Minimalistic peptide supramolecular co-assembly: expanding the conformational space for nanotechnology.

Science.gov (United States)

Makam, Pandeeswar; Gazit, Ehud

2018-05-21

Molecular self-assembly is a ubiquitous process in nature and central to bottom-up nanotechnology. In particular, the organization of peptide building blocks into ordered supramolecular structures has gained much interest due to the unique properties of the products, including biocompatibility, chemical and structural diversity, robustness and ease of large-scale synthesis. In addition, peptides, as short as dipeptides, contain all the molecular information needed to spontaneously form well-ordered structures at both the nano- and the micro-scale. Therefore, peptide supramolecular assembly has been effectively utilized to produce novel materials with tailored properties for various applications in the fields of material science, engineering, medicine, and biology. To further expand the conformational space of peptide assemblies in terms of structural and functional complexity, multicomponent (two or more) peptide supramolecular co-assembly has recently evolved as a promising extended approach, similar to the structural diversity of natural sequence-defined biopolymers (proteins) as well as of synthetic covalent co-polymers. The use of this methodology was recently demonstrated in various applications, such as nanostructure physical dimension control, the creation of non-canonical complex topologies, mechanical strength modulation, the design of light harvesting soft materials, fabrication of electrically conducting devices, induced fluorescence, enzymatic catalysis and tissue engineering. In light of these significant advancements in the field of peptide supramolecular co-assembly in the last few years, in this tutorial review, we provide an updated overview and future prospects of this emerging subject.

From metal-organic squares to porous zeolite-like supramolecular assemblies

KAUST Repository

Wang, Shuang; Zhao, Tingting; Li, Guanghua; Wojtas, Łukasz; Huo, Qisheng; Eddaoudi, Mohamed; Liu, Yunling

2010-01-01

We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal

Photoluminescence Spectra of Self-Assembling Helical Supramolecular Assemblies: A Theoretical Study

NARCIS (Netherlands)

van Dijk, Leon; Kersten, Sander P.; Jonkheijm, Pascal; van der Schoot, Paul; Bobbert, Peter A.

2008-01-01

The reversible assembly of helical supramolecular polymers of chiral molecular building blocks is known to be governed by the interplay between mass action and the competition between weakly and strongly bound states of these building blocks. The highly co-operative transition from free monomers at

Supramolecular Lego assembly towards three-dimensional multi-responsive hydrogels.

Science.gov (United States)

Ma, Chunxin; Li, Tiefeng; Zhao, Qian; Yang, Xuxu; Wu, Jingjun; Luo, Yingwu; Xie, Tao

2014-08-27

Inspired by the assembly of Lego toys, hydrogel building blocks with heterogeneous responsiveness are assembled utilizing macroscopic supramolecular recognition as the adhesion force. The Lego hydrogel provides 3D transformation upon pH variation. After disassembly of the building blocks by changing the oxidation state, they can be re-assembled into a completely new shape. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predicting supramolecular self-assembly on reconstructed metal surfaces

Science.gov (United States)

Roussel, Thomas J.; Barrena, Esther; Ocal, Carmen; Faraudo, Jordi

2014-06-01

The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern.The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule

Proteins evolve on the edge of supramolecular self-assembly

Science.gov (United States)

Garcia-Seisdedos, Hector; Empereur-Mot, Charly; Elad, Nadav; Levy, Emmanuel D.

2017-08-01

The self-association of proteins into symmetric complexes is ubiquitous in all kingdoms of life. Symmetric complexes possess unique geometric and functional properties, but their internal symmetry can pose a risk. In sickle-cell disease, the symmetry of haemoglobin exacerbates the effect of a mutation, triggering assembly into harmful fibrils. Here we examine the universality of this mechanism and its relation to protein structure geometry. We introduced point mutations solely designed to increase surface hydrophobicity among 12 distinct symmetric complexes from Escherichia coli. Notably, all responded by forming supramolecular assemblies in vitro, as well as in vivo upon heterologous expression in Saccharomyces cerevisiae. Remarkably, in four cases, micrometre-long fibrils formed in vivo in response to a single point mutation. Biophysical measurements and electron microscopy revealed that mutants self-assembled in their folded states and so were not amyloid-like. Structural examination of 73 mutants identified supramolecular assembly hot spots predictable by geometry. A subsequent structural analysis of 7,471 symmetric complexes showed that geometric hot spots were buffered chemically by hydrophilic residues, suggesting a mechanism preventing mis-assembly of these regions. Thus, point mutations can frequently trigger folded proteins to self-assemble into higher-order structures. This potential is counterbalanced by negative selection and can be exploited to design nanomaterials in living cells.

Self-Assembly of Coordinative Supramolecular Polygons with Open Binding Sites.

Science.gov (United States)

Zheng, Yao-Rong; Wang, Ming; Kobayashi, Shiho; Stang, Peter J

2011-04-27

The design and synthesis of coordinative supramolecular polygons with open binding sites is described. Coordination-driven self-assembly of 2,6-bis(pyridin-4-ylethynyl)pyridine with 60° and 120° organoplatinum acceptors results in quantitative formation of a supramolecular rhomboid and hexagon, respectively, both bearing open pyridyl binding sites. The structures were determined by multinuclear ((31)P and (1)H) NMR spectroscopy and electrospray ionization (ESI) mass spectrometry, along with a computational study.

Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

Science.gov (United States)

Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

2014-11-04

A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation.

Synergy in supramolecular chemistry

CERN Document Server

Nabeshima, Tatsuya

2014-01-01

Synergy and Cooperativity in Multi-metal Supramolecular Systems, T. NabeshimaHierarchically Assembled Titanium Helicates, Markus AlbrechtSupramolecular Hosts and Catalysts Formed by Self-assembly of Multinuclear Zinc Complexes in Aqueous Solution, Shin AokiSupramolecular Assemblies Based on Interionic Interactions, H. MaedaSupramolecular Synergy in the Formation and Function of Guanosine Quadruplexes, Jeffery T. DavisOn-Surface Chirality in Porous Self-Assembled Monolayers at Liquid-Solid Interface, Kazukuni Tahar

Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity

Science.gov (United States)

Jiang, Linhai; Xu, Dawei; Sellati, Timothy J.; Dong, He

2015-11-01

Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications.Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would

Self-assembly of a supramolecular square between [Ni(dppe(TOF2] and 4,4'-Bipyridine

Directory of Open Access Journals (Sweden)

Paulo Torres

2013-08-01

Full Text Available The main interest of this research is to contribute to the development and understanding of supramolecular chemistry and molecular architectures, which are constructed by the self-assembly of supramolecular entities. Therefore, the synthesis and characterization (IR, UV, 1H NMR, 31P, 19F, 1H-1H COSY of a nickel (II supramolecular square [7] was performed through the synthesis between nickel chloride [1] and diphenylphosphinoethane (dppe [2] to form the precursor complex [Ni(dppeCl2] [3]. This was followed by the synthesis of the complex of interest, [Ni(dppe(TOF2] [5], using the precursor and silver trifluoromethanesulfonate (Ag-TOF. Finally, the self-assembly was performed between the complex [1,2-bis(diphenylphosphinoethanebistriflatonickel(II] [Ni(dppe(OSO2CF32] [5] and the organic ligand 4,4'-bipyridine [6], which act as vertex and edge, respectively.According to various analyses, it was found that the self-assembly generated only one supramolecular species; a square is the most probable thermodynamic structure.

From metal-organic squares to porous zeolite-like supramolecular assemblies

KAUST Repository

Wang, Shuang

2010-12-29

We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

A Dynamic Combinatorial Approach for Identifying Side Groups that Stabilize DNA-Templated Supramolecular Self-Assemblies

Directory of Open Access Journals (Sweden)

Delphine Paolantoni

2015-02-01

Full Text Available DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.

Bio-inspired supramolecular materials by orthogonal self-assembly of hydrogelators and phospholipids

NARCIS (Netherlands)

Boekhoven, J.; Brizard, AMA; Stuart, M. C A; Florusse, L.J.; Raffy, G.; Del Guerzo, A.; van Esch, J.H.

2016-01-01

The orthogonal self-assembly of multiple components is a powerful strategy towards the formation of complex biomimetic architectures, but so far the rules for designing such systems are unclear. Here we show how to identify orthogonal self-assembly at the supramolecular level and describe

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors.

Science.gov (United States)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C A; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L

2018-02-01

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large proteins, in which mechanical stress induces a coordinated movement. However, artificial molecular muscles have often relied on covalent polymer-based actuators. Here, we describe the macroscopic contractile muscle-like motion of a supramolecular system (comprising 95% water) formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor. The molecular motor first assembles into nanofibres, which further assemble into aligned bundles that make up centimetre-long strings. Irradiation induces rotary motion of the molecular motors, and propagation and accumulation of this motion lead to contraction of the fibres towards the light source. This system supports large-amplitude motion, fast response, precise control over shape, as well as weight-lifting experiments in water and air.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors

Science.gov (United States)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C. A.; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L.

2018-02-01

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large proteins, in which mechanical stress induces a coordinated movement. However, artificial molecular muscles have often relied on covalent polymer-based actuators. Here, we describe the macroscopic contractile muscle-like motion of a supramolecular system (comprising 95% water) formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor. The molecular motor first assembles into nanofibres, which further assemble into aligned bundles that make up centimetre-long strings. Irradiation induces rotary motion of the molecular motors, and propagation and accumulation of this motion lead to contraction of the fibres towards the light source. This system supports large-amplitude motion, fast response, precise control over shape, as well as weight-lifting experiments in water and air.

Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

Energy Technology Data Exchange (ETDEWEB)

Shcherbina, M. A., E-mail: shcherbina@ispm.ru; Bakirov, A. V. [Russian Academy of Sciences, Institute of Synthetic Polymer Materials (Russian Federation); Yakunin, A. N. [Karpov Institute of Physical Chemistry (Russian Federation); Percec, V. [University of Pennsylvania (United States); Beginn, U. [Universitaet Osnabrueck, Institut fuer Chemie (Germany); Moeller, M. [Institute for Technical and Macromolecular Chemistry (Germany); Chvalun, S. N. [Russian Academy of Sciences, Institute of Synthetic Polymer Materials (Russian Federation)

2012-03-15

The main stages of the self-assembling of supramolecular ensembles have been revealed by studying different functional wedged macromolecules: polymethacrylates with tapered side chains based on gallic acid, their macromonomers, and salts of 2,3,4- and 3,4,5-tris(dodecyloxy)benzenesulphonic acid. The first stage is the formation of individual supramolecular aggregates (long cylinders or spherical micelles) due to the weak noncovalent interactions of mesogenic groups and the subsequent ordering in these aggregates, which is accompanied by a decrease in the free energy of the system. Supramolecular aggregates, in turn, form 2D or 3D lattices. The shape of supramolecular aggregates and its change with temperature are delicate functions of the mesogen chemical structure; this circumstance makes it possible to rationally design complex self-assembling systems with the ability to respond smartly to external stimuli. X-ray diffraction analysis allows one to study the structure of supramolecular systems with different degrees of order, determine the type of mesophases formed by these systems, and reveal the phase behavior of the material. Particular attention has been paid to the method for reconstruction of electron density distribution from the relative reflection intensity. The application of a suite of experimental methods, including wide- and small-angle X-ray diffraction, molecular modeling, differential scanning calorimetry, and polarization optical microscopy, allows one to establish the relationship between the shape of the structural unit (molecule or molecular aggregate), the nature of the interaction, and the phase behavior of the material.

Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

International Nuclear Information System (INIS)

Shcherbina, M. A.; Bakirov, A. V.; Yakunin, A. N.; Percec, V.; Beginn, U.; Möller, M.; Chvalun, S. N.

2012-01-01

The main stages of the self-assembling of supramolecular ensembles have been revealed by studying different functional wedged macromolecules: polymethacrylates with tapered side chains based on gallic acid, their macromonomers, and salts of 2,3,4- and 3,4,5-tris(dodecyloxy)benzenesulphonic acid. The first stage is the formation of individual supramolecular aggregates (long cylinders or spherical micelles) due to the weak noncovalent interactions of mesogenic groups and the subsequent ordering in these aggregates, which is accompanied by a decrease in the free energy of the system. Supramolecular aggregates, in turn, form 2D or 3D lattices. The shape of supramolecular aggregates and its change with temperature are delicate functions of the mesogen chemical structure; this circumstance makes it possible to rationally design complex self-assembling systems with the ability to respond smartly to external stimuli. X-ray diffraction analysis allows one to study the structure of supramolecular systems with different degrees of order, determine the type of mesophases formed by these systems, and reveal the phase behavior of the material. Particular attention has been paid to the method for reconstruction of electron density distribution from the relative reflection intensity. The application of a suite of experimental methods, including wide- and small-angle X-ray diffraction, molecular modeling, differential scanning calorimetry, and polarization optical microscopy, allows one to establish the relationship between the shape of the structural unit (molecule or molecular aggregate), the nature of the interaction, and the phase behavior of the material.

Molecular self-assembly approaches for supramolecular electronic and organic electronic devices

Science.gov (United States)

Yip, Hin-Lap

Molecular self-assembly represents an efficient bottom-up strategy to generate structurally well-defined aggregates of semiconducting pi-conjugated materials. The capability of tuning the chemical structures, intermolecular interactions and nanostructures through molecular engineering and novel materials processing renders it possible to tailor a large number of unprecedented properties such as charge transport, energy transfer and light harvesting. This approach does not only benefit traditional electronic devices based on bulk materials, but also generate a new research area so called "supramolecular electronics" in which electronic devices are built up with individual supramolecular nanostructures with size in the sub-hundred nanometers range. My work combined molecular self-assembly together with several novel materials processing techniques to control the nucleation and growth of organic semiconducting nanostructures from different type of pi-conjugated materials. By tailoring the interactions between the molecules using hydrogen bonds and pi-pi stacking, semiconducting nanoplatelets and nanowires with tunable sizes can be fabricated in solution. These supramolecular nanostructures were further patterned and aligned on solid substrates through printing and chemical templating methods. The capability to control the different hierarchies of organization on surface provides an important platform to study their structural-induced electronic properties. In addition to using molecular self-assembly to create different organic nanostructures, functional self-assembled monolayer (SAM) formed by spontaneous chemisorption on surfaces was used to tune the interfacial property in organic solar cells. Devices showed dramatically improved performance when appropriate SAMs were applied to optimize the contact property for efficiency charge collection.

Supramolecular assembled three-dimensional graphene hybrids: Synthesis and applications in supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Ni, Lubin [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China); Zhang, Wang [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China); Graduate School of Convergence Science and Technology, Seoul National University, Seoul, 151-742 (Korea, Republic of); Wu, Zhen; Sun, Chunyu; Cai, Yin; Yang, Guang; Chen, Ming [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China); Piao, Yuanzhe, E-mail: parkat9@snu.ac.kr [Graduate School of Convergence Science and Technology, Seoul National University, Seoul, 151-742 (Korea, Republic of); Diao, Guowang, E-mail: gwdiao@yzu.edu.cn [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China)

2017-02-28

Graphical abstract: Supramolecular assembled three-dimensdional graphene-based architectures were built by host-guest interactions of β-cyclodextrin polymers(β-CDPs) with adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD), exhibit significantly improved electrochemical performances of supercapacitor in terms of high specific capacitance, remarkable rate capability, and excellent cycling stability compared to pristine reduced graphene oxide. - Highlights: • Supramolecular assembled three-Dimensional (3D) graphene was first fabricated by host-guest interactions of β-CDPs with PEG-AD linkers. • The incorporation of PEG-AD linker into rGO sheets can provide efficient 3D electron transfer pathways and ion diffusion channels. • The 3D self-assembled graphene exhibits high specific capacitance, remarkable rate capability, and excellent cycling stability. • This study shed new lights to design 3D self-assembled graphene materials and their urgent applications in energy storage. - Abstract: Graphene-based materials have received worldwide attention in the focus of forefront energy storage investigations. Currently, the design of novel three-dimensional (3D) graphene structures with high energy capability, superior electron and ion conductivity, and robust mechanical flexibility is still a great challenge. Herein, we have successfully demonstrated a novel approach to fabricate 3D assembled graphene through the supramolecular interactions of β-cyclodextrin polymers (β-CDP) with an adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD). The incorporation of PEG-AD linker into rGO sheets increased the interlayer spacing of rGO sheets to form 3D graphene materials, which can provide efficient 3D electron transfer pathways and ion diffusion channels, and facilitate the infiltration of gel electrolyte. The as-prepared 3D self-assembled graphene materials exhibit significantly improved electrochemical performances of supercapacitor in terms

Supramolecular assembled three-dimensional graphene hybrids: Synthesis and applications in supercapacitors

International Nuclear Information System (INIS)

Ni, Lubin; Zhang, Wang; Wu, Zhen; Sun, Chunyu; Cai, Yin; Yang, Guang; Chen, Ming; Piao, Yuanzhe; Diao, Guowang

2017-01-01

Graphical abstract: Supramolecular assembled three-dimensdional graphene-based architectures were built by host-guest interactions of β-cyclodextrin polymers(β-CDPs) with adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD), exhibit significantly improved electrochemical performances of supercapacitor in terms of high specific capacitance, remarkable rate capability, and excellent cycling stability compared to pristine reduced graphene oxide. - Highlights: • Supramolecular assembled three-Dimensional (3D) graphene was first fabricated by host-guest interactions of β-CDPs with PEG-AD linkers. • The incorporation of PEG-AD linker into rGO sheets can provide efficient 3D electron transfer pathways and ion diffusion channels. • The 3D self-assembled graphene exhibits high specific capacitance, remarkable rate capability, and excellent cycling stability. • This study shed new lights to design 3D self-assembled graphene materials and their urgent applications in energy storage. - Abstract: Graphene-based materials have received worldwide attention in the focus of forefront energy storage investigations. Currently, the design of novel three-dimensional (3D) graphene structures with high energy capability, superior electron and ion conductivity, and robust mechanical flexibility is still a great challenge. Herein, we have successfully demonstrated a novel approach to fabricate 3D assembled graphene through the supramolecular interactions of β-cyclodextrin polymers (β-CDP) with an adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD). The incorporation of PEG-AD linker into rGO sheets increased the interlayer spacing of rGO sheets to form 3D graphene materials, which can provide efficient 3D electron transfer pathways and ion diffusion channels, and facilitate the infiltration of gel electrolyte. The as-prepared 3D self-assembled graphene materials exhibit significantly improved electrochemical performances of supercapacitor in terms

Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

CERN Document Server

Garti, Nissim

2012-01-01

This book will describe fundamentals and recent developments in the area of Self-Assembled Supramolecular Architecture and their relevance to the  understanding of the functionality of  membranes  as delivery systems for active ingredients. As the heirarchial architectures determine their performance capabilities, attention will be paid to theoretical and design aspects related to the construction of lyotropic liquid crystals: mesophases such as lamellar, hexagonal, cubic, sponge phase micellosomes. The book will bring to the reader mechanistic aspects, compositional c

Self-organization of a self-assembled supramolecular rectangle, square, and three-dimensional cage on Au111 surfaces.

Science.gov (United States)

Yuan, Qun-Hui; Wan, Li-Jun; Jude, Hershel; Stang, Peter J

2005-11-23

The structure and conformation of three self-assembled supramolecular species, a rectangle, a square, and a three-dimensional cage, on Au111 surfaces were investigated by scanning tunneling microscopy. These supramolecular assemblies adsorb on Au111 surfaces and self-organize to form highly ordered adlayers with distinct conformations that are consistent with their chemical structures. The faces of the supramolecular rectangle and square lie flat on the surface, preserving their rectangle and square conformations, respectively. The three-dimensional cage also forms well-ordered adlayers on the gold surface, forming regular molecular rows of assemblies. When the rectangle and cage were mixed together, the assemblies separated into individual domains, and no mixed adlayers were observed. These results provide direct evidence of the noncrystalline solid-state structures of these assemblies and information about how they self-organize on Au111 surfaces, which is of importance in the potential manufacturing of functional nanostructures and devices.

Elasticity-dependent fast underwater adhesion demonstrated by macroscopic supramolecular assembly.

Science.gov (United States)

Ju, Guannan; Cheng, Mengjiao; Guo, Fengli; Zhang, Qian; Shi, Feng

2018-05-30

Macroscopic supramolecular assembly (MSA) is a recent progress in supramolecular chemistry to associate visible building blocks through non-covalent interactions in a multivalent manner. Although various substrates (e. g. hydrogels, rigid materials) have been used, a general design rule of building blocks in MSA systems and interpretation of the assembly mechanism are still lacking and urgently in demand. Here we design three model systems with varied modulus and correlated the MSA probability with the elasticity. Based on the effects of substrate deformability on multivalency, we have proposed an elastic-modulus-dependent rule that building blocks below a critical modulus of 2.5 MPa can achieve MSA for the used host/guest system. Moreover, this MSA rule applies well to the design of materials applicable for fast underwater adhesion: Soft substrates (0.5 MPa) can achieve underwater adhesion within 10 s with one magnitude higher strength than that of rigid substrates (2.5 MPa). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Layer-by-Layer Assembly of 3D Multicomponent Nanostructures via Multivalent Molecular Recognition

NARCIS (Netherlands)

Ling, X.Y.; Phang, In Yee; Reinhoudt, David; Vancso, Gyula J.; Huskens, Jurriaan

2008-01-01

The supramolecular layer-by-layer assembly of 3D multicomponent nanostructures of nanoparticles is demonstrated. Nanoimprint lithography (NIL) was used as the patterning tool for making patterned β-cyclodextrin (CD) self-assembled monolayers (SAMs) and for the confinement of nanoparticles on the

Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

International Nuclear Information System (INIS)

Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo

2016-01-01

Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification

Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

Energy Technology Data Exchange (ETDEWEB)

Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of)

2016-10-15

Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification.

Strong supramolecular control over protein self-assembly using a polyamine decorated β-cyclodextrin as synthetic recognition element

NARCIS (Netherlands)

Uhlenheuer, D.A.; Milroy, L.G.; Neirynck, P.; Brunsveld, L.

2011-01-01

The supramolecular host molecule heptakis-[6-deoxy-6-(2-aminoethylsulfanyl)]-ß-cyclodextrin provides strong control over protein self-assembly in synthetic supramolecular protein constructs. Mono-functionalization of this modified ß-cyclodextrin with a cysteine residue allows for site-selective

Reversible Self-Assembly of Supramolecular Vesicles and Nanofibers Driven by Chalcogen-Bonding Interactions.

Science.gov (United States)

Chen, Liang; Xiang, Jun; Zhao, Yue; Yan, Qiang

2018-05-29

Chalcogen-bonding interactions have been viewed as new noncovalent forces in supramolecular chemistry. However, harnessing chalcogen bonds to drive molecular self-assembly processes is still unexplored. Here we report for the first time a novel class of supra-amphiphiles formed by Te···O or Se···O chalcogen-bonding interactions, and their self-assembly into supramolecular vesicles and nanofibers. A quasi-calix[4]chalcogenadiazole (C4Ch) as macrocyclic donor and a tailed pyridine N-oxide surfactant as molecular acceptor are designed to construct the donor-acceptor complex via chalcogen-chalcogen connection between the chalcogenadiazole moieties and oxide anion. The affinity of such chalcogen-bonding can dictate the geometry of supra-amphiphiles, driving diverse self-assembled morphologies. Furthermore, the reversible disassembly of these nanostructures can be promoted by introducing competing anions, such as halide ions, or by decreasing the systemic pH value.

Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces.

Science.gov (United States)

Ciesielski, Artur; Samorì, Paolo

2011-04-01

Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.

Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes

NARCIS (Netherlands)

Eisele, D. M.; Cone, C. W.; Bloemsma, E. A.; Vlaming, S. M.; van der Kwaak, C. G. F.; Silbey, R. J.; Bawendi, M. G.; Knoester, J.; Rabe, J. P.; Vanden Bout, D. A.

Supramolecular assemblies that interact with light have recently garnered much interest as well-defined nanoscale materials for electronic excitation energy collection and transport. However, to control such complex systems it is essential to understand how their various parts interact and whether

Supramolecular ribbons from amphiphilic trisamides self-assembly.

Science.gov (United States)

García, Fátima; Buendía, Julia; Sánchez, Luis

2011-08-05

Two amphiphilic C(3)-symmetric OPE-based trisamides have been synthesized and their self-assembling features investigated in solution and on surface. Variable-temperature UV-vis experiments demonstrate the cooperative supramolecular polymerization of these trisamides that self-assemble by the operation of triple C═O···H-N H-bonding arrays between the amide functional groups and π-π stacking between the aromatic units. The helical organization of the aggregates has been demonstrated by circular dichroism at a concentration as low as 1 × 10(-4) M in acetonitrile. In the reported trisamides, the large hydrophobic aromatic core acts as a solvophobic module impeding the interaction between the polar TEG chains and the amide H-bonds. This strategy makes unnecessary the separation of the amide functional groups to the polar tri(ethylene glycol) chains by paraffinic fragments. Achiral trisamide 1 self-assembles into flat ribbon-like structures that experience an amplification of chirality by the addition of a small amount of chiral 2 that generates twisted stripes.

Computation-Guided Design of a Stimulus-Responsive Multienzyme Supramolecular Assembly.

Science.gov (United States)

Yang, Lu; Dolan, Elliott M; Tan, Sophia K; Lin, Tianyun; Sontag, Eduardo D; Khare, Sagar D

2017-10-18

The construction of stimulus-responsive supramolecular complexes of metabolic pathway enzymes, inspired by natural multienzyme assemblies (metabolons), provides an attractive avenue for efficient and spatiotemporally controllable one-pot biotransformations. We have constructed a phosphorylation- and optically responsive metabolon for the biodegradation of the environmental pollutant 1,2,3-trichloropropane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Ferrocene-Based Catecholamide Ligand: the Consequences of Ligand Swivel for Directed Supramolecular Self-Assembly

Energy Technology Data Exchange (ETDEWEB)

Mugridge, Jeffrey; Fiedler, Dorothea; Raymond, Kenneth

2010-02-04

A ferrocene-based biscatecholamide ligand was prepared and investigated for the formation of metal-ligand supramolecular assemblies with different metals. Reaction with Ge(IV) resulted in the formation of a variety of Ge{sub n}L{sub m} coordination complexes, including [Ge{sub 2}L{sub 3}]{sup 4-} and [Ge{sub 2}L{sub 2}({mu}-OMe){sub 2}]{sup 2-}. The ligand's ability to swivel about the ferrocenyl linker and adopt different conformations accounts for formation of many different Ge{sub n}L{sub m} species. This study demonstrates why conformational ligand rigidity is essential in the rational design and directed self-assembly of supramolecular complexes.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors

NARCIS (Netherlands)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C A; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large

Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anion-π Interactions

Energy Technology Data Exchange (ETDEWEB)

Yu, Zhilin; Erbas, Aykut; Tantakitti, Faifan; Palmer, Liam C.; Jackman, Joshua A.; Olvera de la Cruz, Monica; Cho, Nam-Joon; Stupp, Samuel I. (Nanyang); (NWU)

2017-06-01

Co-assembly of binary systems driven by specific non-covalent interactions can greatly expand the structural and functional space of supramolecular nanostructures. We report here on the self-assembly of peptide amphiphiles and fatty acids driven primarily by anion-π interactions. The peptide sequences investigated were functionalized with a perfluorinated phenylalanine residue to promote anion-π interactions with carboxylate headgroups in fatty acids. These interactions were verified here by NMR and circular dichroism experiments as well as investigated using atomistic simulations. Positioning the aromatic units close to the N-terminus of the peptide backbone near the hydrophobic core of cylindrical nanofibers leads to strong anion-π interactions between both components. With a low content of dodecanoic acid in this position, the cylindrical morphology is preserved. However, as the aromatic units are moved along the peptide backbone away from the hydrophobic core, the interactions with dodecanoic acid transform the cylindrical supramolecular morphology into ribbon-like structures. Increasing the ratio of dodecanoic acid to PA leads to either the formation of large vesicles in the binary systems where the anion-π interactions are strong, or a heterogeneous mixture of assemblies when the peptide amphiphiles associate weakly with dodecanoic acid. Our findings reveal how co-assembly involving designed specific interactions can drastically change supramolecular morphology and even cross from nano to micro scales.

Supramolecular nanoparticles generated by the self-assembly of polyrotaxanes for antitumor drug delivery

Directory of Open Access Journals (Sweden)

Liu R

2012-10-01

Full Text Available Rong Liu,1,2,* Yusi Lai,1,* Bin He,1 Yuan Li,1 Gang Wang,1 Shuang Chang,1 Zhongwei Gu1 1National Engineering Research Center for Biomaterials, Sichuan University, Chengdu, China; 2Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China*These authors contributed equally to this paperAbstract: A new approach of fabricating supramolecular nanoparticles generated by self-assembly polyrotaxanes for antitumor drug delivery has been reported. Cinnamic-acid-modified poly(ethylene glycol chains were threaded in a-cyclodextrins to form polyrotaxanes. The polyrotaxanes self-assembled supramolecular nanoparticles. The morphology of the nanoparticles was changed from nanovesicle to micelle after the antitumor drug, doxorubicin, was loaded. The release profile of the drug-loaded nanoparticles was investigated, and it was found that the sustaining release time could last for 32 hours. The drug-loaded nanoparticles were co-cultured with mouse 4T1 breast cancer cells with a drug concentration of 10 µg/mL; the cell survival rate was 3.3% after a 72-hour incubation. In an in vivo study of breast cancer in a mouse model, the drug-loaded nanoparticles were injected in the tail veins of mice with a dose of 5 mg/kg body weight. The tumor inhibition rate of drug-loaded nanoparticles was 53%, which was better than that of doxorubicin hydrochloride. The cardiac toxicity of doxorubicin was decreased greatly after the encapsulation into supramolecular polyrotaxane nanoparticles.Keywords: polyrotaxane, self-assembly, nanoparticle, doxorubicin, supermolecular

Macromolecularly crowded in vitro microenvironments accelerate the production of extracellular matrix-rich supramolecular assemblies.

Science.gov (United States)

Kumar, Pramod; Satyam, Abhigyan; Fan, Xingliang; Collin, Estelle; Rochev, Yury; Rodriguez, Brian J; Gorelov, Alexander; Dillon, Simon; Joshi, Lokesh; Raghunath, Michael; Pandit, Abhay; Zeugolis, Dimitrios I

2015-03-04

Therapeutic strategies based on the principles of tissue engineering by self-assembly put forward the notion that functional regeneration can be achieved by utilising the inherent capacity of cells to create highly sophisticated supramolecular assemblies. However, in dilute ex vivo microenvironments, prolonged culture time is required to develop an extracellular matrix-rich implantable device. Herein, we assessed the influence of macromolecular crowding, a biophysical phenomenon that regulates intra- and extra-cellular activities in multicellular organisms, in human corneal fibroblast culture. In the presence of macromolecules, abundant extracellular matrix deposition was evidenced as fast as 48 h in culture, even at low serum concentration. Temperature responsive copolymers allowed the detachment of dense and cohesive supramolecularly assembled living substitutes within 6 days in culture. Morphological, histological, gene and protein analysis assays demonstrated maintenance of tissue-specific function. Macromolecular crowding opens new avenues for a more rational design in engineering of clinically relevant tissue modules in vitro.

Hierarchical assembly of branched supramolecular polymers from (cyclic Peptide)-polymer conjugates.

Science.gov (United States)

Koh, Ming Liang; Jolliffe, Katrina A; Perrier, Sébastien

2014-11-10

We report the synthesis and assembly of (N-methylated cyclic peptide)-polymer conjugates for which the cyclic peptide is attached to either the α- or both α- and ω- end groups of a polymer. A combination of chromatographic, spectroscopic, and scattering techniques reveals that the assembly of the conjugates follows a two-level hierarchy, initially driven by H-bond formation between two N-methylated cyclic peptides, followed by unspecific, noncovalent aggregation of this peptide into small domains that behave as branching points and lead to the formation of branched supramolecular polymers.

Supramolecular assembly of organic bicapped Keggin polyoxometalate

International Nuclear Information System (INIS)

Han Zhangang; Zhao Yulong; Peng Jun; Ma Huiyuan; Liu Qun; Wang Enbo; Hu Ninghai

2004-01-01

Two novel supramolecular assemblies of organic bicapped Keggin polyoxometalates (pbpy) 8 H 3 [PW 12 O 40 ]·2H 2 O (1) and (pbpy) 4 H[PMo 12 O 40 (VO)] (2) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Crystallographic data for compound (1), C 128 H 103 N 16 O 42 PW 12 , triclinic, space group P1-bar: a=13.4759(8) A, b=14.6395(11) A, c=16.5743(10) A, α=95.764(2) deg., β=102.166(2) deg., γ=92.9870(10) deg., Z=1, V=3171.1(4) A 3 ; for compound (2), C 64 H 49 N 8 O 41 PMo 12 V, triclinic, space group P1-bar: a=11.5377(11) A, b=12.7552(8) A, c=14.9599(10) A, α=72.270(4) deg., β=88.916(2) deg., γ=67.865(4) deg., Z=1, V=1931.0(3) A 3 . X-ray analyses show that both 1 and 2 represent rare organic bicapped Keggin structures and are supported by supramolecular interactions to extend into a 3D framework. In particular, the unusual structure feature of compound 2 contains a simultaneously organic and inorganic capped structure

A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

International Nuclear Information System (INIS)

Cao, Jing; Liu, Jia-Cheng; Deng, Wen-Ting; Li, Ren-Zhi; Jin, Neng-Zhi

2013-01-01

Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO 2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO 2 electrode surface in supramolecular solar cells

Cucurbit[8]uril templated supramolecular ring structure formation and protein assembly modulation

NARCIS (Netherlands)

Ramaekers, M.; Wijnands, S.P.W.; van Dongen, J.L.J.; Brunsveld, L.; Dankers, P.Y.W.

2015-01-01

The interplay of Phe-Gly-Gly (FGG)-tagged proteins and bivalent FGG-tagged penta(ethylene glycol) as guest molecules with cucurbit[8]uril (Q8) hosts is studied to modulate the supramolecular assembly process. Ring structure formation of the bivalent guest molecule with Q8 leads to enhanced binding

Graphene–cyclodextrin–cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability

Energy Technology Data Exchange (ETDEWEB)

Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian, E-mail: qiantang@swu.edu.cn; Liu, Chang-Hua; Ma, Xue-Bing

2014-06-01

This study aimed to develop a new graphene-based layered assembly, named graphene–cyclodextrin–cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN–CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN–CD assembly to form a layered self-assembled structure, GN–CD–Cyt c, through electrostatic interaction. Compared with GNs and GN–CD, GN–CD–Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. - Highlights: • A new tertiary layered assembly named GN–CD–Cyt c was prepared. • Compared with GNs and GN–CD, GN–CD–Cyt c shows improved electron transfer rate. • GN–CD–Cyt c displays high supramolecular recognition capability.

Graphene–cyclodextrin–cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability

International Nuclear Information System (INIS)

Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian; Liu, Chang-Hua; Ma, Xue-Bing

2014-01-01

This study aimed to develop a new graphene-based layered assembly, named graphene–cyclodextrin–cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN–CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN–CD assembly to form a layered self-assembled structure, GN–CD–Cyt c, through electrostatic interaction. Compared with GNs and GN–CD, GN–CD–Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. - Highlights: • A new tertiary layered assembly named GN–CD–Cyt c was prepared. • Compared with GNs and GN–CD, GN–CD–Cyt c shows improved electron transfer rate. • GN–CD–Cyt c displays high supramolecular recognition capability

Self-assembly of poly(ionic liquid) (PIL)-based amphiphilic homopolymers into vesicles and supramolecular structures with dyes and silver nanoparticles

KAUST Repository

Manojkumar, Kasina

2017-04-27

The incorporation of both hydrophilic and hydrophobic segments in homopolymers leads to their self-assembly into nanostructures in selective solvents, owing to their amphiphilic character. Here we report the RAFT polymerization of N-imidazole-3-propylmethacrylamide and the further quaternization of the resulting polymer with different alkyl bromides of a varying chain length, which afforded well-defined polymeric ionic liquids (PILs) 1-4. These PILs are characterized by the presence of both hydrophobic alkyl chains and hydrophilic ionic moieties, allowing their spontaneous self-assembly in water, forming distinct polymeric vesicles (= polymersomes) the size of which can be varied as a function of alkyl chain length. As demonstrated by the dye-encapsulation study, a particular organic-soluble PIL, 3, consisting of a dodecyl side-chain enabled the transfer of the water-soluble Rose Bengal dye, from an aqueous solution to the organic phase. In addition, polymersomes obtained from a PIL (2) featuring butyl side chains were used as templates and polymeric stabilizers of silver nanoparticles (NPs), i.e. leading to AgNP@PIL hybrids, as observed by transmission electron microscopy (TEM). It was found that the extent of functionalization of polymersomes by the Ag-based NPs varied greatly before and after the end-group removal of the PIL. Altogether, this report emphasizes the facile synthesis of amphiphilic homoPILs and their manipulation in water for dye encapsulation and for stabilization of silver NPs.

Self-assembly of poly(ionic liquid) (PIL)-based amphiphilic homopolymers into vesicles and supramolecular structures with dyes and silver nanoparticles

KAUST Repository

Manojkumar, Kasina; Mecerreyes, David; Taton, Daniel; Gnanou, Yves; Vijayakrishna, Kari

2017-01-01

The incorporation of both hydrophilic and hydrophobic segments in homopolymers leads to their self-assembly into nanostructures in selective solvents, owing to their amphiphilic character. Here we report the RAFT polymerization of N-imidazole-3-propylmethacrylamide and the further quaternization of the resulting polymer with different alkyl bromides of a varying chain length, which afforded well-defined polymeric ionic liquids (PILs) 1-4. These PILs are characterized by the presence of both hydrophobic alkyl chains and hydrophilic ionic moieties, allowing their spontaneous self-assembly in water, forming distinct polymeric vesicles (= polymersomes) the size of which can be varied as a function of alkyl chain length. As demonstrated by the dye-encapsulation study, a particular organic-soluble PIL, 3, consisting of a dodecyl side-chain enabled the transfer of the water-soluble Rose Bengal dye, from an aqueous solution to the organic phase. In addition, polymersomes obtained from a PIL (2) featuring butyl side chains were used as templates and polymeric stabilizers of silver nanoparticles (NPs), i.e. leading to AgNP@PIL hybrids, as observed by transmission electron microscopy (TEM). It was found that the extent of functionalization of polymersomes by the Ag-based NPs varied greatly before and after the end-group removal of the PIL. Altogether, this report emphasizes the facile synthesis of amphiphilic homoPILs and their manipulation in water for dye encapsulation and for stabilization of silver NPs.

Self-assembly of heterogeneous supramolecular structures with uniaxial anisotropy.

Science.gov (United States)

Ruiz-Osés, M; Gonzalez-Lakunza, N; Silanes, I; Gourdon, A; Arnau, A; Ortega, J E

2006-12-28

Uniaxial anisotropy in two-dimensional self-assembled supramolecular structures is achieved by the coadsorption of two different linear molecules with complementary amine and imide functionalization. The two-dimensional monolayer is defined by a one-dimensional stack of binary chains, which can be forced to line up along steps in vicinal surfaces. The competing driving forces in the self-organization process are discussed in light of the structures observed during single molecule adsorption and coadsorption on flat and vicinal surfaces and the corresponding theoretical calculations.

Narrowing the diversification of supramolecular assemblies by preorganization.

Science.gov (United States)

Wang, Zhongyan; Liang, Chunhui; Shang, Yuna; He, Shuangshuang; Wang, Ling; Yang, Zhimou

2018-03-13

We designed and synthesized three phosphorylated peptides as precursors of the same peptide Nap-YYY. We found that different precursors led to different materials with almost identical chemical compositions at the final stages. Only Nap-YpYY could form very uniform nanofibers in a stable supramolecular hydrogel by enzyme-instructed self-assembly (EISA) at the physiological temperature (37 °C). In contrast, de-phosphorylation of the other two precursors (Nap-pYYY and Nap-YYpY) resulted in diverse nanostructures in metastable hydrogels with precipitates. The formation of uniform nanomaterials in the stable hydrogels was due to the preorganization property of the precursor Nap-YpYY, which facilitated rapid folding and accelerated the kinetics of hydrogelation of the resulting peptide Nap-YYY generated by the EISA process. Our study demonstrated the importance of the precursor for the self-assembly of nanomaterials and provided a useful strategy to manipulate them.

Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.

Science.gov (United States)

Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël

2008-09-01

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

Supramolecular Assembly of Comb-like Macromolecules Induced by Chemical Reactions that Modulate the Macromolecular Interactions In Situ.

Science.gov (United States)

Xia, Hongwei; Fu, Hailin; Zhang, Yanfeng; Shih, Kuo-Chih; Ren, Yuan; Anuganti, Murali; Nieh, Mu-Ping; Cheng, Jianjun; Lin, Yao

2017-08-16

Supramolecular polymerization or assembly of proteins or large macromolecular units by a homogeneous nucleation mechanism can be quite slow and require specific solution conditions. In nature, protein assembly is often regulated by molecules that modulate the electrostatic interactions of the protein subunits for various association strengths. The key to this regulation is the coupling of the assembly process with a reversible or irreversible chemical reaction that occurs within the constituent subunits. However, realizing this complex process by the rational design of synthetic molecules or macromolecules remains a challenge. Herein, we use a synthetic polypeptide-grafted comb macromolecule to demonstrate how the in situ modulation of interactions between the charged macromolecules affects their resulting supramolecular structures. The kinetics of structural formation was studied and can be described by a generalized model of nucleated polymerization containing secondary pathways. Basic thermodynamic analysis indicated the delicate role of the electrostatic interactions between the charged subunits in the reaction-induced assembly process. This approach may be applicable for assembling a variety of ionic soft matters that are amenable to chemical reactions in situ.

Asymmetric noncovalent synthesis of self-assembled one-dimensional stacks by a chiral supramolecular auxiliary approach

NARCIS (Netherlands)

George, S.J.; Tomovic, Z.; Averbeke, Van B.; Beljonne, D.; Lazzaroni, R.; Schenning, A.P.H.J.; Meijer, E.W.

2012-01-01

Stereoselective noncovalent synthesis of one-dimensional helical self-assembled stacks of achiral oligo(p-phenylenevinylene) ureidotriazine (AOPV3) monomers is obtained by a chiral supramolecular auxiliary approach. The racemic mixture of helical stacks of achiral AOPV3 molecules is converted into

Construction of diverse supramolecular assemblies of dimetal ...

Indian Academy of Sciences (India)

presence or absence of the lattice water molecules are the keys to forming the diverse supramolecular assem- blies. In 1 and 3, ... Supramolecular; hydrogen bonding; flexible ligand; dicarboxylates. 1. ... The reaction mixture was stirred for another 3 to 4 hours at room ..... Funding for this work was provided by IISER, Mohali.

Combining supramolecular chemistry with biology

NARCIS (Netherlands)

Uhlenheuer, D.A.; Petkau - Milroy, K.; Brunsveld, L.

2010-01-01

Supramolecular chemistry has primarily found its inspiration in biological molecules, such as proteins and lipids, and their interactions. Currently the supramolecular assembly of designed compounds can be controlled to great extent. This provides the opportunity to combine these synthetic

Non-equilibrium supramolecular polymerization.

Science.gov (United States)

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

2017-09-18

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

Two-photon absorption of a supramolecular pseudoisocyanine J-aggregate assembly

International Nuclear Information System (INIS)

Belfield, Kevin D.; Bondar, Mykhailo V.; Hernandez, Florencio E.; Przhonska, Olga V.; Yao, Sheng

2006-01-01

Linear spectral properties, including excitation anisotropy, of pseudoisocyanine or 1,1'-diethyl-2,2'-cyanine iodide (PIC) J-aggregates in aqueous solutions with J-band position at 573 nm were investigated. Two-photon absorption of PIC J-aggregates and monomer molecules was studied using an open aperture Z-scan technique. A strong enhancement of the two-photon absorption cross-section of PIC in the supramolecular J-aggregate assembly was observed in aqueous solution. This enhancement is attributed to a strong coupling of the molecular transition dipoles. No two-photon absorption at the peak of the J-band was detected

Competitive Self-Assembly Manifests Supramolecular Darwinism in Soft-Oxometalates

Science.gov (United States)

Das, Santu; Kumar, Saurabh; Mallick, Apabrita; Roy, Soumyajit

2015-09-01

Topological transformation manifested in inorganic materials shows manifold possibilities. In our present work, we show a clear topological transformation in a soft-oxometalate (SOM) system which was formed from its polyoxometalate (POM) precursor [PMo12@Mo72Fe30]. This topological transformation was observed due to time dependent competitive self-assembly of two different length scale soft-oxometalate moieties formed from this two-component host-guest reaction. We characterized different morphologies by scanning electron microscopy, electron dispersive scattering spectroscopy, dynamic light scattering, horizontal attenuated total reflection-infrared spectroscopy and Raman spectroscopy. The predominant structure is selected by its size in a sort of supramolecular Darwinian competition in this process and is described here.

Self-assembled materials and supramolecular chemistry within microfluidic environments: from common thermodynamic states to non-equilibrium structures.

Science.gov (United States)

Sevim, S; Sorrenti, A; Franco, C; Furukawa, S; Pané, S; deMello, A J; Puigmartí-Luis, J

2018-05-01

Self-assembly is a crucial component in the bottom-up fabrication of hierarchical supramolecular structures and advanced functional materials. Control has traditionally relied on the use of encoded building blocks bearing suitable moieties for recognition and interaction, with targeting of the thermodynamic equilibrium state. On the other hand, nature leverages the control of reaction-diffusion processes to create hierarchically organized materials with surprisingly complex biological functions. Indeed, under non-equilibrium conditions (kinetic control), the spatio-temporal command of chemical gradients and reactant mixing during self-assembly (the creation of non-uniform chemical environments for example) can strongly affect the outcome of the self-assembly process. This directly enables a precise control over material properties and functions. In this tutorial review, we show how the unique physical conditions offered by microfluidic technologies can be advantageously used to control the self-assembly of materials and of supramolecular aggregates in solution, making possible the isolation of intermediate states and unprecedented non-equilibrium structures, as well as the emergence of novel functions. Selected examples from the literature will be used to confirm that microfluidic devices are an invaluable toolbox technology for unveiling, understanding and steering self-assembly pathways to desired structures, properties and functions, as well as advanced processing tools for device fabrication and integration.

Hierarchical self-assembly, coassembly, and self-organization of novel liquid crystalline lattices and superlattices from a twin-tapered dendritic benzamide and its four-cylinder-bundle supramolecular polymer.

Science.gov (United States)

Percec, Virgil; Bera, Tushar K; Glodde, Martin; Fu, Qiongying; Balagurusamy, Venkatachalapathy S K; Heiney, Paul A

2003-02-17

The synthesis and structural analysis of the twin-dendritic benzamide 10, based on the first-generation, self-assembling, tapered dendrons 3,4,5-tris(4'-dodecyloxybenzyloxy)benzoic acid and 3,4,5-tris(4'-dodecyloxybenzyloxy)-1-aminobenzene, and the polymethacrylate, 20, which contains 10 as side groups, are presented. Benzamide 10 self-assembles into a supramolecular cylindrical dendrimer that self-organizes into a columnar hexagonal (Phi(h)) liquid crystalline (LC) phase. Polymer 20 self-assembles into an imperfect four-cylinder-bundle supramolecular dendrimer, and creates a giant vesicular supercylinder that self-organizes into a columnar nematic (N(c)) LC phase which displays short-range hexagonal order. In mixtures of 20 and 10, 10 acts as a guest and 20 as a host to create a perfect four-cylinder-bundle host-guest supramolecular dendrimer that coorganizes with 10. A diversity of Phi(h), simple rectangular columnar (Phi(r-s)) and centered rectangular columnar (Phi(r-c)), superlattices are produced at different ratios between 20 and 10. This diversity of LC lattices and superlattices is facilitated by the architecture of the twin-dendritic building block, polymethacrylate, the host-guest supramolecular assembly, and by hydrogen bonding along the center of the supramolecular cylinders generated from 10 and 20.

Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

Science.gov (United States)

Lin, Tao

Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin

Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

KAUST Repository

Patil, Sachin; Moosa, Basem; Alsaiari, Shahad; Alamoudi, Kholod; Alshamsan, Aws; Almailk, Abdulaziz; Adil, Karim; Eddaoudi, Mohamed; Khashab, Niveen M.

2016-01-01

Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond

Multivalency in supramolecular chemistry and nanofabrication

NARCIS (Netherlands)

Mulder, A.; Huskens, Jurriaan; Reinhoudt, David

2004-01-01

Multivalency is a powerful and versatile self-assembly pathway that confers unique thermodynamic and kinetic behavior onto supramolecular complexes. The diversity of the examples of supramolecular multivalent systems discussed in this perspective shows that the concept of multivalency is a general

Structural Consequences of Anionic Host-Cationic Guest Interactions in a Supramolecular Assembly

Energy Technology Data Exchange (ETDEWEB)

Pluth, Michael D.; Johnson, Darren W.; Szigethy, Geza; Davis, Anna V.; Teat, Simon J.; Oliver, Allen G.; Bergman, Robert G.; Raymond, Kenneth N.

2008-07-09

The molecular structure of the self-assembled supramolecular assembly [M{sub 4}L{sub 6}]{sup 12-} has been explored with different metals (M = Ga{sup III}, Fe{sup III}, Ti{sup IV}) and different encapsulated guests (NEt{sub 4}{sup +}, BnNMe{sub 3}{sup +}, Cp{sub 2}Co{sup +}, Cp*{sub 2}Co{sup +}) by X-ray crystallography. While the identity of the metal ions at the vertices of the M{sub 4}L{sub 6} structure is found to have little effect on the assembly structure, encapsulated guests significantly distort the size and shape of the interior cavity of the assembly. Cations on the exterior of the assembly are found to interact with the assembly through either {pi}-{pi}, cation-{pi}, or CH-{pi} interactions. In some cases, the exterior guests interact with only one assembly, but cations with the ability to form multiple {pi}-{pi} interactions are able to interact with adjacent assemblies in the crystal lattice. The solvent accessible cavity of the assembly is modeled using the rolling probe method and found to range from 253-434 {angstrom}{sup 3}, depending on the encapsulated guest. Based on the volume of the guest and the volume of the cavity, the packing coefficient for each host-guest complex is found to range from 0.47-0.67.

Supramolecular materials based on hydrogen-bonded polymers

NARCIS (Netherlands)

ten Brinke, Gerrit; Ruokolainen, Janne; Ikkala, Olli; Binder, W

2007-01-01

Combining supramolecular principles with block copolymer self-assembly offers unique possibilities to create materials with responsive and/or tunable properties. The present chapter focuses on supramolecular materials based on hydrogen bonding and (block co-) polymers. Several cases will be

Dynamic reciprocity in bio-inspired supramolecular materials

NARCIS (Netherlands)

Bastings, M.M.C.

2012-01-01

Dynamic reciprocity, the spatio-temporal bidirectional process between evolving partners in a functional system is not only found in nature, but also applies to supramolecularly assembling architectures. In this thesis, the focus was on the understanding of nature-inspired supramolecular

A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons

Directory of Open Access Journals (Sweden)

Ping Du

2015-03-01

Full Text Available Two-dimensional (2D, supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications.

The Versatile SALSAC Approach to Heteroleptic Copper(I Dye Assembly in Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Frederik J. Malzner

2018-05-01

Full Text Available Surface-bound heteroleptic copper(I dyes [Cu(Lanchor(Lancillary]+ are assembled using the “surfaces-as-ligands, surfaces as complexes” (SALSAC approach by three different procedures. The anchoring and ancillary ligands chosen are ((6,6′-dimethyl-[2,2′-bipyridine]-4,4′-diyl-bis(4,1-phenylenebis(phosphonic acid (3 and 4,4′-bis(4-iodophenyl-6,6′-diphenyl-2,2′-bipyridine (4, respectively. In the first SALSAC procedure, the FTO/TiO2 electrode is functionalized with 3 in the first dye bath, and then undergoes ligand exchange with the homoleptic complex [Cu(42][PF6] to give surface-bound [Cu(3(4]+. In the second method, the FTO/TiO2 electrode functionalized with 3 is immersed in a solution containing a 1:1 mixture of [Cu(MeCN4][PF6] and 4 to give surface-anchored [Cu(3(4]+. In the third procedure, the anchor 3, copper(I ion and ancillary ligand 4 are introduced in a sequential manner. The performances of the DSSCs show a dependence on the dye assembly procedure. The sequential method leads to the best-performing DSSCs with the highest values of JSC (7.85 and 7.73 mA cm−2 for fully masked cells and overall efficiencies (η = 2.81 and 2.71%, representing 41.1 and 39.6% relative to an N719 reference DSSC. Use of the 1:1 mixture of [Cu(MeCN4][PF6] and 4 yields DSSCs with higher VOC values but lower JSC values compared to those assembled using the sequential approach; values of η are 2.27 and 2.29% versus 6.84% for the N719 reference DSSC. The ligand exchange procedure leads to DSSCs that perform relatively poorly. The investigation demonstrates the versatile and powerful nature of SALSAC in preparing dyes for copper-based DSSCs, allowing the photoconversion efficiency of dye to be optimized for a given dye. The SALSAC strategy provides alternative hierarchical strategies where the isolation of the homoleptic [Cu(Lancillary2]+ is difficult or time-consuming; stepwise strategies are more atom-economic than ligand exchange involving the

Carbohydrates in Supramolecular Chemistry.

Science.gov (United States)

Delbianco, Martina; Bharate, Priya; Varela-Aramburu, Silvia; Seeberger, Peter H

2016-02-24

Carbohydrates are involved in a variety of biological processes. The ability of sugars to form a large number of hydrogen bonds has made them important components for supramolecular chemistry. We discuss recent advances in the use of carbohydrates in supramolecular chemistry and reveal that carbohydrates are useful building blocks for the stabilization of complex architectures. Systems are presented according to the scaffold that supports the glyco-conjugate: organic macrocycles, dendrimers, nanomaterials, and polymers are considered. Glyco-conjugates can form host-guest complexes, and can self-assemble by using carbohydrate-carbohydrate interactions and other weak interactions such as π-π interactions. Finally, complex supramolecular architectures based on carbohydrate-protein interactions are discussed.

Supramolecular oligothiophene microfibers spontaneously assembled on surfaces or coassembled with proteins inside live cells.

