Sample records for soluble self-assembled supramolecular

  1. Self assembling nanocomposites for protein delivery: supramolecular interactions of soluble polymers with protein drugs. (United States)

    Salmaso, Stefano; Caliceti, Paolo


    Translation of therapeutic proteins to pharmaceutical products is often encumbered by their inadequate physicochemical and biopharmaceutical properties, namely low stability and poor bioavailability. Over the last decades, several academic and industrial research programs have been focused on development of biocompatible polymers to produce appropriate formulations that provide for enhanced therapeutic performance. According to their physicochemical properties, polymers have been exploited to obtain a variety of formulations including biodegradable microparticles, 3-dimensional hydrogels, bioconjugates and soluble nanocomposites. Several soluble polymers bearing charges or hydrophobic moieties along the macromolecular backbone have been found to physically associate with proteins to form soluble nanocomplexes. Physical complexation is deemed a valuable alternative tool to the chemical bioconjugation. Soluble protein/polymer nanocomplexes formed by physical specific or unspecific interactions have been found in fact to possess peculiar physicochemical, and biopharmaceutical properties. Accordingly, soluble polymeric systems have been developed to increase the protein stability, enhance the bioavailability, promote the absorption across the biological barriers, and prolong the protein residence in the bloodstream. Furthermore, a few polymers have been found to favour the protein internalisation into cells or boost their immunogenic potential by acting as immunoadjuvant in vaccination protocols. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Controlled Self-Assembly of Photofunctional Supramolecular Nanotubes. (United States)

    Cohen, Erez; Weissman, Haim; Pinkas, Iddo; Shimoni, Eyal; Rehak, Pavel; Král, Petr; Rybtchinski, Boris


    Designing supramolecular nanotubes (SNTs) with distinct dimensions and properties is highly desirable, yet challenging, since structural control strategies are lacking. Furthermore, relatively complex building blocks are often employed in SNT self-assembly. Here, we demonstrate that symmetric bolaamphiphiles having a hydrophobic core comprised of two perylene diimide moieties connected via a bipyridine linker and bearing polyethylene glycol (PEG) side chains can self-assemble into diverse molecular nanotubes. The structure of the nanotubes can be controlled by assembly conditions (solvent composition and temperature) and a PEG chain length. The resulting nanotubes differ both in diameter and cross section geometry, having widths of 3 nm (triangular-like cross-section), 4 nm (rectangular), and 5 nm (hexagonal). Molecular dynamics simulations provide insights into the stability of the tubular superstructures and their initial stages of self-assembly, revealing a key role of oligomerization via side-by-side aromatic interactions between bis-aromatic cores. Probing electronic and photonic properties of the nanotubes revealed extended electron delocalization and photoinduced charge separation that proceeds via symmetry breaking, a photofunction distinctly different from that of the fibers assembled from the same molecules. A high degree of structural control and insights into SNT self-assembly advance design approaches toward functional organic nanomaterials.

  3. Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

    CERN Document Server

    Garti, Nissim


    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

  4. Preface: special topic on supramolecular self-assembly at surfaces. (United States)

    Bartels, Ludwig; Ernst, Karl-Heinz; Gao, Hong-Jun; Thiel, Patricia A


    Supramolecular self-assembly at surfaces is one of the most exciting and active fields in Surface Science today. Applications can take advantage of two key properties: (i) versatile pattern formation over a broad length scale and (ii) tunability of electronic structure and transport properties, as well as frontier orbital alignment. It provides a new frontier for Chemical Physics as it uniquely combines the versatility of Organic Synthesis and the Physics of Interfaces. The Journal of Chemical Physics is pleased to publish this Special Topic Issue, showcasing recent advances and new directions.

  5. Self-assembling graphene-anthraquinone-2-sulphonate supramolecular nanostructures with enhanced energy density for supercapacitors (United States)

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


    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).

  6. Supramolecular Hydrogels Based on DNA Self-Assembly. (United States)

    Shao, Yu; Jia, Haoyang; Cao, Tianyang; Liu, Dongsheng


    viability in the three-dimensional matrix to several weeks and also provides an easy way to prepare interpenetrating double network materials. In this Account, we outline the stream of hydrogels based on DNA self-assembly and discuss the mechanism that brings outstanding properties to the materials. Unlike most reported hydrogel systems, the all-in-one character of the DNA hydrogel avoids the "cask effect" in the properties. We believe the hydrogel will greatly benefit cell behavior studies especially in the following aspects: (1) stem cell differentiation can be studied with solely tunable mechanical strength of the matrix; (2) the dynamic nature of the network can allow cell migration through the hydrogel, which will help to build a more realistic model to observe the migration of cancer cells in vivo; (3) combination with rapidly developing three-dimension printing technology, the hydrogel will boost the construction of three-dimensional tissues and artificial organs.

  7. Self-assembly of a supramolecular hexagram and a supramolecular pentagram (United States)

    Jiang, Zhilong; Li, Yiming; Wang, Ming; Song, Bo; Wang, Kun; Sun, Mingyu; Liu, Die; Li, Xiaohong; Yuan, Jie; Chen, Mingzhao; Guo, Yuan; Yang, Xiaoyu; Zhang, Tong; Moorefield, Charles N.; Newkome, George R.; Xu, Bingqian; Li, Xiaopeng; Wang, Pingshan


    Five- and six-pointed star structures occur frequently in nature as flowers, snow-flakes, leaves and so on. These star-shaped patterns are also frequently used in both functional and artistic man-made architectures. Here following a stepwise synthesis and self-assembly approach, pentagonal and hexagonal metallosupramolecules possessing star-shaped motifs were prepared based on the careful design of metallo-organic ligands (MOLs). In the MOL design and preparation, robust ruthenium-terpyridyl complexes were employed to construct brominated metallo-organic intermediates, followed by a Suzuki coupling reaction to achieve the required ensemble. Ligand LA (VRu2+X, V=bisterpyridine, X=tetraterpyridine, Ru=Ruthenium) was initially used for the self-assembly of an anticipated hexagram upon reaction with Cd2+ or Fe2+ however, unexpected pentagonal structures were formed, that is, [Cd5LA5]30+ and [Fe5LA5]30+. In our redesign, LB [V(Ru2+X)2] was synthesized and treated with 60° V-shaped bisterpyridine (V) and Cd2+ to create hexagonal hexagram [Cd12V3LB3]36+ along with traces of the triangle [Cd3V3]6+. Finally, a pure supramolecular hexagram [Fe12V3LB3]36+ was successfully isolated in a high yield using Fe2+ with a higher assembly temperature.

  8. Amphiphiles Self-Assembly: Basic Concepts and Future Perspectives of Supramolecular Approaches

    Directory of Open Access Journals (Sweden)

    Domenico Lombardo


    Full Text Available Amphiphiles are synthetic or natural molecules with the ability to self-assemble into a wide variety of structures including micelles, vesicles, nanotubes, nanofibers, and lamellae. Self-assembly processes of amphiphiles have been widely used to mimic biological systems, such as assembly of lipids and proteins, while their integrated actions allow the performance of highly specific cellular functions which has paved a way for bottom-up bionanotechnology. While amphiphiles self-assembly has attracted considerable attention for decades due to their extensive applications in material science, drug and gene delivery, recent developments in nanoscience stimulated the combination of the simple approaches of amphiphile assembly with the advanced concept of supramolecular self-assembly for the development of more complex, hierarchical nanostructures. Introduction of stimulus responsive supramolecular amphiphile assembly-disassembly processes provides particularly novel approaches for impacting bionanotechnology applications. Leading examples of these novel self-assembly processes can be found, in fact, in biosystems where assemblies of different amphiphilic macrocomponents and their integrated actions allow the performance of highly specific biological functions. In this perspective, we summarize in this tutorial review the basic concept and recent research on self-assembly of traditional amphiphilic molecules (such as surfactants, amphiphile-like polymers, or lipids and more recent concepts of supramolecular amphiphiles assembly which have become increasingly important in emerging nanotechnology.

  9. Surface-Assisted Self-Assembly Strategies Leading to Supramolecular Hydrogels. (United States)

    Vigier-Carrière, Cécile; Boulmedais, Fouzia; Schaaf, Pierre; Jierry, Loïc


    Localized molecular self-assembly processes leading to the growth of nanostructures exclusively from the surface of a material is one of the great challenges in surface chemistry. In the last decade, several works have been reported on the ability of modified or unmodified surfaces to manage the self-assembly of low-molecular-weight hydrogelators (LMWH) resulting in localized supramolecular hydrogel coatings mainly based on nanofiber architectures. This Minireview highlights all strategies that have emerged recently to initiate and localize LMWH supramolecular hydrogel formation, their related fundamental issues and applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Zwitterionic supramolecular nanoparticles: self-assembly and responsive properties

    NARCIS (Netherlands)

    Stoffelen, C.; Huskens, Jurriaan


    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

  11. Supramolecular self-assembly of nonlinear amphiphilic and double hydrophilic block copolymers in aqueous solutions. (United States)

    Ge, Zhishen; Liu, Shiyong


    Supramolecular self-assembly of block copolymers in aqueous solution has received ever-increasing interest over the past few decades due to diverse biological and technological applications in drug delivery, imaging, sensing and catalysis. In addition to relative block lengths, molecular weights and solution conditions, chain architectures of block copolymers can also dramatically affect their self-assembling properties in selective solvents. This feature article mainly focuses on recent developments in the field of supramolecular self-assembly of amphiphilic and double hydrophilic block copolymers (DHBCs) possessing nonlinear chain topologies, including miktoarm star polymers, dendritic-linear block copolymers, cyclic block copolymers and comb-shaped copolymer brushes. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Self-assembly of boron-based supramolecular structures


    Christinat, Nicolas


    This work describes the synthesis and characterization of boronic acid-based supramolecular structures. Macrocycles, dendritic structures, polymers, rotaxanes, and cages were assembled using four types of reversible reactions. The key point of the strategy is the parallel utilization of two –or more– of these reactions. Initially, aryl and alkylboronic acids were condensed with dihydroxypyridine ligands to give tetrameric or pentameric macrocycles, in which four or five boronate esters are co...

  13. Self-assembling graphene-anthraquinone-2-sulphonate supramolecular nanostructures with enhanced energy density for supercapacitors. (United States)

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


    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).

  14. 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)


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shcherbina, M. A., E-mail:; 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)


    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.

  16. Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons (United States)

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


    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.

  17. Supramolecular self-assembling in mesostructured materials through charge tuning in the inorganic phase


    Roca, Manuel; El Haskouri, Jamal; Cabrera Medina, Saúl; Beltrán Porter, Aurelio; Álamo Serrano, Jaime; Beltrán Porter, Daniel; Marcos, María Dolores; Amorós del Toro, Pedro José


    Supramolecular self-assembling of organic CTA+ micelles and inorganic [VO(H2O)PO4]n^q-2 2D-anions for the isolation of hexagonal mesostructured materials can be reached by charge tuning in the inorganic phase through the adjustment of the vanadium mean oxidation state. El Haskouri, Jamal, ; Cabrera Medina, Saul, ; Beltran Porter, Aurelio, ; Alamo Serrano, Jaime, ; Beltran Porter, Daniel, ; ...

  18. Light- and pH Switchable Supramolecular Nanoparticles through Electrostatic Self-Assembly (United States)

    Groehn, Franziska; Willerich, Immanuel


    Supramolecular structures that can respond to external triggers are of high interest for example for nanotechnology or drug delivery. Recently we have introduced an approach to electrostatic self-assembly for the formation of supramolecular particles in solution: polyelectrolytes and multivalent stiff organic counterions build well-defined and stable nano-objects. In addition to electrostatics, secondary interactions between counterions such as pi-pi stacking directs the association. Aggregates with narrow size distribution and varying shape such as spheres, cylinders, vesicles and networks result. PH-responsive assemblies can be repeatedly switched ``on'' and ``off'' through pH. Furthermore, light is an elegant, non-invasive stimulus offering possibilities for new functional nanostructures. By electrostatic self-assembly, supramolecular particles can be built the size of which can be triggered by light. For example, assemblies of dendrimer macroions and divalent azobenzene counterions can respond to light with a size increase from 30 nm to 165 nm radius. Detailed characterization by static and dynamic light scattering, AFM, SANS and zeta-potential measurements as well as thermodynamic studies yield insight into driving forces and structural control in the self-assembly process.

  19. Design and construction of self-assembling supramolecular protein complexes using artificial and fusion proteins as nanoscale building blocks. (United States)

    Kobayashi, Naoya; Arai, Ryoichi


    The central goal of nanobiotechnology is to design and construct novel biomaterials of nanometer sizes. In this short review, we describe recent progress of several approaches for designing and creating artificial self-assembling protein complexes and primarily focus on the following biotechnological strategies for using artificial and fusion proteins as nanoscale building blocks: fusion proteins designed for symmetrical self-assembly; three-dimensional domain-swapped oligomers; self-assembling designed coiled-coil peptide modules; metal-directed self-assembling engineered proteins; computationally designed self-assembling de novo proteins; and self-assembling protein nanobuilding blocks (PN-Blocks) using an intermolecularly folded dimeric de novo protein. These state-of-the-art nanobiotechnologies for designing supramolecular protein complexes will facilitate the development of novel functional nanobiomaterials. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Liu R


    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

  1. Highly stereoselective recognition and deracemization of amino acids by supramolecular self-assembly. (United States)

    So, Soon Mog; Moozeh, Kimia; Lough, Alan J; Chin, Jik


    The highly stereoselective supramolecular self-assembly of α-amino acids with a chiral aldehyde derived from binol and a chiral guanidine derived from diphenylethylenediamine (dpen) to form the imino acid salt is reported. This system can be used to cleanly convert D-amino acids into L-amino acids or vice versa at ambient temperature. It can also be used to synthesize α-deuterated D- or L-amino acids. A crystal structure of the ternary complex together with DFT computation provided detailed insight into the origin of the stereoselective recognition of amino acids. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Communication: Self-assembly of a model supramolecular polymer studied by replica exchange with solute tempering (United States)

    Arefi, Hadi H.; Yamamoto, Takeshi


    Conventional molecular-dynamics (cMD) simulation has a well-known limitation in accessible time and length scales, and thus various enhanced sampling techniques have been proposed to alleviate the problem. In this paper, we explore the utility of replica exchange with solute tempering (REST) (i.e., a variant of Hamiltonian replica exchange methods) to simulate the self-assembly of a supramolecular polymer in explicit solvent and compare the performance with temperature-based replica exchange MD (T-REMD) as well as cMD. As a test system, we consider a relatively simple all-atom model of supramolecular polymerization (namely, benzene-1,3,5-tricarboxamides in methylcyclohexane solvent). Our results show that both REST and T-REMD are able to predict highly ordered polymer structures with helical H-bonding patterns, in contrast to cMD which completely fails to obtain such a structure for the present model. At the same time, we have also experienced some technical challenge (i.e., aggregation-dispersion transition and the resulting bottleneck for replica traversal), which is illustrated numerically. Since the computational cost of REST scales more moderately than T-REMD, we expect that REST will be useful for studying the self-assembly of larger systems in solution with enhanced rearrangement of monomers.

  3. Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels

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    Shawn Matthew Dirk


    Full Text Available Phenylpropanoid metabolism yields a mixture of monolignols that undergo chaotic, non-enzymatic reactions such as free radical polymerization and spontaneous self-assembly in order to form the polyphenolic lignin which is a barrier to cost-effective lignocellulosic biofuels. Post-synthesis lignin integration into the plant cell wall is unclear, including how the hydrophobic lignin incorporates into the wall in an initially hydrophilic milieu. Self-assembly, self-organization and aggregation give rise to a complex, 3D network of lignin that displays randomly branched topology and fractal properties. Attempts at isolating lignin, analogous to archaeology, are instantly destructive and non-representative of in planta. Lack of plant ligninases or enzymes that hydrolyze specific bonds in lignin-carbohydrate complexes (LCCs also frustrate a better grasp of lignin. Supramolecular self-assembly, nano-mechanical properties of lignin-lignin, lignin-polysaccharide interactions and association-dissociation kinetics affect biomass deconstruction and thereby cost-effective biofuels production.

  4. Monosaccharides as Versatile Units for Water-Soluble Supramolecular Polymers. (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


    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.

  5. A dynamic combinatorial approach for identifying side groups that stabilize DNA-templated supramolecular self-assemblies. (United States)

    Paolantoni, Delphine; Cantel, Sonia; Dumy, Pascal; Ulrich, Sébastien


    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.

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

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    Delphine Paolantoni


    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.

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

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


    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.

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

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    Paulo Torres


    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.

  9. Construction of an organelle-like nanodevice via supramolecular self-assembly for robust biocatalysts. (United States)

    Li, Hongxia; Zheng, Guojun; Zhu, Shaozhou


    When using the microbial cell factories for green manufacturing, several important issues need to be addressed such as how to maintain the stability of biocatalysts used in the bioprocess and how to improve the synthetic efficiency of the biological system. One strategy widely used during natural evolution is the creation of organelles which can be used for regional control. This kind of compartmentalization strategy has inspired the design of artificial organelle-like nanodevice for synthetic biology and "green chemistry". Mimicking the natural concept of functional compartments, here we show that the engineered thermostable ketohydroxyglutarate aldolase from Thermotoga maritima could be developed as a general platform for nanoreactor design via supramolecular self-assembly. An industrial biocatalyst-(+)-γ-lactamase was selected as a model catalyst and successful encapsulated in the nanoreactor with high copies. These nanomaterials could easily be synthesized by Escherichia coli by heterologous expression and subsequently self-assembles into the target organelle-like nanoreactors both in vivo and in vitro. By probing their structural characteristics via transmission electronic microscopy and their catalytic activity under diverse conditions, we proved that these nanoreactors could confer a significant benefit to the cargo proteins. The encapsulated protein exhibits significantly improved stability under conditions such as in the presence of organic solvent or proteases, and shows better substrate tolerance than free enzyme. Our biodesign strategy provides new methods to develop new catalytically active protein-nanoreactors and could easily be applied into other biocatalysts. These artificial organelles could have widely application in sustainable catalysis, synthetic biology and could significantly improve the performance of microbial cell factories.

  10. Self-assembly of amphiphilic Janus dendrimers into mechanically robust supramolecular hydrogels for sustained drug release. (United States)

    Nummelin, Sami; Liljeström, Ville; Saarikoski, Eve; Ropponen, Jarmo; Nykänen, Antti; Linko, Veikko; Seppälä, Jukka; Hirvonen, Jouni; Ikkala, Olli; Bimbo, Luis M; Kostiainen, Mauri A


    Compounds that can gelate aqueous solutions offer an intriguing toolbox to create functional hydrogel materials for biomedical applications. Amphiphilic Janus dendrimers with low molecular weights can readily form self-assembled fibers at very low mass proportion (0.2 wt %) to create supramolecular hydrogels (G'≫G'') with outstanding mechanical properties and storage modulus of G'>1000 Pa. The G' value and gel melting temperature can be tuned by modulating the position or number of hydrophobic alkyl chains in the dendrimer structure; thus enabling exquisite control over the mesoscale material properties in these molecular assemblies. The gels are formed within seconds by simple injection of ethanol-solvated dendrimers into an aqueous solution. Cryogenic TEM, small-angle X-ray scattering, and SEM were used to confirm the fibrous structure morphology of the gels. Furthermore, the gels can be efficiently loaded with different bioactive cargo, such as active enzymes, peptides, or small-molecule drugs, to be used for sustained release in drug delivery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Self-assembly of a highly organized, hexameric supramolecular architecture: formation, structure and properties. (United States)

    Schaeffer, Gaël; Fuhr, Olaf; Fenske, Dieter; Lehn, Jean-Marie


    Two derivatives, (3)L and (9)L, of a ditopic, multiply hydrogen-bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self-assembly into a complex supramolecular species. The solid-state molecular structure of (3)L, determined by single-crystal X-ray crystallography, revealed that it forms a highly organized hexameric entity (3)L6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen-bonding interactions. The complicated (1)H NMR spectra observed in o-dichlorobenzene (o-DCB) for (3)L and (9)L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen-bond-disrupting solvent, such as DMSO, the (1)H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature-dependent (1)H NMR studies in o-DCB showed that the L6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Encapsulated-guest rotation in a self-assembled heterocapsule directed toward a supramolecular gyroscope (United States)

    Kitagawa, Hitomi; Kobori, Yasuhiro; Yamanaka, Masamichi; Yoza, Kenji; Kobayashi, Kenji


    The self-assembled heterocapsule 1·2, which is formed by the hydrogen bonds of tetra(4-pyridyl)-cavitand 1 and tetrakis(4-hydroxyphenyl)-cavitand 2, encapsulates 1 molecule of guests such as 1,4-diacetoxybenzene 3a, 1,4-diacetoxy-2,5-dimethylbenzene 3b, 1,4-diacetoxy-2,5-dialkoxybenzenes (3c, OCH3; 3d, OC2H5; 3e, OC3H7; 3f, OC4H9; 3g, OC5H11; 3h, OC6H13; 3i, OC8H17), 1,4-diacetoxy-2,5-difluorobenzene 4a, and 1,4-diacetoxy-2,3-difluorobenzene 4b. The X-ray crystallographic analysis of 3c@(1·2) showed that the acetoxy groups at the 1,4-positions of 3c are oriented toward the 2 aromatic cavity ends of 1·2 and that 3c can rotate along the long axis of 1·2. Thus, the 1·2 (stator) with the encapsulation guest (rotator) behaves as a supramolecular gyroscope. A variable temperature (VT) 1H NMR study in CDCl3 showed that 3a, 3b, 4a, and 4b within 1·2 rotate rapidly even at 218 K, whereas guest rotation is almost inhibited for 3h and 3i even at 323 K. In this respect, 4b with a large dipole moment is a good candidate for the rotator of 1·2. For 3c–3g, the enthalpic (ΔH‡) and entropic (ΔS‡) contributions to the free energy of activation (ΔG‡) for the guest-rotational steric barriers within 1·2 were obtained from Eyring plots based on line-shape analysis of the VT 1H NMR spectra. The value of ΔG‡ increased in the order 3c guest rotation within 1·2. PMID:19416810

  13. Self assembly of amphiphilic C60 fullerene derivatives into nanoscale supramolecular structures

    Directory of Open Access Journals (Sweden)

    Casscells S Ward


    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.

  14. From fundamental supramolecular chemistry to self-assembled nanomaterials and medicines and back again - how Sam inspired SAMul. (United States)

    Smith, David K


    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.

  15. 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


    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

  16. Self-assembly of P-chiral supramolecular phosphines on rhodium and direct evidence for Rh-catalyst-substrate interactions. (United States)

    Koshti, Vijay S; Sen, Anirban; Shinde, Dinesh; Chikkali, Samir H


    Supramolecular phosphine-derived catalysts are known to provide high enantioselectivity in asymmetric transformations such as hydrogenation, but direct evidence unravelling the role of secondary interactions is largely missing. As a representative case study, the role of hydrogen bonding in asymmetric hydrogenation catalysed by p-chiral supramolecular phosphines is investigated. To establish the nature of hydrogen bonding in the self-assembled Rh-complex, NMR experiments were performed at different concentrations and temperatures. It was found that with increasing concentration of 1-(3-(phenyl(o-tolyl)phosphanyl)phenyl)urea ligand (L1), the NH and NH 2 peaks shift downfield. This indicated the presence of intermolecular hydrogen bonding in L1. This observation was further supported by variable temperature NMR experiments wherein, with decreasing temperature, the NH and NH 2 resonances of L1 shifted downfield. The downfield shift once again suggests the existence of intermolecular hydrogen bonding in L1. In contrast, the chemical shift of NH and NH 2 signals did not significantly change with increasing concentration of the self-assembled Rh-complex (C1). This observation suggested the existence of intramolecular hydrogen bonding in the self-assembled complex. The concentration experiment was further corroborated by variable temperature NMR experiments. No change in the chemical shift of NH 2 resonance could be detected with decreasing temperature, which corroborates the existence of intramolecular hydrogen bonding in C1. In a stoichiometric experiment, C1 was treated with hydrogenation substrate N-acetyldehydrophenylalanine (S2) and the proton NMR was recorded. The NH 2 protons of the self-assembled Rh-complex were found to shift downfield, as compared to untreated parent C1. These observations indicated that there is a hydrogen bonding interaction between the Rh-complex and the substrate. To further attest this hypothesis, NH and NH 2 groups were exchanged with ND

  17. 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


    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

  18. Brønsted Acid-Catalyzed Carbonyl-Olefin Metathesis inside a Self-Assembled Supramolecular Host. (United States)

    Catti, Lorenzo; Tiefenbacher, Konrad


    Carbonyl-olefin metathesis represents a powerful yet underdeveloped method for the formation of carbon-carbon bonds. So far, no Brønsted acid based method for the catalytic carbonyl-olefin metathesis has been described. Herein, a cocatalytic system based on a simple Brønsted acid (HCl) and a self-assembled supramolecular host is presented. The developed system compares well with the current benchmark catalyst for carbonyl-olefin metathesis in terms of substrate scope and yield of isolated product. Control experiments provide strong evidence that the reaction proceeds inside the cavity of the supramolecular host. A mechanistic probe indicates that a stepwise reaction mechanism is likely. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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


    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.

  20. Supramolecular Complexation of Carbohydrates for the Bioavailability Enhancement of Poorly Soluble Drugs. (United States)

    Cho, Eunae; Jung, Seunho


    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.

  1. Catalytic Deprotection of Acetals In Strongly Basic Solution Usinga Self-Assembled Supramolecular 'Nanozyme'

    Energy Technology Data Exchange (ETDEWEB)

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


    Acetals are among the most commonly used protecting groups for aldehydes and ketones in organic synthesis due to their ease of installation and resistance to cleavage in neutral or basic solution.[1] The common methods for hydrolyzing acetals almost always involve the use of either Broensted acid or Lewis acid catalysts.[2] Usually aqueous acids or organic solutions acidified with organic or inorganic acids have been used for reconversion of the acetal functionality to the corresponding carbonyl group; however, recently a number of reports have documented a variety of strategies for acetal cleavage under mild conditions. These include the use of Lewis acids such as bismuth(III)[3] or cerium(IV),[4, 5] functionalized silica gel, such as silica sulfuric acid[6] or silica-supported pyridinium p-toluene sulfonate,[7] or the use of silicon-based reagents such as TESOTf-2,6-Lutidine.[8] Despite these mild reagents, all of the above conditions require either added acid or overall acidic media. Marko and co-workers recently reported the first example of acetal deprotection under mildly basic conditions using catalytic cerium ammonium nitrate at pH 8 in a water-acetonitrile solution.[5] Also recently, Rao and co-workers described a purely aqueous system at neutral pH for the deprotection of acetals using {beta}-cyclodextrin as the catalyst.[9] Herein, we report the hydrolysis of acetals in strongly basic aqueous solution using a self-assembled supramolecular host as the catalyst. During the last decade, we have used metal-ligand interactions for the formation of well-defined supramolecular assemblies with the stoichiometry M{sub 4}L{sub 6}6 (M = Ga{sup III} (1 refers to K{sub 12}[Ga{sub 4}L{sub 6}]), Al{sup III}, In{sup III}, Fe{sup III}, Ti{sup IV}, or Ge{sup IV}, L = N,N{prime}-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) (Figure 1).[10] The metal ions occupy the vertices of the tetrahedron and the bisbidentate catecholamide ligands span the edges. The strong

  2. Template-directed supramolecular self-assembly of coordination dumbbells at surfaces. (United States)

    Lin, Nian; Langner, Alexander; Tait, Steven L; Rajadurai, Chandrasekar; Ruben, Mario; Kern, Klaus


    Scanning tunneling microscopy reveals, at single-molecular resolution, how external parameters--substrate morphology and guest addition--re-direct the assembly of dumbbell-shaped coordination supramolecules towards different surface-confined supramolecular organizations.

  3. Application of atomic force microscopy to protein anatomy:. Imaging of supramolecular structures of self-assemblies formed from synthetic peptides (United States)

    Shibata-Seki, T.; Masai, J.; Ogawa, Y.; Sato, K.; Yanagawa, H.

    This paper reports morphological studies of structures of self-assemblies from synthetic peptide fragments with the use of atomic force microscope (AFM) and transmission electron microscope (TEM). Two systems of synthetic peptides have been examined: one is peptides from barnase (a ribonuclease) and the other is those from tau protein (Alzheimer's disease-related protein). The AFM observation was carried out by using a commercially available AFM operated in the tapping mode in air. The general appearance in shape and size of the peptide assemblies in AFM images was essentially similar to that in TEM images, except that the AFM images provide us with fruitful three-dimensional information about the assemblies. For assemblies from barnase peptides, possible formation processes of the supramolecular structures from the corresponding peptide fragment have been proposed on the basis of the AFM images.

  4. Self-assembly of a supramolecular, three-dimensional, spoked, bicycle-like wheel. (United States)

    Lu, Xiaocun; Li, Xiaopeng; Cao, Yan; Schultz, Anthony; Wang, Jin-Liang; Moorefield, Charles N; Wesdemiotis, Chrys; Cheng, Stephen Z D; Newkome, George R


    Where there's a wheel, there's a way: The terpyridine-based title system has been synthesized through a facile self-assembly process. Two tris(terpyridine) ligands possessing angles of either 120° or 60° between adjacent tpy units were mixed with a stoichiometric amount of Zn(2+) (2:6:12) to generate the desired coordination-driven bicycle-like wheel (90 % yield). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Design of supramolecular nanomaterials : from molecular recognition to hierarchical self-assembly


    El Idrissi, Mohamed


    In the present thesis, are reported new strategies for the design of nanostructures to partly address environmental issues. The work carried out has been divided into three parts: the design of cyclodextrin (CD)-based polymeric materials, the molecular engineering of a pyrene derivative for the formation of self-assembled nanostructures and the design of smart nanocarriers. Considerable efforts have been devoted to the design of molecular receptors capable of specific recognition of a wid...

  6. Novel Soluble Dietary Fiber-Tannin Self-Assembled Film: A Promising Protein Protective Material. (United States)

    Song, Guo-Bin; Xu, Juan; Zheng, Hua; Feng, Ying; Zhang, Wen-Wen; Li, Kun; Ge, Shuang-shuang; Li, Kai; Zhang, Hong


    In this experiment, a natural promising protein protective film was fabricated through soluble dietary fiber (SDF)-tannin nanocluster self-assembly. FT-IR, XRD, and DSC tests were employed to investigate the interaction between the SDF and tannins before and after cross-linking induced by calcium ion. On the other hand, referring to the SEM and TEM results, the self-assembly process of the protein protective film could be indicated as follows: first, calcium ion, with its cross-ability, served as the "nucleus"; SDF and tannins were combined to prepare the nanoscale SDF-tannin clusters; then, the clusters were homogeneously deposited on the surface of protein to form a protective film by self-assembling hydrogen bond between tannin component of clusters as "adhesive" and protein in aqueous solutions under very mild conditions. Film thickness could also be controlled by tannin of different concentrations ranging from 114 to 1384 μm. Antibacterial test and in vitro cytotoxicity test proved that the film had a broad spectrum of antimicrobial properties and excellent cell biocompatibility, respectively, which might open up new applications in the food preservation and biomedical fields.

  7. 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.


    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

  8. Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films. (United States)

    Hsu, Chih-Hao; Dong, Xue-Hui; Lin, Zhiwei; Ni, Bo; Lu, Pengtao; Jiang, Zhang; Tian, Ding; Shi, An-Chang; Thomas, Edwin L; Cheng, Stephen Z D


    The self-assembly behavior of specifically designed giant surfactants is systematically studied in thin films using grazing incidence X-ray scattering and transmission electron microscopy, focusing on the effects of molecular nanoparticle (MNP) functionalities and molecular architectures on nanostructure formation. Two MNPs with different surface functionalities, i.e., hydrophilic carboxylic acid functionalized [60]fullerene (AC60) and omniphobic fluorinated polyhedral oligomeric silsesquioxane (FPOSS), are utilized as the head portions of the giant surfactants. By covalently tethering these functional MNPs onto the end point or junction point of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, linear and star-like giant surfactants with different molecular architectures are constructed. With fixed length of the PEO block, changing the molecular weight of the PS block leads to the formation of various ordered phases and phase transitions. Due to the distinct affinity, the AC60-based and FPOSS-based giant surfactants form two- or three-component morphologies, respectively. A stretching parameter for the PS block is introduced to characterize the PS chain conformation in the different morphologies. The highly diverse self-assembled nanostructures with high etch resistance between components in small dimensions obtained from the giant surfactant thin films suggest that these macromolecules could provide a promising and robust platform for nanolithography applications.

  9. Supramolecular Self-Assembly of a Model Hydrogelator: Characterization of Fiber Formation and Morphology

    Directory of Open Access Journals (Sweden)

    Yuan Gao


    Full Text Available Hydrogels are of intense recent interest in connection with biomedical applications ranging from 3-D cell cultures and stem cell differentiation to regenerative medicine, controlled drug delivery, and tissue engineering. This prototypical form of soft matter has many emerging material science applications outside the medical field. The physical processes underlying this type of solidification are incompletely understood, and this limits design efforts aimed at optimizing these materials for applications. We address this general problem by applying multiple techniques (e.g., NMR, dynamic light scattering, small angle neutron scattering, rheological measurements to the case of a peptide derivative hydrogelator (molecule 1, NapFFKYp over a broad range of concentration and temperature to characterize both the formation of individual nanofibers and the fiber network. We believe that a better understanding of the hierarchical self-assembly process and control over the final morphology of this kind of material should have broad significance for biological and medicinal applications utilizing hydrogels.

  10. Reverse self-assemblies based on amphiphilic polyphosphazenes for encapsulation of water-soluble molecules (United States)

    Qiu, Liyan; Zhang, Jianxiang; Yan, Meiqiu; Jin, Yi; Zhu, Kangjie


    A novel series of amphiphilic polyphosphazenes (PNIPAm/AA-PPP) containing hydrophilic oligo-(N-isopropylacrylamide) (oligo-NIPAm) and various hydrophobic aliphatic amines as co-substitutes was synthesized via a two-step substitution reaction. The extraction and solubilization of water-soluble substances such as fluorescein sodium and trypan blue from an aqueous phase into the chloroform phase were supposed to result from the formation of polyphosphazene reverse self-assemblies in the organic phase. A field emission scanning electronic microscope was adopted to characterize the morphology of reverse assemblies in chloroform. Additionally, a significant improvement of encapsulation and release profiles of water-soluble substances was found for poly(lactic-co-glycolic acid) (PLGA) microparticles in the presence of amphiphilic copolymers, which was associated with the chemical structure of copolymers as well as the content of copolymer in the microparticles.

  11. Two novel self-assemblies of supramolecular solar cells using N-heterocyclic-anchoring porphyrins (United States)

    Zhang, Qian; Wu, Fang-Yuan; Liu, Jia-Cheng; Li, Ren-Zhi; Jin, Neng-Zhi


    Two novel N-substituted anchoring porphyrins (ZnPAtz and ZnPAim) have been devised and synthesized. Moreover, these two anchoring porphyrins were linked to the TiO2 semiconductor through carboxyl groups and then a zinc porphyrin ZnP was bound to the anchoring porphyrin using a zinc-to-ligand axial coordination approach. The different performances of these assemblies were compared with single anchoring porphyrin devices ZnPAtz and ZnPAim. The photoelectric conversion efficiency of the new supramolecular solar cells sensitized by ZnP-ZnPAx (x = tz, im) has been improved. The ZnP-ZnPAtz-based DSSCs provided the highest photovoltaic efficiency (1.86%). Fundamental studies showed that incorporation of these assemblies promote light-harvesting efficiency.

  12. 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


    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.

  13. Supramolecular Self-Assembly and Dual-Switch Vapochromic, Vapoluminescent, and Resistive Memory Behaviors of Amphiphilic Platinum(II) Complexes. (United States)

    Li, Yongguang; Chen, Ling; Ai, Yeye; Hong, Eugene Yau-Hin; Chan, Alan Kwun-Wa; Yam, Vivian Wing-Wah


    A series of amphiphilic platinum(II) complexes with tridentate N-donor ligands has been synthesized and characterized. Different supramolecular architectures are constructed using the amphiphilic molecules as the building blocks through the formation of Pt···Pt and π-π stacking interactions in aqueous media. The aggregation-deaggregation-aggregation self-assembly behavior together with obvious spectroscopic changes could be fine-tuned by the addition of THF in aqueous media. More interestingly, one of the complexes is found to show fast response and high selectivity toward alcohol and water vapors with good reversibility, leading to drastic color and luminescence changes, and hence unique dual switching behavior, with the water molecules readily displaced by the alcohol vapor. Rapid writing and erasure have been realized via the control of a jet or a stream of alcohol vapor flow. In addition, it has been employed as active materials in the fabrication of small-molecule solution-processable resistive memory devices, exhibiting stable and promising binary memory performance with threshold voltages of ca. 3.4 V, high ON/OFF ratios of up to 10 5 and long retention times of over 10 4 s. The vapochromic and vapoluminescent materials are demonstrated to have potential applications in chemosensing, logic gates, VOC monitoring, and memory functions.

  14. Supramolecular self-assembly on the B-Si(111)-(√3x√3) R30° surface: From single molecules to multicomponent networks (United States)

    Makoudi, Younes; Jeannoutot, Judicaël; Palmino, Frank; Chérioux, Frédéric; Copie, Guillaume; Krzeminski, Christophe; Cleri, Fabrizio; Grandidier, Bruno


    Understanding the physical and chemical processes in which local interactions lead to ordered structures is of particular relevance to the realization of supramolecular architectures on surfaces. While spectacular patterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneous organization of supramolecular networks on semiconductor surfaces, where the formation of covalent bonds between organics and adatoms usually hamper the diffusion of molecules and their subsequent interactions with each other. However, the saturation of the dangling bonds at a semiconductor surface is known to make them inert and offers a unique way for the engineering of molecular patterns on these surfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30° surface, that enable the self-assembly of molecules into a rich variety of extended and regular structures on silicon. Particular attention is given to computational methods based on multi-scale simulations that allow to rationalize the relative contribution of the dispersion forces involved in the self-assembled networks observed with scanning tunneling microscopy. A summary of state of the art studies, where a fine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploiting the construction of supramolecular structures on semiconductor surfaces.

  15. Fluorescent polystyrene photonic crystals self-assembled with water-soluble conjugated polyrotaxanes

    Directory of Open Access Journals (Sweden)

    Francesco Di Stasio


    Full Text Available We demonstrate control of the photoluminescence spectra and decay rates of water-soluble green-emitting conjugated polyrotaxanes by incorporating them in polystyrene opals with a stop-band spectrally tuned on the rotaxane emission (405–650 nm. We observe a suppression of the luminescence within the photonic stop-band and a corresponding enhancement of the high-energy edge (405–447 nm. Time-resolved measurements reveal a wavelength-dependent modification of the emission lifetime, which is shortened at the high-energy edge (by ∼11%, in the range 405–447 nm, but elongated within the stop-band (by ∼13%, in the range 448–482 nm. We assign both effects to the modification of the density of photonic states induced by the photonic crystal band structure. We propose the growth of fluorescent composite photonic crystals from blends of “solvent-compatible” non-covalently bonded nanosphere-polymer systems as a general method for achieving a uniform distribution of polymeric dopants in three-dimensional self-assembling photonic structures.

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

    KAUST Repository

    Patil, Sachin


    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.

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

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


    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.

  18. Self-assembling nanocomposites for protein delivery: supramolecular interactions between PEG-cholane and rh-G-CSF. (United States)

    Salmaso, Stefano; Bersani, Sara; Mastrotto, Francesca; Tonon, Giancarlo; Schrepfer, Rodolfo; Genovese, Stefano; Caliceti, Paolo


    PEG(5 kDa)-cholane, PEG(10 kDa)-cholane and PEG(20 kDa)-cholane self-assembling polymers have been synthesised by the end-functionalisation of 5, 10 and 20 kDa linear amino-terminating monomethoxy-poly(ethylene glycol) (PEG-NH(2)) with 5β-cholanic acid. Spectroscopic studies and isothermal titration calorimetry showed that the CMC of the PEG-cholane derivatives increased from 23.5 ± 1.8 to 60.2 ± 2.4 μM as the PEG molecular weight increased. Similarly, light scattering analysis showed that the micelle size increased from 15.8 ± 4.9 to 23.2 ± 11.1 nm with the PEG molecular weight. Gel permeation studies showed that the polymer bioconjugates associate with recombinant human granulocyte colony stimulating factor (rh-G-CSF) to form supramolecular nanocomposites according to multi-modal association profiles. The protein loadings obtained with PEG(5 kDa)-cholane, PEG(10 kDa)-cholane and PEG(20 kDa)-cholane were 7.4 ± 1.1, 2.7 ± 0.3 and 2.1 ± 0.4% (protein/polymer, w/w %), respectively. Scatchard and Klotz analyses showed that the protein/polymer affinity constant increased and that the number of PEG-cholane molecules associated to rh-G-CSF decreased as the PEG molecular weight increased. Isothermal titration calorimetry confirmed the protein/polymer multi-modal association. Circular dichroism analyses showed that the polymer association alters the secondary structure of the protein. Nevertheless, in vitro studies performed with NFS-60 cells showed that the polymer interaction does not impair the biological activity of the cytokine. In vivo studies performed by intravenous and subcutaneous administrations of rh-G-CSF to rats showed that the association with PEG(5 kDa)-cholane prolongs the body exposure of the protein. After subcutaneous administration, the protein t(max) values obtained with rh-G-CSF and 1:14 and 1:21 rh-G-CSF/PEG(5 kDa)-cholane (w/w ratio) nanocomplexes were 2, 8 and 24h, respectively. The 1:21 (w/w) rh-G-CSF/PEG(5kDa)-cholane formulation

  19. Design and Sensing Properties of a Self-Assembled Supramolecular Oligomer (Chem. Eur. J. 6/2016)

    DEFF Research Database (Denmark)

    Bähring, Steffen; Martín-Gomis, Luis; Olsen, Gunnar


    The controlled self-assembly of electron-rich and electron-deficient components to create a stimulus responsive oligomeric ensemble that functions as a sensor system for nitroaromatic explosives is depicted schematically on the cover. More information can be found in the Full Paper by Á. Sastre...

  20. Hydrogen bonds induced supramolecular self-assembly of azobenzene derivatives on the highly oriented pyrolytic graphite surface (United States)

    Miao, Xinrui; Cheng, Zhiyu; Ren, Biye; Deng, Wenli


    The self-assembly of azobenzene derivatives (CnAzCOOH) with various lengths of peripheral alkyl chains (with carbon number of n = 8, 10, 12, 14, 16) were observed by scanning tunneling microscopy on highly oriented pyrolytic graphite (HOPG) surface. The effect of van der Waals interactions and the intermolecular hydrogen bonding on the two-dimensional self-assembly was systematically studied. No alkyl-chain length effect was observed according to the STM images. All kinds of CnAzCOOH adopting the same pattern self-assembled on the HOPG surface, suggesting the formation of the two-dimensional structures was dominated by the hydrogen bonding of the functional groups. It could be found that two CnAzCOOH molecules formed a hydrogen-bonded dimer with “head-to-head” fashion as expected; however, the dimers organized themselves in the form of relative complex lamellae. Three dimers as a group arranged side by side and formed a well-defined stripe with periodic dislocations due to the registry mechanism of the alkyl chain with the underlying HOPG surface. The hydrogen bonds between the adjacent dimers in one lamella were formed and dominated the self-assembled pattern.

  1. Construction of nanostructures for selective lithium ion conduction using self-assembled molecular arrays in supramolecular solids. (United States)

    Moriya, Makoto


    In the development of innovative molecule-based materials, the identification of the structural features in supramolecular solids and the understanding of the correlation between structure and function are important factors. The author investigated the development of supramolecular solid electrolytes by constructing ion conduction paths using a supramolecular hierarchical structure in molecular crystals because the ion conduction path is an attractive key structure due to its ability to generate solid-state ion diffusivity. The obtained molecular crystals exhibited selective lithium ion diffusion via conduction paths consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and small molecules such as ether or amine compounds. In the present review, the correlation between the crystal structure and ion conductivity of the obtained molecular crystals is addressed based on the systematic structural control of the ionic conduction paths through the modification of the component molecules. The relationship between the crystal structure and ion conductivity of the molecular crystals provides a guideline for the development of solid electrolytes based on supramolecular solids exhibiting rapid and selective lithium ion conduction.

  2. High-Resolution Structure of a Self-Assembly-Competent Form of a Hydrophobic Peptide Captured in a Soluble [beta]-Sheet Scaffold

    Energy Technology Data Exchange (ETDEWEB)

    Makabe, Koki; Biancalana, Matthew; Yan, Shude; Tereshko, Valentina; Gawlak, Grzegorz; Miller-Auer, Hélène; Meredith, Stephen C.; Koide, Shohei (UC)


    {beta}-Rich self-assembly is a major structural class of polypeptides, but still little is known about its atomic structures and biophysical properties. Major impediments for structural and biophysical studies of peptide self-assemblies include their insolubility and heterogeneous composition. We have developed a model system, termed peptide self-assembly mimic (PSAM), based on the single-layer {beta}-sheet of Borrelia outer surface protein A. PSAM allows for the capture of a defined number of self-assembly-like peptide repeats within a water-soluble protein, making structural and energetic studies possible. In this work, we extend our PSAM approach to a highly hydrophobic peptide sequence. We show that a penta-Ile peptide (Ile{sub 5}), which is insoluble and forms {beta}-rich self-assemblies in aqueous solution, can be captured within the PSAM scaffold in a form capable of self-assembly. The 1.1-{angstrom} crystal structure revealed that the Ile{sub 5} stretch forms a highly regular {beta}-strand within this flat {beta}-sheet. Self-assembly models built with multiple copies of the crystal structure of the Ile5 peptide segment showed no steric conflict, indicating that this conformation represents an assembly-competent form. The PSAM retained high conformational stability, suggesting that the flat {beta}-strand of the Ile{sub 5} stretch primed for self-assembly is a low-energy conformation of the Ile{sub 5} stretch and rationalizing its high propensity for self-assembly. The ability of the PSAM to 'solubilize' an otherwise insoluble peptide stretch suggests the potential of the PSAM approach to the characterization of self-assembling peptides.

  3. Influence of Odd and Even Alkyl Chains on Supramolecular Nanoarchitecture via Self-Assembly of Tetraphenylethylene-Based AIEgens

    Directory of Open Access Journals (Sweden)

    Mina Salimimarand


    Full Text Available The Tetraphenylethylene (TPE based dumbbell shaped molecules TPE-Pi, TPE-Su, TPE-Az, and TPE-Se were synthesised bearing odd-even alkyl chains containing 7, 8, 9 and 10 carbons respectively. These molecules reveal typical Aggregation Induced Emission (AIE behaviour. The influence of the odd or even alkyl chain length was shown by studying the morphology of self-assembled nanostructures formed in a range of tetrahydrofuran (THF/water solvent systems. For example, with a water fraction of 80%, TPE derivatives with odd alkyl chains (TPE-Pi and TPE-Az self-assembled into nanosphere structures, while TPE-Su with 8 alkyl chains formed microbelts and TPE-Se with 10 alkyl chains aggregated into flower-like superstructures. These TPE derivatives also revealed interesting mechanochromic properties upon grinding, fuming and heating, which reveal the importance of molecular stacking in the crystal structure to the luminescent properties of the aggregates .The mechanochromic properties of TPE-Pi, TPE-Su, and TPE-Az were also demonstrated by the process of grounding, fuming, and heating.

  4. High-definition self-assemblies driven by the hydrophobic effect: synthesis and properties of a supramolecular nanocapsule. (United States)

    Liu, Simin; Gibb, Bruce C


    High definition self-assemblies, those that possess order at the molecular level, are most commonly made from subunits possessing metals and metal coordination sites, or groups capable of partaking in hydrogen bonding. In other words, enthalpy is the driving force behind the free energy of assembly. The hydrophobic effect engenders the possibility of (nominally) relying not on enthalpy but entropy to drive assembly. Towards this idea, we describe how template molecules can trigger the dimerization of a cavitand in aqueous solution, and in doing so are encapsulated within the resulting capsule. Although not held together by (enthalpically) strong and directional non-covalent forces, these capsules possess considerable thermodynamic and kinetic stability. As a result, they display unusual and even unique properties. We discuss some of these, including the use of the capsule as a nanoscale reaction chamber and how they can bring about the separation of hydrocarbon gases.

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

    KAUST Repository

    Manojkumar, Kasina


    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.

  6. Improved enzyme-mediated synthesis and supramolecular self-assembly of naturally occurring conjugates of β-sitosterol. (United States)

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


    Naturally occurring acylated β-sitosteryl glucosides have been investigated for their novel properties. The synthetic protocol based on the literature data was improved and optimized. The main improvement consists in employing systems of ionic liquids combined with organic solvents in lipase-mediated esterification of (3β)-stigmast-5-en-3-yl β-d-glucopyranoside to get (3β)-stigmast-5-en-3-yl 6-O-acyl-β-d-glucopyranosides. Maximum yields of these products were achieved with Candida antarctica lipase B immobilized on Immobead 150, recombinant from yeast, in absolute THF and in the presence of either ionic liquid [1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM]BF 4 ) or 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM]PF 6 )] employed. Pharmacological activity of (3β)-stigmast-5-en-3-yl 6-O-acyl-β-d-glucopyranosides was studied in tests on MCF7 tumor cell lines; the compounds displayed moderate activity which was higher than the activity of β-sitosterol. Supramolecular characteristics were discovered at (3β)-stigmast-5-en-3-yl 6-O-dodecanoyl-β-d-glucopyranoside that formed supramolecular polymer through multiple H-bonds in a methanol/water system (60/40). Its formation was confirmed by the independent UV-vis measurements during certain time period, by variable temperature DOSY-NMR measurement in deuteriochloroform, and visualized by transmission electron microscopy (TEM) and atomic force microscopy (AFM) showing chiral helical structures and complex superassembly systems based on fibrous supramolecular polymer. In contrary, no such properties have been observed for the other two (3β)-stigmast-5-en-3-yl 6-O-acyl-β-d-glucopyranosides under the given experimental conditions. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. 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: [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: [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)


    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.

  8. Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring. (United States)

    Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Di Leandro, Luana; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo


    Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the "double-faced" Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml(-1). Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and "green" routes to 3D reduced GO-metal composite materials.

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

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


    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.

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

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


    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.

  11. Effect of H-bonding interactions of water molecules in the self assembly of supramolecular architecture-joint experimental and computational studies (United States)

    Jassal, Amanpreet Kaur; Kaur, Rajwinder; Islam, Nasarul; Anu; Mudsainiyan, Rahul Kumar


    A new {[Cu(4,4‧-BP)2.(H2O)4].2,6-NDC.3(H2O)} complex has been synthesized by refluxing Cu(NO3)2, 2,6-NDC and 4,4‧-BP (1:1:1 ratio) (2,6-NDC = 2,6-Naphthalene Dicarboxylic acid, 4,4‧-BP = 4,4'-bipyridine) in methanol/ammonia mixture and characterized by various spectroscopic techniques. The geometry around Cu2+ ion is typical octahedral in cationic complex, while the deprotonated 2,6-NDC act as a charge balancing counter anionic part. Water molecules (lattice and coordinated) also play important role in the self-assembly by forming Hsbnd bonded supramolecular architecture involving strong inter/intramolecular secondary interactions. The luminescence property and thermogravimetric analyses were also investigated. Both the intermolecular interactions of molecular and crystal structures of this complex were compared and discussed using Hirshfeld surface analysis and 2D-fingerprint plots. Hirshfeld surface analysis indicates that H⋯H, O⋯H and π···π contacts can account for 40.4, 19.3 and 7.7% respectively of the total Hirshfeld surface area. The DFT calculation at the CAM-B3LYP level of theory revealed the existence of three hydrogens binds in the complex. These hydrogen bonds exist between the oxygen atom of ligand and the hydrogen of coordinated water molecules.

