influence supramolecular organization on the nanoscale. Moreover, we believe that a deep understanding of the self-assembly process may provide fundamental insights that will facilitate the development of optimal amino-acid-based low-molecular-weight hydrogelators for a wide range of applications.


Nanomaterials ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 1468
Author(s):  
Sangheon Jeon ◽  
Jihye Lee ◽  
Rowoon Park ◽  
Jeonghwa Jeong ◽  
Min Chan Shin ◽  
...  

Patterning of surfaces with a simple strategy provides insights into the functional interfaces by suitable modification of the surface by novel techniques. Especially, highly ordered structural topographies and chemical features from the wide range of interfaces have been considered as important characteristics to understand the complex relationship between the surface chemistries and biological systems. Here, we report a simple fabrication method to create patterned surfaces over large areas using evaporative self-assembly that is designed to produce a sacrificial template and lithographic etch masks of polymeric stripe patterns, ranging from micrometer to nanoscale. By facilitating a roll-on-plate geometry, the periodically patterned surface structures formed by repetitive slip-stick motions were thoroughly examined to be used for the deposition of the Au nanoparticles decorated graphene oxide (i.e., AuNPs, ~21 nm) and the formation of conductive graphene channels. The fluorescently labeled thiol-modified DNA was applied on the patterned arrays of graphene oxide (GO)/AuNPs, and biotin-streptavidin sensitive devices built with graphene-based transistors (GFETs, effective mobility of ~320 cm2 V−1 s−1) were demonstrated as examples of the platform for the next-generation biosensors with the high sensing response up to ~1 nM of target analyte (i.e., streptavidin). Our strategy suggests that the stripe patterned arrays of polymer films as sacrificial templates can be a simple route to creating highly sensitive biointerfaces and highlighting the development of new chemically patterned surfaces composed of graphene-based nanomaterials.


2019 ◽  
Vol 7 (9) ◽  
pp. 3832-3845 ◽  
Author(s):  
Catherine E. Vasey ◽  
Amanda K. Pearce ◽  
Federica Sodano ◽  
Robert Cavanagh ◽  
Thais Abelha ◽  
...  
Keyword(s):  

Control in ROP allows polymers to be synthesized with a wide range of architectures and self-assembly properties.


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