Science.gov (United States)

Barbarella, Giovanna; Di Maria, Francesca

2015-08-18

During the last few decades, multifunctional nano- and microfibers made of semiconducting π-conjugated oligomers and polymers have generated much interest because of a broad range of applications extending from sensing to bioelectronic devices and (opto)electronics. The simplest technique for the fabrication of these anisotropic supramolecular structures is to let the molecules do the work by spontaneous organization driven by the information encoded in their molecular structure. Oligothiophenes-semiconducting and fluorescent compounds that have been extensively investigated for applications in thin-film field-effect transistors and solar cells and to a lesser extent as dyes for fluorescent labeling of proteins, DNA, and live cells-are particularly suited as building blocks for supramolecular architectures because of the peculiar properties of the thiophene ring. Because of the great polarizability of sulfur outer-shell electrons and the consequent facile geometric deformability and adaptability of the ring to the environment, thiophene can generate multiple nonbonding interactions to promote non-covalent connections between blocks. Furthermore, sulfur can be hypervalent, i.e., it can accommodate more than the eight electrons normally associated with s and p shells. Hypervalent oligothiophene-S,S-dioxides whose oxygen atoms can be involved in hydrogen bonding have been synthesized. These compounds are amphiphilic, and some of them are able to spontaneously cross the membrane of live cells. Hypervalent nonbonding interactions of divalent sulfur, defined as weak coordination to a proximate nitrogen or oxygen, have also been invoked in the solid-state packing of many organic molecules and in the architecture of proteins. In this Account, we describe two different types of thiophene-based building blocks that can induce the spontaneous formation of nanostructured microfibers in very different environments. The first, based on the synthesis of "sulfur

Generation of Supramolecular Chirality around Twofold Rotational or Helical Axes in Crystalline Assemblies of Achiral Components

Directory of Open Access Journals (Sweden)

Mikiji Miyata

2015-10-01

Full Text Available A multi-point approximation method clarifies supramolecular chirality of twofold rotational or helical assemblies as well as bundles of the one-dimensional (1D assemblies. While one-point approximation of materials claims no chirality generation of such assemblies, multi-point approximations do claim possible generation in the 1D assemblies of bars and plates. Such chirality derives from deformations toward three-axial directions around the helical axes. The chiral columns are bundled in chiral ways through symmetry operations. The preferable right- or left-handed columns are bundled together to yield chiral crystals with right- or left-handedness, respectively, indicating that twofold helix symmetry operations cause chiral crystals composed of achiral components via a three-stepwise and three-directional process.

Tuning Gas Adsorption Properties of Zeolite-like Supramolecular Assemblies with gis Topology via Functionalization of Isoreticular Metal–Organic Squares

KAUST Repository

Wang, Shuang; Belmabkhout, Youssef; Cairns, Amy; Li, Guanghua; Huo, Qisheng; Liu, Yunling; Eddaoudi, Mohamed

2017-01-01

A strategy based on metal-ligand directed assembly of metal-organic squares (MOSs), built-up from four-membered ring (4MR) secondary building units (SBUs), has been employed for the design and construction of isoreticular zeolite-like supramolecular

Proton Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

Energy Technology Data Exchange (ETDEWEB)

Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2009-04-10

Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK{sub a} units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization

Proton-Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

International Nuclear Information System (INIS)

Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2009-01-01

Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK a units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization of

From micelle supramolecular assemblies in selective solvents to isoporous membranes

KAUST Repository

Nunes, Suzana Pereira; Karunakaran, Madhavan; Neelakanda, Pradeep; Behzad, Ali Reza; Hooghan, Bobby; Sougrat, Rachid; He, Haoze; Peinemann, Klaus-Viktor

2011-01-01

The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

From micelle supramolecular assemblies in selective solvents to isoporous membranes

KAUST Repository

Nunes, Suzana Pereira

2011-08-16

The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

Painting Supramolecular Polymers in Organic Solvents by Super-resolution Microscopy

Science.gov (United States)

2018-01-01

Despite the rapid development of complex functional supramolecular systems, visualization of these architectures under native conditions at high resolution has remained a challenging endeavor. Super-resolution microscopy was recently proposed as an effective tool to unveil one-dimensional nanoscale structures in aqueous media upon chemical functionalization with suitable fluorescent probes. Building upon our previous work, which enabled photoactivation localization microscopy in organic solvents, herein, we present the imaging of one-dimensional supramolecular polymers in their native environment by interface point accumulation for imaging in nanoscale topography (iPAINT). The noncovalent staining, typical of iPAINT, allows the investigation of supramolecular polymers’ structure in situ without any chemical modification. The quasi-permanent adsorption of the dye to the polymer is exploited to identify block-like arrangements within supramolecular fibers, which were obtained upon mixing homopolymers that were prestained with different colors. The staining of the blocks, maintained by the lack of exchange of the dyes, permits the imaging of complex structures for multiple days. This study showcases the potential of PAINT-like strategies such as iPAINT to visualize multicomponent dynamic systems in their native environment with an easy, synthesis-free approach and high spatial resolution. PMID:29697958

Self assembly of amphiphilic C60 fullerene derivatives into nanoscale supramolecular structures

Directory of Open Access Journals (Sweden)

Casscells S Ward

2007-08-01

Full Text Available Abstract Background The amphiphilic fullerene monomer (AF-1 consists of a "buckyball" cage to which a Newkome-like dendrimer unit and five lipophilic C12 chains positioned octahedrally to the dendrimer unit are attached. In this study, we report a novel fullerene-based liposome termed 'buckysome' that is water soluble and forms stable spherical nanometer sized vesicles. Cryogenic electron microscopy (Cryo-EM, transmission electron microscopy (TEM, and dynamic light scattering (DLS studies were used to characterize the different supra-molecular structures readily formed from the fullerene monomers under varying pH, aqueous solvents, and preparative conditions. Results Electron microscopy results indicate the formation of bilayer membranes with a width of ~6.5 nm, consistent with previously reported molecular dynamics simulations. Cryo-EM indicates the formation of large (400 nm diameter multilamellar, liposome-like vesicles and unilamellar vesicles in the size range of 50–150 nm diameter. In addition, complex networks of cylindrical, tube-like aggregates with varying lengths and packing densities were observed. Under controlled experimental conditions, high concentrations of spherical vesicles could be formed. In vitro results suggest that these supra-molecular structures impose little to no toxicity. Cytotoxicity of 10–200 μM buckysomes were assessed in various cell lines. Ongoing studies are aimed at understanding cellular internalization of these nanoparticle aggregates. Conclusion In this current study, we have designed a core platform based on a novel amphiphilic fullerene nanostructure, which readily assembles into supra-molecular structures. This delivery vector might provide promising features such as ease of preparation, long-term stability and controlled release.

Unravelling the High-Pressure Behaviour of Dye-Zeolite L Hybrid Materials

Directory of Open Access Journals (Sweden)

Lara Gigli

2018-02-01

Full Text Available Self-assembly of chromophores nanoconfined in porous materials such as zeolite L has led to technologically relevant host-guest systems exploited in solar energy harvesting, photonics, nanodiagnostics and information technology. The response of these hybrid materials to compression, which would be crucial to enhance their application range, has never been explored to date. By a joint high-pressure in situ synchrotron X-ray powder diffraction and ab initio molecular dynamics approach, herein we unravel the high-pressure behaviour of hybrid composites of zeolite L with fluorenone dye. High-pressure experiments were performed up to 6 GPa using non-penetrating pressure transmitting media to study the effect of dye loading on the structural properties of the materials under compression. Computational modelling provided molecular-level insight on the response to compression of the confined dye assemblies, evidencing a pressure-induced strengthening of the interaction between the fluorenone carbonyl group and zeolite L potassium cations. Our results reveal an impressive stability of the fluorenone-zeolite L composites at GPa pressures. The remarkable resilience of the supramolecular organization of dye molecules hyperconfined in zeolite L channels may open the way to the realization of optical devices able to maintain their functionality under extreme conditions.

Gelation induced supramolecular chirality: chirality transfer, amplification and application.

Science.gov (United States)

Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

2014-08-14

Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

Graphene-cyclodextrin-cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability.

Science.gov (United States)

Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian; Liu, Chang-Hua; Ma, Xue-Bing

2014-06-01

This study aimed to develop a new graphene-based layered assembly, named graphene-cyclodextrin-cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN-CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN-CD assembly to form a layered self-assembled structure, GN-CD-Cyt c, through electrostatic interaction. Compared with GNs and GN-CD, GN-CD-Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

Solvent induced supramolecular anisotropy in molecular gels

Energy Technology Data Exchange (ETDEWEB)

Rogers, Michael A., E-mail: mroger09@uoguelph.ca [Department of Food Science, University of Guelph, Guelph, Ontario, N3C3X9 (Canada); Corradini, Maria G. [Department of Food Science, University of Massachusetts Amherst, Amherst, MA, 01003 (United States); Emge, Thomas [Department of Chemistry and Biochemistry, Rutgers University, New Brunswick, NJ, 08901 (United States)

2017-06-15

Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

Solvent induced supramolecular anisotropy in molecular gels

International Nuclear Information System (INIS)

Rogers, Michael A.; Corradini, Maria G.; Emge, Thomas

2017-01-01

Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

Supramolecular systems chemistry

NARCIS (Netherlands)

Mattia, Elio; Otto, Sijbren

The field of supramolecular chemistry focuses on the non-covalent interactions between molecules that give rise to molecular recognition and self-assembly processes. Since most non-covalent interactions are relatively weak and form and break without significant activation barriers, many

Supramolecularly assembled water layers stabilized by sebacic anions in complexes of Zn(II) and Co(II)

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

Two three-dimensional supramolecular water architectures,[Zn(phen)3]2 ·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(1) and [Co(phen)3]2 ·[Co(H2O)6]·(C10H16O4)3·30H2O(2)[phen=1,10-Phenanthroline,C10H16O4=sebacic dianion],have been synthesized and characterized by IR,elemental analysis,thermogravimetric analysis,and single-crystal X-ray diffractions.The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions.The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.

Supramolecular assembly affording a ratiometric two-photon fluorescent nanoprobe for quantitative detection and bioimaging.

Science.gov (United States)

Wang, Peng; Zhang, Cheng; Liu, Hong-Wen; Xiong, Mengyi; Yin, Sheng-Yan; Yang, Yue; Hu, Xiao-Xiao; Yin, Xia; Zhang, Xiao-Bing; Tan, Weihong

2017-12-01

Fluorescence quantitative analyses for vital biomolecules are in great demand in biomedical science owing to their unique detection advantages with rapid, sensitive, non-damaging and specific identification. However, available fluorescence strategies for quantitative detection are usually hard to design and achieve. Inspired by supramolecular chemistry, a two-photon-excited fluorescent supramolecular nanoplatform ( TPSNP ) was designed for quantitative analysis with three parts: host molecules (β-CD polymers), a guest fluorophore of sensing probes (Np-Ad) and a guest internal reference (NpRh-Ad). In this strategy, the TPSNP possesses the merits of (i) improved water-solubility and biocompatibility; (ii) increased tissue penetration depth for bioimaging by two-photon excitation; (iii) quantitative and tunable assembly of functional guest molecules to obtain optimized detection conditions; (iv) a common approach to avoid the limitation of complicated design by adjustment of sensing probes; and (v) accurate quantitative analysis by virtue of reference molecules. As a proof-of-concept, we utilized the two-photon fluorescent probe NHS-Ad-based TPSNP-1 to realize accurate quantitative analysis of hydrogen sulfide (H 2 S), with high sensitivity and good selectivity in live cells, deep tissues and ex vivo -dissected organs, suggesting that the TPSNP is an ideal quantitative indicator for clinical samples. What's more, TPSNP will pave the way for designing and preparing advanced supramolecular sensors for biosensing and biomedicine.

Supramolecular hair dyes: a new application of cocrystallization

DEFF Research Database (Denmark)

Delori, Amit; Urquhart, Andrew; Oswald, Iain D. H.

2016-01-01

The manuscript presents the first report of hair dyes of various colors formed by cocrystallization. Unlike the most popular oxidative hair dye (OHD) products, these dyes are NH3 free and do not require H2O2 as a color developer. The importance of these new hair dyes products is further enhanced...

Ionic liquid-induced aggregate formation and their applications.

Science.gov (United States)

Dutta, Rupam; Kundu, Sangita; Sarkar, Nilmoni

2018-06-01

In the last two decades, researchers have extensively studied highly stable and ordered supramolecular assembly formation using oppositely charged surfactants. Thereafter, surface-active ionic liquids (SAILs), a special class of room temperature ionic liquids (RTILs), replace the surfactants to form various supramolecular aggregates. Therefore, in the last decade, the building blocks of the supramolecular aggregates (micelle, mixed micelle, and vesicular assemblies) have changed from oppositely charged surfactant/surfactant pair to surfactant/SAIL and SAIL/SAIL pair. It is also found that various biomolecules can also interact with SAILs to construct biologically important supramolecular assemblies. The very latest addition to this combination of ion pairs is the dye molecules having a long hydrophobic chain part along with a hydrophilic ionic head group. Thus, dye/surfactant or dye/SAIL pair also produces different assemblies through electrostatic, hydrophobic, and π-π stacking interactions. Vesicles are one of the important self-assemblies which mimic cellular membranes, and thus have biological application as a drug carrier. Moreover, vesicles can act as a suitable microreactor for nanoparticle synthesis.

Hydrogen bonded supramolecular materials

CERN Document Server

Li, Zhan-Ting

2015-01-01

This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

Geometry directed self-selection in the coordination-driven self-assembly of irregular supramolecular polygons.

Science.gov (United States)

Zheng, Yao-Rong; Northrop, Brian H; Yang, Hai-Bo; Zhao, Liang; Stang, Peter J

2009-05-01

The self-assembly of irregular metallo-supramolecular hexagons and parallelograms has been achieved in a self-selective manner upon mixing 120 degrees unsymmetrical dipyridyl ligands with 60 degrees or 120 degrees organoplatinum acceptors in a 1:1 ratio. The polygons have been characterized using (31)P and (1)H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS) as well as X-ray crystallography. Geometric features of the molecular subunits direct the self-selection process, which is supported by molecular force field computations.

Supramolecular chemistry-general principles and selected examples from anion recognition and metallosupramolecular chemistry.

Science.gov (United States)

Albrecht, Markus

2007-12-01

This review gives an introduction into supramolecular chemistry describing in the first part general principles, focusing on terms like noncovalent interaction, molecular recognition, self-assembly, and supramolecular function. In the second part those will be illustrated by simple examples from our laboratories. Supramolecular chemistry is the science that bridges the gap between the world of molecules and nanotechnology. In supramolecular chemistry noncovalent interactions occur between molecular building blocks, which by molecular recognition and self-assembly form (functional) supramolecular entities. It is also termed the "chemistry of the noncovalent bond." Molecular recognition is based on geometrical complementarity based on the "key-and-lock" principle with nonshape-dependent effects, e.g., solvatization, being also highly influential. Self-assembly leads to the formation of well-defined aggregates. Hereby the overall structure of the target ensemble is controlled by the symmetry features of the certain building blocks. Finally, the aggregates can possess special properties or supramolecular functions, which are only found in the ensemble but not in the participating molecules. This review gives an introduction on supramolecular chemistry and illustrates the fundamental principles by recent examples from our group.

Control over Structure and Function of Peptide Amphiphile Supramolecular Assemblies through Molecular Design and Energy Landscapes

Science.gov (United States)

Tantakitti, Faifan

Supramolecular chemistry is a powerful tool to create a material of a defined structure with tunable properties. This strategy has led to catalytically active, bioactive, and environment-responsive materials, among others, that are valuable in applications ranging from sensor technology to energy and medicine. Supramolecular polymers formed by peptide amphiphiles (PAs) have been especially relevant in tissue regeneration due to their ability to form biocompatible structures and mimic many important signaling molecules in biology. These supramolecular polymers can form nanofibers that create networks which mimic natural extracellular matrices. PA materials have been shown to induce growth of blood vessels, bone, cartilage, and nervous tissue, among others. The work described in this thesis not only studied the relationship between molecular structure and functions of PA assemblies, but also uncovered a powerful link between the energy landscape of their supramolecular self-assembly and the ability of PA materials to interact with cells. In chapter 2, it is argued that fabricating fibrous nanostructures with defined mechanical properties and decoration with bioactive molecules is not sufficient to create a material that can effectively communicate with cells. By systemically placing the fibronectin-derived RGDS epitope at increasing distances from the surface of PA nanofibers through a linker of one to five glycine residues, integrin-mediated RGDS signaling was enhanced. The results suggested that the spatial presentation of an epitope on PA nanofibers strongly influences the bioactivity of the PA substrates. In further improving functionality of a PA-based scaffold to effectively direct cell growth and differentiation, chapter 3 explored the use of a cell microcarrier to compartmentalize and simultaneously tune insoluble and soluble signals in a single matrix. PA nanofibers were incorporated at the surface of the microcarrier in order to promote cell adhesion, while

A redox-assisted supramolecular assembly of manganese oxide nanotube

International Nuclear Information System (INIS)

Tao Li; Sun Chenggao; Fan Meilian; Huang Caijuan; Wu Hailong; Chao Zisheng; Zhai Hesheng

2006-01-01

In this paper, we report the hydrothermal synthesis of manganese oxide nanotube from an aqueous medium of pH 7, using KMnO 4 and MnCl 2 as inorganic precursors, polyoxyethylene (10) nonyl phenyl ether (TX-10) a surfactant and acetaldehyde an additive. The characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and N 2 adsorption at 77 K (BET) reveals that the synthesized manganese oxide nanotube has a mesopore size of ca. 3.65 nm and a wall thickness of ca. 12 nm, with the wall being composed of microporous crystals of monoclinic manganite. The X-ray photoelectron spectroscopy (XPS) result demonstrates a decrease of the binding energy of the Mn 3+ in the manganese oxide nanotube, which may be related to both the nanotubular morphology and the crystalline pore wall. A mechanism of a redox-assisted supramolecular assembly, regulated by acetaldehyde, is postulated

Interactions and Supramolecular Organization of Sulfonated Indigo and Thioindigo Dyes in Layered Hydroxide Hosts.

Science.gov (United States)

Costa, Ana L; Gomes, Ana C; Pereira, Ricardo C; Pillinger, Martyn; Gonçalves, Isabel S; Pineiro, Marta; Seixas de Melo, J Sérgio

2018-01-09

Supramolecularly organized host-guest systems have been synthesized by intercalating water-soluble forms of indigo (indigo carmine, IC) and thioindigo (thioindigo-5,5'-disulfonate, TIS) in zinc-aluminum-layered double hydroxides (LDHs) and zinc-layered hydroxide salts (LHSs) by coprecipitation routes. The colors of the isolated powders were dark blue for hybrids containing only IC, purplish blue or dark lilac for cointercalated samples containing both dyes, and ruby/wine for hybrids containing only TIS. The as-synthesized and thermally treated materials were characterized by Fourier transform infrared, Fourier transform Raman, and nuclear magnetic resonance spectroscopies, powder X-ray diffraction, scanning electron microscopy, and elemental and thermogravimetric analyses. The basal spacings found for IC-LDH, TIS-LDH, IC-LHS, and TIS-LHS materials were 21.9, 21.05, 18.95, and 21.00 Å, respectively, with intermediate spacings being observed for the cointercalated samples that either decreased (LDHs) or increased (LHSs) with increasing TIS content. UV-visible and fluorescence spectroscopies (steady-state and time-resolved) were used to probe the molecular distribution of the immobilized dyes. The presence of aggregates together with the monomer units is suggested for IC-LDH, whereas for TIS-LDH, IC-LHS, and TIS-LHS, the dyes are closer to the isolated situation. Accordingly, while emission from the powder H 2 TIS is strongly quenched, an increment in the emission of about 1 order of magnitude was observed for the TIS-LDH/LHS hybrids. Double-exponential fluorescence decays were obtained and associated with two monomer species interacting differently with cointercalated water molecules. The incorporation of both TIS and IC in the LDH and LHS hosts leads to an almost complete quenching of the fluorescence, pointing to a very efficient energy transfer process from (fluorescent) TIS to (nonfluorescent) IC.

Supramolecular tunneling junctions

NARCIS (Netherlands)

Wimbush, K.S.

2012-01-01

In this study a variety of supramolecular tunneling junctions were created. The basis of these junctions was a self-assembled monolayer of heptathioether functionalized ß-cyclodextrin (ßCD) formed on an ultra-flat Au surface, i.e., the bottom electrode. This gave a well-defined hexagonally packed

Improved enzyme-mediated synthesis and supramolecular self-assembly of naturally occurring conjugates of beta-sitosterol

Czech Academy of Sciences Publication Activity Database

Wimmerová, Martina; Siglerová, Věra; Šaman, David; Šlouf, Miroslav; Kaletová, Eva; Wimmer, Zdeněk

2017-01-01

Roč. 117, JAN (2017), s. 38-43 ISSN 0039-128X R&D Projects: GA MŠk LD15012; GA MŠk(CZ) LO1507 Institutional support: RVO:61389030 ; RVO:61388963 ; RVO:61389013 Keywords : glycosides * esterification * resolution * sterols * esters * foods * l. * beta-Sitosterol * Acylated steryl glycoside * Lipase * Ionic liquid * Supramolecular self-assembly * Pharmacological activity Subject RIV: CC - Organic Chemistry; CD - Macromolecular Chemistry (UMCH-V) OBOR OECD: Organic chemistry; Polymer science (UMCH-V); Organic chemistry (UOCHB-X) Impact factor: 2.282, year: 2016

Effects of subtle differences in ligand constitution and conformation in metallo-supramolecular self-assembled polygons.

Science.gov (United States)

Brusilowskij, Boris; Dzyuba, Egor V; Troff, Ralf W; Schalley, Christoph A

2011-12-07

3,3'-Bis(pyridin-[n]-ylethynyl)biphenyl (n = 3, 4) and the corresponding 2,2'-bipyridines assemble with (dppp)Pt(II) triflate into metallo-supramolecular polygons. Depending on the position of the terminal pyridine N atoms, the assembly reaction leads to different equilibrium products. With the slow ligand exchange on Pt(II) complexes, the equilibrium is reached on a many-hour time-scale. During the assembly process, larger polygons form under kinetic control. This was confirmed by time-dependent (1)H and (31)P NMR spectroscopy in line with complementary ESI mass spectrometric experiments. The constitutional difference in the pyridine N-atom position is reflected in the tandem mass spectra of the complex ions. In addition, a highly specific fragmentation process of mass-selected M(3)L(3) ions was observed, which proceeds through a ring contraction yielding smaller M(2)L(2) ions.

Supramolecular fluorene based materials

NARCIS (Netherlands)

Abbel, R.J.

2008-01-01

This thesis describes the use of noncovalent interactions in order to manipulate and control the self-assembly and morphology of electroactive fluorene-based materials. The supramolecular arrangement of p-conjugated polymers and oligomers can strongly influence their electronic and photophysical

From fundamental supramolecular chemistry to self-assembled nanomaterials and medicines and back again - how Sam inspired SAMul.

Science.gov (United States)

Smith, David K

2018-05-08

This feature article provides a personal insight into the research from my group over the past 10 years. In particular, the article explains how, inspired in 2005 by meeting my now-husband, Sam, who had cystic fibrosis, and who in 2011 went on to have a double lung transplant, I took an active decision to follow a more applied approach to some of our research, attempting to use fundamental supramolecular chemistry to address problems of medical interest. In particular, our strategy uses self-assembly to fabricate biologically-active nanosystems from simple low-molecular-weight building blocks. These systems can bind biological polyanions in highly competitive conditions, allowing us to approach applications in gene delivery and coagulation control. In the process, however, we have also developed new fundamental principles such as self-assembled multivalency (SAMul), temporary 'on-off' multivalency, and adaptive/shape-persistent multivalent binding. By targeting materials with applications in drug formulation and tissue engineering, we have discovered novel self-assembling low-molecular-weight hydrogelators based on the industrially-relevant dibenzylidenesorbitol framework and developed innovative approaches to spatially-resolved gels and functional multicomponent hybrid hydrogels. In this way, taking an application-led approach to research has also delivered significant academic value and conceptual advances. Furthermore, beginning to translate fundamental supramolecular chemistry into real-world applications, starts to demonstrate the power of this approach, and its potential to transform the world around us for the better.

Artificial Nacre from Supramolecular Assembly of Graphene Oxide.

Science.gov (United States)

Wang, Yang; Li, Ting; Ma, Piming; Zhang, Shengwen; Zhang, Hongji; Du, Mingliang; Xie, Yi; Chen, Mingqing; Dong, Weifu; Ming, Weihua

2018-06-14

Inspired by the "brick-and-mortar" structure and remarkable mechanical performance of nacre, many efforts have been devoted to fabricating nacre-mimicking materials. Herein, a class of graphene oxide (GO) based artificial nacre material with quadruple hydrogen-bonding interactions was fabricated by functionalization of polydopamine-capped graphene oxide (PDG) with 2-ureido-4[1 H]-pyrimidinone (UPy) self-complementary quadruple hydrogen-bonding units followed by supramolecular assembly process. The artificial nacre displays a strict "brick-and-mortar" structure, with PDG nanosheets as the brick and UPy units as the mortar. The resultant nanocomposite shows an excellent balance of strength and toughness. Because of the strong strengthening via quadruple hydrogen bonding, the tensile strength and toughness can reach 325.6 ± 17.8 MPa and 11.1 ± 1.3 MJ m -3 , respectively, thus exceeding natural nacre, and reaching 3.6 and 10 times that of a pure GO artificial nacre. Furthermore, after further H 2 O treatment, the resulting H 2 O-treated PDG-UPy actuator displays significant bending actuations when driven by heat. This work provides a pathway for the development of artificial nacre for their potential applications in energy conversion, temperature sensor, and thermo-driven actuator.

Direct and quantitative characterization of dynamic ligand exchange between coordination-driven self-assembled supramolecular polygons.

Science.gov (United States)

Zheng, Yao-Rong; Stang, Peter J

2009-03-18

The direct observation of dynamic ligand exchange between Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable (1)H/(2)D isotope labeling of the pyridyl donors and electrospray ionization mass spectrometry combined with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established on the basis of quantitative mass spectral results. Further investigation has shown that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counteranions.

Supramolecular Nanoparticles for Molecular Diagnostics and Therapeutics

Science.gov (United States)

Chen, Kuan-Ju

Over the past decades, significant efforts have been devoted to explore the use of various nanoparticle-based systems in the field of nanomedicine, including molecular imaging and therapy. Supramolecular synthetic approaches have attracted lots of attention due to their flexibility, convenience, and modularity for producing nanoparticles. In this dissertation, the developmental story of our size-controllable supramolecular nanoparticles (SNPs) will be discussed, as well as their use in specific biomedical applications. To achieve the self-assembly of SNPs, the well-characterized molecular recognition system (i.e., cyclodextrin/adamantane recognition) was employed. The resulting SNPs, which were assembled from three molecular building blocks, possess incredible stability in various physiological conditions, reversible size-controllability and dynamic disassembly that were exploited for various in vitro and in vivo applications. An advantage of using the supramolecular approach is that it enables the convenient incorporation of functional ligands onto SNP surface that confers functionality ( e.g., targeting, cell penetration) to SNPs. We utilized SNPs for molecular imaging such as magnetic resonance imaging (MRI) and positron emission tomography (PET) by introducing reporter systems (i.e., radio-isotopes, MR contrast agents, and fluorophores) into SNPs. On the other hand, the incorporation of various payloads, including drugs, genes and proteins, into SNPs showed improved delivery performance and enhanced therapeutic efficacy for these therapeutic agents. Leveraging the powers of (i) a combinatorial synthetic approach based on supramolecular assembly and (ii) a digital microreactor, a rapid developmental pathway was developed that is capable of screening SNP candidates for the ideal structural and functional properties that deliver optimal performance. Moreover, SNP-based theranostic delivery systems that combine reporter systems and therapeutic payloads into a

Sensitization effects of supramolecular assemblies on the luminescence of terbium-ion prulifloxacin complexes

Energy Technology Data Exchange (ETDEWEB)

Wang Hong; Yi Chongyue; Li Xue; Fang Fang [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Yang Yajiang, E-mail: yjyang@mail.hust.edu.c [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

2011-04-15

Luminescence enhancement of terbium-ion prulifloxacin complexes (Tb(III)-PUFX) in supramolecular hydrogels formed by assembly of 1,3:2,4-di-O-benzylidene-D-sorbitol (DBS) was investigated by steady-state fluorescence, varying temperature fluorescence and time-resolved fluorescence. The luminescence images show that Tb(III)-PUFX were dispersed in the DBS gels. The luminescence intensity of Tb(III)-PUFX in the DBS gels was significantly increased in comparison with that in corresponding aqueous solutions. The varying temperature fluorescent spectra show that the luminescence intensity of Tb(III)-PUFX decreased with an increase in the temperature. This implies that the luminescence enhancement of Tb(III)-PUFX is related to the dissociation and the formation of the DBS assemblies. Time-resolved fluorescence measurements show slower rotational motion in DBS gels in comparison with that in the corresponding aqueous solutions. This may be ascribed to a unique microstructure of three-dimensional network formed by DBC aggregates, resulting in deactivation of the nonradiative relaxation. The images of field emission scanning electron microscopy and polarized optical microscopy indicate that the morphology of the DBS assemblies was not influenced upon addition of Tb(III)-PUFX to the DBS gels.

Size-controlled and redox-responsive supramolecular nanoparticles

NARCIS (Netherlands)

Weinhart-Mejia, R.; Kronig, G.A.; Huskens, Jurriaan

2015-01-01

Control over the assembly and disassembly of nanoparticles is pivotal for their use as drug delivery vehicles. Here, we aim to form supramolecular nanoparticles (SNPs) by combining advantages of the reversible assembly properties of SNPs using host–guest interactions and of a stimulus-responsive

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

Science.gov (United States)

Pekkanen, Allison M; Mondschein, Ryan J; Williams, Christopher B; Long, Timothy E

2017-09-11

Supramolecular chemistry continues to experience widespread growth, as fine-tuned chemical structures lead to well-defined bulk materials. Previous literature described the roles of hydrogen bonding, ionic aggregation, guest/host interactions, and π-π stacking to tune mechanical, viscoelastic, and processing performance. The versatility of reversible interactions enables the more facile manufacturing of molded parts with tailored hierarchical structures such as tissue engineered scaffolds for biological applications. Recently, supramolecular polymers and additive manufacturing processes merged to provide parts with control of the molecular, macromolecular, and feature length scales. Additive manufacturing, or 3D printing, generates customizable constructs desirable for many applications, and the introduction of supramolecular interactions will potentially increase production speed, offer a tunable surface structure for controlling cell/scaffold interactions, and impart desired mechanical properties through reinforcing interlayer adhesion and introducing gradients or self-assembled structures. This review details the synthesis and characterization of supramolecular polymers suitable for additive manufacture and biomedical applications as well as the use of supramolecular polymers in additive manufacturing for drug delivery and complex tissue scaffold formation. The effect of supramolecular assembly and its dynamic behavior offers potential for controlling the anisotropy of the printed objects with exquisite geometrical control. The potential for supramolecular polymers to generate well-defined parts, hierarchical structures, and scaffolds with gradient properties/tuned surfaces provides an avenue for developing next-generation biomedical devices and tissue scaffolds.

Monosaccharides as Versatile Units for Water-Soluble Supramolecular Polymers.

Science.gov (United States)

Leenders, Christianus M A; Jansen, Gijs; Frissen, Martijn M M; Lafleur, René P M; Voets, Ilja K; Palmans, Anja R A; Meijer, E W

2016-03-18

We introduce monosaccharides as versatile water-soluble units to compatibilise supramolecular polymers based on the benzene-1,3,5-tricarboxamide (BTA) moiety with water. A library of monosaccharide-based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α-glucose, β-glucose, α-mannose and α-galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one-dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self-assembly process is operative and that the introduction of different monosaccharides does not significantly change the self- assembly behaviour. Finally, we investigate the potential of post-assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

KAUST Repository

Fathalla, Maher; Strutt, Nathan; Srinivasan, Sampath; Katsiev, Khabiboulakh; Hartlieb, Karel J.; Bakr, Osman; Stoddart, J. Fraser

2015-01-01

A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

KAUST Repository

Fathalla, Maher

2015-05-18

A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

Towards supramolecular engineering of functional nanomaterials: pre-programming multi-component 2D self-assembly at solid-liquid interfaces.

Science.gov (United States)

Ciesielski, Artur; Palma, Carlos-Andres; Bonini, Massimo; Samorì, Paolo

2010-08-24

Materials with a pre-programmed order at the supramolecular level can be engineered with a sub-nanometer precision making use of reversible non- covalent interactions. The intrinsic ability of supramolecular materials to recognize and exchange their constituents makes them constitutionally dynamic materials. The tailoring of the materials properties relies on the full control over the self-assembly behavior of molecular modules exposing recognition sites and incorporating functional units. In this review we focus on three classes of weak-interactions to form complex 2D architectures starting from properly designed molecular modules: van der Waals, metallo-ligand and hydrogen bonding. Scanning tunneling microscopy studies will provide evidence with a sub-nanometer resolution, on the formation of responsive multicomponent architectures with controlled geometries and properties. Such endeavor enriches the scientist capability of generating more and more complex smart materials featuring controlled functions and unprecedented properties.

Force and time-dependent self-assembly, disruption and recovery of supramolecular peptide amphiphile nanofibers.

Science.gov (United States)

Dikecoglu, F Begum; Topal, Ahmet E; Ozkan, Alper D; Tekin, E Deniz; Tekinay, Ayse B; Guler, Mustafa O; Dana, Aykutlu

2018-07-13

Biological feedback mechanisms exert precise control over the initiation and termination of molecular self-assembly in response to environmental stimuli, while minimizing the formation and propagation of defects through self-repair processes. Peptide amphiphile (PA) molecules can self-assemble at physiological conditions to form supramolecular nanostructures that structurally and functionally resemble the nanofibrous proteins of the extracellular matrix, and their ability to reconfigure themselves in response to external stimuli is crucial for the design of intelligent biomaterials systems. Here, we investigated real-time self-assembly, deformation, and recovery of PA nanofibers in aqueous solution by using a force-stabilizing double-pass scanning atomic force microscopy imaging method to disrupt the self-assembled peptide nanofibers in a force-dependent manner. We demonstrate that nanofiber damage occurs at tip-sample interaction forces exceeding 1 nN, and the damaged fibers subsequently recover when the tip pressure is reduced. Nanofiber ends occasionally fail to reconnect following breakage and continue to grow as two individual nanofibers. Energy minimization calculations of nanofibers with increasing cross-sectional ellipticity (corresponding to varying levels of tip-induced fiber deformation) support our observations, with high-ellipticity nanofibers exhibiting lower stability compared to their non-deformed counterparts. Consequently, tip-mediated mechanical forces can provide an effective means of altering nanofiber integrity and visualizing the self-recovery of PA assemblies.

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Energy Technology Data Exchange (ETDEWEB)

Surbella, Robert G. [Department; Ducati, Lucas C. [Department; Pellegrini, Kristi L. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; McNamara, Bruce K. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Autschbach, Jochen [Department; Schwantes, Jon M. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Cahill, Christopher L. [Department

2017-07-26

A family of twelve supramolecular [AnO2Cl4]2- (An = U, Np, Pu) containing compounds assembled via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I) is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence pure [An(VI)O2Cl4]2- (An = U, Np, Pu) tectons are the norm. We present a hierarchy of assembly criteria based on crystallographic observations, and subsequently quantify the strengths of the non-covalent interactions using Kohn-Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials (ESPs) of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction (NCI) acceptor-donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ~2 kJ mol-1 across the AnO22+ series, indicating the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen N-H+. Subsequent analyses using the Quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) approaches support this conclusion and highlight the structure directing role of the cations. Whereas one can infer that the 2 Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.

A redox responsive, fluorescent supramolecular metallohydrogel consists of nanofibers with single-molecule width

KAUST Repository

Zhang, Ye

2013-04-03

The integration of a tripeptide derivative, which is a versatile self-assembly motif, with a ruthenium(II)tris(bipyridine) complex affords the first supramolecular metallo-hydrogelator that not only self assembles in water to form a hydrogel but also exhibits gel-sol transition upon oxidation of the metal center. Surprisingly, the incorporation of the metal complex in the hydrogelator results in the nanofibers, formed by the self-assembly of the hydrogelator in water, to have the width of a single molecule of the hydrogelator. These results illustrate that metal complexes, besides being able to impart rich optical, electronic, redox, or magnetic properties to supramolecular hydrogels, also offer a unique geometrical control to prearrange the self-assembly motif prior to self-assembling. The use of metal complexes to modulate the dimensionality of intermolecular interactions may also help elucidate the interactions of the molecular nanofibers with other molecules, thus facilitating the development of supramolecular hydrogel materials for a wide range of applications. © 2013 American Chemical Society.

Self-assembling multivalency : supramolecular polymers assembled from monovalent mannose-labelled discotic molecules

NARCIS (Netherlands)

Petkau - Milroy, K.; Brunsveld, L.

2013-01-01

Supramolecular synthesis, the "bottom-up" construction of higher-order structures from monomeric building blocks, represents a flexible approach for the generation of multivalent materials. Here, monovalent building blocks decorated with a single bioactive ligand were synthesized. In water, these

Zwitterionic supramolecular nanoparticles: self-assembly and responsive properties

NARCIS (Netherlands)

Stoffelen, C.; Huskens, Jurriaan

2015-01-01

Supramolecular nanoparticles (SNPs) are of high interest in both nanoscience and molecular diagnostics and therapeutics, because of their reversible and designable properties. To ensure colloidal stabilization and biocompatibility, most reported strategies require the use of hydrophilic long-chain

Fabrication of Supramolecular Chirality from Achiral Molecules at the Liquid/Liquid Interface Studied by Second Harmonic Generation.

Science.gov (United States)

Lin, Lu; Zhang, Zhen; Guo, Yuan; Liu, Minghua

2018-01-09

We present the investigation into the supramolecular chirality of 5-octadecyloxy-2-(2-pyridylazo)phenol (PARC18) at water/1,2-dichloroethane interface by second harmonic generation (SHG). We observe that PARC18 molecules form supramolecular chirality through self-assembly at the liquid/liquid interface although they are achiral molecules. The bulk concentration of PARC18 in the organic phase has profound effects on the supramolecular chirality. By increasing bulk concentration, the enantiomeric excess at the interface first grows and then decreases until it eventually vanishes. Further analysis reveals that the enantiomeric excess is determined by the twist angle of PARC18 molecules at the interface rather than their orientational angle. At lower and higher bulk concentrations, the average twist angle of PARC18 molecules approaches zero, and the assemblies are achiral; whereas at medium bulk concentrations, the average twist angle is nonzero, so that the assemblies show supramolecular chirality. We also estimate the coverage of PARC18 molecules at the interface versus the bulk concentration and fit it to Langmuir adsorption model. The result indicates that PARC18 assemblies show strongest supramolecular chirality in a half-full monolayer. These findings highlight the opportunities for precise control of supramolecular chirality at liquid/liquid interfaces by manipulating the bulk concentration.

Chapter 8: Selective Stoichiometric and Catalytic Reactivity in the Confines of a Chiral Supramolecular Assembly

Energy Technology Data Exchange (ETDEWEB)

University of California, Berkeley; Lawrence Berkeley National Laboratory; Raymond, Kenneth; Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

2007-09-27

increased complexity of synthetic host molecules, most assembly conditions utilize self-assembly to form complex highly-symmetric structures from relatively simple subunits. For supramolecular assemblies able to encapsulate guest molecules, the chemical environment in each assembly--defined by the size, shape, charge, and functional group availability--greatly influences the guest-binding characteristics.[6, 13-17

Assembly of one-dimensional supramolecular objects: From monomers to networks

Science.gov (United States)

Sayar, Mehmet; Stupp, Samuel I.

2005-07-01

One-dimensional supramolecular aggregates can form networks at exceedingly low concentrations. Recent experiments in several laboratories, including our own, have demonstrated the formation of gels by these systems at concentrations well under 1% by weight. The systems of interest in our laboratory form either cylindrical nanofibers or ribbons as a result of strong noncovalent interactions among monomers. The stiffness and interaction energies among these thread-like objects can vary significantly depending on the chemical structure of the monomers used. We have used Monte Carlo simulations to study the structure of the threads and their ability to form networks through bundle formation. The persistence length of the threads was found to be strongly affected not only by stiffness, but also by the strength of attractive two-body interactions among thread segments. The relative values of stiffness and attractive two-body interaction strength determine if threads collapse or create bundles. Only in the presence of sufficiently long threads and bundle formation can these systems assemble into networks of high connectivity.

Uses of neutron scattering in supramolecular chemistry

International Nuclear Information System (INIS)

Lindoy, L.F.

1998-01-01

Full text: A major thrust in recent chemical research has been the development of supramolecular chemistry 1 - broadly the chemistry of large multicomponent molecular assemblies in which the component structural units are held together by either covalent linkages or by a variety of weaker (non-covalent) interactions that include hydrogen bonding, dipole stacking, π-stacking, van der Waals q forces and favourable hydrophobic interactions. Much of the activity in the area has been motivated by the known behaviour of biological molecules (such as enzymes). Thus molecular assemblies are ubiquitous in natural systems but, with a limited number of exceptions, have only recently been the subject of increasing investigation by chemists. A feature of much of this recent work has been its focus on molecular design for achieving complementarity between single molecule hosts and guests. The use of single crystal neutron diffraction coupled with molecular modelling and a range of other techniques to investigate the nature of individual supramolecular systems will be discussed. By way of example, in one such study the supramolecular array formed by co-crystallisation of 1,2- diaminoethane and benzoic acid has been investigated; the system self-assembles into an unusual layered structure composed of two-dimensional hydrogen bonded networks sandwiched between layers of edge-to-face stacked aromatic systems. The number of hydrogen-bond donors and acceptors is balanced in this structure

Self-Assembly of Supramolecular Aggregates Based on Sector- and Cone-Shaped Dendrons and Bolaamphiphiles

Science.gov (United States)

Shcherbina, M. A.; Chvalun, S. N.

2018-06-01

Using a number of classes of such sector-shaped macromolecules as derivatives of 2,3,4- and 3,4,5- tri(dodecyloxy)benzenesulfonic acid and dendrimers based on gallic acid as an example, the main stages in the formation of supramolecular ensembles are considered: the formation of individual supramolecular aggregates due to the weak noncovalent interactions of mesogenic groups, and the subsequent ordering within these aggregates, which lowers the free energy of a system. Supramolecular aggregates are in turn organized into two- or three-dimensional supramolecular lattices. It is shown that the shape of the supramolecular aggregates and its change along with temperature are functions of the chemical structure of the mesogenic group (resulting in the controlled design of complex self-organizing systems with a given response to external stimuli).

Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets.

Science.gov (United States)

Kulkarni, Chidambar; Korevaar, Peter A; Bejagam, Karteek K; Palmans, Anja R A; Meijer, E W; George, Subi J

2017-10-04

Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

Design of Molecular Materials: Supramolecular Engineering

Science.gov (United States)

Simon, Jacques; Bassoul, Pierre

2001-02-01

This timely and fascinating book is destined to be recognised as THE book on supramolecular engineering protocols. It covers this sometimes difficult subject in an approachable form, gathering together information from many sources. Supramolecular chemistry, which links organic chemistry to materials science, is one of the fastest growth areas of chemistry research. This book creates a correlation between the structure of single molecules and the physical and chemical properties of the resulting materials. By making systematic changes to the component molecules, the resulting solid can be engineered for optimum performance. There is a clearly written development from synthesis of designer molecules to properties of solids and further on to devices and complex materials systems, providing guidelines for mastering the organisation of these systems. Topics covered include: Systemic chemistry Molecular assemblies Notions of symmetry Supramolecular engineering Principe de Curie Organisation in molecular media Molecular semiconductors Industrial applications of molecular materials This superb book will be invaluable to researchers in the field of supramolecular materials and also to students and teachers of the subject.

Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career.

Science.gov (United States)

Anslyn, Eric V

2016-01-01

While the strict definition of supramolecular chemistry is "chemistry beyond the molecule", meaning having a focus on non-covalent interactions, the field is primarily associated with the creation of synthetic receptors and self-assembly. For synthetic ease, the receptors and assemblies routinely possess a high degree of symmetry, which lends them an aspect of aesthetic beauty. Pictures of electron orbitals similarly can be seen as akin to works of art. This similarity was an early draw for me to the fields of supramolecular chemistry and molecular orbital theory, because I grew up in a household filled with art. In addition to art, my childhood was filled with repairing and constructing mechanical entities, such as internal combustion motors, where many components work together to achieve a function. Analogously, the field of supramolecular chemistry creates systems of high complexity that achieve functions or perform tasks. Therefore, in retrospect a career in supramolecular chemistry appears to be simply an extension of childhood hobbies involving art and auto-mechanics.

Self-assembly of a triangle-shaped, hexaplatinum-incorporated, supramolecular amphiphile in solution and at interfaces.

Science.gov (United States)

Maran, Umamageswaran; Britt, David; Fox, Christopher B; Harris, Joel M; Orendt, Anita M; Conley, Hiram; Davis, Robert; Hlady, Vladamir; Stang, Peter J

2009-08-24

The self-assembly and characterization of a novel supramolecular amphiphile built from a new 60 degree amphiphilic precursor that incorporates hydrophilic platinum(II) metals and hydrophobic dioctadecyloxy chains is reported. The amphiphilic macrocycle and its precursor compound have been characterized by multinuclear NMR spectroscopy, ESI-MS, and other standard techniques. The coacervate morphology of the amphiphile at the liquid-liquid interface has been studied by using confocal optical microscopy and in situ Raman spectroscopy. The self-assembly of the amphiphilic macrocycle at the air-water interface has been investigated through Langmuir-trough techniques. The study indicates the possible formation of surface micelle-like aggregates. The disparity between the experimental molecular areas and those derived from molecular models support the idea of aggregation. AFM images of the surface aggregates show the formation of a flat topology with arbitrary ridgelike patterns. Reasonable molecular-packing arrangements are proposed to explain the molecular organization within the observed structures.

Aerosolized droplet mediated self-assembly of photosynthetic pigment analogues and deposition onto substrates.

Science.gov (United States)

Shah, Vivek B; Biswas, Pratim

2014-02-25

Self-assembled photosynthetic molecules have a high extinction coefficient and a broad absorption in the infrared region, and these properties can be used to improve the efficiency of solar cells. We have developed a single-step method for the self-assembly of synthetic chlorin molecules (analogues of native bacteriochlorophylls) in aerosolized droplets, containing a single solvent and two solvents, to synthesize biomimetic light-harvesting structures. In the single-solvent approach, assembly is promoted by a concentration-driven process due to evaporation of the solvent. The peak absorbance of Zn(II) 3-(1-hydroxyethyl)-10-phenyl-13(1)-oxophorbine (1) in methanol shifted from 646 nm to 725 nm (∼ 80 nm shift) after assembly, which is comparable to the shift observed in the naturally occurring assembly of bacteriochlorophyll c. Although assembly is thermodynamically favorable, the kinetics of self-assembly play an important role, and this was demonstrated by varying the initial concentration of the pigment monomer. To overcome kinetic limitations, a two-solvent approach using a volatile solvent (tetrahydrofuran) in which the dye is soluble and a less volatile solvent (ethanol) in which the dye is sparingly soluble was demonstrated to be effective. The effect of molecular structure is demonstrated by spraying the sterically hindered Zn(II) 3-(1-hydroxyethyl)-10-mesityl-13(1)-oxophorbine (2), which is an analogue of 1, under similar conditions. The results illustrate a valuable and facile aerosol-based method for the formation of films of supramolecular assemblies.

Building new discrete supramolecular assemblies through the interaction of iso-tellurazole N-oxides with Lewis acids and bases.

Science.gov (United States)

Ho, Peter C; Jenkins, Hilary A; Britten, James F; Vargas-Baca, Ignacio

2017-10-13

The supramolecular macrocycles spontaneously assembled by iso-tellurazole N-oxides are stable towards Lewis bases as strong as N-heterocyclic carbenes (NHC) but readily react with Lewis acids such as BR 3 (R = Ph, F). The electron acceptor ability of the tellurium atom is greatly enhanced in the resulting O-bonded adducts, which consequently enables binding to a variety of Lewis bases that includes acetonitrile, 4-dimethylaminopyridine, 4,4'-bipyridine, triphenyl phosphine, a N-heterocyclic carbene and a second molecule of iso-tellurazole N-oxide.

Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

OpenAIRE

Gooch, Adam; Murphy, Natasha S.; Thomson, Neil H.; Wilson, Andrew J.

2013-01-01

Derivatives of thymine have been extensively used to promote supramolecular materials assembly. Such derivatives can be synthetically challenging to access and may be susceptible to degradation. The current article uses a conformer-independent acceptor-donor-acceptor array (ureidopyrimidine) which forms moderate affinity interactions with diamidopyridine derivatives to effect supramolecular blend formation between polystyrene and poly(methyl methacrylate) polymers obtained by RAFT which have ...

Helical self-organization and hierarchical self-assembly of an oligoheterocyclic pyridine-pyridazine strand into extended supramolecular fibers.

Science.gov (United States)

Cuccia, Louis A; Ruiz, Eliseo; Lehn, Jean-Marie; Homo, Jean-Claude; Schmutz, Marc

2002-08-02

The synthesis and characterization of an alternating pyridine-pyridazine strand comprising thirteen heterocycles are described. Spontaneous folding into a helical secondary structure is based on a general molecular self-organization process enforced by the conformational information encoded within the primary structure of the molecular strand itself. Conformational control based on heterocyclic "helicity codons" illustrates a strategy for designing folding properties into synthetic oligomers (foldamers). Strong intermolecular interactions of the highly ordered lock-washer subunits of compound 3 results in hierarchical supramolecular self-assembly into protofibrils and fibrils. Compound 3 also forms mechanically stable two-dimensional Langmuir-Blodgett and cast thin films.

Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career

Directory of Open Access Journals (Sweden)

Eric V. Anslyn

2016-02-01

Full Text Available While the strict definition of supramolecular chemistry is “chemistry beyond the molecule”, meaning having a focus on non-covalent interactions, the field is primarily associated with the creation of synthetic receptors and self-assembly. For synthetic ease, the receptors and assemblies routinely possess a high degree of symmetry, which lends them an aspect of aesthetic beauty. Pictures of electron orbitals similarly can be seen as akin to works of art. This similarity was an early draw for me to the fields of supramolecular chemistry and molecular orbital theory, because I grew up in a household filled with art. In addition to art, my childhood was filled with repairing and constructing mechanical entities, such as internal combustion motors, where many components work together to achieve a function. Analogously, the field of supramolecular chemistry creates systems of high complexity that achieve functions or perform tasks. Therefore, in retrospect a career in supramolecular chemistry appears to be simply an extension of childhood hobbies involving art and auto-mechanics.

Mesoscopic self-organization of a self-assembled supramolecular rectangle on highly oriented pyrolytic graphite and Au(111) surfaces.

Science.gov (United States)

Gong, Jian-Ru; Wan, Li-Jun; Yuan, Qun-Hui; Bai, Chun-Li; Jude, Hershel; Stang, Peter J

2005-01-25

A self-assembled supramolecular metallacyclic rectangle was investigated with scanning tunneling microscopy on highly oriented pyrolytic graphite and Au(111) surfaces. The rectangles spontaneously adsorb on both surfaces and self-organize into well ordered adlayers. On highly oriented pyrolytic graphite, the long edge of the rectangle stands on the surface, forming a 2D molecular network. In contrast, the face of the rectangle lays flat on the Au(111) surface, forming linear chains. The structures and intramolecular features obtained through high-resolution scanning tunneling microscopy imaging are discussed.

Water-Insoluble Photosensitizer Nanocolloids Stabilized by Supramolecular Interfacial Assembly towards Photodynamic Therapy

Science.gov (United States)

Liu, Yamei; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Shen, Guizhi; Yan, Xuehai

2017-02-01

Nanoengineering of hydrophobic photosensitizers (PSs) is a promising approach for improved tumor delivery and enhanced photodynamic therapy (PDT) efficiency. A variety of delivery carriers have been developed for tumor delivery of PSs through the enhanced permeation and retention (EPR) effect. However, a high-performance PS delivery system with minimum use of carrier materials with excellent biocompatibility is highly appreciated. In this work, we utilized the spatiotemporal interfacial adhesion and assembly of supramolecular coordination to achieve the nanoengineering of water-insoluble photosensitizer Chlorin e6 (Ce6). The hydrophobic Ce6 nanoparticles are well stabilized in a aqueous medium by the interfacially-assembled film due to the coordination polymerization of tannic acid (TA) and ferric iron (Fe(III)). The resulting Ce6@TA-Fe(III) complex nanoparticles (referenced as Ce6@TA-Fe(III) NPs) significantly improves the drug loading content (~65%) and have an average size of 60 nm. The Ce6@TA-Fe(III) NPs are almost non-emissive as the aggregated states, but they can light up after intracellular internalization, which thus realizes low dark toxicity and excellent phototoxicity under laser irradiation. The Ce6@TA-Fe(III) NPs prolong blood circulation, promote tumor-selective accumulation of PSs, and enhanced antitumor efficacy in comparison to the free-carrier Ce6 in vivo evaluation.

A multilayered supramolecular self-assembled structure from soybean oil by in situ polymerization and its applications.

Science.gov (United States)

Kavitha, Varadharajan; Gnanamani, Arumugam

2013-05-01

The present study emphasizes in situ transformation of soybean oil to self-assembled supramolecular multilayered biopolymer material. The said polymer material was characterized and the entrapment efficacy of both hydrophilic and hydrophobic moieties was studied. In brief, soybean oil at varying concentration was mixed with mineral medium and incubated under agitation (200 rpm) at 37 degrees C for 240 h. Physical observations were made till 240 h and the transformed biopolymer was separated and subjected to physical, chemical and functional characterization. The maximum size of the polymer material was measured as 2 cm in diameter and the cross sectional view displayed the multilayered onion rings like structures. SEM analysis illustrated the presence of multilayered honeycomb channeled structures. Thermal analysis demonstrated the thermal stability (200 degrees C) and high heat enthalpy (1999 J/g). Further, this multilayered assembly was able to entrap both hydrophilic and hydrophobic components simultaneously, suggesting the potential industrial application of this material.