  12. 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: [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: [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)


    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.

  13. Electrochemical characterization of mixed self-assembled films of water-soluble single-walled carbon nanotube-poly(m-aminobenzene sulfonic acid) and Iron(II) tetrasulfophthalocyanine

    CSIR Research Space (South Africa)

    Agboola, BO


    Full Text Available The redox activities of water-soluble iron(II) tetrasulfophthalocyanine (FeTSPc) and single-walled carbon nanotube-poly(m-aminobenzene sulfonic acid) (SWCNT-PABS) adsorbed on a gold surface precoated with a self-assembled monolayer (SAM) of 2...

  14. Hirshfeld surface analyses and crystal structures of supramolecular self-assembly thiourea derivatives directed by non-covalent interactions (United States)

    Gumus, Ilkay; Solmaz, Ummuhan; Binzet, Gun; Keskin, Ebru; Arslan, Birdal; Arslan, Hakan


    The novel N-(bis(3,5-dimethoxybenzyl)carbamothioyl)-4-R-benzamide (R: H, Cl, CH3 and OCH3) compounds have been synthesized and characterized by FT-IR, 1H NMR and 13C NMR spectroscopy. Their crystal structures were also determined by single-crystal X-ray diffraction studies. Hirshfeld surfaces analysis and their associated two dimensional fingerprint plots of compounds were used as theoretical approach to assess driving force for crystal structure formation via the intermolecular interactions in the crystal lattices of synthesized compounds. The study of X-ray single crystal diffraction and Hirshfeld surfaces analysis of the prepared compounds shows that hydrogen bonding and other weaker interactions such as Nsbnd H⋯S, weak Csbnd H⋯S, Csbnd H⋯O, Csbnd H⋯N and Csbnd H···π intermolecular interactions and π-π stacking, among molecules of synthesized compounds participate in a cooperative way to stabilize the supramolecular structures.

  15. A Water-Soluble Cyclotriveratrylene-Based Supra-amphiphile: Synthesis, pH-Responsive Self-Assembly in Water, and Its Application in Controlled Drug Release. (United States)

    Xia, Danyu; Li, Yang; Jie, Kecheng; Shi, Bingbing; Yao, Yong


    A new water-soluble cyclotriveratrylene (WCTV) was designed and synthesized, and benzyldimethyldodecylammonium chloride (G) was chosen as the guest molecule to construct a supra-amphiphile by the host-guest interaction between WCTV and G in water, which is pH responsive. The supra-amphiphiles self-assembled into vesicles in water. When the pH of the solution was below 7.0, the supra-amphiphile disassociated, and the vesicles collapsed. Then, the pH-responsive self-assembly system was utilized for controlled drug release.

  16. Cytotoxicity and photocytotoxicity of structure-defined water-soluble C{sub 60}/micelle supramolecular nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Metanawin, Tanapak; Tang Tian; Chen Rongjun; Wang Xiaosong [School of Chemistry, University of Leeds, LS2 9TJ (United Kingdom); Vernon, David, E-mail: [School of Biological Sciences, University of Leeds, LS2 9TJ (United Kingdom)


    Well-defined, water-soluble C{sub 60}/micelle hierarchical colloids with varied amounts of C{sub 60} sitting on the surface of micellar cores were prepared via the self-assembly of PS-b-PDMA block copolymer micelles and C{sub 60}. The composites can generate a significant amount of reactive oxygen upon irradiation with red light. Cell studies showed that the colloids were either strongly associated with, or internalized by, the cells after 2 h incubation, but did not show obvious toxicity in the dark. In contrast, efficient cell killing was observed when the colloid-incubated cells were exposed to red light. This indicates that the supramolecular colloids are promising as photosensitizers for photodynamic cancer therapy.

  17. Triangles and tetrahedra: metal directed self-assembly of metallo-supramolecular structures incorporating bis-beta-diketonato ligands. (United States)

    Clegg, Jack K; Lindoy, Leonard F; Moubaraki, Boujema; Murray, Keith S; McMurtrie, John C


    The interaction of six aryl-linked bis-beta-diketones, including a new naphthylene linked species, with copper(II), iron(III) and, in one instance gallium(III), has been investigated with the aim of obtaining metallo-supramolecular assemblies exhibiting different geometries. New examples of two assembly types incorporating the above bis-beta-diketones (L) were generated. The first type is represented by a range of molecular triangles of formula [Cu(3)(L-H(2))(3)](solvent)(n) while the second is given by a corresponding selection of less-common neutral molecular tetrahedra of formula [Fe(4)(L-H(2))(6)](solvent)(n) as well as [Ga(4)(L-H(2))(6)].8.5THF.0.5H(2)O; an example of each type has been characterised by X-ray crystallography. A magnetochemical investigation of [Fe(4)(-H(2))(6)].6THF is reported. The susceptibility is Curie like and consistent with very weak coupling occurring between the iron(III) d(5)(high spin) centres. The X-ray structures of two trinuclear copper(II) as well as a tetranuclear iron(III) and a tetranuclear gallium(III) assembly confirm their discrete triangular and tetrahedral geometries, respectively. The structure of the gallium(III) species is closely related to that of the corresponding iron(III) species. The tetrahedral structures provide rare examples of such assemblies encapsulating guest solvent molecules--in each case tetrahydrofuran is incorporated in the central cavity.

  18. Self-Assembled Polymeric Micellar Nanoparticles as Nanocarriers for Poorly Soluble Anticancer Drug Ethaselen

    Directory of Open Access Journals (Sweden)

    Yang Zhuoli


    Full Text Available Abstract A series of monomethoxy poly(ethylene glycol-poly(lactide (mPEG-PLA diblock copolymers were synthesized, and mPEG-PLA micelle was fabricated and used as a nanocarrier for solubilization and delivery of a promising anticancer drug ethaselen. Ethaselen was efficiently encapsulated into the micelles by the dialysis method, and the solubility of ethaselen in water was remarkably increased up to 82 μg/mL before freeze-drying. The mean diameter of ethaselen-loaded micelles ranged from 51 to 98 nm with a narrow size distribution and depended on the length of PLA block. In vitro hemolysis study indicated that mPEG-PLA copolymers and ethaselen-loaded polymeric micelles had no hemolytic effect on the erythrocyte. The enhanced antitumor efficacy and reduced toxic effect of ethaselen-loaded polymeric micelle when compared with ethaselen-HP-β-CD inclusion were observed at the same dose in H22human liver cancer cell bearing mouse models. These suggested that mPEG-PLA polymeric micelle nanoparticles had great potential as nanocarriers for effective solubilization of poorly soluble ethaselen and further reducing side effects and toxicities of the drug.

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

    Directory of Open Access Journals (Sweden)

    Akihiko Tsuda


    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.

  20. Synergistic Effect of Binary Mixed-Pluronic Systems on Temperature Dependent Self-assembly Process and Drug Solubility

    Directory of Open Access Journals (Sweden)

    Chin-Fen Lee


    Full Text Available Mixed Pluronic micelles from very hydrophobic and very hydrophilic copolymers were selected to scrutinize the synergistic effect on the self-assembly process as well as the solubilization capacity of ibuprofen. The tendency of mixing behavior between parent copolymers was systematically examined from two perspectives: different block chain lengths at same hydrophilicity (L92 + F108, +F98, +F88, and +F68, as well as various hydrophobicities at the same PPO moiety (L92 + F88, +F87, and +P84. Temperature-dependent micellization in these binary systems was clearly inspected by the combined use of high sensitivity differential scanning calorimeter (HSDSC and dynamic light scattering (DLS. Changes in heat capacity and size of aggregates at different temperatures during the whole micellization process were simultaneously observed and examined. While distinction of block chain length between parent copolymers increases, the monodispersity of the binary Pluronic systems decreases. However, parent copolymers with distinct PPO moieties do not affirmatively lead to non-cooperative binding, such as the L92 + P84 system. The addition of ibuprofen promotes micellization as well as stabilizes aggregates in the solution. The partial replacement of the hydrophilic Pluronic by a more hydrophobic Pluronic L92 would increase the total hydrophobicity of mixed Pluronics used in the system to substantially enhance the solubility of ibuprofen. The solubility of ibuprofen in the 0.5 wt % L92 + 0.368 wt % P84 system is as high as 4.29 mg/mL, which is 1.4 times more than that of the 0.868 wt % P84 system and 147 times more than that in pure water at 37 °C.

  1. Molecular self-assembly advances and applications

    CERN Document Server

    Dequan, Alex Li


    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

  2. 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.


    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

  3. Synergy in supramolecular chemistry

    CERN Document Server

    Nabeshima, Tatsuya


    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

  4. A One-Pot Self-Assembly Reaction to Prepare a Supramolecular Palladium(II) Cyclometalated Complex: An Undergraduate Organometallic Laboratory Experiment (United States)

    Fernandez, Alberto; Lopez-Torres, Margarita; Fernandez, Jesus J.; Vazquez-Garcia, Digna; Vila, Jose M.


    A laboratory experiment for students in advanced inorganic chemistry is described. Students prepare palladium(II) cyclometalated complexes. A terdentate [C,N,O] Schiff base ligand is doubly deprotonated upon reaction with palladium(II) acetate in a self-assembly process to give a palladacycle with a characteristic tetranuclear structure. This…

  5. Peptide amphiphile self-assembly (United States)

    Iscen, Aysenur; Schatz, George C.


    Self-assembly is a process whereby molecules organize into structures with hierarchical order and complexity, often leading to functional materials. Biomolecules such as peptides, lipids and DNA are frequently involved in self-assembly, and this leads to materials of interest for a wide variety of applications in biomedicine, photonics, electronics, mechanics, etc. The diversity of structures and functions that can be produced provides motivation for developing theoretical models that can be used for a molecular-level description of these materials. Here we overview recently developed computational methods for modeling the self-assembly of peptide amphiphiles (PA) into supramolecular structures that form cylindrical nanoscale fibers using molecular-dynamics simulations. Both all-atom and coarse-grained force field methods are described, and we emphasize how these calculations contribute insight into fiber structure, including the importance of β-sheet formation. We show that the temperature at which self-assembly takes place affects the conformations of PA chains, resulting in cylindrical nanofibers with higher β-sheet content as temperature increases. We also present a new high-density PA model that shows long network formation of β-sheets along the long axis of the fiber, a result that correlates with some experiments. The β-sheet network is mostly helical in nature which helps to maintain strong interactions between the PAs both radially and longitudinally. Contribution to Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

  6. Comparing and Correlating Solubility Parameters Governing the Self-Assembly of Molecular Gels Using 1,3:2,4-Dibenzylidene Sorbitol as the Gelator (United States)


    Solvent properties play a central role in mediating the aggregation and self-assembly of molecular gelators and their growth into fibers. Numerous attempts have been made to correlate the solubility parameters of solvents and gelation abilities of molecular gelators, but a comprehensive comparison of the most important parameters has yet to appear. Here, the degree to which partition coefficients (log P), Henry’s law constants (HLC), dipole moments, static relative permittivities (εr), solvatochromic ET(30) parameters, Kamlet–Taft parameters (β, α, and π), Catalan’s solvatochromic parameters (SPP, SB, and SA), Hildebrand solubility parameters (δi), and Hansen solubility parameters (δp, δd, δh) and the associated Hansen distance (Rij) of 62 solvents (covering a wide range of properties) can be correlated with the self-assembly and gelation of 1,3:2,4-dibenzylidene sorbitol (DBS) gelation, a classic molecular gelator, is assessed systematically. The approach presented describes the basis for each of the parameters and how it can be applied. As such, it is an instructional blueprint for how to assess the appropriate type of solvent parameter for use with other molecular gelators as well as with molecules forming other types of self-assembled materials. The results also reveal several important insights into the factors favoring the gelation of solvents by DBS. The ability of a solvent to accept or donate a hydrogen bond is much more important than solvent polarity in determining whether mixtures with DBS become solutions, clear gels, or opaque gels. Thermodynamically derived parameters could not be correlated to the physical properties of the molecular gels unless they were dissected into their individual HSPs. The DBS solvent phases tend to cluster in regions of Hansen space and are highly influenced by the hydrogen-bonding HSP, δh. It is also found that the fate of this molecular gelator, unlike that of polymers, is influenced not only by the

  7. 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.


    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.

  8. Covalent defects restrict supramolecular self-assembly of homopolypeptides: case study of β2-fibrils of poly-L-glutamic acid.

    Directory of Open Access Journals (Sweden)

    Aleksandra Fulara

    Full Text Available Poly-L-glutamic acid (PLGA often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I' band below 1600 cm(-1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I' band with peaks at ca. 1616 and 1683 cm(-1. Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA, as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding that could obscure their actual propensities to adopt different conformations, and limit applications in the field of

  9. Covalent Defects Restrict Supramolecular Self-Assembly of Homopolypeptides: Case Study of β2-Fibrils of Poly-L-Glutamic Acid (United States)

    Fulara, Aleksandra; Hernik, Agnieszka; Nieznańska, Hanna; Dzwolak, Wojciech


    Poly-L-glutamic acid (PLGA) often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I′ band below 1600 cm−1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H) groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I′ band with peaks at ca. 1616 and 1683 cm−1). Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA), as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding) that could obscure their actual propensities to adopt different conformations, and limit applications in the field of synthetic

  10. A combined experimental and theoretical study of the supramolecular self-assembly of Cu(II) malonate complex assisted by various weak forces and water dimer

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Prankrishna [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Ray Choudhury, Somnath [Central Chemical Laboratory, Geological Survey of India, 15 A and B Kyd Street, Kolkata 700 016 (India); Mitra, Monojit [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Kumar Seth, Saikat [Department of Physics, M. G. Mahavidyalaya, Bhupatinagar, Purba Medinipur, West Bengal 721 425 (India); Helliwell, Madeleine [School of Chemistry, The University of Manchester, Brunswick Street, Manchester M13 9PL (United Kingdom); Bauzá, Antonio [Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares) (Spain); Frontera, Antonio, E-mail: [Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares) (Spain); Mukhopadhyay, Subrata, E-mail: [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India)


    A Cu(II) malonate complex with formula [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O (1) [C{sub 6}H{sub 8}N{sub 2}=2-picolylamine, C{sub 3}H{sub 2}O{sub 4}{sup 2−}=malonate dianion] has been synthesized by mixing the reactants in their stoichiometric proportion and its crystal structure has been determined by single-crystal X-ray diffraction. In 1, monomeric neutral metal malonate units [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)] are interlinked with each other through hydrogen bonds, weak lone pair⋯π and cuprophilic interactions to generate supramolecular dimers, which in turn further associated through hydrogen bonding to form infinite 1D chains. Water dimers, through series of hydrogen bonds and weak π–stacking forces are found to be responsible for interconnection of 1D chains, which resulted in a 3D network. A density functional (DFT) study of the energetic features of several noncovalent interactions observed in the solid state have been analyzed and characterized using Bader's theory of “atoms-in-molecules”. We also present here Hirshfeld surface analysis to investigate the close intermolecular contacts. - Graphical Abstract: Interplay of weak forces like hydrogen bonding, lone pair⋯π, Cu⋯Cu and π–stacking interactions leading to the formation of supramolecular network in [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O complex. - Highlights: • A complex of Cu(II) with malonate and 2-picolylamine is synthesized and X-ray characterized. • We report a density functional study of the energetic features of several noncovalent interactions • We perform Hirshfeld surface analysis to investigate the close intermolecular contacts.

  11. Supramolecular Langmuir monolayers and multilayered vesicles of self-assembling DNA–lipid surface structures and their further implications in polyelectrolyte-based cell transfections

    Energy Technology Data Exchange (ETDEWEB)

    Demirsoy, Fatma Funda Kaya [Ankara University, The Central Laboratory of The Institute of Biotechnology (Turkey); Eruygur, Nuraniye [Gazi University, Department of Pharmacognosy, Faculty of Pharmacy (Turkey); Süleymanoğlu, Erhan, E-mail: [Gazi University, Department of Pharmaceutical Chemistry, Faculty of Pharmacy (Turkey)


    The basic interfacial characteristics of DNA–lipid recognitions have been studied. The complex structures of individual unbound DNA molecules and their binary and ternary complexes with zwitterionic lipids and divalent cations were followed by employing lipid monolayers at the air–liquid interfaces, as well as by performing various microscopic, spectroscopic, and thermodynamic measurements with multilayered vesicles. The pressure-area isotherms depicted that Mg{sup 2+}-ions increase the surface pressure of lipid films and thus give rise to electrostatic and hydrophobic lipid–DNA interactions in terms of DNA adsorption, adhesion, and compaction. These features were further approached by using multilamellar vesicles with a mean diameter of 850 nm, where a metal ion-directed nucleic acid compaction and condensation effects were shown. The data obtained show the effectiveness of Langmuir monolayers and lipid multilayers in studying nucleic acid–lipid recognitions. The data provide with further details and support previous reports on mainly structural features of these recognitions. Biomolecular surface recognition events were presented in direct link with spectral and thermodynamic features of lipid vesicle–polynucleotide complex formations. The results serve to build a theoretical model considering the use of neutral lipids in lipoplex designs as a polyelectrolyte alternatives to the currently employed cytotoxic cationic liposomes. The supramolecular structures formed and their possible roles in interfacial electrostatic and hydrophobic mechanisms of endosomal escape in relevant cell transfection assays are particularly emphasized.

  12. Self-Assembly, Interfacial Nanostructure, and Supramolecular Chirality of the Langmuir-Blodgett Films of Some Schiff Base Derivatives without Alkyl Chain

    Directory of Open Access Journals (Sweden)

    Tifeng Jiao


    Full Text Available A special naphthyl-containing Schiff base derivative, N,N′-bis(2-hydroxy-1-naphthylidene-1,2-phenylenediamine, was synthesized, and its coordination with various metal ions in situ at the air/water interface has been investigated. Although the ligand contains no alkyl chain, it can be spread on water surface. When metal ions existed in the subphase, an interfacial coordination between the ligand and different metal ions occurred in the spreading film, while different Nanostructures were fabricated in the monolayers. Interestingly to note that among various metal ions, only the in situ coordination-induced Cu(II-complex film showed supramolecular chirality, although the multilayer films from the ligand or preformed complex are achiral. The chirality of the in situ Cu(II-coordinated Langmuir film was developed due to the special distorted coordination reaction and the spatial limitation at the air/water interface. A possible organization mechanism at the air/water interface was suggested.

  13. Singlet and triplet energy transfer dynamics in self-assembled axial porphyrin-anthracene complexes: towards supra-molecular structures for photon upconversion. (United States)

    Gray, Victor; Küçüköz, Betül; Edhborg, Fredrik; Abrahamsson, Maria; Moth-Poulsen, Kasper; Albinsson, Bo


    Energy and electron transfer reactions are central to many different processes and research fields, from photosynthesis and solar energy harvesting to biological and medical applications. Herein we report a comprehensive study of the singlet and triplet energy transfer dynamics in porphyrin-anthracene coordination complexes. Seven newly synthesized pyridine functionalized anthracene ligands, five with various bridge lengths and two dendrimer structures containing three and seven anthracene units, were prepared. We found that triplet energy transfer from ruthenium octaethylporphyrin to an axially coordinated anthracene is possible, and is in some cases followed by back triplet energy transfer to the porphyrin. The triplet energy transfer follows an exponential distance dependence with an attenuation factor, β, of 0.64 Å -1 . Further, singlet energy transfer from anthracene to the ruthenium porphyrin appears to follow a R 6 Förster distance dependence. Porphyrin-anthracene complexes are also used as triplet sensitizers for triplet-triplet annihilation (TTA) based photon upconversion, demonstrating their potential for photophysical and photochemical applications. The triplet lifetime of the complex is extended by the anthracene ligands, resulting in a threefold increase in the upconversion efficiency, Φ UC to 4.5%, compared to the corresponding ruthenium porphyrin-pyridine complex. Based on the results herein we discuss the future design of supra-molecular structures for TTA upconversion.

  14. Acceleration of Amide Bond Rotation by Encapsulation in the Hydrophobic Interior of a Water-Soluble Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

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


    The hydrophobic interior cavity of a self-assembled supramolecular assembly exploits the hydrophobic effect for the encapsulation of tertiary amides. Variable temperature 1H NMR experiments reveal that the free energy barrier for rotation around the C-N amide bond is lowered by up to 3.6 kcal/mol upon encapsulation. The hydrophobic cavity of the assembly is able to stabilize the less polar transition state of the amide rotation process. Carbon-13 labeling studies showed that the {sup 13}C NMR carbonyl resonance increases with temperature for the encapsulated amides which suggests that the assembly is able to favor a twisted for of the amide.

  15. Geometrical frustration yields fiber formation in self-assembly. (United States)

    Lenz, Martin; Witten, Thomas A


    Controlling the self-assembly of supramolecular structures is vital for living cells, and a central challenge for engineering at the nano- and microscales [1, 2]. Nevertheless, even particles without optimized shapes can robustly form well-defined morphologies. This is the case in numerous medical conditions where normally soluble proteins aggregate into fibers [3, 4]. Beyond the diversity of molecular mechanisms involved [5, 6], we propose that fibers generically arise from the aggregation of irregular particles with short-range interactions. Using a minimal model of ill-fitting, sticky particles, we demonstrate robust fiber formation for a variety of particle shapes and aggregation conditions. Geometrical frustration plays a crucial role in this process, and accounts for the range of parameters in which fibers form as well as for their metastable character.

  16. Geometrical frustration yields fibre formation in self-assembly (United States)

    Lenz, Martin; Witten, Thomas A.


    Controlling the self-assembly of supramolecular structures is vital for living cells, and a central challenge for engineering at the nano- and microscales. Nevertheless, even particles without optimized shapes can robustly form well-defined morphologies. This is the case in numerous medical conditions where normally soluble proteins aggregate into fibres. Beyond the diversity of molecular mechanisms involved, we propose that fibres generically arise from the aggregation of irregular particles with short-range interactions. Using a minimal model of ill-fitting, sticky particles, we demonstrate robust fibre formation for a variety of particle shapes and aggregation conditions. Geometrical frustration plays a crucial role in this process, and accounts for the range of parameters in which fibres form as well as for their metastable character.

  17. Programming protein self assembly with coiled coils (United States)

    Dietz, Hendrik; Bornschlögl, Thomas; Heym, Roland; König, Frauke; Rief, Matthias


    The controlled assembly of protein domains into supramolecular structures will be an important prerequisite for the use of functional proteins in future nanotechnology applications. Coiled coils are multimerization motifs whose dimerization properties can be programmed by amino acid sequence. Here, we report programmed supramolecular self-assembly of protein molecules using coiled coils and directly demonstrate its potential on the single molecule level by AFM force spectroscopy. We flanked two different model proteins, Ig27 from human cardiac titin and green fluorescent protein (GFP), by coiled coil binding partners and studied the capability of these elementary building blocks to self-assemble into linear chains. Simple sterical constraints are shown to control the assembly process, providing evidence that many proteins can be assembled with this method. An application for this technique is the design of polyproteins for single molecule force spectroscopy with an integrated force-calibration standard.

  18. Water-Soluble Polymer Nanoparticles Constructed by Three-Component Self-Assembly: An Efficient Theranostic Agent for Phosphorescent Imaging and Photodynamic Therapy. (United States)

    Yang, Qi; Shi, Min; Zhao, Heng; Lin, Jiaomin; An, Lu; Cui, Lili; Yang, Hong; Zhou, Zhiguo; Tian, Qiwei; Yang, Shiping


    Water-soluble polymer nanoparticles NP-1 and NP-2 were prepared by using a three-component self-assembly of an iridium complex, poly(4-vinyl pyridine-b-ethylene oxide) (P4VP-b-PEO), and methane sulfonic acid (MSA). Due to the unique metal-ligand charge-transfer transition property and the heavy-atom effect of the iridium atom, NP-1 and NP-2 showed bright phosphorescence and generated the singlet oxygen ( 1 O 2 ) species effectively under visible-light irradiation (λ>400 nm) with a power density of 300 mW cm -2 . NP-2, an example of the polymer nanoparticles, showed minimal cytotoxic activity in the dark. Laser confocal fluorescence and flow-cytometry microscopy experiments demonstrated that NP-2 could be taken up by a model cancer-cell line of 4T1 cells, which could be used as a phosphorescent probe for cell imaging by preferentially staining the cytoplasm. After 6 hours of incubation with NP-2 (100 μg mL -1 ), the cell viability of 4T1 cells decreased to approximately 10 % upon visible-light irradiation (λ>400 nm, 300 mW cm -2 ) only for 10 minutes as a result of the generation of the 1 O 2 species, thus indicating a proof of concept for effective photodynamic therapy for cancer cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Self-Assembly, Supramolecular Organization, and Phase Behavior of L-Alanine Alkyl Esters (n = 9-18) and Characterization of Equimolar L-Alanine Lauryl Ester/Lauryl Sulfate Catanionic Complex. (United States)

    Sivaramakrishna, D; Swamy, Musti J


    A homologous series of l-alanine alkyl ester hydrochlorides (AEs) bearing 9-18 C atoms in the alkyl chain have been synthesized and characterized with respect to self-assembly, supramolecular structure, and phase transitions. The CMCs of AEs bearing 11-18 C atoms were found to range between 0.1 and 10 mM. Differential scanning calorimetric (DSC) studies showed that the transition temperatures (Tt), enthalpies (ΔHt) and entropies (ΔSt) of AEs in the dry state exhibit odd-even alternation, with the odd-chain-length compounds having higher Tt values, but the even-chain-length homologues showing higher values of ΔHt and ΔSt. In DSC measurements on hydrated samples, carried out at pH 5.0 and pH 10.0 (where they exist in cationic and neutral forms, respectively), compounds with 13-18 C atoms in the alkyl chain showed sharp gel-to-liquid crystalline phase transitions, and odd-even alternation was not seen in the thermodynamic parameters. The molecular structure, packing properties, and intermolecular interactions of AEs with 9 and 10 C atoms in the alkyl chain were determined by single crystal X-ray diffraction, which showed that the alkyl chains are packed in a tilted interdigitated bilayer format. d-Spacings obtained from powder X-ray diffraction studies exhibited a linear dependence on the alkyl chain length, suggesting that the other AEs also adopt an interdigitated bilayer structure. Turbidimetric, fluorescence spectroscopic, and isothermal titration calorimetric (ITC) studies established that in aqueous dispersions l-alanine lauryl ester hydrochloride (ALE·HCl) and sodium dodecyl sulfate (SDS) form an equimolar complex. Transmission electron microscopic and DSC studies indicate that the complex exists as unilamellar liposomes, which exhibit a sharp phase transition at ∼39 °C. The aggregates were disrupted at high pH, suggesting that the catanionic complex would be useful to develop a base-labile drug delivery system. ITC studies indicated that ALE·HCl forms

  20. Nanoscale isoindigo-carriers: self-assembly and tunable properties

    Directory of Open Access Journals (Sweden)

    Tatiana N. Pashirova


    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.

  1. Supramolecular Host-Guest System as Ratiometric Fe3+ Ion Sensor Based on Water-Soluble Pillar[5]arene. (United States)

    Yao, Qianfang; Lü, Baozhong; Ji, Chendong; Cai, Yang; Yin, Meizhen


    Developing a specific, ratiometric, and reversible detection method for metal ions is significant to guard against the threat of metal-caused environmental pollution and organisms poisoning. Here a supramolecular host-guest system (WP5⊃G) based on water-soluble pillar[5]arene (WP5) and water-soluble quaternized perylene diimide derivative (G) was constructed. Morphological transformation was achieved during the process of adding WP5 into G aqueous solution, and a fluorescence "turn-off" phenomenon was observed which was caused by supramolecular photoinduced electron transfer (PET). Meanwhile, hydrophobic effect and electrostatic interaction played important roles in this supramolecular process, which was confirmed by isothermal titration calorimeter (ITC) and ζ potential experiments. Furthermore, the supramolecular host-guest system could be a "turn-on" fluorescent probe for Fe 3+ ion detection through the process of interdicting supramolecular PET. Moreover, the Fe 3+ ion detection showed specific, ratiometric, and reversible performances with a detection limit of 2.13 × 10 -7 M, which might have great potentials in biological and environmental monitoring.

  2. Self-assembled nanostructures

    CERN Document Server

    Zhang, Jin Z; Liu, Jun; Chen, Shaowei; Liu, Gang-yu


    Nanostructures refer to materials that have relevant dimensions on the nanometer length scales and reside in the mesoscopic regime between isolated atoms and molecules in bulk matter. These materials have unique physical properties that are distinctly different from bulk materials. Self-Assembled Nanostructures provides systematic coverage of basic nanomaterials science including materials assembly and synthesis, characterization, and application. Suitable for both beginners and experts, it balances the chemistry aspects of nanomaterials with physical principles. It also highlights nanomaterial-based architectures including assembled or self-assembled systems. Filled with in-depth discussion of important applications of nano-architectures as well as potential applications ranging from physical to chemical and biological systems, Self-Assembled Nanostructures is the essential reference or text for scientists involved with nanostructures.

  3. Side-chain-controlled self-assembly of polystyrene-polypeptide miktoarm star copolymers

    KAUST Repository

    Junnila, Susanna


    We show how the self-assembly of miktoarm star copolymers can be controlled by modifying the side chains of their polypeptide arms, using A 2B and A 2B 2 type polymer/polypeptide hybrids (macromolecular chimeras). Initially synthesized PS 2PBLL and PS 2PBLL 2 (PS, polystyrene; PBLL, poly(ε-tert-butyloxycarbonyl-l-lysine) ) miktoarms were first deprotected to PS 2PLLHCl and PS 2PLLHCl 2 miktoarms (PLLHCl, poly(l-lysine hydrochloride)) and then complexed ionically with sodium dodecyl sulfonate (DS) to give the supramolecular complexes PS 2PLL(DS) and PS 2(PLL(DS)) 2. The solid-state self-assemblies of these six miktoarm systems were studied by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and small- and wide-angle X-ray scattering (SAXS, WAXS). The side chains of the polypeptide arms were observed to have a large effect on the solubility, polypeptide conformation, and self-assembly of the miktoarms. Three main categories were observed: (i) lamellar self-assemblies at the block copolymer length scale with packed layers of α-helices in PS 2PBLL and PS 2PBLL 2; (ii) charge-clustered polypeptide micelles with less-defined conformations in a nonordered lattice within a PS matrix in PS 2PLLHCl and PS 2PLLHCl 2; (iii) lamellar polypeptide-surfactant self-assemblies with β-sheet conformation in PS 2PLL(DS) and PS 2(PLL(DS)) 2 which dominate over the formation of block copolymer scale structures. Differences between the 3- and 4-arm systems illustrate how packing frustration between the coil-like PS arms and rigid polypeptide conformations can be relieved by the right number of arms, leading to differences in the extent of order. © 2012 American Chemical Society.

  4. Suprmolecular chirality of self-assembled systems in solution

    NARCIS (Netherlands)

    Mateos timoneda, Miguel; Crego Calama, Mercedes; Reinhoudt, David


    Self-assembly plays an important role in the formation of many (chiral) biological structures, such as DNA, α-helices or ß-sheets of proteins. This process, which is the main tool of Supramolecular Chemistry (i.e. the chemistry of the molecular assemblies and of the intermolecular bonds), starts to

  5. 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


    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

  6. Photovoltaic self-assembly.

    Energy Technology Data Exchange (ETDEWEB)

    Lavin, Judith; Kemp, Richard Alan; Stewart, Constantine A.


    This late-start LDRD was focused on the application of chemical principles of self-assembly on the ordering and placement of photovoltaic cells in a module. The drive for this chemical-based self-assembly stems from the escalating prices in the 'pick-and-place' technology currently used in the MEMS industries as the size of chips decreases. The chemical self-assembly principles are well-known on a molecular scale in other material science systems but to date had not been applied to the assembly of cells in a photovoltaic array or module. We explored several types of chemical-based self-assembly techniques, including gold-thiol interactions, liquid polymer binding, and hydrophobic-hydrophilic interactions designed to array both Si and GaAs PV chips onto a substrate. Additional research was focused on the modification of PV cells in an effort to gain control over the facial directionality of the cells in a solvent-based environment. Despite being a small footprint research project worked on for only a short time, the technical results and scientific accomplishments were significant and could prove to be enabling technology in the disruptive advancement of the microelectronic photovoltaics industry.

  7. Macroscopic magnetic Self assembly

    NARCIS (Netherlands)

    Löthman, Per Arvid


    Exploring the macroscopic scale's similarities to the microscale is part and parcel of this thesis as reflected in the research question: what can we learn about the microscopic scale by studying the macroscale? Investigations of the environment in which the self-assembly takes place, and the

  8. Silk nanofibril self-assembly versus electrospinning. (United States)

    Humenik, Martin; Lang, Gregor; Scheibel, Thomas


    Natural silk fibers represent one of the most advanced blueprints for (bio)polymer scientists, displaying highly optimized mechanical properties due to their hierarchical structures. Biotechnological production of silk proteins and implementation of advanced processing methods enabled harnessing the potential of these biopolymer not just based on the mechanical properties. In addition to fibers, diverse morphologies can be produced, such as nonwoven meshes, films, hydrogels, foams, capsules and particles. Among them, nanoscale fibrils and fibers are particularly interesting concerning medical and technical applications due to their biocompatibility, environmental and mechanical robustness as well as high surface-to-volume ratio. Therefore, we introduce here self-assembly of silk proteins into hierarchically organized structures such as supramolecular nanofibrils and fabricated materials based thereon. As an alternative to self-assembly, we also present electrospinning a technique to produce nanofibers and nanofibrous mats. Accordingly, we introduce a broad range of silk-based dopes, used in self-assembly and electrospinning: natural silk proteins originating from natural spinning glands, natural silk protein solutions reconstituted from fibers, engineered recombinant silk proteins designed from natural blueprints, genetic fusions of recombinant silk proteins with other structural or functional peptides and moieties, as well as hybrids of recombinant silk proteins chemically conjugated with nonproteinaceous biotic or abiotic molecules. We highlight the advantages but also point out drawbacks of each particular production route. The scope includes studies of the natural self-assembly mechanism during natural silk spinning, production of silk fibrils as new nanostructured non-native scaffolds allowing dynamic morphological switches, as well as studying potential applications. This article is categorized under:  Biology-Inspired Nanomaterials

  9. 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

  10. Biocompatible or biodegradable hyperbranched polymers: from self-assembly to cytomimetic applications. (United States)

    Jin, Haibao; Huang, Wei; Zhu, Xinyuan; Zhou, Yongfeng; Yan, Deyue


    Self-assembly of amphiphilic hyperbranched polymers (HBPs) is a newly emerging research area and has attracted increasing attention due to the great advantages in biomedical applications. This tutorial review focuses on the self-assembly of biocompatible or biodegradable amphiphilic HBPs and their cytomimetic applications, and specialities or advantages therein owing to the hyperbranched structure have also been summarized. As shown here, various supramolecular structures including micelles, vesicles, tubes, fibers and films have been prepared through the primary self-assembly processes. The primary self-assemblies can be further assembled into more complex structures through hierachical self-assembly processes. Besides, the hyperbranched polymer vesicles have demonstrated great potential to be used as model membranes to mimic cellular behaviors, such as fusion, fission and cell aggregation. Other biomedical applications of HBPs as well as their self-assemblies are also briefly summarized.

  11. Self-assembly of self-assembled molecular triangles

    Indian Academy of Sciences (India)

    While the solution state structure of 1 can be best described as a trinuclear complex, in the solidstate well-fashioned intermolecular - and CH- interactions are observed. Thus, in the solid-state further self-assembly of already self-assembled molecular triangle is witnessed. The triangular panels are arranged in a linear ...

  12. Aerosolized droplet mediated self-assembly of photosynthetic pigment analogues and deposition onto substrates. (United States)

    Shah, Vivek B; Biswas, Pratim


    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.

  13. Tailoring two-dimensional PTCDA-melamine self-assembled architectures at room temperature by tuning molecular ratio

    NARCIS (Netherlands)

    Sun, Xiaonan; Jonkman, Harry T.; Silly, Fabien


    Engineering and tuning multi-component supramolecular self-assemblies on surfaces is one of the challenges of nanotechnology. We use scanning tunneling microscopy to investigate the influence of molecular ratio on the self-assembly of PTCDA-melamine structures on Au(111)-(22 x root 3). Our

  14. Self-assembly of novel supramolecular silver(I) compound based on mixed ligands bipy/TST3- H3TST=2,4,6-tris (4-sulfophenylamino)-1,3,5-triazine

    NARCIS (Netherlands)

    Yu, Yunfang; Wei, Yongqin; Broer, Ria; Wu, Kechen


    The novel supramolecular silver(I) compound with formula [Ag-6(TST)(2)(bipy)(6)(H2O)(2)](n) center dot 3nH(2)O (1) based on assembly of Ag(I) and mixed ligand bipy/TST3-, bipy = 2,2'-bipyridine, H3TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the

  15. Phosphorylation Modulates Ameloblastin Self-assembly and Ca2+ Binding

    Directory of Open Access Journals (Sweden)

    Øystein Stakkestad


    Full Text Available Ameloblastin (AMBN, an important component of the self-assembled enamel extra cellular matrix, contains several in silico predicted phosphorylation sites. However, to what extent these sites actually are phosphorylated and the possible effects of such post-translational modifications are still largely unknown. Here we report on in vitro experiments aimed at investigating what sites in AMBN are phosphorylated by casein kinase 2 (CK2 and protein kinase A (PKA and the impact such phosphorylation has on self-assembly and calcium binding. All predicted sites in AMBN can be phosphorylated by CK2 and/or PKA. The experiments show that phosphorylation, especially in the exon 5 derived part of the molecule, is inversely correlated with AMBN self-assembly. These results support earlier findings suggesting that AMBN self-assembly is mostly dependent on the exon 5 encoded region of the AMBN gene. Phosphorylation was significantly more efficient when the AMBN molecules were in solution and not present as supramolecular assemblies, suggesting that post-translational modification of AMBN must take place before the enamel matrix molecules self-assemble inside the ameloblast cell. Moreover, phosphorylation of exon 5, and the consequent reduction in self-assembly, seem to reduce the calcium binding capacity of AMBN suggesting that post-translational modification of AMBN also can be involved in control of free Ca2+ during enamel extra cellular matrix biomineralization. Finally, it is speculated that phosphorylation can provide a functional crossroad for AMBN either to be phosphorylated and act as monomeric signal molecule during early odontogenesis and bone formation, or escape phosphorylation to be subsequently secreted as supramolecular assemblies that partake in enamel matrix structure and mineralization.

  16. Supramolecular polymers for organocatalysis in water. (United States)

    Neumann, Laura N; Baker, Matthew B; Leenders, Christianus M A; Voets, Ilja K; Lafleur, René P M; Palmans, Anja R A; Meijer, E W


    A water-soluble benzene-1,3,5-tricarboxamide (BTA) derivative that self-assembles into one-dimensional, helical, supramolecular polymers is functionalised at the periphery with one L-proline moiety. In water, the BTA-derivative forms micrometre long supramolecular polymers, which are stabilised by hydrophobic interactions and directional hydrogen bonds. Furthermore, we co-assemble a catalytically inactive, but structurally similar, BTA with the L-proline functionalised BTA to create co-polymers. This allows us to assess how the density of the L-proline units along the supramolecular polymer affects its activity and selectivity. Both the supramolecular polymers and co-polymers show high activity and selectivity as catalysts for the aldol reaction in water when using p-nitrobenzaldehyde and cyclohexanone as the substrates for the aldol reaction. After optimisation of the reaction conditions, a consistent conversion of 92 ± 7%, deanti of 92 ± 3%, and eeanti of 97 ± 1% are obtained with a concentration of L-proline as low as 1 mol%.

  17. Self-assembled Nanomaterials for Chemotherapeutic Applications (United States)

    Shieh, Aileen

    The self-assembly of short designed peptides into functional nanostructures is becoming a growing interest in a wide range of fields from optoelectronic devices to nanobiotechnology. In the medical field, self-assembled peptides have especially attracted attention with several of its attractive features for applications in drug delivery, tissue regeneration, biological engineering as well as cosmetic industry and also the antibiotics field. We here describe the self-assembly of peptide conjugated with organic chromophore to successfully deliver sequence independent micro RNAs into human non-small cell lung cancer cell lines. The nanofiber used as the delivery vehicle is completely non-toxic and biodegradable, and exhibit enhanced permeability effect for targeting malignant tumors. The transfection efficiency with nanofiber as the delivery vehicle is comparable to that of the commercially available RNAiMAX lipofectamine while the toxicity is significantly lower. We also conjugated the peptide sequence with camptothecin (CPT) and observed the self-assembly of nanotubes for chemotherapeutic applications. The peptide scaffold is non-toxic and biodegradable, and drug loading of CPT is high, which minimizes the issue of systemic toxicity caused by extensive burden from the elimination of drug carriers. In addition, the peptide assembly drastically increases the solubility and stability of CPT under physiological conditions in vitro, while active CPT is gradually released from the peptide chain under the slight acidic tumor cell environment. Cytotoxicity results on human colorectal cancer cells and non-small cell lung cancer cell lines display promising anti-cancer properties compared to the parental CPT drug, which cannot be used clinically due to its poor solubility and lack of stability in physiological conditions. Moreover, the peptide sequence conjugated with 5-fluorouracil formed a hydrogel with promising topical chemotherapeutic applications that also display

  18. Template-directed self-assembly of dynamic covalent capsules with polar interiors. (United States)

    Galán, Albano; Escudero-Adán, Eduardo C; Ballester, Pablo


    Chiral polyimine molecular capsules with polar interiors have been prepared through template covalent dynamic self-assembly. An aryl-extended tetraaldehyde calix[4]pyrrole scaffold was condensed with suitable diamines as linkers using templates for efficient self-assembly. The capsular complexes were characterized in solution, gas phase and the solid-state. Unprecedented transfer of asymmetry was observed from a chiral diamine linker to the resulting supramolecular capsular assembly.

  19. Self-assembly of polar food lipids. (United States)

    Leser, Martin E; Sagalowicz, Laurent; Michel, Martin; Watzke, Heribert J


    Polar lipids, such as monoglycerides and phospholipids, are amphiphilic molecules commonly used as processing and stabilization aids in the manufacturing of food products. As all amphiphilic molecules (surfactants, emulsifiers) they show self-assembly phenomena when added into water above a certain concentration (the critical aggregation concentration). The variety of self-assembly structures that can be formed by polar food lipids is as rich as it is for synthetic surfactants: micelles (normal and reverse micelles), microemulsions, and liquid crystalline phases can be formulated using food-grade ingredients. In the present work we will first discuss microemulsion and liquid crystalline phase formation from ingredients commonly used in food industry. In the last section we will focus on three different potential application fields, namely (i) solubilization of poorly water soluble ingredients, (ii) controlled release, and (iii) chemical reactivity. We will show how the interfacial area present in self-assembly structures can be used for (i) the delivery of functional molecules, (ii) controlling the release of functional molecules, and (iii) modulating the chemical reactivity between reactive molecules, such as aromas.

  20. Multivalency in supramolecular chemistry and nanofabrication

    NARCIS (Netherlands)

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


    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

  1. Hydrazine-mediated construction of nanocrystal self-assembly materials. (United States)

    Zhou, Ding; Liu, Min; Lin, Min; Bu, Xinyuan; Luo, Xintao; Zhang, Hao; Yang, Bai


    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.

  2. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting


    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

  3. Self-assembling biomolecular catalysts for hydrogen production (United States)

    Jordan, Paul C.; Patterson, Dustin P.; Saboda, Kendall N.; Edwards, Ethan J.; Miettinen, Heini M.; Basu, Gautam; Thielges, Megan C.; Douglas, Trevor


    The chemistry of highly evolved protein-based compartments has inspired the design of new catalytically active materials that self-assemble from biological components. A frontier of this biodesign is the potential to contribute new catalytic systems for the production of sustainable fuels, such as hydrogen. Here, we show the encapsulation and protection of an active hydrogen-producing and oxygen-tolerant [NiFe]-hydrogenase, sequestered within the capsid of the bacteriophage P22 through directed self-assembly. We co-opted Escherichia coli for biomolecular synthesis and assembly of this nanomaterial by expressing and maturing the EcHyd-1 hydrogenase prior to expression of the P22 coat protein, which subsequently self assembles. By probing the infrared spectroscopic signatures and catalytic activity of the engineered material, we demonstrate that the capsid provides stability and protection to the hydrogenase cargo. These results illustrate how combining biological function with directed supramolecular self-assembly can be used to create new materials for sustainable catalysis.

  4. Self-assembly of self-assembled molecular triangles

    Indian Academy of Sciences (India)

    (tmeda), 2,2 -bipyridine (bpy), and 1,10-phenanthroline. (phen), etc. The synthesis and dynamic studies of a vari- ety of designed Pd(II) cages are well studied1a−d but the crystal engineering of Pd(II)-based self-assembled coordination cages has been less explored.4 Recently we have been investigating the significance of ...

  5. Quantitative self-assembly prediction yields targeted nanomedicines (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.


    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.

  6. Pt–Ru decorated self-assembled TiO2–carbon hybrid nanostructure ...

    Indian Academy of Sciences (India)

    Accordingly, titanium oxide–carbon nanocomposite with mesoporous structure is directly synthesized as a cata- lyst support via supramolecular self-assembly with an in situ crystallization process in order to achieve high surface area. Active sites on such a porous structure would be ea- sily accessible to the reactant leading ...

  7. Self-assembled M2L4 coordination cages : Synthesis and potential applications

    NARCIS (Netherlands)

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


    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

  8. Self-assembly of cyclodextrins

    DEFF Research Database (Denmark)

    Fülöp, Z.; Kurkov, S.V.; Nielsen, T.T.


    that increases upon formation of inclusion complexes with lipophilic drugs. However, the stability of such aggregates is not sufficient for parenteral administration. In this review CD polymers and CD containing nanoparticles are categorized, with focus on self-assembled CD nanoparticles. It is described how...

  9. Rapid self-assembly of block copolymers to photonic crystals (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.


    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.

  10. Nanoporous network channels from self-assembled triblock copolymer supramolecules. (United States)

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


    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.

  11. Photocontrolled reversible self-assembly of dodecamer nitrilase. (United States)

    Yu, Qiao; Wang, Yong; Zhao, Shengyun; Ren, Yuhong


    Naturally photoswitchable proteins act as a powerful tool for the spatial and temporal control of biological processes by inducing the formation of a photodimerizer. In this study, a method for the precise and reversible inducible self-assembly of dodecamer nitrilase in vivo (in Escherichia coli ) and in vitro (in a cell-free solution) was developed by means of the photoswitch-improved light-inducible dimer (iLID) system which could induce protein-protein dimerization. Nitrilase was fused with the photoswitch protein AsLOV2-SsrA to achieve the photocontrolled self-assembly of dodecamer nitrilase. The fusion protein self-assembled into a supramolecular assembly when illuminated at 470 nm. Scanning electron microscopy showed that the assembly formed a circular sheet structure. Self-assembly was also induced by light in E. coli . Dynamic light scattering and turbidity assay experiments showed that the assemblies formed within a few seconds under 470-nm light and completely disassembled within 5 min in the dark. Assembly and disassembly could be maintained for at least five cycles. Both in vitro and in vivo, the assemblies retained 90% of the initial activity of nitrilase and could be reused at least four times in vitro with 90% activity. An efficient method was developed for the photocontrolled assembly and disassembly of dodecamer nitrilase and for scaffold-free reversible self-assembly of multiple oligomeric enzymes in vivo and in vitro, providing new ideas and methods for immobilization of enzyme without carrier.

  12. 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


    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.

  13. Carbohydrates in Supramolecular Chemistry. (United States)

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


    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.

  14. Self-assembled nanoparticles of glycol chitosan – Ergocalciferol succinate conjugate, for controlled release

    DEFF Research Database (Denmark)

    Quinones, Javier Perez; Gothelf, Kurt Vesterager; Kjems, Jørgen


    Glycol chitosan was linked to vitamin D2 hemisuccinate (ergocalciferol hemisuccinate) for controlled release through water-soluble carbodiimide activation. The resulting conjugate formed self-assembled nanoparticles in aqueous solution with particle size of 279 nm and ergocalciferol hemisuccinate...

  15. Encapsulating fluorescein using adipic acid self-assembly on the surface of PPI-3 dendrimer. (United States)

    Chai, Minghui; Holley, Aaron K; Kruskamp, Michael


    A water-soluble self-assembly has been formed by associating adipic acid molecules onto the surface of the third generation poly(propyleneimine) dendrimer and this system has been used to encapsulate fluorescein.