Self-assembly behaviour of conjugated terthiophene surfactants in water

NARCIS (Netherlands)

van Rijn, Patrick; Janeliunas, Dainius; Brizard, Aurelie M.; Stuart, Marc C. A.; Koper, Ger J. M.; Eelkema, Rienk; van Esch, Jan H.

2011-01-01

Conjugated self-assembled systems in water are of great interest because of their potential application in biocompatible supramolecular electronics, but so far their supramolecular chemistry remains almost unexplored. Here we present amphiphilic terthiophenes as a general self-assembling platform

Energy Landscapes for the Self-Assembly of Supramolecular Polyhedra

Science.gov (United States)

Russell, Emily R.; Menon, Govind

2016-06-01

We develop a mathematical model for the energy landscape of polyhedral supramolecular cages recently synthesized by self-assembly (Sun et al. in Science 328:1144-1147, 2010). Our model includes two essential features of the experiment: (1) geometry of the organic ligands and metallic ions; and (2) combinatorics. The molecular geometry is used to introduce an energy that favors square-planar vertices (modeling {Pd}^{2+} ions) and bent edges with one of two preferred opening angles (modeling boomerang-shaped ligands of two types). The combinatorics of the model involve two-colorings of edges of polyhedra with four-valent vertices. The set of such two-colorings, quotiented by the octahedral symmetry group, has a natural graph structure and is called the combinatorial configuration space. The energy landscape of our model is the energy of each state in the combinatorial configuration space. The challenge in the computation of the energy landscape is a combinatorial explosion in the number of two-colorings of edges. We describe sampling methods based on the symmetries of the configurations and connectivity of the configuration graph. When the two preferred opening angles encompass the geometrically ideal angle, the energy landscape exhibits a very low-energy minimum for the most symmetric configuration at equal mixing of the two angles, even when the average opening angle does not match the ideal angle.

Supramolecular fluorene based materials

OpenAIRE

Abbel, R.J.

2008-01-01

This thesis describes the use of noncovalent interactions in order to manipulate and control the self-assembly and morphology of electroactive fluorene-based materials. The supramolecular arrangement of p-conjugated polymers and oligomers can strongly influence their electronic and photophysical properties. Therefore, a detailed understanding of such organisation processes is essential for the optimisation of the performance of these materials as applied in optoelectronic devices. In order to...

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof

Science.gov (United States)

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-01

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting

Self-assembled ultra small ZnO nanocrystals for dye-sensitized solar cell application

Energy Technology Data Exchange (ETDEWEB)

Patra, Astam K.; Dutta, Arghya; Bhaumik, Asim, E-mail: msab@iacs.res.in

2014-07-01

We demonstrate a facile chemical approach to produce self-assembled ultra-small mesoporous zinc oxide nanocrystals using sodium salicylate (SS) as a template under hydrothermal conditions. These ZnO nanomaterials have been successfully fabricated as a photoanode for the dye-sensitized solar cell (DSSC) in the presence of N719 dye and iodine–triiodide electrolyte. The structural features, crystallinity, purity, mesophase and morphology of the nanostructure ZnO are investigated by several characterization tools. N{sub 2} sorption analysis revealed high surface areas (203 m{sup 2} g{sup −1}) and narrow pore size distributions (5.1–5.4 nm) for different samples. The mesoporous structure and strong photoluminescence facilitates the high dye loading at the mesoscopic void spaces and light harvesting in DSSC. By utilizing this ultra-small ZnO photoelectrode with film thickness of about 7 μm in the DSSC with an open-circuit voltage (V{sub OC}) of 0.74 V, short-circuit current density (J{sub SC}) of 3.83 mA cm{sup −2} and an overall power conversion efficiency of 1.12% has been achieved. - Graphical abstract: Ultra-small ZnO nanocrystals have been synthesized with sodium salicylate as a template and using it as a photoanode in a dye-sensitized solar cell 1.12% power conversion efficiency has been observed. - Highlights: • Synthesis of self-assembled ultra-small mesoporous ZnO nanocrystals by using sodium salicylate as a template. • Mesoporous ZnO materials have high BET surface areas and void space. • ZnO nanoparticles serve as a photoanode for the dye-sensitized solar cell (DSSC). • Using ZnO nanocrystals as photoelectrode power conversion efficiency of 1.12% has been achieved.

Supramolecular luminescence from oligofluorenol-based supramolecular polymer semiconductors.

Science.gov (United States)

Zhang, Guang-Wei; Wang, Long; Xie, Ling-Hai; Lin, Jin-Yi; Huang, Wei

2013-11-13

Supramolecular luminescence stems from non-covalent exciton behaviors of active π-segments in supramolecular entities or aggregates via intermolecular forces. Herein, a π-conjugated oligofluorenol, containing self-complementary double hydrogen bonds, was synthesized using Suzuki coupling as a supramolecular semiconductor. Terfluorenol-based random supramolecular polymers were confirmed via concentration-dependent nuclear magnetic resonance (NMR) and dynamic light scattering (DLS). The photoluminescent spectra of the TFOH-1 solution exhibit a green emission band (g-band) at approximately ~520 nm with reversible features, as confirmed through titration experiments. Supramolecular luminescence of TFOH-1 thin films serves as robust evidence for the aggregates of g-band. Our results suggest that the presence of polyfluorene ketone defects is a sufficient condition, rather than a sufficient-necessary condition for the g-band. Supramolecular electroluminescence will push organic devices into the fields of supramolecular optoelectronics, spintronics, and mechatronics.

A Novel Reconfigurable Logic Unit Based on the DNA-Templated Potassium-Concentration-Dependent Supramolecular Assembly.

Science.gov (United States)

Yang, Chunrong; Zou, Dan; Chen, Jianchi; Zhang, Linyan; Miao, Jiarong; Huang, Dan; Du, Yuanyuan; Yang, Shu; Yang, Qianfan; Tang, Yalin

2018-03-15

Plenty of molecular circuits with specific functions have been developed; however, logic units with reconfigurability, which could simplify the circuits and speed up the information process, are rarely reported. In this work, we designed a novel reconfigurable logic unit based on a DNA-templated, potassium-concentration-dependent, supramolecular assembly, which could respond to the input stimuli of H + and K + . By inputting different concentrations of K + , the logic unit could implement three significant functions, including a half adder, a half subtractor, and a 2-to-4 decoder. Considering its reconfigurable ability and good performance, the novel prototypes developed here may serve as a promising proof of principle in molecular computers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Luminescence from Oligofluorenol-Based Supramolecular Polymer Semiconductors

Directory of Open Access Journals (Sweden)

Guang-Wei Zhang

2013-11-01

Full Text Available Supramolecular luminescence stems from non-covalent exciton behaviors of active π-segments in supramolecular entities or aggregates via intermolecular forces. Herein, a π-conjugated oligofluorenol, containing self-complementary double hydrogen bonds, was synthesized using Suzuki coupling as a supramolecular semiconductor. Terfluorenol-based random supramolecular polymers were confirmed via concentration-dependent nuclear magnetic resonance (NMR and dynamic light scattering (DLS. The photoluminescent spectra of the TFOH-1 solution exhibit a green emission band (g-band at approximately ~520 nm with reversible features, as confirmed through titration experiments. Supramolecular luminescence of TFOH-1 thin films serves as robust evidence for the aggregates of g-band. Our results suggest that the presence of polyfluorene ketone defects is a sufficient condition, rather than a sufficient-necessary condition for the g-band. Supramolecular electroluminescence will push organic devices into the fields of supramolecular optoelectronics, spintronics, and mechatronics.

Two new Ni(II) supramolecular complexes based on ethyl isonicotinate and ethyl nicotinate for removal of acid blue 92 dye

Science.gov (United States)

Etaiw, Safaa El-din H.; Marie, Hassan

2018-03-01

Two new luminescent supramolecular complexes (SC); [Ni(EIN)4(NCS)2] SC1 and [Ni2(EN)8(NCS)4] SC2, (EIN = ethyl isonicotinate, EN = ethyl nicotinate), have been synthesized by self-assembly method and structurally characterized by X-ray single crystal, FT-IR and UV-Vis spectra, PXRD, elemental and thermogravimetric analyses. Both SC1 and SC2 are monoclinic crystals however, they have different asymmetric units. Ni(II) atoms in both SC are isostructural and have similar hexa-coordinate environment. The structures of SC1 and SC2 consist of parallel polymeric 1D-chains, extended in two and three dimensional supramolecular frameworks by intermolecular hydrogen bonding interactions. SC1 and SC2 are luminescent materials which can be used in applications as molecular sensing systems. SC1 and SC2 were used as heterogeneous catalysts for degradation of acid blue 92 (AB-92) under sun light irradiation. The fluorescence measurements of terephthalic acid technique as a probe molecule were used to determine the •OH radicals. Also the radicals trapping experiments using isopropanol alcohol (IPA) as radical scavenger were discussed. In addition a mechanism of degradation was proposed and discussed.

Multivalent protein assembly using monovalent self-assembling building blocks

NARCIS (Netherlands)

Petkau - Milroy, K.; Sonntag, M.H.; Colditz, A.; Brunsveld, L.

2013-01-01

Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard

Application of the principle of supramolecular chemistry in the fields of radiochemistry and radiation chemistry

International Nuclear Information System (INIS)

Shen Xinghai; Chen Qingde; Gao Hongcheng

2008-01-01

Supramolecular chemistry, one of the front fields in chemistry, is defined as 'chemistry beyond the molecule', bearing on the organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces. This article focuses on the application of the principle of supramolecular chemistry in the fields of radiochemistry and radiation chemistry. The following aspects are concerned: (1) the recent progress of supramolecular chemistry; (2) the application of the principle of supramolecular chemistry and the functions of supramolecular system, i.e., recognition, assembly and translocation, in the extraction of nuclides; (3) the application of microemulsion, ionic imprinted polymers, ionic liquids and cloud point extraction in the enrichment of nuclides; (4) the radiation effect of supramolecular systems. (authors)

Applications of supramolecular chemistry

CERN Document Server

Schneider, Hans-Jörg

2012-01-01

""The time is ripe for the present volume, which gathers thorough presentations of the numerous actually realized or potentially accessible applications of supramolecular chemistry by a number of the leading figures in the field. The variety of topics covered is witness to the diversity of the approaches and the areas of implementation…a broad and timely panorama of the field assembling an eminent roster of contributors.""-Jean-Marie Lehn, 1987 Noble Prize Winner in Chemistry

Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems.

Science.gov (United States)

Zhang, Xin; Rehm, Stefanie; Safont-Sempere, Marina M; Würthner, Frank

2009-11-01

Water-soluble, self-assembled nanocapsules composed of a functional bilayer membrane and enclosed guest molecules can provide smart (that is, condition responsive) sensors for a variety of purposes. Owing to their outstanding optical and redox properties, perylene bisimide chromophores are interesting building blocks for a functional bilayer membrane in a water environment. Here, we report water-soluble perylene bisimide vesicles loaded with bispyrene-based energy donors in their aqueous interior. These loaded vesicles are stabilized by in situ photopolymerization to give nanocapsules that are stable over the entire aqueous pH range. On the basis of pH-tunable spectral overlap of donors and acceptors, the donor-loaded polymerized vesicles display pH-dependent fluorescence resonance energy transfer from the encapsulated donors to the bilayer dye membrane, providing ultrasensitive pH information on their aqueous environment with fluorescence colour changes covering the whole visible light range. At pH 9.0, quite exceptional white fluorescence could be observed for such water-soluble donor-loaded perylene vesicles.

Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

KAUST Repository

Patil, Sachin

2016-06-29

Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond is established between the imidazole moieties while the second involves the oxygen atom of one amide group and the hydrogen atom of a second amide group. When protonated in acidic aqueous media, HDA successfully complexes siRNA yielding spherical nanostructures. This biocompatible platform controllably delivers siRNA with high efficacy upon visible light irradiation leading up to 90% of gene silencing in live cells.

Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

Science.gov (United States)

Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

2017-10-23

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine.

Science.gov (United States)

Mattioli, Giuseppe; Larciprete, Rosanna; Alippi, Paola; Bonapasta, Aldo Amore; Filippone, Francesco; Lacovig, Paolo; Lizzit, Silvano; Paoletti, Anna Maria; Pennesi, Giovanna; Ronci, Fabio; Zanotti, Gloria; Colonna, Stefano

2017-11-16

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc) 2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc) 2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc) 2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible Assembly of Graphitic Carbon Nitride 3D Network for Highly Selective Dyes Absorption and Regeneration.

Science.gov (United States)

Zhang, Yuye; Zhou, Zhixin; Shen, Yanfei; Zhou, Qing; Wang, Jianhai; Liu, Anran; Liu, Songqin; Zhang, Yuanjian

2016-09-27

Responsive assembly of 2D materials is of great interest for a range of applications. In this work, interfacial functionalized carbon nitride (CN) nanofibers were synthesized by hydrolyzing bulk CN in sodium hydroxide solution. The reversible assemble and disassemble behavior of the as-prepared CN nanofibers was investigated by using CO2 as a trigger to form a hydrogel network at first. Compared to the most widespread absorbent materials such as active carbon, graphene and previously reported supramolecular gel, the proposed CN hydrogel not only exhibited a competitive absorbing capacity (maximum absorbing capacity of methylene blue up to 402 mg/g) but also overcame the typical deficiencies such as poor selectivity and high energy-consuming regeneration. This work would provide a strategy to construct a 3D CN network and open an avenue for developing smart assembly for potential applications ranging from environment to selective extraction.

Photophysical behavior of layer-by-layer electrostatic self-assembled film of azo dye Chromotrope-2R and a polycation

Energy Technology Data Exchange (ETDEWEB)

Hansda, Chaitali [Department of Physics, Jadavpur University, Jadavpur, Kolkata 700032 (India); Department of Physics, The University of Burdwan, Golapbag, Burdwan 713104 (India); Dutta, Bipan [Department of Physics, Sammilani Mahavidyalaya, Baghajatin Station, E.M. Bypass, Kolkata 700075 (India); Chakraborty, Utsav; Singha, Tanmoy [Department of Physics, Jadavpur University, Jadavpur, Kolkata 700032 (India); Hussain, Syed Arshad; Bhattacharjee, Debajyoti [Department of Physics, Tripura University, Suryamaninagar 799022, Tripura West (India); Paul, Sharmistha [West Bengal State Council of Science and Technology, Vigyan Chetana Bhavan, Sector-I, Salt Lake, Kolkata 700064 (India); Paul, Pabitra Kumar, E-mail: pabitra_tu@yahoo.co.in [Department of Physics, Jadavpur University, Jadavpur, Kolkata 700032 (India)

2016-10-15

This communication reports the fabrication of layer-by-layer electrostatic self-assembled films of an azo dye Chromotrope-2R (CH2R) and a Polycation poly(allylamine hydrochloride) (PAH) onto solid substrate. UV–vis absorption and steady state fluorescence emission spectroscopy successfully confirm the incorporation of dye molecules onto the PAH coated quartz substrate. The adsorption behavior of CH2R onto PAH backbone in LbL films highly depends upon the variation of the microenvironment namely pH of the dye solution from which the film was fabricated. PAH layer onto quartz substrate was able to swell sufficiently in the dye solution at very high pH. The Density functional theory was also utilized here to explain the origin of various spectral transitions from the ground electronic states for both in neutral and anionic form of CH2R. In LbL films the more closure association of dye molecules causes their aggregations which are reflected in their absorption and steady state fluorescence emission spectra when compared to those of pure dye solution. Atomic force microscopic images of LbL films assembled from CH2R aqueous solution at different pH clearly reveal the change in the surface morphology of the films and different degree of association of dye molecules in LbL films deposited at various pH of CH2R.

Photophysical behavior of layer-by-layer electrostatic self-assembled film of azo dye Chromotrope-2R and a polycation

International Nuclear Information System (INIS)

Hansda, Chaitali; Dutta, Bipan; Chakraborty, Utsav; Singha, Tanmoy; Hussain, Syed Arshad; Bhattacharjee, Debajyoti; Paul, Sharmistha; Paul, Pabitra Kumar

2016-01-01

This communication reports the fabrication of layer-by-layer electrostatic self-assembled films of an azo dye Chromotrope-2R (CH2R) and a Polycation poly(allylamine hydrochloride) (PAH) onto solid substrate. UV–vis absorption and steady state fluorescence emission spectroscopy successfully confirm the incorporation of dye molecules onto the PAH coated quartz substrate. The adsorption behavior of CH2R onto PAH backbone in LbL films highly depends upon the variation of the microenvironment namely pH of the dye solution from which the film was fabricated. PAH layer onto quartz substrate was able to swell sufficiently in the dye solution at very high pH. The Density functional theory was also utilized here to explain the origin of various spectral transitions from the ground electronic states for both in neutral and anionic form of CH2R. In LbL films the more closure association of dye molecules causes their aggregations which are reflected in their absorption and steady state fluorescence emission spectra when compared to those of pure dye solution. Atomic force microscopic images of LbL films assembled from CH2R aqueous solution at different pH clearly reveal the change in the surface morphology of the films and different degree of association of dye molecules in LbL films deposited at various pH of CH2R.

Self-assembling graphene-anthraquinone-2-sulphonate supramolecular nanostructures with enhanced energy density for supercapacitors

Science.gov (United States)

Gao, Lifang; Gan, Shiyu; Li, Hongyan; Han, Dongxue; Li, Fenghua; Bao, Yu; Niu, Li

2017-07-01

Boosting the energy density of capacitive energy storage devices remains a crucial issue for facilitating applications. Herein, we report a graphene-anthraquinone supramolecular nanostructure by self-assembly for supercapacitors. The sulfonated anthraquinone exhibits high water solubility, a π-conjugated structure and redox active features, which not only serve as a spacer to interact with and stabilize graphene but also introduce extra pseudocapacitance contributions. The formed nest-like three-dimensional (3D) nanostructure with further hydrothermal treatment enhances the accessibility of ion transfer and exposes the redox-active quinone groups in the electrolytes. A fabricated all-solid-state flexible symmetric device delivers a high specific capacitance of 398.5 F g-1 at 1 A g-1 (1.5 times higher than graphene), superior energy density (52.24 Wh kg-1 at about 1 kW kg-1) and good stability (82% capacitance retention after 10 000 cycles).

Reversible optical transcription of supramolecular chirality into molecular chirality

NARCIS (Netherlands)

Jong, Jaap J.D. de; Lucas, Linda N.; Kellogg, Richard M.; Esch, Jan H. van; Feringa, Bernard

2004-01-01

In nature, key molecular processes such as communication, replication, and enzyme catalysis all rely on a delicate balance between molecular and supramolecular chirality. Here we report the design, synthesis, and operation of a reversible, photoresponsive, self-assembling molecular system in which

Supramolecular Drug Delivery Systems Based on Water-Soluble Pillar[n]arenes.

Science.gov (United States)

Wu, Xuan; Gao, Lei; Hu, Xiao-Yu; Wang, Leyong

2016-06-01

Supramolecular drug delivery systems (SDDSs), including various kinds of nanostructures that are assembled by reversible noncovalent interactions, have attracted considerable attention as ideal drug carriers owing to their fascinating ability to undergo dynamic switching of structure, morphology, and function in response to various external stimuli, which provides a flexible and robust platform for designing and developing functional and smart supramolecular nano-drug carriers. Pillar[n]arenes represent a new generation of macrocyclic hosts, which have unique structures and excellent properties in host-guest chemistry. This account describes recent progress in our group to develop pillararene-based stimuli-responsive supramolecular nanostructures constructed by reversible host-guest interactions for controllable anticancer drug delivery. The potential applications of these supramolecular drug carriers in cancer treatment and the fundamental questions facing SDDSs are also discussed. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Orange Side of Disperse Red 1: Humidity-Driven Color Switching in Supramolecular Azo-Polymer Materials Based on Reversible Dye Aggregation.

Science.gov (United States)

Schoelch, Simon; Vapaavuori, Jaana; Rollet, Frédéric-Guillaume; Barrett, Christopher J

2017-01-01

Humidity detection, and the quest for low-cost facile humidity-sensitive indicator materials is of great interest for many fields, including semi-conductor processing, food transport and storage, and pharmaceuticals. Ideal humidity-detection materials for a these applications might be based on simple clear optical readout with no power supply, i.e.: a clear color change observed by the naked eye of any untrained observer, since it doesn't require any extra instrumentation or interpretation. Here, the introduction of a synthesis-free one-step procedure, based on physical mixing of easily available commercial materials, for producing a humidity memory material which can be easily painted onto a wide variety of surfaces and undergoes a remarkable color change (approximately 100 nm blue-shift of λ MAX ) upon exposure to various thresholds of levels of ambient humidity is reported. This strong color change, easily visible to as a red-to-orange color switch, is locked in until inspection, but can then be restored reversibly if desired, after moderate heating. By taking advantage of spontaneously-forming reversible 'soft' supramolecular bonds between a red-colored azo dye and a host polymer matrix, a reversible dye 'migration' aggregation appearing orange, and dis-aggregation back to red can be achieved, to function as the sensor. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular assembly of a series of chiral dendrimers in interfacial films

International Nuclear Information System (INIS)

Yuan Jing; Deng Guojun; Fan Qinghua; Liu Minghua

2004-01-01

Supramolecular assembly and interfacial properties of a series of novel binaphthyl containing dendrimers from generation 1 through generation 4 have been investigated at the air/water interface and in solid substrates. Due to the lack of either long alkyl chains or strong hydrophilic groups, the dendrimer molecules tend to aggregate together to form stable two-dimensional ultrathin films, as verified by π-A and A-t measurements. Atomic force microscope (AFM) measurements of the transferred one-layer ultrathin films indicate that all the dendrimers show disk-like morphologies, which could be varied in particle size upon changing the surface pressure. The height profiles reveal that the height of the disks is between that of a monolayer and a bilayer, indicating that they are formed due to the aggregation of dendrimers with a distortion and/or partial overlapping. Circular dichroism (CD) spectra of the transferred multilayer films show Cotton effects due to the exciton couplet of the aromatic moieties adjacent to the bis(diphenylphosphino)-binaphthyl moiety, which is an active catalytic site for the dendrimer. With the increment of the generation, the intensity of the Cotton effects increased, suggesting that the optical active site of the dendrimer can be controlled by the outside wedge

Encoding complexity within supramolecular analogues of frustrated magnets

Science.gov (United States)

Cairns, Andrew B.; Cliffe, Matthew J.; Paddison, Joseph A. M.; Daisenberger, Dominik; Tucker, Matthew G.; Coudert, François-Xavier; Goodwin, Andrew L.

2016-05-01

The solid phases of gold(I) and/or silver(I) cyanides are supramolecular assemblies of inorganic polymer chains in which the key structural degrees of freedom—namely, the relative vertical shifts of neighbouring chains—are mathematically equivalent to the phase angles of rotating planar (‘XY’) spins. Here, we show how the supramolecular interactions between chains can be tuned to mimic different magnetic interactions. In this way, the structures of gold(I) and/or silver(I) cyanides reflect the phase behaviour of triangular XY magnets. Complex magnetic states predicted for this family of magnets—including collective spin-vortices of relevance to data storage applications—are realized in the structural chemistry of these cyanide polymers. Our results demonstrate how chemically simple inorganic materials can behave as structural analogues of otherwise inaccessible ‘toy’ spin models and also how the theoretical understanding of those models allows control over collective (‘emergent’) phenomena in supramolecular systems.

On the kinetics of body versus end evaporation and addition of supramolecular polymers

NARCIS (Netherlands)

Tiwari, Nitin S.; van der Schoot, Paul

2017-01-01

Abstract.: The kinetics of the self-assembly of supramolecular polymers is dictated by how monomers, dimers, trimers etc., attach to and detach from each other. It is for this reasons that researchers have proposed a plethora of pathways to explain the kinetics of various self-assembling

On the kinetics of body versus end evaporation and addition of supramolecular polymers

NARCIS (Netherlands)

Tiwari, N.; van der Schoot, P.P.A.M.

2017-01-01

The kinetics of the self-assembly of supramolecular polymers is dictated by how monomers, dimers, trimers etc., attach to and detach from each other. It is for this reasons that researchers have proposed a plethora of pathways to explain the kinetics of various self-assembling supramolecules,

Explosive decomposition of a melamine-cyanuric acid supramolecular assembly for fabricating defect-rich nitrogen-doped carbon nanotubes with significantly promoted catalysis.

Science.gov (United States)

Zhao, Zhongkui; Dai, Yitao; Ge, Guifang; Wang, Guiru

2015-05-26

A facile and scalable approach for fabricating structural defect-rich nitrogen-doped carbon nanotubes (MCSA-CNTs) through explosive decomposition of melamine-cyanuric acid supramolecular assembly is presented. In comparison to pristine carbon nanotubes, MCSA-CNT exhibits significantly enhanced catalytic performance in oxidant- and steam-free direct dehydrogenation of ethylbenzene, demonstrating the potential for metal-free clean and energy-saving styrene production. This finding also opens a new horizon for preparing highly-efficient carbocatalysts rich in structural defect sites for diverse transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assembly of three organic–inorganic hybrid supramolecular materials based on reduced molybdenum(V) phosphates

Energy Technology Data Exchange (ETDEWEB)

Zhang, He [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Yu, Kai, E-mail: hlyukai188@163.com [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Lv, Jing-Hua; Wang, Chun-Mei; Wang, Chun-Xiao [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Zhou, Bai-Bin, E-mail: zhou_bai_bin@163.com [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China)

2014-09-15

Three supramolecular materials based on (P{sub 4}Mo{sub 6}) polyoxoanions, (Hbbi){sub 2}(H{sub 2}bbi)[Cu{sub 3}Mo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}O){sub 6}(HPO{sub 4}){sub 4}(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 2}]·3H{sub 2}O (1), (Hbbi){sub 2}(H{sub 2}bbi)[Ni{sub 3}Mo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}O){sub 2}(HPO{sub 4}){sub 4}(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 2}]·9H{sub 2}O (2), (Hbpy)(bpy){sub 3}[Ni{sub 2}(H{sub 2}O){sub 10}Na(PCA){sub 2}][NiMo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}PO{sub 4}){sub 6}(PO{sub 4}){sub 2}]·6H{sub 2}O (3) (bbi=1,1′-(1,4-butanediyl)bis(imidazole), bpy=4,4′-bipyridine, PCA=pyridine-4-carboxylic acid), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV–vis, PXRD and the single-crystal X-ray diffraction. Compounds 1 and 2 exhibit covalent 1-D chains constructed from M[P{sub 4}Mo{sub 6}]{sub 2} dimeric cluster and (M(H{sub 2}O){sub n}) (M=Cu, n=3 for 1 and M=Ni, n=1 for 2) linker. Compound 3 possesses an unusual POMMOF supramolecular layers based on [Ni(P{sub 4}Mo{sub 6})]{sub 2} dimeric units and 1-D metal–organic strings [Ni(H{sub 2}O){sub 5}Na(PCA)]{sub n}, in which an in situ ligand of PCA from 1,3-bis(4-pyridyl)propane (bpp) precursor was observed. Furthermore, the electrochemical behavior of 1–3-CPE and magnetic properties of 1–3 have been investigated in detail. - Graphical abstract: As new linking unit, Cu(H{sub 2}O){sub 3}, Ni(H{sub 2}O), and (Ni{sub 2}(H{sub 2}O){sub 10}Na(PCA){sub 2}) are introduced into (TM(P{sub 4}Mo{sub 6}){sub 2}) reaction systems to assemble three supramolecular materials under hydrothermal conditions via changing organic ligand and transition metal. - Highlights: • Tree new supramolecular hybrids based on (P{sub 4}Mo{sub 6}) cluster are reported. • Cu(H{sub 2}O){sub 3} and Ni(H{sub 2}O) as linker are introduced into the (TM(P{sub 4}Mo{sub 6}){sub 2}) systems. • 3 shows unusual layers based on

On the characterization of dynamic supramolecular systems: a general mathematical association model for linear supramolecular copolymers and application on a complex two-component hydrogen-bonding system.

Science.gov (United States)

Odille, Fabrice G J; Jónsson, Stefán; Stjernqvist, Susann; Rydén, Tobias; Wärnmark, Kenneth

2007-01-01

A general mathematical model for the characterization of the dynamic (kinetically labile) association of supramolecular assemblies in solution is presented. It is an extension of the equal K (EK) model by the stringent use of linear algebra to allow for the simultaneous presence of an unlimited number of different units in the resulting assemblies. It allows for the analysis of highly complex dynamic equilibrium systems in solution, including both supramolecular homo- and copolymers without the recourse to extensive approximations, in a field in which other analytical methods are difficult. The derived mathematical methodology makes it possible to analyze dynamic systems such as supramolecular copolymers regarding for instance the degree of polymerization, the distribution of a given monomer in different copolymers as well as its position in an aggregate. It is to date the only general means to characterize weak supramolecular systems. The model was fitted to NMR dilution titration data by using the program Matlab, and a detailed algorithm for the optimization of the different parameters has been developed. The methodology is applied to a case study, a hydrogen-bonded supramolecular system, salen 4+porphyrin 5. The system is formally a two-component system but in reality a three-component system. This results in a complex dynamic system in which all monomers are associated to each other by hydrogen bonding with different association constants, resulting in homo- and copolymers 4n5m as well as cyclic structures 6 and 7, in addition to free 4 and 5. The system was analyzed by extensive NMR dilution titrations at variable temperatures. All chemical shifts observed at different temperatures were used in the fitting to obtain the DeltaH degrees and DeltaS degrees values producing the best global fit. From the derived general mathematical expressions, system 4+5 could be characterized with respect to above-mentioned parameters.

Glucosamine-Based Supramolecular Nanotubes for Human Mesenchymal Cell Therapy.

Science.gov (United States)

Talloj, Satish Kumar; Cheng, Bill; Weng, Jen-Po; Lin, Hsin-Chieh

2018-04-23

Herein, we demonstrate an example of glucosamine-based supramolecular hydrogels that can be used for human mesenchymal cell therapy. We designed and synthesized a series of amino acid derivatives based on a strategy of capping d-glucosamine moiety at the C-terminus and fluorinated benzyl group at the N-terminus. From a systematic study on chemical structures, we discovered that the glucosamine-based supramolecular hydrogel [pentafluorobenzyl (PFB)-F-Glu] self-assembled with one-dimensional nanotubular structures at physiological pH. The self-assembly of a newly discovered PFB-F-Glu motif is attributed to the synergistic effect of π-π stacking and extensive intermolecular hydrogen bonding network in aqueous medium. Notably, PFB-F-Glu nanotubes are proven to be nontoxic to human mesenchymal stem cells (hMSCs) and have been shown to enhance hMSC proliferation while maintaining their pluripotency. Retaining of pluripotency capabilities provides potentially unlimited source of undifferentiated cells for the treatment of future cell therapies. Furthermore, hMSCs cultured on PFB-F-Glu are able to secrete paracrine factors that downregulate profibrotic gene expression in lipopolysaccharide-treated human skin fibroblasts, which demonstrates that PFB-F-Glu nanotubes have the potential to be used for wound healing applications. Overall, this article addresses the importance of chemical design to generate supramolecular biomaterials for stem cell therapy.

Supramolecular core-shell nanoparticles for photoconductive device applications

Science.gov (United States)

Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong

2016-08-01

We report a breakthrough discovery involving supramolecular-based strategies to construct novel core-shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices.

Luminescent lanthanide complexes with 4-acetamidobenzoate: Synthesis, supramolecular assembly via hydrogen bonds, crystal structures and photoluminescence

International Nuclear Information System (INIS)

Yin Xia; Fan Jun; Wang Zhihong; Zheng Shengrun; Tan Jingbo; Zhang Weiguang

2011-01-01

Four new luminescent complexes, namely, [Eu(aba) 2 (NO 3 )(C 2 H 5 OH) 2 ] (1), [Eu(aba) 3 (H 2 O) 2 ].0.5 (4, 4'-bpy).2H 2 O (2), [Eu 2 (aba) 4 (2, 2'-bpy) 2 (NO 3 ) 2 ].4H 2 O (3) and [Tb 2 (aba) 4 (phen) 2 (NO 3 ) 2 ].2C 2 H 5 OH (4) were obtained by treating Ln(NO 3 ) 3 .6H 2 O and 4-acetamidobenzoic acid (Haba) with different coligands (4, 4'-bpy=4, 4'-bipyridine, 2, 2'-bpy=2, 2'-bipyridine, and phen=1, 10-phenanthroline). They exhibit 1D chains (1-2) and dimeric structures (3-4), respectively. This structural variation is mainly attributed to the change of coligands and various coordination modes of aba molecules. Moreover, the coordination units are further connected via hydrogen bonds to form 2D even 3D supramolecular networks. These complexes show characteristic emissions in the visible region at room temperature. In addition, thermal behaviors of four complexes have been investigated under air atmosphere. The relationship between the structures and physical properties has been discussed. - Graphical abstract: Structure variation of four complexes is attributed to the change of coligands and various coordination modes of aba molecules. Moreover, they show characteristic emissions in the visible region. Highlights: → Auxiliary ligands have played the crucial roles on the structures of the resulting complexes. → Isolated structure units are further assembled via H-bonds to form supramolecular networks. → These solid-state complexes exhibit strong, characteristic emissions in the visible region.

CH3NH3PbI3 and CsPbI3 Supramolecular Clusters in 1D: Do They Evolve with the Same Principle of Cooperative Binding?

Science.gov (United States)

Varadwaj, Arpita; Varadwaj, Pradeep R.; Yamashita, Koichi

Development of novel semiconductor-based photo-catalytic and -voltaic systems is a major area of research in nanoscience and technologies, and engineering. The process can be either direct or indirect in converting the light energy into electricity. Some of the photovoltaics include the organic, dye-sensitized, and halide perovskite solar cells, among others. Methylammonium lead iodide (CH3NH3PbI3) inorganic-organic hybrid perovskite is one among the many highly valued semiconductors reported till date, comparable with the inorganic cesium lead iodide (CsPbI3) perovskite. These are competitive candidates in the solar energy race. Nevertheless, this study was concentrated on the fundamental understanding of the rational designs of the CH3NH3PbI3 and CsPbI3 supramolecular materials using first-principles calculations, emerged though the self-assembly of the respective building blocks. It therefore addresses the question whether the (CH3NH3PbI3)n and (CsPbI3)n (n =1-10) supramolecular clusters are the consequences of additivity, or non-additive cooperative binding? For addressing this question, the supramolecular properties such as the polarizability, the intermolecular charge transfer, and the binding energy, etc., all w.r.t the cluster size n, are exploited. CREST-JST, 7 Gobancho, Chiyoda-ku, Tokyo, Japan 102-0076.

Supramolecular interactions in the solid state

Directory of Open Access Journals (Sweden)

Giuseppe Resnati

2015-11-01

Full Text Available In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1 an overview and historical review of halogen bonding; (2 exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3 the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4 strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

Supramolecular gel electrophoresis of large DNA fragments.

Science.gov (United States)

Tazawa, Shohei; Kobayashi, Kazuhiro; Oyoshi, Takanori; Yamanaka, Masamichi

2017-10-01

Pulsed-field gel electrophoresis is a frequent technique used to separate exceptionally large DNA fragments. In a typical continuous field electrophoresis, it is challenging to separate DNA fragments larger than 20 kbp because they migrate at a comparable rate. To overcome this challenge, it is necessary to develop a novel matrix for the electrophoresis. Here, we describe the electrophoresis of large DNA fragments up to 166 kbp using a supramolecular gel matrix and a typical continuous field electrophoresis system. C 3 -symmetric tris-urea self-assembled into a supramolecular hydrogel in tris-boric acid-EDTA buffer, a typical buffer for DNA electrophoresis, and the supramolecular hydrogel was used as a matrix for electrophoresis to separate large DNA fragments. Three types of DNA marker, the λ-Hind III digest (2 to 23 kbp), Lambda DNA-Mono Cut Mix (10 to 49 kbp), and Marker 7 GT (10 to 165 kbp), were analyzed in this study. Large DNA fragments of greater than 100 kbp showed distinct mobility using a typical continuous field electrophoresis system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prion-like nanofibrils of small molecules (PriSM): A new frontier at the intersection of supramolecular chemistry and cell biology.

Science.gov (United States)

Zhou, Jie; Du, Xuewen; Xu, Bing

2015-01-01

Formed by non-covalent interactions and not defined at genetic level, the assemblies of small molecules in biology are complicated and less explored. A common morphology of the supramolecular assemblies of small molecules is nanofibrils, which coincidentally resembles the nanofibrils formed by proteins such as prions. So these supramolecular assemblies are termed as prion-like nanofibrils of small molecules (PriSM). Emerging evidence from several unrelated fields over the past decade implies the significance of PriSM in biology and medicine. This perspective aims to highlight some recent advances of the research on PriSM. This paper starts with description of the intriguing similarities between PriSM and prions, discusses the paradoxical features of PriSM, introduces the methods for elucidating the biological functions of PriSM, illustrates several examples of beneficial aspects of PriSM, and finishes with the promises and current challenges in the research of PriSM. We anticipate that the research of PriSM will contribute to the fundamental understanding at the intersection of supramolecular chemistry and cell biology and ultimately lead to a new paradigm of molecular (or supramolecular) therapeutics for biomedicine.

Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

Science.gov (United States)

Lehn, Jean-Marie

2012-01-01

Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

Insight into the chiral induction in supramolecular stacks through preferential chiral salvation

NARCIS (Netherlands)

George, S.J.; Tomovic, Z.; Schenning, A.P.H.J.; Meijer, E.W.

2011-01-01

Preferred handedness in the supramolecular chirality of self-assembled achiral oligo(p-phenylenevinylene) (OPV) derivatives is induced by chiral solvents and spectroscopic probing provides insight into the mechanistic aspects of this chiral induction through chiral solvation

Molecular self-assembly advances and applications

CERN Document Server

Dequan, Alex Li

2012-01-01

In the past several decades, molecular self-assembly has emerged as one of the main themes in chemistry, biology, and materials science. This book compiles and details cutting-edge research in molecular assemblies ranging from self-organized peptide nanostructures and DNA-chromophore foldamers to supramolecular systems and metal-directed assemblies, even to nanocrystal superparticles and self-assembled microdevices

Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

Science.gov (United States)

Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

2016-05-01

Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

Biomedical Applications of Self-Assembling Peptides

NARCIS (Netherlands)

Radmalekshahi, Mazda; Lempsink, Ludwijn; Amidi, Maryam; Hennink, Wim E.; Mastrobattista, Enrico

2016-01-01

Self-assembling peptides have gained increasing attention as versatile molecules to generate diverse supramolecular structures with tunable functionality. Because of the possibility to integrate a wide range of functional domains into self-assembling peptides including cell attachment sequences,

Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms.

Science.gov (United States)

Ohmann, Robin; Meyer, Jörg; Nickel, Anja; Echeverria, Jorge; Grisolia, Maricarmen; Joachim, Christian; Moresco, Francesca; Cuniberti, Gianaurelio

2015-08-25

A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W.

Chiral Induction and amplification in supramolecular systems at the liquid-solid interface

NARCIS (Netherlands)

Xu, Hong; Ghijsens, E.; George, S.J.; Wolffs, M.; Tomovic, Z.; Schenning, A.P.H.J.; Feyter, de S.

2013-01-01

Chiral induction and amplification in surface-confined supramolecular monolayers are investigated at the liquid–solid interface. Scanning tunneling microscopy (STM) proves that achiral molecules can self-assemble into globally chiral patterns through a variety of approaches, including induction by

Dynamic peptide libraries for the discovery of supramolecular nanomaterials

Science.gov (United States)

Pappas, Charalampos G.; Shafi, Ramim; Sasselli, Ivan R.; Siccardi, Henry; Wang, Tong; Narang, Vishal; Abzalimov, Rinat; Wijerathne, Nadeesha; Ulijn, Rein V.

2016-11-01

Sequence-specific polymers, such as oligonucleotides and peptides, can be used as building blocks for functional supramolecular nanomaterials. The design and selection of suitable self-assembling sequences is, however, challenging because of the vast combinatorial space available. Here we report a methodology that allows the peptide sequence space to be searched for self-assembling structures. In this approach, unprotected homo- and heterodipeptides (including aromatic, aliphatic, polar and charged amino acids) are subjected to continuous enzymatic condensation, hydrolysis and sequence exchange to create a dynamic combinatorial peptide library. The free-energy change associated with the assembly process itself gives rise to selective amplification of self-assembling candidates. By changing the environmental conditions during the selection process, different sequences and consequent nanoscale morphologies are selected.

Epoxy resin-inspired reconfigurable supramolecular networks

OpenAIRE

Balkenende Diederik; Olson Rebecca; Balog Sandor; Weder Christoph; Montero de Espinosa Lucas

2016-01-01

With the goal to push the mechanical properties of reconfigurable supramolecular polymers toward those of thermoset resins we prepared and investigated a new family of hydrogen bonded polymer networks that are assembled from isophthalic acid terminated oligo(bisphenol A co epichlorohydrin) and different bipyridines. These materials display high storage moduli of up to 3.9 GPa can be disassembled upon heating to form melts with a viscosity of as low as 2.1 Pa·s and fully reassemble upon coolin...

Octanol-assisted liposome assembly on chip

NARCIS (Netherlands)

Deshpande, S.R.; Caspi, Y.; Meijering, A.E.C.; Dekker, C.

2016-01-01

Liposomes are versatile supramolecular assemblies widely used in basic and applied sciences. Here we present a novel microfluidics-based method, octanol-assisted liposome assembly (OLA), to form monodisperse, cell-sized (5–20 μm), unilamellar liposomes with excellent encapsulation efficiency. Akin

Noncovalent assembly. A rational strategy for the realization of chain-growth supramolecular polymerization.

Science.gov (United States)

Kang, Jiheong; Miyajima, Daigo; Mori, Tadashi; Inoue, Yoshihisa; Itoh, Yoshimitsu; Aida, Takuzo

2015-02-06

Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer. Copyright © 2015, American Association for the Advancement of Science.

The Supramolecular Organization of a Peptide-Based Nanocarrier at High Molecular Detail

NARCIS (Netherlands)

Rad-Malekshahi, Mazda; Visscher, Koen M.; Rodrigues, João P.G.L.M.; De Vries, Renko; Hennink, Wim E.; Baldus, Marc; Bonvin, Alexandre M.J.J.; Mastrobattista, Enrico; Weingarth, Markus

2015-01-01

Nanovesicles self-assembled from amphiphilic peptides are promising candidates for applications in drug delivery. However, complete high-resolution data on the local and supramolecular organization of such materials has been elusive thus far, which is a substantial obstacle to their rational design.

Encapsulation of Protonated Diamines in a Water-Soluble Chiral, Supramolecular Assembly Allows for Measurement of Hydrogen-Bond Breaking Followed by Nitrogen Inversion/Rotation (NIR)

Energy Technology Data Exchange (ETDEWEB)

Meux, Susan C.; Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

2007-09-19

Amine nitrogen inversion, difficult to observe in aqueous solution, is followed in a chiral, supramolecular host molecule with purely-rotational T-symmetry that reduces the local symmetry of encapsulated monoprotonated diamines and enables the observation and quantification of {Delta}G{double_dagger} for the combined hydrogen-bond breaking and nitrogen inversion rotation (NIR) process. Free energies of activation for the combined hydrogen-bond breaking and NIR process inside of the chiral assembly were determined by the NMR coalescence method. Activation parameters for ejection of the protonated amines from the assembly confirm that the NIR process responsible for the coalescence behavior occurs inside of the assembly rather than by a guest ejection/NIR/re-encapsulation mechanism. For one of the diamines, N,N,N{prime},N{prime}-tetramethylethylenediamine (TMEDA), the relative energy barriers for the hydrogen-bond breaking and NIR process were calculated at the G3(MP2)//B3LYP/6-31++G(d,p) level of theory, and these agreed well with the experimental data.

Rapid fabrication of hierarchically structured supramolecular nanocomposite thin films in one minute

Energy Technology Data Exchange (ETDEWEB)

Xu, Ting; Kao, Joseph

2016-11-08

Functional nanocomposites containing nanoparticles of different chemical compositions may exhibit new properties to meet demands for advanced technology. It is imperative to simultaneously achieve hierarchical structural control and to develop rapid, scalable fabrication to minimize degradation of nanoparticle properties and for compatibility with nanomanufacturing. The assembly kinetics of supramolecular nanocomposite in thin films is governed by the energetic cost arising from defects, the chain mobility, and the activation energy for inter-domain diffusion. By optimizing only one parameter, the solvent fraction in the film, the assembly kinetics can be precisely tailored to produce hierarchically structured thin films of supramolecular nanocomposites in approximately one minute. Moreover, the strong wavelength dependent optical anisotropy in the nanocomposite highlights their potential applications for light manipulation and information transmission. The present invention opens a new avenue in designing manufacture-friendly continuous processing for the fabrication of functional nanocomposite thin films.

TOPICAL REVIEW: Metallo-supramolecular modules as a paradigm for materials science

Directory of Open Access Journals (Sweden)

Dirk G Kurth

2008-01-01

Full Text Available Metal ion coordination in discrete or extended metallo-supramolecular assemblies offers ample opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. A key challenge is to improve and develop methodologies for placing these active modules in suitable device architectures, such as thin films or mesophases. This review highlights recent developments in extended, polymeric metallo-supramolecular systems and discrete polyoxometalates with an emphasis on materials science.

Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

Science.gov (United States)

Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

2018-03-15

Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug

Triblock-Terpolymer-Directed Self-Assembly of Mesoporous TiO2: High-Performance Photoanodes for Solid-State Dye-Sensitized Solar Cells

KAUST Repository

Docampo, Pablo

2012-04-30

A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO 2 films is presented, based on the triblock terpolymer poly(isoprene - b - styrene - b - ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solidstate dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triblock-Terpolymer-Directed Self-Assembly of Mesoporous TiO2: High-Performance Photoanodes for Solid-State Dye-Sensitized Solar Cells

KAUST Repository

Docampo, Pablo; Stefik, Morgan; Guldin, Stefan; Gunning, Robert; Yufa, Nataliya A.; Cai, Ning; Wang, Peng; Steiner, Ullrich; Wiesner, Ulrich; Snaith, Henry J.

2012-01-01

A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO 2 films is presented, based on the triblock terpolymer poly(isoprene - b - styrene - b - ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solidstate dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

International Nuclear Information System (INIS)

Kim, Taehyung; Kim, Ju Chang; Lough, Alan J.

2013-01-01

Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions

Chlorophyll J-aggregates: from bioinspired dye stacks to nanotubes, liquid crystals, and biosupramolecular electronics.

Science.gov (United States)

Sengupta, Sanchita; Würthner, Frank

2013-11-19

Among the natural light-harvesting (LH) systems, those of green sulfur and nonsulfur photosynthetic bacteria are exceptional because they lack the support of a protein matrix. Instead, these so-called chlorosomes are based solely on "pigments". These are self-assembled bacteriochlorophyll c, d, and e derivatives, which consist of a chlorophyll skeleton bearing a 3(1)-hydroxy functional group. Chemists consider the latter as an essential structural unit to direct the formation of light-harvesting self-assembled dye aggregates with J-type excitonic coupling. The intriguing properties of chlorosomal J-type aggregates, particularly narrow red-shifted absorption bands, compared with monomers and their ability to delocalize and migrate excitons, have inspired intense research activities toward synthetic analogues in this field. The ultimate goal of this research field is the development of (opto-)electronic devices based on the architectural principle of chlorosomal LH systems. In this regard, the challenge is to develop small, functional building blocks with appropriate substituents that are preprogrammed to self-assemble across different length scales and to emulate functions of natural LH systems or to realize entirely new functions beyond those found in nature. In this Account, we highlight our achievements in the past decade with semisynthetic zinc chlorins (ZnChls) as model compounds of bacteriochlorophylls obtained from the naturally most abundant chlorin precursor: chlorophyll a. To begin, we explore how supramolecular strategies involving π-stacking, hydrogen bonding, and metal-oxygen coordination can be used to design ZnChl-based molecular stack, tube, and liquid crystalline assemblies conducive to charge and energy transport. Our design principle is based on the bioinspired functionalization of the 3(1)-position of ZnChl with a hydroxy or methoxy group; the former gives rise to tubular assemblies, whereas the latter induces stack assemblies. Functionalization

Biomimetic growth of gallic acid–ZnO hybrid assemblies and their applications

International Nuclear Information System (INIS)

Sarker, Nazmul H.; Barnaby, Stacey N.; Fath, Karl R.; Frayne, Stephen H.; Nakatsuka, Nako; Banerjee, Ipsita A.

2012-01-01

In this study, we probed the biomimetic formation of gallic acid (GA)–ZnO nanoparticle hybrids. It was found that the morphologies formed were dependent upon pH values, resulting in GA–ZnO hybrids of varying shapes such as micro or nanoplates or fibers. The formed supramolecular GA–ZnO hybrids were found to be luminescent as indicated by confocal microscopy and were utilized for the photocatalytic degradation of the organic dye methylene blue. We also explored the bactericidal effects of the hybrids on Staphylococcus aureus (S. aureus) as well as Escherichia Coli (E. Coli). Thus, we have developed a new class of shape-controlled nanohybrid assemblies via mild, green synthetic methods that may be utilized for photocatalytic degradation for environmental remediation as well as for antibacterial applications.

Biomimetic growth of gallic acid-ZnO hybrid assemblies and their applications

Energy Technology Data Exchange (ETDEWEB)

Sarker, Nazmul H.; Barnaby, Stacey N. [Fordham University, Department of Chemistry (United States); Fath, Karl R. [City University of New York and Graduate Center, Department of Biology, Queens College (United States); Frayne, Stephen H.; Nakatsuka, Nako; Banerjee, Ipsita A., E-mail: banerjee@fordham.edu [Fordham University, Department of Chemistry (United States)

2012-03-15

In this study, we probed the biomimetic formation of gallic acid (GA)-ZnO nanoparticle hybrids. It was found that the morphologies formed were dependent upon pH values, resulting in GA-ZnO hybrids of varying shapes such as micro or nanoplates or fibers. The formed supramolecular GA-ZnO hybrids were found to be luminescent as indicated by confocal microscopy and were utilized for the photocatalytic degradation of the organic dye methylene blue. We also explored the bactericidal effects of the hybrids on Staphylococcus aureus (S. aureus) as well as Escherichia Coli (E. Coli). Thus, we have developed a new class of shape-controlled nanohybrid assemblies via mild, green synthetic methods that may be utilized for photocatalytic degradation for environmental remediation as well as for antibacterial applications.

Biomimetic growth of gallic acid-ZnO hybrid assemblies and their applications

Science.gov (United States)

Sarker, Nazmul H.; Barnaby, Stacey N.; Fath, Karl R.; Frayne, Stephen H.; Nakatsuka, Nako; Banerjee, Ipsita A.

2012-03-01

In this study, we probed the biomimetic formation of gallic acid (GA)-ZnO nanoparticle hybrids. It was found that the morphologies formed were dependent upon pH values, resulting in GA-ZnO hybrids of varying shapes such as micro or nanoplates or fibers. The formed supramolecular GA-ZnO hybrids were found to be luminescent as indicated by confocal microscopy and were utilized for the photocatalytic degradation of the organic dye methylene blue. We also explored the bactericidal effects of the hybrids on Staphylococcus aureus ( S. aureus) as well as Escherichia Coli ( E. Coli). Thus, we have developed a new class of shape-controlled nanohybrid assemblies via mild, green synthetic methods that may be utilized for photocatalytic degradation for environmental remediation as well as for antibacterial applications.

Selective Organic and Organometallic Reactions in Water-Soluble Host-Guest Supramolecular Systems

Energy Technology Data Exchange (ETDEWEB)

Pluth, Michael D.; Raymond, Kenneth N.; Bergman, Robert G.

2008-02-16

Inspired by the efficiency and selectivity of enzymes, synthetic chemists have designed and prepared a wide range of host molecules that can bind smaller molecules with their cavities; this area has become known as 'supramolecular' or 'host-guest' chemistry. Pioneered by Lehn, Cram, Pedersen, and Breslow, and followed up by a large number of more recent investigators, it has been found that the chemical environment in each assembly - defined by the size, shape, charge, and functional group availability - greatly influences the guest-binding characteristics of these compounds. In contrast to the large number of binding studies that have been carried out in this area, the exploration of chemistry - especially catalytic chemistry - that can take place inside supramolecular host cavities is still in its infancy. For example, until the work described here was carried out, very few examples of organometallic reactivity inside supramolecular hosts were known, especially in water solution. For that reason, our group and the group directed by Kenneth Raymond decided to take advantage of our complementary expertise and attempt to carry out metal-mediated C-H bond activation reactions in water-soluble supramolecular systems. This article begins by providing background from the Raymond group in supramolecular coordination chemistry and the Bergman group in C-H bond activation. It goes on to report the results of our combined efforts in supramolecular C-H activation reactions, followed by extensions of this work into a wider range of intracavity transformations.

Photoactive assemblies of organic compounds and biomolecules: drug-protein supramolecular systems

OpenAIRE

Vayá Pérez, Ignacio; Lhiaubet-Vallet, Virginie Lyria; Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

2014-01-01

[EN] The properties of singlet and triplet excited states are strongly medium-dependent. Hence, these species constitute valuable tools as reporters to probe compartmentalised microenvironments, including drug@protein supramolecular systems. In the present review, the attention is focused on the photophysical properties of the probe drugs (rather than those of the protein chromophores) using transport proteins (serum albumins and 1-acid glycoproteins) as hosts. Specifically, f...

Supracolloidal Architectures Self-Assembled in Microdroplets.

Science.gov (United States)

Xu, Xuejiao; Tian, Feng; Liu, Xin; Parker, Richard M; Lan, Yang; Wu, Yuchao; Yu, Ziyi; Scherman, Oren A; Abell, Chris

2015-10-26

We demonstrate a novel method for the formation of a library of structured colloidal assemblies by exploiting the supramolecular heteroternary host-guest interaction between cucurbit[8]uril (CB[8]) and methyl viologen- and naphthalene-functionalised particles. The approach is dependent upon compartmentalisation in microdroplets generated by a microfluidic platform. Though the distribution of colloidal particles encapsulated within each microdroplet followed a Poisson distribution, tuning the concentration of the initial colloidal particle suspensions provided some level of control over the structure of the formed colloidal assemblies. This ability to direct the assembly of complementarily-functionalised colloids through a supramolecular interaction, without the need for complex modification of the colloidal surface or external stimuli, presents an exciting new approach towards the design of structured colloidal materials with the potential to produce many challenging structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

Directory of Open Access Journals (Sweden)

GAO Shan

2017-12-01

Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

Functional organic materials based on polymerized liquid-crystal monomers: supramolecular hydrogen-bonded systems

NARCIS (Netherlands)

Broer, D.J.; Bastiaansen, C.W.M.; Debije, M.G.; Schenning, A.P.H.J.