  16. Dual photo- and pH-responsive supramolecular nanocarriers based on water-soluble pillar[6]arene and different azobenzene derivatives for intracellular anticancer drug delivery. (United States)

    Hu, Xiao-Yu; Jia, Keke; Cao, Yu; Li, Yan; Qin, Shan; Zhou, Fan; Lin, Chen; Zhang, Dongmei; Wang, Leyong


    Two novel types of supramolecular nanocarriers fabricated by the amphiphilic host-guest inclusion complex formed from water-soluble pillar[6]arene (WP6) and azobenzene derivatives G1 or G2 have been developed, in which G1 is structurally similar to G2 but has an extra phenoxy group in its hydrophobic region. Supramolecular micelles can be initially formed by WP6 with G1, which gradually transform into layered structures with liquid-crystalline properties, whereas stable supramolecular vesicles are obtained from WP6 and G2, which exhibit dual photo- and pH-responsiveness. Notably, the resulting WP6⊃G2 vesicles can efficiently encapsulate anticancer drug mitoxantrone (MTZ) to achieve MTZ-loaded vesicles, which maintain good stability in a simulated normal physiological environment, whereas in an acid environment similar to that of tumor cells or with external UV irradiation, the encapsulated drug is promptly released. More importantly, cytotoxicity assay indicates that such vesicles have good biocompatibility and the MTZ-loaded vesicles exhibit comparable anticancer activity to free MTZ, especially with additional UV stimulus, whereas its cytotoxicity for normal cells was remarkably reduced. Flow cytometric analysis further confirms that the cancer cell death caused by MTZ-loaded vesicles is associated with apoptosis. Therefore, the dual pH- and UV-responsive supramolecular vesicles are a potential platform for controlled release and targeted anticancer drug delivery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A novel soluble supramolecular system for sustained rh-GH delivery. (United States)

    Salmaso, Stefano; Bersani, Sara; Scomparin, Anna; Balasso, Anna; Brazzale, Chiara; Barattin, Michela; Caliceti, Paolo


    Methoxy-poly(ethylene glycol)s bearing a terminal cholanic moiety (mPEG(5kDa)-cholane, mPEG(10kDa)-cholane and mPEG(20kDa)-cholane) were physically combined with recombinant human growth hormone (rh-GH) to obtain supramolecular assemblies for sustained hormone delivery. The association constants (Ka) calculated by Scatchard analysis of size exclusion chromatography (SEC) data were in the order of 10(5)M(-1). The complete rh-GH association with mPEG(5kDa)-cholane, mPEG(10kDa)-cholane and mPEG(20kDa)-cholane was achieved with 7.5 ± 1.1, 3.9 ± 0.4 and 2.6 ± 0.4 w/w% rh-GH/mPEG-cholane, respectively. Isothermal titration calorimetry (ITC) yielded association constants similar to that calculated by SEC and showed that rh-GH has 21-25 binding sites for mPEG-cholane, regardless the polymer molecular weight. Dialysis studies showed that the mPEG-cholane association strongly delays the protein release; 80-90% of the associated rh-GH was released in 200 h. However, during the first 8h the protein formulations obtained with mPEG(10kDa)-cholane and mPEG(20kDa)-cholane showed a burst release of 8 and 28%, respectively. Circular dichroism (CD) analyses showed that the mPEG(5kDa)-cholane association does not alter the secondary structure of the protein. Furthermore, mPEG(5kDa)-cholane was found to enhance both the enzymatic and physical stability of rh-GH. In vivo pharmacokinetic and pharmacodynamic studies were performed by subcutaneous administration of rh-GH and rh-GH/mPEG(5kDa)-cholane to normal and hypophysectomised rats. The study showed that mPEG(5kDa)-cholane decreases the maximal concentration in the blood but prolongs the body exposure of the protein, which resulted in 55% bioavailability increase. Finally, rh-GH formulated with mPEG(5kDa)-cholane yielded prolonged weight increase of hypophysectomised rats as compared to rh-GH in buffer or formulated with mPEG(5kDa)-OH. After the second administration the weight of the animals treated with rh-GH formulated with m

  18. Molecular dynamics simulations reveal disruptive self-assembly in dynamic peptide libraries. (United States)

    Sasselli, I R; Moreira, I P; Ulijn, R V; Tuttle, T


    There is significant interest in the use of unmodified self-assembling peptides as building blocks for functional, supramolecular biomaterials. Recently, dynamic peptide libraries (DPLs) have been proposed to select self-assembling materials from dynamically exchanging mixtures of dipeptide inputs in the presence of a nonspecific protease enzyme, where peptide sequences are selected and amplified based on their self-assembling tendencies. It was shown that the results of the DPL of mixed sequences (e.g. starting from a mixture of dileucine, L 2 , and diphenylalanine, F 2 ) did not give the same outcome as the separate L 2 and F 2 libraries (which give rise to the formation of F 6 and L 6 ), implying that interactions between these sequences could disrupt the self-assembly. In this study, coarse grained molecular dynamics (CG-MD) simulations are used to understand the DPL results for F 2 , L 2 and mixed libraries. CG-MD simulations demonstrate that interactions between precursors can cause the low formation yield of hexapeptides in the mixtures of dipeptides and show that this ability to disrupt is influenced by the concentration of the different species in the DPL. The disrupting self-assembly effect between the species in the DPL is an important effect to take into account in dynamic combinatorial chemistry as it affects the possible discovery of new materials. This work shows that combined computational and experimental screening can be used complementarily and in combination providing a powerful means to discover new supramolecular peptide nanostructures.

  19. A triaxial supramolecular weave (United States)

    Lewandowska, Urszula; Zajaczkowski, Wojciech; Corra, Stefano; Tanabe, Junki; Borrmann, Ruediger; Benetti, Edmondo M.; Stappert, Sebastian; Watanabe, Kohei; Ochs, Nellie A. K.; Schaeublin, Robin; Li, Chen; Yashima, Eiji; Pisula, Wojciech; Müllen, Klaus; Wennemers, Helma


    Despite recent advances in the synthesis of increasingly complex topologies at the molecular level, nano- and microscopic weaves have remained difficult to achieve. Only a few diaxial molecular weaves exist—these were achieved by templation with metals. Here, we present an extended triaxial supramolecular weave that consists of self-assembled organic threads. Each thread is formed by the self-assembly of a building block comprising a rigid oligoproline segment with two perylene-monoimide chromophores spaced at 18 Å. Upon π stacking of the chromophores, threads form that feature alternating up- and down-facing voids at regular distances. These voids accommodate incoming building blocks and establish crossing points through CH-π interactions on further assembly of the threads into a triaxial woven superstructure. The resulting micrometre-scale supramolecular weave proved to be more robust than non-woven self-assemblies of the same building block. The uniform hexagonal pores of the interwoven network were able to host iridium nanoparticles, which may be of interest for practical applications.

  20. Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles. (United States)

    Wang, Chao; Wang, Zhiqiang; Zhang, Xi


    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

  1. Generation of Low-Dimensional Architectures through the Self-Assembly of Pyromellitic Diimide Derivatives. (United States)

    Musumeci, Chiara; Wałe Sa-Chorab, Monika; Gorczyński, Adam; Markiewicz, Grzegorz; Bogucki, Andrzej; Świetlik, Roman; Hnatejko, Zbigniew; Jankowski, Wojciech; Hoffmann, Marcin; Orgiu, Emanuele; Stefankiewicz, Artur R; Patroniak, Violetta; Ciesielski, Artur; Samorì, Paolo


    Small π-conjugated molecules can be designed and synthesized to undergo controlled self-assembly forming low-dimensional architectures, with programmed order at the supramolecular level. Such order is of paramount importance because it defines the property of the obtained material. Here, we have focused our attention to four pyromellitic diimide derivatives exposing different types of side chains. The joint effect of different noncovalent interactions including π-π stacking, H-bonding, and van der Waals forces on the four derivatives yielded different self-assembled architectures. Atomic force microscopy studies, corroborated with infrared and nuclear magnetic resonance spectroscopic measurements, provided complementary multiscale insight into these assemblies.

  2. Design of novel supramolecular self-assembly creating ...

    Indian Academy of Sciences (India)


    To the best of our knowledge this is the third structure reported in the area of neutral rectangular assembly. The staggered stacking between the 2D sheets makes the structure less intriguing and reducing the cavity size which accommodates two water molecules by O–H… O interaction. Proc. Indian Acad. Sci. (Chem. Sci.) ...

  3. Design of novel supramolecular self-assembly creating ...

    Indian Academy of Sciences (India)


    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 ...

  4. Self-assembled nanostructured metamaterials (United States)

    Ponsinet, Virginie; Baron, Alexandre; Pouget, Emilie; Okazaki, Yutaka; Oda, Reiko; Barois, Philippe


    The concept of metamaterials emerged in the years 2000 with the achievement of artificial structures enabling nonconventional propagation of electromagnetic waves, such as negative phase velocity or negative refraction. The electromagnetic response of metamaterials is generally based on the presence of optically resonant elements —or meta-atoms— of sub-wavelength size and well-designed morphology so as to provide the desired electric and magnetic optical properties. Top-down technologies based on lithography techniques have been intensively used to fabricate a variety of efficient electric and magnetic resonators operating from microwave to visible light frequencies. However, the technological limits of the top-down approach are reached in visible light where a huge number of nanometre-sized elements is required. We show here that the bottom-up fabrication route based on the combination of nanochemistry and the self-assembly methods of colloidal physics provide an excellent alternative for the large-scale synthesis of complex meta-atoms, as well as for the fabrication of 2D and 3D samples exhibiting meta-properties in visible light. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

  5. Supramolecular materials based on hydrogen-bonded polymers

    NARCIS (Netherlands)

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


    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

  6. Solvent induced supramolecular anisotropy in molecular gels

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Michael A., E-mail: [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)


    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.

  7. Solvent induced supramolecular anisotropy in molecular gels

    International Nuclear Information System (INIS)

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


    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.

  8. Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions. (United States)

    Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin


    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.

  9. Chemical reactions directed Peptide self-assembly. (United States)

    Rasale, Dnyaneshwar B; Das, Apurba K


    Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

  10. Chemical Reactions Directed Peptide Self-Assembly

    Directory of Open Access Journals (Sweden)

    Dnyaneshwar B. Rasale


    Full Text Available Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

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

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


    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.

  12. Hierarchical Formation of Fibrillar and Lamellar Self-Assemblies from Guanosine-Based Motifs

    Directory of Open Access Journals (Sweden)

    Paolo Neviani


    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.

  13. Pt–Ru decorated self-assembled TiO2–carbon hybrid nanostructure ...

    Indian Academy of Sciences (India)

    Porous titanium oxide–carbon hybrid nanostructure (TiO2–C) with a specific surface area of 350 m2/g and an average pore-radius of 21.8 Å is synthesized via supramolecular self-assembly with an in situ crystallization process. Subsequently, TiO2–C supported Pt–Ru electro-catalyst (Pt–Ru/TiO2–C) is obtained and ...

  14. Self-Assembly of Infinite Structures

    Directory of Open Access Journals (Sweden)

    Scott M. Summers


    Full Text Available We review some recent results related to the self-assembly of infinite structures in the Tile Assembly Model. These results include impossibility results, as well as novel tile assembly systems in which shapes and patterns that represent various notions of computation self-assemble. Several open questions are also presented and motivated.

  15. Self-assembled nanomaterials for photoacoustic imaging. (United States)

    Wang, Lei; Yang, Pei-Pei; Zhao, Xiao-Xiao; Wang, Hao


    In recent years, extensive endeavors have been paid to construct functional self-assembled nanomaterials for various applications such as catalysis, separation, energy and biomedicines. To date, different strategies have been developed for preparing nanomaterials with diversified structures and functionalities via fine tuning of self-assembled building blocks. In terms of biomedical applications, bioimaging technologies are urgently calling for high-efficient probes/contrast agents for high-performance bioimaging. Photoacoustic (PA) imaging is an emerging whole-body imaging modality offering high spatial resolution, deep penetration and high contrast in vivo. The self-assembled nanomaterials show high stability in vivo, specific tolerance to sterilization and prolonged half-life stability and desirable targeting properties, which is a kind of promising PA contrast agents for biomedical imaging. Herein, we focus on summarizing recent advances in smart self-assembled nanomaterials with NIR absorption as PA contrast agents for biomedical imaging. According to the preparation strategy of the contrast agents, the self-assembled nanomaterials are categorized into two groups, i.e., the ex situ and in situ self-assembled nanomaterials. The driving forces, assembly modes and regulation of PA properties of self-assembled nanomaterials and their applications for long-term imaging, enzyme activity detection and aggregation-induced retention (AIR) effect for diagnosis and therapy are emphasized. Finally, we conclude with an outlook towards future developments of self-assembled nanomaterials for PA imaging.

  16. Supramolecular Assembly of Water-Soluble Poly(ferrocenylsilanes): Multilayer Structures on Flat Interfaces and Permeability of Microcapsules

    NARCIS (Netherlands)

    Ma, Y.; Dong, Wen-Fei; Kooij, Ernst S.; Hempenius, Mark A.; Mohwald, Helmuth; Vancso, Gyula J.


    We report on the layer-by-layer (LBL) supramolecular assembly of redox responsive, organometallic polyion films on planar and curved (spherical) substrates. Organometallic poly(ferrocenylsilane) (PFS) polyanions and polycations were first used to assemble multilayers on planar quartz, silicon and

  17. Physical principles of filamentous protein self-assembly kinetics

    International Nuclear Information System (INIS)

    Michaels, Thomas C T; Liu, Lucie X; Meisl, Georg; Knowles, Tuomas P J


    The polymerization of proteins and peptides into filamentous supramolecular structures is an elementary form of self-organization of key importance to the functioning biological systems, as in the case of actin biofilaments that compose the cellular cytoskeleton. Aberrant filamentous protein self-assembly, however, is associated with undesired effects and severe clinical disorders, such as Alzheimer’s and Parkinson’s diseases, which, at the molecular level, are associated with the formation of certain forms of filamentous protein aggregates known as amyloids. Moreover, due to their unique physicochemical properties, protein filaments are finding extensive applications as biomaterials for nanotechnology. With all these different factors at play, the field of filamentous protein self-assembly has experienced tremendous activity in recent years. A key question in this area has been to elucidate the microscopic mechanisms through which filamentous aggregates emerge from dispersed proteins with the goal of uncovering the underlying physical principles. With the latest developments in the mathematical modeling of protein aggregation kinetics as well as the improvement of the available experimental techniques it is now possible to tackle many of these complex systems and carry out detailed analyses of the underlying microscopic steps involved in protein filament formation. In this paper, we review some classical and modern kinetic theories of protein filament formation, highlighting their use as a general strategy for quantifying the molecular-level mechanisms and transition states involved in these processes. (topical review)

  18. Surfaces wettability and morphology modulation in a fluorene derivative self-assembly system

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xinhua, E-mail:; Gao, Aiping; Zhao, Na; Yuan, Fangyuan; Liu, Chenxi; Li, Ruru


    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.

  19. Recent Advances in Supramolecular Gels and Catalysis. (United States)

    Fang, Weiwei; Zhang, Yang; Wu, Jiajie; Liu, Cong; Zhu, Haibo; Tu, Tao


    Over the past two decades, supramolecular gels have attracted significant attention from scientists in diverse research fields and have been extensively developed. This review mainly focuses on the significant achievements in supramolecular gels and catalysis. First, by incorporating diverse catalytic sites and active organic functional groups into gelator molecules, supramolecular gels have been considered as a novel matrix for catalysis. In addition, these rationally designed supramolecular gels also provide a variety of templates to access metal nanocomposites, which may function as catalysts and exhibit high activity in diverse catalytic transformations. Finally, as a new kind of biomaterial, supramolecular gels formed in situ by self-assembly triggered by catalytic transformations are also covered herein. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Structural Determinants of the Supramolecular Organization of G Protein-Coupled Receptors in Bilayers

    NARCIS (Netherlands)

    Periole, Xavier; Knepp, Adam M.; Sakmar, Thomas P.; Marrink, Siewert J.; Huber, Thomas


    The G protein-coupled receptor (GPCR) rhodopsin self-assembles into supramolecular structures in native bilayers, but the structural determinants of receptor oligomerization are not known. We carried out multiple self-assembly coarse-grained molecular dynamics (CGMD) simulations of model membranes

  1. Polymorphism of lipid self-assembly systems

    International Nuclear Information System (INIS)

    Takahashi, Hiroshi


    When lipid molecules are dispersed into an aqueous medium, various self-organized structures are formed, depending on conditions (temperature, concentration, etc), in consequence of the amphipathic nature of the molecules. In addition, lipid self-assembly systems exhibit polymorphic phase transition behavior. Since lipids are one of main components of biomembranes, studies on the structure and thermodynamic properties of lipid self-assembly systems are fundamentally important for the consideration of the stability of biomembranes. (author)

  2. Directed Self-Assembly of Nanodispersions

    Energy Technology Data Exchange (ETDEWEB)

    Furst, Eric M [University of Delaware


    Directed self-assembly promises to be the technologically and economically optimal approach to industrial-scale nanotechnology, and will enable the realization of inexpensive, reproducible and active nanostructured materials with tailored photonic, transport and mechanical properties. These new nanomaterials will play a critical role in meeting the 21st century grand challenges of the US, including energy diversity and sustainability, national security and economic competitiveness. The goal of this work was to develop and fundamentally validate methods of directed selfassembly of nanomaterials and nanodispersion processing. The specific aims were: 1. Nanocolloid self-assembly and interactions in AC electric fields. In an effort to reduce the particle sizes used in AC electric field self-assembly to lengthscales, we propose detailed characterizations of field-driven structures and studies of the fundamental underlying particle interactions. We will utilize microscopy and light scattering to assess order-disorder transitions and self-assembled structures under a variety of field and physicochemical conditions. Optical trapping will be used to measure particle interactions. These experiments will be synergetic with calculations of the particle polarizability, enabling us to both validate interactions and predict the order-disorder transition for nanocolloids. 2. Assembly of anisotropic nanocolloids. Particle shape has profound effects on structure and flow behavior of dispersions, and greatly complicates their processing and self-assembly. The methods developed to study the self-assembled structures and underlying particle interactions for dispersions of isotropic nanocolloids will be extended to systems composed of anisotropic particles. This report reviews several key advances that have been made during this project, including, (1) advances in the measurement of particle polarization mechanisms underlying field-directed self-assembly, and (2) progress in the

  3. Self-Assembly of Small Molecules for Organic Photovoltaic Applications (United States)

    Aytun, Taner

    Organic photovoltaic (OPV) solar cells aim to provide efficient, flexible and lightweight photovoltaics (PV) with simple processing and low-cost. Advances in device optimization, structural and molecular design, as well as mechanistic understanding have helped increase device efficiency and performance. Within the framework of active layer optimization, systematically improving bulk heterojunction (BHJ) morphology could improve the power conversion efficiency of OPVs. However, most strategies aimed at improving morphology focus on annealing methods or the use of solvent additives. Rational approaches in supramolecular self-assembly can potentially offer additional control over the morphology of BHJ active layers and lead to improved power conversion efficiencies. In Chapter 2, the author explores the effect of molecular shape on the assembly of electron donating small molecules, and its ensuing effect on OPV performance. Two tripodal 'star-shaped' donor molecules with diketopyrrolopyrrole (DPP) side chains were used to generate solution-processed BHJ OPVs. It was found that the tripod molecules neither aggregate in solution nor form crystalline domains in thin films when a branched alkyl solubilizing group is used. On the other hand, linear alkyl chains promote the formation of one-dimensional (1D) nanowires and crystalline domains as well. This work demonstrated that the one-dimensional assembly of donor molecules enhances the performance of the corresponding solution-processed OPVs by 50%. This is attributed to the reduction of trap states in the 1D nanowires, resulting in a significant increase in the fill factor of the devices. In Chapter 3, experiments are described in which the electron donor is a hairpin-shaped molecule containing a trans-1,2-diamidocyclohexane core and two DPP conjugated segments, and a fullerene derivative as the electron acceptor. Self-assembly of the donor molecule is driven by the synergistic interaction between hydrogen bonds and pi

  4. Designing thiophene-based azomethine oligomers with tailored properties: Self-assembly and charge carrier mobility

    DEFF Research Database (Denmark)

    Kiriy, N.; Bocharova, V.; Kiriy, A.


    This paper describes synthesis and characterization of two thiophene-based azomethines designed to optimize solubility, self-assembly, and charge carrier mobility. We found that incorporation of azomethine and amide moieties in the alpha,omega-position, and hexyl chains in the beta-position of th......This paper describes synthesis and characterization of two thiophene-based azomethines designed to optimize solubility, self-assembly, and charge carrier mobility. We found that incorporation of azomethine and amide moieties in the alpha,omega-position, and hexyl chains in the beta...

  5. Composition and method for self-assembly and mineralization of peptide amphiphiles (United States)

    Stupp, Samuel I [Chicago, IL; Beniash, Elia [Newton, MA; Hartgerink, Jeffrey D [Houston, TX


    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  6. Composition and method for self-assembly and mineralization of peptide-amphiphiles (United States)

    Stupp, Samuel I [Chicago, IL; Beniash, Elia [Newton, MA; Hartgerink, Jeffrey D [Pearland, TX


    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

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

    Directory of Open Access Journals (Sweden)

    Charlotte A.E. Hauser


    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.

  8. Hierarchised luminescent organic architectures: design, synthesis, self-assembly, self-organisation and functions. (United States)

    Maggini, Laura; Bonifazi, Davide


    This critical review aims at highlighting the prevailing supramolecular approaches employed nowadays in the preparation of luminescent hierarchised materials. Specifically, it has the ambition to illustrate how progresses in the control of the supramolecular interaction toolbox ultimately led to the development of spectacular luminescent nano- and micro-architectures, through a combination of molecular self-assembly and self-organisation processes involving organic π-conjugated molecules. The reader will be guided through a systematic exploration of the most common avenues to prepare and characterise luminescent self-assembled/self-organised materials embedded into one-, two- or three-dimensional networks, accompanied by a critical discussion of their main advantages and limitations. Key representative examples of this research field will be thoroughly described, with a particular focus on those systems displaying potential on the device application scene. Particular attention will be devoted to the design and synthetic approaches aimed at the preparation of the primary π-conjugated molecular modules, the chemical, structural and electronic properties of which dramatically influence the fate and the features of the self-assembled/self-organised material (215 references). This journal is © The Royal Society of Chemistry 2012

  9. Temperature dependent coordinating self-assembly. (United States)

    Wang, Yijie; Gao, Xuedong; Xiao, Yunlong; Zhao, Qiang; Yang, Jiang; Yan, Yun; Huang, Jianbin


    Self-assemblies dominated by coordination interaction are hardly responsive to thermal stimuli. We show that in case the coordinating mode changes with temperature, the resultant assemblies also exhibit temperature dependence. The self-assemblies are constructed with perylene tetracarboxylate and metal ions. Compounds containing a perylene skeleton often self-assemble into micro-belts, which is also true for the combination of perylene tetracarboxylate and metal ions. However, a unique pinecone structure was observed upon increasing the temperature of the coordinating system. The structural transition is triggered by the change of coordinating mode between the carboxylate group and the metal ion. At low temperature, intermolecular coordination occurs which favours the growth of the coordinating self-assembly along the long axis of the perylene. However, upon the elevation of temperature, the coordination is overwhelmed by intra-molecular mode. This is against the extension of the coordinating assembly due to the loss of connection between neighbouring perylenes. As a result, the pinecone structure is observed. We expect that the cases introduced in this work may inspire the design of structurally controllable temperature-dependent soft materials based on coordinating self-assembly.

  10. Systematic Moiety Variations of Ultrashort Peptides Produce Profound Effects on Self-Assembly, Nanostructure Formation, Hydrogelation, and Phase Transition

    KAUST Repository

    Chan, Kiat Hwa


    Self-assembly of small biomolecules is a prevalent phenomenon that is increasingly being recognised to hold the key to building complex structures from simple monomeric units. Small peptides, in particular ultrashort peptides containing up to seven amino acids, for which our laboratory has found many biomedical applications, exhibit immense potential in this regard. For next-generation applications, more intricate control is required over the self-assembly processes. We seek to find out how subtle moiety variation of peptides can affect self-assembly and nanostructure formation. To this end, we have selected a library of 54 tripeptides, derived from systematic moiety variations from seven tripeptides. Our study reveals that subtle structural changes in the tripeptides can exert profound effects on self-assembly, nanostructure formation, hydrogelation, and even phase transition of peptide nanostructures. By comparing the X-ray crystal structures of two tripeptides, acetylated leucine-leucine-glutamic acid (Ac-LLE) and acetylated tyrosine-leucine-aspartic acid (Ac-YLD), we obtained valuable insights into the structural factors that can influence the formation of supramolecular peptide structures. We believe that our results have major implications on the understanding of the factors that affect peptide self-assembly. In addition, our findings can potentially assist current computational efforts to predict and design self-assembling peptide systems for diverse biomedical applications.

  11. Non-equilibrium supramolecular polymerization. (United States)

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


    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.

  12. Interfacial rheological properties of self-assembling biopolymer microcapsules. (United States)

    Xie, Kaili; de Loubens, Clément; Dubreuil, Frédéric; Gunes, Deniz Z; Jaeger, Marc; Léonetti, Marc


    Tuning the mechanical properties of microcapsules through a cost-efficient route of fabrication is still a challenge. The traditional method of layer-by-layer assembly of microcapsules allows building a tailored composite multi-layer membrane but is technically complex as it requires numerous steps. The objective of this article is to characterize the interfacial rheological properties of self-assembling biopolymer microcapsules that were obtained in one single facile step. This thorough study provides new insights into the mechanics of these weakly cohesive membranes. Firstly, suspensions of water-in-oil microcapsules were formed in microfluidic junctions by self-assembly of two oppositely charged polyelectrolytes, namely chitosan (water soluble) and phosphatidic fatty acid (oil soluble). In this way, composite membranes of tunable thickness (between 40 and 900 nm measured by AFM) were formed at water/oil interfaces in a single step by changing the composition. Secondly, microcapsules were mechanically characterized by stretching them up to break-up in an extensional flow chamber which extends the relevance and convenience of the hydrodynamic method to weakly cohesive membranes. Finally, we show that the design of microcapsules can be 'engineered' in an extensive way since they present a wealth of interfacial rheological properties in terms of elasticity, plasticity and yield stress whose magnitudes can be controlled by the composition. These behaviors are explained by the variation of the membrane thickness with the physico-chemical parameters of the process.

  13. Remote control of self-assembled microswimmers (United States)

    Grosjean, G.; Lagubeau, G.; Darras, A.; Hubert, M.; Lumay, G.; Vandewalle, N.


    Physics governing the locomotion of microorganisms and other microsystems is dominated by viscous damping. An effective swimming strategy involves the non-reciprocal and periodic deformations of the considered body. Here, we show that a magnetocapillary-driven self-assembly, composed of three soft ferromagnetic beads, is able to swim along a liquid-air interface when powered by an external magnetic field. More importantly, we demonstrate that trajectories can be fully controlled, opening ways to explore low Reynolds number swimming. This magnetocapillary system spontaneously forms by self-assembly, allowing miniaturization and other possible applications such as cargo transport or solvent flows.

  14. Self-assembling segmented coiled tubing (United States)

    Raymond, David W.


    Self-assembling segmented coiled tubing is a concept that allows the strength of thick-wall rigid pipe, and the flexibility of thin-wall tubing, to be realized in a single design. The primary use is for a drillstring tubular, but it has potential for other applications requiring transmission of mechanical loads (forces and torques) through an initially coiled tubular. The concept uses a spring-loaded spherical `ball-and-socket` type joint to interconnect two or more short, rigid segments of pipe. Use of an optional snap ring allows the joint to be permanently made, in a `self-assembling` manner.

  15. Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies. (United States)

    Han, Youngkyu; Carrillo, Jan-Michael Y; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S; Do, Changwoo


    Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. This study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Sustained and controlled release of lipophilic drugs from a self-assembling amphiphilic peptide hydrogel

    DEFF Research Database (Denmark)

    Briuglia, Maria-Lucia; Urquhart, Andrew; Lamprou, Dimitrios A.


    . In this work, we have investigated the diffusion properties of Pindolol, Quinine and Timolol maleate from RADA16 in PBS and in BSS-PLUS at 37°C. A sustained, controlled, reproducible and efficient drug release has been detected for all the systems, which allows to understand the dependence of release kinetics......Materials which undergo self-assembly to form supramolecular structures can provide alternative strategies to drug loading problems in controlled release application. RADA 16 is a simple and versatile self-assembling peptide with a designed structure formed of two distinct surfaces, one hydrophilic...... and one hydrophobic that are positioned in such a well-ordered fashion allowing precise assembly into a predetermined organization. A "smart" architecture in nanostructures can represent a good opportunity to use RADA16 as a carrier system for hydrophobic drugs solving problems of drugs delivery...

  17. Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility. (United States)

    Cai, Yunsong; Guo, Zhiqian; Chen, Jianmei; Li, Wenlong; Zhong, Liubiao; Gao, Ya; Jiang, Lin; Chi, Lifeng; Tian, He; Zhu, Wei-Hong


    Light-driven transcription and replication are always subordinate to a delicate chirality transfer. Enabling light work in construction of the helical self-assembly with reversible chiral transformation becomes attractive. Herein we demonstrate that a helical hydrogen-bonded self-assembly is reversibly photoswitched between photochromic open and closed forms upon irradiation with alternative UV and visible light, in which molecular chirality is amplified with the formation of helixes at supramolecular level. The characteristics in these superhelixes such as left-handed or right-handed twist and helical length, height, and pitch are revealed by SEM and AFM. The helical photoswitchable nanostructure provides an easily accessible route to an unprecedented photoreversible modulation in morphology, fluorescence, and helicity, with precise assembly/disassembly architectures similar to biological systems such as protein and DNA.

  18. Unfolding a molecular trefoil derived from a zwitterionic metallopeptide to form self-assembled nanostructures

    KAUST Repository

    Zhang, Ye


    While used extensively by nature to control the geometry of protein structures, and dynamics of proteins, such as self-organization, hydration forces and ionic interactions received less attention for controlling the behaviour of small molecules. Here we describe the synthesis and characterization of a novel zwitterionic metallopeptide consisting of a cationic core and three distal anionic groups linked by self-assembling peptide motifs. 2D NMR spectra, total correlated spectroscopy and nuclear Overhauser effect spectroscopy, show that the molecule exhibits a three-fold rotational symmetry and adopts a folded conformation in dimethyl sulfoxide due to Coulombic forces. When hydrated in water, the molecule unfolds to act as a self-assembling building block of supramolecular nanostructures. By combining ionic interactions with the unique geometry from metal complex and hydrophobic interactions from simple peptides, we demonstrate a new and effective way to design molecules for smart materials through mimicking a sophisticated biofunctional system using a conformational switch.

  19. Thermosensitive Self-Assembling Block Copolymers as Drug Delivery Systems

    Directory of Open Access Journals (Sweden)

    Giovanni Filippo Palmieri


    Full Text Available Self-assembling block copolymers (poloxamers, PEG/PLA and PEG/PLGA diblock and triblock copolymers, PEG/polycaprolactone, polyether modified poly(Acrylic Acid with large solubility difference between hydrophilic and hydrophobic moieties have the property of forming temperature dependent micellar aggregates and, after a further temperature increase, of gellifying due to micelle aggregation or packing. This property enables drugs to be mixed in the sol state at room temperature then the solution can be injected into a target tissue, forming a gel depot in-situ at body temperature with the goal of providing drug release control. The presence of micellar structures that give rise to thermoreversible gels, characterized by low toxicity and mucomimetic properties, makes this delivery system capable of solubilizing water-insoluble or poorly soluble drugs and of protecting labile molecules such as proteins and peptide drugs.

  20. From dynamic self-assembly to networked chemical systems. (United States)

    Grzybowski, Bartosz A; Fitzner, Krzysztof; Paczesny, Jan; Granick, Steve


    Although dynamic self-assembly, DySA, is a relatively new area of research, the past decade has brought numerous demonstrations of how various types of components - on scales from (macro)molecular to macroscopic - can be arranged into ordered structures thriving in non-equilibrium, steady states. At the same time, none of these dynamic assemblies has so far proven practically relevant, prompting questions about the field's prospects and ultimate objectives. The main thesis of this Review is that formation of dynamic assemblies cannot be an end in itself - instead, we should think more ambitiously of using such assemblies as control elements (reconfigurable catalysts, nanomachines, etc.) of larger, networked systems directing sequences of chemical reactions or assembly tasks. Such networked systems would be inspired by biology but intended to operate in environments and conditions incompatible with living matter (e.g., in organic solvents, elevated temperatures, etc.). To realize this vision, we need to start considering not only the interactions mediating dynamic self-assembly of individual components, but also how components of different types could coexist and communicate within larger, multicomponent ensembles. Along these lines, the review starts with the discussion of the conceptual foundations of self-assembly in equilibrium and non-equilibrium regimes. It discusses key examples of interactions and phenomena that can provide the basis for various DySA modalities (e.g., those driven by light, magnetic fields, flows, etc.). It then focuses on the recent examples where organization of components in steady states is coupled to other processes taking place in the system (catalysis, formation of dynamic supramolecular materials, control of chirality, etc.). With these examples of functional DySA, we then look forward and consider conditions that must be fulfilled to allow components of multiple types to coexist, function, and communicate with one another within the

  1. From self-assembly fundamental knowledge to nanomedicine developments. (United States)

    Monduzzi, Maura; Lampis, Sandrina; Murgia, Sergio; Salis, Andrea


    This review highlights the key role of NMR techniques in demonstrating the molecular aspects of the self-assembly of surfactant molecules that nowadays constitute the basic knowledge which modern nanoscience relies on. The aim is to provide a tutorial overview. The story of a rigorous scientific approach to understand self-assembly in surfactant systems and biological membranes starts in the early seventies when the progresses of SAXRD and NMR technological facilities allowed to demonstrate the existence of ordered soft matter, and the validity of Tanford approach concerning self-assembly at a molecular level. Particularly, NMR quadrupolar splittings, NMR chemical shift anisotropy, and NMR relaxation of dipolar and quadrupolar nuclei in micellar solutions, microemulsions, and liquid crystals proved the existence of an ordered polar-apolar interface, on the NMR time scale. NMR data, rationalized in terms of the two-step model of relaxation, allowed to quantify the dynamic aspects of the supramolecular aggregates in different soft matter systems. In addition, NMR techniques allowed to obtain important information on counterion binding as well as on size of the aggregate through molecular self-diffusion. Indeed NMR self-diffusion proved without any doubt the existence of bicontinuous microemulsions and bicontinuous cubic liquid crystals, suggested by pioneering and brilliant interpretation of SAXRD investigations. Moreover, NMR self-diffusion played a fundamental role in the understanding of microemulsion and emulsion nanostructures, phase transitions in phase diagrams, and particularly percolation phenomena in microemulsions. Since the nineties, globalization of the knowledge along with many other technical facilities such as electron microscopy, particularly cryo-EM, produced huge progresses in surfactant and colloid science. Actually we refer to nanoscience: bottom up/top down strategies allow to build nanodevices with applications spanning from ICT to food

  2. A real time analysis of the self-assembly process using thermal analysis inside the differential scanning calorimeter instrument. (United States)

    Roy, Debmalya; Shastri, Babita; Mukhopadhyay, K


    The supramolecular assembly of the regioregular poly-3-hexylthiophene (rr-P3HT) in solution has been investigated thoroughly in the past. In the current study, our focus is on the enthalpy of nanofiber formation using thermal analysis techniques by performing the self-assembly process inside the differential scanning calorimetry (DSC) instrument. Thermogravimetric analysis (TGA) was carried out to check the concentration of the solvent during the self-assembly process of P3HT in p-xylene. Ultraviolet visible (UV-vis) spectophotometric technique, small-angle X-ray scattering (SAXS) experiment, atomic force microscopic (AFM), and scanning electron microscopic (SEM) images were used to characterize the different experimental yields generated by cooling the reaction mixture at desired temperatures. Comparison of the morphologies of self-assembled products at different fiber formation temperatures gives us an idea about the possible crystallization parameters which could affect the P3HT nanofiber morphology.

  3. Self-assembling bisphosphonates into nanofibers to enhance their inhibitory capacity on bone resorption (United States)

    Tang, Anming; Qian, Yu; Liu, Shuang; Wang, Weijuan; Xu, Bing; Qin, An; Liang, Gaolin


    Osteoporosis (OP) is an important aging-related disease and the effective prevention/treatment of this disease remains challenging. Considering the acidic microenvironment of bone resorption lacunae, herein, we rationally designed two pamidronate (Pami)-derivative and alendronate (Alen)-derivative hydrogelators Pami-D and Alen-D which self-assemble into nanofibers to form supramolecular hydrogels under acidic conditions. Cell viability assay, osteoclastogenesis, osteoclastic gene expression, and in vitro bone resorption results indicated that both Pami-D and Alen-D have better inhibitory effects on osteoclastic formation and bone resorption than Pami and Alen, respectively. We anticipate that our new drugs Pami-D and Alen-D could ``smartly'' self-assemble and locally concentrate the drugs at bone resorption lacunae in vivo and subsequently prevent/treat osteoporosis more efficiently.Osteoporosis (OP) is an important aging-related disease and the effective prevention/treatment of this disease remains challenging. Considering the acidic microenvironment of bone resorption lacunae, herein, we rationally designed two pamidronate (Pami)-derivative and alendronate (Alen)-derivative hydrogelators Pami-D and Alen-D which self-assemble into nanofibers to form supramolecular hydrogels under acidic conditions. Cell viability assay, osteoclastogenesis, osteoclastic gene expression, and in vitro bone resorption results indicated that both Pami-D and Alen-D have better inhibitory effects on osteoclastic formation and bone resorption than Pami and Alen, respectively. We anticipate that our new drugs Pami-D and Alen-D could ``smartly'' self-assemble and locally concentrate the drugs at bone resorption lacunae in vivo and subsequently prevent/treat osteoporosis more efficiently. Electronic supplementary information (ESI) available: Experiment methods and details; syntheses and characterization of Pami-D and Alen-D; HPLC conditions; Fig. S1-S15, Schemes S1 and S2, Tables S1 and S2

  4. Bola-amphiphile self-assembly

    DEFF Research Database (Denmark)

    Svaneborg, Carsten


    Bola-amphiphiles are rod-like molecules where both ends of the molecule likes contact with water, while the central part of the molecule dislikes contact with water. What do such molecules do when they are dissolved in water? They self-assemble into micelles. This is a Dissipartive particle...

  5. Stabilization of Self-Assembled Alumina Mesophases

    NARCIS (Netherlands)

    Perez, Lidia Lopez; Perdriau, Sebastien; ten Brink, Gert; Kooi, Bart J.; Heeres, Hero Jan; Melian-Cabrera, Ignacio


    An efficient route to stabilize alumina mesophases derived from evaporation-induced self-assembly is reported after investigating various aspects in-depth: influence of the solvent (EtOH, s-BuOH, and t-BuOH) on the textural and structural properties of the mesophases based on aluminum

  6. Self-assembled nanogaps for molecular electronics

    International Nuclear Information System (INIS)

    Tang Qingxin; Tong Yanhong; Jain, Titoo; Hassenkam, Tue; Moth-Poulsen, Kasper; Bjoernholm, Thomas; Wan Qing


    A nanogap for molecular devices was realized using solution-based self-assembly. Gold nanorods were assembled to gold nanoparticle-coated conducting SnO 2 :Sb nanowires via thiol end-capped oligo(phenylenevinylene)s (OPVs). The molecular gap was easily created by the rigid molecule itself during self-assembly and the gap length was determined by the molecule length. The gold nanorods and gold nanoparticles, respectively covalently bonded at the two ends of the molecule, had very small dimensions, e.g. a width of ∼20 nm, and hence were expected to minimize the screening effect. The ultra-long conducting SnO 2 :Sb nanowires provided the bridge to connect one of the electrodes of the molecular device (gold nanoparticle) to the external circuit. The tip of the atomic force microscope (AFM) was contacted onto the other electrode (gold nanorod) for the electrical measurement of the OPV device. The conductance measurement confirmed that the self-assembly of the molecules and the subsequent self-assembly of the gold nanorods was a feasible method for the fabrication of the nanogap of the molecular devices.

  7. Self Assembly and Pyroelectric Poling for Organics (United States)


    and semiconducting molecular phosphonic acid (PA) self-assembled monolayers (SAMs) have been developed for applications in organic field-effect...SAM structure and electronic performance of various commonly used organic semiconducting small molecules/polymers. Mechanisms for improving device...Fig. 3). This study represents a major advancement in understanding the mechanisms at play between SAMs and linear organic semiconducting molecules. A

  8. Self-assembly of patchy colloidal dumbbells

    NARCIS (Netherlands)

    Avvisati, Guido; Vissers, Teun; Dijkstra, Marjolein


    We employ Monte Carlo simulations to investigate the self-assembly of patchy colloidal dumbbells interacting via a modified Kern-Frenkel potential by probing the system concentration and dumbbell shape. We consider dumbbells consisting of one attractive sphere with diameter sigma(1) and one

  9. Self-assembled nanogaps for molecular electronics

    DEFF Research Database (Denmark)

    Tang, Qingxin; Tong, Yanhong; Jain, Titoo


    A nanogap for molecular devices was realized using solution-based self-assembly. Gold nanorods were assembled to gold nanoparticle-coated conducting SnO2:Sb nanowires via thiol end-capped oligo(phenylenevinylene)s (OPVs). The molecular gap was easily created by the rigid molecule itself during self...

  10. Self-assembled nanolaminate coatings (SV)

    Energy Technology Data Exchange (ETDEWEB)

    Fan, H.


    Sandia National Laboratories (Sandia) and Lockheed Martin Aeronautics (LM Aero) are collaborating to develop affordable, self-assembled, nanocomposite coatings and associated fabrication processes that will be tailored to Lockheed Martin product requirements. The purpose of this project is to develop a family of self-assembled coatings with properties tailored to specific performance requirements, such as antireflective (AR) optics, using Sandia-developed self-assembled techniques. The project met its objectives by development of a simple and economic self-assembly processes to fabricate multifunctional coatings. Specifically, materials, functionalization methods, and associated coating processes for single layer and multiple layers coatings have been developed to accomplish high reflective coatings, hydrophobic coatings, and anti-reflective coatings. Associated modeling and simulations have been developed to guide the coating designs for optimum optical performance. The accomplishments result in significant advantages of reduced costs, increased manufacturing freedom/producibility, improved logistics, and the incorporation of new technology solutions not possible with conventional technologies. These self-assembled coatings with tailored properties will significantly address LMC's needs and give LMC a significant competitive lead in new engineered materials. This work complements SNL's LDRD and BES programs aimed at developing multifunctional nanomaterials for microelectronics and optics as well as structure/property investigations of self-assembled nanomaterials. In addition, this project will provide SNL with new opportunities to develop and apply self-assembled nanocomposite optical coatings for use in the wavelength ranges of 3-5 and 8-12 micrometers, ranges of vital importance to military-based sensors and weapons. The SANC technologies will be applied to multiple programs within the LM Company including the F-35, F-22, ADP (Future Strike Bomber

  11. Switching surface chemistry with supramolecular machines.

    Energy Technology Data Exchange (ETDEWEB)

    Dunbar, Timothy D.; Kelly, Michael James; Jeppesen, Jan O. (University of California, Los Angeles, CA); Bunker, Bruce Conrad; Matzke, Carolyn M.; Stoddart, J. Fraser; Huber, Dale L.; Kushmerick, James G.; Flood, Amar H. (University of California, Los Angeles, CA); Perkins, Julie (University of California, Los Angeles, CA); Cao, Jianguo (University of California, Los Angeles, CA)


    Tethered supramolecular machines represent a new class of active self-assembled monolayers in which molecular configurations can be reversibly programmed using electrochemical stimuli. We are using these machines to address the chemistry of substrate surfaces for integrated microfluidic systems. Interactions between the tethered tetracationic cyclophane host cyclobis(paraquat-p-phenylene) and dissolved {pi}-electron-rich guest molecules, such as tetrathiafulvalene, have been reversibly switched by oxidative electrochemistry. The results demonstrate that surface-bound supramolecular machines can be programmed to adsorb or release appropriately designed solution species for manipulating surface chemistry.

  12. Morphology-tunable and photoresponsive properties in a self-assembled two-component gel system. (United States)

    Zhou, Yifeng; Xu, Miao; Yi, Tao; Xiao, Shuzhang; Zhou, Zhiguo; Li, Fuyou; Huang, Chunhui


    Photoresponsive C3-symmetrical trisurea self-assembling building blocks containing three azobenzene groups (LC10 and LC4) at the rim were designed and synthesized. By introducing a trisamide gelator (G18), which can self-aggregate through hydrogen bonds of acylamino moieties to form a fibrous network, the mixture of LC10 (or LC4) and G18 forms an organogel with coral-like supramolecular structure from 1,4-dioxane. The cooperation of hydrogen bonding and the hydrophobic diversity between these components are the main contributions to the specific superstructure. The two-component gel exhibits reversible photoisomerization from trans to cis transition without breakage of the gel state.

  13. Chirality effects at each amino acid position on tripeptide self-assembly into hydrogel biomaterials (United States)

    Marchesan, S.; Easton, C. D.; Styan, K. E.; Waddington, L. J.; Kushkaki, F.; Goodall, L.; McLean, K. M.; Forsythe, J. S.; Hartley, P. G.


    Hydrogels formed by ultrashort peptides are emerging as cost-effective materials for cell culture. However, l-peptides are labile to proteases, while their d-isomers are thought to not support cell growth as well. In contrast, the self-assembly behaviour and biological performance of heterochiral peptides (i.e., made of both d and l amino acids) are largely unknown. In this study, we evaluate the effects of amino acid chirality on tripeptide self-assembly and hydrogelation at physiological pH, and cytocompatibility in fibroblast cell culture. A series of uncapped hydrophobic tripeptides with all combinations of d, l amino acids was prepared, tested for self-assembly under physiological conditions, and analysed by circular dichroism, FT-IR, cryo-TEM, AFM, and Thioflavin T fluorescence imaging. Amino acid chirality has a profound effect on the peptides' supramolecular behaviour. Only selected isomers form hydrogels, and of amyloid structure, as confirmed by rheology and XRD. Importantly, they are able to maintain the viability and proliferation of fibroblasts in vitro. This study identifies two heterochiral gels that perform well in cell culture and will assist in the design of innovative and cost-effective peptide gel biomaterials.Hydrogels formed by ultrashort peptides are emerging as cost-effective materials for cell culture. However, l-peptides are labile to proteases, while their d-isomers are thought to not support cell growth as well. In contrast, the self-assembly behaviour and biological performance of heterochiral peptides (i.e., made of both d and l amino acids) are largely unknown. In this study, we evaluate the effects of amino acid chirality on tripeptide self-assembly and hydrogelation at physiological pH, and cytocompatibility in fibroblast cell culture. A series of uncapped hydrophobic tripeptides with all combinations of d, l amino acids was prepared, tested for self-assembly under physiological conditions, and analysed by circular dichroism, FT

  14. Self-assembled discrete molecules for sensing nitroaromatics. (United States)

    Shanmugaraju, Sankarasekaran; Mukherjee, Partha Sarathi


    Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO2 -containing electron-deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron-rich self-assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several π-electron-rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal-ligand coordination-bonding interactions, with enough internal space to accommodate electron-deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A Novel Strategy for Synthesis of Gold Nanoparticle Self Assemblies

    NARCIS (Netherlands)

    Verma, Jyoti; Lal, Sumit; van Veen, Henk A.; van Noorden, Cornelis J. F.


    Gold nanoparticle self assemblies are one-dimensional structures of gold nanoparticles. Gold nanoparticle self assemblies exhibit unique physical properties and find applications in the development of biosensors. Methodologies currently available for lab-scale and commercial synthesis of gold

  16. Self-assembly between biomacromolecules and lipids (United States)

    Liang, Hongjun

    Anionic DNA and cationic lipsomes can self-assemble into a multi-lamellar structure where two-dimensional (2-D) lipid sheets confine a periodic one-dimensional (1-D) lattice of parallel DNA chains, between which Cd2+ ions can condense, and be subsequently reacted with H 2S to template CdS nanorods with crystallographic control analogous to biomineralization. The strong electrostatic interactions align the templated CdS (002) polar planes parallel to the negatively charged sugar-phosphate DNA backbone, which indicates that molecular details of the DNA molecule are imprinted onto the inorganic crystal structure. The resultant nanorods have (002) planes tilted by ˜60° with respect to the rod axis, in contrast to all known II-VI semiconductor nanorods. Rational design of the biopolymer-membrane templates is possible, as demonstrated by the self-assembly between anionic M13 virus and cationic membrane. The filamentous virus has diameter ˜3x larger but similar surface charge density as DNA, the self-assembled complexes maintain the multi-lamellar structure, but pore sizes are ˜10x larger in area, which can be used to package and organize large functional molecules. Not only the counter-charged objects can self-assemble, the like-charged biopolymer and membrane can also self-assemble with the help of multivalent ions. We have investigated anionic lipid-DNA complexes induced by a range of divalent ions to show how different ion-mediated interactions are expressed in the self-assembled structures, which include two distinct lamellar phases and an inverted hexagonal phase. DNA can be selectively organized into or expelled out of the lamellar phases depending on membrane charge density and counterion concentration. For a subset of ion (Zn2+ etc.) at high enough concentration, 2-D inverted hexagonal phase can be formed where DNA strands are coated with anionic lipid tubes via interaction with Zn2+ ions. We suggest that the effect of ion binding on lipid's spontaneous

  17. Cooperative effects of fibronectin matrix assembly and initial cell-substrate adhesion strength in cellular self-assembly. (United States)

    Brennan, James R; Hocking, Denise C


    The cell-dependent polymerization of intercellular fibronectin fibrils can stimulate cells to self-assemble into multicellular structures. The local physical cues that support fibronectin-mediated cellular self-assembly are largely unknown. Here, fibronectin matrix analogs were used as synthetic adhesive substrates to model cell-matrix fibronectin fibrils having different integrin-binding specificity, affinity, and/or density. We utilized this model to quantitatively assess the relationship between adhesive forces derived from cell-substrate interactions and the ability of fibronectin fibril assembly to induce cellular self-assembly. Results indicate that the strength of initial, rather than mature, cell-substrate attachments correlates with the ability of substrates to support fibronectin-mediated cellular self-assembly. The cellular response to soluble fibronectin was bimodal and independent of the integrin-binding specificity of the substrate; increasing soluble fibronectin levels above a critical threshold increased aggregate cohesion on permissive substrates. Once aggregates formed, continuous fibronectin polymerization was necessary to maintain cohesion. During self-assembly, soluble fibronectin decreased cell-substrate adhesion strength and induced aggregate cohesion via a Rho-dependent mechanism, suggesting that the balance of contractile forces derived from fibronectin fibrils within cell-cell versus cell-substrate adhesions controls self-assembly and aggregate cohesion. Thus, initial cell-substrate attachment strength may provide a quantitative basis with which to build predictive models of fibronectin-mediated microtissue fabrication on a variety of substrates. Cellular self-assembly is a process by which cells and extracellular matrix (ECM) proteins spontaneously organize into three-dimensional (3D) tissues in the absence of external forces. Cellular self-assembly can be initiated in vitro, and represents a potential tool for tissue engineers to

  18. Supramolecular structures constructed from three novel rare earth ...

    Indian Academy of Sciences (India)

    Three complexes assembled into 3D frameworks based on C-H··· O, O-H··· O hydrogen bond linkages. Keywords. Rare earth metal complex; crystal structure; hydrogen bonds; 3D supramolecular structure. 1. Introduction. The self-assembly of supramolecules via non-covalent bonds is currently an interesting topic of ...

  19. pH-Responsive Self-Assembly of Polysaccharide through a Rugged Energy Landscape. (United States)

    Morrow, Brian H; Payne, Gregory F; Shen, Jana


    Self-assembling polysaccharides can form complex networks with structures and properties highly dependent on the sequence of triggering cues. Controlling the emergence of such networks provides an opportunity to create soft matter with unique features; however, it requires a detailed understanding of the subtle balance between the attractive and repulsive forces that drives the stimuli-induced self-assembly. Here we employ all-atom molecular dynamics simulations on the order of 100 ns to study the mechanisms of the pH-responsive gelation of the weakly basic aminopolysaccharide chitosan. We find that low pH induces a sharp transition from gel to soluble state, analogous to pH-dependent folding of proteins, while at neutral and high pH self-assembly occurs via a rugged energy landscape, reminiscent of RNA folding. A surprising role of salt is to lubricate the conformational search for the thermodynamically stable states. Although our simulations represent the early events in the self-assembly process of chitosan, which may take seconds or minutes to complete, the atomically detailed insights are consistent with recent experimental observations and provide a basis for understanding how environmental conditions modulate the structure and mechanical properties of the self-assembled polysaccharide systems. The ability to control structure and properties via modification of process conditions will aid in the technological efforts to create complex soft matter with applications ranging from bioelectronics to regenerative medicine.

  20. Ternary self-assemblies in water

    DEFF Research Database (Denmark)

    Hill, Leila R.; Blackburn, Octavia A.; Jones, Michael W.


    The self-assembly of higher order structures in water is realised by using the association of 1,3-biscarboxylates to binuclear meta-xylyl bridged DO3A complexes. Two dinicotinate binding sites are placed at a right-angle in a rhenium complex, which is shown to form a 1 : 2 complex with α,α'-bis(E......The self-assembly of higher order structures in water is realised by using the association of 1,3-biscarboxylates to binuclear meta-xylyl bridged DO3A complexes. Two dinicotinate binding sites are placed at a right-angle in a rhenium complex, which is shown to form a 1 : 2 complex with α...