2012-01-01

Functional organic materials are of great interest for a variety of applications. To obtain precise functional properties, well-defined hierarchically ordered supramolecular materials are crucial. The self-assembly of liquid crystals has proven to be an extremely useful tool in the development of

Supramolecular Control of Oligothienylenevinylene-Fullerene Interactions: Evidence for a Ground-State EDA Complex

NARCIS (Netherlands)

McClenaghan, N.D.; Grote, Z.; Darriet, K.; Zimine, M.Y.; Williams, R.M.; De Cola, L.; Bassani, D.M.

2005-01-01

Complementary hydrogen-bonding interactions between a barbituric acid-substituted fullerene derivative (1) and corresponding receptor (2) bearing thienylenevinylene units are used to assemble a 1:1 supramolecular complex ( K ) 5500 M-1). Due to the close proximity of the redox-active moieties within

Thermoresponsive Interplay of Water Insoluble Poly(2-alkyl-2-oxazolines Composition and Supramolecular Host–Guest Interactions

Directory of Open Access Journals (Sweden)

Victor R. de la Rosa

2015-04-01

Full Text Available A series of water insoluble poly[(2-ethyl-2-oxazoline-ran-(2-nonyl-2-oxazoline] amphiphilic copolymers was synthesized and their solubility properties in the presence of different supramolecular host molecules were investigated. The resulting polymer-cavitand assemblies exhibited a thermoresponsive behavior that could be modulated by variation of the copolymer composition and length. Interestingly, the large number of hydrophobic nonyl units across the polymer chain induced the formation of kinetically-trapped nanoparticles in solution. These nanoparticles further agglomerate into larger aggregates at a temperature that is dependent on the polymer composition and the cavitand type and concentration. The present research expands the understanding on the supramolecular interactions between water insoluble copolymers and supramolecular host molecules.

Fluorescent supramolecular micelles for imaging-guided cancer therapy

Science.gov (United States)

Sun, Mengmeng; Yin, Wenyan; Dong, Xinghua; Yang, Wantai; Zhao, Yuliang; Yin, Meizhen

2016-02-01

A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth-inhibitory studies reveal a better therapeutic effect of FSMs after CPT encapsulation when compared with the free CPT drug. The multifunctional FSM nanomedicine platform as a nanovehicle has great potential for fluorescence imaging-guided cancer therapy.A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth

PEG-bis phosphonic acid based ionic supramolecular structures

DEFF Research Database (Denmark)

Gonzalez, Lidia; Skov, Anne Ladegaard; Hvilsted, Søren

2014-01-01

. The resulting ionic assemblies are very comprehensively characterized by ATR-FTIR, proton, and carbon-13 NMR spectroscopy that unequivocally demonstrate the ionic network formation through ammonium phophonates. The resulting salt and ionic networks are additionally analyzed by differential scanning calorimetry...... and thermogravimetric analysis. The conclusion is that mixing the virgin components at room temperature spontaneously form either a salt or ionic supramolecular networks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

Triblock-terpolymer-directed self-assembly of mesoporous TiO{sub 2}: High-performance photoanodes for solid-state dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Docampo, Pablo; Gunning, Robert; Snaith, Henry J. [Clarendon Laboratory, Department of Physics, University of Oxford, Parks Road, Oxford OX1 3PU (United Kingdom); Stefik, Morgan; Wiesner, Ulrich [Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853 (United States); Guldin, Stefan; Yufa, Nataliya A.; Steiner, Ullrich [Department of Physics, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Cai, Ning; Wang, Peng [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

2012-06-15

A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO{sub 2} films is presented, based on the triblock terpolymer poly(isoprene-b-styrene-b-ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solid-state dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Supramolecular chemistry: from molecular information towards self-organization and complex matter

International Nuclear Information System (INIS)

Lehn, Jean-Marie

2004-01-01

Molecular chemistry has developed a wide range of very powerful procedures for constructing ever more sophisticated molecules from atoms linked by covalent bonds. Beyond molecular chemistry lies supramolecular chemistry, which aims at developing highly complex chemical systems from components interacting via non-covalent intermolecular forces. By the appropriate manipulation of these interactions, supramolecular chemistry became progressively the chemistry of molecular information, involving the storage of information at the molecular level, in the structural features, and its retrieval, transfer, and processing at the supramolecular level, through molecular recognition processes operating via specific interactional algorithms. This has paved the way towards apprehending chemistry also as an information science. Numerous receptors capable of recognizing, i.e. selectively binding, specific substrates have been developed, based on the molecular information stored in the interacting species. Suitably functionalized receptors may perform supramolecular catalysis and selective transport processes. In combination with polymolecular organization, recognition opens ways towards the design of molecular and supramolecular devices based on functional (photoactive, electroactive, ionoactive, etc) components. A step beyond preorganization consists in the design of systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined supramolecular architectures by self-assembly from their components. Self-organization processes, directed by the molecular information stored in the components and read out at the supramolecular level through specific interactions, represent the operation of programmed chemical systems. They have been implemented for the generation of a variety of discrete functional architectures of either organic or inorganic nature. Self-organization processes also give access to advanced supramolecular materials, such as

Two new hydrogen bond-supported supramolecular compounds assembly from polyoxovanadate and organoamines

International Nuclear Information System (INIS)

Duan Weijie; Cui Xiaobing; Xu Yan; Xu Jiqing; Yu Haihui; Yi Zhihui; Cui Jiwen; Wang Tiegang

2007-01-01

Two novel organic-inorganic hybrid compounds based on organoamines and polyoxovanadates formulated as (H 2 dien) 4 [H 10 V 18 O 42 (PO 4 )](PO 4 ).2H 2 O (1) (dien=diethylenetriamine) and (Him) 8 [HV 18 O 42 (PO 4 )] (2) (im=imidazole) have been prepared under hydrothermal conditions by using different starting materials, and characterized by elemental analyses, IR, ESR, XPS, TGA and single-crystal X-ray diffraction analyses. Crystal data for compound 1: C 16 H 74 N 12 O 52 V 18 P 2 , Monoclinic, space group C2/c, a=23.9593(4) A, b=13.0098(2) A, c=20.1703(4) A, β=105.566(3) o , V=6056.6(19) A 3 , Z=4; for compound 2, C 24 H 41 N 16 O 46 V 18 P, Tetragonal, space group I4/mmm, a=13.5154(8) A, b=13.5154(8) A, c=19.1136 A, β=90 o , V=3491.4(3) A 3 , Z=2. Compound 1 consists of protonated diens together with polyoxovanadates [H 10 V 18 O 42 (PO 4 )] 5- . Compound 2 is composed of protonated ims and polyoxovanadates [HV 18 O 42 (PO 4 )] 8- . There are hydrogen-bonding interactions between polyoxovanadates and different organoamines in 1 and 2. Polyoxovanadates are linked through H 2 dien into a three-dimensional network via hydrogen bonds in 1, while polyoxovanadates are linked by Him into a two-dimensional layer network via hydrogen bonds in 2. The crystal packing patterns of the two compounds reveal various supramolecular frameworks. - Graphical abstract: Two new organic-inorganic hybrid compounds based on [V 18 O 42 (PO 4 )] building blocks have been hydrothermally synthesized. 1 is the first 3-D supramolecular network structure consisting of [V 18 O 42 (PO 4 )] unit, while 2 possesses 2-D layered supramolecular structure

Analysis of supramolecular surface nanostructures using secondary ion mass spectrometry (poster)

International Nuclear Information System (INIS)

Halaszova, S.; Velic, D.

2013-01-01

Our system consists of host molecules β-cyclodextrin (C 42 H 70 O 35 ), of implemented Iron nanoparticles (guest). Whole supramolecular complex is placed on a gold substrate. In our project we work with monotiolated β-cyclodextrin (C 42 H 70 O 34 S), consisting of seven α-D-1-4 glucopyranose units. Cyclodextrins have been selected deliberately because of their ability to form inclusion complexes .They are also capable of forming structures similar to self-assembly monolayers. To study the formation of these supramolecular surface nanostructures mass secondary ion spectrometry is used. With this technique fragmentation of monotiolated β-cyclodextrin and the presence of the supramolecular complex on a gold surface can be examined. The observed fragments of monotiolated cyclodextrines films can be divided into three groups: Au X H Y S Z , fragments originating from cyclodextrin molecules associated with Au. Fragments as (C 42 H 70 O 34 S)Na + , (C 42 H 70 O 35 )Na + and (AuC 42 H 69 O 34 S)Na + were identified as well as fragments thereof in cationized form with K + . The main objective of the project is a detailed study and preparation of supramolecular nanostructures consisting of complex guest-host monotiolated β-cyclodextrin host-iron), and a gold substrate. (Authors)

Precise Steric Control over 2D versus 3D Self-Assembly of Antimony(III) Alkoxide Cages through Strong Secondary Bonding Interactions.

Science.gov (United States)

Moaven, Shiva; Yu, Jingze; Yasin, Jason; Unruh, Daniel K; Cozzolino, Anthony F

2017-07-17

Antimony(III) alkoxide cages were designed as building blocks for predictable supramolecular self-assembly. Supramolecular synthons featuring two Sb···O secondary bonding interactions (SBIs), each SBI stronger than 30 kJ/mol, were used to drive the formation of the supramolecular architectures. Judicious choice of pendant groups provided predictable control over the formation of self-assembled 3D columnar helices, which crystallized with hollow morphologies, or a self-assembled 2D bilayer. The Sb-O stretching frequency provides a spectroscopic signature of Sb···O SBI formation.

Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

Science.gov (United States)

Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

2018-04-01

We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

Conjugated material self-assembly : towards supramolecular electronics

NARCIS (Netherlands)

Leclère, P.E.L.G.; Surin, M.; Cavallini, M.; Jonkheijm, P.; Henze, O.; Schenning, A.P.H.J.; Biscarini, F.; Grimsdale, A.C.; Feast, W.J.; Meijer, E.W.; Müllen, K.; Brédas, J.L.; Lazzaroni, R.

2004-01-01

Properties of organic electronic materials in solid-state are determined as individual molecules and molecular assembly. It is essential to optimize conjugated materials to control performance of molecular assembly that constitute electronic devices such as light-emitting diodes and solar cells, and

3D Printing of Biocompatible Supramolecular Polymers and their Composites.

Science.gov (United States)

Hart, Lewis R; Li, Siwei; Sturgess, Craig; Wildman, Ricky; Jones, Julian R; Hayes, Wayne

2016-02-10

A series of polymers capable of self-assembling into infinite networks via supramolecular interactions have been designed, synthesized, and characterized for use in 3D printing applications. The biocompatible polymers and their composites with silica nanoparticles were successfully utilized to deposit both simple cubic structures, as well as a more complex twisted pyramidal feature. The polymers were found to be not toxic to a chondrogenic cell line, according to ISO 10993-5 and 10993-12 standard tests and the cells attached to the supramolecular polymers as demonstrated by confocal microscopy. Silica nanoparticles were then dispersed within the polymer matrix, yielding a composite material which was optimized for inkjet printing. The hybrid material showed promise in preliminary tests to facilitate the 3D deposition of a more complex structure.

Cd (II) and holodirected lead (II) 3D-supramolecular coordination polymers based on nicotinic acid: Structure, fluorescence property and photocatalytic activity

Science.gov (United States)

Etaiw, Safaa El-din H.; Abd El-Aziz, Dina M.; Marie, Hassan; Ali, Elham

2018-05-01

Two new supramolecular coordination polymers namely {[Cd(NA)2(H2O)]}, SCP 1 and {[Pb(NA)2]}, SCP 2, (NA = nicotinate ligand) were synthesized by self-assembly method and structurally characterized by different analytical and spectroscopic methods. Single-crystal X-ray diffraction showed that SCP 1 extend in three dimensions containing bore structure where the 3D- network is constructed via interweaving zigzag chains. The Cd atom coordinates to (O4N2) atoms forming distorted-octahedral configuration. The structure of SCP 2 extend down the projection of the b-axis creating parallel zigzag 1D-chains connected by μ2-O2 atoms and H-bonds forming a holodirected lead (II) hexagonal bi-pyramid configuration. SCP 2 extend to 3D-network via coordinate and hydrogen bonds. The thermal stability, photoluminescence properties, photocatalytic activity for the degradation of methylene blue dye (MB) under UV-irradiation and sunlight irradiation were also studied.

Supramolecular chemistry at interfaces: host-guest interactions for fabricating multifunctional biointerfaces.

Science.gov (United States)

Yang, Hui; Yuan, Bin; Zhang, Xi; Scherman, Oren A

2014-07-15

CONSPECTUS: Host-guest chemistry can greatly improve the selectivity of biomolecule-ligand binding on account of recognition-directed interactions. In addition, functional structures and the actuation of supramolecular assemblies in molecular systems can be controlled efficiently through various host-guest chemistry. Together, these highly selective, strong yet dynamic interactions can be exploited as an alternative methodology for applications in the field of programmable and controllable engineering of supramolecular soft materials through the reversible binding between complementary components. Many processes in living systems such as biotransformation, transportation of matter, and energy transduction begin with interfacial molecular recognition, which is greatly influenced by various external stimuli at biointerfaces. Detailed investigations about the molecular recognition at interfaces can result in a better understanding of life science, and further guide us in developing new biomaterials and medicines. In order to mimic complicated molecular-recognition systems observed in nature that adapt to changes in their environment, combining host-guest chemistry and surface science is critical for fabricating the next generation of multifunctional biointerfaces with efficient stimuli-responsiveness and good biocompatibility. In this Account, we will summarize some recent progress on multifunctional stimuli-responsive biointerfaces and biosurfaces fabricated by cyclodextrin- or cucurbituril-based host-guest chemistry and highlight their potential applications including drug delivery, bioelectrocatalysis, and reversible adsorption and resistance of peptides, proteins, and cells. In addition, these biointerfaces and biosurfaces demonstrate efficient response toward various external stimuli, such as UV light, pH, redox chemistry, and competitive guests. All of these external stimuli can aid in mimicking the biological stimuli evident in complex biological environments

Preparation of supramolecular hydrogel-enzyme hybrids exhibiting biomolecule-responsive gel degradation.

Science.gov (United States)

Shigemitsu, Hajime; Fujisaku, Takahiro; Onogi, Shoji; Yoshii, Tatsuyuki; Ikeda, Masato; Hamachi, Itaru

2016-09-01

Hydrogelators are small, self-assembling molecules that form supramolecular nanofiber networks that exhibit unique dynamic properties. Development of supramolecular hydrogels that degrade in response to various biomolecules could potentially be used for applications in areas such as drug delivery and diagnostics. Here we provide a synthetic procedure for preparing redox-responsive supramolecular hydrogelators that are used to create hydrogels that degrade in response to oxidizing or reducing conditions. The synthesis takes ∼2-4 d, and it can potentially be carried out in parallel to prepare multiple hydrogelator candidates. This described solid-phase peptide synthesis protocol can be used to produce previously described hydrogelators or to construct a focused molecular library to efficiently discover and optimize new hydrogelators. In addition, we describe the preparation of redox-responsive supramolecular hydrogel-enzyme hybrids that are created by mixing aqueous solutions of hydrogelators and enzymes, which requires 2 h for completion. The resultant supramolecular hydrogel-enzyme hybrids exhibit gel degradation in response to various biomolecules, and can be rationally designed by connecting the chemical reactions of the hydrogelators with enzymatic reactions. Gel degradation in response to biomolecules as triggers occurs within a few hours. We also describe the preparation of hydrogel-enzyme hybrids arrayed on flat glass slides, enabling high-throughput analysis of biomolecules such as glucose, uric acid, lactate and so on by gel degradation, which is detectable by the naked eye. The protocol requires ∼6 h to prepare the hydrogel-enzyme hybrid array and to complete the biomolecule assay.

Research in the Laboratory of Supramolecular Chemistry: functional nanostructures, sensors, and catalysts.

Science.gov (United States)

Severin, Kay

2011-01-01

This article summarizes research activities in the Laboratory of Supramolecular Chemistry (LCS) at the EPFL. Three topics will be discussed: a) the construction of functional nanostructures by multicomponent self-assembly processes, b) the development of chemosensors using specific receptors or ensembles of crossreactive sensors, and c) the investigation of novel synthetic procedures with organometallic catalysts.

Supramolecular assembly of biological molecules purified from bovine nerve cells: from microtubule bundles and necklaces to neurofilament networks

International Nuclear Information System (INIS)

Needleman, Daniel J; Jones, Jayna B; Raviv, Uri; Ojeda-Lopez, Miguel A; Miller, H P; Li, Y; Wilson, L; Safinya, C R

2005-01-01

With the completion of the human genome project, the biosciences community is beginning the daunting task of understanding the structures and functions of a large number of interacting biological macromolecules. Examples include the interacting molecules involved in the process of DNA condensation during the cell cycle, and in the formation of bundles and networks of filamentous actin proteins in cell attachment, motility and cytokinesis. In this proceedings paper we present examples of supramolecular assembly based on proteins derived from the vertebrate nerve cell cytoskeleton. The axonal cytoskeleton in vertebrate neurons provides a rich example of bundles and networks of neurofilaments, microtubules (MTs) and filamentous actin, where the nature of the interactions, structures, and structure-function correlations remains poorly understood. We describe synchrotron x-ray diffraction, electron microscopy, and optical imaging data, in reconstituted protein systems purified from bovine central nervous system, which reveal unexpected structures not predicted by current electrostatic theories of polyelectrolyte bundling, including three-dimensional MT bundles and two-dimensional MT necklaces

Selective hydrolysis of phosphate monoester by a supramolecular phosphatase formed by the self-assembly of a bis(Zn(2+)-cyclen) complex, cyanuric acid, and copper in an aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane).

Science.gov (United States)

Zulkefeli, Mohd; Suzuki, Asami; Shiro, Motoo; Hisamatsu, Yosuke; Kimura, Eiichi; Aoki, Shin

2011-10-17

In Nature, organized nanoscale structures such as proteins and enzymes are formed in aqueous media via intermolecular interactions between multicomponents. Supramolecular and self-assembling strategies provide versatile methods for the construction of artificial chemical architectures for controlling reaction rates and the specificities of chemical reactions, but most are designed in hydrophobic environments. The preparation of artificial catalysts that have potential in aqueous media mimicking natural enzymes such as hydrolases remains a great challenge in the fields of supramolecular chemistry. Herein, we describe that a dimeric Zn(2+) complex having a 2,2'-bipyridyl linker, cyanuric acid, and a Cu(2+) ion automatically assembles in an aqueous solution to form a 4:4:4 complex, which is stabilized by metal-ligand coordination bonds, π-π-stacking interactions, and hydrogen bonding and contains μ-Cu(2)(OH)(2) cores analogous to the catalytic centers of phosphatase, a dinuclear metalloenzyme. The 4:4:4 complex selectively accelerates the hydrolysis of a phosphate monoester, mono(4-nitrophenyl)phosphate, at neutral pH.

Tuning Gas Adsorption Properties of Zeolite-like Supramolecular Assemblies with gis Topology via Functionalization of Isoreticular Metal-Organic Squares.

Science.gov (United States)

Wang, Shuang; Belmabkhout, Youssef; Cairns, Amy J; Li, Guanghua; Huo, Qisheng; Liu, Yunling; Eddaoudi, Mohamed

2017-10-04

A strategy based on metal-ligand directed assembly of metal-organic squares (MOSs), built-up from four-membered ring (4MR) secondary building units (SBUs), has been employed for the design and construction of isoreticular zeolite-like supramolecular assemblies (ZSAs). Four porous Co-based ZSAs having the same underlying gis topology, but differing only with respect to the capping and bridging linkers, were successfully isolated and fully characterized. In this series, each MOS in ZSA-3-ZSA-6 possess an ideal square geometry and is connected to four neighboring MOS via a total of 16 hydrogen bonds to give a 3-periodic porous network.To systematically assess the effect of the pore system (size and functionality) on the gas adsorption properties, we evaluated the MOSs for their affinity for different probe molecules such as CO 2 and light hydrocarbons. ZSA-3-ZSA-6 showed high thermal stability (up to 300 °C) and was proven highly porous as evidenced by gas adsorption studies. Notably, alkyl-functionalized MOSs were found to offer potential for selective separation of CO 2 , C 3 H 6 , and C 3 H 8 from CH 4 and H 2 containing gas stream, such as natural gas and refinery-off gases.

Tuning Gas Adsorption Properties of Zeolite-like Supramolecular Assemblies with gis Topology via Functionalization of Isoreticular Metal–Organic Squares

KAUST Repository

Wang, Shuang

2017-07-11

A strategy based on metal-ligand directed assembly of metal-organic squares (MOSs), built-up from four-membered ring (4MR) secondary building units (SBUs), has been employed for the design and construction of isoreticular zeolite-like supramolecular assemblies (ZSAs). Four porous Co-based ZSAs having the same underlying gis topology, but differing only with respect to the capping and bridging linkers, were successfully isolated and fully characterized. In this series, each MOS in ZSA-3-ZSA-6 possess an ideal square geometry and is connected to four neighboring MOS via a total of 16 hydrogen bonds to give a 3-periodic porous network.To systematically assess the effect of the pore system (size and functionality) on the gas adsorption properties, we evaluated the MOSs for their affinity for different probe molecules such as CO2 and light hydrocarbons. ZSA-3-ZSA-6 showed high thermal stability (up to 300 °C) and was proven highly porous as evidenced by gas adsorption studies. Notably, alkyl-functionalized MOSs were found to offer potential for selective separation of CO2, C3H6, and C3H8 from CH4 and H2 containing gas stream, such as natural gas and refinery-off gases.

Porphyrin Diacid-Polyelectrolyte Assemblies: Effective Photocatalysts in Solution

Directory of Open Access Journals (Sweden)

Sabine Frühbeißer

2016-05-01

Full Text Available Developing effective and versatile photocatalytic systems is of great potential in solar energy conversion. Here we investigate the formation of supramolecular catalysts by electrostatic self-assembly in aqueous solution: Combining positively charged porphyrins with negatively charged polyelectrolytes leads to nanoscale assemblies where, next to electrostatic interactions, π–π interactions also play an important role. Porphyrin diacid-polyelectrolyte assemblies exhibit a substantially enhanced catalytic activity for the light-driven oxidation of iodide. Aggregates with the hexavalent cationic porphyrin diacids show up to 22 times higher catalytic activity than the corresponding aggregates under neutral conditions. The catalytic activity can be increased by increasing the valency of the porphyrin and by choice of the loading ratio. The structural investigation of the supramolecular catalysts took place via atomic force microscopy and small angle neutron scattering. Hence, a new facile concept for the design of efficient and tunable self-assembled photocatalysts is presented.

Light induced assembly and self-sorting of silica microparticles

NARCIS (Netherlands)

Vilanova Garcia, N.; De Feijter, I.; Teunissen, A.J.P.; Voets, I.K.

2018-01-01

To tailor the properties of colloidal materials, precise control over the self-assembly of their constituents is a prerequisite. Here, we govern the assembly of silica particles by functionalization with supramolecular moieties which interact with each other via directional and reversible hydrogen

Functional chiral hydrogen-bonded assemblies

NARCIS (Netherlands)

Mateos timoneda, Miguel

2005-01-01

In this thesis different aspects of functional hydrogen-bonded (double and tetrarosette) assemblies are described. The functions were inspired by naturally occurring mechanisms such as molecular recognition, supramolecular chirality and its origin, and biostrategies for the correct folding of

[Special impact of supramolecular chemistry on Chinese medicine theories].

Science.gov (United States)

He, Fu-Yuan; Zhou, Yi-Qun; Deng, Kai-Wen; Deng, Jun-Lin; Shi, Ji-Lian; Liu, Wen-Long; Yang, Yan-Tao; Tang, Yu; Liu, Zhi-Gang

2014-04-01

The paper aimed to elucidate the specific impact of supramolecular chemistry on the Chinese medicine theories (CMT) in their modernization, after had summarized up the research status of supramolecular chemistry and analyzed the possible supramolecular forms of Chinese medicine (CM), as well as considered the problems in modernization of CM theories. On comparison of the classical chemistry that delt with chemical bonds among atoms, the supramolecular chemistry was rather concerned with varietes of weak noncovalent bonds intermolecules, and reflected the macro-apparent chemical properties of each molecules, and was the most appropriate chemical theories to explain the CMT and microcosmic materials. The molecules in the human body and Chinese material medica (CMM) formed supramolecules by way of self-assembly, self-organization, self-recognition and self-replication, with themselves or with complexation, composition, chelation, inclusion, neutralization etc. Meridian and Zang-fu viscera in CMT might be a space channel structure continuously consisted of unique molecules cavity that was imprinted with the supramolecularly template inside and outside of cells, through which the molecules in CMM interacted with the meridian and Zang-fu viscera. When small molecules in human body imprinted with macromolecules in meridian and Zang-fu viscera, in other words, they migrated along within imprinting channels of meridian and Zang-fu viscera on behavior of "Qi chromatography" impulsed by the heart beat, finally showed up on macroscopic the anisotropy of tissue and organ, as described namely as visceral manifestation in Chinese medical science. When small molecules in CMM interacted with imprinting channel on meridian and Zang-fu viscera, the natural properties and efficacy regularities of CMM was reflected on macroscopic. Therefore, the special representation forms of basic CMT is based on the macroscopic expression of "Qi chromatography" abided by imprinting effect

Structural characterization of supramolecular assemblies by {sup 13}C spin dilution and 3D solid-state NMR

Energy Technology Data Exchange (ETDEWEB)

Habenstein, Birgit; Loquet, Antoine; Giller, Karin; Becker, Stefan; Lange, Adam, E-mail: adla@nmr.mpibpc.mpg.de [Max Planck Institute for Biophysical Chemistry, Department of NMR-based Structural Biology (Germany)

2013-01-15

{sup 13}C spin diluted protein samples can be produced using [1-{sup 13}C] and [2-{sup 13}C]-glucose (Glc) carbon sources in the bacterial growth medium. The {sup 13}C spin dilution results in favorable {sup 13}C spectral resolution and polarization transfer behavior. We recently reported the combined use of [1-{sup 13}C]- and [2-{sup 13}C]-Glc labeling to facilitate the structural analysis of insoluble and non-crystalline biological systems by solid-state NMR (ssNMR), including sequential assignment, detection of long-range contacts and structure determination of macromolecular assemblies. In solution NMR the beneficial properties of sparsely labeled samples using [2-{sup 13}C]-glycerol ({sup 13}C labeled C{alpha} sites on a {sup 12}C diluted background) have recently been exploited to provide a bi-directional assignment method (Takeuchi et al. in J Biomol NMR 49(1):17-26, 2011 ). Inspired by this approach and our own recent results using [2-{sup 13}C]-Glc as carbon sources for the simplification of ssNMR spectra, we present a strategy for a bi-directional sequential assignment of solid-state NMR resonances and additionally the detection of long-range contacts using the combination of {sup 13}C spin dilution and 3D NMR spectroscopy. We illustrate our results with the sequential assignment and the collection of distance restraints on an insoluble and non-crystalline supramolecular assembly, the Salmonella typhimurium type III secretion system needle.

Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

KAUST Repository

Samai, Suman

2016-02-15

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

KAUST Repository

Samai, Suman; Sapsanis, Christos; Patil, Sachin; Ezzeddine, Alaa; Moosa, Basem; Omran, Hesham; Emwas, Abdul-Hamid M.; Salama, Khaled N.; Khashab, Niveen M.

2016-01-01

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

Synthesis and characterization of maltose-based amphiphiles as supramolecular hydrogelators.

Science.gov (United States)

Clemente, María J; Fitremann, Juliette; Mauzac, Monique; Serrano, José L; Oriol, Luis

2011-12-20

Low molecular mass amphiphilic glycolipids have been prepared by linking a maltose polar head and a hydrophobic linear chain either by amidation or copper(I)-catalyzed azide-alkyne [3 + 2] cycloaddition. The liquid crystalline properties of these amphiphilic materials have been characterized. The influence of the chemical structure of these glycolipids on the gelation properties in water has also been studied. Glycolipids obtained by the click coupling of the two components give rise to stable hydrogels at room temperature. The fibrillar structure of supramolecular hydrogels obtained by the self-assembly of these gelators have been characterized by electron microscopy. Fibers showed some torsion, which could be related with a chiral supramolecular arrangement of amphiphiles, as confirmed by circular dichroism (CD). The sol-gel transition temperature was also determined by differential scanning calorimetry (DSC) and NMR. © 2011 American Chemical Society

Fabrication of CO2 Facilitated Transport Channels in Block Copolymer through Supramolecular Assembly

Directory of Open Access Journals (Sweden)

Yao Wang

2014-05-01

Full Text Available In this paper, the molecule 12-amidine dodecanoic acid (M with ending groups of carboxyl and amidine groups respectively was designed and synthesized as CO2-responsive guest molecules. The block copolymer polystyrene-b-polyethylene oxide (PS-b-PEO was chosen as the host polymer to fabricate a composite membrane through H-bonding assembly with guest molecule M. We attempted to tune the phase separation structure of the annealed film by varying the amount of M added, and investigated the nanostructures via transmission electron microscope (TEM, fourier transform infrared (FT-IR etc. As a result, a reverse worm-like morphology in TEM image of bright PS phase in dark PEO/M matrix was observed for PS-b-PEO/M1 membrane in which the molar ratio of EO unit to M was 1:1. The following gas permeation measurement indicated that the gas flux of the annealed membranes dramatically increased due to the forming of ordered phase separation structure. As we expected, the obtained composite membrane PS-b-PEO/M1 with EO:M mole ratio of 1:1 presented an evident selectivity for moist CO2 permeance, which is identical with our initial proposal that the guest molecule M in the membranes will play the key role for CO2 facilitated transportation since the amidine groups of M could react reversibly with CO2 molecules in membranes. This work provides a supramolecular approach to fabricating CO2 facilitated transport membranes.

Supramolecular assembly of borate with quaternary ammonium: Crystal structure and tunable luminescent properties

Energy Technology Data Exchange (ETDEWEB)

Liang, Jie; Wang, Yong-gang [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Wang, Ying-xia, E-mail: wangyx@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Liao, Fu-hui [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Lin, Jian-hua, E-mail: jhlin@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

2013-04-15

A new borate [C{sub 6}H{sub 16}N][B{sub 5}O{sub 6}(OH){sub 4}] (1) is synthesized hydrothermally by the reaction of isopropyltrimethylammonium hydroxide with boric acid. It crystallizes in the triclinic space group P-1 with the parameters a=9.1578(10) Å, b=9.372(9) Å, c=9.9812(10) Å, α=66.508(2)°, β=74.751(2)°, γ=81.893(2)°. The [B{sub 5}O{sub 6}(OH){sub 4}]{sup −} anions are interlinked via hydrogen bonding forming a 3D supramolecular network containing large cavities, where reside the (CH{sub 3}){sub 3}(i-C{sub 3}H{sub 7}) N{sup +} cations. This borate shows tunable luminescent properties with temperature, heating-treatment, exciting-light, and solvents. The fluorescent intensity of 1 enhances 6-fold with decreasing the temperature from 25 K to 78 K. By treatment under different temperatures, the luminescence of 1 shifted from blue to white and the sample treated at 230 °C emits bright white light to naked eyes. The hybrid borate can disperse in different solvents, and shows a red-shifted and intense emission in polar solvents. - Graphical abstract: The new quaternary ammonium borate [C{sub 6}H{sub 17}N][B{sub 5}O{sub 6}(OH){sub 4}] contains a 3D supramolecular network formed by hydrogen bond linked [B{sub 5}O{sub 6}(OH){sub 4}]{sup −} anions and shows tunable luminescent properties with temperature, excitation light, and solvents. Highlights: ► A novel quaternary ammonium borate was synthesized. ► It possesses a supramolecular network fomed by H-bonded [B{sub 5}O{sub 6}(OH){sub 4}]{sup −} anions. ► This borate shows tunable luminescent properties with temperature, heating treatment, excitation light, and solvents.

Supramolecular Complexation of Carbohydrates for the Bioavailability Enhancement of Poorly Soluble Drugs.

Science.gov (United States)

Cho, Eunae; Jung, Seunho

2015-10-27

In this review, a comprehensive overview of advances in the supramolecular complexes of carbohydrates and poorly soluble drugs is presented. Through the complexation process, poorly soluble drugs could be efficiently delivered to their desired destinations. Carbohydrates, the most abundant biomolecules, have diverse physicochemical properties owing to their inherent three-dimensional structures, hydrogen bonding, and molecular recognition abilities. In this regard, oligosaccharides and their derivatives have been utilized for the bioavailability enhancement of hydrophobic drugs via increasing the solubility or stability. By extension, polysaccharides and their derivatives can form self-assembled architectures with poorly soluble drugs and have shown increased bioavailability in terms of the sustained or controlled drug release. These supramolecular systems using carbohydrate will be developed consistently in the field of pharmaceutical and medical application.

Azobenzene dye-coupled quadruply hydrogen-bonding modules as colorimetric indicators for supramolecular interactions

Directory of Open Access Journals (Sweden)

Yagang Zhang

2012-04-01

Full Text Available The facile coupling of azobenzene dyes to the quadruply hydrogen-bonding modules 2,7-diamido-1,8-naphthyridine (DAN and 7-deazaguanine urea (DeUG is described. The coupling of azobenzene dye 2 to mono-amido DAN units 4, 7, and 9 was effected by classic 4-(dimethylaminopyridine (DMAP-catalyzed peptide synthesis with N-(3-dimethylaminopropyl-N’-ethyl carbodiimide hydrochloride (EDC as activating agent, affording the respective amide products 5, 8, and 10 in 60–71% yield. The amide linkage was formed through either the aliphatic or aromatic ester group of 2, allowing both the flexibility and absorption maximum to be tuned. Azobenzene dye 1 was coupled to the DeUG unit 11 by Steglich esterification to afford the product amide 12 in 35% yield. Alternatively, azobenzene dye 16 underwent a room-temperature copper-catalyzed azide–alkyne Huisgen cycloaddition with DeUG alkyne 17 to give triazole 18 in 71% yield. Azobenzene coupled DAN modules 5, 8, and 10 are bright orange–red in color, and azobenzene coupled DeUG modules 12 and 18 are orange–yellow in color. Azobenzene coupled DAN and DeUG modules were successfully used as colorimetric indicators for specific DAN–DeUG and DAN–UPy (2-ureido-4(1H-pyrimidone quadruply hydrogen-bonding interactions.

Hydrodynamic and Thermophoretic Effects on the Supramolecular Chirality of Pyrene-Derived Nanosheets.

Science.gov (United States)

Micali, Norberto; Vybornyi, Mykhailo; Mineo, Placido; Khorev, Oleg; Häner, Robert; Villari, Valentina

2015-06-22

Chiroptical properties of two-dimensional (2D) supramolecular assemblies (nanosheets) of achiral, charged pyrene trimers (Py3 ) are rendered chiral by asymmetric physical perturbations. Chiral stimuli in a cuvette can originate either from controlled temperature gradients or by very gentle stirring. The chiroptical activity strongly depends on the degree of supramolecular order of the nanosheets, which is easily controlled by the method of preparation. The high degree of structural order ensures strong cooperative effects within the aggregates, rendering them more susceptible to external stimuli. The samples prepared by using slow thermal annealing protocols are both CD and LD active (in stagnant and stirred solutions), whereas for isothermally aged samples chiroptical activity was in all cases undetectable. In the case of temperature gradients, the optical activity of 2D assemblies could be recorded for a stagnant solution due to migration of the aggregates from the hottest to the coldest regions of the system. However, a considerably stronger exciton coupling, coinciding with the J-band of the interacting pyrenes, is developed upon subtle vortexing (0.5 Hz, 30 rpm) of the aqueous solution of the nanosheets. The sign of the exciton coupling is inverted upon switching between clockwise and counter-clockwise rotation. The supramolecular chirality is evidenced by the appearance of CD activity. To exclude artefacts from proper CD spectra, the contribution from LD to the observed CD was determined. The data suggest that the aggregates experience asymmetrical deformation and alignment effects because of the presence of chiral flows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predominantly ligand guided non-covalently linked assemblies of ...

Indian Academy of Sciences (India)

JUBARAJ B BARUAH

2018-05-12

May 12, 2018 ... Abstract. Various non-covalently linked inorganic self-assemblies formed by the supramolecular interacting .... metal-organic frameworks.59 Inorganic chemists rou- ...... two-dimensional organic–inorganic layered perovskite.

Information processing in the CNS: a supramolecular chemistry?

Science.gov (United States)

Tozzi, Arturo

2015-10-01

How does central nervous system process information? Current theories are based on two tenets: (a) information is transmitted by action potentials, the language by which neurons communicate with each other-and (b) homogeneous neuronal assemblies of cortical circuits operate on these neuronal messages where the operations are characterized by the intrinsic connectivity among neuronal populations. In this view, the size and time course of any spike is stereotypic and the information is restricted to the temporal sequence of the spikes; namely, the "neural code". However, an increasing amount of novel data point towards an alternative hypothesis: (a) the role of neural code in information processing is overemphasized. Instead of simply passing messages, action potentials play a role in dynamic coordination at multiple spatial and temporal scales, establishing network interactions across several levels of a hierarchical modular architecture, modulating and regulating the propagation of neuronal messages. (b) Information is processed at all levels of neuronal infrastructure from macromolecules to population dynamics. For example, intra-neuronal (changes in protein conformation, concentration and synthesis) and extra-neuronal factors (extracellular proteolysis, substrate patterning, myelin plasticity, microbes, metabolic status) can have a profound effect on neuronal computations. This means molecular message passing may have cognitive connotations. This essay introduces the concept of "supramolecular chemistry", involving the storage of information at the molecular level and its retrieval, transfer and processing at the supramolecular level, through transitory non-covalent molecular processes that are self-organized, self-assembled and dynamic. Finally, we note that the cortex comprises extremely heterogeneous cells, with distinct regional variations, macromolecular assembly, receptor repertoire and intrinsic microcircuitry. This suggests that every neuron (or group of

Supramolecular organization and chiral resolution of p-terphenyl-m-dicarbonitrile on the Ag(111) surface.

Science.gov (United States)

Marschall, Matthias; Reichert, Joachim; Seufert, Knud; Auwärter, Willi; Klappenberger, Florian; Weber-Bargioni, Alexander; Klyatskaya, Svetlana; Zoppellaro, Giorgio; Nefedov, Alexei; Strunskus, Thomas; Wöll, Christof; Ruben, Mario; Barth, Johannes V

2010-05-17

The supramolecular organization and layer formation of the non-linear, prochiral molecule [1, 1';4',1'']-terphenyl-3,3"-dicarbonitrile adsorbed on the Ag(111) surface is investigated by scanning tunneling microscopy (STM) and near-edge X-ray absorption fine-structure spectroscopy (NEXAFS). Upon two-dimensional confinement the molecules are deconvoluted in three stereoisomers, that is, two mirror-symmetric trans- and one cis-species. STM measurements reveal large and regular islands following room temperature deposition, whereby NEXAFS confirms a flat adsorption geometry with the electronic pi-system parallel to the surface plane. The ordering within the expressed supramolecular arrays reflects a substrate templating effect, steric constraints and the operation of weak lateral interactions mainly originating from the carbonitrile endgroups. High-resolution data at room temperature reveal enantiormorphic characteristics of the molecular packing schemes in different domains of the arrays, indicative of chiral resolution during the 2D molecular self-assembly process. At submonolayer coverage supramolecular islands coexist with a disordered fluid phase of highly mobile molecules. Following thermal quenching (down to 6 K) we find extended supramolecular ribbons stabilised again by attractive and directional noncovalent interactions, the formation of which reflects a chiral resolution of trans-species.

Protein-based polymers that bond to DNA : design of virus-like particles and supramolecular nanostructures

NARCIS (Netherlands)

Hernandez Garcia, A.

2014-01-01

In this thesis it is demonstrated that it is possible to use Protein-based Polymers (PbPs) as synthetic binders of DNA (or any other negatively charged polyelectrolyte). The PbPs co-assemble with their DNA templates to form highly organized virus-like particles and supramolecular structures. A

Natural supramolecular building blocks: from virus coat proteins to viral nanoparticles.

Science.gov (United States)

Liu, Zhi; Qiao, Jing; Niu, Zhongwei; Wang, Qian

2012-09-21

Viruses belong to a fascinating class of natural supramolecular structures, composed of multiple copies of coat proteins (CPs) that assemble into different shapes with a variety of sizes from tens to hundreds of nanometres. Because of their advantages including simple/economic production, well-defined structural features, unique shapes and sizes, genetic programmability and robust chemistries, recently viruses and virus-like nanoparticles (VLPs) have been used widely in biomedical applications and materials synthesis. In this critical review, we highlight recent advances in the use of virus coat proteins (VCPs) and viral nanoparticles (VNPs) as building blocks in self-assembly studies and materials development. We first discuss the self-assembly of VCPs into VLPs, which can efficiently incorporate a variety of different materials as cores inside the viral protein shells. Then, the self-assembly of VNPs at surfaces or interfaces is summarized. Finally, we discuss the co-assembly of VNPs with different functional materials (178 references).

Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media： Self-Assembly and Reversible Conversion of Vesicles and Gels%Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media： Self-Assembly and Reversible Conversion of Vesicles and Gels

Institute of Scientific and Technical Information of China (English)

杜平; 孔军; 王贵涛; 赵新; 李光玉; 蒋锡夔; 黎占亭

2011-01-01

In a preliminary letter （Tetrahedron Lett. 2010, 51, 188）, we reported two new hydrazide-based quadruple hydrogen-bonding motifs, this is, two monopodal （la and lb） and five dipodal （2a, 2b and 3a--3c） aromatic hydrazide derivatives, and the formation of supramolecular polymers and vesicles from the dipodal motifs in hydrocarbons. In this paper, we present a full picture on the properties of these hydrogen-bonding motifs with an emphasis on their self-assembling behaviors in aqueous media. SEM, AFM, TEM and fluorescent micrographs indicate that all the dipodal compounds also form vesicles in polar methanol and water-methanol （up to 50% of water） mixtures. Control experiments show that lb does not form vesicles in same media. Addition of lb to the solution of the dipodal compounds inhibits the latter＇s capacity of forming vesicles. At high concentrations, 3b and 3c also gelate discrete solvents, including hydrocarbons, esters, methanol, and methanol-water mixture. Concentration-dependent SEM investigations reveal that the vesicles of 3b and 3c fuse to form gels and the gel of 3c can de-aggregate to form the vesicles reversibly.

Microfluidic Droplet-Facilitated Hierarchical Assembly for Dual Cargo Loading and Synergistic Delivery.

Science.gov (United States)

Yu, Ziyi; Zheng, Yu; Parker, Richard M; Lan, Yang; Wu, Yuchao; Coulston, Roger J; Zhang, Jing; Scherman, Oren A; Abell, Chris

2016-04-06

Bottom-up hierarchical assembly has emerged as an elaborate and energy-efficient strategy for the fabrication of smart materials. Herein, we present a hierarchical assembly process, whereby linear amphiphilic block copolymers are self-assembled into micelles, which in turn are accommodated at the interface of microfluidic droplets via cucurbit[8]uril-mediated host-guest chemistry to form supramolecular microcapsules. The monodisperse microcapsules can be used for simultaneous carriage of both organic (Nile Red) and aqueous-soluble (fluorescein isothiocyanate-dextran) cargo. Furthermore, the well-defined compartmentalized structure benefits from the dynamic nature of the supramolecular interaction and offers synergistic delivery of cargos with triggered release or through photocontrolled porosity. This demonstration of premeditated hierarchical assembly, where interactions from the molecular to microscale are designed, illustrates the power of this route toward accessing the next generation of functional materials and encapsulation strategies.

Controlling Photoconductivity in PBI Films by Supramolecular Assembly.

Science.gov (United States)

Draper, Emily R; Archibald, Lewis J; Nolan, Michael C; Schweins, Ralf; Zwijnenburg, Martijn A; Sproules, Stephen; Adams, Dave J

2018-03-15

Perylene bisimides (PBIs) self-assemble in solution. The solubility of the PBIs is commonly changed through the choice of substituents at the imide positions. It is generally assumed this substitution does not affect the electronic properties of the PBI, and that the properties of the self-assembled aggregate are essentially that of the isolated molecule. However, substituents do affect the self-assembly, resulting in potentially different packing in the formed aggregates. Here, we show that the photoconductivity of films formed from a library of substituted PBIs varies strongly with the substituent and demonstrate that this is due to the different ways in which they pack. Our results open the possibility for tuning the optoelectronic properties of self-assembled PBIs by controlling the aggregate structure through careful choice of substituent, as demonstrated by us here optimising the photoconductivity of PBI films in this way. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Regulated assembly of a supramolecular centrosome scaffold in vitro

DEFF Research Database (Denmark)

Woodruff, J. B.; Wueseke, O.; Viscardi, V.

2015-01-01

are not well understood. In Caenorhabditis elegans, PCM assembly requires the coiled-coil protein SPD-5. We found that recombinant SPD-5 could polymerize to form micrometer-sized porous networks in vitro. Network assembly was accelerated by two conserved regulators that control PCM assembly in vivo, Polo...

Effect of intermolecular dipole-dipole interactions on interfacial supramolecular structures of C3-symmetric hexa-peri-hexabenzocoronene derivatives.

Science.gov (United States)

Mu, Zhongcheng; Shao, Qi; Ye, Jun; Zeng, Zebing; Zhao, Yang; Hng, Huey Hoon; Boey, Freddy Yin Chiang; Wu, Jishan; Chen, Xiaodong

2011-02-15

Two-dimensional (2D) supramolecular assemblies of a series of novel C(3)-symmetric hexa-peri-hexabenzocoronene (HBC) derivatives bearing different substituents adsorbed on highly oriented pyrolytic graphite were studied by using scanning tunneling microscopy at a solid-liquid interface. It was found that the intermolecular dipole-dipole interactions play a critical role in controlling the interfacial supramolecular assembly of these C(3)-symmetric HBC derivatives at the solid-liquid interface. The HBC molecule bearing three -CF(3) groups could form 2D honeycomb structures because of antiparallel dipole-dipole interactions, whereas HBC molecules bearing three -CN or -NO(2) groups could form hexagonal superstructures because of a special trimeric arrangement induced by dipole-dipole interactions and weak hydrogen bonding interactions ([C-H···NC-] or [C-H···O(2)N-]). Molecular mechanics and dynamics simulations were performed to reveal the physics behind the 2D structures as well as detailed functional group interactions. This work provides an example of how intermolecular dipole-dipole interactions could enable fine control over the self-assembly of disklike π-conjugated molecules.

Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors.

Science.gov (United States)

Li, Wanwan; Gao, Fengxian; Wang, Xiaoqian; Zhang, Ning; Ma, Mingming

2016-08-01

We report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline-polyvinyl alcohol hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochemical capacitance (928 F g(-1) ). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm(-2) and 153 F g(-1) ) and a high energy density of 13.6 Wh kg(-1) , superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mechanical folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Systems and Chemical Reactions in Single-Molecule Break Junctions.

Science.gov (United States)

Li, Xiaohui; Hu, Duan; Tan, Zhibing; Bai, Jie; Xiao, Zongyuan; Yang, Yang; Shi, Jia; Hong, Wenjing

2017-04-01

The major challenges of molecular electronics are the understanding and manipulation of the electron transport through the single-molecule junction. With the single-molecule break junction techniques, including scanning tunneling microscope break junction technique and mechanically controllable break junction technique, the charge transport through various single-molecule and supramolecular junctions has been studied during the dynamic fabrication and continuous characterization of molecular junctions. This review starts from the charge transport characterization of supramolecular junctions through a variety of noncovalent interactions, such as hydrogen bond, π-π interaction, and electrostatic force. We further review the recent progress in constructing highly conductive molecular junctions via chemical reactions, the response of molecular junctions to external stimuli, as well as the application of break junction techniques in controlling and monitoring chemical reactions in situ. We suggest that beyond the measurement of single molecular conductance, the single-molecule break junction techniques provide a promising access to study molecular assembly and chemical reactions at the single-molecule scale.

Sandwich morphology and superior dye-removal performances for nanofiltration membranes self-assemblied via graphene oxide and carbon nanotubes

Science.gov (United States)

Kang, Hui; Shi, Jie; Liu, Liyan; Shan, Mingjing; Xu, Zhiwei; Li, Nan; Li, Jing; Lv, Hanming; Qian, Xiaoming; Zhao, Lihuan

2018-01-01

To tune interlayer spacing, regulate water channel and improve stability of composite membrane, graphene oxide (GO) and oxidized carbon nanotubes (OCNTs) were assembled alternately to form sandwich morphology on a polyacrylonitrile substrate by layer-by-layer self-assembly technique. Polyelectrolyte played a part in cross-linking between GO and OCNTs. The effects about concentration ratio of GO and OCNTs on nanofiltration performance were investigated in detail. The composite membrane was used for dye rejection. When composite membrane with concentration ratio of GO and OCNTs was 10:1, water flux and rejection rate for methyl blue reached 21.71 L/(m2 h) and 99.3%, respectively. Meanwhile, this composite membrane had higher flux compared with reported literatures in which rejection also reached up to 99%. When concentration ratio of composite membranes about GO and OCNTs were 10:1 and 15:1, dye rejection for methyl blue remained 99.3% and 99.6% respectively after operating time of 50 h. Irreversible fouling ratio of composite membrane in a concentration ratio of 10:1 was only 4.4%, indicating that composite membrane had excellent antifouling performance for Bovine Serum Albumin. It was speculated that proper distribution of OCNTs in the sandwich morphology formed proper support points and water channels which benefited for a more stable performance.

Interfacial assembly structures and nanotribological properties of saccharic acids.

Science.gov (United States)

Shi, Hongyu; Liu, Yuhong; Zeng, Qingdao; Yang, Yanlian; Wang, Chen; Lu, Xinchun

2017-01-04

Saccharides have been recognized as potential bio-lubricants because of their good hydration ability. However, the interfacial structures of saccharides and their derivatives are rarely studied and the molecular details of interaction mechanisms have not been well understood. In this paper, the supramolecular assembly structures of saccharic acids (including galactaric acid and lactobionic acid), mediated by hydrogen bonds O-HN and O-HO, were successfully constructed on a highly oriented pyrolytic graphite (HOPG) surface by introducing pyridine modulators and were explicitly revealed by using scanning tunneling microscopy (STM). Furthermore, friction forces were measured in the saccharic acid/pyridine co-assembled system by atomic force microscopy (AFM), revealing a larger value than a pristine saccharic acid system, which could be attributed to the stronger tip-assembled molecule interactions that lead to the higher potential energy barrier needed to overcome. The effort on saccharide-related supramolecular self-assembly and nanotribological behavior could provide a novel and promising pathway to explore the interaction mechanisms underlying friction and reveal the structure-property relationship at the molecular level.

[Study on meridian tropism of medicinal property theory for Chines medicines by supramolecular chemistry (I)].

Science.gov (United States)

He, Fu-yuan; Deng, Kai-wen; Yang, Yan-tao; Zhou, Yi-qun; Shi, Ji-lian; Liu, Wen-long; Tang, Yu

2015-04-01

In this paper, based on the special influence of supramolecular chemistry on the basic theory of Chinese medicines ( CM) , the authors further analyzed the history of meridian tropism and natural origins of CM organisms and explained CM ingredients and the universal regularity of the automatic action of the supramolecular "imprinting templates" hole channel structure. After entering human bodies, CMs, as the aggregation of supramolecular "imprinting templates" , automatically seek supramolecular subjects that are matched with their "imprinting templates" in human meridians and organs for the purpose of self-recognition, self-organization, self-assembly and self-replication, so as to generate specific efficacy in meridians and organs, which is reflected as the meridian tropism phenomena at macro level. This regularity can be studied by in vitro and in vivo experimental studies. In vitro methods are mostly supra molecular structure analysis and kinetic and thermodynamic parameter calculation; Whereas in vivo methods are dominated by the analysis on object component distribution, chromatopharmacodynamic parameters and network chromatopharmacodynamic parameters; Particularly, the acupoint-medicine method can simplify to study the supramolecular subject-object relations. Consequently, CM's'meridian tropism reveals the universal regularity for interactions of macromolecular and micromolecular "imprinting templates" of subjects and objects in natural organisms. As the first barrier for the material base of the CM theory and breakthrough in the modernization of the basic CM theory, meridian tropism plays an important role in studies on basic theories of the basic CM theory.

Effect of dye extracting solvents and sensitization time on photovoltaic performance of natural dye sensitized solar cells

Science.gov (United States)

Hossain, Md. Khalid; Pervez, M. Firoz; Mia, M. N. H.; Mortuza, A. A.; Rahaman, M. S.; Karim, M. R.; Islam, Jahid M. M.; Ahmed, Farid; Khan, Mubarak A.

In this study, natural dye sensitizer based solar cells were successfully fabricated and photovoltaic performance was measured. Sensitizer (turmeric) sources, dye extraction process, and photoanode sensitization time of the fabricated cells were analyzed and optimized. Dry turmeric, verdant turmeric, and powder turmeric were used as dye sources. Five distinct types of solvents were used for extraction of natural dye from turmeric. Dyes were characterized by UV-Vis spectrophotometric analysis. The extracted turmeric dye was used as a sensitizer in the dye sensitized solar cell's (DSSC) photoanode assembly. Nano-crystalline TiO2 was used as a film coating semiconductor material of the photoanode. TiO2 films on ITO glass substrate were prepared by simple doctor blade technique. The influence of the different parameters VOC, JSC, power density, FF, and η% on the photovoltaic characteristics of DSSCs was analyzed. The best energy conversion performance was obtained for 2 h adsorption time of dye on TiO2 nano-porous surface with ethanol extracted dye from dry turmeric.

Rheology of Supramolecular Polymers

DEFF Research Database (Denmark)

Shabbir, Aamir

Supramolecular polymers are a broad class of materials that include all polymerscapable of associating via secondary interactions. These materials represent an emerging class of systems with superior versatility compared to classical polymers with applications in food stuff, coatings, cost...... efficient processes or biomedical areas. Design and development of supramolecular polymers using ionic, hydrogen bonding or transition metal complexes with tailored properties requires deep understanding of dynamics both in linear and non-linear deformations. While linear rheology is important to understand...... the dynamics under equilibrium conditions, extensional rheology is relevant during the processing or in the usage of polymers utilizing supramolecular associations for example, acrylic based pressure sensitive adhesives are subjected to extensional deformations during the peeling where strain hardening...

Cucurbit[8]uril ternary complexes for biomolecular assemblies in solution and at interfaces

NARCIS (Netherlands)

Cavatorta, E.

2016-01-01

Self-assembly allows for rationally designed molecular platforms that exploit specific, directional, tunable and reversible non-covalent interactions. The dynamic nature of such supramolecular interactions gives rise to self-assembled systems that can sense and respond to physiological cues, or that

Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies.

Science.gov (United States)

Patil, Avinash J; Li, Mei; Mann, Stephen

2013-08-21

Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of "inorganic molecular wrapping" of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as "armour-plated" enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies

Science.gov (United States)

Patil, Avinash J.; Li, Mei; Mann, Stephen

2013-07-01

Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of ``inorganic molecular wrapping'' of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as ``armour-plated'' enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

Self-Assembly of ZnO-Nanorods and Its Performance in Quasi Solid Dye Sensitized Solar Cells

Science.gov (United States)

Aprilia, A.; Erdienzy, A.; Bahtiar, A.; Safriani, L.; Syakir, N.; Risdiana; Saragi, T.; Hidayat, S.; Fitrilawati; Hidayat, R.; Siregar, R. E.

2017-07-01

Zinc oxide (ZnO) nanorods (NRs) were successfully prepared by self-assembly methods using zinc nitrate hexahydrate and hexamethylenetetramine as raw materials. ZnO-NRs were grown on FTO/ZnO seed layer and to enhance dye adsorption it was continued by deposition of titania (TiO2) paste by screen printing method. Deposition time of ZnO-NRs were varied, for 120, 150 and 180 minutes and subsequently stacked with one layer of TiO2 mesoporous. The resulting heterojunction layers of FTO/ZnO-Nrs/TiO2 was then applied as a photoanode in quasi-solid dye sensitized solar cell (QS- DSSC) with polymer gel electrolyte (PGE) as a hole conductor. UV-Vis spectrometer was used to investigate the changes of dye adsorption in photoanode with/without inserting titania mesoporous. Characterizations of scanning electron microscopy (SEM) and X-ray diffraction was carried out and the results shows that increasing the deposition time produces a smaller average grain size, diameter and denser layer of ZnO-nanorods. From current-voltage measurement, higher efficiency (η = 2.53%) was obtained for 120 min ZnO nanorods with short circuit current density (Jsc ) of 2.84 mA/cm2 and open circuit voltage (Voc) of 0.7 V. The combination of TiO2 and ZnO-NRs shows a better performance in solar cells characteristics due to increases of dye adsorption on photoanode and high photogenerated electron transport rate. This work emphasizes an optimum condition of ZnO-NRs in combination with TiO2 mesoporous as an alternative photoanode in QS-DSSC.

Metallo-supramolecular block copolymer micelles

NARCIS (Netherlands)

Gohy, J.M.W.

2009-01-01

Supramolecular copolymers have become of increasing interest in recent years in the search for new materials with tunable properties. In particular, metallo-supramolecular block copolymers in which metal-ligand complexes are introduced in block copolymer architectures, have known important progress,

Cataphoretic assembly of cationic dyes and deposition of carbon nanotube and graphene films.

Science.gov (United States)

Su, Y; Zhitomirsky, I

2013-06-01

Cathodic electrophoretic deposition (EPD) method has been developed for the fabrication of thin films from aqueous solutions of crystal violet (CV) dyes. The films contained rod-like particles with a long axis oriented perpendicular to the substrate surface. The proposed deposition mechanism involved cataphoresis of cationic CV(+) species, base generation in the cathodic reactions, and charge neutralization at the electrode surface. The assembly of rod-like particles was governed by π-π interactions of polyaromatic CV molecules. The deposition kinetics was studied by quartz crystal microbalance. CV dyes allowed efficient dispersion of multiwalled carbon nanotubes (MWCNTs) and graphene in water at relatively low CV concentrations. The feasibility of cathodic EPD of MWCNT and graphene from aqueous suspensions, containing CV, has been demonstrated. The deposition yield was investigated at different CV concentrations and deposition voltages. The relatively high deposition yield of MWCNT and graphene indicated that CV is an efficient dispersing, charging, and film forming agent for EPD. Electron microscopy data showed that at low CV concentrations in MWCNT or graphene suspensions and low deposition voltages, the films contained mainly MWCNT or graphene. The increase in the CV concentration and/or deposition voltage resulted in enhanced co-deposition of CV. The EPD method developed in this investigation paves the way for the fabrication of advanced nanocomposites by cathodic electrodeposition. Copyright © 2013 Elsevier Inc. All rights reserved.

Supramolecular Assemblies from Poly(styrene-block-poly(4-vinylpyridine Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

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Jean-François Gohy

2013-06-01

Full Text Available Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA, with poly(styrene-block-poly(4-vinylpyridine (PS-b-P4VP diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine (P4VP blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.

Organização supramolecular da ftalocianina de cobalto(II e seu efeito na oxidação do aminoácido cisteína Supramolecular organization of cobalt (II phthalocyanine on the pathway of cysteine oxidation

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Amanda Costa Santos

2010-01-01

Full Text Available The interest in the chemistry of cobalt (II tetrasulfonated phthalocyanine (PcTsCo comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride (PAH in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.

Effect of dye extracting solvents and sensitization time on photovoltaic performance of natural dye sensitized solar cells

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Md. Khalid Hossain

Full Text Available In this study, natural dye sensitizer based solar cells were successfully fabricated and photovoltaic performance was measured. Sensitizer (turmeric sources, dye extraction process, and photoanode sensitization time of the fabricated cells were analyzed and optimized. Dry turmeric, verdant turmeric, and powder turmeric were used as dye sources. Five distinct types of solvents were used for extraction of natural dye from turmeric. Dyes were characterized by UV–Vis spectrophotometric analysis. The extracted turmeric dye was used as a sensitizer in the dye sensitized solar cell’s (DSSC photoanode assembly. Nano-crystalline TiO2 was used as a film coating semiconductor material of the photoanode. TiO2 films on ITO glass substrate were prepared by simple doctor blade technique. The influence of the different parameters VOC, JSC, power density, FF, and η% on the photovoltaic characteristics of DSSCs was analyzed. The best energy conversion performance was obtained for 2 h adsorption time of dye on TiO2 nano-porous surface with ethanol extracted dye from dry turmeric. Keywords: DSSC, Natural dye, TiO2 photoanode, Dye extracting solvent, Dye-adsorption time

Natural dyes as photosensitizers for dye-sensitized solar cell

Energy Technology Data Exchange (ETDEWEB)

Hao, Sancun; Wu, Jihuai; Huang, Yunfang; Lin, Jianming [Institute of Materials Physical Chemistry, Huaqiao University, Quanzhou, Fujian 362021 (China)

2006-02-15

The dye-sensitized solar cells (DSC) were assembled by using natural dyes extracted from black rice, capsicum, erythrina variegata flower, rosa xanthina, and kelp as sensitizers. The I{sub SC} from 1.142mA to 0.225mA, the V{sub OC} from 0.551V to 0.412V, the fill factor from 0.52 to 0.63, and P{sub max} from 58{mu}W to 327{mu}W were obtained from the DSC sensitized with natural dye extracts. In the extracts of natural fruit, leaves and flower chosen, the black rice extract performed the best photosensitized effect, which was due to the better interaction between the carbonyl and hydroxyl groups of anthocyanin molecule on black rice extract and the surface of TiO{sub 2} porous film. The blue-shift of absorption wavelength of the black rice extract in ethanol solution on TiO{sub 2} film and the blue-shift phenomenon from absorption spectrum to photoaction spectrum of DSC sensitized with black rice extract are discussed in the paper. Because of the simple preparation technique, widely available and low cheap cost natural dye as an alternative sensitizer for dye-sensitized solar cell is promising. (author)

Supramolecular effects in dendritic systems containing photoactive groups

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GIANLUCA CAMILLO AZZELLINI

2000-03-01

Full Text Available In this article are described dendritic structures containing photoactive groups at the surface or in the core. The observed supramolecular effects can be attributed to the nature of the photoactive group and their location in the dendritic architecture. The peripheric azobenzene groups in these dendrimeric compounds can be regarded as single residues that retain the spectroscopic and photochemical properties of free azobenzene moiety. The E and Z forms of higher generation dendrimer, functionalized with azobenzene groups, show different host ability towards eosin dye, suggesting the possibility of using such dendrimer in photocontrolled host-guest systems. The photophysical properties of many dendritic-bipyridine ruthenium complexes have been investigated. Particularly in aerated medium more intense emission and a longer excited-state lifetime are observed as compared to the parent unsubstituted bipyridine ruthenium complexes. These differences can be attributed to a shielding effect towards dioxygen quenching originated by the dendritic branches.

Transfer and Dynamic Inversion of Coassembled Supramolecular Chirality through 2D-Sheet to Rolled-Up Tubular Structure.

Science.gov (United States)

Choi, Heekyoung; Cho, Kang Jin; Seo, Hyowon; Ahn, Junho; Liu, Jinying; Lee, Shim Sung; Kim, Hyungjun; Feng, Chuanliang; Jung, Jong Hwa

2017-12-13

Transfer and inversion of supramolecular chirality from chiral calix[4]arene analogs (3D and 3L) with an alanine moiety to an achiral bipyridine derivative (1) with glycine moieties in a coassembled hydrogel are demonstrated. Molecular chirality of 3D and 3L could transfer supramolecular chirality to an achiral bipyridine derivative 1. Moreover, addition of 0.6 equiv of 3D or 3L to 1 induced supramolecular chirality inversion of 1. More interestingly, the 2D-sheet structure of the coassembled hydrogels formed with 0.2 equiv of 3D or 3L changed to a rolled-up tubular structure in the presence of 0.6 equiv of 3D or 3L. The chirality inversion and morphology change are mainly mediated by intermolecular hydrogen-bonding interactions between the achiral and chiral molecules, which might be induced by reorientations of the assembled molecules, confirmed by density functional theory calculations.

Main-chain supramolecular block copolymers.

Science.gov (United States)

Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

2011-01-01

Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

Synthesis and Self-Assembly of Triangulenium Salts

DEFF Research Database (Denmark)

Shi, Dong

in influencing the assembling process and morphology of the assembled nanostructures. Tailoring the ATOTA+ system with alkyl chains of different length showed large effect on the final morphology of assembled supramolecular structures. The first two chapters give a brief introduction to molecular self....... Addition of soft counter ion into the nanosheets solution could induce gluing of the nanosheets. The solid thin film formed from the formed nanosheets after water evaporation showed crystalline patterning order as revealed by x-ray diffraction (XRD) measurements. Chpater 5 reports the counter ion effect...

Ultrasmall Peptides Self-Assemble into Diverse Nanostructures: Morphological Evaluation and Potential Implications

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Charlotte A.E. Hauser

2011-09-01

Full Text Available In this study, we perform a morphological evaluation of the diverse nanostructures formed by varying concentration and amino acid sequence of a unique class of ultrasmall self-assembling peptides. We modified these peptides by replacing the aliphatic amino acid at the C-aliphatic terminus with different aromatic amino acids. We tracked the effect of introducing aromatic residues on self-assembly and morphology of resulting nanostructures. Whereas aliphatic peptides formed long, helical fibers that entangle into meshes and entrap >99.9% water, the modified peptides contrastingly formed short, straight fibers with a flat morphology. No helical fibers were observed for the modified peptides. For the aliphatic peptides at low concentrations, different supramolecular assemblies such as hollow nanospheres and membrane blebs were found. Since the ultrasmall peptides are made of simple, aliphatic amino acids, considered to have existed in the primordial soup, study of these supramolecular assemblies could be relevant to understanding chemical evolution leading to the origin of life on Earth. In particular, we propose a variety of potential applications in bioengineering and nanotechnology for the diverse self-assembled nanostructures.

Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

KAUST Repository

Börjesson, Karl

2010-09-28

We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption. © 2010 American Chemical Society.

Thermoresponsive Supramolecular Chemotherapy by "V"-Shaped Armed β-Cyclodextrin Star Polymer to Overcome Drug Resistance.

Science.gov (United States)

Fan, Xiaoshan; Cheng, Hongwei; Wang, Xiaoyuan; Ye, Enyi; Loh, Xian Jun; Wu, Yun-Long; Li, Zibiao

2018-04-01

Pump mediated drug efflux is the key reason to result in the failure of chemotherapy. Herein, a novel star polymer β-CD-v-(PEG-β-PNIPAAm) 7 consisting of a β-CD core, grafted with thermo-responsive poly(N-isopropylacrylamide) (PNIPAAm) and biocompatible poly(ethylene glycol) (PEG) in the multiple "V"-shaped arms is designed and further fabricated into supramolecular nanocarriers for drug resistant cancer therapy. The star polymer could encapsulate chemotherapeutics between β-cyclodextrin and anti-cancer drug via inclusion complex (IC). Furthermore, the temperature induced chain association of PNIPAAm segments facilitated the IC to form supramolecular nanoparticles at 37 °C, whereas the presence of PEG impart great stability to the self-assemblies. When incubated with MDR-1 membrane pump regulated drug resistant tumor cells, much higher and faster cellular uptake of the supramolecular nanoparticles were detected, and the enhanced intracellular retention of drugs could lead to significant inhibition of cell growth. Further in vivo evaluation showed high therapeutic efficacy in suppressing drug resistant tumor growth without a significant impact on the normal functions of main organs. This work signifies thermo-responsive supramolecular chemotherapy is promising in combating pump mediated drug resistance in both in vitro and in vivo models, which may be encouraging for the advanced drug delivery platform design to overcome drug resistant cancer. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoscopic Self-Assembly: A Shift to Complexity

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Massimo eMastrangeli

2015-06-01

Full Text Available By focusing on the construction of thermodynamically stable structures, the self-assembly of mesoscopic systems has proven capable of formidable achievements in the bottom-up engineering of micro- and nanosystems. Yet, inspired by an analogous evolution in supramolecular chemistry, synthetic mesoscopic self-assembly may have a lot more ahead, within reach of a shift toward fully three-dimensional architectures, collective interactions of building blocks and kinetic control. All over these challenging fronts, complexity holds the key.

A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device

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Jurriaan Huskens

2011-10-01

Full Text Available A supramolecular platform based on self-assembled monolayers (SAMs has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. A Eu(III-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host-guest interactions. The self-assembly of the Eu(III-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Among these analytes, adenosine triphosphate (ATP and pyrophosphate, as well as dipicolinic acid (DPA which is a biomarker for anthrax, showed a strong response. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a multiplexed format that allows a general detection platform for both analyte systems in a single test run with µM and nM detection sensitivity for ATP and DPA, respectively.

Design of novel supramolecular self-assembly creating ...

Indian Academy of Sciences (India)

Administrator

Metal–organic composite materials with appropriate building blocks which can assemble into structures with specific and desired frameworks are challenging both for their solid state technology and for their chemical architecture. Of special interest is the construction of a microporous network that can exhibit reversible guest ...

Activation of ice recrystallization inhibition activity of poly(vinyl alcohol) using a supramolecular trigger

OpenAIRE

Phillips, Daniel J.; Congdon, Thomas; Gibson, Matthew I.

2016-01-01

Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity – a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-t...

Activation of Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol) using a Supramolecular Trigger†

OpenAIRE

Phillips, Daniel J.; Congdon, Thomas R.; Gibson, Matthew I.

2016-01-01

Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity – a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate ac...

Vortex-Induced Alignment of a Water Soluble Supramolecular Nanofiber Composed of an Amphiphilic Dendrimer

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Akihiko Tsuda

2013-06-01

Full Text Available We have synthesized a novel amphiphilic naphthalene imide bearing a cationic dendrimer wedge (NID. NID molecules in water self-assemble to form a two-dimensional ribbon, which further coils to give a linear supramolecular nanofiber. The sample solution showed linear dichroism (LD upon stirring of the solution, where NID nanofibers dominantly align at the center of vortex by hydrodynamic interaction with the downward torsional flows.

Multifunctional Nanoparticles Self-Assembled from Small Organic Building Blocks for Biomedicine.

Science.gov (United States)

Xing, Pengyao; Zhao, Yanli

2016-09-01

Supramolecular self-assembly shows significant potential to construct responsive materials. By tailoring the structural parameters of organic building blocks, nanosystems can be fabricated, whose performance in catalysis, energy storage and conversion, and biomedicine has been explored. Since small organic building blocks are structurally simple, easily modified, and reproducible, they are frequently employed in supramolecular self-assembly and materials science. The dynamic and adaptive nature of self-assembled nanoarchitectures affords an enhanced sensitivity to the changes in environmental conditions, favoring their applications in controllable drug release and bioimaging. Here, recent significant research advancements of small-organic-molecule self-assembled nanoarchitectures toward biomedical applications are highlighted. Functionalized assemblies, mainly including vesicles, nanoparticles, and micelles are categorized according to their topological morphologies and functions. These nanoarchitectures with different topologies possess distinguishing advantages in biological applications, well incarnating the structure-property relationship. By presenting some important discoveries, three domains of these nanoarchitectures in biomedical research are covered, including biosensors, bioimaging, and controlled release/therapy. The strategies regarding how to design and characterize organic assemblies to exhibit biomedical applications are also discussed. Up-to-date research developments in the field are provided and research challenges to be overcome in future studies are revealed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates

Science.gov (United States)

Ocakoglu, Kasim; Joya, Khurram S.; Harputlu, Ersan; Tarnowska, Anna; Gryko, Daniel T.

2014-07-01

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ~120 nm in a 60 μm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates.Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The

Eight supramolecular assemblies constructed from bis(benzimidazole) and organic acids through strong classical hydrogen bonding and weak noncovalent interactions

Science.gov (United States)

Jin, Shouwen; Wang, Daqi

2014-05-01

Eight crystalline organic acid-base adducts derived from alkane bridged bis(N-benzimidazole) and organic acids (2,4,6-trinitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 5-sulfosalicylic acid and oxalic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. Of the eight compounds five are organic salts (1, 4, 6, 7 and 8) and the other three (2, 3, and 5) are cocrystals. In all of the adducts except 1 and 8, the ratio of the acid and the base is 2:1. All eight supramolecular assemblies involve extensive intermolecular classical hydrogen bonds as well as other noncovalent interactions. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, all the complexes displayed 3D framework structure. The results presented herein indicate that the strength and directionality of the classical N+-H⋯O-, O-H⋯O, and O-H⋯N hydrogen bonds (ionic or neutral) and other nonbonding associations between acids and ditopic benzimidazoles are sufficient to bring about the formation of cocrystals or organic salts.

Supramolecular Pharmaceutical Sciences: A Novel Concept Combining Pharmaceutical Sciences and Supramolecular Chemistry with a Focus on Cyclodextrin-Based Supermolecules.

Science.gov (United States)

Higashi, Taishi; Iohara, Daisuke; Motoyama, Keiichi; Arima, Hidetoshi

2018-01-01

Supramolecular chemistry is an extremely useful and important domain for understanding pharmaceutical sciences because various physiological reactions and drug activities are based on supramolecular chemistry. However, it is not a major domain in the pharmaceutical field. In this review, we propose a new concept in pharmaceutical sciences termed "supramolecular pharmaceutical sciences," which combines pharmaceutical sciences and supramolecular chemistry. This concept could be useful for developing new ideas, methods, hypotheses, strategies, materials, and mechanisms in pharmaceutical sciences. Herein, we focus on cyclodextrin (CyD)-based supermolecules, because CyDs have been used not only as pharmaceutical excipients or active pharmaceutical ingredients but also as components of supermolecules.

Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

Science.gov (United States)

Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

2015-09-30

We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

Effects of Introducing Methoxy Groups into the Ancillary Ligands in Bis(diimine Copper(I Dyes for Dye-Sensitized Solar Cells

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Annika Büttner

2018-04-01

Full Text Available A systematic investigation of four heteroleptic bis(diimine copper(I dyes in n-type Dye-Sensitized Solar Cells (DSSCs is presented. The dyes are assembled using a stepwise, on-surface assembly. The dyes contain a phosphonic acid-functionalized 2,2′-bipyridine (bpy anchoring domain (5 and ancillary bpy ligands that bear peripheral phenyl (1, 4-methoxyphenyl (2, 3,5-dimethoxyphenyl (3, or 3,4,5-trimethoxyphenyl (4 substituents. In masked DSSCs, the best overall photoconversion efficiency was obtained with the dye [Cu(5(4]+ (1.96% versus 5.79% for N719. Values of JSC for both [Cu(5(2]+ (in which the 4-MeO group is electron releasing and [Cu(5(4]+ (which combines electron-releasing and electron-withdrawing effects of the 4- and 3,5-substituents and are enhanced with respect to [Cu(5(1]+. DSSCs with [Cu(5(3]+ show the lowest JSC. Solid-state absorption spectra and external quantum efficiency spectra reveal that [Cu(5(4]+ benefits from an extended spectral range at higher energies. Values of VOC are in the order [Cu(5(4]+ > [Cu(5(1]+ > [Cu(5(2]+ > [Cu(5(3]+. Density functional theory calculations suggest that methoxyphenyl character in MOs within the HOMO manifold in [Cu(5(2]+ and [Cu(5(4]+ may contribute to the enhanced performances of these dyes with respect to [Cu(5(1]+.

Supramolecular dendritic pi-conjugated systems: synthesis of glycinylurea functionalized pi-conjugated diphenylanthracene guests and their complexation with dendritic hosts. Part I.

NARCIS (Netherlands)

Precup, F.S.; Schenning, A.P.H.J.; Meijer, E.W.; Hubca, G.

2007-01-01

Glycinylurea functionalized p-conjugated diphenylanthracene guests (DPA guests) that bind to adamantyl urea modified dendritic hosts were synthesized and fully characterized by NMR spectroscopy (1H-NMR, 13C-NMR) and MALDI-TOF-MS. The resulting supramolecular assemblies have been investigated with

Photoelectric characterization of fabricated dye-sensitized solar cell using dye extracted from red Siahkooti fruit as natural sensitizer

Science.gov (United States)

Mozaffari, Sayed Ahmad; Saeidi, Mahsa; Rahmanian, Reza

2015-05-01

Natural dye extracted from Siahkooti fruit with/without purification by solid phase extraction (SPE) technique was used in the fabrication of DSSC as natural sensitizer. The UV-Vis absorption spectroscopy and Fourier transform infrared (FTIR) were employed to indicate the presence of anthocyanins in the fruit of red Siahkooti. The photoelectrochemical performance and the efficiency of assembled DSSC using Siahkooti fruit dye extract were evaluated and efficiency enhancement was obtained by a preliminary purification of extracted dye. The efficiency and fill factor of the DSSC using purified Siahkooti fruit dye were 0.32% and 0.73%, respectively. The results successfully showed that the DSSC, using Siahkooti fruit extract as a dye sensitizer, is useful for the preparation of environmentally friendly, low-cost, renewable and clean sources of energy.

Solubilization of Hydrophobic Dyes in Surfactant Solutions

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Ali Reza Tehrani-Bagha

2013-02-01

Full Text Available In this paper, the use of surfactants for solubilization of hydrophobic organic dyes (mainly solvent and disperse dyes has been reviewed. The effect of parameters such as the chemical structures of the surfactant and the dye, addition of salt and of polyelectrolytes, pH, and temperature on dye solubilization has been discussed. Surfactant self-assemble into micelles in aqueous solution and below the concentration where this occurs—the critical micelle concentration (CMC—there is no solubilization. Above the CMC, the amount of solubilized dye increases linearly with the increase in surfactant concentration. It is demonstrated that different surfactants work best for different dyes. In general, nonionic surfactants have higher solubilization power than anionic and cationic surfactants. It is likely that the reason for the good performance of nonionic surfactants is that they allow dyes to be accommodated not only in the inner, hydrocarbon part of the micelle but also in the headgroup shell. It is demonstrated that the location of a dye in a surfactant micelle can be assessed from the absorption spectrum of the dye-containing micellar solution.

Synthesis and Characterization of thermo/pH-responsive Supramolecular G-Quadruplexes for the Construction of Supramolecular Hacky Sacks for Biorelevant Applications

Science.gov (United States)

Negron Rios, Luis M.

The impact of size, shape, and distribution of lipophilic regions on the surfaces of nanoscopic objects that are amphiphilic or patchy (such as proteins) are yet to be fully understood. One of the reasons for this is the lack of an appropriate model systems in which to probe this question. Our group has previously reported 2'-deoxyguanosine (8ArG) derivatives that self-assemble in aqueous media into discrete supramolecular hexadecamers that show the lower critical solution temperature (LCST) phenomenon. The LCST phenomenon is a convenient and rigorous strategy to measure the hydrophobicity of a system. Although these SGQs are potentially attractive for biomedical applications like drug-delivery, the narrow window of physiological temperatures complicates their implementation. This moved us to redesign the constituent 8ArG subunits to incorporate imidazole moieties that would lead to pH-responsive SGQs, working isothermally. Upon reaching a threshold temperature (Lower Critical Solution Temperature, LCST) at pH 7, these dual-responsive SGQs further self-assemble to form nano/micro hydrogel globules that we called them supramolecular hacky sacks (SHS). However, we can isolate kinetically stable versions of these SHS by lowering the ionic strength of the medium (i.e., from the molar to the millimolar range) in a process that we term "fixing the SHS", in which these SHS maintain their integrity (size and shape) and stability without the requirement of crosslinking agents. After structural characterization and in vitro studies of SHS, we performed encapsulation studies of DOX, rhodamine, dsDNA (F26T), thrombin binding aptamer (TBA) and dextran (3 kDa) Texas Red conjugate. Then we performed in vivo studies of cell internalization and drug delivery with neuroblastoma SY-SH5Y. The performed studies will bring new approaches for the development of new biotechnology for fundamental applications and the emerging of novel therapeutic agents for biomedical applications.

Nanoporous Network Channels from Self-Assembled Triblock Copolymer Supramolecules

NARCIS (Netherlands)

du Sart, Gerrit Gobius; Vukovic, Ivana; Vukovic, Zorica; Polushkin, Evgeny; Hiekkataipale, Panu; Ruokolainen, Janne; Loos, Katja; ten Brinke, Gerrit

2011-01-01

Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded

Muscle assembly: a titanic achievement?

Science.gov (United States)

Gregorio, C C; Granzier, H; Sorimachi, H; Labeit, S

1999-02-01

The formation of perfectly aligned myofibrils in striated muscle represents a dramatic example of supramolecular assembly in eukaryotic cells. Recently, considerable progress has been made in deciphering the roles that titin, the third most abundant protein in muscle, has in this process. An increasing number of sarcomeric proteins (ligands) are being identified that bind to specific titin domains. Titin may serve as a molecular blueprint for sarcomere assembly and turnover by specifying the precise position of its ligands within each half-sarcomere in addition to functioning as a molecular spring that maintains the structural integrity of the contracting myofibrils.

Steering Self-Assembly of Amphiphilic Molecular Nanostructures via Halogen Exchange

NARCIS (Netherlands)

Kriete, Björn; Bondarenko, Anna S.; Jumde, Varsha R.; Franken, Linda E.; Minnaard, Adriaan J.; Jansen, Thomas L. C.; Knoester, Jasper; Pshenichnikov, Maxim S.

2017-01-01

In the field of self-assembly, the quest for gaining control over the supramolecular architecture without affecting the functionality of the individual molecular building blocks is intrinsically challenging. By using a combination of synthetic chemistry, cryogenic transmission electron microscopy,

Functional supramolecular polymers for biomedical applications.

Science.gov (United States)

Dong, Ruijiao; Zhou, Yongfeng; Huang, Xiaohua; Zhu, Xinyuan; Lu, Yunfeng; Shen, Jian

2015-01-21

As a novel class of dynamic and non-covalent polymers, supramolecular polymers not only display specific structural and physicochemical properties, but also have the ability to undergo reversible changes of structure, shape, and function in response to diverse external stimuli, making them promising candidates for widespread applications ranging from academic research to industrial fields. By an elegant combination of dynamic/reversible structures with exceptional functions, functional supramolecular polymers are attracting increasing attention in various fields. In particular, functional supramolecular polymers offer several unique advantages, including inherent degradable polymer backbones, smart responsiveness to various biological stimuli, and the ease for the incorporation of multiple biofunctionalities (e.g., targeting and bioactivity), thereby showing great potential for a wide range of applications in the biomedical field. In this Review, the trends and representative achievements in the design and synthesis of supramolecular polymers with specific functions are summarized, as well as their wide-ranging biomedical applications such as drug delivery, gene transfection, protein delivery, bio-imaging and diagnosis, tissue engineering, and biomimetic chemistry. These achievements further inspire persistent efforts in an emerging interdisciplin-ary research area of supramolecular chemistry, polymer science, material science, biomedical engineering, and nanotechnology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties

Energy Technology Data Exchange (ETDEWEB)

Gao, Zhu-Qing, E-mail: zqgao2008@163.com [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Li, Hong-Jin [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Zhang, Qing-Hua [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisbon (Portugal)

2016-09-15

Four new crystalline solids, namely [Co{sub 2}(µ{sub 2}-5-Clnic){sub 2}(µ{sub 3}-5-Clnic){sub 2}(µ{sub 2}-H{sub 2}O)]{sub n} (1), [Co(5-Clnic){sub 2}(H{sub 2}O){sub 4}]·2(5-ClnicH) (2), [Pb(µ{sub 2}-5-Clnic){sub 2}(phen)]{sub n} (3), and [Cd(5-Clnic){sub 2}(phen){sub 2}]·3H{sub 2}O (4) were generated by hydrothermal self-assembly methods from the corresponding metal(II) chlorides, 5-chloronicotinic acid (5-ClnicH) as a principal building block, and 1,10-phenanthroline (phen) as an ancillary ligand (optional). All the products 1–4 were characterized by IR spectroscopy, elemental analysis, thermogravimetric (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Their structures range from an intricate 3D metal-organic network 1 with the 3,6T7 topology to a ladder-like 1D coordination polymer 3 with the 2C1 topology, whereas compounds 2 and 4 are the discrete 0D monomers. The structures of 2 and 4 are further extended (0D→2D or 0D→3D) by hydrogen bonds, generating supramolecular networks with the 3,8L18 and ins topologies, respectively. Synthetic aspects, structural features, thermal stability, magnetic (for 1) and luminescent (for 3 and 4) properties were also investigated and discussed. - Graphical abstract: A new series of crystalline solids was self-assembled and fully characterized; their structural, topological, luminescent and magnetic features were investigated. Display Omitted.

Self-assembling peptide semiconductors

Science.gov (United States)

Tao, Kai; Makam, Pandeeswar; Aizen, Ruth; Gazit, Ehud

2017-01-01

Semiconductors are central to the modern electronics and optics industries. Conventional semiconductive materials bear inherent limitations, especially in emerging fields such as interfacing with biological systems and bottom-up fabrication. A promising candidate for bioinspired and durable nanoscale semiconductors is the family of self-assembled nanostructures comprising short peptides. The highly ordered and directional intermolecular π-π interactions and hydrogen-bonding network allow the formation of quantum confined structures within the peptide self-assemblies, thus decreasing the band gaps of the superstructures into semiconductor regions. As a result of the diverse architectures and ease of modification of peptide self-assemblies, their semiconductivity can be readily tuned, doped, and functionalized. Therefore, this family of electroactive supramolecular materials may bridge the gap between the inorganic semiconductor world and biological systems. PMID:29146781

Self-assembled monolayers of bimetallic Au/Ag nanospheres with superior surface-enhanced Raman scattering activity for ultra-sensitive triphenylmethane dyes detection.

Science.gov (United States)

Tian, Yue; Zhang, Hua; Xu, Linlin; Chen, Ming; Chen, Feng

2018-02-15

The bimetallic Au/Ag self-assembled monolayers (SAMs) were constructed by using mono-dispersed Au/Ag nanospheres (Ag: 4.07%-34.53%) via evaporation-based assembly strategy. The composition-dependent surface-enhanced Raman scattering (SERS) spectroscopy revealed that the Au/Ag (Ag: 16.83%) SAMs provide maximized activity for triphenylmethane dyes detection. With the inter-metallic synergy, the optimized SAMs enable the Raman intensity of crystal violet molecules to be about 223 times higher than that of monometallic Au SAMs. Moreover, the SERS signals with excellent uniformity (<5% variation) are sensitive down to 10 -13   M concentrations because of the optimal matching between bimetallic plasmon resonance and the incident laser wavelength.

Photoactive assemblies of organic compounds and biomolecules: drug-protein supramolecular systems.

Science.gov (United States)

Vayá, Ignacio; Lhiaubet-Vallet, Virginie; Jiménez, M Consuelo; Miranda, Miguel A

2014-06-21

The properties of singlet and triplet excited states are strongly medium-dependent. Hence, these species constitute valuable tools as reporters to probe compartmentalised microenvironments, including drug@protein supramolecular systems. In the present review, the attention is focused on the photophysical properties of the probe drugs (rather than those of the protein chromophores) using transport proteins (serum albumins and α1-acid glycoproteins) as hosts. Specifically, fluorescence measurements allow investigation of the structural and dynamic properties of biomolecules or their complexes. Thus, the emission quantum yields and the decay kinetics of the drug singlet excited states provide key information to determine important parameters such as the stoichiometry of the complex, the binding constant, the relative degrees of occupancy of the different compartments, etc. Application of the FRET concept allows determination of donor-acceptor interchromophoric distances. In addition, anisotropy measurements can be related to the orientation of the drug within the binding sites, where the degrees of freedom for conformational relaxation are restricted. Transient absorption spectroscopy is also a potentially powerful tool to investigate the binding of drugs to proteins, where formation of encapsulated triplet excited states is favoured over other possible processes leading to ionic species (i.e. radical ions), and their photophysical properties are markedly sensitive to the microenvironment experienced within the protein binding sites. Even under aerobic conditions, the triplet lifetimes of protein-complexed drugs are remarkably long, which provides a broad dynamic range for identification of distinct triplet populations or for chiral discrimination. Specific applications of the laser flash photolysis technique include the determination of drug distribution among the bulk solution and the protein binding sites, competition of two types of proteins to bind a drug

Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

Science.gov (United States)

Maity, Sibaprasad; Das, Priyadip; Reches, Meital

2015-01-01

Natural helical structures have inspired the formation of well-ordered peptide-based chiral nanostructures in vitro. These structures have drawn much attention owing to their diverse applications in the area of asymmetric catalysts, chiral photonic materials, and nanoplasmonics. The self-assembly of two enantiomeric fluorinated aromatic dipeptides into ordered chiral fibrillar nanostructures upon sonication is described. These fibrils form organogels. Our results clearly indicate that fluorine-fluorine interactions play an important role in self-assembly. Circular dichroism analysis revealed that both peptides (peptides 1 and 2), containing two fluorines, depicted opposite cotton effects in their monomeric form compared with their aggregated form. This shows that supramolecular chirality inversion took place during the stimuli-responsive self-aggregation process. Conversely, peptide 3, containing one fluorine, did not exhibit chirality inversion in sonication-induced organogelation. Therefore, our results clearly indicate that fluorination plays an important role in the organogelation process of these aromatic dipeptides. Our findings may have broad implications regarding the design of chiral nanostructures for possible applications such as chiroptical switches, asymmetric catalysis, and chiral recognitions. PMID:26553508

Magnetism: a supramolecular function

International Nuclear Information System (INIS)

Decurtins, S.; Pellaux, R.; Schmalle, H.W.

1996-01-01

The field of molecule-based magnetism has developed tremendously in the last few years. Two different extended molecular - hence supramolecular -systems are presented. The Prussian-blue analogues show some of the highest magnetic ordering temperature of any class of molecular magnets, T c = 315 K, whereas the class of transition-metal oxalate-bridged compounds exhibits a diversity of magnetic phenomena. Especially for the latter compounds, the elastic neutron scattering technique has successfully been proven to trace the magnetic structure of these supramolecular and chiral compounds. (author) 18 figs., 25 refs

Magnetism: a supramolecular function

Energy Technology Data Exchange (ETDEWEB)

Decurtins, S; Pellaux, R; Schmalle, H W [Zurich Univ., Inst. fuer Anorganische Chemie, Zurich (Switzerland)

1996-11-01

The field of molecule-based magnetism has developed tremendously in the last few years. Two different extended molecular - hence supramolecular -systems are presented. The Prussian-blue analogues show some of the highest magnetic ordering temperature of any class of molecular magnets, T{sub c} = 315 K, whereas the class of transition-metal oxalate-bridged compounds exhibits a diversity of magnetic phenomena. Especially for the latter compounds, the elastic neutron scattering technique has successfully been proven to trace the magnetic structure of these supramolecular and chiral compounds. (author) 18 figs., 25 refs.

The influence of aquaporin-4 isoform interaction on supramolecular water channel assembly in astrocytoma cells

OpenAIRE

Deville, Sarah

2012-01-01

Traumatic brain injury (TBI) is often complicated by the development of brain edema. Despite its clinical importance, the underlying pathological mechanisms are poorly understood. Nevertheless, a central role for aquaporin-4 (AQP4) has been suggested. AQP4 is the predominant water channel of the central nervous system, where it forms supramolecular structures named orthogonal arrays of particles (OAP). This organization is essential for channel opening. OAP formation is regulated by the diffe...

Encapsulation of dye molecules into mesoporous polymer resin and mesoporous polymer-silica films by an evaporation-induced self-assembly method

Energy Technology Data Exchange (ETDEWEB)

Chi Yue; Li Nan; Tu Jinchun; Zhang Yujie [School of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, Changchun 130012 (China); Li Xiaotian, E-mail: xiaotianli@jlu.edu.c [School of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, Changchun 130012 (China); Shao Changlu, E-mail: clshao@nenu.edu.c [Center for Advanced Optoelectronic Functional Materials Research, Northeast Normal University, Changchun 130024 (China)

2010-03-15

Polymer resin and polymer-silica films with highly ordered mesostructure have been used as host materials to encapsulate DCM (4-(dicyanomethylene) -2-methyl-6-(4-dimethylaminostyryl)-4h-pyran), a kind of fluorescent dye, through evaporation-induced self-assembly method (EISA). After encapsulation, the composites show significant blue-shift in photoluminescence (PL) spectra. Particularly, by changing the excitation wavelength, the samples show different emission bands. These phenomena are related to the mesostructure and the positions of DCM molecules in the host.

Automatic Assignment of Methyl-NMR Spectra of Supramolecular Machines Using Graph Theory.

Science.gov (United States)

Pritišanac, Iva; Degiacomi, Matteo T; Alderson, T Reid; Carneiro, Marta G; Ab, Eiso; Siegal, Gregg; Baldwin, Andrew J

2017-07-19

Methyl groups are powerful probes for the analysis of structure, dynamics and function of supramolecular assemblies, using both solution- and solid-state NMR. Widespread application of the methodology has been limited due to the challenges associated with assigning spectral resonances to specific locations within a biomolecule. Here, we present Methyl Assignment by Graph Matching (MAGMA), for the automatic assignment of methyl resonances. A graph matching protocol examines all possibilities for each resonance in order to determine an exact assignment that includes a complete description of any ambiguity. MAGMA gives 100% accuracy in confident assignments when tested against both synthetic data, and 9 cross-validated examples using both solution- and solid-state NMR data. We show that this remarkable accuracy enables a user to distinguish between alternative protein structures. In a drug discovery application on HSP90, we show the method can rapidly and efficiently distinguish between possible ligand binding modes. By providing an exact and robust solution to methyl resonance assignment, MAGMA can facilitate significantly accelerated studies of supramolecular machines using methyl-based NMR spectroscopy.

Extension of the charge separated-state lifetime by supramolecular association of a tetrathiafulvalene electron donor to a zinc/gold bisporphyrin.

Science.gov (United States)

Boixel, Julien; Fortage, Jérôme; Blart, Errol; Pellegrin, Yann; Hammarström, Leif; Becker, Hans-Christian; Odobel, Fabrice

2010-02-14

Supramolecular triads were prepared by self-assembly of 4'-pyridyl-2-tetrathiafulvalene axially bound on ZnP-spacer-AuP(+) dyads; the lifetime of the charge separated state ((+)TTF-ZnP-Spacer-AuP ) formed upon light excitation of the triad is greatly increased with respect to that found in the parent dyad.

New self-assembled material based on Ru nanoparticles and 4-sulfocalix[4]arene as an efficient and recyclable catalyst for reduction of brilliant yellow azo dye in water: a new model catalytic reaction

Energy Technology Data Exchange (ETDEWEB)

Rambabu, Darsi; Pradeep, Chullikkattil P.; Dhir, Abhimanew, E-mail: abhimanew@iitmandi.ac.in [Indian Institute of Technology (India)

2016-12-15

New self-assembled material (Ru@SC) with ruthenium nanoparticles (Ru NPs) and 4-sulfocalix[4]arene (SC) is synthesized in water at room temperature. Ru@SC is characterized by thermal gravimetric analysis, FT-IR, powder x-ray diffraction, TEM and SEM analysis. The size of Ru nanoparticles in the self-assembly is approximately 5 nm. The self-assembled material Ru@SC shows an efficient catalytic reduction of toxic ‘brilliant yellow’ (BY) azo dye. The reduced amine products were successfully separated and confirmed by single-crystal XRD, NMR and UV-Vis spectroscopy. Ru@SC showed a better catalytic activity in comparison with commercial catalysts Ru/C (ruthenium on charcoal 5 %) and Pd/C (palladium on charcoal 5 and 10 %). The catalyst also showed a promising recyclability and heterogeneous nature as a catalyst for reduction of ‘BY’ azo dye.

Supramolecular polymeric materials via cyclodextrin-guest interactions.

Science.gov (United States)

Harada, Akira; Takashima, Yoshinori; Nakahata, Masaki

2014-07-15

CONSPECTUS: Cyclodextrins (CDs) have many attractive functions, including molecular recognition, hydrolysis, catalysis, and polymerization. One of the most important uses of CDs is for the molecular recognition of hydrophobic organic guest molecules in aqueous solutions. CDs are desirable host molecules because they are environmentally benign and offer diverse functions. This Account demonstrates some of the great advances in the development of supramolecular materials through host-guest interactions within the last 10 years. In 1990, we developed topological supramolecular complexes with CDs, polyrotaxane, and CD tubes, and these preparation methods take advantage of self-organization between the CDs and the polymers. The combination of polyrotaxane with αCD forms a hydrogel through the interaction of αCDs with the OH groups on poly(ethylene glycol). We categorized these polyrotaxane chemistries within main chain type complexes. At the same time, we studied the interactions of side chain type supramolecular complexes with CDs. In these systems the guest molecules modified the polymers and selectively formed inclusion complexes with CDs. The systems that used low molecular weight compounds did not show such selectivity with CDs. The multivalency available within the complex cooperatively enhances the selective binding of CD with guest molecules via the polymer side chains, a phenomenon that is analogous to binding patterns observed in antigen-antibody complexes. To incorporate the molecular recognition properties of CDs within the polymer side chains, we first prepared stimuli-responsive sol-gel switching materials through host-guest interactions. We chose azobenzene derivatives for their response to light and ferrocene derivatives for their response to redox conditions. The supramolecular materials were both redox-responsive and self-healing, and these properties resulted from host-guest interactions. These sol-gels with built in switches gave us insight for

The dominant role of side chains in supramolecular double helical organisation in synthetic tripeptides

Science.gov (United States)

Sharma, Ankita; Tiwari, Priyanka; Dutt Konar, Anita

2018-06-01

Peptide self-assembled nanostructures have attracted attention recently owing to their promising applications in diversified avenues. To validate the importance of sidechains in supramolecular architectural stabilization, herein this report describes the self-assembly propensities involving weak interactions in a series of model tripeptides Boc-Xaa-Aib-Yaa-OMe I-IV, (where Xaa = 4-F-Phe/NMeSer/Ile & Yaa = Tyr in peptide I-III respectively and Xaa = 4-F-Phe & Yaa = Ile in peptide IV) differing in terminal side chains. The solid state structural analysis reveals that tripeptide (I) displays supramolecular preference for double helical architecture. However, when slight modification has been introduced in the N-terminal side chains disfavour the double helical organisation (Peptide II and III). Indeed the peptides display sheet like ensemble within the framework. Besides replacement of C-terminal Tyr by Ile in peptide I even do not promote the architecture, emphasizing the dominant role of balance of side chains in stabilizing double helical organisation. The CD measurements, concentration dependant studies, NMR titrations and ROESY spectra are well in agreement with the solid state conformational investigation. Moreover the morphological experiments utilizing FE-SEM, support the heterogeneity present in the peptides. Thus this work may not only hold future promise in understanding the structure and function of neurodegenerative diseases but also assist in rational design of protein modification in biologically active peptides.

Enhanced intermolecular forces in supramolecular polymer nanocomposites

Directory of Open Access Journals (Sweden)

F. Lin

2017-09-01

Full Text Available Ureido-pyrimidone (Upy can dimerize in a self-complementary array of quadruple hydrogen bonds. In this paper, supramolecular polymer composites were prepared by blending Upy functionalized nanosilica with Upy end-capped polycarbonatediol. Surface characteristics of Upy functionalized nanosilica and influences of supramolecular forces on interfacial binding were researched. Fourier transform infrared spectroscopy (FTIR, Nuclear magnetic resonance (NMR and Gel permeation chromatography (GPC were used to characterize the synthesized molecules. Grafting ratio of Upy segments on the surface of nanosilica was analysed by Thermogravimetic analysis (TGA. Hydrophobicity and morphology of Upy modified nanosilica were analysed by Contact angle tester and Scanning electron microscope (SEM. Furthermore, dynamic thermo mechanical properties, mechanical properties and distribution of nanosilica in supramolecular polymer composites were also researched. Compared with the matrix resin, tensile stress and young's modulus of supramolecular polymer composites containing 5 wt% modified nanosilica were increased by 292 and 198% respectively.

Syntheses and structures of three supramolecular complexes based on 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid

Science.gov (United States)

Yu, Xiao-Yang; Zhang, Xiao; Liu, Zhi-Gang; Cui, Xiao-Bing; Xu, Jia-Ning; Luo, Yu-Hui

2017-11-01

Three new supramolecular compounds, [Cu(o-HPIDC)(bpy)(H2O)]·2H2O 1, [Cu(o-H2PIDC)(phen)Cl]·[Cu(phen)2Cl]·10H2O·Cl 2 and {[Cd(o-H2PIDC)(H2O)2Cl]·H2O}23 (o-H3PIDC = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline), were hydrothermally synthesized and characterized. In compound 1, the adjacent two supramolecular layers are constructed from different types of helical chains with the same pitch. In compound 2, the adjacent 2D water-chloride layers, {[(H2O)10Cl]-}n, are pillared by [Cu(o-H2PIDC)(phen)Cl] units to form the overall 3D supramolecular network with 1D channels through Osbnd H⋯O hydrogen bond interactions. In compound 3, two Cd(II) are linked into a binuclear [Cd2(o-H2PIDC)2(H2O)4Cl2] with a ten-membered ring by two o-H2PIDC- ligands. The three compounds self-assemble into 3D supramolecular structures via hydrogen bond and π-π stacking interactions. The fluorescence properties of compound 3 was also investigated.

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates

KAUST Repository

Ocakoǧlu, Kasim; Joya, Khurram Saleem; Harputlu, Ersan; Tarnowska, Anna; Gryko, Daniel T.

2014-01-01

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C 18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ∼120 nm in a 60 μm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates. © 2014 the Partner Organisations.

Progress Toward the Clinical Translation of Bioinspired Peptide and Protein Assemblies.

Science.gov (United States)

Hainline, Kelly M; Fries, Chelsea N; Collier, Joel H

2018-03-01

Supramolecular materials composed of proteins and peptides have been receiving considerable attention toward a range of diseases and conditions from vaccines to drug delivery. Owing to the relative newness of this class of materials, the bulk of work to date has been preclinical. However, examples of approved treatments particularly in vaccines, dentistry, and hemostasis demonstrate the translational potential of supramolecular polypeptides. Critical milestones in the clinical development of this class of materials and currently approved supramolecular polypeptide therapies are described in this study. Additional examples of not-yet-approved materials that are steadily advancing toward clinical use are also featured. Spherical assemblies such as virus-like particles, designed protein nanoparticles, and spherical peptide amphiphiles are highlighted, followed by fiber-forming systems such as fibrillizing peptides, fiber-forming peptide-amphiphiles, and filamentous bacteriophages. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal selective co-ordinative self-assembly of π-donors

Indian Academy of Sciences (India)

Metal selective co-ordinative nanostructures were constructed by the supramolecular ... observed an anomalous binding of metal ion to the core sulphur groups causing redox changes in the TTF ... attention on metal-assisted co-ordinative self-assembly ..... M TTF-Py in 1:1 CHCl3: MeCN and (c) photographs showing visual.

Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes.

Science.gov (United States)

Robinson, Matthew E; Nazemi, Ali; Lunn, David J; Hayward, Dominic W; Boott, Charlotte E; Hsiao, Ming-Siao; Harniman, Robert L; Davis, Sean A; Whittell, George R; Richardson, Robert M; De Cola, Luisa; Manners, Ian

2017-09-26

Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEG n , where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG 16 , self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG 16 complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore "static" with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG 12 exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG 12 fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG 7 yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG 16 ), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.

Vertically aligned ZnO nanorods via self-assembled spray pyrolyzed nanoparticles for dye-sensitized solar cells

International Nuclear Information System (INIS)

Dwivedi, Charu; Dutta, V

2012-01-01

Well-aligned zinc oxide (ZnO) nanorods are fabricated on indium-tin-oxide (ITO) coated glass substrates via self-assembly of ZnO nanoparticles created using continuous spray pyrolysis (CoSP) technique. The method involves pre-treatment by dip-coating the substrate with a solution comprising of zinc salt for creating a seed layer, and then spray-pyrolyzed ZnO nanoparticles self-assemble on the pre-treated substrate. The effect of the substrate pre-treatment and the deposition time (t dep ) of nanoparticles is investigated. The results show that the substrate pre-treatment influences the growth of ZnO nanorods which are absent without the pre-treatment. Nanoparticle collection and nanorod growth on different substrates are done simultaneously. The thin films of as-grown nanorods are used as photoelectrode materials to fabricate dye-sensitized solar cells (DSSCs) and the effect of nanorods grown for different times has been studied. The best performance with this cell structure is found for the layer with t dep =15 min, which showed a conversion efficiency of 1.77% for the cell area of 0.25 cm 2

Enzyme-Like Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation

Energy Technology Data Exchange (ETDEWEB)

Hastings, Courtney; Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2010-03-29

A primary goal in the design and synthesis of molecular hosts has been the selective recognition and binding of a variety of guests using non-covalent interactions. Supramolecular catalysis, which is the application of such hosts towards catalysis, has much in common with many enzymatic reactions, chiefly the use of both spatially appropriate binding pockets and precisely oriented functional groups to recognize and activate specific substrate molecules. Although there are now many examples which demonstrate how selective encapsulation in a host cavity can enhance the reactivity of a bound guest, all have failed to reach the degree of increased reactivity typical of enzymes. We now report the catalysis of the Nazarov cyclization by a self-assembled coordination cage, a carbon-carbon bond-forming reaction which proceeds under mild, aqueous conditions. The acceleration in this system is over a million-fold, and represents the first example of supramolecular catalysis that achieves the level of rate enhancement comparable to that observed in several enzymes. We explain the unprecedented degree of rate increase as due to the combination of (a) preorganization of the encapsulated substrate molecule, (b) stabilization of the transition state of the cyclization by constrictive binding, and (c) increase in the basicity of the complexed alcohol functionality.

D-amino acid-containing supramolecular nanofibers for potential cancer therapeutics.

Science.gov (United States)

Wang, Huaimin; Feng, Zhaoqianqi; Xu, Bing

2017-02-01

Nanostructures formed by peptides that self-assemble in water through non-covalent interactions have attracted considerable attention because peptides possess several unique advantages, such as modular design and easiness of synthesis, convenient modification with known functional motifs, good biocompatibility, low immunogenicity and toxicity, inherent biodegradability, and fast responses to a wide range of external stimuli. After about two decades of development, peptide-based supramolecular nanostructures have already shown great potentials in the fields of biomedicine. Among a range of biomedical applications, using such nanostructures for cancer therapy has attracted increased interests since cancer remains the major threat for human health. Comparing with L-peptides, nanostructures containing peptides made of D-amino acid (i.e., D-peptides) bear a unique advantage, biostability (i.e., resistance towards most of endogenous enzymes). The exploration of nanostructures containing D-amino acids, especially their biomedical applications, is still in its infancy. Herein we review the recent progress of D-amino acid-containing supramolecular nanofibers as an emerging class of biomaterials that exhibit unique features for the development of cancer therapeutics. In addition, we give a brief perspective about the challenges and promises in this research direction. Copyright © 2016 Elsevier B.V. All rights reserved.

Topological dynamics in supramolecular rotors.

Science.gov (United States)

Palma, Carlos-Andres; Björk, Jonas; Rao, Francesco; Kühne, Dirk; Klappenberger, Florian; Barth, Johannes V

2014-08-13

Artificial molecular switches, rotors, and machines are set to establish design rules and applications beyond their biological counterparts. Herein we exemplify the role of noncovalent interactions and transient rearrangements in the complex behavior of supramolecular rotors caged in a 2D metal-organic coordination network. Combined scanning tunneling microscopy experiments and molecular dynamics modeling of a supramolecular rotor with respective rotation rates matching with 0.2 kcal mol(-1) (9 meV) precision, identify key steps in collective rotation events and reconfigurations. We notably reveal that stereoisomerization of the chiral trimeric units entails topological isomerization whereas rotation occurs in a topology conserving, two-step asynchronous process. In supramolecular constructs, distinct displacements of subunits occur inducing a markedly lower rotation barrier as compared to synchronous mechanisms of rigid rotors. Moreover, the chemical environment can be instructed to control the system dynamics. Our observations allow for a definition of mechanical cooperativity based on a significant reduction of free energy barriers in supramolecules compared to rigid molecules.