  1. Self-assembling membranes and related methods thereof (United States)

    Capito, Ramille M; Azevedo, Helena S; Stupp, Samuel L


    The present invention relates to self-assembling membranes. In particular, the present invention provides self-assembling membranes configured for securing and/or delivering bioactive agents. In some embodiments, the self-assembling membranes are used in the treatment of diseases, and related methods (e.g., diagnostic methods, research methods, drug screening).

  2. SUPPORTING INFORMATION Gold nanodots self-assembled ...

    Indian Academy of Sciences (India)


    Figure S1. Catalytic test reactions carried out for different AuNDs catalysts. Figure S2. Catalytic test reactions carried out for AuNDs prepared using different Au concentrations. Figure S3. AFM images of self-assembled AuNDs and bare PADA films. Figure S4. Recycle study of catalytic plate. Figure S5-S16. 1H and 13C NMR ...

  3. Self-Assembly of Nanoparticle Surfactants (United States)

    Lombardo, Michael T.

    Self-assembly utilizes non-covalent forces to organize smaller building blocks into larger, organized structures. Nanoparticles are one type of building block and have gained interest recently due to their unique optical and electrical properties which have proved useful in fields such as energy, catalysis, and advanced materials. There are several techniques currently used to self-assemble nanoparticles, each with its own set of benefits and drawbacks. Here, we address the limited number of techniques in non-polar solvents by introducing a method utilizing amphiphilic gold nanoparticles. Grafted polymer chains provide steric stabilization while small hydrophilic molecules induce assembly through short range attractive forces. The properties of these self-assembled structures are found to be dependent on the polymer and small molecules surface concentrations and chemistries. These particles act as nanoparticle surfactants and can effectively stabilize oil-water interfaces, such as in an emulsion. In addition to the work in organic solvent, similar amphiphilic particles in aqueous media are shown to effectively stabilize oil-in-water emulsions that show promise as photoacoustic/ultrasound theranostic agents.

  4. Crystalline particles from self-assembled divinyl oligomers

    International Nuclear Information System (INIS)

    Naves, Alliny F.; Carmona-Ribeiro, Ana M.; Casarano, Romeu; Catalani, Luiz Henrique; Kawano, Yoshio; Petri, Denise F.S.


    Ethylene glycol dimethacrylate (EGDMA) and/or triethylene glycol dimethacrylate (TEGDMA) oligomers formation was catalyzed in aqueous medium by horseradish peroxidase (HRP) in the presence of H 2 O 2 at room temperature. EGDMA and/or TEGDMA oligomers were characterized by means of gel permeation chromatography, infrared vibrational spectroscopy and 1 H NMR spectroscopy. Self-assembling of oligomers led to right-angled crystalline particles, as evidenced by scanning electron microscopy and differential scanning calorimetry. EGDMA, TEGDMA and EGDMA-co-TEGDMA oligomers synthesized in the presence of HRP-H 2 O 2 system presented pendant vinyl groups along the chains, good solubility in chloroform, and well-defined melting point. These features evidenced few cross-linking or cyclization and revealed that the catalytic properties of HRP led to oligomeric materials with new characteristics

  5. Computationally designed peptides for self-assembly of nanostructured lattices. (United States)

    Zhang, Huixi Violet; Polzer, Frank; Haider, Michael J; Tian, Yu; Villegas, Jose A; Kiick, Kristi L; Pochan, Darrin J; Saven, Jeffery G


    Folded peptides present complex exterior surfaces specified by their amino acid sequences, and the control of these surfaces offers high-precision routes to self-assembling materials. The complexity of peptide structure and the subtlety of noncovalent interactions make the design of predetermined nanostructures difficult. Computational methods can facilitate this design and are used here to determine 29-residue peptides that form tetrahelical bundles that, in turn, serve as building blocks for lattice-forming materials. Four distinct assemblies were engineered. Peptide bundle exterior amino acids were designed in the context of three different interbundle lattices in addition to one design to produce bundles isolated in solution. Solution assembly produced three different types of lattice-forming materials that exhibited varying degrees of agreement with the chosen lattices used in the design of each sequence. Transmission electron microscopy revealed the nanostructure of the sheetlike nanomaterials. In contrast, the peptide sequence designed to form isolated, soluble, tetrameric bundles remained dispersed and did not form any higher-order assembled nanostructure. Small-angle neutron scattering confirmed the formation of soluble bundles with the designed size. In the lattice-forming nanostructures, the solution assembly process is robust with respect to variation of solution conditions (pH and temperature) and covalent modification of the computationally designed peptides. Solution conditions can be used to control micrometer-scale morphology of the assemblies. The findings illustrate that, with careful control of molecular structure and solution conditions, a single peptide motif can be versatile enough to yield a wide range of self-assembled lattice morphologies across many length scales (1 to 1000 nm).

  6. Self-assembled biomimetic nanoreactors I: Polymeric template (United States)

    McTaggart, Matt; Malardier-Jugroot, Cecile; Jugroot, Manish


    The variety of nanoarchitectures made feasible by the self-assembly of alternating copolymers opens new avenues for biomimicry. Indeed, self-assembled structures allow the development of nanoreactors which combine the efficiency of high surface area metal active centres to the effect of confinement due to the very small cavities generated by the self-assembly process. A novel self-assembly of high molecular weight alternating copolymers is characterized in the present study. The self-assembly is shown to organize into nanosheets, providing a 2 nm hydrophobic cavity with a 1D confinement.

  7. Morphological Evolution of Self-Assembled Structures Induced by the Molecular Architecture of Supra-Amphiphiles. (United States)

    Wang, Juan; Li, Boxuan; Wang, Xing; Yang, Fei; Shen, Hong; Wu, Decheng


    A series of telechelic supramolecular amphiphiles [POSS-Azo 8 @(β-CD-PDMAEMA) 1→8 ] was accomplished by orthogonally coupling the multiarm host polymer β-cyclodextrin-poly(dimethylaminoethyl methacrylate) (β-CD-PDMAEMA) with an octatelechelic guest molecule azobenzene modified-polyhedral oligomeric silsesquioxanes (POSS-Azo 8 ) under different host-guest ratios. These telechelic supramolecular amphiphiles possess a rigid core and flexible corona. Increasing the multiarm host polymer coupled onto the rigid POSS core made the molecular architecture tend to be symmetrical and spherical. POSS-Azo 8 @[β-CD-PDMAEMA] 1→8 could self-assemble into diverse morphologies evolving from spherical micelles, wormlike micelles, and branched aggregates to bowl-shaped vesicles. Distinct from the traditional linear amphiphilic polymers, we discovered that the self-assembly of POSS-Azo 8 @[β-CD-PDMAEMA] 1→8 was dominantly regulated by their molecular architectures instead of hydrophilicity, which has also been verified using computer simulation results.

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

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming


    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.

  9. Nanostructure to microstructure self-assembly of aliphatic polyurethanes: the effect on mechanical properties. (United States)

    Mishra, Abhinay; Aswal, Vinod K; Maiti, Pralay


    We report the step by step self-assembly from nanostructure to microstructure (bottom-up approach through X-ray diffraction (1.6 nm), small angle neutron scattering (SANS) (11.6 nm), atomic force microscopy (70 nm smaller crystallite from enlarged image and 450 nm greater crystallites), and polarizing optical microscope (2 microm)) of aliphatic polyurethanes (PU) in contrast to aromatic polyurethanes depending on hard segment content (HSC). Polyurethanes of 10 to 80% HSC have been synthesized by using appropriate amount of polyol and chain extender. The effect of self-assembled patterns on mechanical properties both in solid and liquid state has been established exhibiting structure-property relationship of supramolecular polyurethanes. The crystallinity enhances but the degradation temperature decreases with increasing HSC. The characteristic length (measure of gap between lamellar crystallites), as revealed from SANS, gradually decreases with increasing HSC suggesting compactness of the crystallites through extensive hydrogen bonding. The Young's modulus increases with increasing HSC with a percolation threshold of hard segment (50%) while the toughness improves up to 30% HSC followed by gradual decrease in presence of bigger crystallites which promote brittle fracture. The origin of self-assembly in aliphatic PUs has been demonstrated through electronic structure calculations to form a loop structure with minimum intermolecular distance (2.2 A) while that distance is quite large in aromatic polyurethanes (4.6 A) that cannot form hydrogen bonds. The unique splintering of domain structure and its subsequent reformation under dynamic shear experiment has been established.

  10. Disassembly of Bacterial Biofilms by the Self-Assembled Glycolipids Derived from Renewable Resources. (United States)

    Prasad, Yadavali Siva; Miryala, Sandeep; Lalitha, Krishnamoorthy; Ranjitha, K; Barbhaiwala, Shehnaz; Sridharan, Vellaisamy; Maheswari, C Uma; Srinandan, C S; Nagarajan, Subbiah


    More than 80% of chronic infections of bacteria are caused by biofilms. It is also a long-term survival strategy of the pathogens in a nonhost environment. Several amphiphilic molecules have been used in the past to potentially disrupt biofilms; however, the involvement of multistep synthesis, complicated purification and poor yield still remains a major problem. Herein, we report a facile synthesis of glycolipid based surfactant from renewable feedstocks in good yield. The nature of carbohydrate unit present in glycolipid influence the ring chain tautomerism, which resulted in the existence of either cyclic structure or both cyclic and acyclic structures. Interestingly, these glycolipids self-assemble into gel in highly hydrophobic solvents and vegetable oils, and displayed foam formation in water. The potential application of these self-assembled glycolipids to disrupt preformed biofilm was examined against various pathogens. It was observed that glycolipid 6a disrupts Staphylococcus aureus and Listeria monocytogenes biofilm, while the compound 6c was effective in disassembling uropathogenic E. coli and Salmonella enterica Typhimurium biofilms. Altogether, the supramolecular self-assembled materials, either as gel or as surfactant solution could be potentially used for surface cleansing in hospital environments or the food processing industries to effectively reduce pathogenic biofilms.

  11. Nanoscale protein arrays of rich morphologies via self-assembly on chemically treated diblock copolymer surfaces

    International Nuclear Information System (INIS)

    Song Sheng; Milchak, Marissa; Zhou Hebing; Lee, Thomas; Hanscom, Mark; Hahm, Jong-in


    Well-controlled assembly of proteins on supramolecular templates of block copolymers can be extremely useful for high-throughput biodetection. We report the adsorption and assembly characteristics of a model antibody protein to various polystyrene-block-poly(4-vinylpyridine) templates whose distinctive nanoscale structures are obtained through time-regulated exposure to chloroform vapor. The strong adsorption preference of the protein to the polystyrene segment in the diblock copolymer templates leads to an easily predictable, controllable, rich set of nanoscale protein morphologies through self-assembly. We also demonstrate that the chemical identities of various subareas within individual nanostructures can be readily elucidated by investigating the corresponding protein adsorption behavior on each chemically distinct area of the template. In our approach, a rich set of intricate nanoscale morphologies of protein arrays that cannot be easily attained through other means can be generated straightforwardly via self-assembly of proteins on chemically treated diblock copolymer surfaces, without the use of clean-room-based fabrication tools. Our approach provides much-needed flexibility and versatility for the use of block copolymer-based protein arrays in biodetection. The ease of fabrication in producing well-defined and self-assembled templates can contribute to a high degree of versatility and simplicity in acquiring an intricate nanoscale geometry and spatial distribution of proteins in arrays. These advantages can be extremely beneficial both for fundamental research and biomedical detection, especially in the areas of solid-state-based, high-throughput protein sensing. (paper)

  12. Graphene controlled H- and J-stacking of perylene dyes into highly stable supramolecular nanostructures for enhanced photocurrent generation

    DEFF Research Database (Denmark)

    Gan, Shiyu; Zhong, Lijie; Engelbrekt, Christian


    We report a new method for controlling H- and J-stacking in supramolecular self-assembly. Graphene nanosheets act as structure inducers to direct the self-assembly of a versatile organic dye, perylene into two distinct types of functional nanostructures, i.e. one-dimensional nanotubes via J-stack......-junction solar cells.......We report a new method for controlling H- and J-stacking in supramolecular self-assembly. Graphene nanosheets act as structure inducers to direct the self-assembly of a versatile organic dye, perylene into two distinct types of functional nanostructures, i.e. one-dimensional nanotubes via J......-stacking and two-dimensional branched nanobuds through H-stacking. Graphene integrated supramolecular nanocomposites are highly stable and show significant enhancement of photocurrent generation in these two configurations of photosensing devices, i.e. solid-state optoelectronic constructs and liquid...

  13. pH-Dependent In-Cell Self-Assembly of Peptide Inhibitors Increases the Anti-Prion Activity While Decreasing the Cytotoxicity. (United States)

    Waqas, Muhammad; Jeong, Woo-Jin; Lee, Young-Joo; Kim, Dae-Hwan; Ryou, Chongsuk; Lim, Yong-Beom


    The first step in the conventional approach to self-assembled biomaterials is to develop well-defined nanostructures in vitro, which is followed by disruption of the preformed nanostructures at the inside of the cell to achieve bioactivity. Here, we propose an inverse strategy to develop in-cell gain-of-function self-assembled nanostructures. In this approach, the supramolecular building blocks exist in a unimolecular/unordered state in vitro or at the outside of the cell and assemble into well-defined nanostructures after cell internalization. We used block copolypeptides of an oligoarginine and a self-assembling peptide as building blocks and investigated correlations among the nanostructural state, antiprion bioactivity, and cytotoxicity. The optimal bioactivity (i.e., the highest antiprion activity and lowest cytotoxicity) was obtained when the building blocks existed in a unimolecular/unordered state in vitro and during the cell internalization process, exerting minimal cytotoxic damage to cell membranes, and were subsequently converted into high-charge-density vesicles in the low pH endosome/lysosomes in vivo, thus, resulting in the significantly enhanced antiprion activity. In particular, the in-cell self-assembly concept presents a feasible approach to developing therapeutics against protein misfolding diseases. In general, the in-cell self-assembly provides a novel inverse methodology to supramolecular bionanomaterials.

  14. Intrinsic disorder modulates protein self-assembly and aggregation. (United States)

    De Simone, Alfonso; Kitchen, Craig; Kwan, Ann H; Sunde, Margaret; Dobson, Christopher M; Frenkel, Daan


    Protein molecules have evolved to adopt distinctive and well-defined functional and soluble states under physiological conditions. In some circumstances, however, proteins can self-assemble into fibrillar aggregates designated as amyloid fibrils. In vivo these processes are normally associated with severe pathological conditions but can sometimes have functional relevance. One such example is the hydrophobins, whose aggregation at air-water interfaces serves to create robust protein coats that help fungal spores to resist wetting and thus facilitate their dispersal in the air. We have performed multiscale simulations to address the molecular determinants governing the formation of functional amyloids by the class I fungal hydrophobin EAS. Extensive samplings of full-atom replica-exchange molecular dynamics and coarse-grained simulations have allowed us to identify factors that distinguish aggregation-prone from highly soluble states of EAS. As a result of unfavourable entropic terms, highly dynamical regions are shown to exert a crucial influence on the propensity of the protein to aggregate under different conditions. More generally, our findings suggest a key role that specific flexible structural elements can play to ensure the existence of soluble and functional states of proteins under physiological conditions.

  15. Exploiting Biocatalysis in the Synthesis of Supramolecular Polymers (United States)

    Roy, Sangita; Ulijn, Rein V.

    This chapter details the exploitation of biocatalysis in generating supramolecular polymers. This approach provides highly dynamic supramolecular structures, inspired by biological polymeric systems found in the intra- and extracellular space. The molecular design of the self-assembling precursors is discussed in terms of enzyme recognition, molecular switching mechanisms and non-covalent interactions that drive the supramolecular polymerisation process, with an emphasis on aromatic peptide amphiphiles. We discuss a number of unique features of these systems, including spatiotemporal control of nucleation and growth of supramolecular polymers and the possibility of kinetically controlling mechanical properties. Fully reversible systems that operate under thermodynamic control allow for defect correction and selection of the most stable structures from mixtures of monomers. Finally, a number of potential applications of enzymatic supramolecular polymerisations are discussed in the context of biomedicine and nanotechnology.

  16. Supramolecular polymers

    National Research Council Canada - National Science Library

    Ciferri, A


    ... to the new class of self-assembled polymers that undergo reversible growth by the formation of noncovalent bonds. This class (Part II) is wider than expected: not only mainchain assemblies of hydrogen-bonded repeating units, but also planar organization of S-layer proteins, micellar and related three-dimensional structures of blo...

  17. Self-assembled nanostructures of oligopyridine molecules. (United States)

    Ziener, Ulrich


    The high potential of self-assembly processes of molecular building blocks is reflected in the vast variety of different functional nanostructures reported in the literature. The constituting units must fulfill several requirements like synthetic accessibility, presence of functional groups for appropriate intermolecular interactions and depending on the type of self-assembly processsignificant chemical and thermal stability. It is shown that oligopyridines are versatile building blocks for two- and three-dimensional (2D and 3D) self-assembly. They can be employed for building up different architectures like gridlike metal complexes in solution. By the appropriate tailoring of the heterocycles, further metal coordinating and/or hydrogen bonding capabilities to the heteroaromatic molecules can be added. Thus, the above-mentioned architectures can be extended in one-step processes to larger entities, or in a hierarchical fashion to infinite assemblies in the solid state, respectively. Besides the organizational properties of small molecules in solution, 2D assemblies on surfaces offer certain advantages over 3D arrays. By precise tailoring of the molecular structures, the intermolecular interactions can be fine-tuned expressed by a large variety of resulting 2D patterns. Oligopyridines prove to be ideal candidates for 2D assemblies on graphite and metal sufaces, respectively, expressing highly ordered structures. A slight structural variation in the periphery of the molecules leads to strongly changed 2D packing motifs based on weak hydrogen bonding interactions. Such 2D assemblies can be exploited for building up host-guest networks which are attractive candidates for manipulation experiments on the single-molecule level. Thus, "erasing" and "writing" processes by the scanning tunneling microscopy (STM) tip at the liquid/solid interface are shown. The 2D networks are also employed for performing coordination chemistry experiments at surfaces.

  18. Self-assembly of colloidal surfactants (United States)

    Kegel, Willem


    We developed colloidal dumbbells with a rough and a smooth part, based on a method reported in Ref. [1]. Specific attraction between the smooth parts occurs upon addition of non-adsorbing polymers of appropriate size. We present the first results in terms of the assemblies that emerge in these systems. [4pt] [1] D.J. Kraft, W.S. Vlug, C.M. van Kats, A. van Blaaderen, A. Imhof and W.K. Kegel, Self-assembly of colloids with liquid protrusions, J. Am. Chem. Soc. 131, 1182, (2009)

  19. Self-assembled silicon oxide nanojunctions

    International Nuclear Information System (INIS)

    Lin, L W; Tang, Y H; Chen, C S


    Novel silicon oxide nanojunction structures with various shapes, such as X type, Y type, T type, ringlike and treelike, are fabricated in a self-assembled manner by the hydrothermal method without any metallic catalyst. In the silicon oxide nanojunctions, both the silicon oxide nanowire part and the junction part consist of the same chemical composition, forming homogeneous homojunctions and being made suitable for application in nanoscale optoelectronics devices. The formation of silicon oxide nanojunctions may be influenced by the surrounding environment in the reaction kettle, growth space among the silicon oxide nanowires and the weight of SiO droplets at the growth tip.

  20. Supramolecular Chemistry

    Indian Academy of Sciences (India)

    antigen interactions. working in different areas such as chemical science, biological science, physical science, material science and so on. On the whole, supramolecular chemistry focuses on two over- lapping areas, 'supramolecules' and ...

  1. Imaging and Quantitation of a Succession of Transient Intermediates Reveal the Reversible Self-Assembly Pathway of a Simple Icosahedral Virus Capsid. (United States)

    Medrano, María; Fuertes, Miguel Ángel; Valbuena, Alejandro; Carrillo, Pablo J P; Rodríguez-Huete, Alicia; Mateu, Mauricio G


    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.

  2. New Hybrid Nanomaterial Based on Self-Assembly of Cyclodextrins and Cobalt Prussian Blue Analogue Nanocubes (United States)

    Carvalho, Caio L. C.; Silva, Anna T. B.; Macedo, Lucyano J. A.; Luz, Roberto A. S.; Neto, José M. Moita; Filho, Ubirajara P. Rodrigues; Cantanhêde, Welter


    Supramolecular self-assembly has been demonstrated to be a useful approach to developing new functional nanomaterials. In this work, we used a cobalt Prussian blue analogue (PBA, Co3[Co(CN)6]2) compound and a β-cyclodextrin (CD) macrocycle to develop a novel host-guest PBA-CD nanomaterial. The preparation of the functional magnetic material involved the self-assembly of CD molecules onto a PBA surface by a co-precipitation method. According to transmission electronic microscopy results, PBA-CD exhibited a polydisperse structure composed of 3D nanocubes with a mean edge length of 85 nm, which became shorter after CD incorporation. The supramolecular arrangement and structural, crystalline and thermal properties of the hybrid material were studied in detail by vibrational and electronic spectroscopies and X-ray diffraction. The cyclic voltammogram of the hybrid material in a 0.1 mol·L−1 NaCl supporting electrolyte exhibited a quasi-reversible redox process, attributed to Co2+/Co3+ conversion, with an E1/2 value of 0.46 V (vs. SCE), with higher reversibility observed for the system in the presence of CD. The standard rate constants for PBA and PBA-CD were determined to be 0.07 and 0.13 s−1, respectively, which suggests that the interaction between the nanocubes and CD at the supramolecular level improves electron transfer. We expect that the properties observed for the hybrid material make it a potential candidate for (bio)sensing designs with a desirable capability for drug delivery. PMID:26132565

  3. Quantifying quality in DNA self-assembly (United States)

    Wagenbauer, Klaus F.; Wachauf, Christian H.; Dietz, Hendrik


    Molecular self-assembly with DNA is an attractive route for building nanoscale devices. The development of sophisticated and precise objects with this technique requires detailed experimental feedback on the structure and composition of assembled objects. Here we report a sensitive assay for the quality of assembly. The method relies on measuring the content of unpaired DNA bases in self-assembled DNA objects using a fluorescent de-Bruijn probe for three-base ‘codons’, which enables a comparison with the designed content of unpaired DNA. We use the assay to measure the quality of assembly of several multilayer DNA origami objects and illustrate the use of the assay for the rational refinement of assembly protocols. Our data suggests that large and complex objects like multilayer DNA origami can be made with high strand integration quality up to 99%. Beyond DNA nanotechnology, we speculate that the ability to discriminate unpaired from paired nucleic acids in the same macromolecule may also be useful for analysing cellular nucleic acids. PMID:24751596

  4. Self-assembly of patchy colloidal dumbbells. (United States)

    Avvisati, Guido; Vissers, Teun; Dijkstra, Marjolein


    We employ Monte Carlo simulations to investigate the self-assembly of patchy colloidal dumbbells interacting via a modified Kern-Frenkel potential by probing the system concentration and dumbbell shape. We consider dumbbells consisting of one attractive sphere with diameter σ1 and one repulsive sphere with diameter σ2 and center-to-center distance d between the spheres. For three different size ratios, we study the self-assembled structures for different separations l = 2d/(σ1 + σ2) between the two spheres. In particular, we focus on structures that can be assembled from the homogeneous fluid, as these might be of interest in experiments. We use cluster order parameters to classify the shape of the formed structures. When the size of the spheres is almost equal, q = σ2/σ1 = 1.035, we find that, upon increasing l, spherical micelles are transformed to elongated micelles and finally to vesicles and bilayers. For size ratio q = 1.25, we observe a continuously tunable transition from spherical to elongated micelles upon increasing the sphere separation. For size ratio q = 0.95, we find bilayers and vesicles, plus faceted polyhedra and liquid droplets. Our results identify key parameters to create colloidal vesicles with attractive dumbbells in experiments.

  5. Self-assembly, Self-organization, Nanotechnology and vitalism


    Bensaude Vincent, Bernadette


    International audience; Over the past decades, self-assembly has attracted a lot of research attention and transformed the relations between chemistry, materials science and biology. The paper explores the impact of the current interest in self-assembly techniques on the traditional debate over the nature of life. The first section describes three different research programs of self-assembly in nanotechnology in order to characterize their metaphysical implications: -1- Hybridization ( using ...

  6. Supramolecular chemistry-general principles and selected examples from anion recognition and metallosupramolecular chemistry. (United States)

    Albrecht, Markus


    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.

  7. Self-assembled software and method of overriding software execution (United States)

    Bouchard, Ann M.; Osbourn, Gordon C.


    A computer-implemented software self-assembled system and method for providing an external override and monitoring capability to dynamically self-assembling software containing machines that self-assemble execution sequences and data structures. The method provides an external override machine that can be introduced into a system of self-assembling machines while the machines are executing such that the functionality of the executing software can be changed or paused without stopping the code execution and modifying the existing code. Additionally, a monitoring machine can be introduced without stopping code execution that can monitor specified code execution functions by designated machines and communicate the status to an output device.

  8. Magnetic self-assembly of small parts (United States)

    Shetye, Sheetal B.

    Modern society's propensity for miniaturized end-user products is compelling electronic manufacturers to assemble and package different micro-scale, multi-technology components in more efficient and cost-effective manners. As the size of the components gets smaller, issues such as part sticking and alignment precision create challenges that slow the throughput of conventional robotic pick-n-place systems. As an alternative, various self-assembly approaches have been proposed to manipulate micro to millimeter scale components in a parallel fashion without human or robotic intervention. In this dissertation, magnetic self-assembly (MSA) is demonstrated as a highly efficient, completely parallel process for assembly of millimeter scale components. MSA is achieved by integrating permanent micromagnets onto component bonding surfaces using wafer-level microfabrication processes. Embedded bonded powder methods are used for fabrication of the magnets. The magnets are then magnetized using pulse magnetization methods, and the wafers are then singulated to form individual components. When the components are randomly mixed together, self-assembly occurs when the intermagnetic forces overcome the mixing forces. Analytical and finite element methods (FEM) are used to study the force interactions between the micromagnets. The multifunctional aspects of MSA are presented through demonstration of part-to-part and part-to-substrate assembly of 1 mm x 1mm x 0.5 mm silicon components. Part-to-part assembly is demonstrated by batch assembly of free-floating parts in a liquid environment with the assembly yield of different magnetic patterns varying from 88% to 90% in 20 s. Part-to-substrate assembly is demonstrated by assembling an ordered array onto a fixed substrate in a dry environment with the assembly yield varying from 86% to 99%. In both cases, diverse magnetic shapes/patterns are used to control the alignment and angular orientation of the components. A mathematical model is

  9. Hierarchical Self-Assembly of Peptide Amphiphiles: Form and Function at Multiple Length Scales (United States)

    Zha, Runye Helen

    Hierarchical self-assembly, the organization of molecules into supramolecular structures of increasing size and complexity, is a potent tool for materials synthesis and requires understanding the connections of structure across multiple length scales. Herein, self-assembly of peptide amphiphiles (PAs) into nanoscopic and macroscopic materials is explored, and their anti-cancer applications are investigated. First, nanoscale assembly is examined in the context of an anti-angiogenic PA bearing the G-helix motif of maspin, a tumor suppressor protein. Assembly of this maspin-mimetic PA (MMPA) stabilizes the native G-helix conformation and improves binding to endothelial cells. Furthermore, PA nanostructures significantly increase cell adhesion to fibronectin as compared to G-helix peptide alone. Combined with its inhibitory effect on cell migration, MMPA nanostructures thus show anti-angiogenic activity on par with maspin protein in vitro and in vivo. Second, assembly of cationic PAs with hyaluronic acid (HA), an anionic polyelectrolyte, into macroscopic membranes is explored using PAs with identical formal charge but systematically varied self-assembly domains. Results suggest that membrane formation is dictated by the initial moments of component aggregation and is highly sensitive to PA molecular structure via nanoscale assembly. Specifically, PAs with beta-sheet forming residues are nanofibrous and have high surface charge density, leading to robust membranes with aligned-fiber microstructure. PAs without beta-sheet forming residues are nanospherical and have low surface charge density, leading to weak membranes with non-fibrous finger-like microstructure. Lastly, the principles of PA-HA membrane assembly are applied towards development of anti-cancer therapeutic biomaterials. Here, cytotoxic PAs bearing the epitope (KLAKLAKbeta)2 are co-assembled with non-bioactive cationic PA in order to achieve varying nanoscale morphology. These nanostructures are then

  10. Self-Assembling Brush Polymers Bearing Multisaccharides. (United States)

    Lee, Jongchan; Kim, Jin Chul; Lee, Hoyeol; Song, Sungjin; Kim, Heesoo; Ree, Moonhor


    Three different series of brush polymers bearing glucosyl, maltosyl, or maltotriosyl moiety at the bristle end are successfully prepared by using cationic ring-opening polymerization and two sequential postmodification reactions. All brush polymers, except for the polymer containing 100 mol% maltotriosyl moiety, demonstrate the formation of multibilayer structure in films, always providing saccharide-enriched surface. These self-assembling features are remarkable, regarding the bulkiness of saccharide moieties and the kink in the bristle due to the triazole linker. The saccharide-enriched film surfaces reveal exceptionally high specific binding affinity to concanavalin A but suppress nonspecific binding of plasma proteins severely. Overall, the brush polymers bearing saccharide moieties of various kinds in this study are highly suitable materials for biomedical applications including biosensors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Controlling water evaporation through self-assembly. (United States)

    Roger, Kevin; Liebi, Marianne; Heimdal, Jimmy; Pham, Quoc Dat; Sparr, Emma


    Water evaporation concerns all land-living organisms, as ambient air is dryer than their corresponding equilibrium humidity. Contrarily to plants, mammals are covered with a skin that not only hinders evaporation but also maintains its rate at a nearly constant value, independently of air humidity. Here, we show that simple amphiphiles/water systems reproduce this behavior, which suggests a common underlying mechanism originating from responding self-assembly structures. The composition and structure gradients arising from the evaporation process were characterized using optical microscopy, infrared microscopy, and small-angle X-ray scattering. We observed a thin and dry outer phase that responds to changes in air humidity by increasing its thickness as the air becomes dryer, which decreases its permeability to water, thus counterbalancing the increase in the evaporation driving force. This thin and dry outer phase therefore shields the systems from humidity variations. Such a feedback loop achieves a homeostatic regulation of water evaporation.

  12. Shape Restoration by Active Self-Assembly

    Directory of Open Access Journals (Sweden)

    D. Arbuckle


    Full Text Available Shape restoration is defined as the problem of constructing a desired, or goal, solid shape Sg by growing an initial solid Si, which is a subset of the goal but is otherwise unknown. This definition attempts to capture abstractly a situation that often arises in the physical world when a solid object loses its desired shape due to wear and tear, corrosion or other phenomena. For example, if the top of the femur becomes distorted, the hip joint no longer functions properly and may have to be replaced surgically. Growing it in place back to its original shape would be an attractive alternative to replacement. This paper presents a solution to the shape restoration problem by using autonomous assembly agents (robots that self-assemble to fill the volume between Sg and Si. If the robots have very small dimension (micro or nano, the desired shape is approximated with high accuracy. The assembly agents initially execute a random walk. When two robots meet, they may exchange a small number of messages. The robot behavior is controlled by a finite state machine with a small number of states. Communication contact models chemical communication, which is likely to be the medium of choice for robots at the nanoscale, while small state and small messages are limitations that also are expected of nanorobots. Simulations presented here show that swarms of such robots organize themselves to achieve shape restoration by using distributed algorithms. This is one more example of an interesting geometric problem that can be solved by the Active Self-Assembly paradigm introduced in previous papers by the authors.

  13. 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)


    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.

  14. Self-Assembly of Magnetic Colloids in Soft Confinement

    NARCIS (Netherlands)

    Liu, P.


    The central theme in this thesis is the effect of the soft confinements consisting of molecular microtubes and fluid interfaces, on the self-assembly of colloids. We have specially focused on the synthesis of magnetic colloids and the magnetic responses of self-assembled structures including

  15. Electrostatic Self-Assembly of Polysaccharides into Nanofibers

    DEFF Research Database (Denmark)

    Mendes, Ana Carina Loureiro; Strohmenger, Timm; Goycoolea, Francisco


    components were tested and observed to affect the diameter, which ranged from 100 to 500 nm, and morphology of the self-assembled nanofibers. The release of diclofenac, as model drug, from self-assembled xanthan-chitosan nanofibers was demonstrated, suggesting that these nanostructures can be used...

  16. Self-assembled nanofiber coatings for controlling cell responses

    NARCIS (Netherlands)

    Barros, Raquel C.; Gelens, Edith; Bulten, Erna; Tuin, Annemarie; de Jong, Menno R; Kuijer, Roel; van Kooten, Theo G

    Nanofibers are thought to enhance cell adhesion, growth, and function. We demonstrate that the choice of building blocks in self-assembling nanofiber systems can be used to control cell behavior. The use of 2 D-coated, self-assembled nanofibers in controlling lens epithelial cells, fibroblasts, and

  17. Different carboxylic acid homodimers in self-assemblies of adducts ...

    Indian Academy of Sciences (India)

    H2cpa) observed inthe self-assemblies of salts or cocrystals of H2cpa with nitrogen containing compounds are discussed. Pyridiniumsalt of the H2cpa is a self-assembly of Hcpa with the pyridinium cation. The assembly is a combinationof ...

  18. Tetrahymena dynamin-related protein 6 self-assembles ...

    Indian Academy of Sciences (India)

    Usha P Kar


    Dec 30, 2017 ... We discuss the self-assembly structure of Drp6 and explain the basis for lack of membrane-stimulated GTPase activity. Keywords. Drp6; dynamin; GTPase activity; membrane remodelling; self-assembly; Tetrahymena. 1. Introduction. The Tetrahymena dynamin-related protein 6 (Drp6) localizes.

  19. Hierarchical self-assembly of two-length-scale multiblock copolymers

    International Nuclear Information System (INIS)

    Brinke, Gerrit ten; Loos, Katja; Vukovic, Ivana; Du Sart, Gerrit Gobius


    The self-assembly in diblock copolymer-based supramolecules, obtained by hydrogen bonding short side chains to one of the blocks, as well as in two-length-scale linear terpolymers results in hierarchical structure formation. The orientation of the different domains, e.g. layers in the case of a lamellar-in-lamellar structure, is determined by the molecular architecture, graft-like versus linear, and the relative magnitude of the interactions involved. In both cases parallel and perpendicular arrangements have been observed. The comb-shaped supramolecules approach is ideally suited for the preparation of nanoporous structures. A bicontinuous morphology with the supramolecular comb block forming the channels was finally achieved by extending the original approach to suitable triblock copolymer-based supramolecules.

  20. Self-assemblies of magnetic nanoparticles and di-block copolymers: Magnetic micelles and vesicles

    International Nuclear Information System (INIS)

    Lecommandoux, S.; Sandre, O.; Checot, F.; Rodriguez-Hernandez, J.; Perzynski, R.


    Magnetic nanocomposites are obtained by the self-assembly in water of polypeptide-based di-block copolymers polybutadiene-b-poly(glutamic acid) combined with hydrophobic γ-Fe 2 O 3 nanoparticles. These hybrid supramolecular objects are either-(3D) spherical micelles filled with a hydrophobic ferrofluid at a concentration as high as 45 vol% or-hollow vesicles with a (2D) magnetic membrane. In this last case, the organic amphiphile copolymers are able to confine the hydrophobic nanoparticles within the thin layer of polybutadiene blocks. We probe these objects by atomic force microscopy, by small-angle neutron scattering (SANS) and by light scattering. Furthermore, anisotropic SANS data bring the experimental evidence of the capability to modify the shape of the mineralized membranes in response to a magnetic field intensity as low as 290 G

  1. Enantioselective Light Harvesting with Perylenediimide Guests on Self-Assembled Chiral Naphthalenediimide Nanofibers. (United States)

    Sethy, Ramarani; Kumar, Jatish; Métivier, Rémi; Louis, Marine; Nakatani, Keitaro; Mecheri, Nila Mohan Thazhe; Subhakumari, Akhila; Thomas, K George; Kawai, Tsuyoshi; Nakashima, Takuya


    Self-assembling molecular systems often display amplified chirality compared to the monomeric state, which makes the molecular recognition more sensitive to chiral analytes. Herein, we report the almost absolute enantioselective recognition of a chiral perylenediimide (PDI) molecule by chiral supramolecular nanofibers of a bichromophoric naphthalenediimide (NDI) derivative. The chiral recognition was evaluated through the Förster resonance energy transfer (FRET) from the NDI-based host nanofibers to the guest PDI molecules. The excitation energy was successfully transferred to the guest molecule through efficient energy migration along the host nanofiber, thus demonstrating the light-harvesting capability of these hybrid systems. Furthermore, circularly polarized luminescence (CPL) was enantioselectively sensitized by the guest molecule as the wavelength band and sign of the CPL signal were switched in response to the chiral guest molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Self-assembled nanostructures in oxide ceramics (United States)

    Ansari, Haris Masood

    Self-assembled nanoislands in the gadolinia-doped ceria (GDC)/ yttria-stabilized zirconia (YSZ) system have recently been discovered. This dissertation is an attempt to study the mechanism by which these nanoislands form. Nanoislands in the GDC/YSZ system form via a strain based mechanism whereby the stress accumulated in the GDC-doped surface layer on the YSZ substrate is relieved by creation of self-assembled nanoislands by a mechanism similar to the ATG instability. Unlike what was previously believed, a modified surface layer is not required prior to annealing, that is, this modification can occur during annealing by surface diffusion of dopants from the GDC sources (distributed on the YSZ surface in either lithographically defined patch or powder form) with simultaneous breakup, which occurs at the hold temperature independent of the subsequent cooling. Additionally, we have developed a simple powder based process of producing nanoislands which bypasses lithography and thin film deposition setups. The versatility of the process is apparent in the fact that it allows us to study the effect of experimental parameters such as soak time, temperature, cooling rate and the effect of powder composition on nanoisland properties in a facile way. With the help of this process, we have shown that nanoislands are not peculiar to Gd containing oxide source materials on YSZ substrates and can also be produced with other source materials such as La2O3, Nd2O3, Sm 2O3, Eu2O3, Tb2O3 and even Y2O3, which is already present in the substrate and hence simplifies the system further. We have extended our work to include YSZ substrates of the (110) surface orientation and have found that instead of nanoisland arrays, we obtain an array of parallel nanobars which have their long axes oriented along the [1-10] direction on the YSZ-(110) surface. STEM EDS performed on both the bars and the nanoislands has revealed that they are solid YSZ-rich solid solutions with the dopant species and

  3. RNA self-assembly and RNA nanotechnology. (United States)

    Grabow, Wade W; Jaeger, Luc


    CONSPECTUS: Nanotechnology's central goal involves the direct control of matter at the molecular nanometer scale to build nanofactories, nanomachines, and other devices for potential applications including electronics, alternative fuels, and medicine. In this regard, the nascent use of nucleic acids as a material to coordinate the precise arrangements of specific molecules marked an important milestone in the relatively recent history of nanotechnology. While DNA served as the pioneer building material in nucleic acid nanotechnology, RNA continues to emerge as viable alternative material with its own distinct advantages for nanoconstruction. Several complementary assembly strategies have been used to build a diverse set of RNA nanostructures having unique structural attributes and the ability to self-assemble in a highly programmable and controlled manner. Of the different strategies, the architectonics approach uniquely endeavors to understand integrated structural RNA architectures through the arrangement of their characteristic structural building blocks. Viewed through this lens, it becomes apparent that nature routinely uses thermodynamically stable, recurrent modular motifs from natural RNA molecules to generate unique and more complex programmable structures. With the design principles found in natural structures, a number of synthetic RNAs have been constructed. The synthetic nanostructures constructed to date have provided, in addition to affording essential insights into RNA design, important platforms to characterize and validate the structural self-folding and assembly properties of RNA modules or building blocks. Furthermore, RNA nanoparticles have shown great promise for applications in nanomedicine and RNA-based therapeutics. Nevertheless, the synthetic RNA architectures achieved thus far consist largely of static, rigid particles that are still far from matching the structural and functional complexity of natural responsive structural elements such

  4. Solvent mediated self-assembly of solids

    Energy Technology Data Exchange (ETDEWEB)

    De Yoreo, J.; Wilson, W.D.; Palmore, T.


    Solvent-mediated crystallization represents a robust approach to self-assembly of nanostructures and microstructures. In organic systems, the relative ease with which the structure of hydrogen- bonded molecules can be manipulated allows for generation of a wide variety of nanoscale crystal structures. In living organisms, control over the micron-to-millimeter form of inorganic crystals is achieved through introduction of bio-organic molecules. The purpose of this proposal is to understand the interplay between solution chemistry, molecular structure, surface chemistry, and the processes of nucleation and crystal growth in solvent-mediated systems, with the goal of developing the atomic and molecular basis of a solvent-mediated self-assembly technology. We will achieve this purpose by: (1) utilizing an atomic force microscopy (AFM) approach that provides in situ, real time imaging during growth from solutions, (2) by modifying kinetic Monte Carlo (KMC) models to include solution-surface kinetics, (3) by introducing quantum chemistry (QC) calculations of the potentials of the relevant chemical species and the near-surface structure of the solution, and (4) by utilizing molecular dynamics (MD) simulations to identify the minimum energy pathways to the solid state. Our work will focus on two systems chosen to address both the manometer and micron-to-millimeter length scales of assembly, the family of 2,5- diketopiperazines (X-DKPs) and the system of CaCO{sub 3} with amino acids. Using AFM, we will record the evolution of surface morphology, critical lengths, step speeds, and step-step interactions as a function of supersaturation and temperature. In the case of the X-DKPs, these measurements will be repeated as the molecular structure of the growth unit is varied. In the case of CaCO{sub 3}, they will be performed as a function of solution chemistry including pH, ionic strength, and amino acid content. In addition, we will measure nucleation rates and orientations of

  5. Solid state nanofibers based on self-assemblies : from cleaving from self-assemblies to multilevel hierarchical constructs

    NARCIS (Netherlands)

    Ikkala, Olli; Ras, Robin H. A.; Houbenov, Nikolay; Ruokolainen, Janne; Paakko, Marjo; Laine, Janne; Leskela, Markku; Berglund, Lars A.; Lindstrom, Tom; ten Brinke, Gerrit; Iatrou, Hermis; Hadjichristidis, Nikos; Faul, Charl F. J.; Pääkkö, Marjo; Leskelä, Markku; Lindström, Tom


    Self-assemblies and their hierarchies are useful to construct soft materials with structures at different length scales and to tune the materials properties for various functions. Here we address routes for solid nanofibers based on different forms of self-assemblies. On the other hand, we discuss

  6. On the solution self-assembly of nanocolloidal brushes: insights from simulations

    International Nuclear Information System (INIS)

    Striolo, Alberto


    The synthesis of novel nanoparticles with exceptional properties continues to stimulate the search for advanced applications in fields as diverse as solar energy harvesting and polymer reinforcement. It is widely recognized that to practically exploit the promised benefits it is necessary to guide the assembly of the various nanoparticles into well-defined supra-molecular structures. Towards this goal, we report Monte Carlo simulation results for the self-assembly of spherical nanoparticles in implicit solvent. The nanoparticles interact solely via dispersive interactions, modeled as square-well potentials. To control the morphology of the self-assembled aggregates, side chains are grafted on specific locations on the nanoparticle surface (i.e., on the equator, on the tropics, on the entire tropical region, or uniformly on the nanoparticle surface). The results are discussed in terms of average cluster size, probability of observing aggregates of given size, and aggregate radius of gyration and asphericity as a function of the aggregate size. The parameters of interest are the solution conditions and the nanoparticle volume fraction (always in the dilute regime). As shown in previous reports (e.g., Striolo 2007 Small 3 628), the nanoparticles form insoluble agglomerates in the absence of the side chains. When the side chains are long and uniformly distributed on the nanoparticles, these remain individually dispersed in solution. More importantly, when the side chains are grafted on selected locations on the nanoparticles, these self-assemble, yielding structures composed of up to 7-10 nanoparticles. The number of grafted side chains is the parameter that predominantly determines the average aggregate size, while the aggregate morphology can be tuned by appropriately controlling the distribution and length of the grafted side chains.

  7. Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles. (United States)

    Sun, Jing; Jiang, Xi; Lund, Reidar; Downing, Kenneth H; Balsara, Nitash P; Zuckermann, Ronald N


    The folding and assembly of sequence-defined polymers into precisely ordered nanostructures promises a class of well-defined biomimetic architectures with specific function. Amphiphilic diblock copolymers are known to self-assemble in water to form a variety of nanostructured morphologies including spheres, disks, cylinders, and vesicles. In all of these cases, the predominant driving force for assembly is the formation of a hydrophobic core that excludes water, whereas the hydrophilic blocks are solvated and extend into the aqueous phase. However, such polymer systems typically have broad molar mass distributions and lack the purity and sequence-defined structure often associated with biologically derived polymers. Here, we demonstrate that purified, monodisperse amphiphilic diblock copolypeptoids, with chemically distinct domains that are congruent in size and shape, can behave like molecular tile units that spontaneously assemble into hollow, crystalline nanotubes in water. The nanotubes consist of stacked, porous crystalline rings, and are held together primarily by side-chain van der Waals interactions. The peptoid nanotubes form without a central hydrophobic core, chirality, a hydrogen bond network, and electrostatic or π-π interactions. These results demonstrate the remarkable structure-directing influence of n-alkane and ethyleneoxy side chains in polymer self-assembly. More broadly, this work suggests that flexible, low-molecular-weight sequence-defined polymers can serve as molecular tile units that can assemble into precision supramolecular architectures.

  8. Molecular self-assembly in substituted alanine derivatives: XRD, Hirshfeld surfaces and DFT studies (United States)

    Rajalakshmi, Periasamy; Srinivasan, Navaneethakrishnan; Sivaraman, Gandhi; Razak, Ibrahim Abdul; Rosli, Mohd Mustaqim; Krishnakumar, Rajaputi Venkatraman


    The molecular assemblage in the crystal structures of three modified chiral amino acids, two of which are isomeric D- and L-pairs boc-L-benzothienylalanine (BLA), boc-D-benzothienylalanine (BDA) and the other boc-D-naphthylalanine (NDA) differing from this pair very slightly in the chemical modification introduced, is accurately described. The aggregation of amino acid molecules is similar in all the crystals and may be described as a twisted double helical ladder in which two complementary long helical chains formed through O-H⋯O hydrogen bonds are interconnected through the characteristic head-to-tail N-H⋯O hydrogen bonds. Thus the molecular aggregation enabled through classical hydrogen bonds may be regarded as a mimic of the characteristic double helical structure of DNA. Also, precise structural information involving these amino acid molecules with lower symmetry exhibiting higher trigonal symmetry in their self-assembly is expected to throw light on the nature and strength of intermolecular interactions and their role in self-assembly of molecular aggregates, which are crucial in developing new or at least supplement existing crystal engineering strategies. Single crystal X-ray analysis and their electronic structures were calculated at the DFT level with a detailed analysis of Hirshfeld surfaces and fingerprint plots facilitating a comparison of intermolecular interactions in building different supramolecular architectures.

  9. Ultrashort cationic naphthalene-derived self-assembled peptides as antimicrobial nanomaterials. (United States)

    Laverty, Garry; McCloskey, Alice P; Gilmore, Brendan F; Jones, David S; Zhou, Jie; Xu, Bing


    Self-assembling dipeptides conjugated to naphthalene show considerable promise as nanomaterial structures, biomaterials, and drug delivery devices. Biomaterial infections are responsible for high rates of patient mortality and morbidity. The presence of biofilm bacteria, which thrive on implant surfaces, are a huge burden on healthcare budgets, as they are highly resistant to current therapeutic strategies. Ultrashort cationic self-assembled peptides represent a highly innovative and cost-effective strategy to form antibacterial nanomaterials. Lysine conjugated variants display the greatest potency with 2% w/v NapFFKK hydrogels significantly reducing the viable Staphylococcus epidermidis biofilm by 94%. Reducing the size of the R-group methylene chain on cationic moieties resulted in reduction of antibiofilm activity. The primary amine of the protruding R-group tail may not be as readily available to interact with negatively charged bacterial membranes. Cryo-SEM, FTIR, CD spectroscopy, and oscillatory rheology provided evidence of supramolecular hydrogel formation at physiological pH (pH 7.4). Cytotoxicity assays against murine fibroblast (NCTC 929) cell lines confirmed the gels possessed reduced cytotoxicity relative to bacterial cells, with limited hemolysis upon exposure to equine erythrocytes. The results presented in this paper highlight the significant potential of ultrashort cationic naphthalene peptides as future biomaterials.

  10. Self-assembling of calcium salt of the new DNA base 5-carboxylcytosine

    Energy Technology Data Exchange (ETDEWEB)

    Irrera, Simona [Department of Chemistry, SAPIENZA University of Rome, Piazzale A. Moro 5, 00185 Rome (Italy); Department of Chemistry, University College London, 20 Grodon Street, WC1H0AJ London (United Kingdom); Ruiz-Hernandez, Sergio E. [School of Chemistry, Cardiff University Main Building, Park Place, CF103AT Cardiff (United Kingdom); Reggente, Melania [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Passeri, Daniele, E-mail: [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Natali, Marco [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Gala, Fabrizio [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Department of Medical-Surgical, Techno-Biomedical Sciences and Translational Medicine of SAPIENZA University of Rome, Sant’Andrea Hospital, Rome (Italy); Zollo, Giuseppe [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Rossi, Marco [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Research Center for Nanotechnology applied to Engineering of SAPIENZA University of Rome (CNIS), Piazzale A. Moro 5, 00185 Rome (Italy); Portalone, Gustavo, E-mail: [Department of Chemistry, SAPIENZA University of Rome, Piazzale A. Moro 5, 00185 Rome (Italy)


    Highlights: • Ca salt of 5-carboxylcytosine has been deposited on HOPG substrate. • Molecules self-assembled in monolayers and filaments. • Height of the features were measured by atomic force microscopy. • Ab-initio calculations confirmed the AFM results. - Abstract: Supramolecular architectures involving DNA bases can have a strong impact in several fields such as nanomedicine and nanodevice manufacturing. To date, in addition to the four canonical nucleobases (adenine, thymine, guanine and cytosine), four other forms of cytosine modified at the 5 position have been identified in DNA. Among these four new cytosine derivatives, 5-carboxylcytosine has been recently discovered in mammalian stem cell DNA, and proposed as the final product of the oxidative epigenetic demethylation pathway on the 5 position of cytosine. In this work, a calcium salt of 5-carboxylcytosine has been synthesized and deposited on graphite surface, where it forms self-assembled features as long range monolayers and up to one micron long filaments. These structures have been analyzed in details combining different theoretical and experimental approaches: X-ray single-crystal diffraction data were used to simulate the molecule-graphite interaction, first using molecular dynamics and then refining the results using density functional theory (DFT); finally, data obtained with DFT were used to rationalize atomic force microscopy (AFM) results.

  11. Understanding recognition and self-assembly in biology using the chemist's toolbox. Insight into medicinal chemistry. (United States)

    Quirolo, Z B; Benedini, L A; Sequeira, M A; Herrera, M G; Veuthey, T V; Dodero, V I


    Medicinal chemistry is intimately connected with basic science such as organic synthesis, chemical biology and biophysical chemistry among other disciplines. The reason of such connections is due to the power of organic synthesis to provide designed molecules; chemical biology to give tools to discover biological and/or pathological pathways and biophysical chemistry which provides the techniques to characterize and the theoretical background to understand molecular behaviour. The present review provides some selective examples of these research areas. Initially, template dsDNA organic synthesis and the spatio-temporal control of transcription are presenting following by the supramolecular entities used in drug delivery, such as liposomes and liquid crystal among others. Finally, peptides and protein self-assembly is connected with biomaterials and as an important event in the balance between health and disease. The final aim of the present review is to show the power of chemical tools not only for the synthesis of new molecules but also to improve our understanding of recognition and self-assembly in the biological context.

  12. Programming Self-Assembly of DNA Origami Honeycomb Two-Dimensional Lattices and Plasmonic Metamaterials. (United States)

    Wang, Pengfei; Gaitanaros, Stavros; Lee, Seungwoo; Bathe, Mark; Shih, William M; Ke, Yonggang


    Scaffolded DNA origami has proven to be a versatile method for generating functional nanostructures with prescribed sub-100 nm shapes. Programming DNA-origami tiles to form large-scale 2D lattices that span hundreds of nanometers to the micrometer scale could provide an enabling platform for diverse applications ranging from metamaterials to surface-based biophysical assays. Toward this end, here we design a family of hexagonal DNA-origami tiles using computer-aided design and demonstrate successful self-assembly of micrometer-scale 2D honeycomb lattices and tubes by controlling their geometric and mechanical properties including their interconnecting strands. Our results offer insight into programmed self-assembly of low-defect supra-molecular DNA-origami 2D lattices and tubes. In addition, we demonstrate that these DNA-origami hexagon tiles and honeycomb lattices are versatile platforms for assembling optical metamaterials via programmable spatial arrangement of gold nanoparticles (AuNPs) into cluster and superlattice geometries.

  13. Electrostatic self-assembly of biomolecules (United States)

    Olvera de La Cruz, Monica


    Charged filaments and membranes are natural structures abundant in cell media. In this talk we discuss the assembly of amphiphiles into biocompatible fibers, ribbons and membranes. We describe one- and two-dimensional assemblies that undergo re-entrant transitions in crystalline packing in response to changes in the solution pH and/or salt concentration resulting in different mesoscale morphologies and properties. In the case of one-dimensional structures, we discuss self-assembled amphiphiles into highly charged nanofibers in water that order into two-dimensional crystals. These fibers of about 6 nm cross-sectional diameter form crystalline arrays with inter-fiber spacings of up to 130 nm. Solution concentration and temperature can be adjusted to control the inter-fiber spacings. The addition of salt destroys crystal packing, indicating that electrostatic repulsions are necessary for the observed ordering. We describe the crystallization of bundles of filament networks interacting via long-range repulsions in confinement by a phenomenological model. Two distinct crystallization mechanisms in the short and large screening length regimes are discussed and the phase diagram is obtained. Simulation of large bundles predicts the existence of topological defects among bundled filaments. Crystallization processes driven by electrostatic attractions are also discussed. Funded by Center for Bio-Inspired Energy Science (CBES), which is an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0000989.

  14. Self-Assembled Monolayers for Dental Implants

    Directory of Open Access Journals (Sweden)

    Sidónio C. Freitas


    Full Text Available Implant-based therapy is a mature approach to recover the health conditions of patients affected by edentulism. Thousands of dental implants are placed each year since their introduction in the 80s. However, implantology faces challenges that require more research strategies such as new support therapies for a world population with a continuous increase of life expectancy, to control periodontal status and new bioactive surfaces for implants. The present review is focused on self-assembled monolayers (SAMs for dental implant materials as a nanoscale-processing approach to modify titanium surfaces. SAMs represent an easy, accurate, and precise approach to modify surface properties. These are stable, well-defined, and well-organized organic structures that allow to control the chemical properties of the interface at the molecular scale. The ability to control the composition and properties of SAMs precisely through synthesis (i.e., the synthetic chemistry of organic compounds with a wide range of functional groups is well established and in general very simple, being commercially available, combined with the simple methods to pattern their functional groups on complex geometry appliances, makes them a good system for fundamental studies regarding the interaction between surfaces, proteins, and cells, as well as to engineering surfaces in order to develop new biomaterials.

  15. Self-assembling holographic biosensors and biocomputers.

    Energy Technology Data Exchange (ETDEWEB)

    Light, Yooli Kim; Bachand, George David (Sandia National Laboratories, Albuquerque, NM); Schoeniger, Joseph S.; Trent, Amanda M. (Sandia National Laboratories, Albuquerque, NM)


    We present concepts for self-assembly of diffractive optics with potential uses in biosensors and biocomputers. The simplest such optics, diffraction gratings, can potentially be made from chemically-stabilized microtubules migrating on nanopatterned tracks of the motor protein kinesin. We discuss the fabrication challenges involved in patterning sub-micron-scale structures with proteins that must be maintained in aqueous buffers to preserve their activity. A novel strategy is presented that employs dry contact printing onto glass-supported amino-silane monolayers of heterobifunctional crosslinkers, followed by solid-state reactions of these cross-linkers, to graft patterns of reactive groups onto the surface. Successive solution-phase addition of cysteine-mutant proteins and amine-reactive polyethylene glycol allows assembly of features onto the printed patterns. We present data from initial experiments showing successful micro- and nanopatterning of lines of single-cysteine mutants of kinesin interleaved with lines of polyethylene, indicating that this strategy can be employed to arrays of features with resolutions suitable for gratings.

  16. Self-assembled biomimetic superhydrophobic hierarchical arrays. (United States)

    Yang, Hongta; Dou, Xuan; Fang, Yin; Jiang, Peng


    Here, we report a simple and inexpensive bottom-up technology for fabricating superhydrophobic coatings with hierarchical micro-/nano-structures, which are inspired by the binary periodic structure found on the superhydrophobic compound eyes of some insects (e.g., mosquitoes and moths). Binary colloidal arrays consisting of exemplary large (4 and 30 μm) and small (300 nm) silica spheres are first assembled by a scalable Langmuir-Blodgett (LB) technology in a layer-by-layer manner. After surface modification with fluorosilanes, the self-assembled hierarchical particle arrays become superhydrophobic with an apparent water contact angle (CA) larger than 150°. The throughput of the resulting superhydrophobic coatings with hierarchical structures can be significantly improved by templating the binary periodic structures of the LB-assembled colloidal arrays into UV-curable fluoropolymers by a soft lithography approach. Superhydrophobic perfluoroether acrylate hierarchical arrays with large CAs and small CA hysteresis can be faithfully replicated onto various substrates. Both experiments and theoretical calculations based on the Cassie's dewetting model demonstrate the importance of the hierarchical structure in achieving the final superhydrophobic surface states. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Functional Self-Assembled Nanofibers by Electrospinning (United States)

    Greiner, A.; Wendorff, J. H.

    Electrospinning constitutes a unique technique for the production of nanofibers with diameters down to the range of a few nanometers. In strong contrast to conventional fiber producing techniques, it relies on self-assembly processes driven by the Coulomb interactions between charged elements of the fluids to be spun to nanofibers. The transition from a macroscopic fluid object such as a droplet emerging from a die to solid nanofibers is controlled by a set of complex physical instability processes. They give rise to extremely high extensional deformations and strain rates during fiber formation causing among others a high orientational order in the nanofibers as well as enhanced mechanical properties. Electrospinning is predominantly applied to polymer based materials including natural and synthetic polymers, but, more recently, its use has been extended towards the production of metal, ceramic and glass nanofibers exploiting precursor routes. The nanofibers can be functionalized during electrospinning by introducing pores, fractal surfaces, by incorporating functional elements such as catalysts, quantum dots, drugs, enzymes or even bacteria. The production of individual fibers, random nonwovens, or orientationally highly ordered nonwovens is achieved by an appropriate selection of electrode configurations. Broad areas of application exist in Material and Life Sciences for such nanofibers, including not only optoelectronics, sensorics, catalysis, textiles, high efficiency filters, fiber reinforcement but also tissue engineering, drug delivery, and wound healing. The basic electrospinning process has more recently been extended towards compound co-electrospinning and precision deposition electrospinning to further broaden accessible fiber architectures and potential areas of application.

  18. Circuits and programmable self-assembling DNA structures


    Carbone, Alessandra; Seeman, Nadrian C.


    Self-assembly is beginning to be seen as a practical vehicle for computation. We investigate how basic ideas on tiling can be applied to the assembly and evaluation of circuits. We suggest that these procedures can be realized on the molecular scale through the medium of self-assembled DNA tiles. One layer of self-assembled DNA tiles will be used as the program or circuit that leads to the computation of a particular Boolean expression. This layer templates the assembly of tiles, and their as...

  19. Functional self-assembled lipidic systems derived from renewable resources. (United States)

    Silverman, Julian R; Samateh, Malick; John, George


    Self-assembled lipidic amphiphile systems can create a variety of multi-functional soft materials with value-added properties. When employing natural reagents and following biocatalytic syntheses, self-assembling monomers may be inherently designed for degradation, making them potential alternatives to conventional and persistent polymers. By using non-covalent forces, self-assembled amphiphiles can form nanotubes, fibers, and other stimuli responsive architectures prime for further applied research and incorporation into commercial products. By viewing these lipid derivatives under a lens of green principles, there is the hope that in developing a structure-function relationship and functional smart materials that research may remain safe, economic, and efficient.

  20. Magnetic manipulation of self-assembled colloidal asters.

    Energy Technology Data Exchange (ETDEWEB)

    Snezhko, A.; Aranson, I. S. (Materials Science Division)


    Self-assembled materials must actively consume energy and remain out of equilibrium to support structural complexity and functional diversity. Here we show that a magnetic colloidal suspension confined at the interface between two immiscible liquids and energized by an alternating magnetic field dynamically self-assembles into localized asters and arrays of asters, which exhibit locomotion and shape change. By controlling a small external magnetic field applied parallel to the interface, we show that asters can capture, transport, and position target microparticles. The ability to manipulate colloidal structures is crucial for the further development of self-assembled microrobots

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

    KAUST Repository

    Zhang, Ye


    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.

  2. 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


    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

  3. 3D Printing Polymers with Supramolecular Functionality for Biological Applications. (United States)

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


    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.

  4. Self-Assembling Wireless Autonomous Reconfigurable Modules (SWARM) Project (United States)

    National Aeronautics and Space Administration — Payload Systems Inc. and the MIT Space Systems Laboratory propose Self-assembling, Wireless, Autonomous, Reconfigurable Modules (SWARM) as an innovative approach to...

  5. Self-Assembling Wireless Autonomous Reconfigurable Modules (SWARM), Phase II (United States)

    National Aeronautics and Space Administration — Payload Systems Inc. and the MIT Space Systems Laboratory propose Self-assembling, Wireless, Autonomous, Reconfigurable Modules (SWARM) as an innovative approach to...

  6. Self-Assembled Nanostructured Health Monitoring Sensors, Phase I (United States)

    National Aeronautics and Space Administration — The objective of the proposed NASA SBIR program is to design, fabricate and evaluate the performance of self-assembled nanostructured sensors for the health...

  7. Self-Assembling Wireless Autonomous Reconfigurable Modules (SWARM), Phase I (United States)

    National Aeronautics and Space Administration — Payload Systems Inc. and the MIT Space Systems Laboratory propose Self-assembling, Wireless, Autonomous, Reconfigurable Modules (SWARM) as an innovative approach to...

  8. Primordial and Modern Self Assembling Peptides: Synthesis and Characterization (United States)

    Cusumano, Stephen

    The creation and analysis of self-assembling peptides has become a recent research trend due to the wide range of applications and usages. Modern self-assembling such as lanreotide, which is an established anti-cancer drug in the pharmaceutical industry, can be synthetically made. More primitive peptides, such as those discovered to be present in the famous Miller experiment, which replicated the primordial earth atmosphere, are representative of a different aspect of self-assembling peptides. If these novel peptides are found to self-assemble, this will give researchers new insight on how primitive cells first formed on this planet to give rise to life. Using the established nanotube structure of lanreotide, TEM protocols were developed to obtain similar high quality TEM images of primitive peptides, to observe if any structures have begun to form.

  9. Multiresponsive self-assembled liquid crystals with azobenzene groups. (United States)

    Xu, Miao; Chen, Liqin; Zhou, Yifeng; Yi, Tao; Li, Fuyou; Huang, Chunhui


    An optical and electric field-responsive self-assembled complex containing nitril azobenzene groups and 1,3,5-triazine-2,4-diamine was obtained and characterized. Both the azobenzene precursor and the complex form a liquid-crystalline phase in a certain temperature range. The transition temperature from crystalline phase to liquid-crystalline mesophase was obviously decreased in the complex by the self-assembling. The self-assembled liquid crystals revealed good response to both stimuli of light irradiation and electric field, and the induced molecular orientation could be held even after the removal of the stimuli. The structural and mechanical investigation proved that the formation of hydrogen bonds and assembly-induced molecular dipolar change contributed to the multiresponding action. This kind of self-assembled complex thus has potential applications in imaging and data storage.

  10. Understanding emergent functions in self-assembled fibrous networks (United States)

    Sinko, Robert; Keten, Sinan


    Understanding self-assembly processes of nanoscale building blocks and characterizing their properties are both imperative for designing new hierarchical, network materials for a wide range of structural, optoelectrical, and transport applications. Although the characterization and choices of these material building blocks have been well studied, our understanding of how to precisely program a specific morphology through self-assembly still must be significantly advanced. In the recent study by Xie et al (2015 Nanotechnology 26 205602), the self-assembly of end-functionalized nanofibres is investigated using a coarse-grained molecular model and offers fundamental insight into how to control the structural morphology of nanofibrous networks. Varying nanoscale networks are observed when the molecular interaction strength is changed and the findings suggest that self-assembly through the tuning of molecular interactions is a key strategy for designing nanostructured networks with specific topologies.

  11. Noncanonical self-assembly of highly asymmetric genetically encoded polypeptide amphiphiles into cylindrical micelles. (United States)

    McDaniel, Jonathan R; Weitzhandler, Isaac; Prevost, Sylvain; Vargo, Kevin B; Appavou, Marie-Sousai; Hammer, Daniel A; Gradzielski, Michael; Chilkoti, Ashutosh


    Elastin-like polypeptides (ELPs) are a class of biopolymers consisting of the pentameric repeat (VPGαG)n based on the sequence of mammalian tropoelastin that display a thermally induced soluble-to-insoluble phase transition in aqueous solution. We have discovered a remarkably simple approach to driving the spontaneous self-assembly of high molecular weight ELPs into nanostructures by genetically fusing a short 1.5 kDa (XGy)z assembly domain to one end of the ELP. Classical theories of self-assembly based on the geometric mass balance of hydrophilic and hydrophobic block copolymers suggest that these highly asymmetric polypeptides should form spherical micelles. Surprisingly, when sufficiently hydrophobic amino acids (X) are presented in a periodic sequence such as (FGG)8 or (YG)8, these highly asymmetric polypeptides self-assemble into cylindrical micelles whose length can be tuned by the sequence of the morphogenic tag. These nanostructures were characterized by light scattering, tunable resistive pulse sensing, fluorescence spectrophotometry, and thermal turbidimetry, as well as by cryogenic transmission electron microscopy (cryo-TEM) and small-angle neutron scattering (SANS). These short assembly domains provide a facile strategy to control the size, shape, and stability of stimuli responsive polypeptide nanostructures.

  12. Structural study of the self-assembled fullerene carboxylates: monoadducts versus bisadducts. (United States)

    Zhou, Shuiqin; Ouyang, Jianying; Golas, Patricia; Wang, Feng; Pan, Yi


    Laser light scattering and transmission electronic microscopy have been used to study the self-assembled structures of mono- and bisadducts of fullerene carboxylic acids in tetrahydrofuran (THF) and their sodium salts in aqueous solutions, respectively. In THF, the self-association of monoadducts of fullerene carboxylic acid (MFCA) produces large but narrowly distributed particles with R(h) approximately 145 nm. The self-aggregates from the bisadducts of fullerene carboxylic acid (BFCA) in THF are relatively small in size (R(h) approximately 80 nm) due to the better solubility. After the ionization of carboxylic acid groups on the C(60) cage in dilute NaOH solutions, these aggregates dissolved and reorganized. The self-assembly of the monoadducts of sodium carboxylate fullerenes (MSCF) produces small solid spherical particles with R(h) approximately 32 nm. The ratio of R(g)/R(h) approximately 0.83 indicates that the particles have a nearly uniform density. The increase in concentrations leads to strong interparticle associations to form rodlike and irregularly shaped large aggregates. In contrast, the self-assembly of bisadducts of sodium carboxylate fullerenes (BSCF) results in hollow shells with mainly two different size scales of R(h) approximately 23 nm and R(h) approximately 104 nm. At high concentrations, the hollow shells associate and melt together to generate three-dimensional networks.

  13. Promoting self-assembly of collagen-related peptides into various higher-order structures by metal-histidine coordination. (United States)

    Hsu, Wei; Chen, Yi-Lun; Horng, Jia-Cherng


    Collagen is an important and widely used biomaterial and therapeutic. The construction of large-scale collagen structures via the self-assembly of small collagen-related peptides has been extensively studied in the past decade. Here, we report a highly effective and simple means to assemble small synthetic collagen-related peptides into various higher-order structures by utilizing metal-histidine coordination. In this work, two short collagen-related peptides in which histidine residues were incorporated as metal binding sites were designed and chemically synthesized: HG(PPG)(9)GH (X9) and HG(PPG)(4)(PHG)(PPG)(4)GH (PHG). Circular dichroism measurements indicated that these two peptides form only marginally stable collagen triple helices but that their stability can be increased upon the addition of metal ions. Dynamic light scattering analyses, turbidity measurements, TEM, and SEM results demonstrated the metal ion-dependent self-assembly of X9 and PHG into supramolecular structures ranging from various nanofibrils to microscale spherical, laminated, and granulated assemblies. The topology and size of these higher-order structures depends both on the metal ion identity and the location of the binding sites. Most intriguingly, the assembled fibrils show similar D-periodicity to that of natural collagen. Our results demonstrate that metal-histidine coordination can serve as an effective force to induce the self-assembly of unstable collagen-related peptides into higher-order structures.

  14. RT Self-assembly of Silica Nanoparticles on Optical Fibres

    DEFF Research Database (Denmark)

    Canning, John; Lindoy, Lachlan; Huyang, George


    The room temperature deposition of self-assembling silica nanoparticles onto D-shaped optical fibres x201c;D-fibrex201d;), drawn from milled preforms fabricated by modified chemical vapor deposition, is studied and preliminary results reported here.......The room temperature deposition of self-assembling silica nanoparticles onto D-shaped optical fibres x201c;D-fibrex201d;), drawn from milled preforms fabricated by modified chemical vapor deposition, is studied and preliminary results reported here....

  15. Self-Assembled Pyridine-Dipyrrolate Cages. (United States)

    Zhang, Huacheng; Lee, Juhoon; Lammer, Aaron D; Chi, Xiaodong; Brewster, James T; Lynch, Vincent M; Li, Hao; Zhang, Zhan; Sessler, Jonathan L


    An inherently nonlinear pyridine dipyrrolate ligand, namely 2,6-bis(3,4-diethyl-5-carboxy-1H-pyrrol-2yl)pyridine (compound 1), is able to distinguish between different zinc(II) cation sources, namely Zn(acac)2 and Zn(OAc)2, respectively. This differentiation is manifest both in terms of the observed fluorescent behavior in mixed organic media and the reaction chemistry. Treatment of 1 with Zn(acac)2 gives rise to a cage dimer, cage-1, wherein two molecules of compound 1 act as double bridging units to connect two individual cage subunits. As inferred from X-ray crystallographic studies, this cage system consists of discrete zinc dimers with hydroxide bridges that, with the assistance of bound DMF solvent molecules, serve to fix the geometry and orientation of the pyridine dipyrrolate building blocks. When a different zinc source, Zn(OAc)2, is used to carry out an ostensibly similar complexation reaction with compound 1, an acetate-bridged 1D abacus-like cage polymer is obtained as inferred from X-ray diffraction analysis. This extended solid state structure, cage-2, contains individual zinc dimer cage submits and appears stabilized by solvent molecules (DMF) and the counteranion (acetate). Rod-like assemblies are also observed by DLS and SEM. This construct, in contrast to cage-1, proved fluorescent in mixed organic media. The structure of the ligand itself (i.e., in the absence of Zn(II)) was confirmed by X-ray crystallographic analysis and was found to assemble into a supramolecular polymer. Conversion to a dimer form was seen upon the addition of TBAOAc. On the basis of the metric parameters, the structures seen in the solid state are stabilized via hydrogen bonding interactions involving solvent molecules.

  16. From ring-in-ring to sphere-in-sphere: self-assembly of discrete 2D and 3D architectures with increasing stability. (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


    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.

  17. Temperature-Induced, Selective Assembly of Supramolecular Colloids in Water

    NARCIS (Netherlands)

    Van Ravensteijn, Bas G.P.; Vilanova, Neus; De Feijter, Isja; Kegel, Willem K.; Voets, Ilja K.


    In this article, we report the synthesis and physical characterization of colloidal polystyrene particles that carry water-soluble supramolecular N,N′,N″,-trialkyl-benzene-1,3,5-tricarboxamides (BTAs) on their surface. These molecules are known to assemble into one-dimensional supramolecular

  18. Self-Assembly for the Synthesis of Functional Biomaterials. (United States)

    Stephanopoulos, Nicholas; Ortony, Julia H; Stupp, Samuel I


    The use of self-assembly for the construction of functional biomaterials is a highly promising and exciting area of research, with great potential for the treatment of injury or disease. By using multiple noncovalent interactions, coded into the molecular design of the constituent components, self-assembly allows for the construction of complex, adaptable, and highly tunable materials with potent biological effects. This review describes some of the seminal advances in the use of self-assembly to make novel systems for regenerative medicine and biology. Materials based on peptides, proteins, DNA, or hybrids thereof have found application in the treatment of a wide range of injuries and diseases, and this review outlines the design principles and practical applications of these systems. Most of the examples covered focus on the synthesis of hydrogels for the scaffolding or transplantation of cells, with an emphasis on the biological, mechanical, and structural properties of the resulting materials. In addition, we will discuss the distinct advantages conferred by self-assembly (compared with traditional covalent materials), and present some of the challenges and opportunities for the next generation of self-assembled biomaterials.

  19. Physical principles for DNA tile self-assembly. (United States)

    Evans, Constantine G; Winfree, Erik


    DNA tiles provide a promising technique for assembling structures with nanoscale resolution through self-assembly by basic interactions rather than top-down assembly of individual structures. Tile systems can be programmed to grow based on logical rules, allowing for a small number of tile types to assemble large, complex assemblies that can retain nanoscale resolution. Such algorithmic systems can even assemble different structures using the same tiles, based on inputs that seed the growth. While programming and theoretical analysis of tile self-assembly often makes use of abstract logical models of growth, experimentally implemented systems are governed by nanoscale physical processes that can lead to very different behavior, more accurately modeled by taking into account the thermodynamics and kinetics of tile attachment and detachment in solution. This review discusses the relationships between more abstract and more physically realistic tile assembly models. A central concern is how consideration of model differences enables the design of tile systems that robustly exhibit the desired abstract behavior in realistic physical models and in experimental implementations. Conversely, we identify situations where self-assembly in abstract models can not be well-approximated by physically realistic models, putting constraints on physical relevance of the abstract models. To facilitate the discussion, we introduce a unified model of tile self-assembly that clarifies the relationships between several well-studied models in the literature. Throughout, we highlight open questions regarding the physical principles for DNA tile self-assembly.

  20. Sequential programmable self-assembly: Role of cooperative interactions (United States)

    Halverson, Jonathan D.; Tkachenko, Alexei V.


    We propose a general strategy of "sequential programmable self-assembly" that enables a bottom-up design of arbitrary multi-particle architectures on nano- and microscales. We show that a naive realization of this scheme, based on the pairwise additive interactions between particles, has fundamental limitations that lead to a relatively high error rate. This can be overcome by using cooperative interparticle binding. The cooperativity is a well known feature of many biochemical processes, responsible, e.g., for signaling and regulations in living systems. Here we propose to utilize a similar strategy for high precision self-assembly, and show that DNA-mediated interactions provide a convenient platform for its implementation. In particular, we outline a specific design of a DNA-based complex which we call "DNA spider," that acts as a smart interparticle linker and provides a built-in cooperativity of binding. We demonstrate versatility of the sequential self-assembly based on spider-functionalized particles by designing several mesostructures of increasing complexity and simulating their assembly process. This includes a number of finite and repeating structures, in particular, the so-called tetrahelix and its several derivatives. Due to its generality, this approach allows one to design and successfully self-assemble virtually any structure made of a "GEOMAG" magnetic construction toy, out of nanoparticles. According to our results, once the binding cooperativity is strong enough, the sequential self-assembly becomes essentially error-free.

  1. Protonation of Lipids Impacts the Supramolecular and Biological Properties of Their Self-Assembly

    Czech Academy of Sciences Publication Activity Database

    Breton, M.; Berret, J.; F.; Bourgaux, C.; Kral, Teresa; Hof, Martin; Pichon, Ch.; Bessodes, M.; Scherman, D.; Mignet, N.


    Roč. 27, č. 20 (2011), s. 12336-12345 ISSN 0743-7463 R&D Projects: GA AV ČR IAA400400621; GA MŠk(CZ) LC06063 Institutional research plan: CEZ:AV0Z40400503 Keywords : fluorescence correlation spectroscopy * angle neutron - scattering * bilayer thickness Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.186, year: 2011

  2. Self-assembly of designed supramolecular magnetic filaments of different shapes

    Energy Technology Data Exchange (ETDEWEB)

    Novak, E.V. [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); Rozhkov, D.A., E-mail: [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); Sanchez, P.A. [University of Vienna, Sensengasse 8, Vienna (Austria); Kantorovich, S.S. [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); University of Vienna, Sensengasse 8, Vienna (Austria)


    In the present work we study via molecular dynamics simulations filaments of ring and linear shape. Filaments are made of magnetic nanoparticles, possessing a point dipole in their centres. Particles in filaments are crosslinked in a particular way, so that the deviation of the neighbouring dipoles from the head-to-tail orientation is penalised by the bond. We show how the conformation of a single chain and ring filament changes on cooling for different lengths. We also study filament pairs, by fixing filaments at a certain distance and analysing the impact of inter-filament interaction on the equilibrium configurations. Our study opens a perspective to investigate the dispersions of filaments, both theoretically and numerically, by using effective potentials. - Highlights: • Single filament study. • Magnetic particles crosslinked in chains and rings. • Magnetic filament interactions.

  3. Associative Pattern Recognition Through Macro-molecular Self-Assembly (United States)

    Zhong, Weishun; Schwab, David J.; Murugan, Arvind


    We show that macro-molecular self-assembly can recognize and classify high-dimensional patterns in the concentrations of N distinct molecular species. Similar to associative neural networks, the recognition here leverages dynamical attractors to recognize and reconstruct partially corrupted patterns. Traditional parameters of pattern recognition theory, such as sparsity, fidelity, and capacity are related to physical parameters, such as nucleation barriers, interaction range, and non-equilibrium assembly forces. Notably, we find that self-assembly bears greater similarity to continuous attractor neural networks, such as place cell networks that store spatial memories, rather than discrete memory networks. This relationship suggests that features and trade-offs seen here are not tied to details of self-assembly or neural network models but are instead intrinsic to associative pattern recognition carried out through short-ranged interactions.

  4. Synthesis and Self-Assembly of Triangulenium Salts

    DEFF Research Database (Denmark)

    Shi, Dong

    . The formed vesicles showed excellent stability standing over for 7 month at ambient lab conditions or upon heated up to 70 °C as monitored by dynamic light scattering (DLS) method. Chapter 4 reportes the dynamic air–water interfaces catalyzed self-assembly of insoluble aminotriangulenium salts into Stable......–water interfaces and lateral compression of the monolayer results in the collapsing toward the formation of bilayer nanosheets. The nanosheets showed excellent stability after standing over 10 months stocked in a close vial at ambient conditions due to the ionic atmosphere surrounding its charged surfaces...... in the self-assembly of the synthetic amphiphilic triangulenium salt in aqueous media. In this chapter, self-assembled nanotubes, nanorribbons and nanorods are presented and collusions II are made based on the experimental observations. The following chapter 6 repots the chain length effect on the self...

  5. Regulating DNA Self-assembly by DNA-Surface Interactions. (United States)

    Liu, Longfei; Li, Yulin; Wang, Yong; Zheng, Jianwei; Mao, Chengde


    DNA self-assembly provides a powerful approach for preparation of nanostructures. It is often studied in bulk solution and involves only DNA-DNA interactions. When confined to surfaces, DNA-surface interactions become an additional, important factor to DNA self-assembly. However, the way in which DNA-surface interactions influence DNA self-assembly is not well studied. In this study, we showed that weak DNA-DNA interactions could be stabilized by DNA-surface interactions to allow large DNA nanostructures to form. In addition, the assembly can be conducted isothermally at room temperature in as little as 5 seconds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Directed self-assembly of DNA tiles into complex nanocages. (United States)

    Tian, Cheng; Li, Xiang; Liu, Zhiyu; Jiang, Wen; Wang, Guansong; Mao, Chengde


    Tile-based self-assembly is a powerful method in DNA nanotechnology and has produced a wide range of well-defined nanostructures. But the resulting structures are relatively simple. Increasing the structural complexity and the scope of the accessible structures is an outstanding challenge in molecular self-assembly. A strategy to partially address this problem by introducing flexibility into assembling DNA tiles and employing directing agents to control the self-assembly process is presented. To demonstrate this strategy, a range of DNA nanocages have been rationally designed and constructed. Many of them can not be assembled otherwise. All of the resulting structures have been thoroughly characterized by gel electrophoresis and cryogenic electron microscopy. This strategy greatly expands the scope of accessible DNA nanostructures and would facilitate technological applications such as nanoguest encapsulation, drug delivery, and nanoparticle organization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Guided and magnetic self-assembly of tunable magnetoceptive gels. (United States)

    Tasoglu, S; Yu, C H; Gungordu, H I; Guven, S; Vural, T; Demirci, U


    Self-assembly of components into complex functional patterns at microscale is common in nature, and used increasingly in numerous disciplines such as optoelectronics, microfabrication, sensors, tissue engineering and computation. Here, we describe the use of stable radicals to guide the self-assembly of magnetically tunable gels, which we call 'magnetoceptive' materials at the scale of hundreds of microns to a millimeter, each can be programmed by shape and composition, into heterogeneous complex structures. Using paramagnetism of free radicals as a driving mechanism, complex heterogeneous structures are built in the magnetic field generated by permanent magnets. The overall magnetic signature of final structure is erased via an antioxidant vitamin E, subsequent to guided self-assembly. We demonstrate unique capabilities of radicals and antioxidants in fabrication of soft systems with heterogeneity in material properties, such as porosity, elastic modulus and mass density; then in bottom-up tissue engineering and finally, levitational and selective assembly of microcomponents.

  8. Self-Assembly in Biosilicification and Biotemplated Silica Materials

    Directory of Open Access Journals (Sweden)

    Francisco M. Fernandes


    Full Text Available During evolution, living organisms have learned to design biomolecules exhibiting self-assembly properties to build-up materials with complex organizations. This is particularly evidenced by the delicate siliceous structures of diatoms and sponges. These structures have been considered as inspiration sources for the preparation of nanoscale and nanostructured silica-based materials templated by the self-assembled natural or biomimetic molecules. These templates range from short peptides to large viruses, leading to biohybrid objects with a wide variety of dimensions, shapes and organization. A more recent strategy based on the integration of biological self-assembly as the driving force of silica nanoparticles organization offers new perspectives to elaborate highly-tunable, biofunctional nanocomposites.

  9. Self-Assembly in Biosilicification and Biotemplated Silica Materials. (United States)

    Fernandes, Francisco M; Coradin, Thibaud; Aimé, Carole


    During evolution, living organisms have learned to design biomolecules exhibiting self-assembly properties to build-up materials with complex organizations. This is particularly evidenced by the delicate siliceous structures of diatoms and sponges. These structures have been considered as inspiration sources for the preparation of nanoscale and nanostructured silica-based materials templated by the self-assembled natural or biomimetic molecules. These templates range from short peptides to large viruses, leading to biohybrid objects with a wide variety of dimensions, shapes and organization. A more recent strategy based on the integration of biological self-assembly as the driving force of silica nanoparticles organization offers new perspectives to elaborate highly-tunable, biofunctional nanocomposites.

  10. Bioprinting synthetic self-assembling peptide hydrogels for biomedical applications

    International Nuclear Information System (INIS)

    Loo, Yihua; Hauser, Charlotte A E


    Three-dimensional (3D) bioprinting is a disruptive technology for creating organotypic constructs for high-throughput screening and regenerative medicine. One major challenge is the lack of suitable bioinks. Short synthetic self-assembling peptides are ideal candidates. Several classes of peptides self-assemble into nanofibrous hydrogels resembling the native extracellular matrix. This is a conducive microenvironment for maintaining cell survival and physiological function. Many peptides also demonstrate stimuli-responsive gelation and tuneable mechanical properties, which facilitates extrusion before dispensing and maintains the shape fidelity of the printed construct in aqueous media. The inherent biocompatibility and biodegradability bodes well for in vivo applications as implantable tissues and drug delivery matrices, while their short length and ease of functionalization facilitates synthesis and customization. By applying self-assembling peptide inks to bioprinting, the dynamic complexity of biological tissue can be recreated, thereby advancing current biomedical applications of peptide hydrogel scaffolds. (paper)

  11. Hydrodynamic Self-Assembly of Topographical Patterns on Soft Materials

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Satish [Univ. of Minnesota, Minneapolis, MN (United States)


    The objective of this project is to use theoretical tools to explore fundamentally new ways of creating and controlling surface topography on soft materials (e.g., polymeric liquids, gels, colloidal suspensions) that make use of principles from hydrodynamics and self-assembly. Surface topography is known to have a significant impact on the optical, adhesive, and wetting properties of materials, so improved fundamental understanding of how to create and control it will help enable the tailoring of these properties to desired specifications. Self-assembly is the spontaneous organization of an ordered structure, and hydrodynamics often plays an important role in the self-assembly of soft materials. This research supported through this project has led to the discovery of a number of novel phenomena that are described in published journal articles. In this way, the research significantly adds to the fundamental understanding of the topics investigated.

  12. Novel tumor-targeting, self-assembling peptide nanofiber as a carrier for effective curcumin delivery. (United States)

    Liu, Jianfeng; Liu, Jinjian; Xu, Hongyan; Zhang, Yumin; Chu, Liping; Liu, Qingfen; Song, Naling; Yang, Cuihong


    The poor aqueous solubility and low bioavailability of curcumin restrict its clinical application for cancer treatment. In this study, a novel tumor-targeting nanofiber carrier was developed to improve the solubility and tumor-targeting ability of curcumin using a self-assembled Nap-GFFYG-RGD peptide. The morphologies of the peptide nanofiber and the curcumin-encapsulated nanofiber were visualized by transmission electron microscopy. The tumor-targeting activity of the curcumin-encapsulated Nap-GFFYG-RGD peptide nanofiber (f-RGD-Cur) was studied in vitro and in vivo, using Nap-GFFYG-RGE peptide nanofiber (f-RGE-Cur) as the control. Curcumin was encapsulated into the peptide nanofiber, which had a diameter of approximately 10-20 nm. Curcumin showed sustained-release behavior from the nanofibers in vitro. f-RGD-Cur showed much higher cellular uptake in αvβ3 integrin-positive HepG2 liver carcinoma cells than did non-targeted f-RGE-Cur, thereby leading to significantly higher cytotoxicity. Ex vivo studies further demonstrated that curcumin could accumulate markedly in mouse tumors after administration of f-RGD-Cur via the tail vein. These results indicate that Nap-GFFYG-RGD peptide self-assembled nanofibers are a promising hydrophobic drug delivery system for targeted treatment of cancer.

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

    KAUST Repository

    Ocakoǧlu, Kasim


    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.

  14. Self-assembly patterning of organic molecules on a surface

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Minghu; Fuentes-Cabrera, Miguel; Maksymovych, Petro; Sumpter, Bobby G.; Li, Qing


    The embodiments disclosed herein include all-electron control over a chemical attachment and the subsequent self-assembly of an organic molecule into a well-ordered three-dimensional monolayer on a metal surface. The ordering or assembly of the organic molecule may be through electron excitation. Hot-electron and hot-hole excitation enables tethering of the organic molecule to a metal substrate, such as an alkyne group to a gold surface. All-electron reactions may allow a direct control over the size and shape of the self-assembly, defect structures and the reverse process of molecular disassembly from single molecular level to mesoscopic scale.

  15. Self-assembled three-dimensional chiral colloidal architecture (United States)

    Ben Zion, Matan Yah; He, Xiaojin; Maass, Corinna C.; Sha, Ruojie; Seeman, Nadrian C.; Chaikin, Paul M.


    Although stereochemistry has been a central focus of the molecular sciences since Pasteur, its province has previously been restricted to the nanometric scale. We have programmed the self-assembly of micron-sized colloidal clusters with structural information stemming from a nanometric arrangement. This was done by combining DNA nanotechnology with colloidal science. Using the functional flexibility of DNA origami in conjunction with the structural rigidity of colloidal particles, we demonstrate the parallel self-assembly of three-dimensional microconstructs, evincing highly specific geometry that includes control over position, dihedral angles, and cluster chirality.

  16. Sambot II: A self-assembly modular swarm robot (United States)

    Zhang, Yuchao; Wei, Hongxing; Yang, Bo; Jiang, Cancan


    The new generation of self-assembly modular swarm robot Sambot II, based on the original generation of self-assembly modular swarm robot Sambot, adopting laser and camera module for information collecting, is introduced in this manuscript. The visual control algorithm of Sambot II is detailed and feasibility of the algorithm is verified by the laser and camera experiments. At the end of this manuscript, autonomous docking experiments of two Sambot II robots are presented. The results of experiments are showed and analyzed to verify the feasibility of whole scheme of Sambot II.

  17. Self-Assembly of "Chalcone" Type Push-Pull Dye Molecules into Organic Single Crystalline Microribbons and Rigid Microrods for Vis/NIR Range Photonic Cavity Applications. (United States)

    Vattikunta, Radhika; Venkatakrishnarao, Dasari; Mohiddon, Mahamad Ahamad; Chandrasekar, Rajadurai


    A novel supramolecular fluorescent donor-acceptor type dye molecule, (2E,4E)-1-(2-hydroxyphenyl)-5-(pyren-1-yl)penta-2,4-dien-1-one (HPPD) self-assembles in a mixture of ethanol/chloroform through intermolecular π-π stacking (distance ca. 3.384 Å) to form J-aggregated single-crystalline microribbons displaying Fabry-Pèrot (F-P) type visible-range optical resonance. The corresponding borondifluoride dye (HPPD-BF), with a reduced HOMO-LUMO gap, self-assembles into crystalline microrods acting as an F-P type resonator in the near-infrared (NIR) range. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Supramolecular gel electrophoresis of large DNA fragments. (United States)

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


    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.

  19. Graphene controlled H- and J-stacking of perylene dyes into highly stable supramolecular nanostructures for enhanced photocurrent generation (United States)

    Gan, Shiyu; Zhong, Lijie; Engelbrekt, Christian; Zhang, Jingdong; Han, Dongxue; Ulstrup, Jens; Chi, Qijin; Niu, Li


    We report a new method for controlling H- and J-stacking in supramolecular self-assembly. Graphene nanosheets act as structure inducers to direct the self-assembly of a versatile organic dye, perylene into two distinct types of functional nanostructures, i.e. one-dimensional nanotubes via J-stacking and two-dimensional branched nanobuds through H-stacking. Graphene integrated supramolecular nanocomposites are highly stable and show significant enhancement of photocurrent generation in these two configurations of photosensing devices, i.e. solid-state optoelectronic constructs and liquid-junction solar cells.We report a new method for controlling H- and J-stacking in supramolecular self-assembly. Graphene nanosheets act as structure inducers to direct the self-assembly of a versatile organic dye, perylene into two distinct types of functional nanostructures, i.e. one-dimensional nanotubes via J-stacking and two-dimensional branched nanobuds through H-stacking. Graphene integrated supramolecular nanocomposites are highly stable and show significant enhancement of photocurrent generation in these two configurations of photosensing devices, i.e. solid-state optoelectronic constructs and liquid-junction solar cells. Electronic supplementary information (ESI) available: Material and methods, spectroscopic data, AFM and TEM images, materials functional tests and supplementary discussions. See DOI: 10.1039/c4nr02308k

  20. Self-assembled monolayers of metallosalophenes on gold

    NARCIS (Netherlands)

    Beulen, M.W.J.; van Veggel, F.C.J.M.; Reinhoudt, David


    Salophene complexes of transition metals exhibit a reversible electro- chemistry. We have synthesized salophene complexes with sulfur-containing substituents aimed at the formation of self-assembled monolayers on a gold surface. Such monolayers have interesting cation complexating properties. The

  1. Self-assembly of hydrofluorinated Janus graphene monolayer

    DEFF Research Database (Denmark)

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei


    With remarkably interesting surface activities, two-dimensional Janus materials arouse intensive interests recently in many fields. We demonstrate by molecular dynamic simulations that hydrofluorinated Janus graphene (J-GN) can self-assemble into Janus nanoscroll (J-NS) at room temperature. The van...

  2. Self-Assembly on Gold and Graphene for Molecular Electronics

    DEFF Research Database (Denmark)

    Reeler, Nini Elisabeth Abildgaard

    to take place before full coverage of the AuNPs. After full coverage the negatively charged dithiocarbamate end groups tended to repel each other leading to a stabilization of the AuNPs and clusters in the solution. An additional project concerned the fabrication of various self-assembled monolayers (SAMs...

  3. Encapsulation of gold nanoparticles into self-assembling protein nanoparticles


    Yang Yongkun; Burkhard Peter


    Abstract Background Gold nanoparticles are useful tools for biological applications due to their attractive physical and chemical properties. Their applications can be further expanded when they are functionalized with biological molecules. The biological molecules not only provide the interfaces for interactions between nanoparticles and biological environment, but also contribute their biological functions to the nanoparticles. Therefore, we used self-assembling protein nanoparticles (SAPNs...

  4. Self-assembled three-dimensional non-volatile memories

    NARCIS (Netherlands)

    Abelmann, Leon; Tas, Niels Roelof; Berenschot, Johan W.; Elwenspoek, Michael Curt


    The continuous increase in capacity of non-volatile data storage systems will lead to bit densities of one bit per atom in 2020. Beyond this point, capacity can be increased by moving into the third dimension. We propose to use self-assembly of nanosized elements, either as a loosely organised

  5. Hierarchical self-assembly of complex polyhedral microcontainers

    International Nuclear Information System (INIS)

    Filipiak, David J; Leong, Timothy G; Gracias, David H; Azam, Anum


    The concept of self-assembly of a two-dimensional (2D) template to a three-dimensional (3D) structure has been suggested as a strategy to enable highly parallel fabrication of complex, patterned microstructures. We have previously studied the surface-tension-based self-assembly of patterned, microscale polyhedral containers (cubes, square pyramids and tetrahedral frusta). In this paper, we describe the observed hierarchical self-assembly of more complex, patterned polyhedral containers in the form of regular dodecahedra and octahedra. The hierarchical design methodology, combined with the use of self-correction mechanisms, was found to greatly reduce the propagation of self-assembly error that occurs in these more complex systems. It is a highly effective way to mass-produce patterned, complex 3D structures on the microscale and could also facilitate encapsulation of cargo in a parallel and cost-effective manner. Furthermore, the behavior that we have observed may be useful in the assembly of complex systems with large numbers of components

  6. Self-Assembly of Globular Protein-Polymer Diblock Copolymers (United States)

    Thomas, C. S.; Olsen, B. D.


    The self-assembly of globular protein-polymer diblock copolymers into nanostructured phases is demonstrated as an elegant and simple method for structural control in biocatalysis or bioelectronics. In order to fundamentally investigate self-assembly in these complex block copolymer systems, a red fluorescent protein was expressed in E. coli and site-specifically conjugated to a low polydispersity poly(N-isopropyl acrylamide) (PNIPAM) block using thiol-maleimide coupling to form a well-defined model globular protein-polymer diblock. Functional protein materials are obtained by solvent evaporation and solvent annealing above and below the lower critical solution temperature of PNIPAM in order to access different pathways toward self-assembly. Small angle x-ray scattering and microscopy are used to show that the diblock forms lamellar nanostructures and to explore dependence of nanostructure formation on processing conditions. Circular dichroism and UV-vis show that a large fraction of the protein remains in its folded state after conjugation, and wide angle x-ray scattering demonstrates that diblock copolymer self-assembly changes the protein packing symmetry.

  7. Multiphonon capture processes in self-assembled quantum dots

    DEFF Research Database (Denmark)

    Magnúsdóttir, Ingibjörg; Uskov, A.; Bischoff, Svend


    We investigate capture of carriers from states in the continuous part of the energy spectrum into the discrete states of self-assembled InAs/GaAs QDs via emission of one or two phonons. We are not aware of any other investigations of two-phonon mediated capture processes in QDs, but we show that ...

  8. Covalently stabilized self-assembled chlorophyll nanorods by olefin metathesis. (United States)

    Sengupta, Sanchita; Würthner, Frank


    A new chlorophyll derivative with peripheral olefinic chains has been synthesised and its self-assembly properties have been studied, revealing formation of well-defined nanorods. These nanorods were stabilized and rigidified by olefin metathesis reaction as confirmed by spectroscopic and microscopic methods.

  9. Synthesis, characterization and self-assembly of Co 3 complexes ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 5. Synthesis, characterization and self-assembly of Co3+ complexes appended with phenol and catechol groups. Afsar Ali Deepak Bansal Rajeev Gupt. Special issue on Chemical Crystallography Volume 126 Issue 5 September 2014 pp 1535-1546 ...

  10. Self-Assembled Microwires of Terephthalic Acid and Melamine

    Directory of Open Access Journals (Sweden)

    Hong Wang


    Full Text Available Self-assembled microwires of terephthalic acid (TPA and melamine are prepared through the evaporation of water in a solution mixture of TPA and melamine. The microwires were characterized by using scanning electron microscope (SEM, attenuated total reflection infrared (ATR-IR spectra, and cross-polarized optical microscopy (CPOM. The TPA•M microwires showed semi-conductive properties.

  11. Dynamics of self-assembled cytosine nucleobases on graphene (United States)

    Saikia, Nabanita; Johnson, Floyd; Waters, Kevin; Pandey, Ravindra


    Molecular self-assembly of cytosine (C n ) bases on graphene was investigated using molecular dynamics methods. For free-standing C n bases, simulation conditions (gas versus aqueous) determine the nature of self-assembly; the bases prefer to aggregate in the gas phase and are stabilized by intermolecular H-bonds, while in the aqueous phase, the water molecules disrupt base-base interactions, which facilitate the formation of π-stacked domains. The substrate-induced effects, on the other hand, find the polarity and donor-acceptor sites of the bases to govern the assembly process. For example, in the gas phase, the assembly of C n bases on graphene displays short-range ordered linear arrays stabilized by the intermolecular H-bonds. In the aqueous phase, however, there are two distinct configurations for the C n bases assembly on graphene. For the first case corresponding to low surface coverage, the bases are dispersed on graphene and are isolated. The second configuration archetype is disordered linear arrays assembled with medium and high surface coverage. The simulation results establish the role of H-bonding, vdW π-stacking, and the influence of graphene surface towards the self-assembly. The ability to regulate the assembly into well-defined patterns can aid in the design of self-assembled nanostructures for the next-generation DNA based biosensors and nanoelectronic devices.

  12. Self-assembled monolayers on metal oxides : applications in nanotechnology

    NARCIS (Netherlands)

    Yildirim, O.


    The thesis describes the use of phosph(on)ate-based self-assembled monolayers (SAMs) to modify and pattern metal oxides. Metal oxides have interesting electronic and magnetic properties such as insulating, semiconducting, metallic, ferromagnetic etc. and SAMs can tailor the surface properties. FePt

  13. Photophysical characterization of layer-by-layer self-assembled ...

    Indian Academy of Sciences (India)

    D DEY, M N ISLAM∗, S A HUSSAIN and D BHATTACHARJEE. Department of Physics, Tripura University, Suryamaninagar 799 130, India. *Corresponding author. E-mail: md Abstract. This communication reports the photophysical characterization of self- assembled layer-by-layer (LbL) films of ...

  14. Self-assembling electroactive hydrogels for flexible display technology

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Scott L; Wong, Kok Hou; Ladouceur, Francois [School of Electrical Engineering and Telecommunications, University of NSW, Sydney, NSW, 2052 (Australia); Thordarson, Pall, E-mail: [School of Chemistry, University of NSW, Sydney, NSW, 2052 (Australia)


    We have assessed the potential of self-assembling hydrogels for use in conformal displays. The self-assembling process can be used to alter the transparency of the material to all visible light due to scattering by fibres. The reversible transition is shown to be of low energy by differential scanning calorimetry. For use in technology it is imperative that this transition is controlled electrically. We have thus synthesized novel self-assembling hydrogelator molecules which contain an electroactive group. The well-known redox couple of anthraquinone/anthrahydroquinone has been used as the hydrophobic component for a series of small molecule gelators. They are further functionalized with peptide combinations of L-phenylalanine and glycine to provide the hydrophilic group to complete 'head-tail' models of self-assembling gels. The gelation and electroactive characteristics of the series were assessed. Cyclic voltammetry shows the reversible redox cycle to be only superficially altered by functionalization. Additionally, spectroelectrochemical measurements show a reversible transparency and colour change induced by the redox process.

  15. Complex Colloidal Structures by Self-assembly in Electric Fields

    NARCIS (Netherlands)

    Vutukuri, H.R.


    The central theme of this thesis is exploiting the directed self-assembly of both isotropic and anisotropic colloidal particles to achieve the fabrication of one-, two-, and three-dimensional complex colloidal structures using external electric fields and/or a simple in situ thermal annealing

  16. Tetrahymena dynamin-related protein 6 self-assembles ...

    Indian Academy of Sciences (India)

    Usha P Kar


    Dec 30, 2017 ... readily forms high-molecular-weight self-assembled structures as determined by size exclusion chromatography and chemical ..... further by ion exchange chro- matography resulted in substantial loss of the protein without ..... sociates from nuclear envelope during starvation and early conjugation stages ...

  17. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)


    Abstract. Self-assembly provides a simple route to organise suitable organic molecules on noble metal and selected nanocluster surfaces by using monolayers of long chain organic molecules with various functionalities like –SH, –COOH, –NH2, silanes etc. These surfaces can be effectively used to build-up interesting ...

  18. Basic building units, self-assembly and crystallization in the ...

    Indian Academy of Sciences (India)

    The one-dimensional ladder appears to be the primary building unit of these structures. At one stage of the building-up process, spontaneous self-assembly of a low-dimensional structure such as the ladder seems to occur, followed by crys tallization of a two- or three-dimensional structure. Accordingly, many of the higher ...

  19. Self-assembling bilayers of palladiumthiolates in organic media

    Indian Academy of Sciences (India)


    length. There is evidence to suggest that the alkyl chains are orientationally disordered especially prior to melting. Keywords. Self-assembling bilayers; palladiumthiolates; lamellar structures. 1. Introduction. Lipid bilayers have long been recognized as being central to molecular organization. Synthetic analogues mimicking ...