Multifunctional, supramolecular, continuous artificial nacre fibres

Science.gov (United States)

Hu, Xiaozhen; Xu, Zhen; Gao, Chao

2012-10-01

Nature has created amazing materials during the process of evolution, inspiring scientists to studiously mimic them. Nacre is of particular interest, and it has been studied for more than half-century for its strong, stiff, and tough attributes resulting from the recognized ``brick-and-mortar'' (B&M) layered structure comprised of inorganic aragonite platelets and biomacromolecules. The past two decades have witnessed great advances in nacre-mimetic composites, but they are solely limited in films with finite size (centimetre-scale). To realize the adream target of continuous nacre-mimics with perfect structures is still a great challenge unresolved. Here, we present a simple and scalable strategy to produce bio-mimic continuous fibres with B&M structures of alternating graphene sheets and hyperbranched polyglycerol (HPG) binders via wet-spinning assembly technology. The resulting macroscopic supramolecular fibres exhibit excellent mechanical properties comparable or even superior to nacre and bone, and possess fine electrical conductivity and outstanding corrosion-resistance.

Incorporation and Effects of Nanoparticles in a Supramolecular Polymer

Science.gov (United States)

2016-05-01

polymerizations and main-chain supramolecular polymers . Macromolecules. 2009;42:6823–6835. 17. Wojtecki RJ, Meador MA, Rowan SJ. Using the dynamic bond...ARL-TR-7687 ● MAY 2016 US Army Research Laboratory Incorporation and Effects of Nanoparticles in a Supramolecular Polymer by...Laboratory Incorporation and Effects of Nanoparticles in a Supramolecular Polymer by Alice M Savage Oak Ridge Institute of Science and Education

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

International Nuclear Information System (INIS)

Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L.; Siqueira, Jose R.; Zucolotto, Valtencir; Oliveira, Osvaldo N.; Crespilho, Frank N.; Cantanhede da Silva, Welter

2011-01-01

Highlights: → Platforms were assembled from cobalt phthalocyanine, chitosan and carbon nanotubes. → Supramolecular organization of multilayer films was investigated. → Increase of the supramolecular charge transfer after carbon nanotube incorporation. → Functional modulation based on constitutional dynamic chemistry was achieved. - Abstract: The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc} n and {Chit-SWCNTs/CoTsPc} n (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E 1/2 at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)] 5- /[CoTsPc(II)] 4- and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc} 5 multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.

Dynamic Multi-Component Covalent Assembly for the Reversible Binding of Secondary Alcohols and Chirality Sensing

Science.gov (United States)

You, Lei; Berman, Jeffrey S.; Anslyn, Eric V.

2011-01-01

Reversible covalent bonding is often employed for the creation of novel supramolecular structures, multi-component assemblies, and sensing ensembles. In spite of remarkable success of dynamic covalent systems, the reversible binding of a mono-alcohol with high strength is challenging. Here we show that a strategy of carbonyl activation and hemiaminal ether stabilization can be embodied in a four-component reversible assembly that creates a tetradentate ligand and incorporates secondary alcohols with exceptionally high affinity. Evidence is presented that the intermediate leading to binding and exchange of alcohols is an iminium ion. Further, to demonstrate the use of this assembly process we explored chirality sensing and enantiomeric excess determinations. An induced twist in the ligand by a chiral mono-ol results in large Cotton effects in the circular dichroism spectra indicative of the alcohol’s handedness. The strategy revealed in this study should prove broadly applicable for the incorporation of alcohols into supramolecular architecture construction. PMID:22109274

Supra-amphiphiles: a new bridge between colloidal science and supramolecular chemistry.

Science.gov (United States)

Kang, Yuetong; Liu, Kai; Zhang, Xi

2014-06-03

In addition to conventional amphiphiles, an emerging research area is supra-amphiphiles, which are constructed on the basis of noncovalent interactions and dynamic covalent bonds. In this feature article, we have provided a general introduction to the concept, design principles, and topologies of supra-amphiphiles, starting from some rationally tailored building blocks. In addition, we highlight some progress in the functional assembly of supra-amphiphiles, such as responsive nanoscale carriers, antibacterial and antitumor agents, fluorescent-based chemical sensors, and enzyme mimics. The supra-amphiphile is a new bridge between colloidal science and supramolecular chemistry, and it is a field where we can make full use of our imaginative power.

Host-guest supramolecular nanosystems for cancer diagnostics and therapeutics.

Science.gov (United States)

Wang, Lei; Li, Li-li; Fan, Yun-shan; Wang, Hao

2013-07-26

Extensive efforts have been devoted to the construction of functional supramolecular nanosystems for applications in catalysis, energy conversion, sensing and biomedicine. The applications of supramolecular nanosystems such as liposomes, micelles, inorganic nanoparticles, carbon materials for cancer diagnostics and therapeutics have been reviewed by other groups. Here, we will focus on the recent momentous advances in the implementation of typical supramolecular hosts (i.e., cyclodextrins, calixarenes, cucurbiturils and metallo-hosts) and their nanosystems in cancer diagnostics and therapeutics. We discuss the evolutive process of supramolecular nanosystems from the structural control and characterization to their diagnostic and therapeutic function exploitation and even the future potentials for clinical translation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled Thiolated Calix[n]arene (n=4, 6, 8) Films on Gold Electrodes and Application for Electrochemical Determination Dopamine

International Nuclear Information System (INIS)

Zheng, Gang; Chen, Ming; Liu, Xinyue; Zhou, Jun; Xie, Ju; Diao, Guowang

2014-01-01

Highlights: • TCnA/GE was prepared by using a simple self-assembled strategy. • Multilayer self-assembled films of TCnA molecules were fabricated on GE. • TCnA/GE exhibited high supramolecular recognition and enrichment capability. • TC8A/GE showed excellent electrochemical performance for DA. - Abstract: In this study, gold electrodes (GE) modified with three kinds of thiolated calix[4,6,8]arenes (TCnA: TC4A, TC6A, TC8A) were successfully prepared using a simple self-assembly strategy. Three self-assembled films were characterized by cyclic voltammetry measurement, electrochemical impedance spectroscopy, static contact angle measurement and atomic force microscopy. The results confirmed that TCnA molecules effectively absorbed onto the surface of gold electrodes to fabricate the multilayer self-assembled films. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurement showed that the TCnA/GE exhibited high supramolecular recognition and enrichment capability and consequently displayed good electrochemical response toward dopamine (DA). Especially, TC8A/GE exhibited an excellent electrochemical performance for DA with high current densities of 1.5 mA mmol −1 L cm −2 , broad linear range (1 × 10 −6 to 1 × 10 −3 mol L −1 ) and low detection limit (5 × 10 −7 mol L −1 ). The mechanism of supramolecular recognition and enrichment capability of TCnA/GE was discussed

Layer-by-layer cell membrane assembly

Science.gov (United States)

Matosevic, Sandro; Paegel, Brian M.

2013-11-01

Eukaryotic subcellular membrane systems, such as the nuclear envelope or endoplasmic reticulum, present a rich array of architecturally and compositionally complex supramolecular targets that are as yet inaccessible. Here we describe layer-by-layer phospholipid membrane assembly on microfluidic droplets, a route to structures with defined compositional asymmetry and lamellarity. Starting with phospholipid-stabilized water-in-oil droplets trapped in a static droplet array, lipid monolayer deposition proceeds as oil/water-phase boundaries pass over the droplets. Unilamellar vesicles assembled layer-by-layer support functional insertion both of purified and of in situ expressed membrane proteins. Synthesis and chemical probing of asymmetric unilamellar and double-bilayer vesicles demonstrate the programmability of both membrane lamellarity and lipid-leaflet composition during assembly. The immobilized vesicle arrays are a pragmatic experimental platform for biophysical studies of membranes and their associated proteins, particularly complexes that assemble and function in multilamellar contexts in vivo.

Charge Effect on the Formation of Polyoxometalate-Based Supramolecular Polygons Driven by Metal Coordination.

Science.gov (United States)

Piot, Madeleine; Hupin, Sébastien; Lavanant, Hélène; Afonso, Carlos; Bouteiller, Laurent; Proust, Anna; Izzet, Guillaume

2017-07-17

The metal-driven self-assembly of a Keggin-based hybrid bearing two remote pyridine units was investigated. The resulting supramolecular species were identified by combination of 2D diffusion NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS) as a mixture of molecular triangles and squares. This behavior is different from that of the structural analogue Dawson-based hybrid displaying a higher charge, which only led to the formation of molecular triangles. This study highlights the decisive effect of the charge of the POMs in their self-assembly processes that disfavors the formation of large assemblies. An isothermal titration calorimetry (ITC) experiment confirmed the stronger binding in the case of the Keggin hybrids. A correlation between the diffusion coefficient D and the molecular mass M of the POM-based building block and its coordination oligomers was also observed. We show that the diffusion coefficient of these compounds is mainly determined by their occupied volume rather than by their shape.

Implementation of anion-receptor macrocycles in supramolecular tandem assays for enzymes involving nucleotides as substrates, products, and cofactors.

Science.gov (United States)

Florea, Mara; Nau, Werner M

2010-03-07

A supramolecular tandem assay for direct continuous monitoring of nucleotide triphosphate-dependent enzymes such as potato apyrase is described. The underlying principle of the assay relies on the use of anion-receptor macrocycles in combination with fluorescent dyes as reporter pairs. A combinatorial approach was used to identify two complementary reporter pairs, i.e. an amino-gamma-cyclodextrin with 2-anilinonaphtalene-6-sulfonate (ANS) as dye (fluorescence enhancement factor of 17 upon complexation) and a polycationic cyclophane with 8-hydroxy-1,3,6-pyrene trisulfonate (HPTS) as dye (fluorescence decrease by a factor of more than 2000), which allow the kinetic monitoring of potato apyrase activity at different ATP concentration ranges (microM and mM) with different types of photophysical responses (switch-ON and switch-OFF). Competitive fluorescence titrations revealed a differential binding of ATP (strongest competitor) versus ADP and AMP, which constitutes the prerequisite for monitoring enzymatic conversions (dephosphorylation or phosphorylation) involving nucleotides. The assay was tested for different enzyme and substrate concentrations and exploited for the screening of activating additives, namely divalent transition metal ions (Ni(2+), Mg(2+), Mn(2+), and Ca(2+)). The transferability of the assay could be demonstrated by monitoring the dephosphorylation of other nucleotide triphosphates (GTP, TTP, and CTP).

Supramolecular biomaterials : a modular approach towards tissue engineering

NARCIS (Netherlands)

Dankers, P.Y.W.; Meijer, E.W.

2007-01-01

Supramolecular chemistry is an exciting area of science that plays a central role in bringing different disciplines together, ranging from molecular medicine to nanotechnology. Materials science based on supramolecular interactions is an emerging field, which has made important steps forward in the

High-Efficiency Solid-State Dye-Sensitized Solar Cells: Fast Charge Extraction through Self-Assembled 3D Fibrous Network of Crystalline TiO 2 Nanowires

KAUST Repository

Tétreault, Nicolas

2010-12-28

Herein, we present a novel morphology for solid-state dye-sensitized solar cells based on the simple and straightforward self-assembly of nanorods into a 3D fibrous network of fused single-crystalline anatase nanowires. This architecture offers a high roughness factor, significant light scattering, and up to several orders of magnitude faster electron transport to reach a near-record-breaking conversion efficiency of 4.9%. © 2010 American Chemical Society.

Toward a versatile toolbox for cucurbit[n]uril-based supramolecular hydrogel networks through in situ polymerization.

Science.gov (United States)

Liu, Ji; Soo Yun Tan, Cindy; Lan, Yang; Scherman, Oren A

2017-09-15

The success of exploiting cucurbit[ n ]uril (CB[ n ])-based molecular recognition in self-assembled systems has sparked a tremendous interest in polymer and materials chemistry. In this study, polymerization in the presence of host-guest complexes is applied as a modular synthetic approach toward a diverse set of CB[8]-based supramolecular hydrogels with desirable properties, such as mechanical strength, toughness, energy dissipation, self-healing, and shear-thinning. A range of vinyl monomers, including acrylamide-, acrylate-, and imidazolium-based hydrophilic monomers, could be easily incorporated as the polymer backbones, leading to a library of CB[8] hydrogel networks. This versatile strategy explores new horizons for the construction of supramolecular hydrogel networks and materials with emergent properties in wearable and self-healable electronic devices, sensors, and structural biomaterials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3105-3109.

Crystal structure of a supramolecular lithium complex of p-tert-butylcalix[4]arene

Directory of Open Access Journals (Sweden)

Manabu Yamada

2018-05-01

Full Text Available Crystals of a supramolecular lithium complex with a calix[4]arene derivative, namely tetramethanollithium 5,11,17,23-tetra-tert-butyl-25,26,27-trihydroxy-28-oxidocalix[4]arene methanol monosolvate, [Li(CH3OH4](C44H55O4·CH3OH or [Li(CH3OH4]+·(calix[4]arene−]·CH3OH (where calix[4]arene− represents a mono-anion species because of deprotonation of one H atom of the calixarene hydroxy groups, were obtained from p-tert-butylcalix[4]arene reacted with LiH in tetrahydrofuran, followed by recrystallization from methanol. The asymmetric unit comprises one mono-anionic calixarene molecule, one Li+ cation coordinated to four methanol molecules, and one methanol molecule included in the calixarene cavity. The calixarene molecule maintains a cone conformation by intramolecular hydrogen bonding between one phenoxide (–O− and three pendent calixarene hydroxy groups (–OH. The coordinated methanol molecules around the metal cation play a significant role in forming the supramolecular assembly. The crystal structure of this assembly is stabilized by three sets of intermolecular interactions: (i hydrogen bonds involving the –OH and –O− moieties of the calixarene molecules, the –OH groups of the coordinated methanol molecules, and the –OH group of the methanol molecule included in the calixarene cavity; (ii C—H...π interactions between the calixarene molecules and/or the coordinated methanol molecules; (iii O—H...π interactions between the calixarene molecule and the included methanol molecule.

Self-assembled M2L4 coordination cages : Synthesis and potential applications

NARCIS (Netherlands)

Schmidt, Andrea; Casini, Angela; Kuehn, Fritz E.

2014-01-01

Metal-mediated self-assemblies of the general formula MxLy (M = metal ion, L = ligand) have emerged as a promising research area of supramolecular chemistry because of their applicability in various fields such as molecular recognition, catalysis and drug delivery. The focus of this review is on

Quantitative self-assembly prediction yields targeted nanomedicines

Science.gov (United States)

Shamay, Yosi; Shah, Janki; Işık, Mehtap; Mizrachi, Aviram; Leibold, Josef; Tschaharganeh, Darjus F.; Roxbury, Daniel; Budhathoki-Uprety, Januka; Nawaly, Karla; Sugarman, James L.; Baut, Emily; Neiman, Michelle R.; Dacek, Megan; Ganesh, Kripa S.; Johnson, Darren C.; Sridharan, Ramya; Chu, Karen L.; Rajasekhar, Vinagolu K.; Lowe, Scott W.; Chodera, John D.; Heller, Daniel A.

2018-02-01

Development of targeted nanoparticle drug carriers often requires complex synthetic schemes involving both supramolecular self-assembly and chemical modification. These processes are generally difficult to predict, execute, and control. We describe herein a targeted drug delivery system that is accurately and quantitatively predicted to self-assemble into nanoparticles based on the molecular structures of precursor molecules, which are the drugs themselves. The drugs assemble with the aid of sulfated indocyanines into particles with ultrahigh drug loadings of up to 90%. We devised quantitative structure-nanoparticle assembly prediction (QSNAP) models to identify and validate electrotopological molecular descriptors as highly predictive indicators of nano-assembly and nanoparticle size. The resulting nanoparticles selectively targeted kinase inhibitors to caveolin-1-expressing human colon cancer and autochthonous liver cancer models to yield striking therapeutic effects while avoiding pERK inhibition in healthy skin. This finding enables the computational design of nanomedicines based on quantitative models for drug payload selection.

Supramolecular polyaniline hydrogel as a support for urease

International Nuclear Information System (INIS)

Słoniewska, Anna; Pałys, Barbara

2014-01-01

Supramolecular hydrogels of conducting polymers are successfully used in bioelectrochemistry because of their mechanical and swelling properties of gels added to the specific electron transport properties of conducting polymers. We have studied polyaniline-poly(styrene sulfonate) (PANI–PSS) hydrogel as a substrate for the urease. The hydrogels were synthesized at pH = 0 and pH = 5. PANI–PSS hydrogel is a supramolecular self-assembly material consisting of positively-charged PANI chains and negatively-charged PSS chains. The hydrogel was studied by cyclic voltammetry, infrared and Raman spectroscopy and Scanning Electron Microscopy (SEM). Raman spectra revealed presence of phenazine rings in the hydrogel structure. Phenazine rings form covalent cross-linkers contributing to the hydrogel mechanical stability. The covalent cross-linkers influence the cyclic voltammetry responses of the hydrogel in acidic media. We tested the activity of urease immobilized in the PANI–PSS hydrogel by the physical adsorption or by the covalent bonding with the carbodiimide reaction. The enzyme immobilized in hydrogels prepared at higher pH value reveals significantly higher sensitivity. The method of the enzyme immobilization has smaller impact on the sensitivity. All hydrogel sensors reveal largely higher sensitivity to urea comparing to urease immobilized in the typical electrochemically deposited PANI films. The sensitivity of urease covalently bond to the hydrogel obtained at pH = 5 was as high as 1693 μA/(mol dm 3 ). The sensor response was linear in the urea concentration range from 10 −4 to 7 × 10 −2 mol/dm 3

Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

Science.gov (United States)

Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

2017-11-01

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engineering responsive supramolecular biomaterials: Toward smart therapeutics.

Science.gov (United States)

Webber, Matthew J

2016-09-01

Engineering materials using supramolecular principles enables generalizable and modular platforms that have tunable chemical, mechanical, and biological properties. Applying this bottom-up, molecular engineering-based approach to therapeutic design affords unmatched control of emergent properties and functionalities. In preparing responsive materials for biomedical applications, the dynamic character of typical supramolecular interactions facilitates systems that can more rapidly sense and respond to specific stimuli through a fundamental change in material properties or characteristics, as compared to cases where covalent bonds must be overcome. Several supramolecular motifs have been evaluated toward the preparation of "smart" materials capable of sensing and responding to stimuli. Triggers of interest in designing materials for therapeutic use include applied external fields, environmental changes, biological actuators, applied mechanical loading, and modulation of relative binding affinities. In addition, multistimuli-responsive routes can be realized that capture combinations of triggers for increased functionality. In sum, supramolecular engineering offers a highly functional strategy to prepare responsive materials. Future development and refinement of these approaches will improve precision in material formation and responsiveness, seek dynamic reciprocity in interactions with living biological systems, and improve spatiotemporal sensing of disease for better therapeutic deployment.

Fabrication of Two Columns Dye-Sensitized Solar-Cell

International Nuclear Information System (INIS)

Phyu Sin Khaing Oo; Su Su Hlaing; Khin Lay Thwe; Nwe Ni Khin

2011-12-01

A two columns dye-sensitized solar cell has been fabricated using dye extract form teak leaves. This solar cell was assembled with two 20-30 ohms conductive glasses (one for TiO2 coated electrode and another for carbon coated electrode), TiO2 nano-powder P25, iodide electrolyte solution and soft graphite pencil for carbon coating. It was found that the open circuit voltage Voc was 0.688V and the short circuit Isc was 0.724mA

Effectiveness of dye sensitised solar cell under low light condition using wide band dye

Energy Technology Data Exchange (ETDEWEB)

Sahmer, Ahmad Zahrin, E-mail: ahmadzsahmer@gmail.com; Mohamed, Norani Muti, E-mail: noranimuti-mohamed@petronas.com.my; Zaine, Siti Nur Azella, E-mail: ct.azella@gmail.com [Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

2015-07-22

Dye sensistised solar cell (DSC) based on nanocrystalline TiO{sub 2} has the potential to be used in indoor consumer power application. In realizing this, the DSC must be optimized to generate power under low lighting condition and under wider visible light range. The use of wide band dye N749 which has a wider spectrum sensitivity increases the photon conversion to electron between the visible light spectrums of 390nm to 700nm. This paper reports the study on the effectiveness of the dye solar cell with N749 dye under low light condition in generating usable power which can be used for indoor consumer application. The DSC was fabricated using fluorine doped tin oxide (FTO) glass with screen printing method and the deposited TiO{sub 2} film was sintered at 500°C. The TiO{sub 2} coated FTO glass was then soaked in the N749 dye, assembled into test cell, and tested under the standard test condition at irradiance of 1000 W/m{sup 2} with AM1.5 solar soaker. The use of the 43T mesh for the dual pass screen printing TiO{sub 2} paste gives a uniform TiO{sub 2} film layer of 16 µm. The low light condition was simulated using 1/3 filtered irradiance with the solar soaker. The fabricated DSC test cell with the N749 dye was found to have a higher efficiency of 6.491% under low light condition compared to the N719 dye. Under the standard test condition at 1 sun the N749 test cell efficiency is 4.55%. The increases in efficiency is attributed to the wider spectral capture of photon of the DSC with N749 dye. Furthermore, the use of N749 dye is more effective under low light condition as the V{sub OC} decrement is less significant compared to the latter.

Helically structured metal–organic frameworks fabricated by using supramolecular assemblies as templates† †Electronic supplementary information (ESI) available: Detailed TEM images and other extensive figures. See DOI: 10.1039/c4sc03278k Click here for additional data file.

Science.gov (United States)

Wang, Hui; Zhu, Wei; Li, Jian; Tian, Tian; Lan, Yue; Gao, Ning; Wang, Chen; Zhang, Meng; Faul, Charl F. J.

2015-01-01

The controlled formation of MOF-based superstructures with well-defined nanoscale sizes and exquisite morphologies represents a big challenge, but can trigger a new set of properties distinct from their bulk counterparts. Here we report on the use of a self-assembled organic object to template the first example of a nanoscale metal–organic framework (MOF) with a helical morphology. Two prototypical MOFs (HKUST-1 and MIL-100) were used to exemplify the growth of such materials on supramolecular assemblies. Interestingly, it was found that, dependent on the nature of the precursors, not only could well-defined helical MOF nanotubes be facilely fabricated, but novel helical bundle nanostructures could also be formed. These resultant MOF superstructures show additional optical properties and could be used as precursors for the preparation of chiral nanocarbons. PMID:28757993

Supramolecular Photodimerization of Coumarins

Directory of Open Access Journals (Sweden)

Koichi Tanaka

2012-02-01

Full Text Available Stereoselective photodimerization of coumarin and its derivatives in supra-molecular systems is reviewed. The enantioselective photodimerization of coumarin and thiocoumarin in inclusion crystals with optically active host compounds is also described.

Artificial evolution of coumarin dyes for dye sensitized solar cells.

Science.gov (United States)

Venkatraman, Vishwesh; Abburu, Sailesh; Alsberg, Bjørn Kåre

2015-11-07

The design and discovery of novel molecular structures with optimal properties has been an ongoing effort for materials scientists. This field has in general been dominated by experiment driven trial-and-error approaches that are often expensive and time-consuming. Here, we investigate if a de novo computational design methodology can be applied to the design of coumarin-based dye sensitizers with improved properties for use in Grätzel solar cells. To address the issue of synthetic accessibility of the designed compounds, a fragment-based assembly is employed, wherein the combination of chemical motifs (derived from the existing databases of structures) is carried out with respect to user-adaptable set of rules. Rather than using computationally intensive density functional theory (DFT)/ab initio methods to screen candidate dyes, we employ quantitative structure-property relationship (QSPR) models (calibrated from empirical data) for rapid estimation of the property of interest, which in this case is the product of short circuit current (Jsc) and open circuit voltage (Voc). Since QSPR models have limited validity, pre-determined applicability domain criteria are used to prevent unacceptable extrapolation. DFT analysis of the top-ranked structures provides supporting evidence of their potential for dye sensitized solar cell applications.

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

Energy Technology Data Exchange (ETDEWEB)

Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L. [Departamento de Quimica, Centro de Ciencias da Natureza, Universidade Federal do Piaui, Teresina - PI, CEP 64049-550 (Brazil); Siqueira, Jose R. [Instituto de Ciencias Exatas, Naturais e Educacao, Universidade Federal do Triangulo Mineiro, Uberaba - MG, CEP 38025-180, Brazil (Brazil); Zucolotto, Valtencir; Oliveira, Osvaldo N. [Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos - SP, CEP 13560-970 (Brazil); Crespilho, Frank N. [Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC, Santo Andre - SP, CEP 09210-170 (Brazil); Cantanhede da Silva, Welter, E-mail: welter@ufpi.edu.br [Departamento de Quimica, Centro de Ciencias da Natureza, Universidade Federal do Piaui, Teresina - PI, CEP 64049-550 (Brazil)

2011-11-01

Highlights: {yields} Platforms were assembled from cobalt phthalocyanine, chitosan and carbon nanotubes. {yields} Supramolecular organization of multilayer films was investigated. {yields} Increase of the supramolecular charge transfer after carbon nanotube incorporation. {yields} Functional modulation based on constitutional dynamic chemistry was achieved. - Abstract: The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {l_brace}Chit/CoTsPc{r_brace}{sub n} and {l_brace}Chit-SWCNTs/CoTsPc{r_brace}{sub n} (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E{sub 1/2} at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]{sup 5-}/[CoTsPc(II)]{sup 4-} and CoTsPc(II) to CoTsPc(III), respectively. The {l_brace}Chit-SWCNTs/CoTsPc{r_brace}{sub 5} multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the

Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

Directory of Open Access Journals (Sweden)

Timothy J. Deming

2013-01-01

Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

Mesoporous CdS via Network of Self-Assembled Nanocrystals: Synthesis, Characterization and Enhanced Photoconducting Property.

Science.gov (United States)

Patra, Astam K; Banerjee, Biplab; Bhaumik, Asim

2018-01-01

Semiconduction nanoparticles are intensively studied due to their huge potential in optoelctronic applications. Here we report an efficient chemical route for hydrothermal synthesis of aggregated mesoporous cadmium sulfide (CdS) nanoparticles using supramolecular-assembly of ionic and water soluble sodium salicylate as the capping agent. The nanostructure, mesophase, optical property and photoconductivity of these mesoporous CdS materials have been characterized by using small and wide angle powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2-sorption, Raman analysis, Fourier transformed infrared (FT-IR), UV-Visible DSR spectroscopy, and photoconductivity measurement. Wide angle XRD pattern and high resolution TEM image analysis suggested that the particle size of the materials is within 10 nm and the nanoparticles are in well-crystallized cubic phase. Mesoporous CdS nanoparticles showed drastically enhanced photoelectrochemical response under visible light irradiation on entrapping a photosensitizer (dye) molecule in the interparticle spaces. Efficient synthesis strategy and the enhanced photo response in the mesoporous CdS material could facilitate the designing of other porous semiconductor oxide/sulfide and their applications in photon-to-electron conversion processes.

Stoichiometric control of multiple different tectons in coordination-driven self-assembly: preparation of fused metallacyclic polygons.

Science.gov (United States)

Lee, Junseong; Ghosh, Koushik; Stang, Peter J

2009-09-02

We present a general strategy for the synthesis of stable, multicomponent fused polygon complexes in which coordination-driven self-assembly allows for single supramolecular species to be formed from multicomponent self-assembly and the shape of the obtained polygons can be controlled simply by changing the ratio of individual components. The compounds have been characterized by multinuclear NMR spectroscopy and electrospray ionization mass spectrometry.

Novel nanostructures for next generation dye-sensitized solar cells

KAUST Repository

Té treault, Nicolas; Grä tzel, Michael

2012-01-01

Herein, we review our latest advancements in nanostructured photoanodes for next generation photovoltaics in general and dye-sensitized solar cells in particular. Bottom-up self-assembly techniques are developed to fabricate large-area 3D

Deposition of metal Islands, metal clusters and metal containing single molecules on self-assembled monolayers

NARCIS (Netherlands)

Speets, Emiel Adrianus

2005-01-01

The central topic of this thesis is the deposition of metals on Self-Assembled Monolayers (SAMs). Metals are deposited in the form of submicron scale islands, nanometer scale clusters, and as supramolecular, organometallic coordination cages. Several SAMs on various substrates were prepared and

Supramolecular Gold Metallogelators: The Key Role of Metallophilic Interactions

Directory of Open Access Journals (Sweden)

João Carlos Lima

2014-12-01

Full Text Available Gold metallogelators is an emerging area of research. The number of results published in the literature is still scarce. The majority of these gels is observed in organic solvents, and the potential applications are still to be explored. In this work, we present an overview about gold metallogelators divided in two different groups depending on the type of solvent used in the gelation process (organogelators and hydrogelators. A careful analysis of the data shows that aurophilic interactions are a common motif directly involved in gelation involving Au(I complexes. There are also some Au(III derivatives able to produce gels but in this case the organic ligands determine the aggregation process. A last section is included about the potential applications that have been reported until now with this new and amazing class of supramolecular assemblies.

Induced Förster resonance energy transfer by encapsulation of DNA-scaffold based probes inside a plant virus based protein cage

Science.gov (United States)

de Ruiter, Mark V.; Overeem, Nico J.; Singhai, Gaurav; Cornelissen, Jeroen J. L. M.

2018-05-01

Insight into the assembly and disassembly of viruses can play a crucial role in developing cures for viral diseases. Specialized fluorescent probes can benefit the study of interactions within viruses, especially during cell studies. In this work, we developed a strategy based on Förster resonance energy transfer (FRET) to study the assembly of viruses without labeling the exterior of viruses. Instead, we exploit their encapsulation of nucleic cargo, using three different fluorescent ATTO dyes linked to single-stranded DNA oligomers, which are hybridised to a longer DNA strand. FRET is induced upon assembly of the cowpea chlorotic mottle virus, which forms monodisperse icosahedral particles of about 22 nm, thereby increasing the FRET efficiency by a factor of 8. Additionally, encapsulation of the dyes in virus-like particles induces a two-step FRET. When the formed constructs are disassembled, this FRET signal is fully reduced to the value before encapsulation. This reversible behavior makes the system a good probe for studying viral assembly and disassembly. It, furthermore, shows that multi-component supramolecular materials are stabilized in the confinement of a protein cage.

Green-fuel-mediated synthesis of self-assembled NiO nano-sticks for dual applications—photocatalytic activity on Rose Bengal dye and antimicrobial action on bacterial strains

Science.gov (United States)

Iyyappa Rajan, P.; Vijaya, J. Judith; Jesudoss, S. K.; Kaviyarasu, K.; Kennedy, L. John; Jothiramalingam, R.; Al-Lohedan, Hamad A.; Vaali-Mohammed, Mansoor-Ali

2017-08-01

With aim of promoting the employability of green fuels in the synthesis of nano-scaled materials with new kinds of morphologies for multiple applications, successful synthesis of self-assembled NiO nano-sticks was achieved through a 100% green-fuel-mediated hot-plate combustion reaction. The synthesized NiO nano-sticks show excellent photocatalytic activity on Rose Bengal dye and superior antibacterial potential towards both Gram-positive and Gram-negative bacteria.

Modelling Polar Self Assembly

Science.gov (United States)

Olvera de La Cruz, Monica; Sayar, Mehmet; Solis, Francisco J.; Stupp, Samuel I.

2001-03-01

Recent experimental studies in our group have shown that self assembled thin films of noncentrosymmetric supramolecular objects composed of triblock rodcoil molecules exhibit finite polar order. These aggregates have both long range dipolar and short range Ising-like interactions. We study the ground state of a simple model with these competing interactions. We find that the competition between Ising-like and dipolar forces yield a periodic domain structure, which can be controlled by adjusting the force constants and film thickness. When the surface forces are included in the potential, the system exhibits a finite macroscopic polar order.

Supramolecule-to-supramolecule transformations of coordination-driven self-assembled polygons.

Science.gov (United States)

Zhao, Liang; Northrop, Brian H; Stang, Peter J

2008-09-10

Two types of supramolecular transformations, wherein a self-assembled Pt(II)-pyridyl metal-organic polygon is controllably converted into an alternative polygon, have been achieved through the reaction between cobalt carbonyl and the acetylene moiety of a dipyridyl donor ligand. A [6 + 6] hexagon is transformed into two [3 + 3] hexagons, and a triangle-square mixture is converted into [2 + 2] rhomboids. 1H and 31P NMR spectra are used to track the transformation process and evaluate the yield of new self-assembled polygons. Such transformed species are identified by electrospray ionization (ESI) mass spectrometry. This new kind of supramolecule-to-supramolecule transformations provides a viable means for constructing, and then converting, new self-assembled polygons.

Three's company: co-crystallization of a self-assembled S(4) metallacyclophane with two diastereomeric metallacycle intermediates.

Science.gov (United States)

Lindquist, Nathan R; Carter, Timothy G; Cangelosi, Virginia M; Zakharov, Lev N; Johnson, Darren W

2010-05-28

Three discrete supramolecular self-assembled arsenic(iii) complexes including an unusual S(4)-symmetric tetranuclear [As(4)L(2)Cl(4)] metallacyclophane and two diastereomeric cis/trans-[As(2)LCl(2)] metallacycle intermediates co-crystallize within a single crystal lattice.

Nanotrumpets and circularly polarized luminescent nanotwists hierarchically self-assembled from an achiral C3-symmetric ester.

Science.gov (United States)

Sang, Yutao; Duan, Pengfei; Liu, Minghua

2018-04-17

An achiral C3-symmetric molecule was found to self-assemble into various hierarchical nanostructures such as nanotwists, nanotrumpets and nanobelts, in which the twisted fibers showed supramolecular chirality as well as circularly polarized luminescence although the compound is achiral.

Self-assembly mechanism of 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol and control of the supramolecular chirality.

Science.gov (United States)

Li, Jingjing; Fan, Kaiqi; Guan, Xidong; Yu, Yingzhe; Song, Jian

2014-11-11

Dibenzylidene-D-sorbitol (DBS) and its derivatives are known to form gels in organic solvents; however, the mechanism of the gel formation has been a subject of much debate. The present work is undertaken to elucidate the organization mechanism of a DBS derivative, 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol (DCDBS), by taking into account the solvent effects and comparing the experiment data with theoretical calculation. These molecules form smooth nonhelical fibers with a rest circular dichroism (CD) signal in polar solvents, in contrast to rope-liked left-helical fibers with a strong negative CD signal observed in nonpolar solvents. The molecular complexes thus formed were characterized by means of Fourier transform infrared spectra, ultraviolet-visible spectra, X-ray diffraction patterns, static contact angles, and theoretical calculations. It was proposed that the interactions between the gelator and the solvents could subtly change the stacking of the molecules and hence their self-assembled nanostructures. In nonpolar solvents, the gelator molecules appear as a distorted T-shaped structure with the 6-OH forming intermolecular hydrogen bonds with the acetal oxygens of adjacent gelator molecule. In addition, because of differential stacking interactions on both sides of the 10-member ring skeleton of the gelator, the oligomers may assemble in a helix fashion to minimize the energy, leading to helical fibers. In polar solvents, however, the gelator molecules show a rigid planelike structure and thus stack on top of each other because of strong parallel-displaced π interactions. The balanced driving force on both sides of the 10-member ring skeleton made it difficult for the dimers to bend, thus resulting in nonhelical nanostructure. As expected from the mechanisms proposed here, twisted ribbon fibers with a medium strength CD signal were obtained when solvents of different polarities were mixed. Thus, solvent effects revealed in this work represent an

Self-assembly of pi-conjugated peptides in aqueous environments leading to energy-transporting bioelectronic nanostructures

Energy Technology Data Exchange (ETDEWEB)

Tavor, John [Johns Hopkins Univ., Baltimore, MD (United States)

2016-12-06

The realization of new supramolecular pi-conjugated organic structures inspired and driven by peptide-based self-assembly will offer a new approach to interface with the biotic environment in a way that will help to meet many DOE-recognized grand challenges. Previously, we developed pi-conjugated peptides that undergo supramolecular self-assembly into one-dimensional (1-D) organic electronic nanomaterials under benign aqueous conditions. The intermolecular interactions among the pi-conjugated organic segments within these nanomaterials lead to defined perturbations of their optoelectronic properties and yield nanoscale conduits that support energy transport within individual nanostructures and throughout bulk macroscopic collections of nanomaterials. Our objectives for future research are to construct and study biomimetic electronic materials for energy-related technology optimized for harsher non-biological environments where peptide-driven self-assembly enhances pi-stacking within nanostructured biomaterials, as detailed in the following specific tasks: (1) synthesis and detailed optoelectronic characterization of new pi-electron units to embed within homogeneous self assembling peptides, (2) molecular and data-driven modeling of the nanomaterial aggregates and their higher-order assemblies, and (3) development of new hierarchical assembly paradigms to organize multiple electronic subunits within the nanomaterials leading to heterogeneous electronic properties (i.e. gradients and localized electric fields). These intertwined research tasks will lead to the continued development and fundamental mechanistic understanding of a powerful bioinspired materials set capable of making connections between nanoscale electronic materials and macroscopic bulk interfaces, be they those of a cell, a protein or a device.

Monitoring the layer-by-layer self-assembly of graphene and graphene oxide by spectroscopic ellipsometry.

Science.gov (United States)

Zhou, Kai-Ge; Chang, Meng-Jie; Wang, Hang-Xing; Xie, Yu-Long; Zhang, Hao-Li

2012-01-01

Thin films of graphene oxide, graphene and copper (II) phthalocyanine dye have been successfully fabricated by electrostatic layer-by-layer (LbL) assembly approach. We present the first variable angle spectroscopic ellipsometry (VASE) investigation on these graphene-dye hybrid thin films. The thickness evaluation suggested that our LbL assembly process produces highly uniform and reproducible thin films. We demonstrate that the refractive indices of the graphene-dye thin films undergo dramatic variation in the range close to the absorption of the dyes. This investigation provides new insight to the optical properties of graphene containing thin films and shall help to establish an appropriate optical model for graphene-based hybrid materials.

From supramolecular polymers to multi-component biomaterials.

Science.gov (United States)

Goor, Olga J G M; Hendrikse, Simone I S; Dankers, Patricia Y W; Meijer, E W

2017-10-30

The most striking and general property of the biological fibrous architectures in the extracellular matrix (ECM) is the strong and directional interaction between biologically active protein subunits. These fibers display rich dynamic behavior without losing their architectural integrity. The complexity of the ECM taking care of many essential properties has inspired synthetic chemists to mimic these properties in artificial one-dimensional fibrous structures with the aim to arrive at multi-component biomaterials. Due to the dynamic character required for interaction with natural tissue, supramolecular biomaterials are promising candidates for regenerative medicine. Depending on the application area, and thereby the design criteria of these multi-component fibrous biomaterials, they are used as elastomeric materials or hydrogel systems. Elastomeric materials are designed to have load bearing properties whereas hydrogels are proposed to support in vitro cell culture. Although the chemical structures and systems designed and studied today are rather simple compared to the complexity of the ECM, the first examples of these functional supramolecular biomaterials reaching the clinic have been reported. The basic concept of many of these supramolecular biomaterials is based on their ability to adapt to cell behavior as a result of dynamic non-covalent interactions. In this review, we show the translation of one-dimensional supramolecular polymers into multi-component functional biomaterials for regenerative medicine applications.

Monolayer self-assembly at liquid-solid interfaces: chirality and electronic properties of molecules at surfaces

International Nuclear Information System (INIS)

Amabilino, David B; Gomar-Nadal, Elba; Veciana, Jaume; Rovira, Concepcio; Iavicoli, Patrizia; PuigmartI-Luis, Josep; Feyter, Steven De; Abdel-Mottaleb, Mohamed M; Mamdouh, Wael; Psychogyiopoulou, Krystallia; Xu Hong; Lazzaroni, Roberto; Linares, Mathieu; Minoia, Andrea

2008-01-01

The spontaneous formation of supramolecular assemblies at the boundary between solids and liquids is a process which encompasses a variety of systems with diverse characteristics: chemisorbed systems in which very strong and weakly reversible bonds govern the assembly and physisorbed aggregates which are dynamic thanks to the weaker interactions between adsorbate and surface. Here we review the interest and advances in the study of chiral systems at the liquid-solid interface, and also the application of this configuration for the study of systems of interest in molecular electronics, self-assembled from the bottom up

Integrated effect of supramolecular self-assembled sandwich-like melamine cyanurate/MoS{sub 2} hybrid sheets on reducing fire hazards of polyamide 6 composites

Energy Technology Data Exchange (ETDEWEB)

Feng, Xiaming [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou, Jiangsu 215123 (China); Wang, Xin, E-mail: wxcmx@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Cai, Wei; Hong, Ningning [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Hu, Yuan, E-mail: yuanhu@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou, Jiangsu 215123 (China); Liew, Kim Meow [Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou, Jiangsu 215123 (China); Department of Architectural and Civil Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon (Hong Kong)

2016-12-15

A novel strategy of using supramolecular self-assembly for preparing sandwich-like melamine cyanurate/MoS{sub 2} sheets as the hybrid flame retardants for polyamide 6 (PA6) is reported for the first time. The introduction of MoS{sub 2} sheets function not only as a template to induce the formation of two-dimensional melamine cyanurate capping layers but also as a synergist to generate integrated flame-retarding effect of hybrid sheets, as well as a high-performance smoke suppressor to reduce fire hazards of PA6 materials. Once incorporating this well-designed structures (4 wt%) into PA6 matrix, there resulted in a remarkable drop (40%) in the peak heat release rate and a 25% reduction in total heat release. Moreover, the smoke production and pyrolysis gaseous products were efficiently suppressed by the addition of sandwich-like hybrid sheets. The integrated functions consisting of inherent flame retarding effect, physical barrier performance and catalytic activity are believed to the crucial guarantee for the reduced fire hazards of PA6 nanocomposites. Furthermore, this novel strategy with facile and scalable features may provide reference for developing various kinds of MoS{sub 2} based hybrid sheets for diverse applications.

Plastic encapsulated, dye sensitised photovoltaic cells

Energy Technology Data Exchange (ETDEWEB)

Potter, R.J.; Otley, L.C.; Durrant, J.R.; Haque, S.; Xu, C. [Imperial College of Science, Technology and Medicine, London (United Kingdom); Holmes, A.B.; Park, T.; Schulte, N. [Cambridge Univ. (United Kingdom)

2004-07-01

The report presents the results of a collaborative project that aimed to demonstrate the technical feasibility of a plastic-encapsulated, solid state, dye-sensitised solar cell (DSSC) with an energy conversion efficiency (ECE) of at least 3%. DSSCs offer a possible 'step change' in photovoltaic technology resulting in lower costs compared with existing technologies. The project involved a series of eight main tasks: the development of first and second generation HTM electrolytes; the development of polymer-supported electrolytes; the development of low temperature electrode coating procedures; dye development; cell assembly and testing; component integration; and overall process development. A wide range of innovative HTMs have been synthesised, including materials incorporating both hole-transporting and ion-chelating functional groups. The ruthenium-based dye, N3, remained the preferred sensitising component. The project has produced a system that can routinely achieve over 5% ECE at 0.1 Sun illumination on 1 cm{sup 2} cells using polymer-supported electrolytes.

Mesoporous anatase TiO_2 microspheres with interconnected nanoparticles delivering enhanced dye-loading and charge transport for efficient dye-sensitized solar cells

International Nuclear Information System (INIS)

Chu, Liang; Qin, Zhengfei; Zhang, Qiaoxia; Chen, Wei; Yang, Jian; Yang, Jianping; Li, Xing’ao

2016-01-01

Graphical abstract: The photoelectrodes of DSSCs consisted of mesoporous anatase TiO_2 microspheres with interconnected nanoparticles. The interconnected nanoparticles enhance dye-loading capacity and charge transport. - Highlights: • The mesoporous anatase TiO_2 microspheres were synthesized by a template-free, one-step fast solvothermal process. • The mesoporous anatase TiO_2 microspheres with interconnected nanoparticles have the advantages of large surface area and connected-structure for electron transfer. • The mesoporous anatase TiO_2 microspheres were further utilized as efficient photoelectrodes for dye-sensitized solar cells. - Abstract: Mesoporous anatase TiO_2 microspheres with interconnected nanostructures meet both large surface area and connected-structure for electron transfer as ideal nano/micromaterials for application in solar cells, energy storage, catalysis, water splitting and gas sensing. In this work, mesoporous anatase TiO_2 microspheres consisting of interconnected nanoparticles were synthesized by template-free, one-step fast solvothermal process, where urea was used as capping agent to control phase and promote oriented growth. The morphology was assembled by nucleation-growth-assembly-mechanism. The mesoporous anatase TiO_2 microspheres with interconnected nanoparticles were further utilized as efficient photoelectrodes of dye-sensitized solar cells (DSSCs), which were beneficial to capacity of dye loading and charge transfer. The power conversion efficiency (PCE) based on the optimized thickness of TiO_2 photoelectrodes was up to 7.13% under standard AM 1.5 G illumination (100 mW/cm"2).

From ring-in-ring to sphere-in-sphere: self-assembly of discrete 2D and 3D architectures with increasing stability.

Science.gov (United States)

Sun, Bin; Wang, Ming; Lou, Zhichao; Huang, Mingjun; Xu, Chenglong; Li, Xiaohong; Chen, Li-Jun; Yu, Yihua; Davis, Grant L; Xu, Bingqian; Yang, Hai-Bo; Li, Xiaopeng

2015-02-04

Directed by increasing the density of coordination sites (DOCS) to increase the stability of assemblies, discrete 2D ring-in-rings and 3D sphere-in-sphere were designed and self-assembled by one tetratopic pyridyl-based ligand with 180° diplatinum(II) acceptors and naked Pd(II), respectively. The high DOCS resulted by multitopic ligand provided more geometric constraints to form discrete structures with high stability. Compared to reported supramolecular hexagons and polyhedra by ditotpic ligands, the self-assembly of such giant architectures using multitopic ligands with all rigid backbone emphasized the structural integrity with precise preorganization of entire architecture, and required elaborate synthetic operations for ligand preparation. In-depth structural characterization was conducted to support desired structures, including multinuclear NMR ((1)H, (31)P, and (13)C) analysis, 2D NMR spectroscopy (COSY and NOESY), diffusion-ordered NMR spectroscopy (DOSY), multidimensional mass spectrometry, TEM and AFM. Furthermore, a quantitative definition of DOCS was proposed to compare 2D and 3D structures and correlate the DOCS and stability of assemblies in a quantitative manner. Finally, ring-in-rings in DMSO or DMF could undergo hierarchical self-assembly into the ordered nanostructures and generated translucent supramolecular metallogels.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer.

Science.gov (United States)

Baker, Matthew B; Albertazzi, Lorenzo; Voets, Ilja K; Leenders, Christianus M A; Palmans, Anja R A; Pavan, Giovanni M; Meijer, E W

2015-02-20

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

Science.gov (United States)

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

2015-02-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Small molecule-guided thermoresponsive supramolecular assemblies

KAUST Repository

Rancatore, Benjamin J.

2012-10-23

Small organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.

Small molecule-guided thermoresponsive supramolecular assemblies

KAUST Repository

Rancatore, Benjamin J.; Mauldin, Clayton E.; Frechet, Jean; Xu, Ting

2012-01-01

Small organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.

[1]Benzothieno[3,2-b]benzothiophene-Based Organic Dyes for Dye-Sensitized Solar Cells.

Science.gov (United States)

Capodilupo, Agostina L; Fabiano, Eduardo; De Marco, Luisa; Ciccarella, Giuseppe; Gigli, Giuseppe; Martinelli, Carmela; Cardone, Antonio

2016-04-15

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

Octanol-assisted liposome assembly on chip

Science.gov (United States)

Deshpande, Siddharth; Caspi, Yaron; Meijering, Anna E. C.; Dekker, Cees

2016-01-01

Liposomes are versatile supramolecular assemblies widely used in basic and applied sciences. Here we present a novel microfluidics-based method, octanol-assisted liposome assembly (OLA), to form monodisperse, cell-sized (5-20 μm), unilamellar liposomes with excellent encapsulation efficiency. Akin to bubble blowing, an inner aqueous phase and a surrounding lipid-carrying 1-octanol phase is pinched off by outer fluid streams. Such hydrodynamic flow focusing results in double-emulsion droplets that spontaneously develop a side-connected 1-octanol pocket. Owing to interfacial energy minimization, the pocket splits off to yield fully assembled solvent-free liposomes within minutes. This solves the long-standing fundamental problem of prolonged presence of residual oil in the liposome bilayer. We demonstrate the unilamellarity of liposomes with functional α-haemolysin protein pores in the membrane and validate the biocompatibility by inner leaflet localization of bacterial divisome proteins (FtsZ and ZipA). OLA offers a versatile platform for future analytical tools, delivery systems, nanoreactors and synthetic cells.

Narcissistic self-sorting in self-assembled cages of rare Earth metals and rigid ligands.

Science.gov (United States)

Johnson, Amber M; Wiley, Calvin A; Young, Michael C; Zhang, Xing; Lyon, Yana; Julian, Ryan R; Hooley, Richard J

2015-05-04

Highly selective, narcissistic self-sorting can be achieved in the formation of self-assembled cages of rare earth metals with multianionic salicylhydrazone ligands. The assembly process is highly sensitive to the length of the ligand and the coordination geometry. Most surprisingly, high-fidelity sorting is possible between ligands of identical coordination angle and geometry, differing only in a single functional group on the ligand core, which is not involved in the coordination. Supramolecular effects allow discrimination between pendant functions as similar as carbonyl or methylene groups in a complex assembly process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polo-like kinase phosphorylation determines Caenorhabditis elegans centrosome size and density by biasing SPD-5 toward an assembly-competent conformation

Directory of Open Access Journals (Sweden)

Oliver Wueseke

2016-10-01

Full Text Available Centrosomes are major microtubule-organizing centers composed of centrioles surrounded by an extensive proteinacious layer called the pericentriolar material (PCM. In Caenorhabditis elegans embryos, the mitotic PCM expands by Polo-like kinase 1 (PLK-1 phosphorylation-accelerated assembly of SPD-5 molecules into supramolecular scaffolds. However, how PLK-1 phosphorylation regulates SPD-5 assembly is not known. We found that a mutant version of SPD-5 that is insensitive to PLK-1 phosphorylation (SPD-54A could localize to PCM but was unable to rescue the reduction in PCM size and density when wild-type SPD-5 levels were decreased. In vitro, purified SPD-54A self-assembled into functional supramolecular scaffolds over long time scales, suggesting that phosphorylation only controls the rate of SPD-5 scaffold assembly. Furthermore, the SPD-5 scaffold, once assembled, remained intact and supported microtubule nucleation in the absence of PLK-1 activity in vivo. We conclude that PLK-1 is required for rapid assembly of the PCM scaffold but not for scaffold maintenance or function. Based on this idea, we developed a theoretical model that adequately predicted PCM growth rates in different mutant conditions in vivo. We propose that PLK-1 phosphorylation-dependent conversion of SPD-5 into an assembly-competent form underlies PCM formation in vivo and that the rate of this conversion determines final PCM size and density.

Supra-molecular networks for CO2 capture

Science.gov (United States)

Sadowski, Jerzy; Kestell, John

Utilizing capabilities of low-energy electron microscopy (LEEM) for non-destructive interrogation of the real-time molecular self-assembly, we have investigated supramolecular systems based on carboxylic acid-metal complexes, such as trimesic and mellitic acid, doped with transition metals. Such 2D networks can act as host systems for transition-metal phthalocyanines (MPc; M = Fe, Ti, Sc). The electrostatic interactions of CO2 molecules with transition metal ions can be tuned by controlling the type of TM ion and the size of the pore in the host network. We further applied infrared reflection-absorption spectroscopy (IRRAS) to determine of the molecular orientation of the functional groups and the whole molecule in the 2D monolayers of carboxylic acid. The kinetics and mechanism of the CO2 adsorption/desorption on the 2D molecular network, with and without the TM ion doping, have been also investigated. This research used resources of the Center for Functional Nanomaterials, which is the U.S. DOE Office of Science User Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

Building inorganic supramolecular architectures using principles adopted from the organic solid state

Directory of Open Access Journals (Sweden)

Marijana Đaković

2018-01-01

Full Text Available In order to develop transferable and practical avenues for the assembly of coordination complexes into architectures with specific dimensionality, a strategy utilizing ligands capable of simultaneous metal coordination and self-complementary hydrogen bonding is presented. The three ligands used, 2(1H-pyrazinone, 4(3H-pyrimidinone and 4(3H-quinazolinone, consistently deliver the required synthetic vectors in a series of CdII coordination polymers, allowing for reproducible supramolecular synthesis that is insensitive to the different steric and geometric demands from potentially disruptive counterions. In all nine crystallographically characterized compounds presented here, directional intermolecular N—H...O hydrogen bonds between ligands on adjacent complex building blocks drive the assembly and orientation of discrete building blocks into largely predictable topologies. Furthermore, whether the solids are prepared from solution or through liquid-assisted grinding, the structural outcome is the same, thus emphasizing the robustness of the synthetic protocol. The details of the molecular recognition events that take place in this series of compounds have been clearly delineated and rationalized in the context of calculated molecular electrostatic potential surfaces.

Dye-sensitized solar cells: a successful combination of materials

Directory of Open Access Journals (Sweden)

Longo Claudia

2003-01-01

Full Text Available Dye-sensitized TiO2 solar cells, DSSC, are a promising alternative for the development of a new generation of photovoltaic devices. DSSC are a successful combination of materials, consisting of a transparent electrode coated with a dye-sensitized mesoporous film of nanocrystalline particles of TiO2, an electrolyte containing a suitable redox-couple and a Pt coated counter-electrode. In general, Ru bipyridyl complexes are used as the dye sensitizers. The light-to-energy conversion performance of the cell depends on the relative energy levels of the semiconductor and dye and on the kinetics of the electron-transfer processes at the sensitized semiconductor | electrolyte interface. The rate of these processes depends on the properties of its components. This contribution presents a discussion on the influence of each of the materials which constitute the DSSC of the overall process for energy conversion. An overview of the results obtained for solid-state dye-sensitized TiO2 solar cells assembled with polymer electrolytes is also presented.

Supramolecular Nanocomposites Under Confinement: Chiral Optically Active Nanoparticle Assemblies and Beyond

Science.gov (United States)

Bai, Peter; Yang, Sui; Bao, Wei; Salmeron, Miquel; Zhang, Xiang; Xu, Ting

2015-03-01

Block copolymer-based supramolecules provide a versatile platform to direct the self-assembly of nanoparticles (NPs) into precisely controlled nanostructures in bulk and thin film geometries. A supramolecule, PS-b-P4VP(PDP), composed of the small molecule 3-pentadecylphenol (PDP) hydrogen bonded to a diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), was subjected to 2-D volume confinement in cylindrical anodic aluminum oxide (AAO) membrane pores. TEM and 3-D TEM tomography reveal that the morphologies accessible by the supramolecule and supramolecule/NP composites, such as NP clusters, arrays, stacked rings, and single and double helical ribbons, are significantly different from those in the bulk or thin film. Furthermore, single molecule dark field scattering measurements demonstrate strong chiral optical response of single helical Au NP ribbon nanostructures in the near infrared wavelength regime. These studies demonstrate 2-D confinement to be an effective means to tailor self-assembled NP structure within supramolecule nanocomposites and pave the way for this assembly approach to be applied towards next generation chiral metamaterials and optoelectronic devices.