  20. Extending the self-assembly of coiled-coil hybrids

    NARCIS (Netherlands)

    Robson Marsden, Hana


    Of the various biomolecular building blocks in use in nature, coiled-coil forming peptides are amongst those with the most potential as building blocks for the synthetic self-assembly of nanostructures. Native coiled coils have the ability to function in, and influence, complex systems composed of

  1. Critical Self-assembly Concentration of Bolaamphiphilic Peptides ...

    African Journals Online (AJOL)

    The study of the self-assembly properties of peptides and proteins is important for the understanding of molecular recognition processes and for the rational design of functional biomaterials. Novel bolaamphiphilic peptides and peptide hybrids incorporating non-natural aminoacids were designed around a model ...

  2. Self-assembling electroactive hydrogels for flexible display technology

    International Nuclear Information System (INIS)

    Jones, Scott L; Wong, Kok Hou; Ladouceur, Francois; Thordarson, Pall


    We have assessed the potential of self-assembling hydrogels for use in conformal displays. The self-assembling process can be used to alter the transparency of the material to all visible light due to scattering by fibres. The reversible transition is shown to be of low energy by differential scanning calorimetry. For use in technology it is imperative that this transition is controlled electrically. We have thus synthesized novel self-assembling hydrogelator molecules which contain an electroactive group. The well-known redox couple of anthraquinone/anthrahydroquinone has been used as the hydrophobic component for a series of small molecule gelators. They are further functionalized with peptide combinations of L-phenylalanine and glycine to provide the hydrophilic group to complete 'head-tail' models of self-assembling gels. The gelation and electroactive characteristics of the series were assessed. Cyclic voltammetry shows the reversible redox cycle to be only superficially altered by functionalization. Additionally, spectroelectrochemical measurements show a reversible transparency and colour change induced by the redox process.

  3. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)

    Self-assembly provides a simple route to organise suitable organic molecules on noble metal and selected nanocluster surfaces by using monolayers of long chain organic molecules with various functionalities like -SH, -COOH, -NH2, silanes etc. These surfaces can be effectively used to build-up interesting nano level ...

  4. Hydrogen-Bonded Polymer-Porphyrin Assemblies in Water: Supramolecular Structures for Light Energy Conversion. (United States)

    Kutz, Anne; Alex, Wiebke; Krieger, Anja; Gröhn, Franziska


    In this study, a new type of functional, self-assembled nanostructure formed from porphyrins and polyamidoamine dendrimers based on hydrogen bonding in an aqueous solution is presented. As the aggregates formed are promising candidates for solar-energy conversion, their photocatalytic activity is tested using the model reaction of methyl viologen reduction. The self-assembled structures show significantly increased activity as compared to unassociated porphyrins. Details of interaction forces driving the supramolecular structure formation and regulating catalytic efficiency are fundamentally discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Functionalized 2,6-bis-(2-anilinoethynyl) pyridine: Anion-mediated self-assembly and chemosensing (United States)

    Stimpson, Calden Nathaniel Carroll

    in vitro sensors for halides. This chapter concludes with recent results regarding their self-assembly on the micro-scale. This dissertation contains my previously published and co-authored work.

  6. Building polyhedra by self-assembly: theory and experiment. (United States)

    Kaplan, Ryan; Klobušický, Joseph; Pandey, Shivendra; Gracias, David H; Menon, Govind


    We investigate the utility of a mathematical framework based on discrete geometry to model biological and synthetic self-assembly. Our primary biological example is the self-assembly of icosahedral viruses; our synthetic example is surface-tension-driven self-folding polyhedra. In both instances, the process of self-assembly is modeled by decomposing the polyhedron into a set of partially formed intermediate states. The set of all intermediates is called the configuration space, pathways of assembly are modeled as paths in the configuration space, and the kinetics and yield of assembly are modeled by rate equations, Markov chains, or cost functions on the configuration space. We review an interesting interplay between biological function and mathematical structure in viruses in light of this framework. We discuss in particular: (i) tiling theory as a coarse-grained description of all-atom models; (ii) the building game-a growth model for the formation of polyhedra; and (iii) the application of these models to the self-assembly of the bacteriophage MS2. We then use a similar framework to model self-folding polyhedra. We use a discrete folding algorithm to compute a configuration space that idealizes surface-tension-driven self-folding and analyze pathways of assembly and dominant intermediates. These computations are then compared with experimental observations of a self-folding dodecahedron with side 300 μm. In both models, despite a combinatorial explosion in the size of the configuration space, a few pathways and intermediates dominate self-assembly. For self-folding polyhedra, the dominant intermediates have fewer degrees of freedom than comparable intermediates, and are thus more rigid. The concentration of assembly pathways on a few intermediates with distinguished geometric properties is biologically and physically important, and suggests deeper mathematical structure.

  7. The dynamic self-assembly of peptides into nanostructures (United States)

    Perumal, Shiamalee

    Progress in the new and interdisciplinary field of biophysics holds great promise for new understandings and practical applications. Applying the methods of physics and chemistry to biological systems provides us with a valuable insight into the fundamental processes of life. In this study, the advanced physical techniques of neutron reflection and small-angle neutron scattering are applied to investigate the dynamic self-assembly of peptide systems at the solid-liquid and air-liquid interface, and in bulk solution. The characterisation of various peptides and an in-depth evaluation of their interfacial structural conformations and their outstanding ability to form well-defined nanostructures in aqueous solution will be presented in this thesis. The key adsorption factors of peptide concentration, solution pH, temperature, salt addition, and time were found to have imperative and varying effects on these self-assembled peptide structures. The hydrophobic nature of certain ?-sheet forming peptides resulted in an adsorption where the peptides were predominantly afloat on the surface of water. Point mutations of four other analogously designed peptides were reported to self-assemble into either ?-helix or ?-sheet secondary structures in order of increasing hydrophobicity. Short ionic peptides that had the potential to solubilise and stabilise membrane proteins were also discovered to self-assemble into aqueous solution to form a co-existing mixture of nanotube and nanovesicle structures of varying diversity with an unwavering bilayer wall thickness also consistent with interfacial structural parameters. These self-assembled peptide conformations were of course highly dependent on solution conditions and on the physical properties of the interface.

  8. Self-assembling peptide hydrogels immobilized on silicon surfaces

    International Nuclear Information System (INIS)

    Franchi, Stefano; Battocchio, Chiara; Galluzzi, Martina; Navisse, Emanuele; Zamuner, Annj; Dettin, Monica; Iucci, Giovanna


    The hydrogels of self-assembling ionic complementary peptides have collected in the scientific community increasing consensus as mimetics of the extracellular matrix that can offer 3D supports for cell growth or be vehicles for the delivery of stem cells or drugs. Such scaffolds have also been proposed as bone substitutes for small defects as they promote beneficial effects on human osteoblasts. In this context, our research deals with the introduction of a layer of self-assembling peptides on a silicon surface by covalent anchoring and subsequent physisorption. In this work, we present a spectroscopic investigation of the proposed bioactive scaffolds, carried out by surface-sensitive spectroscopic techniques such as XPS (X-ray photoelectron spectroscopy) and RAIRS (Reflection Absorption Infrared Spectroscopy) and by state-of-the-art synchrotron radiation methodologies such as angle dependent NEXAFS (Near Edge X-ray Absorption Fine Structure). XPS studies confirmed the change in the surface composition in agreement with the proposed enrichments, and led to assess the self-assembling peptide chemical stability. NEXAFS spectra, collected in angular dependent mode at the N K-edge, allowed to investigate the self-assembling behavior of the macromolecules, as well as to determine their molecular orientation on the substrate. Furthermore, Infrared Spectroscopy measurements demonstrated that the peptide maintains its secondary structure (β-sheet anti-parallel) after deposition on the silicon surface. The complementary information acquired by means of XPS, NEXAFS and RAIRS lead to hypothesize a “layer-by-layer” arrangement of the immobilized peptides, giving rise to an ordered 3D nanostructure. - Highlights: • A self-assembling peptide (SAP) was covalently immobilized of on a flat silicon surface. • A physisorbed SAP layer was grown on top of the covalently immobilized peptide layer. • Molecular order and orientation of the peptide overlayer on the flat silicon

  9. Glucosamine-Based Supramolecular Nanotubes for Human Mesenchymal Cell Therapy. (United States)

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


    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.

  10. Construction Of Micro- And Nanoporous Hydrogels Via Designed Diblock Copolypeptide Self-Assembly And Oligopeptide Self-Assembly (United States)

    Pochan, Darrin; Deming, Tim; Schneider, Joel


    The design, synthesis, and self-assembly of polypeptides as synthetic materials that possess the ability to aggregate and/or “fold” into specifically defined, a priori designed, functional nanostructures is being pursued via two avenues. First, synthetic block copolypeptides will be discussed that are observed to form novel hydrogels with structural and biological properties tailorable by the choice of amino acid (and consequent secondary structure) in the respective blocks. Specifically ionic, amphiphilic diblocks have been designed for tissue engineering hydrogels on assembly in aqueous solution. A bicontinuous morphology is observed at both the nanoscale and microscale. Second, de novo designed oligopeptides that undergo specific folding events triggered by pH, preceding or concurrent with self-assembly, will be discussed. Specifically, the ability of small (20 amino acid residues) molecules to produce relatively very large (approximately 100 micron diameter) spheres and tubes in additino to hydrogels via a hierarchical self-assembly process will be discussed. The assembled oligopeptides have the added design attribute of being responsive to pH, unfolding/disassembling at pH below 6. Both classes of peptide-based self-assembled materials were characterized via laser scanning confocal and cryotransmission electron microscopy combined with small angle neutron and x-ray scattering.

  11. Covalent Tethering and Residues with Bulky Hydrophobic Side Chains Enable Self-Assembly of Distinct Amyloid Structures. (United States)

    Ruiz, Jérémy; Boehringer, Régis; Grogg, Marcel; Raya, Jésus; Schirer, Alicia; Crucifix, Corinne; Hellwig, Petra; Schultz, Patrick; Torbeev, Vladimir


    Polymorphism is a common property of amyloid fibers that complicates their detailed structural and functional studies. Here we report experiments illustrating the chemical principles that enable the formation of amyloid polymorphs with distinct stoichiometric composition. Using appropriate covalent tethering we programmed self-assembly of a model peptide corresponding to the [20-41] fragment of human β2-microglobulin into fibers with either trimeric or dimeric amyloid cores. Using a set of biophysical and biochemical methods we demonstrated their distinct structural, morphological, and templating properties. Furthermore, we showed that supramolecular approaches in which the peptide is modified with bulky substituents can also be applied to modulate the formation of different fiber polymorphs. Such strategies, when applied to disease-related peptides and proteins, will greatly help in the evaluation of the biological properties of structurally distinct amyloids. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Understanding gold-thiolate cluster emission from self-assembled monolayers upon kiloelectronvolt ion bombardment. (United States)

    Arezki, B; Delcorte, A; Garrison, B J; Bertrand, P


    This article focuses on the emission of organometallic clusters upon kiloelectronvolt ion bombardment of self-assembled monolayers. It is particularly relevant for the elucidation of the physical processes underlying secondary ion mass spectrometry (SIMS). The experimental system, an overlayer of octanethiols on gold, was modeled by classical molecular dynamics, using a hydrocarbon potential involving bonding and nonbonding interactions (AIREBO). To validate the model, the calculated mass and energy distributions of sputtered atoms and molecules were compared to experimental data. Our key finding concerns the emission mechanism of large clusters of the form MxAuy up to M6Au5 (where M is the thiolate molecule), which were not observed under sub-kiloelectronvolt projectile bombardment. Statistically, they are predominantly formed in high-yield events, where many atoms, fragments, and (supra)molecular species are desorbed from the surface. From the microscopic viewpoint, these high-yield events mostly stem from the confinement of the projectile and recoil atom energies in a finite microvolume of the sample surface. As a result of the high local energy density, molecular aggregates desorb from an overheated liquidlike region surrounding the impact point of the projectile.

  13. Self-assembly of Renewable  Nano-sized Triterpenoids. (United States)

    Bag, Braja Gopal; Majumdar, Rakhi


    Studies on plant metabolites have gained renewed interest in recent years because these can serve as renewable chemicals for the development of a sustainable society. Among various plant secondary metabolites, terpenoids constitute the major component and triterpenoids are the 30C subset of it. In recent years, triterpenoids have drawn the attention of scientific community due to many of its potential and realized applications in medicine, drug delivery, thermochromic materials, pollutant capture, catalysis, liquid crystals, etc. In this personal review, we have discussed our computational results carried out on sixty representative naturally occurring triterpenoids demonstrating that all the triterpenoids are renewable functional nano-entities. Study of the self-assembly of several triterpenoids such as betulin, betulinic acid, oleanolic acid, glycyrrhetinic acid and arjunolic acid and their derivatives in different liquids have also been discussed. Moreover, the utilization of the resulting supramolecular architectures such as vesicles, spheres, flowers and fibrillar networks of nano- to micrometer dimensions and gels have also been discussed in the perspective of green, renewable and nanos. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Self-Assembly of Silver Metal Clusters of Small Atomicity on Cyclic Peptide Nanotubes. (United States)

    Cuerva, Miguel; García-Fandiño, Rebeca; Vázquez-Vázquez, Carlos; López-Quintela, M Arturo; Montenegro, Javier; Granja, Juan R


    Subnanometric noble metal clusters, composed by only a few atoms, behave like molecular entities and display magnetic, luminescent and catalytic activities. However, noncovalent interactions of molecular metal clusters, lacking of any ligand or surfactant, have not been seen at work. Theoretically attractive and experimentally discernible, van der Waals forces and noncovalent interactions at the metal/organic interfaces will be crucial to understand and develop the next generation of hybrid nanomaterials. Here, we present experimental and theoretical evidence of noncovalent interactions between subnanometric metal (0) silver clusters and aromatic rings and their application in the preparation of 1D self-assembled hybrid architectures with ditopic peptide nanotubes. Atomic force microscopy, fluorescence experiments, circular dichroism and computational simulations verified the occurrence of these interactions in the clean and mild formation of a novel peptide nanotube and metal cluster hybrid material. The findings reported here confirmed the sensitivity of silver metal clusters of small atomicity toward noncovalent interactions, a concept that could find multiple applications in nanotechnology. We conclude that induced supramolecular forces are optimal candidates for the precise spatial positioning and properties modulation of molecular metal clusters. The reported results herein outline and generalize the possibilities that noncovalent interactions will have in this emerging field.

  15. Lamellar Microdomains of Block-Copolymer-Based Ionic Supramolecules Exhibiting a Hierarchical Self-Assembly

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Almdal, Kristoffer; Zhu, Kaizheng


    (Cn; n = 8, 12, and 16) trimethylammonium counterions (i.e., side chains) at various ion (pair) fractions X [i.e., counterion/side-chain grafting density; X = number of alkyl counterions (i.e., side chains) per acidic group of the parent PMAA block] these L-b-AC ionic supramolecules exhibit...... a spherical-in-lamellar hierarchical self-assembly. For these systems, (1) the effective Flory-Huggins interaction parameter between L- and AC-blocks chi'(Cn/x) was extracted, and (2) analysis of the lamellar microdomains showed that when there is an increase in X, alkyl counterion (i.e., side chain) length l......Based on a parent diblock copolymer of poly(styrene)-b-poly(methacrylic acid), PS-b-PMAA, linear-b-amphiphilic comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] are synthesized in which the poly(methacrylate) backbone of the ionic supramolecular AC-block is neutralized by alkyl...

  16. Liquid-crystal nanoscience: an emerging avenue of soft self-assembly. (United States)

    Bisoyi, Hari Krishna; Kumar, Sandeep


    Liquid crystals are finding increasing applications in a wide variety of fields including liquid-crystal display technology, materials science, bioscience, etc., apart from acting as prototype self-organizable supramolecular soft materials and tunable solvents. Recently, keeping in pace with topical science, liquid crystals have entered into the fascinating domains of nanoscience and nanotechnology. This tutorial review describes the recent and significant developments in liquid-crystal nanoscience embracing contemporary nanomaterials such as nanoparticles, nanorods, nanotubes, nanoplatelets, etc. The dispersion of zero-, one- and two-dimensional nanomaterials in liquid crystals for the enhancement of properties, liquid-crystalline phase behavior of nanomaterials themselves, self-assembly and alignment of nanomaterials in liquid-crystalline media, and the synthesis of nanomaterials by using liquid crystals as 'templates' or 'precursors' have been highlighted and discussed. It is almost certain that the 'fourth state of matter' will play more prevalent roles in nanoscience and nanotechnology in the near future. Moreover, liquid-crystal nanoscience reflects itself as a beautiful demonstration of the contemporary theme "crossing the borders: science without boundaries".

  17. Self-assembly of molecular dumbbells into organized bundles with tunable size. (United States)

    Lee, Myongsoo; Jeong, Yang-Seung; Cho, Byoung-Ki; Oh, Nam-Keun; Zin, Wang-Cheol


    Dumbbell-shaped molecules consisting of three biphenyls connected through vinyl linkages as a conjugated rod segment and aliphatic polyether dendritic wedges with different cross-sections (i.e., dibranch (1), tetrabranch (2) and hexabranch (3)) were synthesized and characterized. The molecular dumbbells self-assemble into discrete bundles that organize into three-dimensional superlattices. Molecule 1, based on a dibranched dendritic wedge, organizes into primitive monoclinic-crystalline and body-centered, tetragonal liquid crystalline structures, while molecules 2 and 3, based on tetra- and hexabranched dendritic wedges, respectively, form only body-centered, tetragonal liquid crystalline structures. X-ray diffraction experiments and density measurements showed that the rod-bundle cross-sectional area decreases with increasing cross-section of the dendritic wedges. The influences of supramolecular structure on the bulk-state optical properties were investigated by measuring the UV/Vis absorption and steady state fluorescence spectroscopies. As the cross-section of the dendritic wedge of the molecule increases, the absorption and emission maxima shift to higher energy. This can be attributed to a quantum size effect of the three-dimensionally confined nanostructure.

  18. Self-assembling of calcium salt of the new DNA base 5-carboxylcytosine (United States)

    Irrera, Simona; Ruiz-Hernandez, Sergio E.; Reggente, Melania; Passeri, Daniele; Natali, Marco; Gala, Fabrizio; Zollo, Giuseppe; Rossi, Marco; Portalone, Gustavo


    Supramolecular architectures involving DNA bases can have a strong impact in several fields such as nanomedicine and nanodevice manufacturing. To date, in addition to the four canonical nucleobases (adenine, thymine, guanine and cytosine), four other forms of cytosine modified at the 5 position have been identified in DNA. Among these four new cytosine derivatives, 5-carboxylcytosine has been recently discovered in mammalian stem cell DNA, and proposed as the final product of the oxidative epigenetic demethylation pathway on the 5 position of cytosine. In this work, a calcium salt of 5-carboxylcytosine has been synthesized and deposited on graphite surface, where it forms self-assembled features as long range monolayers and up to one micron long filaments. These structures have been analyzed in details combining different theoretical and experimental approaches: X-ray single-crystal diffraction data were used to simulate the molecule-graphite interaction, first using molecular dynamics and then refining the results using density functional theory (DFT); finally, data obtained with DFT were used to rationalize atomic force microscopy (AFM) results.

  19. Zinc-Triggered Hydrogelation of Self-assembled Small Molecules to Inhibit Bacterial Growth (United States)

    Xu, Chao; Cai, Yanbin; Ren, Chunhua; Gao, Jie; Hao, Jihui


    There is a significant need to develop antibacterial materials that could be applied locally and directly to the places surrounded by large amount of bacteria, in order to address the problems of bacterial antibiotic-resistance or irreversible biofilm formation. Hydrogels are thought to be suitable candidates due to their versatile applications in biomedical field. Among them, small molecular hydrogels have been paid lots of attention because they are easy to design and fabricate and often sensitive to external stimuli. Meanwhile, the antibacterial activity of metal ions are attracting more and more attention because resistance to them are not yet found within bacteria. We therefore designed the zinc ion binding peptide of Nap-GFFYGGGHGRGD, who can self-assemble into hydrogels after binds Zn2+ and inhibit the growth of bacteria due to the excellent antibacterial activity of Zn2+. Upon the addition of zinc ions, solutions containing Nap-GFFYGGGHGRGD transformed into supramolecular hydrogels composed of network of long nano-fibers. Bacterial tests revealed an antibacterial effect of the zinc triggered hydrogels on E. coli. The studied small molecular hydrogel shows great potential in locally addressing bacterial infections.

  20. Protein self-assembly following in situ expression in artificial and mammalian cells. (United States)

    Migas, Urszula M; Quinn, Michelle K; McManus, Jennifer J


    The self-assembly of proteins has been widely studied in controlled in vitro conditions, and more recently in biological environments. The self-assembly of proteins in biology can be a feature of the pathogenesis of protein condensation disease, or can occur during normal physiological function, for example during the formation of intracellular non-membrane bound organelles. To determine the mechanisms for the assembly process fully, controlled in vitro experiments using purified protein solutions are often required. However, making direct connections between insights gathered from controlled experiments and those in complex biological environments remains a challenge. Using the P23T mutant of human γD-crystallin, a protein associated with congenital cataract, we have demonstrated that the equilibrium solubility boundary and solution behavior measured using phase diagrams of purified protein solutions is consistent with the assembly of the protein expressed in cell-free expression medium in artificial cells (without fluorescent labelling) and condensates formed in mammalian cells, thereby directly connecting in vitro measurements with those performed under physiological conditions.

  1. Self-assembly of nanoparticles into biomimetic capsid-like nanoshells (United States)

    Yang, Ming; Chan, Henry; Zhao, Gongpu; Bahng, Joong Hwan; Zhang, Peijun; Král, Petr; Kotov, Nicholas A.


    Nanoscale compartments are one of the foundational elements of living systems. Capsids, carboxysomes, exosomes, vacuoles and other nanoshells easily self-assemble from biomolecules such as lipids or proteins, but not from inorganic nanomaterials because of difficulties with the replication of spherical tiling. Here we show that stabilizer-free polydispersed inorganic nanoparticles (NPs) can spontaneously organize into porous nanoshells. The association of water-soluble CdS NPs into self-limited spherical capsules is the result of scale-modified electrostatic, dispersion and other colloidal forces. They cannot be accurately described by the Derjaguin-Landau-Vervey-Overbeek theory, whereas molecular-dynamics simulations with combined atomistic and coarse-grained description of NPs reveal the emergence of nanoshells and some of their stabilization mechanisms. Morphology of the simulated assemblies formed under different conditions matched nearly perfectly the transmission electron microscopy tomography data. This study bridges the gap between biological and inorganic self-assembling nanosystems and conceptualizes a new pathway to spontaneous compartmentalization for a wide range of inorganic NPs including those existing on prebiotic Earth.

  2. Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

    International Nuclear Information System (INIS)

    Zheng, Yijun; Cui, Jiaxi; Ikeda, Taichi


    Graphical abstract: - Highlights: • Electrochemically-active self-assembled monolayers with phenyl-capped bithiophene were prepared. • Post-functionalization method based on click chemistry solved the solubility issue of phenyl-capped thiophene alkanethiol. • The capture and release of the counter anions during the redox reaction were detectable by E-QCM. - Abstract: We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N 3 -SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N 3 -SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10 −10 mol cm −2 and 4.6 ± 0.3 × 10 −10 mol cm −2 , respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N 3 -SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

  3. Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Yijun; Cui, Jiaxi [Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, Mainz 55128 (Germany); Ikeda, Taichi, E-mail: [Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, Mainz 55128 (Germany); Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044 (Japan)


    Graphical abstract: - Highlights: • Electrochemically-active self-assembled monolayers with phenyl-capped bithiophene were prepared. • Post-functionalization method based on click chemistry solved the solubility issue of phenyl-capped thiophene alkanethiol. • The capture and release of the counter anions during the redox reaction were detectable by E-QCM. - Abstract: We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N{sub 3}-SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N{sub 3}-SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10{sup −10} mol cm{sup −2} and 4.6 ± 0.3 × 10{sup −10} mol cm{sup −2}, respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N{sub 3}-SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

  4. Molecular Design of Bioinspired Nanostructures for Biomedical Applications: Synthesis, Self-Assembly and Functional Properties (United States)

    Xu, Hesheng Victor; Zheng, Xin Ting; Mok, Beverly Yin Leng; Ibrahim, Salwa Ali; Yu, Yong; Tan, Yen Nee


    Biomolecules are the nanoscale building blocks of cells, which play multifaceted roles in the critical biological processes such as biomineralization in a living organism. In these processes, the biological molecules such as protein and nucleic acids use their exclusive biorecognition properties enabled from their unique chemical composition, shape and function to initiate a cascade of cellular events. The exceptional features of these biomolecules, coupled with the recent advancement in nanotechnology, have led to the emergence of a new research field that focuses on the molecular design of bioinspired nanostructures that inherit the extraordinary function of natural biomaterials. These “bioinspired” nanostructures could be formulated by biomimetic approaches through either self-assembling of biomolecules or acting as a biomolecular template/precursor to direct the synthesis of nanocomposite. In either situation, the resulting nanomaterials exhibit phenomenal biocompatibility, superb aqueous solubility and excellent colloidal stability, branding them exceptionally desirable for both in vitro and in vivo biomedical applications. In this review, we will present the recent developments in the preparation of “bioinspired” nanostructures through biomimetic self-assembly and biotemplating synthesis, as well as highlight their functional properties and potential applications in biomedical diagnostics and therapeutic delivery. Lastly, we will conclude this topic with some personal perspective on the challenges and future outlooks of the “bioinspired” nanostructures for nanomedicine.

  5. Self-assembly of gibberellic amide assemblies and their applications in the growth and fabrication of ordered gold nanoparticles

    International Nuclear Information System (INIS)

    Smoak, Evan M; Carlo, Andrew D; Fowles, Catherine C; Banerjee, Ipsita A


    Gibberellins are a group of naturally occurring diterpenoid based phytohormones that play a vital role in plant growth and development. In this work, we have studied the self-assembly of gibberellic acid, a phytohormone, which belongs to the family of gibberellins, and designed amide derivatives of gibberellic acid (GA 3 ) for the facile, green synthesis of gold nanoparticles. It was found that the derivatives self-assembled into nanofibers and nanoribbons in aqueous solutions at varying pH. Further, upon incubation with tetrachloroaurate, the self-assembled GA 3 -amide derivatives efficiently nucleated and formed gold nanoparticles when heated to 60 deg. C. Energy dispersive x-ray spectroscopy, transmission electron microscopy and scanning electron microscopy analyses revealed that uniform coatings of gold nanoparticles in the 10-20 nm range were obtained at low pH on the nanowire surfaces without the assistance of additional reducing agents. This simple method for the development of morphology controlled gold nanoparticles using a plant hormone derivative opens doors for a new class of plant biomaterials which can efficiently yield gold nanoparticles in an environmentally friendly manner. The gold encrusted nanowires formed using biomimetic methods may lead on to the formation of conductive nanowires, which may be useful for a wide range of applications such as in optoelectronics and sensors. Further, the spontaneous formation of highly organized nanostructures obtained from plant phytohormone derivatives such as gibberellic acid is of particular interest as it might help in further understanding the supramolecular assembly mechanism of more highly organized biological structures.

  6. Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process (United States)

    Miao, Xinrui; Li, Jinxing; Zha, Bao; Miao, Kai; Dong, Meiqiu; Wu, Juntian; Deng, Wenli


    The concentration-dependent self-assembly of iodine substituted thienophenanthrene derivative (5,10-DITD) is investigated at the 1-octanic acid/graphite interface using scanning tunneling microscopy. Three kinds of chiral arrangement and transition of 2D molecular assembly mainly driven by halogen bonding is clearly revealed. At high concentration the molecules self-assembled into a honeycomb-like chiral network. Except for the interchain van der Waals forces, this pattern is stabilized by intermolecular continuous Cdbnd O⋯I⋯S halogen bonds in each zigzag line. At moderate concentration, a chiral kite-like nanoarchitecture are observed, in which the Cdbnd O⋯I⋯S and I⋯Odbnd C halogen bonds, along with the molecule-solvent Cdbnd O⋯I⋯H halogen bonds are the dominated forces to determine the structural formation. At low concentration, the molecules form a chiral cyclic network resulting from the solvent coadsorption mainly by molecule-molecule Cdbnd O⋯I⋯S halogen bonds and molecule-solvent Cdbnd O⋯I⋯H halogen bonds. The density of molecular packing becomes lower with the decreasing of the solution concentration. The solution-concentration dependent self-assembly of thienophenanthrene derivative with iodine and ester chain moieties reveals that the type of intermolecular halogen bond and the number of the co-adsorbing 1-octanic acids by molecule-solvent Cdbnd O⋯I⋯H halogen bonds determine the formation and transformation of chirality. This research emphasizes the role of different types of halogen (I) bonds in the controllable supramolecular structures and provides an approach for the fabrication of chirality.

  7. Formation of active inclusion bodies induced by hydrophobic self-assembling peptide GFIL8. (United States)

    Wang, Xu; Zhou, Bihong; Hu, Weike; Zhao, Qing; Lin, Zhanglin


    In the last few decades, several groups have observed that proteins expressed as inclusion bodies (IBs) in bacteria could still be biologically active when terminally fused to an appropriate aggregation-prone partner such as pyruvate oxidase from Paenibacillus polymyxa (PoxB). More recently, we have demonstrated that three amphipathic self-assembling peptides, an alpha helical peptide 18A, a beta-strand peptide ELK16, and a surfactant-like peptide L6KD, have properties that induce target proteins into active IBs. We have developed an efficient protein expression and purification approach for these active IBs by introducing a self-cleavable intein molecule. In this study, the self-assembling peptide GFIL8 (GFILGFIL) with only hydrophobic residues was analyzed, and this peptide effectively induced the formation of cytoplasmic IBs in Escherichia coli when terminally attached to lipase A and amadoriase II. The protein aggregates in cells were confirmed by transmission electron microscopy analysis and retained ~50% of their specific activities relative to the native counterparts. We constructed an expression and separation coupled tag (ESCT) by incorporating an intein molecule, the Mxe GyrA intein. Soluble target proteins were successfully released from active IBs upon cleavage of the intein between the GFIL8 tag and the target protein, which was mediated by dithiothreitol. A variant of GFIL8, GFIL16 (GFILGFILGFILGFIL), improved the ESCT scheme by efficiently eliminating interference from the soluble intein-GFIL8 molecule. The yields of target proteins at the laboratory scale were 3.0-7.5 μg/mg wet cell pellet, which is comparable to the yields from similar ESCT constructs using 18A, ELK16, or the elastin-like peptide tag scheme. The all-hydrophobic self-assembling peptide GFIL8 induced the formation of active IBs in E. coli when terminally attached to target proteins. GFIL8 and its variant GFIL16 can act as a "pull-down" tag to produce purified soluble proteins with

  8. Physics and engineering of peptide supramolecular nanostructures. (United States)

    Handelman, Amir; Beker, Peter; Amdursky, Nadav; Rosenman, Gil


    The emerging "bottom-up" nanotechnology reveals a new field of bioinspired nanomaterials composed of chemically synthesized biomolecules. They are formed from elementary constituents in supramolecular structures by the use of a developed nature self-assembly mechanism. The focus of this perspective paper is on intrinsic fundamental physical properties of bioinspired peptide nanostructures and their small building units linked by weak noncovalent bonds. The observed exceptional optical properties indicate a phenomenon of quantum confinement in these supramolecular structures, which originates from nanoscale size of their elementary building blocks. The dimensionality of the confinement gives insight into intrinsic packing of peptide supramolecular nanomaterials. QC regions, revealed in bioinspired nanostructures, were found by us in amyloid fibrils formed from insulin protein. We describe ferroelectric and related properties found at the nanoscale based on original crystalline asymmetry of the nanoscale building blocks, packing these structures. In this context, we reveal a classic solid state physics phenomenon such as reconstructive phase transition observed in bioorganic peptide nanotubes. This irreversible phase transformation leads to drastic reshaping of their quantum structure from quantum dots to quantum wells, which is followed by variation of their space group symmetry from asymmetric to symmetric. We show that the supramolecular origin of these bioinspired nanomaterials provides them a unique chance to be disassembled into elementary building block peptide nanodots of 1-2 nm size possessing unique electronic, optical and ferroelectric properties. These multifunctional nanounits could lead to a new future step in nanotechnology and nanoscale advanced devices in the fields of nanophotonics, nanobiomedicine, nanobiopiezotronics, etc. This journal is © the Owner Societies 2012

  9. A Case Study of the Likes and Dislikes of DNA and RNA in Self-Assembly. (United States)

    Zuo, Hua; Wu, Siyu; Li, Mo; Li, Yulin; Jiang, Wen; Mao, Chengde


    Programmed self-assembly of nucleic acids (DNA and RNA) is an active research area as it promises a general approach for nanoconstruction. Whereas DNA self-assembly has been extensively studied, RNA self-assembly lags much behind. One strategy to boost RNA self-assembly is to adapt the methods of DNA self-assembly for RNA self-assembly because of the chemical and structural similarities of DNA and RNA. However, these two types of molecules are still significantly different. To enable the rational design of RNA self-assembly, a thorough examination of their likes and dislikes in programmed self-assembly is needed. The current work begins to address this task. It was found that similar, two-stranded motifs of RNA and DNA lead to similar, but clearly different nanostructures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. The self-assembling process and applications in tissue engineering (United States)

    Lee, Jennifer K.; Link, Jarrett M.; Hu, Jerry C. Y.; Athanasiou, Kyriacos A.


    Tissue engineering strives to create neotissues capable of restoring function. Scaffold-free technologies have emerged that can recapitulate native tissue function without the use of an exogenous scaffold. This chapter will survey, in particular, the self-assembling and self-organization processes as scaffold-free techniques. Characteristics and benefits of each process are described, and key examples of tissues created using these scaffold-free processes are examined to provide guidance for future tissue engineering developments. This chapter aims to explore the potential of self-assembly and self-organization scaffold-free approaches, detailing the recent progress in the in vitro tissue engineering of biomimetic tissues with these methods, toward generating functional tissue replacements. PMID:28348174

  11. Molecular Gels Materials with Self-Assembled Fibrillar Networks

    CERN Document Server

    Weiss, Richard G


    Molecular gels and fibrillar networks – a comprehensive guide to experiment and theory Molecular Gels: Materials with Self-Assembled Fibrillar Networks provides a comprehensive treatise on gelators, especially low molecular-mass gelators (LMOGs), and the properties of their gels. The structures and modes of formation of the self-assembled fibrillar networks (SAFINs) that immobilize the liquid components of the gels are discussed experimentally and theoretically. The spectroscopic, rheological, and structural features of the different classes of LMOGs are also presented. Many examples of the application of the principal analytical techniques for investigation of molecular gels (including SANS, SAXS, WAXS, UV-vis absorption, fluorescence and CD spectroscopies, scanning electron, transmission electron and optical microscopies, and molecular modeling) are presented didactically and in-depth, as are several of the theories of the stages of aggregation of individual LMOG molecules leading to SAFINs. Several actua...

  12. Self-assembling enzymes and the origins of the cytoskeleton (United States)

    Barry, Rachael; Gitai, Zemer


    The bacterial cytoskeleton is composed of a complex and diverse group of proteins that self-assemble into linear filaments. These filaments support and organize cellular architecture and provide a dynamic network controlling transport and localization within the cell. Here, we review recent discoveries related to a newly appreciated class of self-assembling proteins that expand our view of the bacterial cytoskeleton and provide potential explanations for its evolutionary origins. Specifically, several types of metabolic enzymes can form structures similar to established cytoskeletal filaments and, in some cases, these structures have been repurposed for structural uses independent of their normal role. The behaviors of these enzymes suggest that some modern cytoskeletal proteins may have evolved from dual-role proteins with catalytic and structural functions. PMID:22014508

  13. Synthesis and Self-Assembly of Triangulenium Salts

    DEFF Research Database (Denmark)

    Shi, Dong

    This thesis describes the design and synthesis of asymmetrically substituted amphiphilic tis(dialkylamino)trioxiatriangulenium (ATOTA+) salts with different counter ions. Attention was focused on exploring the assembling properties of the ATOTA+ salts in aqueous media. A direct vortexing......-processed self-assembling method was developed to make aggregates with uniform morphologies and excellent stabilities in an equilibrium state either with pure ATOTA+ salts or with mixed systems of ATOTA+ salts and lipid molecules in aqueous media. Special emphasis was given to effects of the counterions......-assembly and triangulenium salts. Chapters 3 to 6 are mainly focused on the synthesis and self-assembly of trioxatriangulenium salts in aqueous media. In particular, chapter 3 reports a direct selfassembly of a synthetic triangulenium salt mixed with DMPC lipid (5/95 by molar ratio) to make mono disperse bilayer vesicles...

  14. Environmental and Sensing Applications of Molecular Self-Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Fryxell, Glen E.; Addleman, Raymond S.; Mattigod, Shas V.; Lin, Yuehe; Zemanian, Thomas S.; Wu, Hong; Birnbaum, Jerome C.; Liu, J.; Feng, X.


    In the last decade we have witnessed many exciting new discoveries in the ability to manipulate and measure matter at the nanometer scale. Honeycombed pores structures, spheres, icosahedra, nanotubes and nanorods, self-assembled structural hierarchies; the esthetics of the nanometer regime offers Nature’s elegance in its purest form. Understanding the driving forces behind these shapes and the self-assembly processes provides key understanding for this chemistry to be exploited for positive impact on our daily lives. For this to take place, we must not only understand how the nanoscopic structures impact the structural and chemical properties of these novel new materials, but we must also understand the critical problems that we face today and how these nanoscopic properties can be tailored to address these specific needs and critical problems.

  15. Thermomechanical Response of Self-Assembled Nanoparticle Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yifan [Department; James; Chan, Henry [Center; Narayanan, Badri [Center; McBride, Sean P. [Department; Sankaranarayanan, Subramanian K. R. S. [Center; Lin, Xiao-Min [Center; Jaeger, Heinrich M. [Department; James


    Monolayers composed of colloidal nanoparticles, with a thickness of less than 10 nm, have remarkable mechanical moduli and can suspend over micrometer-sized holes to form free-standing membranes. In this paper, we discuss experiment's and coarse-grained molecular dynamics simulations characterizing the thermomechanical properties of these self-assembled nanoparticle membranes. These membranes remain strong and resilient up to temperatures much higher than previous simulation predictions and exhibit an unexpected hysteretic behavior during the first heating cooling cycle. We show this hysteretic behavior can be explained by an asymmetric ligand configuration from the self assembly process and can be controlled by changing the ligand coverage or cross-linking the ligand molecules. Finally, we show the screening effect of water molecules on the ligand interactions can strongly affect the moduli and thermomechanical behavior.

  16. Numerical approach on dynamic self-assembly of colloidal particles (United States)

    Ibrahimi, Muhamet; Ilday, Serim; Makey, Ghaith; Pavlov, Ihor; Yavuz, Özgàn; Gulseren, Oguz; Ilday, Fatih Omer

    Far from equilibrium systems of artificial ensembles are crucial for understanding many intelligent features in self-organized natural systems. However, the lack of established theory underlies a need for numerical implementations. Inspired by a novel work, we simulate a solution-suspended colloidal system that dynamically self assembles due to convective forces generated in the solvent when heated by a laser. In order to incorporate with random fluctuations of particles and continuously changing flow, we exploit a random-walk based Brownian motion model and a fluid dynamics solver prepared for games, respectively. Simulation results manage to fit to experiments and show many quantitative features of a non equilibrium dynamic self assembly, including phase space compression and an ensemble-energy input feedback loop.

  17. DNA-Based Self-Assembly of Fluorescent Nanodiamonds. (United States)

    Zhang, Tao; Neumann, Andre; Lindlau, Jessica; Wu, Yuzhou; Pramanik, Goutam; Naydenov, Boris; Jelezko, Fedor; Schüder, Florian; Huber, Sebastian; Huber, Marinus; Stehr, Florian; Högele, Alexander; Weil, Tanja; Liedl, Tim


    As a step toward deterministic and scalable assembly of ordered spin arrays we here demonstrate a bottom-up approach to position fluorescent nanodiamonds (NDs) with nanometer precision on DNA origami structures. We have realized a reliable and broadly applicable surface modification strategy that results in DNA-functionalized and perfectly dispersed NDs that were then self-assembled in predefined geometries. With optical studies we show that the fluorescence properties of the nitrogen-vacancy color centers in NDs are preserved during surface modification and DNA assembly. As this method allows the nanoscale arrangement of fluorescent NDs together with other optically active components in complex geometries, applications based on self-assembled spin lattices or plasmon-enhanced spin sensors as well as improved fluorescent labeling for bioimaging could be envisioned.

  18. Lipid Self-Assemblies and Nanostructured Emulsions for Cosmetic Formulations

    Directory of Open Access Journals (Sweden)

    Chandrashekhar V. Kulkarni


    Full Text Available A majority of cosmetic products that we encounter on daily basis contain lipid constituents in solubilized or insolubilized forms. Due to their amphiphilic nature, the lipid molecules spontaneously self-assemble into a remarkable range of nanostructures when mixed with water. This review illustrates the formation and finely tunable properties of self-assembled lipid nanostructures and their hierarchically organized derivatives, as well as their relevance to the development of cosmetic formulations. These lipid systems can be modulated into various physical forms suitable for topical administration including fluids, gels, creams, pastes and dehydrated films. Moreover, they are capable of encapsulating hydrophilic, hydrophobic as well as amphiphilic active ingredients owing to their special morphological characters. Nano-hybrid materials with more elegant properties can be designed by combining nanostructured lipid systems with other nanomaterials including a hydrogelator, silica nanoparticles, clays and carbon nanomaterials. The smart materials reviewed here may well be the future of innovative cosmetic applications.

  19. Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry. (United States)

    Lehn, Jean-Marie


    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.

  20. Biocompatible and Biomimetic Self-Assembly of Functional Nanostructures (United States)


    evaporation induced self-assembly of aqueous silica precursors with a biologically compatible surfactant, glycerol monooleate ( GMO ) via is first deposited, it has a relatively low contact angle with water and remains in a semi-solid state. Upon exposure to UV/ozone, the GMO begins...Figure 8. A) Water contact angle of a GMO -templated silica film as a function of UV light and ozone exposure time, B) Localization of fluorescently

  1. Biocompatible and Biomimetic Self-Assembly of Functional Nanostructures (United States)


    ability to combat antibiotic resistance and fungal infections. In a related way, we assessed encapsulation of bacterial cells in silica based...AFRL-AFOSR-VA-TR-2017-0047 Biocompatible and Biomimetic Self-Assembly of Functional Nanostructures Jeffrey Brinker UNIVERSITY OF NEW MEXICO Final...ORGANIZATION NAME(S) AND ADDRESS(ES) UNIVERSITY OF NEW MEXICO 1700 LOMAS BLVD NE ALBUQUERQUE, NM 87106 US 8. PERFORMING ORGANIZATION REPORT NUMBER 9

  2. Synthesis, characterization and self-assembly with gold nanoparticles

    Indian Academy of Sciences (India)


    molecule of aryl di-isonitrile [1,4-di(4-isocyano- phenylethynyl)-2-ethylbenzene]; Chen et al. 48 have prepared a Au-MPCs based two-dimensional film with a rigid molecule 4,4′-thiobisbenzenethiol. In this paper, we report the controlling of the self-assembly of Au NPs with a rigid molecule TPPY. The tetra- hedral structure ...

  3. Coherence and dephasing in self-assembled quantum dots

    DEFF Research Database (Denmark)

    Hvam, Jørn Märcher; Leosson, K.; Birkedal, Dan


    We measured dephasing times in InGaAl/As self-assembled quantum dots at low temperature using degenerate four-wave mixing. At 0K, the coherence time of the quantum dots is lifetime limited, whereas at finite temperatures pure dephasing by exciton-phonon interactions governs the quantum dot...... coherence. The inferred homogeneous line widths are significantly smaller than the line widths usually observed in the photoluminescence from single quantum dots indicating an additional inhomogeneours broadening mechanism in the latter....

  4. Spin State As a Probe of Vesicle Self-Assembly. (United States)

    Kim, Sanghoon; Bellouard, Christine; Eastoe, Julian; Canilho, Nadia; Rogers, Sarah E; Ihiawakrim, Dris; Ersen, Ovidiu; Pasc, Andreea


    A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compositions and distribution of surfactants between the bilayers and the aqueous bulk.

  5. Spin State As a Probe of Vesicle Self-Assembly


    Kim, Sanghoon; Bellouard, Christine; Eastoe, Julian; Canilho, Nadia; Rogers, Sarah E; Ihiawakrim, Dris; Ersen, Ovidiu; Pasc, Andreea


    A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compo...

  6. Phosphorylation Modulates Ameloblastin Self-assembly and Ca2+ Binding

    Czech Academy of Sciences Publication Activity Database

    Stakkestad, O.; Lyngstadaas, S. P.; Thiede, B.; Vondrášek, Jiří; Skalhegg, B. S.; Reseland, J. E.


    Roč. 8, Jul 27 (2017), č. článku 531. ISSN 1664-042X Institutional support: RVO:61388963 Keywords : ameloblastin * phosphorylation * self-assembly * Ca2+-binding * enamel * intrinsically disordered proteins Subject RIV: CE - Biochemistry OBOR OECD: Biochemistry and molecular biology Impact factor: 4.134, year: 2016

  7. Dispersion of nanoparticulate suspensions using self-assembled surfactant aggregates (United States)

    Singh, Pankaj Kumar

    The dispersion of particles is critical for several industrial applications such as paints, inks, coatings, and cosmetics. Several emerging applications such as abrasives for precision polishing, and drug delivery systems are increasingly relying on nanoparticulates to achieve the desired performance. In the case of nanoparticles, the dispersion becomes more challenging because of the lack of fundamental understanding of dispersant adsorption and interparticle force prediction. Additionally, many of these processes use severe processing environments such as high normal forces (>100 mN/m), high shear forces (>10,000 s -1), and high ionic strengths (>0.1 M). Under such processing conditions, traditionally used dispersants based on electrostatics, and steric force repulsion mechanism may not be adequate. Hence, the development of optimally performing dispersants requires a fundamental understanding of the dispersion mechanism at the atomic/molecular scale. This study explores the use of self-assembled surfactant aggregates at the solid-liquid interface for dispersing nanoparticles in severe processing environments. Surfactant molecules can provide a feasible alternative to polymeric or inorganic dispersants for stabilizing ultrafine particles. The barrier to aggregation in the presence of surfactant molecules was measured using atomic force microscopy. The barrier heights correlated to suspension stability. To understand the mechanism for nanoparticulate suspension stability in the presence of surfactant films, the interface was characterized using zeta potential, contact angle, adsorption, and FT-IR (adsorbed surfactant film structure measurements). The effect of solution conditions such as pH and ionic strength on the suspension stability, and the self-assembled surfactant films was also investigated. It was determined that a transition from a random to an ordered orientation of the surfactant molecules at the interface was responsible for stability of

  8. Self-assembled containers based on extended tetrathiafulvalene. (United States)

    Bivaud, Sébastien; Goeb, Sébastien; Croué, Vincent; Dron, Paul I; Allain, Magali; Sallé, Marc


    Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule.

  9. Nanorings from the self-assembly of amphiphilic molecular dumbbells. (United States)

    Kim, Jung-Keun; Lee, Eunji; Huang, Zhegang; Lee, Myongsoo


    We have prepared amphiphilic dumbbell molecules consisting of hydrophobic alkyl chains and hydrophilic oligoether dendrons at each end of the rod segment. The molecular dumbbells, in aqueous solution, self-assemble into toroids as an intermediate nanostructure between spherical and long cylindrical micelles. The formation of toroidal structure is likely to originate from side by side connections of discrete bundles through the combination of strong hydrophobic interactions and anisotropic aggregation of rod segments.

  10. Electrostatic Force Microscopy of Self Assembled Peptide Structures

    DEFF Research Database (Denmark)

    Clausen, Casper Hyttel; Dimaki, Maria; Pantagos, Spyros P.


    In this report electrostatic force microscopy (EFM) is used to study different peptide self-assembled structures, such as tubes and particles. It is shown that not only geometrical information can be obtained using EFM, but also information about the composition of different structures. In partic...... compared to the radius of the AFM tip used. Finally, an agreement between the detected signal and the structure of the hollow peptide tubes is demonstrated....

  11. Self-assembled magnetic filter for highly efficient immunomagnetic separation. (United States)

    Issadore, David; Shao, Huilin; Chung, Jaehoon; Newton, Andita; Pittet, Mikael; Weissleder, Ralph; Lee, Hakho


    We have developed a compact and inexpensive microfluidic chip, the self-assembled magnetic filter, to efficiently remove magnetically tagged cells from suspension. The self-assembled magnetic filter consists of a microfluidic channel built directly above a self-assembled NdFeB magnet. Micrometre-sized grains of NdFeB assemble to form alternating magnetic dipoles, creating a magnetic field with a very strong magnitude B (from the material) and field gradient ▽B (from the configuration) in the microfluidic channel. The magnetic force imparted on magnetic beads is measured to be comparable to state-of-the-art microfabricated magnets, allowing for efficient separations to be performed in a compact, simple device. The efficiency of the magnetic filter is characterized by sorting non-magnetic (polystyrene) beads from magnetic beads (iron oxide). The filter enriches the population of non-magnetic beads to magnetic beads by a factor of >10(5) with a recovery rate of 90% at 1 mL h(-1). The utility of the magnetic filter is demonstrated with a microfluidic device that sorts tumor cells from leukocytes using negative immunomagnetic selection, and concentrates the tumor cells on an integrated membrane filter for optical detection.

  12. Sequential self-assembly of DNA functionalized droplets. (United States)

    Zhang, Yin; McMullen, Angus; Pontani, Lea-Laetitia; He, Xiaojin; Sha, Ruojie; Seeman, Nadrian C; Brujic, Jasna; Chaikin, Paul M


    Complex structures and devices, both natural and manmade, are often constructed sequentially. From crystallization to embryogenesis, a nucleus or seed is formed and built upon. Sequential assembly allows for initiation, signaling, and logical programming, which are necessary for making enclosed, hierarchical structures. Although biology relies on such schemes, they have not been available in materials science. Here, we demonstrate programmed sequential self-assembly of DNA functionalized emulsions. The droplets are initially inert because the grafted DNA strands are pre-hybridized in pairs. Active strands on initiator droplets then displace one of the paired strands and thus release its complement, which in turn activates the next droplet in the sequence, akin to living polymerization. Our strategy provides time and logic control during the self-assembly process, and offers a new perspective on the synthesis of materials.Natural complex systems are often constructed by sequential assembly but this is not readily available for synthetic systems. Here, the authors program the sequential self-assembly of DNA functionalized emulsions by altering the DNA grafted strands.

  13. Self-assembly of inorganic nanoparticles: Ab ovo (United States)

    Kotov, Nicholas A.