Self-assembling peptide-based building blocks in medical applications

Energy Technology Data Exchange (ETDEWEB)

Acar, Handan; Srivastava, Samanvaya; Chung, Eun Ji; Schnorenberg, Mathew R.; Barrett, John C.; LaBelle, James L.; Tirrell, Matthew

2017-02-01

Peptides and peptide-conjugates, comprising natural and synthetic building blocks, are an increasingly popular class of biomaterials. Self-assembled nanostructures based on peptides and peptide-conjugates offer advantages such as precise selectivity and multifunctionality that can address challenges and limitations in the clinic. In this review article, we discuss recent developments in the design and self-assembly of various nanomaterials based on peptides and peptide-conjugates for medical applications, and categorize them into two themes based on the driving forces of molecular self-assembly. First, we present the self-assembled nanostructures driven by the supramolecular interactions between the peptides, with or without the presence of conjugates. The studies where nanoassembly is driven by the interactions between the conjugates of peptide-conjugates are then presented. Particular emphasis is given to in vivo studies focusing on therapeutics, diagnostics, immune modulation and regenerative medicine. Finally, challenges and future perspectives are presented.

Phycocyanin assemblies onto nanostructured TiO2 for photovoltaic cells

Directory of Open Access Journals (Sweden)

Paula Enciso

2013-01-01

Full Text Available The use of renewable energies is of increasing importance due to depletion of fossil fuel sources and environmental damages caused by their utilization. The energy available from the sun is clean and widely distributed. Solar cells are devices used to convert solar energy into electricity. Among them, dye sensitized solar cells are an interesting alternative to conventional silicon ones, because of their low cost and simple assembly process. They are made of a semiconductor with colored dyes adsorbed onto the surface that work as antennas to catch energy in the visible range of the spectra. In this work, nanostructured TiO2 was synthesized and the protein phycocyanin was used as dye. TiO2 was characterized by electron microscopy, X ray diffraction and infrared spectroscopy (FTIR. Phycocyanin was extracted from commercial Spirulina spp. capsules. The assembly process of the electrode covered with TiO2 and phycocyanin was controlled by cyclic voltammetry and FTIR. Results were in accordance with the assembling of an electrode sensitized with phycocyanin.

Anticancer efficacy of a supramolecular complex of a 2-diethylaminoethyl–dextran–MMA graft copolymer and paclitaxel used as an artificial enzyme

Directory of Open Access Journals (Sweden)

Yasuhiko Onishi

2014-12-01

Full Text Available The anticancer efficacy of a supramolecular complex that was used as an artificial enzyme against multi-drug-resistant cancer cells was confirmed. A complex of diethylaminoethyl–dextran–methacrylic acid methylester copolymer (DDMC/paclitaxel (PTX, obtained with PTX as the guest and DDMC as the host, formed a nanoparticle 50–300 nm in size. This complex is considered to be useful as a drug delivery system (DDS for anticancer compounds since it formed a stable polymeric micelle in water. The resistance of B16F10 melanoma cells to PTX was shown clearly through a maximum survival curve. Conversely, the DDMC/PTX complex showed a superior anticancer efficacy and cell killing rate, as determined through a Michaelis–Menten-type equation, which may promote an allosteric supramolecular reaction to tubulin, in the same manner as an enzymatic reaction. The DDMC/PTX complex showed significantly higher anticancer activity compared to PTX alone in mouse skin in vivo. The median survival times of the saline, PTX, DDMC/PTX4 (particle size 50 nm, and DDMC/PTX5 (particle size 290 nm groups were 120 h (treatment (T/control (C, 1.0, 176 h (T/C, 1.46, 328 h (T/C, 2.73, and 280 h (T/C, 2.33, respectively. The supramolecular DDMC/PTX complex showed twice the effectiveness of PTX alone (p < 0.036. Above all, the DDMC/PTX complex is not degraded in cells and acts as an intact supramolecular assembly, which adds a new species to the range of DDS.

Versatile ruthenium(II) dye towards blue-light emitter and dye-sensitizer for solar cells

Science.gov (United States)

Zanoni, Kassio P. S.; Amaral, Ronaldo C.; Murakami Iha, Neyde Y.; Abreu, Felipe D.; de Carvalho, Idalina M. M.

2018-06-01

A versatile Ru(II) complex bearing an anthracene moiety was synthesized in our search for suitable compounds towards efficient molecular devices. The new engineered dye, cis‑[Ru(dcbH2)(NCS)2(mbpy‑anth)] (dcbH2 = 2,2‧‑bipyridyl‑4,4‧‑dicarboxylic acid, mbpy‑anth = 4‑[N‑(2‑anthryl)carbamoyl]‑4‧‑methyl‑2,2‧‑bipyridine), exhibits a blueish emission in a vibronically structured spectrum ascribed to the fluorescence of a 1LCAnth (ligand centered) excited state in the anthracene and has a potential to be exploited in the fields of smart lighting and displays. This complex was also employed in dye-sensitized solar cells with fairly efficient solar energy conversion with the use of self-assembled TiO2 compact layers beneath the TiO2 mesoporous film to prevent meso‑TiO2/dye back reactions. Further photoelectrochemical investigations through incident photon-to-current efficiency and electrochemical impedance spectra showed that the all-nano-TiO2 compact layer acts as contact layers that increase the electron harvesting in the external circuit, enhancing efficiencies up to 50%.

Synthesis of anatase TiO2 nanoparticles with beta-cyclodextrin as a supramolecular shell.

Science.gov (United States)

Li, Landong; Sun, Xiaohong; Yang, Yali; Guan, Naijia; Zhang, Fuxiang

2006-11-20

We report a novel, green hydrothermal-synthesis route to well-dispersed anatase TiO2 nanoparticles with particle sizes of 9-16 nm in the presence of beta-CD (beta-cyclodextrin). During the synthesis process, the CD-containing synthesis mixture assembled in both longitudinal and latitudinal directions. Driven by the interaction between molecules, the beta-CDs assembled in the longitudinal direction to form long-chain compounds, whereas in the latitudinal direction, they tended to form regular aggregates through coordination with the Ti species from the hydrolysis of tetrabutyl titanate. In view of the effect of the coordination and the steric hindrance of beta-CDs as a supramolecular shell, homogeneous nuclei and slow growth of TiO2 crystals during the synthesis process was observed, which was responsible for the formation of uniform TiO2 nanoparticles. The low beta-CD dosage and the high product yield (>90%) demonstrated well the potential of this synthesis route in the large-scale industrial production of anatase nanoparticles.

Dielectric properties of supramolecular ionic structures obtained from multifunctional carboxylic acids and amines

DEFF Research Database (Denmark)

Gonzalez, Lidia; Yu, Liyun; Hvilsted, Søren

2014-01-01

The dielectric properties of several supramolecular ionic polymers and networks, linked by the ammonium salts of hexamethylene diamine (HMDA), tris(2-aminoethyl)amine (TAEA), poly(propylene imine) (PPI) dendrimers and two short bis carboxymethyl ether-terminated poly(ethylene glycol)s (Di......COOH-PEG), are reported in this paper. All supramolecular ionic polymers and networks exhibit very high relative dielectric permittivities ( 3 0 )( 10 2 – 10 6 ) at low frequencies, and signi fi cantly lower values (from 1 up to 26) at high frequencies. Additionally, the dielectric properties of supramolecular ionic......), are investigated. Here the relative dielectric permittivities of the supramolecular ionic structures formed with the multifunctional carboxylic acids were lower than those from the supramolecular ionic structures formed with the two carboxymethyl ether-terminated poly(ethylene glycol)s....

Solid-phase based synthesis of ureidopyrimidinone-peptide conjugates for supramolecular biomaterials

NARCIS (Netherlands)

Feijter, de I.; Goor, O.J.G.M.; Hendrikse, S.I.S.; Comellas Aragones, M.; Sontjens, S.H.M.; Zaccaria, S.; Fransen, P.P.K.H.; Peeters, J.W.; Milroy, L.G.; Dankers, P.Y.W.

2015-01-01

Supramolecular polymers have shown to be powerful scaffolds for tissue engineering applications. Supramolecular biomaterials functionalized with ureidopyrimidinone (UPy) moieties, which dimerize via quadruple hydrogen-bond formation, are eminently suitable for this purpose. The conjugation of the

From supramolecular electrochemistry to molecular-level devices

Energy Technology Data Exchange (ETDEWEB)

Credi, Alberto; Ferrer Ribera, Belen; Venturi, Margherita

2004-09-15

Supramolecular (multi-component) systems can perform complex functions which result from the cooperation of actions performed by suitably selected molecular components. Looking at supramolecular systems, from the viewpoint of the functions, shows that the concept of macroscopic device can be extended to molecular level. Nature exploits very complex molecular-level devices to substain life, and, in the last twenty years, the development of supramolecular chemistry has allowed the construction of simple molecular-level devices, that are of interest not only for basic research, but also for the growth of nanoscience and nanotechnology. Molecular-level devices operate via electronic and/or nuclear rearrangements, and like macroscopic devices, they need energy to operate and signals to communicate with the operator. Electrochemistry can provide the answer to this dual requirement, since electrons/holes, besides supplying the energy needed to make a devices work, can also be useful to 'read' the state of the system and thus to control and monitor the operation of the device. In this article, some examples of molecular-level devices investigated in our laboratory will be reviewed.

Imaging and Quantitation of a Succession of Transient Intermediates Reveal the Reversible Self-Assembly Pathway of a Simple Icosahedral Virus Capsid.

Science.gov (United States)

Medrano, María; Fuertes, Miguel Ángel; Valbuena, Alejandro; Carrillo, Pablo J P; Rodríguez-Huete, Alicia; Mateu, Mauricio G

2016-11-30

Understanding the fundamental principles underlying supramolecular self-assembly may facilitate many developments, from novel antivirals to self-organized nanodevices. Icosahedral virus particles constitute paradigms to study self-assembly using a combination of theory and experiment. Unfortunately, assembly pathways of the structurally simplest virus capsids, those more accessible to detailed theoretical studies, have been difficult to study experimentally. We have enabled the in vitro self-assembly under close to physiological conditions of one of the simplest virus particles known, the minute virus of mice (MVM) capsid, and experimentally analyzed its pathways of assembly and disassembly. A combination of electron microscopy and high-resolution atomic force microscopy was used to structurally characterize and quantify a succession of transient assembly and disassembly intermediates. The results provided an experiment-based model for the reversible self-assembly pathway of a most simple (T = 1) icosahedral protein shell. During assembly, trimeric capsid building blocks are sequentially added to the growing capsid, with pentamers of building blocks and incomplete capsids missing one building block as conspicuous intermediates. This study provided experimental verification of many features of self-assembly of a simple T = 1 capsid predicted by molecular dynamics simulations. It also demonstrated atomic force microscopy imaging and automated analysis, in combination with electron microscopy, as a powerful single-particle approach to characterize at high resolution and quantify transient intermediates during supramolecular self-assembly/disassembly reactions. Finally, the efficient in vitro self-assembly achieved for the oncotropic, cell nucleus-targeted MVM capsid may facilitate its development as a drug-encapsidating nanoparticle for anticancer targeted drug delivery.

Revolving supramolecular chiral structures powered by light in nanomotor-doped liquid crystals

Science.gov (United States)

Orlova, Tetiana; Lancia, Federico; Loussert, Charles; Iamsaard, Supitchaya; Katsonis, Nathalie; Brasselet, Etienne

2018-04-01

Molecular machines operated by light have been recently shown to be able to produce oriented motion at the molecular scale1,2 as well as do macroscopic work when embedded in supramolecular structures3-5. However, any supramolecular movement irremediably ceases as soon as the concentration of the interconverting molecular motors or switches reaches a photo-stationary state6,7. To circumvent this limitation, researchers have typically relied on establishing oscillating illumination conditions—either by modulating the source intensity8,9 or by using bespoke illumination arrangements10-13. In contrast, here we report a supramolecular system in which the emergence of oscillating patterns is encoded at the molecular level. Our system comprises chiral liquid crystal structures that revolve continuously when illuminated, under the action of embedded light-driven molecular motors. The rotation at the supramolecular level is sustained by the diffusion of the motors away from a localized illumination area. Above a critical irradiation power, we observe a spontaneous symmetry breaking that dictates the directionality of the supramolecular rotation. The interplay between the twist of the supramolecular structure and the diffusion14 of the chiral molecular motors creates continuous, regular and unidirectional rotation of the liquid crystal structure under non-equilibrium conditions.

Supramolecular Architectures and Mimics of Complex Natural Folds Derived from Rationally Designed alpha-Helical Protein Structures

Science.gov (United States)

Tavenor, Nathan Albert

Protein-based supramolecular polymers (SMPs) are a class of biomaterials which draw inspiration from and expand upon the many examples of complex protein quaternary structures observed in nature: collagen, microtubules, viral capsids, etc. Designing synthetic supramolecular protein scaffolds both increases our understanding of natural superstructures and allows for the creation of novel materials. Similar to small-molecule SMPs, protein-based SMPs form due to self-assembly driven by intermolecular interactions between monomers, and monomer structure determines the properties of the overall material. Using protein-based monomers takes advantage of the self-assembly and highly specific molecular recognition properties encodable in polypeptide sequences to rationally design SMP architectures. The central hypothesis underlying our work is that alpha-helical coiled coils, a well-studied protein quaternary folding motif, are well-suited to SMP design through the addition of synthetic linkers at solvent-exposed sites. Through small changes in the structures of the cross-links and/or peptide sequence, we have been able to control both the nanoscale organization and the macroscopic properties of the SMPs. Changes to the linker and hydrophobic core of the peptide can be used to control polymer rigidity, stability, and dimensionality. The gaps in knowledge that this thesis sought to fill on this project were 1) the relationship between the molecular structure of the cross-linked polypeptides and the macroscopic properties of the SMPs and 2) a means of creating materials exhibiting multi-dimensional net or framework topologies. Separate from the above efforts on supramolecular architectures was work on improving backbone modification strategies for an alpha-helix in the context of a complex protein tertiary fold. Earlier work in our lab had successfully incorporated unnatural building blocks into every major secondary structure (beta-sheet, alpha-helix, loops and beta

Hyperbranched quasi-1D nanostructures for solid-state dye-sensitized solar cells.

Science.gov (United States)

Passoni, Luca; Ghods, Farbod; Docampo, Pablo; Abrusci, Agnese; Martí-Rujas, Javier; Ghidelli, Matteo; Divitini, Giorgio; Ducati, Caterina; Binda, Maddalena; Guarnera, Simone; Li Bassi, Andrea; Casari, Carlo Spartaco; Snaith, Henry J; Petrozza, Annamaria; Di Fonzo, Fabio

2013-11-26

In this work we demonstrate hyperbranched nanostructures, grown by pulsed laser deposition, composed of one-dimensional anatase single crystals assembled in arrays of high aspect ratio hierarchical mesostructures. The proposed growth mechanism relies on a two-step process: self-assembly from the gas phase of amorphous TiO2 clusters in a forest of tree-shaped hierarchical mesostructures with high aspect ratio; oriented crystallization of the branches upon thermal treatment. Structural and morphological characteristics can be optimized to achieve both high specific surface area for optimal dye uptake and broadband light scattering thanks to the microscopic feature size. Solid-state dye sensitized solar cells fabricated with arrays of hyperbranched TiO2 nanostructures on FTO-glass sensitized with D102 dye showed a significant 66% increase in efficiency with respect to a reference mesoporous photoanode and reached a maximum efficiency of 3.96% (among the highest reported for this system). This result was achieved mainly thanks to an increase in photogenerated current directly resulting from improved light harvesting efficiency of the hierarchical photoanode. The proposed photoanode overcomes typical limitations of 1D TiO2 nanostructures applied to ss-DSC and emerges as a promising foundation for next-generation high-efficiency solid-state devices comprosed of dyes, polymers, or quantum dots as sensitizers.

Thioflavin T templates amyloid β(1-40) conformation and aggregation pathway

DEFF Research Database (Denmark)

Di Carlo, Maria Giovanna; Minicozzi, Velia; Foderà, Vito

2015-01-01

Aβ(1-40) peptide supramolecular assembly and fibril formation processes are widely recognized to have direct implications in the progression of Alzheimer's disease. The molecular basis of this biological process is still unknown and there is a strong need of developing effective strategies...... in turn rests on the reliability of the probe/labels involved. Here we present evidences of the effect of Thioflavin T (ThT), a worldwide used fluorescent dye to monitor amyloid growth, on the Aβ(1-40) conformation, stability and aggregation. By combining experimental information and Molecular Dynamics...... simulation results, we show that the presence of ThT in solution affects peptide conformation inducing peculiar supramolecular association. In particular ThT interactions with specific Aβ(1-40) residues promote a rigid partially-folded conformation which shifts the balance between different species...

Quantum dot-dye hybrid systems for energy transfer applications

International Nuclear Information System (INIS)

Ren, Ting

2010-01-01

In this thesis, we focus on the preparation of energy transfer-based quantum dot (QD)-dye hybrid systems. Two kinds of QD-dye hybrid systems have been successfully synthesized: QD-silica-dye and QD-dye hybrid systems. In the QD-silica-dye hybrid system, multishell CdSe/CdS/ZnS QDs were adsorbed onto monodisperse Stoeber silica particles with an outer silica shell of thickness 2-24 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the total sensitized acceptor emission, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of QDs with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with Monte-Carlo simulations, and by control experiments confirming attractive interactions between QDs and Texas Red freely dissolved in solution. New QD-dye hybrid system consisting of multishell QDs and organic perylene dyes have been synthesized. We developed a versatile approach to assemble extraordinarily stable QD-dye hybrids, which uses dicarboxylate anchors to bind rylene dyes to QD. This system yields a good basis to study the energy transfer between QD and dye because of its simple and compact design: there is no third kind of molecule linking QD and dye; no spacer; and the affinity of the functional group to the QD surface is strong. The FRET signal was measured for these complexes as a function of both dye to QD ratio and center-to-center distance between QD and dye by controlling number of covered ZnS layers. Data showed that fluorescence resonance energy transfer (FRET) was the dominant mechanism of the energy transfer in our QD-dye hybrid system. FRET efficiency can be controlled by not only adjusting the number of dyes on the QD surface or the QD to dye distance, but also properly choosing different dye and QD components. Due to the strong stability, our QD-dye

Quantum dot-dye hybrid systems for energy transfer applications

Energy Technology Data Exchange (ETDEWEB)

Ren, Ting

2010-07-01

In this thesis, we focus on the preparation of energy transfer-based quantum dot (QD)-dye hybrid systems. Two kinds of QD-dye hybrid systems have been successfully synthesized: QD-silica-dye and QD-dye hybrid systems. In the QD-silica-dye hybrid system, multishell CdSe/CdS/ZnS QDs were adsorbed onto monodisperse Stoeber silica particles with an outer silica shell of thickness 2-24 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the total sensitized acceptor emission, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of QDs with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with Monte-Carlo simulations, and by control experiments confirming attractive interactions between QDs and Texas Red freely dissolved in solution. New QD-dye hybrid system consisting of multishell QDs and organic perylene dyes have been synthesized. We developed a versatile approach to assemble extraordinarily stable QD-dye hybrids, which uses dicarboxylate anchors to bind rylene dyes to QD. This system yields a good basis to study the energy transfer between QD and dye because of its simple and compact design: there is no third kind of molecule linking QD and dye; no spacer; and the affinity of the functional group to the QD surface is strong. The FRET signal was measured for these complexes as a function of both dye to QD ratio and center-to-center distance between QD and dye by controlling number of covered ZnS layers. Data showed that fluorescence resonance energy transfer (FRET) was the dominant mechanism of the energy transfer in our QD-dye hybrid system. FRET efficiency can be controlled by not only adjusting the number of dyes on the QD surface or the QD to dye distance, but also properly choosing different dye and QD components. Due to the strong stability, our QD-dye

Electrochemical aptasensor for highly sensitive determination of cocaine using a supramolecular aptamer and rolling circle amplification

International Nuclear Information System (INIS)

Shen, Bo; Yan, Yurong; Tang, Renkuan; Li, Yongguo; Li, Jianbo; Cheng, Wei; Ju, Huangxian; Ding, Shijia

2015-01-01

We report on a novel strategy for the electrochemical detection of cocaine. It is based on the use of a supramolecular aptamer, rolling circle amplification (RCA), and multiplex binding of a biotin-strepavidin system. The aptamer fragments were assembled to a supramolecular aptamer which, in the presence of cocaine, conjugates to streptavidin for anchoring of biotinylated circular DNA. This initiates RCA and enables sensitive electrochemical-enzymatic readout. A significant signal amplification was obtained by using streptavidin linked to alkaline phosphatase that binds to the remaining biotinylated detection probes and catalyzes the hydrolysis of the synthetic enzyme substrate α-naphthylphosphate. This dual amplification strategy tremendously increases the detection limit of the aptasensor. Under optimal conditions and using differential pulse voltammetry, cocaine can be detected in the concentration range between 2 and 500 nM with a detection limit as low as 1.3 nM (at S/N = 3). The method is specific and acceptably reproducible. It was successfully applied to the detection of cocaine in (spiked) urine samples. The data were in good agreement with those obtained by the GC-MS reference method. (author)

Excimer Pumped Pulsed Tunable Dye Laser

Science.gov (United States)

Littman, Michael G.

1988-06-01

It has been recently shown and reported for the first time at this meeting, that Excimer pumping of a single-mode, short-cavity, grazing-incidence, longitudinally-pumped pulsed dye laser is feasible. In this paper the key concepts upon which this latest development is based are presented and are in a somewhat unusual form. This manuscript describes five specific dye laser examples. The five examples represent a progression from the simplest type of dye laser to the single-mode version mentioned above. The examples thus serve as a tutorial introduction to potential users of dye lasers. The article is organized into five sections or STEPS, each of which describes a different pulsed dye laser. Since the subtle points about dye lasers are best appreciated only after one actually attempts to build a working model, a PROCEDURES category is included in which details about the construction of the particular form of laser are given. As one reads through this category, think of it as looking over the shoulder of the laser builder. The NOTES category which follows is a brief but essential discussion explaining why various components and procedures are used, as well as how laser performance specifications are obtained. This subsection can he viewed as a discussion with the laser builder concerning the reasons for specific actions and choices made in the assembly of the example laser. The last category contains COMMENTS which provide additional related information pertaining to the example laser that goes beyond the earlier annotated discussion. If you like, these are the narrator's comments. At the end of the article, after the five sequential forms of the laser have been presented, there is a brief summation.

Spectro-microscopic study of the formation of supramolecular networks

Science.gov (United States)

Sadowski, Jerzy T.

2015-03-01

Metal-organic frameworks (MOFs) are emerging as a new class of materials for CO2 capture. There are many fundamental questions, including the optimum pore size and arrangement of the molecules in the structure to achieve highest CO2 uptake. As only the surface is of interest for potential applications such as heterogeneous catalysis, nano-templating, and sensing, 2D analogs of MOFs can serve as good model systems. Utilizing capabilities of LEEM/PEEM for non-destructive interrogation of the real-time molecular self-assembly, we investigated supramolecular systems based on carboxylic acid-metal complexes, such as trimesic and mellitic acid, doped with transition metals. Such 2D networks act as host systems for transition-metal phthalocyanines (MPc; M = Fe, Ti, Sc) and the electrostatic interactions of CO2 molecules with transition metal ions, can be tuned by controlling the type of TM ion and the size of the pore in the host network. The understanding of directed self-assembly by controlling the molecule-substrate interaction can enable us to engineer the pore size and density, and thus tune the host's chemical activity. Research carried out at the Center for Functional Nanomaterials and National Synchrotron Light Source, Brookhaven National Laboratory, which are supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10.

Chemistry of supramolecular systems containing porphyrins and metal complexes

OpenAIRE

Araki, Koiti; Toma, Henrique Eisi

2002-01-01

Supramolecular chemistry is expected to keep a high developing pace in the next years, giving support to the advancement of molecular devices and nanotechnology. In this sense, porphyrins and their analogues should play a significant role as a consequence of their catalytic, electrocatalytic, photochemical and photoelectrochemical properties. In this review we focused on our own strategy based on coordination chemistry for the design and build-up of supermolecules and supramolecular structure...

Using Polarized Spectroscopy to Investigate Order in Thin-Films of Ionic Self-Assembled Materials Based on Azo-Dyes

Science.gov (United States)

Ahmad, Mariam; Andersen, Frederik; Brend Bech, Ári; Bendixen, H. Krestian L.; Nawrocki, Patrick R.; Bloch, Anders J.; Bora, Ilkay; Bukhari, Tahreem A.; Bærentsen, Nicolai V.; Carstensen, Jens; Chima, Smeeah; Colberg, Helene; Dahm, Rasmus T.; Daniels, Joshua A.; Dinckan, Nermin; El Idrissi, Mohamed; Erlandsen, Ricci; Førster, Marc; Ghauri, Yasmin; Gold, Mikkel; Hansen, Andreas; Hansen, Kenn; Helmsøe-Zinck, Mathias; Henriksen, Mathias; Hoffmann, Sophus V.; Hyllested, Louise O. H.; Jensen, Casper; Kallenbach, Amalie S.; Kaur, Kirandip; Khan, Suheb R.; Kjær, Emil T. S.; Kristiansen, Bjørn; Langvad, Sylvester; Lund, Philip M.; Munk, Chastine F.; Møller, Theis; Nehme, Ola M. Z.; Nejrup, Mathilde Rove; Nexø, Louise; Nielsen, Simon Skødt Holm; Niemeier, Nicolai; Nikolajsen, Lasse V.; Nøhr, Peter C. T.; Skaarup Ovesen, Jacob; Paustian, Lucas; Pedersen, Adam S.; Petersen, Mathias K.; Poulsen, Camilla M.; Praeger-Jahnsen, Louis; Qureshi, L. Sonia; Schiermacher, Louise S.; Simris, Martin B.; Smith, Gorm; Smith, Heidi N.; Sonne, Alexander K.; Zenulovic, Marko R.; Winther Sørensen, Alma; Vogt, Emil; Væring, Andreas; Westermann, Jonas; Özcan, Sevin B.

2018-01-01

Three series of ionic self-assembled materials based on anionic azo-dyes and cationic benzalkonium surfactants were synthesized and thin films were prepared by spin-casting. These thin films appear isotropic when investigated with polarized optical microscopy, although they are highly anisotropic. Here, three series of homologous materials were studied to rationalize this observation. Investigating thin films of ordered molecular materials relies to a large extent on advanced experimental methods and large research infrastructure. A statement that in particular is true for thin films with nanoscopic order, where X-ray reflectometry, X-ray and neutron scattering, electron microscopy and atom force microscopy (AFM) has to be used to elucidate film morphology and the underlying molecular structure. Here, the thin films were investigated using AFM, optical microscopy and polarized absorption spectroscopy. It was shown that by using numerical method for treating the polarized absorption spectroscopy data, the molecular structure can be elucidated. Further, it was shown that polarized optical spectroscopy is a general tool that allows determination of the molecular order in thin films. Finally, it was found that full control of thermal history and rigorous control of the ionic self-assembly conditions are required to reproducibly make these materials of high nanoscopic order. Similarly, the conditions for spin-casting are shown to be determining for the overall thin film morphology, while molecular order is maintained. PMID:29462883

Using Polarized Spectroscopy to Investigate Order in Thin-Films of Ionic Self-Assembled Materials Based on Azo-Dyes

Directory of Open Access Journals (Sweden)

Miguel R. Carro-Temboury Martin Kühnel

2018-02-01

Full Text Available Three series of ionic self-assembled materials based on anionic azo-dyes and cationic benzalkonium surfactants were synthesized and thin films were prepared by spin-casting. These thin films appear isotropic when investigated with polarized optical microscopy, although they are highly anisotropic. Here, three series of homologous materials were studied to rationalize this observation. Investigating thin films of ordered molecular materials relies to a large extent on advanced experimental methods and large research infrastructure. A statement that in particular is true for thin films with nanoscopic order, where X-ray reflectometry, X-ray and neutron scattering, electron microscopy and atom force microscopy (AFM has to be used to elucidate film morphology and the underlying molecular structure. Here, the thin films were investigated using AFM, optical microscopy and polarized absorption spectroscopy. It was shown that by using numerical method for treating the polarized absorption spectroscopy data, the molecular structure can be elucidated. Further, it was shown that polarized optical spectroscopy is a general tool that allows determination of the molecular order in thin films. Finally, it was found that full control of thermal history and rigorous control of the ionic self-assembly conditions are required to reproducibly make these materials of high nanoscopic order. Similarly, the conditions for spin-casting are shown to be determining for the overall thin film morphology, while molecular order is maintained.

Using Polarized Spectroscopy to Investigate Order in Thin-Films of Ionic Self-Assembled Materials Based on Azo-Dyes.

Science.gov (United States)

Kühnel, Miguel R Carro-Temboury Martin; Ahmad, Mariam; Andersen, Frederik; Bech, Ári Brend; Bendixen, H Krestian L; Nawrocki, Patrick R; Bloch, Anders J; Bora, Ilkay; Bukhari, Tahreem A; Bærentsen, Nicolai V; Carstensen, Jens; Chima, Smeeah; Colberg, Helene; Dahm, Rasmus T; Daniels, Joshua A; Dinckan, Nermin; Idrissi, Mohamed El; Erlandsen, Ricci; Førster, Marc; Ghauri, Yasmin; Gold, Mikkel; Hansen, Andreas; Hansen, Kenn; Helmsøe-Zinck, Mathias; Henriksen, Mathias; Hoffmann, Sophus V; Hyllested, Louise O H; Jensen, Casper; Kallenbach, Amalie S; Kaur, Kirandip; Khan, Suheb R; Kjær, Emil T S; Kristiansen, Bjørn; Langvad, Sylvester; Lund, Philip M; Munk, Chastine F; Møller, Theis; Nehme, Ola M Z; Nejrup, Mathilde Rove; Nexø, Louise; Nielsen, Simon Skødt Holm; Niemeier, Nicolai; Nikolajsen, Lasse V; Nøhr, Peter C T; Orlowski, Dominik B; Overgaard, Marc; Ovesen, Jacob Skaarup; Paustian, Lucas; Pedersen, Adam S; Petersen, Mathias K; Poulsen, Camilla M; Praeger-Jahnsen, Louis; Qureshi, L Sonia; Ree, Nicolai; Schiermacher, Louise S; Simris, Martin B; Smith, Gorm; Smith, Heidi N; Sonne, Alexander K; Zenulovic, Marko R; Sørensen, Alma Winther; Sørensen, Karina; Vogt, Emil; Væring, Andreas; Westermann, Jonas; Özcan, Sevin B; Sørensen, Thomas Just

2018-02-15

Three series of ionic self-assembled materials based on anionic azo-dyes and cationic benzalkonium surfactants were synthesized and thin films were prepared by spin-casting. These thin films appear isotropic when investigated with polarized optical microscopy, although they are highly anisotropic. Here, three series of homologous materials were studied to rationalize this observation. Investigating thin films of ordered molecular materials relies to a large extent on advanced experimental methods and large research infrastructure. A statement that in particular is true for thin films with nanoscopic order, where X-ray reflectometry, X-ray and neutron scattering, electron microscopy and atom force microscopy (AFM) has to be used to elucidate film morphology and the underlying molecular structure. Here, the thin films were investigated using AFM, optical microscopy and polarized absorption spectroscopy. It was shown that by using numerical method for treating the polarized absorption spectroscopy data, the molecular structure can be elucidated. Further, it was shown that polarized optical spectroscopy is a general tool that allows determination of the molecular order in thin films. Finally, it was found that full control of thermal history and rigorous control of the ionic self-assembly conditions are required to reproducibly make these materials of high nanoscopic order. Similarly, the conditions for spin-casting are shown to be determining for the overall thin film morphology, while molecular order is maintained.

Reversible networks in supramolecular polymers

NARCIS (Netherlands)

Havermans - van Beek, D.J.M.

2007-01-01

Non–covalent interactions between low molecular weight polymers form the basis of supramolecular polymers. The material properties of such polymers are determined by the strength and lifetime of the non–covalent reversible interactions. Due to the reversibility of the interactions between the low

Functional organic materials based on polymerized liquid-crystal monomers: supramolecular hydrogen-bonded systems.

Science.gov (United States)

Broer, Dirk J; Bastiaansen, Cees M W; Debije, Michael G; Schenning, Albertus P H J

2012-07-16

Functional organic materials are of great interest for a variety of applications. To obtain precise functional properties, well-defined hierarchically ordered supramolecular materials are crucial. The self-assembly of liquid crystals has proven to be an extremely useful tool in the development of well-defined nanostructured materials. We have chosen the illustrative example of photopolymerizable hydrogen-bonding mesogens to show that a wide variety of functional materials can be made from a relatively simple set of building blocks. Upon mixing these compounds with other reactive mesogens, nematic, chiral nematic, and smectic or columnar liquid-crystalline phases can be formed that can be applied as actuators, sensors and responsive reflectors, and nanoporous membranes, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Membrane and Films Based on Novel Crown-Containing Dyes as Promising Chemosensoring Materials

Directory of Open Access Journals (Sweden)

Sergei Yu. Zaitsev

2010-12-01

Full Text Available This paper discusses several works on supramolecular systems such as monolayer and multilayer, polymer films of various crown-containing dyes, surface-active monomers and polymers. Design, production and investigation of the membrane nanostructures based on crown ethers is a rapidly developing field at the “junction” of materials sciences and nanotechnology. These nanostructures can serve as convenient models for studying the self-organization and molecular recognition processes at interfaces that are typical for biomembranes. Based on the results obtained for such structures by absorption and fluorescence spectroscopy, atomic force and Brewster-angle microscopy, surface pressure and surface potential isotherm measurements, the possibility of developing micro- and nanomaterials possessing a set of specified properties (including chemosensor, photochromic and photorefractive materials is demonstrated.

Versatile supramolecular reactivity of zinc-tetra(4-pyridylporphyrin in crystalline solids: Polymeric grids with zinc dichloride and hydrogen-bonded networks with mellitic acid

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Sophia Lipstman

2009-12-01

Full Text Available Crystal engineering studies confirm that the zinc-tetra(4-pyridylporphyrin building block reveals versatile supramolecular chemistry. In this work, it was found to be reactive in the assembly of both (a a 2D polymeric array by a unique combination of self-coordination and coordination through external zinc dichloride linkers and (b an extended heteromolecular hydrogen-bonded network with mellitic acid sustained by multiple connectivity between the component species.

Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles.

Science.gov (United States)

Wang, Chao; Wang, Zhiqiang; Zhang, Xi

2012-04-17

The process of self-assembly spontaneously creates well-defined structures from various chemical building blocks. Self-assembly can include different levels of complexity: it can be as simple as the dimerization of two small building blocks driven by hydrogen bonding or as complicated as a cell membrane, a remarkable supramolecular architecture created by a bilayer of phospholipids embedded with functional proteins. The study of self-assembly in simple systems provides a fundamental understanding of the driving forces and cooperativity behind these processes. Once the rules are understood, these guidelines can facilitate the research of highly complex self-assembly processes. Among the various components for self-assembly, an amphiphilic molecule, which contains both hydrophilic and hydrophobic parts, forms one of the most powerful building blocks. When amphiphiles are dispersed in water, the hydrophilic component of the amphiphile preferentially interacts with the aqueous phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent. Therefore, the amphiphiles aggregate to form different molecular assemblies based on the repelling and coordinating forces between the hydrophilic and hydrophobic parts of the component molecules and the surrounding medium. In contrast to conventional amphiphiles, supra-amphiphiles are constructed on the basis of noncovalent interactions or dynamic covalent bonds. In supra-amphiphiles, the functional groups can be attached to the amphiphiles by noncovalent synthesis, greatly speeding their construction. The building blocks for supra-amphiphiles can be either small organic molecules or polymers. Advances in the development of supra-amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. When polymers are used to construct supra-amphiphiles, the resulting

Dye-sensitized solar cells based on nanostructured zinc oxide

Energy Technology Data Exchange (ETDEWEB)

Conradt, Jonas; Maier-Flaig, Florian; Sartor, Janos; Fallert, Johannes [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany); Szmytkowski, Jedrzej; Kalt, Heinz [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany); Center for Functional Nanostructures (CFN), Karlsruhe (Germany); Reinhard, Manuel; Colsmann, Alexander [Karlsruhe Institute of Technology (KIT), Lichttechnisches Institut, Karlsruhe (Germany); Lemmer, Uli [Center for Functional Nanostructures (CFN), Karlsruhe (Germany); Karlsruhe Institute of Technology (KIT), Lichttechnisches Institut, Karlsruhe (Germany); Balaban, Teodor Silviu [Center for Functional Nanostructures (CFN), Karlsruhe (Germany); Karlsruhe Institute of Technology (KIT), Institute for Nanotechnology, Karlsruhe (Germany)

2009-07-01

Hybrid solar cells represent a promising (cost-efficient) alternative to pure inorganic solar cells. We present dye-sensitized solar cells (DSSC) which are based on a zinc oxide (ZnO) electrode covered with a ruthenium dye. Our work focuses on the morphology of the ZnO electrode and its impact on the photovoltaic performance of the solar cell. Nanocrystalline ZnO powder layers and arrays of nanorods are incorporated into the DSSCs. The ZnO nanorods are grown by vapor transport deposition. The morphology and doping concentration of the rods can be controlled by the choice of substrate material, growth condition and catalytic metal layers. The nanorod arrays are expected to fasten the electron transport towards the anode and thereby improve the solar cell efficiency. In addition, novel self-assembling (porphyrin) dyes are tested as sensitizer within a DSSC.

Evolution of heterogeneity accompanying sol-gel transitions in a supramolecular hydrogel.

Science.gov (United States)

Matsumoto, Yuji; Shundo, Atsuomi; Ohno, Masashi; Tsuruzoe, Nobutomo; Goto, Masahiro; Tanaka, Keiji

2017-10-18

When a peptide amphiphile is dispersed in water, it self-assembles into a fibrous network, leading to a supramolecular hydrogel. When the gel is physically disrupted by shaking, it transforms into a sol state. After aging at room temperature for a while, it spontaneously returns to the gel state, called sol-gel transition. However, repeating the sol-gel transition often causes a change in the rheological properties of the gel. To gain a better understanding of the sol-gel transition and its reversibility, we herein examined the thermal motion of probe particles at different locations in a supramolecular hydrogel. The sol obtained by shaking the gel was heterogeneous in terms of the rheological properties and the extent decreased with increasing aging time. This time course of heterogeneity, or homogeneity, which corresponded to the sol-to-gel transition, was observed for the 1st cycle. However, this was not the case for the 2nd and 3rd cycles; the heterogeneity was preserved even after aging. Fourier-transform infrared spectroscopy, small-angle X-ray scattering, and atomic force and confocal laser scanning microscopies revealed that, although the molecular aggregation states of amphiphiles both in the gel and sol remained unchanged with the cycles, the fibril density diversified to high and low density regions even after aging. The tracking of particles with different sizes indicated that the partial mesh size in the high density region and the characteristic length scale of the density fluctuation were smaller than 50 nm and 6 μm, respectively.

Self-assembly behaviours of peptide-drug conjugates: influence of multiple factors on aggregate morphology and potential self-assembly mechanism

Science.gov (United States)

Fan, Qin; Ji, Yujie; Wang, Jingjing; Wu, Li; Li, Weidong; Chen, Rui; Chen, Zhipeng

2018-04-01

Peptide-drug conjugates (PDCs) as self-assembly prodrugs have the unique and specific features to build one-component nanomedicines. Supramolecular structure based on PDCs could form various morphologies ranging from nanotube, nanofibre, nanobelt to hydrogel. However, the assembly process of PDCs is too complex to predict or control. Herein, we investigated the effects of extrinsic factors on assembly morphology and the possible formation of nanostructures based on PDCs. To this end, we designed a PDC consisting of hydrophobic drug (S)-ketoprofen (Ket) and valine-glutamic acid dimeric repeats peptide (L-VEVE) to study their assembly behaviour. Our results showed that the critical assembly concentration of Ket-L-VEVE was 0.32 mM in water to form various nanostructures which experienced from micelle, nanorod, nanofibre to nanoribbon. The morphology was influenced by multiple factors including molecular design, assembly time, pH and hydrogen bond inhibitor. On the basis of experimental results, we speculated the possible assembly mechanism of Ket-L-VEVE. The π-π stacking interaction between Ket molecules could serve as an anchor, and hydrogen bonded-induced β-sheets and hydrophilic/hydrophobic balance between L-VEVE peptide play structure-directing role in forming filament-like or nanoribbon morphology. This work provides a new sight to rationally design and precisely control the nanostructure of PDCs based on aromatic fragment.

Dye-sensitization of CdS nano-cage - A density functional theory approach

Energy Technology Data Exchange (ETDEWEB)

Jain, Kalpna; Singh, Kh. S. [Department of Physics, D. J. College, Baraut, U.P.-250611 (India); Kishor, Shyam [Department of Chemistry, J. V. College, Baraut, U.P.-250611 (India); Josefsson, Ida; Odelius, Michael [Fysikum, Albanova University Center, Stockholm University, S-106 91 Stockholm (Sweden); Ramaniah, Lavanya M. [High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085 (India)

2016-05-23

Quantum dots a few nanometer in size exhibit unique properties in comparison to bulk due to quantum confinement. Their properties can be tuned according to their sizes. Dye sensitized quantum dot (DSQD) solar cells are based on the same principle with surface dangling bonds as a challenge. Researches have shown the existence and stability of nano-cages which are assembled such as to minimize the surface dangling bonds and hence maximize stability. Here, we report a first principles DFT study of optical and electronic properties of CdS-cage (Cd{sub 34}S{sub 34}) sensitized with nkx-2388 dye in three different geometric configurations of dye attachment. A significant distortion is found to occur in the geometric structure of the cage when it interacts strongly with the dye. The relative positioning of dye and cage energy levels is found to be different in different configurations. The absorption spectrum has been analyzed with the help of natural transition orbitals (NTO).

DNA-Directed Assembly of Capture Tools for Constitutional Studies of Large Protein Complexes.

Science.gov (United States)

Meyer, Rebecca; Faesen, Alex; Vogel, Katrin; Jeganathan, Sadasivam; Musacchio, Andrea; Niemeyer, Christof M

2015-06-10

Large supramolecular protein complexes, such as the molecular machinery involved in gene regulation, cell signaling, or cell division, are key in all fundamental processes of life. Detailed elucidation of structure and dynamics of such complexes can be achieved by reverse-engineering parts of the complexes in order to probe their interactions with distinctive binding partners in vitro. The exploitation of DNA nanostructures to mimic partially assembled supramolecular protein complexes in which the presence and state of two or more proteins are decisive for binding of additional building blocks is reported here. To this end, four-way DNA Holliday junction motifs bearing a fluorescein and a biotin tag, for tracking and affinity capture, respectively, are site-specifically functionalized with centromeric protein (CENP) C and CENP-T. The latter serves as baits for binding of the so-called KMN component, thereby mimicking early stages of the assembly of kinetochores, structures that mediate and control the attachment of microtubules to chromosomes in the spindle apparatus. Results from pull-down experiments are consistent with the hypothesis that CENP-C and CENP-T may bind cooperatively to the KMN network. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled supramolecular structure of guanosine monophosphate in the interlayer space of layered double hydroxide

Directory of Open Access Journals (Sweden)

Gyeong-Hyeon Gwak

2016-12-01

Full Text Available Guanosine monophosphates (GMPs were intercalated into the interlayer space of layered double hydroxides (LDHs and the molecular arrangement of GMP was controlled in LDHs. The intercalation conditions such as GMP/LDH molar ratio and reaction temperature were systematically adjusted. When the GMP/LDH molar ratio was 1:2, which corresponds to the charge balance between positive LDH sheets and GMP anions, GMP molecules were well-intercalated to LDH. At high temperature (100 and 80 °C, a single GMP molecule existed separately in the LDH interlayer. On the other hand, at lower temperature (20, 40 and 60 °C, GMPs tended to form ribbon-type supramolecular assemblies. Differential scanning calorimetry showed that the ribbon-type GMP assembly had an intermolecular interaction energy of ≈101 kJ/mol, which corresponds to a double hydrogen bond between guanosine molecules. Once stabilized, the interlayer GMP orientations, single molecular and ribbon phase, were successfully converted to the other phase by adjusting the external environment by stoichiometry or temperature control.

Colloidal chirality in wormlike micellar systems exclusively originated from achiral species: Role of secondary assembly and stimulus responsivity.

Science.gov (United States)

Zhao, Wenrong; Hao, Jingcheng

2016-09-15

Colloidal chirality in wormlike micellar systems exclusively originated from achiral species and discussion of the role of secondary assembly of fiber-like aggregates in chirality generation were presented in this paper. Herein, formation of colloidal wormlike micelles for the first time incorporated chirality and redox-responsiveness into one design via noncovalent interaction. A dual-stimuli-responsive gel of wormlike micelles which were designed by employing a dual-responsive cationic surfactant (FTMA) and a strong gelator (AzoNa4) and regulated by redox reaction and host-guest inclusion is presented. Both the redox and host-guest interaction play an important role in regulating the viscosity and supramolecular chirality of gels of the wormlike micelles. The supramolecular chirality and viscosity of the wormlike micelle gels were switched reversibly by exerting chemical redox onto the ferrocenyl groups. For the amphiphile FTMA containing redox-active ferrocenyl group, reversible control of the oxidation state of ferrocenyl groups leads to the charge and hydrophobicity changes of FTMA, therefore change its self-assembly behavior. Of equal interest, β-CD successfully detached the wormlike micelles via the recognition-inclusion behavior with FTMA and invalidate the H-bond and hydrophobic interaction between FTMA and AzoH4. This designed system provides a new strategy to tune the supramolecular chirality of colloidal aggregates and explore the specific packing mode detail within the micelles or the secondary assembly of the inter-micelles. We anticipate this dual-responsive H-bond-directed chiral gel switch could propose a new strategy when researchers designing new, multi-responsive functional gel materials. Copyright © 2016 Elsevier Inc. All rights reserved.

Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black

Science.gov (United States)

Hepel, Maria; Stobiecka, Magdalena

2018-03-01

Oxidative stress biomarkers, including glutathione (GSH) and related compounds, are involved in a variety of interactions enabling redox potential maintenance in living cells and protection against radicals. Since the oxidative stress is promoting and, in many cases, inducing serious illnesses, monitoring of GSH levels can aid in diagnostics and disease prevention. Herein, we report on the discovery of the formation of a supramolecular ensemble of GSH with fluorone black (9-phenyl fluorone, FB) which is optically active and enables sensitive determination of GSH by resonance elastic light scattering (RELS). We have found that supramolecular interactions of GSH with FB can be probed with spectroscopic, RELS, and electrochemical methods. Our investigations show that RELS intensity for FB solutions increases with GSH concentration while fluorescence emission of FB is not affected, as quenching begins only above 0.8 mM GSH. The UV-Vis difference spectra show a positive peak at 383 nm and a negative peak at 458 nm, indicating a higher-energy absorbing complex in comparison to the non-bonded FB host. Supramolecular interactions of FB with GSH have also been corroborated by electrochemical measurements involving two configurations of FB-GSH ensembles on electrodes: (i) an inverted orientation on Au-coated quartz crystal piezoelectrode (Au@SG-FB), with strong thiolate bonding to gold, and (ii) a non-inverted orientation on glassy carbon electrode (GCE@FB-GS), with weak π-π stacking attachment and efficient charge mediation through the ensemble. The formation of a supramolecular ensemble with hydrogen bonding has also been confirmed by quantum mechanical calculations. The discovery of supramolecular FB-GSH ensemble formation enables elucidating the mechanisms of strong RELS responses, changes in UV-Vis absorption spectra, and the electrochemical reactivity. Also, it provides new insights to the understanding of the efficient charge-transfer in redox potential homeostasis

Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black.

Science.gov (United States)

Hepel, Maria; Stobiecka, Magdalena

2018-03-05

Oxidative stress biomarkers, including glutathione (GSH) and related compounds, are involved in a variety of interactions enabling redox potential maintenance in living cells and protection against radicals. Since the oxidative stress is promoting and, in many cases, inducing serious illnesses, monitoring of GSH levels can aid in diagnostics and disease prevention. Herein, we report on the discovery of the formation of a supramolecular ensemble of GSH with fluorone black (9-phenyl fluorone, FB) which is optically active and enables sensitive determination of GSH by resonance elastic light scattering (RELS). We have found that supramolecular interactions of GSH with FB can be probed with spectroscopic, RELS, and electrochemical methods. Our investigations show that RELS intensity for FB solutions increases with GSH concentration while fluorescence emission of FB is not affected, as quenching begins only above 0.8mM GSH. The UV-Vis difference spectra show a positive peak at 383nm and a negative peak at 458nm, indicating a higher-energy absorbing complex in comparison to the non-bonded FB host. Supramolecular interactions of FB with GSH have also been corroborated by electrochemical measurements involving two configurations of FB-GSH ensembles on electrodes: (i) an inverted orientation on Au-coated quartz crystal piezoelectrode (Au@SG-FB), with strong thiolate bonding to gold, and (ii) a non-inverted orientation on glassy carbon electrode (GCE@FB-GS), with weak π-π stacking attachment and efficient charge mediation through the ensemble. The formation of a supramolecular ensemble with hydrogen bonding has also been confirmed by quantum mechanical calculations. The discovery of supramolecular FB-GSH ensemble formation enables elucidating the mechanisms of strong RELS responses, changes in UV-Vis absorption spectra, and the electrochemical reactivity. Also, it provides new insights to the understanding of the efficient charge-transfer in redox potential homeostasis

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

NARCIS (Netherlands)

Baker, M.B.; Albertazzi, L.; Voets, Ilja K.; Leenders, C.M.A.; Palmans, A.R.A.; Pavan, G.M.; Meijer, E. W.

2015-01-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers:

Supramolecular protein immobilization on lipid bilayers

NARCIS (Netherlands)

Bosmans, R.P.G.; Hendriksen, W.E.; Verheijden, Mark Lloyd; Eelkema, R.; Jonkheijm, Pascal; van Esch, J.H.; Brunsveld, Luc

2015-01-01

Protein immobilization on surfaces, and on lipid bilayers specifically, has great potential in biomolecular and biotechnological research. Of current special interest is the immobilization of proteins using supramolecular noncovalent interactions. This allows for a reversible immobilization and

Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions.

Science.gov (United States)

Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin

2015-08-05

In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Complexes Formed in Systems Bile Salt-Bilirubin-Silica

Science.gov (United States)

Vlasova, N. N.; Severinovskaya, O. V.; Golovkova, L. P.

The formation of supramolecular complexes between bilirubin and primary micelles of bile salts has been studied. The association constants of bile salts and binding of bilirubin with these associates have been determined. The adsorption of bilirubin and bile salts from individual and mixed aqueous solutions onto hydrophobic silica surfaces has been investigated. The interaction of bilirubin with primary bile salt micelles and the strong retention in mixed micelles, which are supramolecular complexes, result in the adsorption of bilirubin in free state only.

Facile synthesis of TiO2 hierarchical microspheres assembled by ultrathin nanosheets for dye-sensitized solar cells

International Nuclear Information System (INIS)

Xu, Fang; Zhang, Xuyan; Wu, Yao; Wu, Dapeng; Gao, Zhiyong; Jiang, Kai

2013-01-01

Highlights: •TiO 2 hierarchical spheres were prepared via one-pot solvothermal route. •TiO 2 hierarchical spheres based DSSCs shows a conversion efficiency of 5.56%. •The performance of DSSC is dependence of the thickness of photoanode. -- Abstract: TiO 2 hierarchical microspheres assembled by ultrathin nanosheets were prepared via solvothermal route for dye-sensitized solar cells (DSSCs). The performance of cells was investigated by diffuse and reflectance spectra, photocurrent–voltage measurement, incident-photon-to-current conversion efficiency and electrochemical impedance spectra. Photoanodes with different thickness of TiO 2 hierarchical spheres were studied, which proves that the photoanode with thickness of 15.9 μm exhibits higher performance (short-circuit current density of 12.36 mA cm −2 , open-circuit voltage of 0.73 mV, fill factor of 61.95, and conversion efficiency of 5.56%) than that of P25-based DSSC due to the excellent particle interconnections, low electron recombination and high specific surface area (78 m 2 g −1 )

Nanoparticles functionalized with supramolecular host-guest systems for nanomedicine and healthcare.

Science.gov (United States)

Wu, Zilong; Song, Nan; Menz, Ryan; Pingali, Bharadwaj; Yang, Ying-Wei; Zheng, Yuebing

2015-05-01

Synthetic macrocyclic host compounds can interact with suitable guest molecules via noncovalent interactions to form functional supramolecular systems. With the synergistic integration of the response of molecules and the unique properties at the nanoscale, nanoparticles functionalized with the host-guest supramolecular systems have shown great potentials for a broad range of applications in the fields of nanoscience and nanotechnology. In this review article, we focus on the applications of the nanoparticles functionalized with supramolecular host-guest systems in nanomedicine and healthcare, including therapeutic delivery, imaging, sensing and removal of harmful substances. A large number of examples are included to elucidate the working mechanisms, advantages, limitations and future developments of the nanoparticle-supramolecule systems in these applications.

Structural transition in aqueous lipid/bile salt [DPPC/NaDC] supramolecular aggregates: SANS and DLS study

International Nuclear Information System (INIS)

Kiselev, M.A.; Janich, M.; Hildebrand, A.; Strunz, P.; Neubert, R.H.H.; Lombardo, D.

2013-01-01

Highlights: • Self-assembly in model DPPC lipids and NaDC bile salt by SANS and DLS experiments. • Bile salt creates structural interference against cohesive tendency of DPPC bilayers. • NaDC steric interactions cause transition toward different supramolecular structures. - Abstract: Small angle neutron scattering (SANS) and dynamic light scattering (DLS) were used to study different aggregation states in sodium deoxycholate (NaDC)-phosphatidylcholine systems at T = 60 °C. Size and shape of the aggregates investigated as a function of the NaDC bile salt concentration (at the constant DPPC concentration of 6 mM) indicate a strong dependence of the size and morphology of the generated aggregates on the relative amount of NaDC bile salt. More specifically large occupied area of the bile salt induces a steric interaction which promotes the transition toward a variety of supramolecular structures ranging from ellipsoidal vesicles, ribbon-like structures, up to final spherical mixed micelles at the large amount of bile salt of 10 mM NaDC. The findings of the obtained results give important insight for understanding the formation of different topologies in aqueous lipid–bile salt mixtures as well as stimulate new routes for liposome reconstitution–solubilisation processes suitable for technological applications

Tuning the light emission of novel donor-acceptor phenoxazine dye-based materials towards the red spectral range

Science.gov (United States)

Damaceanu, Mariana-Dana; Constantin, Catalin-Paul

2018-04-01

A novel red fluorescent push-pull system able to generate an intramolecular charge-transfer (ICT) complex was synthesized. The novel dye (R-POX) combines some structural features which are rarely encountered in the design of other push-pull systems: hexyl-substituted phenoxazine as donor moiety, divinylketone as π-linker, and p-fluorobenzene as electron acceptor group. The relationship between the structural motif, photo-physical and electrochemical properties by UV-Vis absorption, photoluminescence and cyclic voltammetry was thoroughly investigated both as red dopant in poly(methylmethacrylate) (PMMA) or polyimide (PI) matrix, and non-doped host emitter. The molecular rigid cores of the synthesized dye formed supramolecular rod-like structures in condensed phase with a strong impact on the emissive centers. The aggregation was totally suppressed when the dye was used as dopant in an amorphous polymeric matrix, such as PMMA or PI. Electrochemical measurements revealed the dye ability for both hole and electron injection and transport. The fluorescence emission was found to be highly sensitive to solvent polarity, rendering blue-green, yellow, orange and red light emission in different organic solvents. The absolute fluorescence quantum yield reached 39.57% in solution, and dropped to 1.2% in solid state and to 14.01% when the dye was used as dopant in PMMA matrix. According to the available CIE 1931 standard, R-POX emitted pure and saturated red light of single wavelength with chromaticity coordinates very close to those of National Television System Committee (NTSC) standard red colour. The R-POX photo-optical features were compared to those of the commercial red emitter 6, 13-diphenylpentacene.

Rapid self-assembly of block copolymers to photonic crystals

Science.gov (United States)

Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

2016-07-05

The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

Nanoporous network channels from self-assembled triblock copolymer supramolecules.

Science.gov (United States)

du Sart, Gerrit Gobius; Vukovic, Ivana; Vukovic, Zorica; Polushkin, Evgeny; Hiekkataipale, Panu; Ruokolainen, Janne; Loos, Katja; ten Brinke, Gerrit

2011-02-16

Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular chemistry and crystal engineering

Indian Academy of Sciences (India)

supramolecular architectures, network structures, multi-component host–guest systems, cocrys- tals, and ... structures is illustrated by two important prototypes – the large unit cell of elusive saccharin hydrate ..... N––– H ··· π interaction is not seen in this view. (d) Infinite .... to atmospheric water vapor without color loss or.

Supramolecular chemistry - interdisciplinary branch of science

International Nuclear Information System (INIS)

Radecka-Paryzek, W.

1997-01-01

The scientific problems connected with supramolecular chemistry have been reviewed. The basic concepts have been defined as well as rules governed of macromolecules formation. The special emphasize has been put on present and possible in future application of such systems

A Supramolecular Approach to Medicinal Chemistry: Medicine Beyond the Molecule

Science.gov (United States)

Smith, David K.

2005-03-01

This article focuses on the essential roles played by intermolecular forces in mediating the interactions between chemical molecules and biological systems. Intermolecular forces constitute a key topic in chemistry programs, yet can sometimes seem disconnected from real-life applications. However, by taking a "supramolecular" view of medicinal chemistry and focusing on interactions between molecules, it is possible to come to a deeper understanding of recent developments in medicine. This allows us to gain a real insight into the interface between biology and chemistry—an interdisciplinary area that is crucial for the development of modern medicinal products. This article emphasizes a conceptual view of medicinal chemistry, which has important implications for the future, as the supramolecular approach to medicinal-chemistry products outlined here is rapidly allowing nanotechnology to converge with medicine. In particular, this article discusses recent developments including the rational design of drugs such as Relenza and Tamiflu, the mode of action of vancomycin, and the mechanism by which bacteria develop resistance, drug delivery using cyclodextrins, and the importance of supramolecular chemistry in understanding protein aggregation diseases such as Alzheimer's and Creutzfield Jacob. The article also indicates how taking a supramolecular approach will enable the development of new nanoscale medicines.

Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

Directory of Open Access Journals (Sweden)

Hironori Izawa

2010-07-01

Full Text Available Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

Supramolecular photocatalyst of RGO-cyclodextrin-TiO2

International Nuclear Information System (INIS)

Shen, Jianfeng; Li, Na; Ye, Mingxin

2013-01-01

Graphical abstract: Supramolecular photocatalyst of RGO-cyclodextrin-TiO 2 was achieved, which showed high photocatalytic activity and adsorption capacity. Highlights: •Supramolecular photocatalyst of RGO-cyclodextrin-TiO 2 was achieved. •β-CD molecules acted as linkers between RGO and monodisperse TiO 2 nanoparticles. •Reduction of GO and preparation of RGO-cyclodextrin-TiO 2 was simultaneous. •The prepared RGO-cyclodextrin-TiO 2 shows high photocatalytic activity and adsorption capacity. -- Abstract: Reduced graphene oxide (RGO)/β-cyclodextrin (β-CD)/titanium oxide (TiO 2 ) supramolecular photocatalyst was synthesized with a one-pot hydrothermal method. The reducing process was accomplished with the attaching of β-CD and generation of TiO 2 . β-CD acted as a linker between RGO and monodisperse TiO 2 nanoparticles. The structure and composition of the hybrid had been characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, thermal gravimetric analysis, X-ray diffraction and Transmission electron microscopy. The as-prepared RGO-CD-TiO 2 showed significant enhanced performance for phenol and Cr (VI) removal, due to the effective transfer of photo-generated electron from TiO2 to RGO and improved absorbance performance of the hybrid

Hierarchical Formation of Fibrillar and Lamellar Self-Assemblies from Guanosine-Based Motifs

Directory of Open Access Journals (Sweden)

Paolo Neviani

2010-01-01

Full Text Available Here we investigate the supramolecular polymerizations of two lipophilic guanosine derivatives in chloroform by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties.

Self-assembly as a design tool for the integration of photonic structures into excitonic solar cells

KAUST Repository

Guldin, S.; Docampo, P.; Hü ttner, S.; Kohn, P.; Stefik, M.; Snaith, H. J.; Wiesner, U.; Steiner, U.

2011-01-01

) into dye-sensitized solar cells (DSCs). In both cases, the self-assembly of soft matter plays a key role in the fabrication process of the TiO2 electrode. One approach relies on a combination of colloidal self-assembly and the self-assembly of block

Fabrication of porous TiO{sub 2} films using a spongy replica prepared by layer-by-layer self-assembly method: Application to dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Tsuge, Yosuke [Department of Applied Physics and Physico-informatics, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama-shi 223-8522 (Japan)]. E-mail: yotsuge@appi.keio.ac.jp; Inokuchi, Kohei [Department of Applied Physics and Physico-informatics, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama-shi 223-8522 (Japan); Onozuka, Katsuhiro [Department of Applied Physics and Physico-informatics, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama-shi 223-8522 (Japan); Shingo, Ohno [Research and Development Division, Bridgestone Corporation, 3-1-1 Ogawahigashi-cho, Kodaira-shi, Tokyo-to 187-8531 (Japan); Sugi, Shinichiro [Research and Development Division, Bridgestone Corporation, 3-1-1 Ogawahigashi-cho, Kodaira-shi, Tokyo-to 187-8531 (Japan); Yoshikawa, Masato [Research and Development Division, Bridgestone Corporation, 3-1-1 Ogawahigashi-cho, Kodaira-shi, Tokyo-to 187-8531 (Japan); Shiratori, Seimei [Department of Applied Physics and Physico-informatics, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama-shi 223-8522 (Japan)]. E-mail: shiratori@appi.keio.ac.jp

2006-03-21

In this study, we report the fabrication of the anatase TiO{sub 2} films with high porosity using a new spongy replica which prepared by layer-by-layer self-assembly technique. The scanning electron microscope photographs revealed that the spongy replica has an extremely porous microstructure and high surface area. Moreover, this porous replica was easily fabricated from a very flat film through the action with silver acetate solution. This method facilitated the porous TiO{sub 2} films with a high surface area. Additionally, by this method, a necking between the TiO{sub 2} films was strong and the amount of loaded dye was increased, so that the increase of forward electron transfer between the TiO{sub 2} films on the surface and the TiO{sub 2} films on the substrate. By using the fabricated porous TiO{sub 2} films as the photoelectrode for dye-sensitized solar cell, the improvement of the photocurrent-voltage characteristic was achieved, resulting in an energy conversion efficiency of Eff = 2.66% with the thickness of approximately 5 {mu}m.

Hybrid Monolith of Graphene/TEMPO-Oxidized Cellulose Nanofiber as Mechanically Robust, Highly Functional, and Recyclable Adsorbent of Methylene Blue Dye

Directory of Open Access Journals (Sweden)

Asif Hussain

2018-01-01

Full Text Available Herein we demonstrate first report on fabrication, characterization, and adsorptive appraisal of graphene/cellulose nanofibers (GO/CNFs monolith for methylene blue (MB dye. Series of hybrid monolith (GO/CNFs were assembled via urea assisted self-assembly method. Hybrid materials were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction patterns, Raman spectroscopy, elemental analysis, thermogravimetric curve analysis, specific surface area, surface charge density measurement, and compressional mechanical analysis. It was proposed that strong chemical interaction (mainly hydrogen bonding was responsible for the formation of hybrid assembly. GO/CNFs monolith showed mechanically robust architecture with tunable pore structure and surface properties. GO/CNFs adsorbent could completely remove trace to moderate concentrations of MB dye and follow pseudo-second-order kinetics model. Adsorption isotherm behaviors were found in the following order: Langmuir isotherm > Freundlich isotherm > Temkin isotherm model. Maximum adsorption capacity of 227.27 mg g−1 was achieved which is much higher than reported graphene based monoliths and magnetic adsorbent. Incorporation of nanocellulose follows exponential relationship with dye uptake capacities. High surface charge density and specific surface area were main dye adsorptive mechanism. Regeneration and recycling efficiency was achieved up to four consecutive cycles with cost-effective recollection and zero recontamination of treated water.

Aerobic Biodegradation Characteristic of Different Water-Soluble Azo Dyes

Directory of Open Access Journals (Sweden)

Shixiong Sheng

2017-12-01

Full Text Available This study investigated the biodegradation performance and characteristics of Sudan I and Acid Orange 7 (AO7 to improve the biological dye removal efficiency in wastewater and optimize the treatment process. The dyes with different water-solubility and similar molecular structure were biologically treated under aerobic condition in parallel continuous-flow mixed stirred reactors. The biophase analysis using microscopic examination suggested that the removal process of the two azo dyes is different. Removal of Sudan I was through biosorption, since it easily assembled and adsorbed on the surface of zoogloea due to its insolubility, while AO7 was biodegraded incompletely and bioconverted, the AO7 molecule was decomposed to benzene series and inorganic ions, since it could reach the interior area of zoogloea due to the low oxidation-reduction potential conditions and corresponding anaerobic microorganisms. The transformation of NH3-N, SO42− together with the presence of tryptophan-like components confirm that AO7 can be decomposed to non-toxic products in an aerobic bioreactor. This study provides a theoretical basis for the use of biosorption or biodegradation mechanisms for the treatment of different azo dyes in wastewater.

The btp [2,6-bis(1,2,3-triazol-4-yl)pyridine] binding motif: a new versatile terdentate ligand for supramolecular and coordination chemistry.

Science.gov (United States)

Byrne, Joseph P; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

2014-08-07

Ligands containing the btp [2,6-bis(1,2,3-triazol-4-yl)pyridine] motif have appeared with increasing regularity over the last decade. This class of ligands, formed in a one pot ‘click’ reaction, has been studied for various purposes, such as for generating d and f metal coordination complexes and supramolecular self-assemblies, and in the formation of dendritic and polymeric networks, etc. This review article introduces btp as a novel and highly versatile terdentate building block with huge potential in inorganic supramolecular chemistry. We will focus on the coordination chemistry of btp ligands with a wide range of metals, and how it compares with other classical pyridyl and polypyridyl based ligands, and then present a selection of applications including use in catalysis, enzyme inhibition, photochemistry, molecular logic and materials, e.g. polymers, dendrimers and gels. The photovoltaic potential of triazolium derivatives of btp and its interactions with anions will also be discussed.

Ytterbium oxide nanodots via block copolymer self-assembly and their efficacy to dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Park, Kwang-Won; Ahn, Sungwoo; Lim, Sung-Hwan; Jin, Ming Hao; Song, Jeemin; Yun, Seung-Young [Department of Chemistry, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 156-756 (Korea, Republic of); Kim, Hyeon Mo; Kim, Gi Jeong [Sooyang Chemtec Co., Ltd., Digital-ro 32-gil, Guro-gu, Seoul 152-777 (Korea, Republic of); Ok, Kang Min [Department of Chemistry, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 156-756 (Korea, Republic of); Hong, Jongin, E-mail: hongj@cau.ac.kr [Department of Chemistry, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 156-756 (Korea, Republic of)

2016-02-28

Graphical abstract: - Highlights: • A novel phosphor, Yb{sub 2}O{sub 3}, was developed as a UV-absorbing spectral converter for dye-sensitized solar cells (DSSCs). • The ordered Yb{sub 2}O{sub 3} nanodots trap more light and prevent charge recombination at the interfaces. • Their multifunctionality improves DSSC performance for both Ru-based and organic dyes. - Abstract: In this study, we develop a novel phosphor, Yb{sub 2}O{sub 3}, to be used as the spectral converter in dye-sensitized solar cells (DSSCs) for the efficient capture of ultraviolet light via down-conversion. These zero-dimensional nanodots with a high refractive index also allow more light to be trapped and can prevent charge recombination at the interfaces in the DSSCs. Compared to DSSCs without the nanodots, the DSSCs fabricated with the Yb{sub 2}O{sub 3} nanodots exhibits higher power-conversion efficiencies for both the N719 (10.5%) and CSD-01 (20.5%) dyes. The multifunctionality of the Yb{sub 2}O{sub 3} nanodots provides a new route for improving the performance of DSSCs.

Hydrazine-mediated construction of nanocrystal self-assembly materials.

Science.gov (United States)

Zhou, Ding; Liu, Min; Lin, Min; Bu, Xinyuan; Luo, Xintao; Zhang, Hao; Yang, Bai

2014-10-28

Self-assembly is the basic feature of supramolecular chemistry, which permits to integrate and enhance the functionalities of nano-objects. However, the conversion of self-assembled structures to practical materials is still laborious. In this work, on the basis of studying one-pot synthesis, spontaneous assembly, and in situ polymerization of aqueous semiconductor nanocrystals (NCs), NC self-assembly materials are produced and applied to design high performance white light-emitting diode (WLED). In producing self-assembly materials, the additive hydrazine (N2H4) is curial, which acts as the promoter to achieve room-temperature synthesis of aqueous NCs by favoring a reaction-controlled growth, as the polyelectrolyte to weaken inter-NC electrostatic repulsion and therewith facilitate the one-dimensional self-assembly, and in particular as the bifunctional monomers to polymerize with mercapto carboxylic acid-modified NCs via in situ amidation reaction. This strategy is versatile for mercapto carboxylic acid-modified aqueous NCs, for example CdS, CdSe, CdTe, CdSe(x)Te(1-x), and Cd(y)Hg(1-y)Te. Because of the multisite modification with carboxyl, the NCs act as macromonomers, thus producing cross-linked self-assembly materials with excellent thermal, solvent, and photostability. The assembled NCs preserve strong luminescence and avoid unpredictable fluorescent resonance energy transfer, the main problem in design WLED from multiple NC components. These advantages allow the fabrication of NC-based WLED with high color rendering index (86), high luminous efficacy (41 lm/W), and controllable color temperature.

Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

Science.gov (United States)

Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

2015-06-28

Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant

Enhancement of dye-sensitized solar cells performances by improving electron density in conduction band of nanostructure TiO2 electrode with using a metalloporphyrin as additional dye

International Nuclear Information System (INIS)

Mojiri-Foroushani, M.; Dehghani, H.; Salehi-Vanani, N.

2013-01-01

Highlights: ► N719 and ZnTCPP dyes were used in a sequential adsorption process. ► By using two dyes, improved the performance of the cell. ► Density of electrons in the conduction band of TiO 2 electrodes improved. -- Abstract: A zinc(II)-porphyrin dye with four carboxyphenyl moiety of ancillary (ZnTCPP) was studied as a sensitizer in combination with a ruthenium complex (N719) in co-sensitized solar cells. The high molar extinction coefficient (ε) of porphyrin dyes leads to high light absorption in the dye-sensitized TiO 2 electrode. In spite of the high ε of porphyrin dyes, they usually have a narrow absorption band and also to suffer from dye aggregation due to their planar structural nature. This causes lower efficiencies of the DSSCs for the porphyrins than the ruthenium complexes. Co-sensitization of two or more dyes with complementary absorption spectra on TiO 2 film is an important method to further enhance the IPCE response and energy conversion efficiency of dye-sensitized solar cells. Interestingly, when the ZnTCPP electrode was used to assemble a co-sensitized solar cell by additional adsorption of N719 dye, the efficiency improved to 6.35% (in comparison to N719 that the efficiency was 4.74%). The results indicated that the co-sensitized device shows enhancements of photovoltaic performance not only in short-circuit current density (J SC ) but also in open-circuit voltage (V OC ). In the present study we have been shown that co-sensitization of a zinc(II)-porphyrin with N719 dye changes the energy levels of the TiO 2 electrode and in result produces further improvement for its device performance

Some features of the molecular assembly of copper porphyrazines

International Nuclear Information System (INIS)

Valkova, L.; Borovkov, N.; Kopranenkov, V.; Pisani, M.; Bossi, M.; Rustichelli, F.

2002-01-01

Floating layers and Langmuir-Blodgett (LB) films of copper porphyrazine (CuPaz) and its tetra-tert-butyl-substituted homologue (CuPaz') are studied. Contrary to phthalocyanines, the monolayer phase in the porphyrazine layers is metastable and transforms directly into the tetralayer one under moderate compression. In diffraction patterns and electronic spectra of the LB films, supramolecular peaks indicating collectivizing of the molecular electron density in direction perpendicular to the main axis of the macrocycle are found. The data obtained indicate the prismatic 3-D supermolecule to be the simplest structural unit of the porphyrazine assembly

Mineral Surface-Templated Self-Assembling Systems: Case Studies from Nanoscience and Surface Science towards Origins of Life Research.

Science.gov (United States)

Gillams, Richard J; Jia, Tony Z

2018-05-08

An increasing body of evidence relates the wide range of benefits mineral surfaces offer for the development of early living systems, including adsorption of small molecules from the aqueous phase, formation of monomeric subunits and their subsequent polymerization, and supramolecular assembly of biopolymers and other biomolecules. Each of these processes was likely a necessary stage in the emergence of life on Earth. Here, we compile evidence that templating and enhancement of prebiotically-relevant self-assembling systems by mineral surfaces offers a route to increased structural, functional, and/or chemical complexity. This increase in complexity could have been achieved by early living systems before the advent of evolvable systems and would not have required the generally energetically unfavorable formation of covalent bonds such as phosphodiester or peptide bonds. In this review we will focus on various case studies of prebiotically-relevant mineral-templated self-assembling systems, including supramolecular assemblies of peptides and nucleic acids, from nanoscience and surface science. These fields contain valuable information that is not yet fully being utilized by the origins of life and astrobiology research communities. Some of the self-assemblies that we present can promote the formation of new mineral surfaces, similar to biomineralization, which can then catalyze more essential prebiotic reactions; this could have resulted in a symbiotic feedback loop by which geology and primitive pre-living systems were closely linked to one another even before life’s origin. We hope that the ideas presented herein will seed some interesting discussions and new collaborations between nanoscience/surface science researchers and origins of life/astrobiology researchers.

Mineral Surface-Templated Self-Assembling Systems: Case Studies from Nanoscience and Surface Science towards Origins of Life Research

Directory of Open Access Journals (Sweden)

Richard J. Gillams

2018-05-01

Full Text Available An increasing body of evidence relates the wide range of benefits mineral surfaces offer for the development of early living systems, including adsorption of small molecules from the aqueous phase, formation of monomeric subunits and their subsequent polymerization, and supramolecular assembly of biopolymers and other biomolecules. Each of these processes was likely a necessary stage in the emergence of life on Earth. Here, we compile evidence that templating and enhancement of prebiotically-relevant self-assembling systems by mineral surfaces offers a route to increased structural, functional, and/or chemical complexity. This increase in complexity could have been achieved by early living systems before the advent of evolvable systems and would not have required the generally energetically unfavorable formation of covalent bonds such as phosphodiester or peptide bonds. In this review we will focus on various case studies of prebiotically-relevant mineral-templated self-assembling systems, including supramolecular assemblies of peptides and nucleic acids, from nanoscience and surface science. These fields contain valuable information that is not yet fully being utilized by the origins of life and astrobiology research communities. Some of the self-assemblies that we present can promote the formation of new mineral surfaces, similar to biomineralization, which can then catalyze more essential prebiotic reactions; this could have resulted in a symbiotic feedback loop by which geology and primitive pre-living systems were closely linked to one another even before life’s origin. We hope that the ideas presented herein will seed some interesting discussions and new collaborations between nanoscience/surface science researchers and origins of life/astrobiology researchers.

Use of grape seed and its natural polyphenol extracts as a natural organic coagulant for removal of cationic dyes.

Science.gov (United States)

Jeon, Jong-Rok; Kim, Eun-Ju; Kim, Young-Mo; Murugesan, Kumarasamy; Kim, Jae-Hwan; Chang, Yoon-Seok

2009-11-01

Natural organic coagulants (NOCs) such as chitosan and Moringa oleifera seeds have been extensively characterized for potential application in water treatment as an alternative to metal-based coagulants. However, the action of both chitosan and M. oleifera seeds is mainly restricted to anionic organic pollutants because of their cationic functional groups affording poor cationic pollutant coagulation by electrostatic repulsion. In this study, we employed ethanolic grape seed extract (GSE) and grape seed-derived polyphenols such as tannic acid and catechin in an effort to find novel NOCs showing stable anionic forms for removal of cationic organic pollutants. The target substances tested were malachite green (MG) and crystal violet (CV), both mutagenic cationic dyes. Polyphenol treatment induced fast decolorization followed by gradual floc formation concomitant with red or blue shifts in maximum absorbance wavelengths of the cationic dyes. Liquid chromatography analysis of flocs formed by polyphenols directly showed that initial supramolecular complexes attributed mainly to electrostatic attraction between polyphenol hydroxyphenyl groups and cationic dyes further progressed into stronger aggregates, leading to precipitation of dye-polyphenol complexes. Consistent with the results obtained using catechin and tannic acid, use of GSE also resulted in effective decolorization and coagulation of soluble MG and CV in aqueous solutions. Screening of several organic GSE components for NOC activity strongly suggested that natural polyphenols are the main organic ingredients causing MG and CV removal via gradual floc formation. The treatment by natural polyphenols and GSE decreased toxicity of MG- or CV-contaminated water.

Octane-Assisted Reverse Micellar Dyeing of Cotton with Reactive Dyes

Directory of Open Access Journals (Sweden)

Alan Yiu-lun Tang

2017-12-01

Full Text Available In this study, we investigated the computer colour matching (CCM of cotton fabrics dyed with reactive dye using the octane-assisted reverse micellar approach. The aim of this study is to evaluate the colour quality and compare the accuracy between CCM forecasting and simulated dyeing produced by conventional water-based dyeing and octane-assisted reverse micellar dyeing. First, the calibration of dyeing databases for both dyeing methods was established. Standard samples were dyed with known dye concentrations. Computer colour matching was conducted by using the colour difference formula of International Commission on Illumination (CIE L*a*b*. Experimental results revealed that the predicted concentrations were nearly the same as the expected known concentrations for both dyeing methods. This indicates that octane-assisted reverse micellar dyeing system can achieve colour matching as good as the conventional water-based dyeing system. In addition, when comparing the colour produced by the conventional water-based dyeing system and the octane-assisted reverse micellar dyeing system, the colour difference (ΔE is ≤1, which indicates that the reverse micellar dyeing system could be applied for industrial dyeing with CCM.

A supramolecular strategy for self-mobile adsorption sites in affinity membrane.

Science.gov (United States)

Lin, Ligang; Dong, Meimei; Liu, Chunyu; Wei, Chenjie; Wang, Yuanyuan; Sun, Hui; Ye, Hui

2014-09-01

Disclosed here is the design of a novel supramolecular membrane with self-mobile adsorption sites for biomolecules purification. In the 3D micropore channels of membrane matrix, the ligands are conjugated onto the cyclic compounds in polyrotaxanes for protein adsorption. During membrane filtration, the adsorption sites can rotate and/or slide along the axial chain, which results in the enhanced adsorption capacity. The excellent performance of supra-molecular membrane is related with the dynamic working manner of adsorption sites, which plays a crucial role on avoiding spatial mismatching and short-circuit effect. The supra-molecular strategy described here has general suggestions for the "sites" involved technologies such as catalysis, adsorption, and sensors, which is of broad interest. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dyeing of Polyester with Disperse Dyes: Part 2. Synthesis and Dyeing Characteristics of Some Azo Disperse Dyes for Polyester Fabrics

Directory of Open Access Journals (Sweden)

Alya M. Al-Etaibi

2016-06-01

Full Text Available The goal of this study was to utilize carrier for accelerating the rate of dyeing not only to enhance dyeing of polyester fabrics dyed with disperse dyes 3a,b, but also to save energy. Both the color strength expressed as dye uptake and the fastness properties of the dyed fabrics were evaluated.

Interpenetrated Binary Supramolecular Nanofibers for Sensitive Fluorescence Detection of Six Classes of Explosives.

Science.gov (United States)

Xiong, Wei; Zhu, Qijian; Gong, Yanjun; Wang, Chen; Che, Yanke; Zhao, Jincai

2018-04-03

In this work, we develop a sequential self-assembly approach to fabricate interpenetrated binary supramolecular nanofibers consisting of carbazole oligomer 1-cobalt(II) (1-Co 2+ ) coordination nanofibers and oligomer 2 nanofibers for the sensitive detection of six classes of explosives. When exposed to peroxide explosives (e.g., H 2 O 2 ), Co 2+ in 1-Co 2+ coordination nanofibers can be reduced to Co + that can transfer an electron to the excited 2 nanofibers and thereby quench their fluorescence. On the other hand, when exposed to the other five classes of explosives, the excited 2 nanofibers can transfer an electron to explosives to quench their fluorescence. On the basis of the distinct fluorescence quenching mechanisms, six classes of explosives can be sensitively detected. Herein, we provide a new strategy to design broad-band fluorescence sensors for a rich identification of threats.

Achieving 3-D Nanoparticle Assembly in Nanocomposite Thin Films via Kinetic Control

Energy Technology Data Exchange (ETDEWEB)

Huang, Jingyu; Xiao, Yihan; Xu, Ting [UCB

2017-02-20

Nanocomposite thin films containing well-ordered nanoparticle (NP) assemblies are ideal candidates for the fabrication of metamaterials. Achieving 3-D assembly of NPs in nanocomposite thin films is thermodynamically challenging as the particle size gets similar to that of a single polymer chain. The entropic penalties of polymeric matrix upon NP incorporation leads to NP aggregation on the film surface or within the defects in the film. Controlling the kinetic pathways of assembly process provides an alternative path forward by arresting the system in nonequilibrium states. Here, we report the thin film 3-D hierarchical assembly of 20 nm NPs in supramolecules with a 30 nm periodicity. By mediating the NP diffusion kinetics in the supramolecular matrix, surface aggregation of NPs was suppressed and NPs coassemble with supramolecules to form new 3-D morphologies in thin films. The present studies opened a viable route to achieve designer functional composite thin films via kinetic control.

Fe-tannic acid complex dye as photo sensitizer for different morphological ZnO based DSSCs

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Çakar, Soner; Özacar, Mahmut

2016-06-01

In this paper we have synthesized different morphological ZnO nanostructures via microwave hydrothermal methods at low temperature within a short time. We described different morphologies of ZnO at different Zn(NO3)2/KOH mole ratio. The ZnO nanostructures were characterized via X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and UV-vis spectrophotometry. All ZnO structures have hexagonal wurtzite type structures. The FESEM images showed various morphologies of ZnO such as plate, rod and nanoparticles. Dye sensitized solar cells have been assembled by these different morphological structures photo electrode and tannic acid or Fe-tannic acid complex dye as sensitizer. We have achieved at maximum efficiencies of photovoltaic cells prepared with ZnO plate in all dye systems. The conversion efficiencies of dye sensitized solar cells are 0.37% and 1.00% with tannic acid and Fe-tannic acid complex dye, respectively.

Nano-dyeing

Directory of Open Access Journals (Sweden)

Ning Cui-Juan

2016-01-01

Full Text Available Dyeing nanofibers is a frontier of both modern textile engineering and nanotechnology. This paper suggest a feasible method for dyeing nanofibers with a natural red (Roselle Calyx by bubble electrospinning. Reactive dye (Red S3B and acid dye (Red 2B were also used in the experiment for comparison. The dyeing process was finished during the spinning process.

Opal-like Multicolor Appearance of Self-Assembled Photonic Array.

Science.gov (United States)

Arnon, Zohar A; Pinotsi, Dorothea; Schmidt, Matthias; Gilead, Sharon; Guterman, Tom; Sadhanala, Aditya; Ahmad, Shahab; Levin, Aviad; Walther, Paul; Kaminski, Clemens F; Fändrich, Marcus; Kaminski Schierle, Gabriele S; Adler-Abramovich, Lihi; Shimon, Linda J W; Gazit, Ehud

2018-06-20

Molecular self-assembly of short peptide building blocks leads to the formation of various material architectures that may possess unique physical properties. Recent studies had confirmed the key role of biaromaticity in peptide self-assembly, with the diphenylalanine (FF) structural family as an archetypal model. Another significant direction in the molecular engineering of peptide building blocks is the use of fluorenylmethoxycarbonyl (Fmoc) modification, which promotes the assembly process and may result in nanostructures with distinctive features and macroscopic hydrogel with supramolecular features and nanoscale order. Here, we explored the self-assembly of the protected, noncoded fluorenylmethoxycarbonyl-β,β-diphenyl-Ala-OH (Fmoc-Dip) amino acid. This process results in the formation of elongated needle-like crystals with notable aromatic continuity. By altering the assembly conditions, arrays of spherical particles were formed that exhibit strong light scattering. These arrays display vivid coloration, strongly resembling the appearance of opal gemstones. However, unlike the Rayleigh scattering effect produced by the arrangement of opal, the described optical phenomenon is attributed to Mie scattering. Moreover, by controlling the solution evaporation rate, i.e., the assembly kinetics, we were able to manipulate the resulting coloration. This work demonstrates a bottom-up approach, utilizing self-assembly of a protected amino acid minimal building block, to create arrays of organic, light-scattering colorful surfaces.

Surfaces wettability and morphology modulation in a fluorene derivative self-assembly system

Energy Technology Data Exchange (ETDEWEB)

Cao, Xinhua, E-mail: caoxhchem@163.com; Gao, Aiping; Zhao, Na; Yuan, Fangyuan; Liu, Chenxi; Li, Ruru

2016-04-15

Graphical abstract: - Highlights: • The different structures could be obtained in this self-assembly system. • A water-drop could freely roll on the xerogel film with the sliding angle of 15.0. • The superhydrophobic surface can be obtained via supramolecular self-assembly. - Abstract: A new organogelator based on fluorene derivative (gelator 1) was designed and synthesized. Organogels could be obtained via the self-assembly of the derivative in acetone, toluene, ethyl acetate, hexane, DMSO and petroleum ether. The self-assembly process was thoroughly characterized using field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), UV–vis, FT-IR and the contact angle. Surfaces with different morphologies and wetting properties were formed via the self-assembly of gelator 1 in the six different solvents. Interestingly, a superhydrophobic surface with a contact angle of 150° was obtained from organogel 1 in DMSO and exhibited the lotus-effect. The sliding angle necessary for a water droplet to move on the glass was only 15°. Hydrogen bonding and van der Waals forces were attributed as the main driving forces for gel formation.

Photoelectrochemical studies of dye-sensitized solar cells using organic dyes

Energy Technology Data Exchange (ETDEWEB)

Marinado, Tannia

2009-10-15

The dye-sensitized solar cell (DSC) is a promising efficient low-cost molecular photovoltaic device. One of the key components in DSCs is the dye, as it is responsible for the capture of sunlight. State-of-the-art DSC devices, based on ruthenium dyes, show record efficiencies of 10-12 %. During the last decade, metal-free organic dyes have been extensively explored as sensitizers for DSC application. The use of organic dyes is particularly attractive as it enables easy structural modifications, due to fairly short synthetic routes and reduced material cost. Novel dye should in addition to the light-harvesting properties also be compatible with the DSC components. In this thesis, a series of new organic dyes are investigated, both when integrated in the DSC device and as individual components. The evaluation methods consisted of different electrochemical and photoelectrochemical techniques. Whereas the light-harvesting properties of the dyes were fairly easily improved, the behavior of the dye integrated in the DSC showed less predictable photovoltaic results. The dye series studied in Papers II and IV revealed that their dye energetics limited vital electron-transfer processes, the dye regeneration (Paper II) and injection quantum yield (Paper IV). Further, in Papers III-VI, it was observed that different dye structures seemed to alter the interfacial electron recombination with the electrolyte. In addition to the dye structure sterics, some organic dyes appear to enhance the interfacial recombination, possibly due to specific dye-redox acceptor interaction (Paper V). The impact of dye sterical modifications versus the use of coadsorbent was explored in Paper VI. The dye layer properties in the presence and absence of various coadsorbents were further investigated in Paper VII. The core of this thesis is the identification of the processes and properties limiting the performance of the DSC device, aiming at an overall understanding of the compatibility between the

Influence of polar solvents on photovoltaic performance of Monascusred dye-sensitized solar cell

Science.gov (United States)

Lee, Jae Wook; Kim, Tae Young; Ko, Hyun Seok; Han, Shin; Lee, Suk-Ho; Park, Kyung Hee

Dye-sensitized solar cells (DSSCs) were assembled using natural dyes extracted from Monascus red pigment as a sensitizer. In this work, we studied the adsorption characteristics for harvesting sunlight and the electrochemical behavior for electron transfer in Monascus red DSSC using different solvents. The effect of polar aprotic and protic solvents including water, ethanol, and dimethylsulfoxide (DMSO) used in the sensitization process was investigated for the improvement in conversion efficiency of a cell. As for the Monascus red dye-sensitized electrode in DMSO solvent, the solar cell yields a short-circuit current density (Jsc) of 1.23 mA/cm2, a photovoltage (Voc) of 0.75 V, and a fill factor of 0.72, corresponding to an energy conversion efficiency (η) of 0.66%.

Porphyrin Dye-Sensitized Zinc Oxide Aggregated Anodes for Use in Solar Cells

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Yu-Kai Syu

2016-08-01

Full Text Available Porphyrin YD2-o-C8-based dyes were employed to sensitize room-temperature (RT chemical-assembled ZnO aggregated anodes for use in dye-sensitized solar cells (DSSCs. To reduce the acidity of the YD2-o-C8 dye solution, the proton in the carboxyl group of a porphyrin dye was replaced with tetrabuthyl ammonium (TBA+ in this work. The short-circuit current density (Jsc of the YD2-o-C8-TBA-sensitized ZnO DSSCs is higher than that of the YD2-o-C8-sensitized cells, resulting in the improvement of the efficiency of the YD2-o-C8-based ZnO DSSCs. With an appropriate incorporation of chenodeoxycholic acid (CDCA as coadsorbate, the Jsc and efficiency of the YD2-o-C8-TBA-sensitized ZnO DSSC are enhanced due to the improvement of the incident-photon-to-current efficiency (IPCE values in the wavelength range of 400–450 nm. Moreover, a considerable increase in Jsc is achieved by the addition of a light scattering layer in the YD2-o-C8-TBA-sensitized ZnO photoanodes. Significant IPCE enhancement in the range 475–600 nm is not attainable by tuning the YD2-o-C8-TBA sensitization processes for the anodes without light scattering layers. Using the RT chemical-assembled ZnO aggregated anode with a light scattering layer, an efficiency of 3.43% was achieved in the YD2-o-C8-TBA-sensitized ZnO DSSC.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry.

Science.gov (United States)

Cremer, Paul S; Flood, Amar H; Gibb, Bruce C; Mobley, David L

2017-12-19

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists - with their expertise in macrocyclic synthesis and measuring supramolecular interactions - have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Science.gov (United States)

Cremer, Paul S.; Flood, Amar H.; Gibb, Bruce C.; Mobley, David L.

2018-01-01

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists -- with their expertise in macrocyclic synthesis and measuring supramolecular interactions -- have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Nanoscale isoindigo-carriers: self-assembly and tunable properties

Directory of Open Access Journals (Sweden)

Tatiana N. Pashirova

2017-02-01

Full Text Available Over the last decade isoindigo derivatives have attracted much attention due to their high potential in pharmacy and in the chemistry of materials. In addition, isoindigo derivatives can be modified to form supramolecular structures with tunable morphologies for the use in drug delivery. Amphiphilic long-chain dialkylated isoindigos have the ability to form stable solid nanoparticles via a simple nanoprecipitation technique. Their self-assembly was investigated using tensiometry, dynamic light scattering, spectrophotometry, and fluorometry. The critical association concentrations and aggregate sizes were measured. The hydrophilic–lipophilic balance of alkylated isoindigo derivatives strongly influences aggregate morphology. In the case of short-chain dialkylated isoindigo derivatives, supramolecular polymers of 200 to 700 nm were formed. For long-chain dialkylated isoindigo derivatives, micellar aggregates of 100 to 200 nm were observed. Using micellar surfactant water-soluble forms of monosubstituted 1-hexadecylisoindigo as well as 1,1′-dimethylisoindigo were prepared for the first time. The formation of mixed micellar structures of different types in micellar anionic surfactant solutions (sodium dodecyl sulfate was determined. These findings are of practical importance and are of potential interest for the design of drug delivery systems and new nanomaterials.

The role of supramolecular chemistry in stimuli responsive and hierarchically structured functional organic materials

NARCIS (Netherlands)

Schenning, A.P.H.J.; Bastiaansen, C.W.M.; Broer, D.J.; Debije, M.G.

2014-01-01

ABSTRACT: In this review, we show the important role of supramolecular chemistry in the fabrication of stimuli responsive and hierarchically structured liquid crystalline polymer networks. Supramolecular interactions can be used to create three dimensional order or as molecular triggers in materials

Characteristics of dye-sensitized solar cells using natural dye

Energy Technology Data Exchange (ETDEWEB)

Furukawa, Shoji, E-mail: furukawa@cse.kyutech.ac.j [Graduate School of Computer Science and Systems Engineering, Kyushu Institute of Technology, 680-4 Kawazu, Iizuka-shi, Fukuoka-ken 820-8502 (Japan); Iino, Hiroshi; Iwamoto, Tomohisa; Kukita, Koudai; Yamauchi, Shoji [Graduate School of Computer Science and Systems Engineering, Kyushu Institute of Technology, 680-4 Kawazu, Iizuka-shi, Fukuoka-ken 820-8502 (Japan)

2009-11-30

Dye-sensitized solar cells are expected to be used for future clean energy. Recently, most of the researchers in this field use Ruthenium complex as dye in the dye-sensitized solar cells. However, Ruthenium is a rare metal, so the cost of the Ruthenium complex is very high. In this paper, various dye-sensitized solar cells have been fabricated using natural dye, such as the dye of red-cabbage, curcumin, and red-perilla. As a result, it was found that the conversion efficiency of the solar cell fabricated using the mixture of red-cabbage and curcumin was about 0.6% (light source: halogen lamp), which was larger than that of the solar cells using one kind of dye. It was also found that the conversion efficiency was about 1.0% for the solar cell with the oxide semiconductor film fabricated using polyethylene glycol (PEG) whose molecular weight was 2,000,000 and red-cabbage dye. This indicates that the cost performance (defined by [conversion efficiency]/[cost of dye]) of the latter solar cell (dye: red-cabbage) is larger by more than 50 times than that of the solar cell using Ruthenium complex, even if the effect of the difference between the halogen lamp and the standard light source is taken into account.

Photon Upconversion and Molecular Solar Energy Storage by Maximizing the Potential of Molecular Self-Assembly.

Science.gov (United States)

Kimizuka, Nobuo; Yanai, Nobuhiro; Morikawa, Masa-Aki

2016-11-29

The self-assembly of functional molecules into ordered molecular assemblies and the fulfillment of potentials unique to their nanotomesoscopic structures have been one of the central challenges in chemistry. This Feature Article provides an overview of recent progress in the field of molecular self-assembly with the focus on the triplet-triplet annihilation-based photon upconversion (TTA-UC) and supramolecular storage of photon energy. On the basis of the integration of molecular self-assembly and photon energy harvesting, triplet energy migration-based TTA-UC has been achieved in varied molecular systems. Interestingly, some molecular self-assemblies dispersed in solution or organogels revealed oxygen barrier properties, which allowed TTA-UC even under aerated conditions. The elements of molecular self-assembly were also introduced to the field of molecular solar thermal fuel, where reversible photoliquefaction of ionic crystals to ionic liquids was found to double the molecular storage capacity with the simultaneous pursuit of switching ionic conductivity. A future prospect in terms of innovating molecular self-assembly toward molecular systems chemistry is also discussed.

Mononuclear, trinuclear, and hetero-trinuclear supramolecular complexes containing a new tri-sulfonate ligand and cobalt(II)/copper(II)-(1,10-phenanthroline)2 building blocks

International Nuclear Information System (INIS)

Yu Yunfang; Wei Yongqin; Broer, Ria; Sa Rongjian; Wu Kechen

2008-01-01

Novel mononuclear, trinuclear, and hetero-trinuclear supermolecular complexes, [Co(phen) 2 (H 2 O)(HTST)].2H 2 O (1), [Co 3 (phen) 6 (H 2 O) 2 (TST) 2 ].7H 2 O (2), and [Co 2 Cu(phen) 6 (H 2 O) 2 (TST) 2 ].10H 2 O (3), have been synthesized by the reactions of a new tri-sulfonate ligand (2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, H 3 TST) with the M 2+ (M=Co, Cu) and the second ligand 1,10-phenanthroline (phen). Complex 1 contains a cis-Co(II)(phen) 2 building block and an HTST as monodentate ligand; complex 2 consists of two TST as bidentate ligands connecting one trans- and two cis-Co(II)(phen) 2 building blocks; complex 3 is formed by replacing the trans-Co(II)(phen) 2 in 2 with a trans-Cu(II)(phen) 2 , which is the first reported hetero-trinuclear supramolecular complex containing both the Co(II)(phen) 2 and Cu(II)(phen) 2 as building blocks. The study shows the flexible multifunctional self-assembly capability of the H 3 TST ligands presenting in these supramolecular complexes through coordinative, H-bonding and even π-π stacking interactions. The photoluminescent optical properties of these complexes are also investigated and discussed as well as the second-order nonlinear optical properties of 1. - Graphical abstract: Novel mononuclear, trinuclear, and hetero-trinuclear supermolecular complexes, [Co(phen) 2 (H 2 O)(HTST)].2H 2 O (1), [Co 3 (phen) 6 (H 2 O) 2 (TST) 2 ].7H 2 O (2), and [Co 2 Cu(phen) 6 (H 2 O) 2 (TST) 2 ].10H 2 O (3), have been synthesized by the reactions of a new tri-sulfonate ligand (2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, H 3 TST) with the M 2+ (M=Co, Cu) and the second ligand 1,10-phenanthroline (phen). The study shows the flexible multifunctional self-assembly capability of H 3 TST ligand presenting in these supramolecular complexes

Dynamic Self-Assembly of Gold/Polymer Nanocomposites: pH-Encoded Switching between 1D Nanowires and 3D Nanosponges.

Science.gov (United States)

Zhang, Qi; Xu, Tian-Yi; Zhao, Cai-Xin; Jin, Wei-Hang; Wang, Qian; Qu, Da-Hui

2017-10-05

The design of tunable dynamic self-assembly of nanoparticles with switchable assembled dimensions and morphologies is a challenging goal whose realization is vital for the evolution of smart nanomaterials. Herein, we report on chitosan polymer as an effective supramolecular "glue" for aldehyde-modified Au nanoparticles to reversibly modulate the states of self-assembled nanocomposites. By simultaneous integration of dynamic covalent Schiff base interactions and noncovalent hydrogen bonds, the chitosan/Au nanocomposites could reversibly transform their assembled morphologies from one-dimensional nanowires to three-dimensional nanosponges in response to the variation of pH value. Moreover, the obtained nanosponges could be used as an efficient pH-controlled cargo release system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Incorporation of graphene into SnO2 photoanodes for dye-sensitized solar cells

Science.gov (United States)

Batmunkh, Munkhbayar; Dadkhah, Mahnaz; Shearer, Cameron J.; Biggs, Mark J.; Shapter, Joseph G.

2016-11-01

In dye-sensitized solar cell (DSSC) photoanodes, tin dioxide (SnO2) structures present a promising alternative semiconducting oxide to the conventional titania (TiO2), but they suffer from poor photovoltaic (PV) efficiency caused by insufficient dye adsorption and low energy value of the conduction band. A hybrid structure consisting of SnO2 and reduced graphene oxide (SnO2-RGO) was synthesized via a microwave-assisted method and has been employed as a photoanode in DSSCs. Incorporation of RGO into the SnO2 photoanode enhanced the power conversion efficiency of DSSC device by 91.5%, as compared to the device assembled without RGO. This efficiency improvement can be attributed to increased dye loading, enhanced electron transfer and addition of suitable energy levels in the photoanode. Finally, the use of RGO addresses the major shortcoming of SnO2 when employed as a DSSC photoanode, namely poor dye adsorption and slow electron transfer rate.

A family of uranyl-aromatic dicarboxylate (pht-, ipa-, tpa-) framework hybrid materials: photoluminescence, surface photovoltage and dye adsorption.

Science.gov (United States)

Gao, Xue; Wang, Che; Shi, Zhong-Feng; Song, Jian; Bai, Feng-Ying; Wang, Ji-Xiao; Xing, Yong-Heng

2015-07-07

Four uranyl complexes [(UO2)(pht)H2O]·H2O (pht = phthalic acid) (1), (UO2)2(Hipa)4(H2O)2 (Hipa = isophthalic acid) (2), (UO2)(tpa)(DMF)2 (tpa = terephthalic acid) (3) and (UO2)(box)2 (box = benzoic acid) (4) were synthesized by the reaction of UO2(CH3COO)2·2H2O as the metal source and phthalic acid, isophthalic acid, terephthalic acid or benzoic acid as the ligand. They were characterized by elemental analyses, IR, UV-Vis, XRD, single crystal X-ray diffraction analysis and thermal gravimetric analysis. The structural analysis reveals that complex 1 exhibits a one-dimensional chain structure constructed by the building unit [(UO2)2(pht)4(H2O)2] and further extends the chain into a 2D supramolecular architecture by hydrogen bonding interactions. Complex 2 is a discrete [(UO2)2(Hipa)4(H2O)2] structure, and by the hydrogen bonding interaction, forms a 3D supramolecular structure. In complexes 3 and 4, adjacent uranyl polyhedra form a 1D chain through bridging terephthalic acid and benzoic acid, respectively. In order to extend their functional properties, their photoluminescence, surface photovoltage and dye adsorption properties have been studied.

Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy.

Science.gov (United States)

Loquet, Antoine; Tolchard, James; Berbon, Melanie; Martinez, Denis; Habenstein, Birgit

2017-09-17

Supramolecular protein assemblies play fundamental roles in biological processes ranging from host-pathogen interaction, viral infection to the propagation of neurodegenerative disorders. Such assemblies consist in multiple protein subunits organized in a non-covalent way to form large macromolecular objects that can execute a variety of cellular functions or cause detrimental consequences. Atomic insights into the assembly mechanisms and the functioning of those macromolecular assemblies remain often scarce since their inherent insolubility and non-crystallinity often drastically reduces the quality of the data obtained from most techniques used in structural biology, such as X-ray crystallography and solution Nuclear Magnetic Resonance (NMR). We here present magic-angle spinning solid-state NMR spectroscopy (SSNMR) as a powerful method to investigate structures of macromolecular assemblies at atomic resolution. SSNMR can reveal atomic details on the assembled complex without size and solubility limitations. The protocol presented here describes the essential steps from the production of 13 C/ 15 N isotope-labeled macromolecular protein assemblies to the acquisition of standard SSNMR spectra and their analysis and interpretation. As an example, we show the pipeline of a SSNMR structural analysis of a filamentous protein assembly.

Location of 3-hydroxyproline residues in collagen types I, II, III, and V/XI implies a role in fibril supramolecular assembly.

Science.gov (United States)

Weis, Mary Ann; Hudson, David M; Kim, Lammy; Scott, Melissa; Wu, Jiann-Jiu; Eyre, David R

2010-01-22

Collagen triple helices are stabilized by 4-hydroxyproline residues. No function is known for the much less common 3-hydroxyproline (3Hyp), although genetic defects inhibiting its formation cause recessive osteogenesis imperfecta. To help understand the pathogenesis, we used mass spectrometry to identify the sites and local sequence motifs of 3Hyp residues in fibril-forming collagens from normal human and bovine tissues. The results confirm a single, essentially fully occupied 3Hyp site (A1) at Pro(986) in A-clade chains alpha1(I), alpha1(II), and alpha2(V). Two partially modified sites (A2 and A3) were found at Pro(944) in alpha1(II) and alpha2(V) and Pro(707) in alpha2(I) and alpha2(V), which differed from A1 in sequence motif. Significantly, the distance between sites 2 and 3, 237 residues, is close to the collagen D-period (234 residues). A search for additional D-periodic 3Hyp sites revealed a fourth site (A4) at Pro(470) in alpha2(V), 237 residues N-terminal to site 3. In contrast, human and bovine type III collagen contained no 3Hyp at any site, despite a candidate proline residue and recognizable A1 sequence motif. A conserved histidine in mammalian alpha1(III) at A1 may have prevented 3-hydroxylation because this site in chicken type III was fully hydroxylated, and tyrosine replaced histidine. All three B-clade type V/XI collagen chains revealed the same three sites of 3Hyp but at different loci and sequence contexts from those in A-clade collagen chains. Two of these B-clade sites were spaced apart by 231 residues. From these and other observations we propose a fundamental role for 3Hyp residues in the ordered self-assembly of collagen supramolecular structures.

Dye-Sensitized Solar Cells with Optimal Gel Electrolyte Using the Taguchi Design Method

Directory of Open Access Journals (Sweden)

Jenn-Kai Tsai

2013-01-01

Full Text Available The Taguchi method was adopted to determine the optimal gel electrolyte used in dye-sensitized solar cells (DSSCs. Since electrolyte is a very important factor in fabrication of high performance and long-term stability DSSCs, to find the optimal composition of gel electrolyte is desired. In this paper, the common ingredients used in the liquid electrolyte were chosen. The ingredients then mixed with cheap ionic liquids and poly(vinylidenefluoride-co-hexafluoropropylene (PVDF-HFP were added to form colloidal electrolyte (gel. The optimal composition of each materials in the gel electrolyte determined by Taguchi method consists of 0.03 M I2, 0.15 M KI, 0.6 M LiI, 0.5 M 4-tertbutylpyridine (TBP, and 10% PVDF-HFP dissolved in the acetonitrile and 3-methoxypropionitrile (MPN solution with volume ratio of 2 : 1. The short circuit current density of 14.11 mA/cm2, the conversion efficiency (η of 5.52%, and the lifetime of over 110 days were observed for the dye-sensitized solar cell assembled with optimal gel electrolyte. The lifetime increases 10 times when compared with the conventional dye-sensitized solar cell assembled with liquid electrolyte.

Supramolecular architecture based on [Fe(CN)6]3- metallotectons and melaminium synthons

Science.gov (United States)

Krichen, Firas; Walha, Siwar; Lhoste, Jérôme; Bulou, Alain; Kabadou, Ahlem; Goutenoire, François

2017-10-01

Assembly involving [Fe(CN)6]3- metallotectons as building units and melaminium organic cation has been envisioned in order to elaborate a hybrid supramolecular based on ionic H-bonds with formula {(H-mel)4[Fe(CN)6]Cl} (H-mel+: melaminium cation). The compound has been prepared by diffusion method and characterized by single-crystal X-ray diffraction, EDX analysis, and Raman-IR spectroscopies with assignment from ab initio calculations. The melaminium exhibit self cationic coupling with cyclic hydrogen bonds to give a one dimensional {[H-mel]+}∝ synthon. Therefore, these cationic ribbons are inter-linked via hydrogen bonds by the anionic tectons [Fe(CN)6]3- and chlorine anion resulting on a 3D network. Molecular hirshfeld surfaces revealed that the crystal structure has been supported mainly by Nsbnd H⋯N and Nsbnd H⋯Cl intermolecular Hydrogen bonds and by favoured C⋯C and C⋯N weak interactions.

Manipulation of Energy Transfer Processes in Nano channels

International Nuclear Information System (INIS)

Devaux, A.; Calzaferri, G.

2010-01-01

The realisation of molecular assemblies featuring specific macroscopic properties is a prime example for the versatility of supramolecular organisation. Microporous materials such as zeolite L are well suited for the preparation of host-guest composites containing dyes, complexes, or clusters. This short tutorial focuses on the possibilities offered by zeolite L to study and influence Forster resonance energy transfer inside of its nano channels. The highly organised host-guest materials can in turn be structured on a larger scale to form macroscopic patterns, making it possible to create large-scale structures from small, highly organised building blocks for novel optical applications.

Strong and Reversible Monovalent Supramolecular Protein Immobilization