    There are numerous remarkable studies related to the self-organization of polymers, coordination compounds, microscale particles, biomolecules, macroscale particles, surfactants, and reactive molecules on surfaces. The focus of this paper is on the self-organization of nanoscale inorganic particles or simply nanoparticles (NPs). Although there are fascinating and profound discoveries made with other self-assembling structures, the ones involving NPs deserve particular attention because they (a) are omnipresent in Nature; (b) have relevance to numerous disciplines (physics, chemistry, biology, astronomy, Earth sciences, and others); (c) embrace most of the features, geometries, and intricacies observed for the self-organization of other chemical species; (d) offer new tools for studies of self-organization phenomena; and (e) have a large economic impact, extending from energy and construction industries, to optoelectronics, biomedical technologies, and food safety. Despite the overall success of the field it is necessary to step back from its multiple ongoing research venues and consider two questions: What is self-assembly of nanoparticles? and Why do we need to study it? The reason to bring them up is to achieve greater scientific depth in the understanding of these omnipresent phenomena and, perhaps, deepen their multifaceted impact. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

  14. Self-assembly of lipopolysaccharide layers on allantoin crystals. (United States)

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Jiang, Qiu Zhen; Gagnon, Pete


    Self-assembly of lipopolysaccharides (LPS) on solid surfaces is important for the study of bacterial membranes, but has not been possible due to technical difficulties and the lack of suitable solid supports. Recently we found that crystals of the natural compound allantoin selectively bind pure LPS with sub-nanomolar affinity. The physicochemical origins of this selectivity and the adsorption mode of LPS on allantoin crystals remain, however, unknown. In this study we present evidence that LPS adsorption on allantoin crystals is initiated through hydrogen-bond attachment of hydrophilic LPS regions. Hydrophobic interactions between alkyl chains of adjacently adsorbed LPS molecules subsequently promote self-assembly of LPS layers. The essential role of hydrogen-bond interactions is corroborated by our finding that allantoin crystals bind to practically any hydrophilic surface chemistry. Binding contributions of hydrophobic interactions between LPS alkyl chains are evidenced by the endothermic nature of the adsorption process and explain why the binding affinity for LPS is several orders of magnitude higher than for proteins (lysozyme, BSA and IgG) and polysaccharides. Self-assembly of LPS layers via hydrogen-bond attachment on allantoin crystals emerges as a novel binding mechanism and could be considered as a practical method for preparing biomimetic membranes on a solid support. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Probabilistic inverse design for self-assembling materials (United States)

    Jadrich, R. B.; Lindquist, B. A.; Truskett, T. M.


    One emerging approach for the fabrication of complex architectures on the nanoscale is to utilize particles customized to intrinsically self-assemble into a desired structure. Inverse methods of statistical mechanics have proven particularly effective for the discovery of interparticle interactions suitable for this aim. Here we evaluate the generality and robustness of a recently introduced inverse design strategy [B. A. Lindquist et al., J. Chem. Phys. 145, 111101 (2016)] by applying this simulation-based machine learning method to optimize for interparticle interactions that self-assemble particles into a variety of complex microstructures as follows: cluster fluids, porous mesophases, and crystalline lattices. Using the method, we discover isotropic pair interactions that lead to the self-assembly of each of the desired morphologies, including several types of potentials that were not previously understood to be capable of stabilizing such systems. One such pair potential led to the assembly of the highly asymmetric truncated trihexagonal lattice and another produced a fluid containing spherical voids, or pores, of designed size via purely repulsive interactions. Through these examples, we demonstrate several advantages inherent to this particular design approach including the use of a parametrized functional form for the optimized interparticle interactions, the ability to constrain the range of said parameters, and compatibility of the inverse design strategy with a variety of simulation protocols (e.g., positional restraints).

  16. Molecular Motions in Functional Self-Assembled Nanostructures

    Directory of Open Access Journals (Sweden)

    Jean-Marc Saiter


    Full Text Available The construction of “smart” materials able to perform specific functions at the molecular scale through the application of various stimuli is highly attractive but still challenging. The most recent applications indicate that the outstanding flexibility of self-assembled architectures can be employed as a powerful tool for the development of innovative molecular devices, functional surfaces and smart nanomaterials. Structural flexibility of these materials is known to be conferred by weak intermolecular forces involved in self-assembly strategies. However, some fundamental mechanisms responsible for conformational lability remain unexplored. Furthermore, the role played by stronger bonds, such as coordination, ionic and covalent bonding, is sometimes neglected while they can be employed readily to produce mechanically robust but also chemically reversible structures. In this review, recent applications of structural flexibility and molecular motions in self-assembled nanostructures are discussed. Special focus is given to advanced materials exhibiting significant performance changes after an external stimulus is applied, such as light exposure, pH variation, heat treatment or electromagnetic field. The crucial role played by strong intra- and weak intermolecular interactions on structural lability and responsiveness is highlighted.

  17. Chitosan Based Self-Assembled Nanoparticles in Drug Delivery

    Directory of Open Access Journals (Sweden)

    Javier Pérez Quiñones


    Full Text Available Chitosan is a cationic polysaccharide that is usually obtained by alkaline deacetylation of chitin poly(N-acetylglucosamine. It is biocompatible, biodegradable, mucoadhesive, and non-toxic. These excellent biological properties make chitosan a good candidate for a platform in developing drug delivery systems having improved biodistribution, increased specificity and sensitivity, and reduced pharmacological toxicity. In particular, chitosan nanoparticles are found to be appropriate for non-invasive routes of drug administration: oral, nasal, pulmonary and ocular routes. These applications are facilitated by the absorption-enhancing effect of chitosan. Many procedures for obtaining chitosan nanoparticles have been proposed. Particularly, the introduction of hydrophobic moieties into chitosan molecules by grafting to generate a hydrophobic-hydrophilic balance promoting self-assembly is a current and appealing approach. The grafting agent can be a hydrophobic moiety forming micelles that can entrap lipophilic drugs or it can be the drug itself. Another suitable way to generate self-assembled chitosan nanoparticles is through the formation of polyelectrolyte complexes with polyanions. This paper reviews the main approaches for preparing chitosan nanoparticles by self-assembly through both procedures, and illustrates the state of the art of their application in drug delivery.

  18. Molecular pathways for defect annihilation in directed self-assembly (United States)

    Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo; Khaira, Gurdaman; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Müller, Marcus; Nealey, Paul F.; de Pablo, Juan J.


    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales—a handful of nanometers—and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail. PMID:26515095

  19. Self-assembly of glutamic acid linked paclitaxel dimers into nanoparticles for chemotherapy. (United States)

    Wang, Zhanfeng; Zhuang, Miao; Sun, Tingting; Wang, Xin; Xie, Zhigang


    In this work, a glutamic acid linked paclitaxel (PTX) dimer (Glu-PTX 2 ) with high PTX content of 88.9wt% was designed and synthesized. Glu-PTX 2 could self-assemble into nanoparticles (Glu-PTX 2 NPs) in aqueous solution to increase the water solubility of PTX. Glu-PTX 2 NPs were characterized by electron microscopy and dynamic light scattering, exhibiting spherical morphology and favorable structural stability in aqueous media. Glu-PTX 2 NPs could be internalized by cancer cells as revealed by confocal laser scanning microscopy and exert potent cytotoxicity. It is envisaged that Glu-PTX 2 NPs would be an alternative formulation for PTX, and such amino acid linked drug dimers could also be applied to other therapeutic agents. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Gold(I) catalysis at extreme concentrations inside self-assembled nanospheres. (United States)

    Gramage-Doria, Rafael; Hessels, Joeri; Leenders, Stefan H A M; Tröppner, Oliver; Dürr, Maximilian; Ivanović-Burmazović, Ivana; Reek, Joost N H


    Homogeneous transition-metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mM or μM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M, inside well-defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mM levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular CO and CC bond-forming cyclization reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis, characterization, and self-assembly of bicarbamates and tri-carbamates (United States)

    Singh, Rajiv Kumar

    Recent decades have witnessed the discovery of a wide variety of nanomaterials. These nanomaterials vary from zero-dimensional nanodots to three-dimensional nanoflowers. However the properties of these nanomaterials have not been fully explored. A majority of the nonmaterials discovered so far are inorganic. There is little information about nanomaterials which are entirely based on organic compounds. Therefore this thesis focuses on the synthesis of two-dimensional nanosheets based on organic frameworks. In this study, a number of two-armed and three-armed carboxamides and carbamates have been synthesized, characterized and self-assembly process was studied. The self-assembly of these amides and carbamates were studied in a large number of single solvents as well as combination of solvents. Two-armed amides and carbamates having aromatic cores are found to have poor solubility in all but DMF and DMSO. The two-armed amides and carbamates having linker alkyl chain are found to have good solubility and crystal formation in a few solvents, but the quality of the crystal is not good enough for the XRD analysis. The polar solvents along with a trace amount of water are found to be more effective in getting perfect crystals of three-armed carbamates for X-ray crystallography. Carbamates with side-arms of three carbons and a cyclohexyl ring form perfect quality crystals in EtOAc, MeCN, and THF:H2O. In the process of growing single crystal several crystallization techniques were used. Slow evaporation process is found to be more efficient in getting good quality crystal. The crystal structures of carbamates have been determined as a part of the project. The morphology of the nanosheets was also studied by the transmission electron microscope (TEM). The TEM image of the carbamates reveals that its morphology is two-dimensional sheet. Additionally, data from powdered XRD have also revealed the formation of same or similar crystalline isoform from a variety of conditions.

  2. Self-Assembly of Plasmonic Nanoclusters for Optical Metauids (United States)

    Schade, Nicholas Benjamin

    I discuss experimental progress towards developing a material with an isotropic, negative index of refraction at optical frequencies. The simplest way to make such a material is to create a metafluid, or a disordered collection of subwavelength, isotropic electromagnetic resonators. Small clusters of metal particles, such as tetrahedra, serve as these constituents. What is needed are methods for manufacturing these structures with high precision and in sufficient yield that their resonances are identical. Jonathan Fan et al. [Science, 328 (5982), 1135-1138, 2010] demonstrated that colloidal self-assembly is a means of preparing electromagnetic resonators from metal nanoparticles. However, the resonances are sensitive to the separation gaps between particles. Standard synthesis routes for metal nanoparticles yield crystals or nanoshells that are inadequate for metafluids due to polydispersity, faceting, and thermal instabilities. To ensure that the separation gaps and resonances are uniform, more monodisperse spherical particles are needed. An additional challenge is the self-assembly of tetrahedral clusters in high yield from these particles. In self-assembly approaches that others have examined previously, the yield of any particular type of cluster is low. In this dissertation I present solutions to several of these problems, developed in collaboration with my research group and others. We demonstrate that slow chemical etching can transform octahedral gold crystals into ultrasmooth, monodisperse nanospheres. The particles can serve as seeds for the growth of larger octahedra which can in turn be etched. The size of the gold nanospheres can therefore be adjusted as desired. We further show that in colloidal mixtures of two sphere species that strongly bind to one another, the sphere size ratio determines the size distribution of self-assembled clusters. At a critical size ratio, tetrahedral clusters assemble in high yield. We explain the experimentally observed

  3. Combustion and self-assembly of nanoenergetic materials (United States)

    Malchi, Jonathan Yaniv

    The recent worldwide interest in nanotechnology spans a wide variety of scientific fields such as electronics, biology, materials science and medicine. Because of their extremely small dimensions, nanoparticles demonstrate properties different from matter at larger scales. Understanding these unusual properties and utilizing them for macroscale devices is an overall goal for nanotechnology. Moreover, manipulating these small particles into organized structures is crucial for taking full advantage of what nanotechnology has to offer, however it has proven to be a difficult task. Recent work utilizing electrostatic forces shows great potential for the self-assembly of nanoparticles into organized two-dimensional and three-dimensional structures. Overall, this work examines how nanotechnology and self-assembly can benefit the field of energetic materials. Because of aluminum's high energy density and low cost, it has been used in the field of energetic materials for several decades. In order to achieve sufficient energy release rates, aluminum is typically manufactured as a powder having spherical particles with diameters on the micron scale. It is well-known that decreasing the original particle diameter of a fuel particle will increase the burning time and, thus, energy release rate. Therefore, aluminum particles have recently been made to have diameters on the nanoscale, and shown to be advantageous for several applications. The combustion of nanoaluminum (nAl) in various systems is the primary focus of this study. A progression of experiments is used to analyze the combustion of nAl: (1) a fully heterogeneous flame spread system, (2) a semi-homogeneous sonicated thermite system and (3) a quasi-homogeneous self-assembled thermite system. The flame spread experiment physically separates the nAl from the gaseous oxidizer allowing for a well-understood convective, diffusive, reactive system to be analyzed. Because of the simplicity of the experimental setup, variables

  4. Self-Assembled Pd@CeO2/γ-Al2O3Catalysts with Enhanced Activity for Catalytic Methane Combustion. (United States)

    Feng, Xilan; Li, Wang; Liu, Dapeng; Zhang, Zheng; Duan, Yang; Zhang, Yu


    Pd@CeO 2 /Al 2 O 3 catalysts are of great importance for real applications, such as three-way catalysis, CO oxidation, and methane combustion. In this article, the Pd@CeO 2 core@shell nanospheres are prepared via the autoredox reaction in aqueous phase. Three kinds of methods are then employed, that is, electrostatic interaction, supramolecular self-assembly, and physical mixing, to support the as-prepared Pd@CeO 2 nanospheres on γ-Al 2 O 3 . A model reaction of catalytic methane-combustion is employed here to evaluate the three Pd@CeO 2 /γ-Al 2 O 3 samples. As a result, the sample Pd@CeO 2 -S-850 prepared via supramolecular self-assembly and calcined at 850 °C exhibits superior catalytic performance to the others, which has a far lower light-off temperature (T 50 of about 364 °C). Moreover, almost no deterioration of Pd@CeO 2 -S-850 is observed after five sequent catalytic cycles. The analysis of H 2 -TPR curves concludes that there exists hydrogen spillover related to the strong metal-support interaction between Pd species and oxides. The strong metal-support interaction and the specific surface areas might be responsible for the catalytic performance of the Pd@CeO 2 samples toward catalytic methane combustion. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Reductant-Assisted Self-Assembly with Cu/Sn Microbump for Three-Dimensional Heterogeneous Integration (United States)

    Ito, Yuka; Fukushima, Takafumi; Lee, Kang-Wook; Choki, Koji; Tanaka, Tetsu; Koyanagi, Mitsumasa


    To establish liquid-assisted assembly processes applicable to heterogeneous system integrations, we present flip-chip self-assembly of dies with Cu/Sn microbumps using the difference in droplet wetting between hydrophilic and hydrophobic areas. Flip-chip self-assembly is assisted by a water-soluble flux that has high surface tension comparable to that of pure water and contains an additive of a reducing agent for metal oxides. Control of the additive concentration in the flux provides high wettability contrast that enable spontaneous and precise alignment of chips to hydrophilic areas formed on substrates within 5 µm in alignment accuracy. In the subsequent chip bonding process, the reductant can eliminate the metal oxide layer and improve the solder wettability of Sn to the corresponding electrode pads formed on the chips. In addition, we confirm, through electrical characteristic evaluation after thermal compression bonding, that the resulting daisy chain formed between the substrates and self-assembled chips with the flux shows sufficiently low contact resistance of below 20 mΩ/bump without disconnection.

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


    Anslyn, Eric V


    Summary 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 dr...

  7. Supramolecular polymers as surface coatings: rapid fabrication of healable superhydrophobic and slippery surfaces. (United States)

    Wei, Qiang; Schlaich, Christoph; Prévost, Sylvain; Schulz, Andrea; Böttcher, Christoph; Gradzielski, Michael; Qi, Zhenhui; Haag, Rainer; Schalley, Christoph A


    Supramolecular polymerization for non-wetting surface coatings is described. The self-assembly of low-molecular-weight gelators (LMWGs) with perfluorinated side chains can be utilized to rapidly construct superhydrophobic, as well as liquid-infused slippery surfaces within minutes. The lubricated slippery surface exhibits impressive repellency to biological li-quids, such as human serum and blood, and very fast self-healing. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metallo-supramolecular Architectures based on Multifunctional N-Donor Ligands


    Tanh Jeazet, Harold Brice


    Self-assembly processes were used to construct supramolecular architectures based on metal-ligand interactions. The structures formed strongly depend on the used metal ion, the ligand type, the chosen counter ion and solvent as well as on the experimental conditions. The focus of the studies was the design of multifunctional N-donor ligands and the characterization of their complexing and structural properties. This work was divided into three distinct main parts: The bis(2-pyridylimine), the...

  9. 3D Printing of Biocompatible Supramolecular Polymers and their Composites. (United States)

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


    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.

  10. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    Energy Technology Data Exchange (ETDEWEB)

    Determan, Michael Duane [Iowa State Univ., Ames, IA (United States)


    The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

  11. Basic building units, self-assembly and crystallization in the ...

    Indian Academy of Sciences (India)


    chemistry and materials design. This is of significance since the chemistry of supramolecular ... This is because we often find organic amine phosphates as side products in the hydrothermal synthesis of open-framework metal ... relatively low temperatures under ambient pressure. Thus, the reaction of 1,3- diaminopropane ...

  12. Self-Assembly Characteristics of a Multipolar Donor-Acceptor ...

    Indian Academy of Sciences (India)


    Integrated Molecular Tweezer. Deepak Asthana, Geeta Hundal and Pritam Mukhopadhyay*. Supramolecular & Material Chemistry Lab, School of Physical Sciences, Jawaharlal Nehru University, New Delhi. 110067, India. e-mail: m_pritam@ Contents. S. No. Topic. Page No. 1. Synthesis and characterization of 1.

  13. Application of a supramolecular-ligand library for the automated search for catalysts for the asymmetric hydrogenation of industrially relevant substrates

    NARCIS (Netherlands)

    Meeuwissen, J.; Kuil, M.; van der Burg, A.M.; Sandee, A.J.; Reek, J.N.H.


    A procedure is described for the automated screening and lead optimization of a supramolecular-ligand library for the rhodium-catalyzed asymmetric hydrogenation of five challenging substrates relevant to industry. Each catalyst is (self-) assembled from two urea-functionalized ligands and a

  14. Self-Assemblies of Single-Walled Carbon Nanotubes through Tunable Tethering of Pyrenes by Dextrin for Rapidly Chiral Sensing


    Wei, Wei-Li; Chen, Qiushui; Li, Haifang; Lin, Jin-Ming


    Pyrene-modified dextrin (Py-Dex) was synthesized via the Schiff base reaction between reducing end of dextrins and 1-aminopyrene, and then self-assemblies of single-walled carbon nanotubes (SWNTs) were fabricated through the tunable tethering of pyrene to SWNTs by dextrin chains. The Py-Dex-SWNTs assemblies were found to be significantly water-soluble because of the synergistic effect of dextrin chains and pyrene moieties. Py-Dex and Py-Dex-SWNTs were adequately characterized by NMR, UV-vis, ...

  15. Self-assembly of amorphous biophotonic nanostructures by phase separation

    Energy Technology Data Exchange (ETDEWEB)

    Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar; Mochrie, Simon G.J.; Cao, Hui; Prum, Richard O.; (Yale)


    Some of the most vivid colors in the animal kingdom are created not by pigments, but by wavelength-selective scattering of light from nanostructures. Here we investigate quasi-ordered nanostructures of avian feather barbs which produce vivid non-iridescent colors. These {beta}-keratin and air nanostructures are found in two basic morphologies: tortuous channels and amorphous packings of spheres. Each class of nanostructure is isotropic and has a pronounced characteristic length scale of variation in composition. These local structural correlations lead to strong backscattering over a narrow range of optical frequencies and little variation with angle of incidence. Such optical properties play important roles in social and sexual communication. To be effective, birds need to precisely control the development of these nanoscale structures, yet little is known about how they grow. We hypothesize that multiple lineages of birds have convergently evolved to exploit phase separation and kinetic arrest to self-assemble spongy color-producing nanostructures in feather barbs. Observed avian nanostructures are strikingly similar to those self-assembled during the phase separation of fluid mixtures; the channel and sphere morphologies are characteristic of phase separation by spinodal decomposition and nucleation and growth, respectively. These unstable structures are locked-in by the kinetic arrest of the {beta}-keratin matrix, likely through the entanglement or cross-linking of supermolecular {beta}-keratin fibers. Using the power of self-assembly, birds can robustly realize a diverse range of nanoscopic morphologies with relatively small physical and chemical changes during feather development.

  16. Electrochemically controlled self-assembly of block copolymer nanostructures (United States)

    Eitouni, Hany Basam

    Organometallic block copolymers, wherein one block is composed of alternating ferrocene and dialkylsilane units in the main chain, undergo self-assembly to form microphase-separated ordered structures similarly to typical organic block copolymers. The 1,1'-dimethylsilylferrocenophane monomer was synthesized and polymerized anionically with other monomers to make a variety of different organometallic block copolymers. The phase behavior and thermodynamic interactions of anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) and poly(isoprene-block-ferrocenyldimethylsilane) (IF) copolymers were examined using depolarized light scattering, small angle x-ray and neutron scattering (SAXS and SANS), and transmission electron microscopy. The temperature-dependence of the Flory-Huggins parameter, chi, and the statistical segment lengths of SF and IF copolymers were determined by SAXS and SANS using the random phase approximation. The thermodynamic interactions in poly(ferrocenyldimethylsilane) diblock copolymers were systematically adjusted by oxidizing the ferrocene moieties with silver salts and examined using SAXS and depolarized light scattering. The polymers retained microphase separated ordered structures upon oxidation and showed systematic changes in the location of the order-disorder transition as a function of extent of oxidation. By controlling the redox properties of the ferrocene moiety in the backbone of the polymer, we present a method for controlling the self-assembled microstructure and hence bulk material properties. Using electrochemical techniques, a novel means of controlling the order-disorder transition of block copolymers was discovered. By applying very small electrical potentials to disordered solutions of organometallic block copolymers, oriented ordered grains were formed near one electrode, the result of electrochemical reactions. After reversing the electrical bias on the system, the ordered grains disappeared and new

  17. Understanding the self-assembly of TCNQ on Cu(111)

    DEFF Research Database (Denmark)

    Stradi, Daniele; Borca, Bogdana; Barja, Sara


    The structure of self-assembled monolayers of 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) adsorbed on Cu(111) has been studied using a combination of scanning tunnelling microscopy (STM) experiments and density functional theory (DFT) calculations. We show that the polymorphism of the self...... perpendicular to the other. Conversely, when the substrate is held at room temperature during deposition and slightly annealed afterwards, a more complex structure with five molecules per unit cell is formed. DFT calculations complement the experimental results by revealing that the building blocks of the two...

  18. Photobleaching-activated micropatterning on self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Scrimgeour, Jan; Kodali, Vamsi K; Kovari, Daniel T; Curtis, Jennifer E, E-mail: jennifer.curtis@physics.gatech.ed [School of Physics and Petit Institute for Bioengineering and Biosciences (IBB), Georgia Institute of Technology, 837 State St, Atlanta, GA 30332 (United States)


    Functional chemical micropatterns were fabricated by exploiting the photobleaching of dye-coupled species near methacrylate self-assembled monolayers. Using this approach we have demonstrated that multiple chemistries can be coupled to the monolayer using a standard fluorescence microscope. The surface bound functional groups remain active and patterns with feature sizes down to 3 {mu}m can be readily achieved with excellent signal-to-noise ratio. Control over the ligand binding density was demonstrated to illustrate the convenient route provided by this platform for fabricating complex spatial gradients in ligand density.

  19. A 3D Optical Metamaterial Made by Self-Assembly

    KAUST Repository

    Vignolini, Silvia


    Optical metamaterials have unusual optical characteristics that arise from their periodic nanostructure. Their manufacture requires the assembly of 3D architectures with structure control on the 10-nm length scale. Such a 3D optical metamaterial, based on the replication of a self-assembled block copolymer into gold, is demonstrated. The resulting gold replica has a feature size that is two orders of magnitude smaller than the wavelength of visible light. Its optical signature reveals an archetypal Pendry wire metamaterial with linear and circular dichroism. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao


    The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

  1. Formation and Characterization of Silicon Self-assembled Nanodots

    International Nuclear Information System (INIS)

    Idrees, Fatima Aldaw; Sakrani, Samsudi; Othaman, Zulkafli


    Silicon self-assembled quantum dots have been successfully prepared on corning glass (7059) substrate. The samples were fabricated using the common technique RF magnetron sputtering system depend on plasma excitation at varying growth parameters and high temperature of more than 500 deg. C. The measurements of average dots size estimated to be 36 nm is confirmed by using AFM. The PL peak located at 570 nm, informed band gap energy = 2.10 eV larger than bulk material band gap, that confirmed the miniaturized of the dots. To measure the Silicon atomic% deposit on corning glass (7059) substrate EDX has been used.

  2. Equation of State for Phospholipid Self-Assembly

    DEFF Research Database (Denmark)

    Marsh, Derek


    of transfer converge at ∼-18°C. An equation of state for the free energy of self-assembly formulated from this thermodynamic data depends on the heat capacity of transfer as the sole parameter needed to specify a particular lipid. For lipids lacking calorimetric data, measurement of the critical micelle...... concentration at a single temperature suffices to define an effective heat capacity according to the model. Agreement with the experimental temperature dependence of the critical micelle concentration is then good. The predictive powers should extend also to amphiphile partitioning and the kinetics of lipid...

  3. Long lived coherence in self-assembled quantum dots

    DEFF Research Database (Denmark)

    Birkedal, Dan; Leosson, Kristjan; Hvam, Jørn Märcher


    We report measurements of ultralong coherence in self-assembled quantum dots. Transient four-wave mixing experiments at 5 K show an average dephasing time of 372 ps, corresponding to a homogeneous linewidth of 3.5 mu eV, which is significantly smaller than the linewidth observed in single-dot...... luminescence. Time-resolved luminescence measurements show a lifetime of the dot ground state of 800 ps, demonstrating the presence of pure dephasing at finite temperature. The homogeneous width is lifetime limited only at temperatures approaching 0 K....

  4. Self-assembling peptides form nanodiscs that stabilize membrane proteins

    DEFF Research Database (Denmark)

    Midtgaard, Søren Roi; Pedersen, Martin Cramer; Kirkensgaard, Jacob Judas Kain


    New methods to handle membrane bound proteins, e.g. G-protein coupled receptors (GPCRs), are highly desirable. Recently, apoliprotein A1 (ApoA1) based lipoprotein particles have emerged as a new platform for studying membrane proteins, and it has been shown that they can self-assemble in combinat......New methods to handle membrane bound proteins, e.g. G-protein coupled receptors (GPCRs), are highly desirable. Recently, apoliprotein A1 (ApoA1) based lipoprotein particles have emerged as a new platform for studying membrane proteins, and it has been shown that they can self...

  5. Biomimetic self-assembly of a functional asymmetrical electronic device. (United States)

    Boncheva, Mila; Gracias, David H; Jacobs, Heiko O; Whitesides, George M


    This paper introduces a biomimetic strategy for the fabrication of asymmetrical, three-dimensional electronic devices modeled on the folding of a chain of polypeptide structural motifs into a globular protein. Millimeter-size polyhedra-patterned with logic devices, wires, and solder dots-were connected in a linear string by using flexible wire. On self-assembly, the string folded spontaneously into two domains: one functioned as a ring oscillator, and the other one as a shift register. This example demonstrates that biomimetic principles of design and self-organization can be applied to generate multifunctional electronic systems of complex, three-dimensional architecture.

  6. Directed self-assembly graphoepitaxy template generation with immersion lithography (United States)

    Ma, Yuansheng; Lei, Junjiang; Andres Torres, J.; Hong, Le; Word, James; Fenger, Germain; Tritchkov, Alexander; Lippincott, George; Gupta, Rachit; Lafferty, Neal; He, Yuan; Bekaert, Joost; Vanderberghe, Geert


    We present an optimization methodology for the template designs of subresolution contacts using directed self-assembly (DSA) with graphoepitaxy and immersion lithography. We demonstrate the flow using a 60-nm-pitch contact design in doublet with Monte Carlo simulations for DSA. We introduce the notion of template error enhancement factor (TEEF) to gauge the sensitivity of DSA printing infidelity to template printing infidelity and evaluate optimized template designs with TEEF metrics. Our data show that source mask optimization and inverse lithography technology are critical to achieve sub-80 nm non-L0 pitches for DSA patterns using 193i.

  7. Long coherence times in self-assembled semiconductor quantum dots

    DEFF Research Database (Denmark)

    Birkedal, Dan; Leosson, K.; Hvam, Jørn Märcher


    We report measurements of ultra-long coherence in self-assembled quantum dots. Transient four-wave mixing experiments at 5 K show an average dephasing time of 372 ps, corresponding to a homogeneous linewidth of 3.5 mueV, which is significantly smaller than the linewidth observed in single-dot...... luminescence. Time-resolved luminescence measurements show a lifetime of the dot ground state of 800 ps demonstrating the presence of pure dephasing at finite temperature. The homogeneous width is lifetime limited only at temperatures approaching 0 K....

  8. Directed Formation of DNA Nanoarrays through Orthogonal Self-Assembly

    Directory of Open Access Journals (Sweden)

    Eugen Stulz


    Full Text Available We describe the synthesis of terpyridine modified DNA strands which selectively form DNA nanotubes through orthogonal hydrogen bonding and metal complexation interactions. The short DNA strands are designed to self-assemble into long duplexes through a sticky-end approach. Addition of weakly binding metals such as Zn(II and Ni(II induces the formation of tubular arrays consisting of DNA bundles which are 50-200 nm wide and 2-50 nm high. TEM shows additional long distance ordering of the terpy-DNA complexes into fibers.

  9. Biomimetic engineering: towards a self-assembled nanotechnology

    International Nuclear Information System (INIS)

    Braach-Maksvytis, V.


    Full text: The Nanoscience and Systems program was set up within CSIRO Telecommunications and Industrial Physics three years ago with an emphasis on biomimetic engineering, with the aim of developing new cross-disciplinary research in traditional physics areas. By combining expertise in experimental and theoretical physics with biology and chemistry, new approaches towards understanding and using nanoscale systems and devices are being explored. Research in the program ranges from using self-assembled lipid membranes for surface passivation of GaAs transistors to the electrical properties of nanoparticle films and devices. An overview of the research will be given, highlighting the diversity of nanotechnology applications

  10. Supramolecular Nanoparticles for Molecular Diagnostics and Therapeutics (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

  11. Ligand design for alkali-metal-templated self-assembly of unique high-nuclearity CuII aggregates with diverse coordination cage units: crystal structures and properties. (United States)

    Du, Miao; Bu, Xian-He; Guo, Ya-Mei; Ribas, Joan


    The construction of two unique, high-nuclearity Cu(II) supramolecular aggregates with tetrahedral or octahedral cage units, [(mu(3)-Cl)[Li subset Cu(4)(mu-L(1))(3)](3)](ClO(4))(8)(H(2)O)(4.5) (1) and [[Na(2) subset Cu(12)(mu-L(2))(8)(mu-Cl)(4)](ClO(4))(8)(H(2)O)(10)(H(3)O(+))(2)](infinity) (2) by alkali-metal-templated (Li(+) or Na(+)) self-assembly, was achieved by the use of two newly designed carboxylic-functionalized diazamesocyclic ligands, N,N'-bis(3-propionyloxy)-1,4-diazacycloheptane (H(2)L(1)) or 1,5-diazacyclooctane-N,N'-diacetate acid (H(2)L(2)). Complex 1 crystallizes in the trigonal R3c space group (a = b = 20.866(3), c = 126.26(4) A and Z = 12), and 2 in the triclinic P1 space group (a = 13.632(4), b = 14.754(4), c = 19.517(6) A, alpha = 99.836(6), beta = 95.793(5), gamma = 116.124(5) degrees and Z = 1). By subtle variation of the ligand structures and the alkali-metal templates, different polymeric motifs were obtained: a dodecanuclear architecture 1 consisting of three Cu(4) tetrahedral cage units with a Li(+) template, and a supramolecular chain 2 consisting of two crystallographically nonequivalent octahedral Cu(6) polyhedra with a Na(+) template. The effects of ligand functionality and alkali metal template ions on the self-assembly processes of both coordination supramolecular aggregates, and their magnetic behaviors are discussed in detail.

  12. Template mediated protein self-assembly as a valuable tool in regenerative therapy. (United States)

    Kundu, B; Eltohamy, M; Yadavalli, V K; Reis, R L; Kim, H W


    The assembly of natural proteinaceous biopolymers into macro-scale architectures is of great importance in synthetic biology, soft-material science and regenerative therapy. The self-assembly of protein tends to be limited due to anisotropic interactions among protein molecules, poor solubility and stability. Here, we introduce a unique platform to self-immobilize diverse proteins (fibrous and globular, positively and negatively charged, low and high molecular weight) using silicon surfaces with pendant -NH 2 groups via a facile one step diffusion limited aggregation (DLA) method. All the experimental proteins (type I collagen, bovine serum albumin and cytochrome C) self-assemble into seaweed-like branched dendritic architectures via classical DLA in the absence of any electrolytes. The notable differences in branching architectures are due to dissimilarities in protein colloidal sub-units, which is typical for each protein type, along with the heterogeneous distribution of surface -NH 2 groups. Fractal analysis of assembled structures is used to explain the underlying route of fractal deposition; which concludes how proteins with different functionality can yield similar assembly. Further, the nano-micro-structured surfaces can be used to provide functional topographical cues to study cellular responses, as demonstrated using rat bone marrow stem cells. The results indicate that the immobilization of proteins via DLA does not affect functionality, instead serving as topographical cues to guide cell morphology. This indicates a promising design strategy at the tissue-material interface and is anticipated to guide future surface modifications. A cost-effective standard templating strategy is therefore proposed for fundamental and applied particle aggregation studies, which can be used at multiple length scales for biomaterial design and surface reformation.

  13. Self assembly of highly-ordered nanoparticle monolayers.

    Energy Technology Data Exchange (ETDEWEB)

    Bigioni, T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.; Univ. of Chicago


    When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

  14. Silver nanoprisms self-assembly on differently functionalized silica surface

    International Nuclear Information System (INIS)

    Pilipavicius, J; Chodosovskaja, A; Beganskiene, A; Kareiva, A


    In this work colloidal silica/silver nanoprisms (NPRs) composite coatings were made. Firstly colloidal silica sols were synthesized by sol-gel method and produced coatings on glass by dip-coating technique. Next coatings were silanized by (3-Aminopropyl)triethoxysilane (APTES), N-[3-(Trimethoxysilyl)propyl]ethylenediamine (AEAPTMS), (3- Mercaptopropyl)trimethoxysilane (MPTMS). Silver NPRs where synthesized via seed-mediated method and high yield of 94±15 nm average edge length silver NPRs were obtained with surface plasmon resonance peak at 921 nm. Silica-Silver NPRs composite coatings obtained by selfassembly on silica coated-functionalized surface. In order to find the most appropriate silanization way for Silver NPRs self-assembly, the composite coatings were characterized by scanning electron microscopy (SEM), dynamic light scattering (DLS), water contact angle (CA) and surface free energy (SFE) methods. Results have showed that surface functionalization is necessary to achieve self-assembled Ag NPRs layer. MPTMS silanized coatings resulted sparse distribution of Ag NPRs. Most homogeneous, even distribution composite coatings obtained on APTES functionalized silica coatings, while AEAPTMS induced strong aggregation of Silver NPRs

  15. Probabilistic Performance Guarantees for Distributed Self-Assembly

    KAUST Repository

    Fox, Michael J.


    In distributed self-assembly, a multitude of agents seek to form copies of a particular structure, modeled here as a labeled graph. In the model, agents encounter each other in spontaneous pairwise interactions and decide whether or not to form or sever edges based on their two labels and a fixed set of local interaction rules described by a graph grammar. The objective is to converge on a graph with a maximum number of copies of a given target graph. Our main result is the introduction of a simple algorithm that achieves an asymptotically maximum yield in a probabilistic sense. Notably, agents do not need to update their labels except when forming or severing edges. This contrasts with certain existing approaches that exploit information propagating rules, effectively addressing the decision problem at the level of subgraphs as opposed to individual vertices. We are able to obey more stringent locality requirements while also providing smaller rule sets. The results can be improved upon if certain requirements on the labels are relaxed. We discuss limits of performance in self-assembly in terms of rule set characteristics and achievable maximum yield.

  16. Silver nanoprisms self-assembly on differently functionalized silica surface (United States)

    Pilipavicius, J.; Chodosovskaja, A.; Beganskiene, A.; Kareiva, A.


    In this work colloidal silica/silver nanoprisms (NPRs) composite coatings were made. Firstly colloidal silica sols were synthesized by sol-gel method and produced coatings on glass by dip-coating technique. Next coatings were silanized by (3-Aminopropyl)triethoxysilane (APTES), N-[3-(Trimethoxysilyl)propyl]ethylenediamine (AEAPTMS), (3- Mercaptopropyl)trimethoxysilane (MPTMS). Silver NPRs where synthesized via seed-mediated method and high yield of 94±15 nm average edge length silver NPRs were obtained with surface plasmon resonance peak at 921 nm. Silica-Silver NPRs composite coatings obtained by selfassembly on silica coated-functionalized surface. In order to find the most appropriate silanization way for Silver NPRs self-assembly, the composite coatings were characterized by scanning electron microscopy (SEM), dynamic light scattering (DLS), water contact angle (CA) and surface free energy (SFE) methods. Results have showed that surface functionalization is necessary to achieve self-assembled Ag NPRs layer. MPTMS silanized coatings resulted sparse distribution of Ag NPRs. Most homogeneous, even distribution composite coatings obtained on APTES functionalized silica coatings, while AEAPTMS induced strong aggregation of Silver NPRs.

  17. Self-Assembling Multifunctional Peptide Dimers for Gene Delivery Systems

    Directory of Open Access Journals (Sweden)

    Kitae Ryu


    Full Text Available Self-assembling multifunctional peptide was designed for gene delivery systems. The multifunctional peptide (MP consists of cellular penetrating peptide moiety (R8, matrix metalloproteinase-2 (MMP-2 specific sequence (GPLGV, pH-responsive moiety (H5, and hydrophobic moiety (palmitic acid (CR8GPLGVH5-Pal. MP was oxidized to form multifunctional peptide dimer (MPD by DMSO oxidation of thiols in terminal cysteine residues. MPD could condense pDNA successfully at a weight ratio of 5. MPD itself could self-assemble into submicron micelle particles via hydrophobic interaction, of which critical micelle concentration is about 0.01 mM. MPD showed concentration-dependent but low cytotoxicity in comparison with PEI25k. MPD polyplexes showed low transfection efficiency in HEK293 cells expressing low level of MMP-2 but high transfection efficiency in A549 and C2C12 cells expressing high level of MMP-2, meaning the enhanced transfection efficiency probably due to MMP-induced structural change of polyplexes. Bafilomycin A1-treated transfection results suggest that the transfection of MPD is mediated via endosomal escape by endosome buffering ability. These results show the potential of MPD for MMP-2 targeted gene delivery systems due to its multifunctionality.

  18. Designing self-assembling 3D structures of microcapsules (United States)

    Li, Like; Shum, Henry; Shklyaev, Oleg; Yashin, Victor; Balazs, Anna

    Self-assembly of complex, three-dimensional structures is commonly achieved by biological cells but difficult to realize in synthetic systems with micron-scale or larger components. Some previous modeling studies have considered only the planar self-assembly of microcapsules on a substrate. In this work, nanoparticles released from the capsules bind to the substrate and to the shells of nearby capsules. The non-uniform nanoparticle deposition on a capsule's surface leads to adhesion gradients, which drive the capsules to effectively ``climb'' on top of one another and self-organize in the vertical direction. We determine conditions that favor this structural organization. In particular, we study how the vertical structuring depends on the background fluid flow, the topography of the microcapsules and the underlying surface, the capsule-capsule interaction and that between the capsules and the substrate. The findings can provide design rules for the autonomous creation of novel nanocomposites, where the layers are formed from nanoparticle-containing and nanoparticle-decorated microcapsules.

  19. Hidden geometries in networks arising from cooperative self-assembly. (United States)

    Šuvakov, Milovan; Andjelković, Miroslav; Tadić, Bosiljka


    Multilevel self-assembly involving small structured groups of nano-particles provides new routes to development of functional materials with a sophisticated architecture. Apart from the inter-particle forces, the geometrical shapes and compatibility of the building blocks are decisive factors. Therefore, a comprehensive understanding of these processes is essential for the design of assemblies of desired properties. Here, we introduce a computational model for cooperative self-assembly with the simultaneous attachment of structured groups of particles, which can be described by simplexes (connected pairs, triangles, tetrahedrons and higher order cliques) to a growing network. The model incorporates geometric rules that provide suitable nesting spaces for the new group and the chemical affinity of the system to accept excess particles. For varying chemical affinity, we grow different classes of assemblies by binding the cliques of distributed sizes. Furthermore, we characterize the emergent structures by metrics of graph theory and algebraic topology of graphs, and 4-point test for the intrinsic hyperbolicity of the networks. Our results show that higher Q-connectedness of the appearing simplicial complexes can arise due to only geometric factors and that it can be efficiently modulated by changing the chemical potential and the polydispersity of the binding simplexes.

  20. Forces that Drive Nanoscale Self-assembly on Solid Surfaces

    International Nuclear Information System (INIS)

    Suo, Z.; Lu, W.


    Experimental evidence has accumulated in the recent decade that nanoscale patterns can self-assemble on solid surfaces. A two-component monolayer grown on a solid surface may separate into distinct phases. Sometimes the phases select sizes about 10 nm, and order into an array of stripes or disks. This paper reviews a model that accounts for these behaviors. Attention is focused on thermodynamic forces that drive the self-assembly. A double-welled, composition-dependent free energy drives phase separation. The phase boundary energy drives phase coarsening. The concentration-dependent surface stress drives phase refining. It is the competition between the coarsening and the refining that leads to size selection and spatial ordering. These thermodynamic forces are embodied in a nonlinear diffusion equation. Numerical simulations reveal rich dynamics of the pattern formation process. It is relatively fast for the phases to separate and select a uniform size, but exceedingly slow to order over a long distance, unless the symmetry is suitably broken

  1. Self-assembled rosette nanotubes encapsulate and slowly release dexamethasone

    Directory of Open Access Journals (Sweden)

    Chen Y


    Full Text Available Yupeng Chen1,2, Shang Song2, Zhimin Yan3, Hicham Fenniri3, Thomas J Webster2,41Department of Chemistry, Brown University, Providence, RI, USA; 2School of Engineering, Brown University, Providence, RI, USA; 3National Institute for Nanotechnology and Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada; 4Department of Orthopedics, Brown University, Providence, RI, USAAbstract: Rosette nanotubes (RNTs are novel, self-assembled, biomimetic, synthetic drug delivery materials suitable for numerous medical applications. Because of their amphiphilic character and hollow architecture, RNTs can be used to encapsulate and deliver hydrophobic drugs otherwise difficult to deliver in biological systems. Another advantage of using RNTs for drug delivery is their biocompatibility, low cytotoxicity, and their ability to engender a favorable, biologically-inspired environment for cell adhesion and growth. In this study, a method to incorporate dexamethasone (DEX, an inflammatory and a bone growth promoting steroid into RNTs was developed. The drug-loaded RNTs were characterized using diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR and UV-Vis spectroscopy. Results showed for the first time that DEX can be easily and quickly encapsulated into RNTs and released to promote osteoblast (bone-forming cell functions over long periods of time. As a result, RNTs are presented as a novel material for the targeted delivery of hydrophobic drugs otherwise difficult to deliver.Keywords: nanotubes, drug delivery, self-assembly, physiological conditions

  2. Self-assembly of colloids with magnetic caps

    Energy Technology Data Exchange (ETDEWEB)

    Novak, E.V., E-mail: [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); Kantorovich, S.S. [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); University of Vienna, Sensengasse 8, Vienna (Austria)


    In our earlier work (Steinbach et al., 2016 ) we investigated a homogeneous system of magnetically capped colloidal particles that self-assembled via two structural patterns of different symmetry. The particles could form a compact, equilateral triangle with a three-fold rotational symmetry and zero dipole moment and a staggered chain with mirror symmetry with a net magnetisation perpendicular to the chain. The system exhibited a bistability already in clusters of three particles. Based on observations of a real magnetic particles system, analytical calculations and molecular dynamics simulations, it has been shown that the bistability is a result of an anisotropic magnetisation distribution with rotational symmetry inside the particles. The present study is a logical extension of the above research and forms a preparatory stage for the study of a self-assembly of such magnetic particles under the influence of an external magnetic field. Since the magnetic field is only an additive contribution to the total ground state energy, we can study the interparticle interaction energies of candidate ground state structures based on the field-free terms. - Highlights: • Analytical calculations of the energies of ground state candidates for colloids with magnetic caps. • Computer simulations confirmed the theoretical model. • The structural transition between ground states was found.

  3. Self-assembly of dodecaphenyl POSS thin films (United States)

    Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor


    The self-assembly abilities of Dodecaphenyl Polyhedral Oligomeric Silsesquioxane thin films on Si(1 0 0) surfaces were studied. Due to their thermal properties - relatively low sublimation temperature and preservation of molecular structure - cage type silsesquioxanes are ideal material for the preparation of a thin films by Physical Vapor Deposition. The Ultra-High Vacuum environment and the deposition precision of the PVD method enable the study of early stages of thin film growth and its molecular organization. X-ray Reflectivity and Atomic Force Microscopy measurements allow to pursuit size-effects in the structure of thin films with thickness ranges from less than a single molecular layer up to several tens of layers. Thermal treatment of the thin films triggered phase change: from a poorly ordered polycrystalline film into a well-ordered multilayer structure. Self-assembly of the layers is the effect of the π-stacking of phenyl rings, which force molecules to arrange in a superlattice, forming stacks of alternating organic-inorganic layers.

  4. Synthesis and self-assembly of complex hollow materials

    KAUST Repository

    Zeng, Hua Chun


    Hollow materials with interiors or voids and pores are a class of lightweight nanostructured matters that promise many future technological applications, and they have received significant research attention in recent years. On the basis of well-known physicochemical phenomena and principles, for example, several solution-based protocols have been developed for the general preparation of these complex materials under mild reaction conditions. This article is thus a short introductory review on the synthetic aspects of this field of development. The synthetic methodologies can be broadly divided into three major categories: (i) template-assisted synthesis, (ii) self-assembly with primary building blocks, and (iii) induced matter relocations. In most cases, both synthesis and self-assembly are involved in the above processes. Further combinations of these methodologies appear to be very important, as they will allow one to prepare functional materials at a higher level of complexity and precision. The synthetic strategies are introduced through some simple case studies with schematic illustrations. Salient features of the methods developed have been summarized, and some urgent issues of this field have also been indicated. © 2011 The Royal Society of Chemistry.

  5. Self-assembled single-phase perovskite nanocomposite thin films. (United States)

    Kim, Hyun-Suk; Bi, Lei; Paik, Hanjong; Yang, Dae-Jin; Park, Yun Chang; Dionne, Gerald F; Ross, Caroline A


    Thin films of perovskite-structured oxides with general formula ABO(3) have great potential in electronic devices because of their unique properties, which include the high dielectric constant of titanates, (1) high-T(C) superconductivity in cuprates, (2) and colossal magnetoresistance in manganites. (3) These properties are intimately dependent on, and can therefore be tailored by, the microstructure, orientation, and strain state of the film. Here, we demonstrate the growth of cubic Sr(Ti,Fe)O(3) (STF) films with an unusual self-assembled nanocomposite microstructure consisting of (100) and (110)-oriented crystals, both of which grow epitaxially with respect to the Si substrate and which are therefore homoepitaxial with each other. These structures differ from previously reported self-assembled oxide nanocomposites, which consist either of two different materials (4-7) or of single-phase distorted-cubic materials that exhibit two or more variants. (8-12) Moreover, an epitaxial nanocomposite SrTiO(3) overlayer can be grown on the STF, extending the range of compositions over which this microstructure can be formed. This offers the potential for the implementation of self-organized optical/ferromagnetic or ferromagnetic/ferroelectric hybrid nanostructures integrated on technologically important Si substrates with applications in magnetooptical or spintronic devices.

  6. Managing lifelike behavior in a dynamic self-assembled system (United States)

    Ropp, Chad; Bachelard, Nicolas; Wang, Yuan; Zhang, Xiang

    Self-organization can arise outside of thermodynamic equilibrium in a process of dynamic self-assembly. This is observed in nature, for example in flocking birds, but can also be created artificially with non-living entities. Such dynamic systems often display lifelike properties, including the ability to self-heal and adapt to environmental changes, which arise due to the collective and often complex interactions between the many individual elements. Such interactions are inherently difficult to predict and control, and limit the development of artificial systems. Here, we report a fundamentally new method to manage dynamic self-assembly through the direct external control of collective phenomena. Our system consists of a waveguide filled with mobile scattering particles. These particles spontaneously self-organize when driven by a coherent field, self-heal when mechanically perturbed, and adapt to changes in the drive wavelength. This behavior is governed by particle interactions that are completely mediated by coherent wave scattering. Compared to hydrodynamic interactions which lead to compact ordered structures, our system displays sinusoidal degeneracy and many different steady-state geometries that can be adjusted using the external field.

  7. Free surface BCP self-assembly process characterization with CDSEM (United States)

    Levi, Shimon; Weinberg, Yakov; Adan, Ofer; Klinov, Michael; Argoud, Maxime; Claveau, Guillaume; Tiron, Raluca


    A simple and common practice to evaluate Block copolymers (BCP) self-assembly performances, is on a free surface wafer. With no guiding pattern the BCP designed to form line space pattern for example, spontaneously rearranges to form a random fingerprint type of a pattern. The nature of the rearrangement is dictated by the physical properties of the BCP moieties, wafer surface treatment and the self-assembly process parameters. Traditional CDSEM metrology algorithms are designed to measure pattern with predefined structure, like linespace or oval via holes. Measurement of pattern with expected geometry can reduce measurement uncertainty. Fingerprint type of structure explored in this dissertation, poses a challenge for CD-SEM measurement uncertainty and offers an opportunity to explore 2D metrology capabilities. To measure this fingerprints we developed a new metrology approach that combines image segmentation and edge detection to measure 2D pattern with arbitrary rearrangement. The segmentation approach enabled to quantify the quality of the BCP material and process, detecting 2D attributes such as: CD and CDU at one axis, and number of intersections, length and number of PS fragments, etched PMMA spaces and donut shapes numbers on the second axis. In this paper we propose a 2D metrology to measure arbitrary BCP pattern on a free surface wafer. We demonstrate experimental results demonstrating precision data, and characterization of PS-b-PMMA BCP, intrinsic period L0 = 38nm (Arkema), processed at different bake time and temperatures.

  8. Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles (United States)

    Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai


    Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.

  9. Hierarchical Self-Assembly of Light Guided Spinning Microgears (United States)

    Aubret, Antoine; Youssef, Mena; Sacanna, Stefano; Palacci, Jeremie; Sacanna Group, NYU Team


    In this work, we demonstrate the self-assembly of microgears obtained from the guided construction of tailored self-propelled particles used as primary building blocks. The experiment relies on our control of phoretic phenomena: the migration of particles in a solute gradient. We activate a photocatalytic material, the hematite, and trigger the decomposition of hydrogen peroxide to set concentration gradient. We use this effect to engineer phototactic swimmers, attracted to the region of high illumination. We guide the swimmers to form robust and highly persistent microgears. They interact with each other through hydrodynamics and diffusiophoretically through the chemical clouds of fuel consumption. Multiple rotors are studied and we specifically address the dynamics of two rotors. We show that the microgears move collectively or synchronize thanks to the interaction of their chemical clouds. Increasing the number of microrotors (N = 2 - 7), we form an active crystal which can rotate, re-organize, change shape, and exhibit phase synchronization between its individual components. Such crystal made of non-equilibrium rotating gears at the microscale is unique. Our study paves the way for better understanding and control of emergent phenomena in collection of active spinning particles. It is a promising avenue for the creation of cutting-edge materials using emergent behavior from hierarchical self-assembly to unveil untapped functionalities. This work is supported by NSF CAREER DMR 1554724.

  10. Dynamic diversity of synthetic supramolecular polymers in water as revealed by hydrogen/deuterium exchange (United States)

    Lou, Xianwen; Lafleur, René P. M.; Leenders, Christianus M. A.; Schoenmakers, Sandra M. C.; Matsumoto, Nicholas M.; Baker, Matthew B.; van Dongen, Joost L. J.; Palmans, Anja R. A.; Meijer, E. W.


    Numerous self-assembling molecules have been synthesized aiming at mimicking both the structural and dynamic properties found in living systems. Here we show the application of hydrogen/deuterium exchange (HDX) mass spectrometry (MS) to unravel the nanoscale organization and the structural dynamics of synthetic supramolecular polymers in water. We select benzene-1,3,5-tricarboxamide (BTA) derivatives that self-assemble in H2O to illustrate the strength of this technique for supramolecular polymers. The BTA structure has six exchangeable hydrogen atoms and we follow their exchange as a function of time after diluting the H2O solution with a 100-fold excess of D2O. The kinetic H/D exchange profiles reveal that these supramolecular polymers in water are dynamically diverse; a notion that has previously not been observed using other techniques. In addition, we report that small changes in the molecular structure can be used to control the dynamics of synthetic supramolecular polymers in water.

  11. Chemical and entropic control on the molecular self-assembly process


    Packwood, Daniel M.; Han, Patrick; Hitosugi, Taro


    Molecular self-assembly refers to the spontaneous assembly of molecules into larger structures. In order to exploit molecular self-assembly for the bottom-up synthesis of nanomaterials, the effects of chemical control (strength of the directionality in the intermolecular interaction) and entropic control (temperature) on the self-assembly process should be clarified. Here we present a theoretical methodology that unambiguously distinguishes the effects of chemical and entropic control on the ...

  12. Combing and self-assembly phenomena in dry films of Taxol-stabilized microtubules

    Directory of Open Access Journals (Sweden)

    Rose Franck


    Full Text Available AbstractMicrotubules are filamentous proteins that act as a substrate for the translocation of motor proteins. As such, they may be envisioned as a scaffold for the self-assembly of functional materials and devices. Physisorption, self-assembly and combing are here investigated as a potential prelude to microtubule-templated self-assembly. Dense films of self-assembled microtubules were successfully produced, as well as patterns of both dendritic and non-dendritic bundles of microtubules. They are presented in the present paper and the mechanism of their formation is discussed.

  13. Protective Coatings for Space System Components Fabricated Using Ionic Self Assembled Monolayer Processes

    National Research Council Canada - National Science Library

    Miler, Mike


    Self-assembled multilayer thin film fabrication methods offer unique opportunities to incorporate multiple functionalities into coatings for space system materials and structures as well as consumer products...

  14. Applications of molecular self-assembly in tissue engineering (United States)

    Harrington, Daniel Anton

    This thesis studied the application of three self-assembling molecular systems, as potential biomaterials for tissue engineering applications. Cholesteryl-(L-lactic acid)n molecules form thermotropic liquid crystals, which could be coated onto the inner and outer pores of biodegradable PLLA scaffolds, while retaining the lamellar order of the neat material. Primary bovine chondrocytes were cultured on these structures, demonstrating improved attachment and extended retention of phenotype on the C-LA-coated scaffolds. No difference in fibronectin adsorption to C-LA and PLLA surfaces was observed, suggesting a strong role for cholesterol in influencing cell phenotype. A family of peptide-amphiphiles, bearing the "RGD" adhesion sequence from fibronectin, was also assessed in the contexts of cartilage and bladder repair. These molecules self-assemble into one-dimensional fibers, with diameters of 6--8 nm, and lengths of 500 nm or greater. Chondrocytes were seeded and cultured on covalently-crosslinked PA gels and embedded within calcium-triggered PA gels. Cells became dormant over time, but remained viable, suggesting an inappropriate display of the adhesion sequence to cells. A family of "branched" PA molecules with lysine dendron headgroups was designed, in an effort to increase the spatial separation between molecules in the assembled state, and to theoretically improve epitope accessibility. These molecules coated reliably onto PGA fiber scaffolds, and dramatically increased the attachment of human bladder smooth muscle cells, possibly through better epitope display or electrostatic attraction. They also formed strong gels with several negatively-charged biologically-relevant macromolecules. In a third system, amphiphilic segmented dendrimers based on phenylene vinylene and L-lysine entered cells through an endocytic pathway with no discernible toxic effect on cell proliferation or morphology. These amphiphiles formed complex aggregates in aqueous solution, likely

  15. Principles Governing the Self Assembly of Polypeptide Nanoparticles (United States)

    Wahome, Newton

    Self assembling systems on the nanometer scale afford the advantage of being able to control submicron level events. In this study, we focus on the self-assembling polypeptide nanoparticles (SAPN). The SAPN scaffold is made up of oligomerizing domains that align along the principle rotational axes of icosahedral symmetry. By aligning them along these axes, a particle with spherical geometry can be achieved. This particle can be utilized as a vaccine, as a drug delivery vehicle, or as a biomedical imaging device. This research will try to answer why the SAPN self-assembles into distinct molecular weight ranges while mostly maintaining a spherical morphology. The first means will be theoretical and computational, where we will utilize a mathematical formalism to find out how the packing of SAPN's monomeric units can occur within symmetric space. Then molecular dynamics will be run within this symmetric space to test the per amino acid residue susceptibility of SAPN towards becoming polymorphic in nature. Means for examining the aggregation propensity of SAPN will be also be tested. Specifically, the relationship of different sequences of SAPN with pH will be elucidated. Co-assembly of SAPN to reduce the surface density of an aggregation prone epitope will be tested. Also, aggregation reduction consisting of the exchange of an anionic denaturant with a positively charged suppressor in order to mitigate a priori peptide association and misfolding, will also be attempted. SAPN has been shown to be an immunogenic platform for the presentation of pathogen derived antigens. We will attempt to show the efficacy of presenting an antigen from HIV-1 which is structurally restrained to best match the native conformation on the virus. Immunological studies will be performed to test the effect of this approach, as well testing the antigenicity of the nanoparticle in the absence of adjuvant. Finally, the antigen presenting nanoparticles will undergo formulation testing, to measure

  16. Seeded on-surface supramolecular growth for large area conductive donor-acceptor assembly. (United States)

    Goudappagouda; Chithiravel, Sundaresan; Krishnamoorthy, Kothandam; Gosavi, Suresh W; Babu, Sukumaran Santhosh


    Charge transport features of organic semiconductor assemblies are of paramount importance. However, large-area extended supramolecular structures of donor-acceptor combinations with controlled self-assembly pathways are hardly accessible. In this context, as a representative example, seeded on-surface supramolecular growth of tetrathiafulvalene and tetracyano-p-quinodimethane (TTF-TCNQ) using active termini of solution-formed sheaves has been introduced to form an extended assembly. We demonstrate for the first time, the creation of a large-area donor-acceptor assembly on the surface, which is practically very tedious, using a seeded, evaporation-assisted growth process. The excellent molecular ordering in this assembly is substantiated by its good electrical conductivity (~10⁻² S cm⁻¹). The on-surface assembly via both internally formed and externally added sheaf-like seeds open new pathways in supramolecular chemistry and device applications.

  17. Supramolecular Photodimerization of Coumarins

    Directory of Open Access Journals (Sweden)

    Koichi Tanaka


    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.

  18. Supramolecular catalysis: Refocusing catalysis

    NARCIS (Netherlands)

    van Leeuwen, P.W.N.M.; Freixa, Z.; van Leeuwen, P.W.N.M.


    This chapter contains sections titled: * Introduction: A Brief Personal History * Secondary Phosphines or Phosphites as Supramolecular Ligands * Host-Guest Catalysis * Ionic Interactions as a Means to Form Heterobidentate Assembly Ligands * Ditopic Ligands for the Construction of Bidentate Phosphine

  19. Mechanical properties of polyelectrolyte multilayer self-assembled films

    International Nuclear Information System (INIS)

    Dai Xinhua; Zhang Yongjun; Guan Ying; Yang Shuguang; Xu Jian


    The mechanical properties of electrostatic self-assembled multilayer films from polyacrylic acid (PAA) and C 60 -ethylenediamine adduct (C 60 -EDA) or poly(allylamine hydrochloride) (PAH) were evaluated by atomic force microscopy (AFM) wear experiments. Because of the higher molecular weight of PAH, the wear resistance of the (PAH/PAA) 10 film is higher than that of the (PAH/PAA) 2 (C 60 -EDA/PAA) 8 film; that is, the former is mechanically more stable than the latter. The mechanical stability of both films can be improved significantly by heat treatment, which changes the nature of the linkage from ionic to covalent. The AFM measurement also reveals that the (PAH/PAA) 2 (C 60 -EDA/PAA) 8 film is softer than the (PAH/PAA) 10 film. The friction properties of the heated films were measured. These films can be developed as potential lubrication coatings for microelectromechanical systems

  20. Phase Diagrams of Electrostatically Self-Assembled Amphiplexes

    Energy Technology Data Exchange (ETDEWEB)

    V Stanic; M Mancuso; W Wong; E DiMasi; H Strey


    We present the phase diagrams of electrostatically self-assembled amphiplexes (ESA) comprised of poly(acrylic acid) (PAA), cetyltrimethylammonium chloride (CTACl), dodecane, pentanol, and water at three different NaCl salt concentrations: 100, 300, and 500 mM. This is the first report of phase diagrams for these quinary complexes. Adding a cosurfactant, we were able to swell the unit cell size of all long-range ordered phases (lamellar, hexagonal, Pm3n, Ia3d) by almost a factor of 2. The added advantage of tuning the unit cell size makes such complexes (especially the bicontinuous phases) attractive for applications in bioseparation, drug delivery, and possibly in oil recovery.

  1. Lithographically-directed self-assembly of nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Liddle, J. Alexander; Cui, Yi; Alivisatos, Paul


    The combination of lithography and self-assembly provides apowerful means of organizing solution-synthesized nanostructures for awide variety of applications. We have developed a fluidic assembly methodthat relies on the local pinning of a moving liquid contact line bylithographically produced topographic features to concentratenanoparticles at those features. The final stages of the assembly processare controlled first by long-range immersion capillary forces and then bythe short-range electrostatic and Van der Waal's interactions. We havesuccessfully assembled nanoparticles from 50 nm to 2 nm in size usingthis technique and have also demonstrated the controlled positioning ofmore complex nanotetrapod structures. We have used this process toassemble Au nanoparticles into pre-patterned electrode structures andhave performed preliminary electrical characterization of the devices soformed. The fluidic assembly method is capable of very high yield, interms of positioning nanostructures at each lithographically-definedlocation, and of excellent specificity, with essentially no particledeposition between features.

  2. Self-assembled tunable photonic hyper-crystals. (United States)

    Smolyaninova, Vera N; Yost, Bradley; Lahneman, David; Narimanov, Evgenii E; Smolyaninov, Igor I


    We demonstrate a novel artificial optical material, the "photonic hyper-crystal", which combines the most interesting features of hyperbolic metamaterials and photonic crystals. Similar to hyperbolic metamaterials, photonic hyper-crystals exhibit broadband divergence in their photonic density of states due to the lack of usual diffraction limit on the photon wave vector. On the other hand, similar to photonic crystals, hyperbolic dispersion law of extraordinary photons is modulated by forbidden gaps near the boundaries of photonic Brillouin zones. Three dimensional self-assembly of photonic hyper-crystals has been achieved by application of external magnetic field to a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing.

  3. Bioengineering towards self-assembly of particulate vaccines. (United States)

    Rehm, Bernd H A


    There is an unmet demand for safe and efficient vaccines for prevention of various infectious diseases. Subunit vaccines comprise selected pathogen specific antigens are a safe alternative to whole organism vaccines. However they often lack immunogenicity. Natural and synthetic self-assembling polymers and proteins will be reviewed in view their use to encapsulate and/or display antigens to serve as immunogenic antigen carriers for induction of protective immunity. Recent advances made in in vivo assembly of antigen-displaying polyester inclusions will be a focus. Particulate vaccines are inherently immunogenic due to enhanced uptake by antigen presenting cells which process antigens mediating adaptive immune responses. Bioengineering approaches enable the design of tailor-made particulate vaccines to fine tune immune responses towards protective immunity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. A self assembled monolayer based microfluidic sensor for urea detection (United States)

    Srivastava, Saurabh; Solanki, Pratima R.; Kaushik, Ajeet; Ali, Md. Azahar; Srivastava, Anchal; Malhotra, B. D.


    Urease (Urs) and glutamate dehydrogenase (GLDH) have been covalently co-immobilized onto a self-assembled monolayer (SAM) comprising of 10-carboxy-1-decanthiol (CDT) via EDC-NHS chemistry deposited onto one of the two patterned gold (Au) electrodes for estimation of urea using poly(dimethylsiloxane) based microfluidic channels (2 cm × 200 μm × 200 μm). The CDT/Au and Urs-GLDH/CDT/Au electrodes have been characterized using Fourier transform infrared (FTIR) spectroscopy, contact angle (CA), atomic force microscopy (AFM) and electrochemical cyclic voltammetry (CV) techniques. The electrochemical response measurement of a Urs-GLDH/CDT/Au bioelectrode obtained as a function of urea concentration using CV yield linearity as 10 to 100 mg dl-1, detection limit as 9 mg dl-1 and high sensitivity as 7.5 μA mM-1 cm-2.

  5. Communication: Programmable self-assembly of thin-shell mesostructures (United States)

    Halverson, Jonathan D.; Tkachenko, Alexei V.


    We study numerically the possibility of programmable self-assembly of various thin-shell architectures. They include clusters isomorphic to fullerenes C20 and C60, finite and infinite sheets, tube-shaped and toroidal mesostructures. Our approach is based on the recently introduced directionally functionalized nanoparticle platform, for which we employ a hybrid technique of Brownian dynamics with stochastic bond formation. By combining a number of strategies, we were able to achieve a near-perfect yield of the desired structures with a reduced "alphabet" of building blocks. Among those strategies are the following: the use of bending rigidity of the interparticle bond as a control parameter, programming the morphology with a seed architecture, use of chirality-preserving symmetries for reduction of the particle alphabet, and the hierarchic approach.

  6. Controlled doping by self-assembled dendrimer-like macromolecules (United States)

    Wu, Haigang; Guan, Bin; Sun, Yingri; Zhu, Yiping; Dan, Yaping


    Doping via self-assembled macromolecules might offer a solution for developing single atom electronics by precisely placing individual dopants at arbitrary location to meet the requirement for circuit design. Here we synthesize dendrimer-like polyglycerol macromolecules with each carrying one phosphorus atom in the core. The macromolecules are immobilized by the coupling reagent onto silicon surfaces that are pre-modified with a monolayer of undecylenic acid. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) are employed to characterize the synthesized macromolecules and the modified silicon surfaces, respectively. After rapid thermal annealing, the phosphorus atoms carried by the macromolecules diffuse into the silicon substrate, forming dopants at a concentration of 1017 cm-3. Low-temperature Hall effect measurements reveal that the ionization process is rather complicated. Unlike the widely reported simple ionization of phosphorus dopants, nitrogen and carbon are also involved in the electronic activities in the monolayer doped silicon.

  7. Infrared spectroscopy of self-assembled monolayer films on silicon (United States)

    Rowell, N. L.; Tay, Lilin; Boukherroub, R.; Lockwood, D. J.


    Infrared vibrational spectroscopy in an attenuated total reflection (ATR) geometry has been employed to investigate the presence of organic thin layers on Si-wafer surfaces. The phenomena have been simulated to show there can be a field enhancement with the presented single-reflection ATR (SR-ATR) approach which is substantially larger than for conventional ATR or specular reflection. In SR-ATR, a discontinuity of the field normal to the film contributes a field enhancement in the lower index thin film causing a two order of magnitude increase in sensitivity. SR-ATR was employed to characterize a single monolayer of undecylenic acid self-assembled on Si(1 1 1) and to investigate a two monolayer system obtained by adding a monolayer of bovine serum albumin protein.

  8. Electrochromic properties of self-assembled nanoparticle multilayer films

    International Nuclear Information System (INIS)

    Xue Bo; Li Hong; Zhang Lanlan; Peng Jun


    Hexagonal tungsten bronze (HTB) nanocrystal and TiO 2 nanoparticles were assembled into thin films by layer-by-layer self-assembly method. HTB nanocrystals were synthesized by hydrothermal route at 155 o C. UV-Vis spectra showed that the HTB/TiO 2 films exhibit a linear increase in film thickness with assembly exposure steps. The electrochromic property of the film was carefully investigated. Cyclic voltammetry indicated that the redox peak was around -0.5 V. The electrochromic contrast, coloration efficiency, switching speed, stability and optical memory were carefully investigated. The films vary from white to blue and finally dark brown. The electrochromic contrast is 63.9% at 633 nm. The coloration efficiency of the films is relatively high. The response time is less than 3 s.

  9. Dynamic simulations of many-body electrostatic self-assembly (United States)

    Lindgren, Eric B.; Stamm, Benjamin; Maday, Yvon; Besley, Elena; Stace, A. J.


    Two experimental studies relating to electrostatic self-assembly have been the subject of dynamic computer simulations, where the consequences of changing the charge and the dielectric constant of the materials concerned have been explored. One series of calculations relates to experiments on the assembly of polymer particles that have been subjected to tribocharging and the simulations successfully reproduce many of the observed patterns of behaviour. A second study explores events observed following collisions between single particles and small clusters composed of charged particles derived from a metal oxide composite. As before, observations recorded during the course of the experiments are reproduced by the calculations. One study in particular reveals how particle polarizability can influence the assembly process. This article is part of the theme issue `Modern theoretical chemistry'.

  10. Bioactive self-assembled peptide nanofibers for corneal stroma regeneration. (United States)

    Uzunalli, G; Soran, Z; Erkal, T S; Dagdas, Y S; Dinc, E; Hondur, A M; Bilgihan, K; Aydin, B; Guler, M O; Tekinay, A B


    Defects in the corneal stroma caused by trauma or diseases such as macular corneal dystrophy and keratoconus can be detrimental for vision. Development of therapeutic methods to enhance corneal regeneration is essential for treatment of these defects. This paper describes a bioactive peptide nanofiber scaffold system for corneal tissue regeneration. These nanofibers are formed by self-assembling peptide amphiphile molecules containing laminin and fibronectin inspired sequences. Human corneal keratocyte cells cultured on laminin-mimetic peptide nanofibers retained their characteristic morphology, and their proliferation was enhanced compared with cells cultured on fibronectin-mimetic nanofibers. When these nanofibers were used for damaged rabbit corneas, laminin-mimetic peptide nanofibers increased keratocyte migration and supported stroma regeneration. These results suggest that laminin-mimetic peptide nanofibers provide a promising injectable, synthetic scaffold system for cornea stroma regeneration. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  11. Graphene growth by conversion of aromatic self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Turchanin, Andrey [Institute of Physical Chemistry, Friedrich Schiller University Jena (Germany); Jena Center for Soft Matter (JCSM), Jena (Germany); Center for Energy and Environmental Chemistry Jena (CEEC), Jena (Germany); Abbe Center of Photonics (ACP), Jena (Germany)


    Despite present diversity of graphene production methods there is still a high demand for improvement of the existing production schemes or development of new. Here a method is reviewed to produce graphene employing aromatic self-assembled monolayers (SAMs) as molecular precursors. This method is based on electron irradiation induced crosslinking of aromatic SAMs resulting in their conversion into carbon nanomembranes (CNMs) with high thermal stability and subsequent pyrolysis of CNMs into graphene in vacuum or in the inert atmosphere. Depending on the production conditions, such as chemical structure of molecular precursors, irradiation and annealing parameters, various properties of the produced graphene sheets including shape, crystallinity, thickness, optical properties and electric transport can be adjusted. The assembly of CNM/graphene van der Waals heterostructures opens a flexible route to non-destructive chemical functionalization of graphene for a variety of applications in electronic and photonic devices. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Vijay, E-mail: [Centre for Nanoscience and Engineering, Indian Institute of Science-Bangalore (India); Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); Puri, Paridhi; Nain, Shivani [Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); Bhat, K. N. [Centre for Nanoscience and Engineering, Indian Institute of Science-Bangalore (India); Sharma, N. N. [Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); School of Automobile, Mechanical & Mechatronics, Manipal University-Jaipur (India)


    Treatment of surfaces to change the interaction of fluids with them is a critical step in constructing useful microfluidics devices, especially those used in biological applications. Selective modification of inorganic materials such as Si, SiO{sub 2} and Si{sub 3}N{sub 4} is of great interest in research and technology. We evaluated the chemical formation of OTS self-assembled monolayers on silicon substrates with different dielectric materials. Our investigations were focused on surface modification of formerly used common dielectric materials SiO{sub 2}, Si{sub 3}N{sub 4} and a-poly. The improvement of wetting behaviour and quality of monolayer films were characterized using Atomic force microscope, Scanning electron microscope, Contact angle goniometer, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) monolayer deposited oxide surface.

  13. Fabrication of bioinspired nanostructured materials via colloidal self-assembly (United States)

    Huang, Wei-Han

    Through millions of years of evolution, nature creates unique structures and materials that exhibit remarkable performance on mechanicals, opticals, and physical properties. For instance, nacre (mother of pearl), bone and tooth show excellent combination of strong minerals and elastic proteins as reinforced materials. Structured butterfly's wing and moth's eye can selectively reflect light or absorb light without dyes. Lotus leaf and cicada's wing are superhydrophobic to prevent water accumulation. The principles of particular biological capabilities, attributed to the highly sophisticated structures with complex hierarchical designs, have been extensively studied. Recently, a large variety of novel materials have been enabled by natural-inspired designs and nanotechnologies. These advanced materials will have huge impact on practical applications. We have utilized bottom-up approaches to fabricate nacre-like nanocomposites with "brick and mortar" structures. First, we used self-assembly processes, including convective self-assembly, dip-coating, and electrophoretic deposition to form well oriented layer structure of synthesized gibbsite (aluminum hydroxide) nanoplatelets. Low viscous monomer was permeated into layered nanoplatelets and followed by photo-curing. Gibbsite-polymer composite displays 2 times higher tensile strength and 3 times higher modulus when compared with pure polymer. More improvement occurred when surface-modified gibbsite platelets were cross-linked with the polymer matrix. We observed ˜4 times higher strength and nearly 1 order of magnitude higher modulus than pure polymer. To further improve the mechanical strength and toughness of inorganicorganic nanocomposites, we exploited ultrastrong graphene oxide (GO), a single atom thick hexagonal carbon sheet with pendant oxidation groups. GO nanocomposite is made by co-filtrating GO/polyvinyl alcohol suspension on 0.2 im pore-sized membrane. It shows ˜2 times higher strength and ˜15 times higher

  14. Magnetic ToF GISANS on self-assembled nanoparticles (United States)

    Glavic, Artur; Josten, Elisabeth; Petracic, Oleg; Lauter, Valeria


    Nanoparticle superlattices can be considered as novel type of materials with controllable electronic, optical and magnetic properties. Their building blocks are nanoparticles (or ``nanocrystals'') from a metallic, metal-oxide, or semiconducting material or hybrid between different materials. Using self-assembling techniques it is possible to create a large amount of highly ordered 3D structures, which we have investigated for their structural and magnetic properties. The lateral ordering is quantified using electron microscopy and grazing incidence small angle X-ray scattering (GISAXS). The macroscopic magnetic behavior and correlations are investigated by superconducting quantum interference device (SQUID) magnetometry. Utilizing the time of flight (ToF) magnetism reflectometer at SNS the magnetic correlations have been studied with polarized GISANS and PNR. This research at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.

  15. Self-Assembled PbSe Nanowire:Perovskite Hybrids

    KAUST Repository

    Yang, Zhenyu


    © 2015 American Chemical Society. Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

  16. Nanophotonic Fabrication Self-Assembly and Deposition Techniques

    CERN Document Server

    Yatsui, Takashi


    Nanophotonics, a novel optical technology, utilizes the local interaction between nanometric particles via optical near fields. The optical near fields are the elementary surface excitations on nanometric particles, i.e. dressed photons that carry material energy. Of the variety of qualitative innovations in optical technology realized by nanophotonics, this books focuses on fabrication. To fabricate nano-scale photonic devices with nanometer-scale controllability in size and position, we developed a self-assembly method for size- and position-controlled ultra-long nanodot chains using a novel effect of near-field optical desorption. A novel deposition and etching scheme under nonresonant conditions is also demonstrated and its origin is reviewed.

  17. Self-Assembled InAs Nanowires as Optical Reflectors. (United States)

    Floris, Francesco; Fornasari, Lucia; Marini, Andrea; Bellani, Vittorio; Banfi, Francesco; Roddaro, Stefano; Ercolani, Daniele; Rocci, Mirko; Beltram, Fabio; Cecchini, Marco; Sorba, Lucia; Rossella, Francesco


    Subwavelength nanostructured surfaces are realized with self-assembled vertically-aligned InAs nanowires, and their functionalities as optical reflectors are investigated. In our system, polarization-resolved specular reflectance displays strong modulations as a function of incident photon energy and angle. An effective-medium model allows one to rationalize the experimental findings in the long wavelength regime, whereas numerical simulations fully reproduce the experimental outcomes in the entire frequency range. The impact of the refractive index of the medium surrounding the nanostructure assembly on the reflectance was estimated. In view of the present results, sensing schemes compatible with microfluidic technologies and routes to innovative nanowire-based optical elements are discussed.

  18. Functional Molecular Junctions Derived from Double Self-Assembled Monolayers. (United States)

    Seo, Sohyeon; Hwang, Eunhee; Cho, Yunhee; Lee, Junghyun; Lee, Hyoyoung


    Information processing using molecular junctions is becoming more important as devices are miniaturized to the nanoscale. Herein, we report functional molecular junctions derived from double self-assembled monolayers (SAMs) intercalated between soft graphene electrodes. Newly assembled molecular junctions are fabricated by placing a molecular SAM/(top) electrode on another molecular SAM/(bottom) electrode by using a contact-assembly technique. Double SAMs can provide tunneling conjugation across the van der Waals gap between the terminals of each monolayer and exhibit new electrical functions. Robust contact-assembled molecular junctions can act as platforms for the development of equivalent contact molecular junctions between top and bottom electrodes, which can be applied independently to different kinds of molecules to enhance either the structural complexity or the assembly properties of molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers. (United States)

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping


    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10(-15) cm(2) s(-1), 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value.

  20. Tuning electronic transport in a self-assembled nanocomposite. (United States)

    Chang, Wei Sea; Liu, Heng-Jui; Tra, Vu Thanh; Chen, Jhih-Wei; Wei, Tzu-Chiao; Tzeng, W Y; Zhu, Yuanmin; Kuo, Ho-Hung; Hsieh, Ying-Hui; Lin, Jheng-Cyuan; Zhan, Qian; Luo, Chih Wei; Lin, Jiunn-Yuan; He, Jr-Hau; Wu, Chung Lin; Chu, Ying-Hao


    Self-assembled nanocomposites with a high interface-to-volume ratio offer an opportunity to overcome limitations in current technology, where intriguing transport behaviors can be tailored by the choice of proper interactions of constituents. Here we integrated metallic perovskite oxide SrRuO3-wurzite semiconductor ZnO nanocomposites to investigate the room-temperature metal-insulator transition and its effect on photoresponse. We demonstrate that the band structure at the interface can be tuned by controlling the interface-to-volume ratio of the nanocomposites. Photoinduced carrier injection driven by visible light was detected across the nanocomposites. This work shows the charge interaction of the vertically integrated multiheterostructures by incorporating a controllable interface-to-volume ratio, which is essential for optimization of the design and functionality of electronic devices.

  1. Modeling self-assembly and phase behavior in complex mixtures. (United States)

    Balazs, Anna C


    Using a variety of computational techniques, I investigate how the self-assembly of complex mixtures can be guided by surfaces or external stimuli to form spatially regular or temporally periodic patterns. Focusing on mixtures in confined geometries, I examine how thermodynamic and hydrodynamic effects can be exploited to create regular arrays of nanowires or monodisperse, particle-filled droplets. I also show that an applied light source and chemical reaction can be harnessed to create hierarchically ordered patterns in ternary, phase-separating mixtures. Finally, I consider the combined effects of confining walls and a chemical reaction to demonstrate that a swollen polymer gel can be driven to form dynamically periodic structures. In addition to illustrating the effectiveness of external factors in directing the self-organization of multicomponent mixtures, the selected examples illustrate how coarse-grained models can be used to capture both the equilibrium phase behavior and the dynamics of these complex systems.

  2. Engineering self-assembled bioreactors from protein microcompartments

    Energy Technology Data Exchange (ETDEWEB)

    Savage, David [Univ. of California, Berkeley, CA (United States)


    The goals of this research are to understand how organisms such as bacteria segregate certain metabolic processes inside of specific structures, or “microcompartments,” in the cell and apply this knowledge to develop novel engineered microcompartments for use in nanotechnology and metabolic engineering. For example, in some bacteria, self-assembling protein microcompartments called carboxysomes encapsulate the enzymes involved in carbon fixation, enabling the cell to utilize carbon dioxide more effectively than if the enzymes were free in the cell. The proposed research will determine how structures such as carboxysomes assemble and function in bacteria and develop a means for creating novel, synthetic microcompartments for optimizing production of specific energy-rich compounds.

  3. Modelling the self-assembly of virus capsids (United States)

    Johnston, Iain G.; Louis, Ard A.; Doye, Jonathan P. K.


    We use computer simulations to study a model, first proposed by Wales (2005 Phil. Trans. R. Soc. A 363 357), for the reversible and monodisperse self-assembly of simple icosahedral virus capsid structures. The success and efficiency of assembly as a function of thermodynamic and geometric factors can be qualitatively related to the potential energy landscape structure of the assembling system. Even though the model is strongly coarse-grained, it exhibits a number of features also observed in experiments, such as sigmoidal assembly dynamics, hysteresis in capsid formation and numerous kinetic traps. We also investigate the effect of macromolecular crowding on the assembly dynamics. Crowding agents generally reduce capsid yields at optimal conditions for non-crowded assembly, but may increase yields for parameter regimes away from the optimum. Finally, we generalize the model to a larger triangulation number T = 3, and observe assembly dynamics more complex than that seen for the original T = 1 model.

  4. Sulfonation of alkyl phenyl ether self-assembled monolayers. (United States)

    Katash, Irit; Luo, Xianglin; Sukenik, Chaim N


    The sulfonation of phenyl ether decorated self-assembled monolayers (SAMs) was studied with an eye toward creating surfaces with a particularly high negative charge density based on a close-packed array of phenyl rings with more than one sulfonic acid group per molecule. The product distribution and kinetics of this process were studied by ultraviolet, infrared, and photoelectron spectroscopies and by monitoring changes in the thickness and wetting properties of the SAM. The sulfonation chemistry could be effected without undermining monolayer integrity and the isomer distribution of ortho- and para-monosulfonated material, along with the percentages of mono- and disulfonated molecules could be established throughout the process. As doubly sulfonated molecules appeared, the reaction slowed drastically. Ultimately, sulfonation stops completely with approximately 60% of the molecules disulfonated and 20% each of the two monosulfonated isomers. This striking constraint on monolayer reactivity and the relationship between the surface chemistry and variations in SAM structure are discussed.

  5. Guided self-assembly of nanostructured titanium oxide

    International Nuclear Information System (INIS)

    Wang Baoxiang; Rozynek, Zbigniew; Fossum, Jon Otto; Knudsen, Kenneth D; Yu Yingda


    A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiO x nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiO x nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiO x nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiO x nanorods with rough surfaces are formed by the self-assembly of TiO x nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiO x nanorods shows stronger ER properties than that of the other nanostructured TiO x particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect. (paper)

  6. Self-assembling hybrid diamond-biological quantum devices (United States)

    Albrecht, A.; Koplovitz, G.; Retzker, A.; Jelezko, F.; Yochelis, S.; Porath, D.; Nevo, Y.; Shoseyov, O.; Paltiel, Y.; Plenio, M. B.


    The realization of scalable arrangements of nitrogen vacancy (NV) centers in diamond remains a key challenge on the way towards efficient quantum information processing, quantum simulation and quantum sensing applications. Although technologies based on implanting NV-centers in bulk diamond crystals or hybrid device approaches have been developed, they are limited by the achievable spatial resolution and by the intricate technological complexities involved in achieving scalability. We propose and demonstrate a novel approach for creating an arrangement of NV-centers, based on the self-assembling capabilities of biological systems and their beneficial nanometer spatial resolution. Here, a self-assembled protein structure serves as a structural scaffold for surface functionalized nanodiamonds, in this way allowing for the controlled creation of NV-structures on the nanoscale and providing a new avenue towards bridging the bio-nano interface. One-, two- as well as three-dimensional structures are within the scope of biological structural assembling techniques. We realized experimentally the formation of regular structures by interconnecting nanodiamonds using biological protein scaffolds. Based on the achievable NV-center distances of 11 nm, we evaluate the expected dipolar coupling interaction with neighboring NV-centers as well as the expected decoherence time. Moreover, by exploiting these couplings, we provide a detailed theoretical analysis on the viability of multiqubit quantum operations, suggest the possibility of individual addressing based on the random distribution of the NV intrinsic symmetry axes and address the challenges posed by decoherence and imperfect couplings. We then demonstrate in the last part that our scheme allows for the high-fidelity creation of entanglement, cluster states and quantum simulation applications.

  7. Mixed carboranethiol self-assembled monolayers on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, Adem [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Sohrabnia, Nima [Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey); Yilmaz, Ayşen [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey); Danışman, M. Fatih, E-mail: [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)


    Highlights: • M1 binds to the gold surface preferentially when co-deposited with M9 or O1. • Contact angles show similar trends regardless of the gold substrate roughness. • Contact angles were lower, with higher hysteresis, on template stripped gold. • Mixed carboranethiol SAMs have similar morphological properties regardless of mixing ratio. - Abstract: Carboranethiol self-assembled monolayers on metal surfaces have been shown to be very convenient systems for surface engineering. Here we have studied pure and mixed self-assembled monolayers (SAMs) of three different carboranethiol (CT) isomers on gold surfaces. The isomers were chosen with dipole moments pointing parallel to (m-1-carboranethiol, M1), out of (m-9-carboranethiol, M9) and into (o-1-carboranethiol, O1) the surface plane, in order to investigate the effect of dipole moment orientation on the film properties. In addition, influence of the substrate surface morphology on the film properties was also studied by using flame annealed (FA) and template stripped (TS) gold surfaces. Contact angle measurements indicate that in M1/M9 and M1/O1 mixed SAMs, M1 is the dominant species on the surface even for low M1 ratio in the growth solution. Whereas for O1/M9 mixed SAMs no clear evidence could be observed indicating dominance of one of the species over the other one. Though contact angle values were lower and hysteresis values were higher for SAMs grown on TS gold surfaces, the trends in the behavior of the contact angles with changing mixing ratio were identical for SAMs grown on both substrates. Atomic force microscopy images of the SAMs on TS gold surfaces indicate that the films have similar morphological properties regardless of mixing ratio.

  8. Self-assembled ordered carbon-nanotube arrays and membranes.

    Energy Technology Data Exchange (ETDEWEB)

    Overmyer, Donald L.; Siegal, Michael P.; Yelton, William Graham


    Imagine free-standing flexible membranes with highly-aligned arrays of carbon nanotubes (CNTs) running through their thickness. Perhaps with both ends of the CNTs open for highly controlled nanofiltration? Or CNTs at heights uniformly above a polymer membrane for a flexible array of nanoelectrodes or field-emitters? How about CNT films with incredible amounts of accessible surface area for analyte adsorption? These self-assembled crystalline nanotubes consist of multiple layers of graphene sheets rolled into concentric cylinders. Tube diameters (3-300 nm), inner-bore diameters (2-15 nm), and lengths (nanometers - microns) are controlled to tailor physical, mechanical, and chemical properties. We proposed to explore growth and characterize nanotube arrays to help determine their exciting functionality for Sandia applications. Thermal chemical vapor deposition growth in a furnace nucleates from a metal catalyst. Ordered arrays grow using templates from self-assembled hexagonal arrays of nanopores in anodized-aluminum oxide. Polymeric-binders can mechanically hold the CNTs in place for polishing, lift-off, and membrane formation. The stiffness, electrical and thermal conductivities of CNTs make them ideally suited for a wide-variety of possible applications. Large-area, highly-accessible gas-adsorbing carbon surfaces, superb cold-cathode field-emission, and unique nanoscale geometries can lead to advanced microsensors using analyte adsorption, arrays of functionalized nanoelectrodes for enhanced electrochemical detection of biological/explosive compounds, or mass-ionizers for gas-phase detection. Materials studies involving membrane formation may lead to exciting breakthroughs in nanofiltration/nanochromatography for the separation of chemical and biological agents. With controlled nanofilter sizes, ultrafiltration will be viable to separate and preconcentrate viruses and many strains of bacteria for 'down-stream' analysis.

  9. Origami inspired self-assembly of patterned and reconfigurable particles. (United States)

    Pandey, Shivendra; Gultepe, Evin; Gracias, David H


    There are numerous techniques such as photolithography, electron-beam lithography and soft-lithography that can be used to precisely pattern two dimensional (2D) structures. These technologies are mature, offer high precision and many of them can be implemented in a high-throughput manner. We leverage the advantages of planar lithography and combine them with self-folding methods(1-20) wherein physical forces derived from surface tension or residual stress, are used to curve or fold planar structures into three dimensional (3D) structures. In doing so, we make it possible to mass produce precisely patterned static and reconfigurable particles that are challenging to synthesize. In this paper, we detail visualized experimental protocols to create patterned particles, notably, (a) permanently bonded, hollow, polyhedra that self-assemble and self-seal due to the minimization of surface energy of liquefied hinges(21-23) and (b) grippers that self-fold due to residual stress powered hinges(24,25). The specific protocol described can be used to create particles with overall sizes ranging from the micrometer to the centimeter length scales. Further, arbitrary patterns can be defined on the surfaces of the particles of importance in colloidal science, electronics, optics and medicine. More generally, the concept of self-assembling mechanically rigid particles with self-sealing hinges is applicable, with some process modifications, to the creation of particles at even smaller, 100 nm length scales(22, 26) and with a range of materials including metals(21), semiconductors(9) and polymers(27). With respect to residual stress powered actuation of reconfigurable grasping devices, our specific protocol utilizes chromium hinges of relevance to devices with sizes ranging from 100 μm to 2.5 mm. However, more generally, the concept of such tether-free residual stress powered actuation can be used with alternate high-stress materials such as heteroepitaxially deposited semiconductor

  10. Structures of self-assembled amphiphilic peptide-heterodimers: effects of concentration, pH, temperature and ionic strength

    KAUST Repository

    Luo, Zhongli


    The amphiphilic double-tail peptides AXG were studied regarding secondary structure and self-assembly in aqueous solution. The two tails A = Ala 6 and G = Gly6 are connected by a central pair X of hydrophilic residues, X being two aspartic acids in ADG, two lysines in AKG and two arginines in ARG. The peptide AD (Ala6Asp) served as a single-tail reference. The secondary structure of the four peptides was characterized by circular dichroism spectroscopy under a wide range of peptide concentrations (0.01-0.8 mM), temperatures (20-98 °C), pHs (4-9.5) and ionic strengths. In salt-free water both ADG and AD form a β-sheet type of structure at high concentration, low pH and low temperature, in a peptide-peptide driven assembly of individual peptides. The transition has a two-state character for ADG but not for AD, which indicates that the added tail in ADG makes the assembly more cooperative. By comparison the secondary structures of AKG and ARG are comparatively stable over the large range of conditions covered. According to dynamic light scattering the two-tail peptides form supra-molecular aggregates in water, but high-resolution AFM-imaging indicate that ordered (self-assembled) structures are only formed when salt (0.1 M NaCl) is added. Since the CD-studies indicate that the NaCl has only a minor effect on the peptide secondary structure we propose that the main role of the added salt is to screen the electrostatic repulsion between the peptide building blocks. According to the AFM images ADG and AKG support a correlation between nanofibers and a β-sheet or unordered secondary structure, whereas ARG forms fibers in spite of lacking β-sheet structure. Since the AKG and ARG double-tail peptides self-assemble into distinct nanostructures while their secondary structures are resistant to environment factors, these new peptides show potential as robust building blocks for nano-materials in various medical and nanobiotechnical applications. © 2010 The Royal Society

  11. All-Atom Multiscale Molecular Dynamics Theory and Simulation of Self-Assembly, Energy Transfer and Structural Transition in Nanosystems (United States)

    Espinosa Duran, John Michael

    The study of nanosystems and their emergent properties requires the development of multiscale computational models, theories and methods that preserve atomic and femtosecond resolution, to reveal details that cannot be resolved experimentally today. Considering this, three long time scale phenomena were studied using molecular dynamics and multiscale methods: self-assembly of organic molecules on graphite, energy transfer in nanosystems, and structural transition in vault nanoparticles. Molecular dynamics simulations of the self-assembly of alkoxybenzonitriles with different tail lengths on graphite were performed to learn about intermolecular interactions and phases exhibited by self-organized materials. This is important for the design of ordered self-assembled organic photovoltaic materials with greater efficiency than the disordered blends. Simulations revealed surface dynamical behaviors that cannot be resolved experimentally today due to the lack of spatiotemporal resolution. Atom-resolved structures predicted by simulations agreed with scanning tunneling microscopy images and unit cell measurements. Then, a multiscale theory based on the energy density as a field variable is developed to study energy transfer in nanoscale systems. For applications like photothermal microscopy or cancer phototherapy is required to understand how the energy is transferred to/from nanosystems. This multiscale theory could be applied in this context and here is tested for cubic nanoparticles immersed in water for energy being transferred to/from the nanoparticle. The theory predicts the energy transfer dynamics and reveals phenomena that cannot be described by current phenomenological theories. Finally, temperature-triggered structural transitions were revealed for vault nanoparticles using molecular dynamics and multiscale simulations. Vault is a football-shaped supramolecular assembly very distinct from the commonly observed icosahedral viruses. It has very promising

  12. Self-Assembling Organic Nanopores as Synthetic Transmembrane Channels with Tunable Functions (United States)

    Wei, Xiaoxi

    A long-standing goal in the area of supramolecular self-assembly involves the development of synthetic ion/water channels capable of mimicking the mass-transport characteristics of biological channels and pores. Few examples of artificial transmembrane channels with large lumen, high conductivity and selectivity are known. A review of pronounced biological transmembrane protein channels and some representative synthetic models have been provided in Chapter 1, followed by our discovery and initial investigation of shape-persistent oligoamide and phenylene ethynylene macrocycles as synthetic ion/water channels. In Chapter 2, the systematic structural modification of oligoamide macrocycles 1, the so-called first-generation of these shape-persistent macrocycles, has led to third-generation macrocycles 3. The third generation was found to exhibit unprecedented, strong intermolecular association in both the solid state and solution via multiple techniques including X-ray diffraction (XRD), SEM, and 1H NMR. Fluorescence spectroscopy paired with dynamic light scattering (DLS) revealed that macrocycles 3 can assemble into a singly dispersed nanotubular structure in solution. The resultant self-assembling pores consisting of 3 were examined by HPTS-LUVs assays and BLM studies (Chapter 3) and found to form cation-selective (PK+/PCl- = 69:1) transmembrane ion channels with large conductance (200 ˜ 2000 pS for alkali cations) and high stability with open times reaching to 103 seconds. Tuning the aggregation state of macrocycles by choosing an appropriate polar solvent mixture (i.e., 3:1, THF:DMF, v/v) and concentration led to the formation of ion channels with well-defined square top behavior. A parallel study using DLS to examine the size of aggregates was used in conjunction with channel activity assays (LUVs/BLM) to reveal the effects of the aggregation state on channel activity. Empirical evidence now clearly indicates that a preassembled state, perhaps that of a

  13. Ordering and dynamics of oligo(phenylene ethynylene) self-assembled monolayers on Au(111)

    NARCIS (Netherlands)

    Wu, Hairong; Sotthewes, Kai; Schön, Peter Manfred; Vancso, Gyula J.; Zandvliet, Henricus J.W.


    Self-assembled monolayers of 4-[4′-(phenylethynyl)-phenylethynyl]-benzenethiolate (PPB-S) molecules on flame annealed Au(111) have been investigated by ultra-high vacuum scanning tunneling microscopy. We have found a hitherto unknown self-assembled monolayer phase. This phase consists of a

  14. Comparative self-assembly studies and self-sorting of two ...

    Indian Academy of Sciences (India)

    The propensity for self-assembly of NDI-1 was greater due to symmetrical placement of two amide groups on either arms of this chromophore which allowed -stacking in tandem with hydrogen-bonding, while NDI-2 formed thermally more stable self-assembled fibres possibly due to location of two amide groups in close ...

  15. From self-organization to self-assembly: a new materialism? (United States)

    Vincent, Bernadette Bensaude


    While self-organization has been an integral part of academic discussions about the distinctive features of living organisms, at least since Immanuel Kant's Critique of Judgement, the term 'self-assembly' has only been used for a few decades as it became a hot research topic with the emergence of nanotechnology. Could it be considered as an attempt at reducing vital organization to a sort of assembly line of molecules? Considering the context of research on self-assembly I argue that the shift of attention from self-organization to self-assembly does not really challenge the boundary between chemistry and biology. Self-assembly was first and foremost investigated in an engineering context as a strategy for manufacturing without human intervention and did not raise new perspectives on the emergence of vital organization itself. However self-assembly implies metaphysical assumptions that this paper tries to disentangle. It first describes the emergence of self-assembly as a research field in the context of materials science and nanotechnology. The second section outlines the metaphysical implications and will emphasize a sharp contrast between the ontology underlying two practices of self-assembly developed under the umbrella of synthetic biology. And unexpectedly, we shall see that chemists are less on the reductionist side than most synthetic biologists. Finally, the third section ventures some reflections on the kind of design involved in self-assembly practices.

  16. Three-dimensional visualization and characterization of polymeric self-assemblies by Transmission Electron Microtomography

    NARCIS (Netherlands)

    H. Jinnai (Hiroshi); T. Higuchi (Takeshi); X. Zhuge (Jason); A. Kumamoto (Akihito); K.J. Batenburg (Joost); Y. Ikuhara (Yuichi)


    textabstractSelf-assembling structures and their dynamical processes in polymeric systems have been investigated using three-dimensional transmission electron microscopy (3D-TEM). Block copolymers (BCPs) self-assemble into nanoscale periodic structures called microphase-separated structures, a deep

  17. Macroscopic equivalence for microscopic motion in a turbulence driven three-dimensional self-assembly reactor

    NARCIS (Netherlands)

    Hageman, T. A. G.; Löthman, P. A.; Dirnberger, M.; Elwenspoek, M.; Manz, A; Abelmann, L.

    We built and characterised a macroscopic self-assembly reactor that agitates magnetic, centimeter-sized particles with a turbulent water flow. By scaling up the self-assembly processes to the centimeter-scale, the characteristic time constant scale also drastically increases. This makes the system a

  18. Challenges and advances in the field of self-assembled membranes

    NARCIS (Netherlands)

    van Rijn, Patrick; Tutus, Murat; Kathrein, Christine; Zhu, Leilei; Wessling, Matthias; Schwaneberg, Ulrich; Boeker, Alexander


    Self-assembled membranes are of vital importance in biological systems e. g. cellular and organelle membranes, however, more focus is being put on synthetic self-assembled membranes not only as an alternative for lipid membranes but also as an alternative for lithographic methods. More

  19. A self-assembled monolayer-assisted surface microfabrication and release technique

    NARCIS (Netherlands)

    Kim, B.J.; Liebau, M.; Huskens, Jurriaan; Reinhoudt, David; Brugger, J.P.


    This paper describes a method of thin film and MEMS processing which uses self-assembled monolayers as ultra-thin organic surface coating to enable a simple removal of microfabricated devices off the surface without wet chemical etching. A 1.5-nm thick self-assembled monolayer of

  20. Self-assembly of virus-like particles of porcine circovirus type 2 capsid protein expressed from Escherichia coli

    Directory of Open Access Journals (Sweden)

    Cai Xuepeng


    Full Text Available Abstract Background Porcine circovirus 2 (PCV2 is a serious problem to the swine industry and can lead to significant negative impacts on profitability of pork production. Syndrome associated with PCV2 is known as porcine circovirus closely associated with post-weaning multisystemic wasting syndrome (PMWS. The capsid (Cap protein of PCV2 is a major candidate antigen for development of recombinant vaccine and serological diagnostic method. The recombinant Cap protein has the ability to self-assemble into virus-like particles (VLPs in vitro, it is particularly opportunity to develop the PV2 VLPs vaccine in Escherichia coli,(E.coli , because where the cost of the vaccine must be weighed against the value of the vaccinated pig, when it was to extend use the VLPs vaccine of PCV2. Results In this report, a highly soluble Cap-tag protein expressed in E.coli was constructed with a p-SMK expression vector with a fusion tag of small ubiquitin-like modifiers (SUMO. The recombinant Cap was purified using Ni2+ affinity resins, whereas the tag was used to remove the SUMO protease. Simultaneously, the whole native Cap protein was able to self-assemble into VLPs in vitro when viewed under an electron microscope. The Cap-like particles had a size and shape that resembled the authentic Cap. The result could also be applied in the large-scale production of VLPs of PCV2 and could be used as a diagnostic antigen or a potential VLP vaccine against PCV2 infection in pigs. Conclusion we have, for the first time, utilized the SUMO fusion motif to successfully express the entire authentic Cap protein of PCV2 in E. coli. After the cleavage of the fusion motif, the nCap protein has the ability to self-assemble into VLPs, which can be used as as a potential vaccine to protect pigs from PCV2-infection.

  1. New amphiphilic glycopolypeptide conjugate capable of self-assembly in water into reduction-sensitive micelles for triggered drug release

    International Nuclear Information System (INIS)

    Yang, Hui-Kang; Zhang, Li-Ming


    For the development of biomimetic carriers for stimuli-sensitive delivery of anticancer drugs, a novel amphiphilic glycopolypeptide conjugate containing the disulfide bond was prepared for the first time by the ring-opening polymerization of benzyl glutamate N-carboxy anhydride in the presence of (propargyl carbamate)ethyl dithio ethylamine and then click conjugation with α-azido dextran. Its structure was characterized by Fourier-transform infrared spectroscopy and nuclear magnetic resonance analyses. Owing to its amphiphilic nature, such a conjugate could self assemble into nanosize micelles in aqueous medium, as confirmed by fluorometry, transmission electron microscopy and dynamic light scattering. For the resultant micelles, it was found to encapsulate poorly water-soluble anticancer drug (methotrexate, MTX) with the loading efficiency of 45.2%. By the in vitro drug release tests, the release rate of encapsulated MTX was observed to be accelerated significantly in the presence of 10 mM 1,4-dithio-DL-threitol (DTT), analogous to the intracellular redox potential. - Graphical abstract: New amphiphilic glycopolypeptide conjugate containing the disulfide bond could self-assemble in aqueous solution into reduction-sensitive micelles for triggered release of an anticancer drug (methotrexate, MTX) in the presence of 10 mM 1,4-dithio-DL-threitol (DTT). - Highlights: • Amphiphilic glycopolypeptide conjugate containing disulfide bond was prepared. • Such a conjugate self assembled in aqueous solution into nanosize micelles. • The resultant micelles could encapsulate effectively methotrexate drug. • The drug-loaded micelles showed a reduction-sensitive drug release behavior

  2. Synthesis of nanocrystals and nanocrystal self-assembly (United States)

    Chen, Zhuoying

    Chapter 1. A general introduction is presented on nanomaterials and nanoscience. Nanoparticles are discussed with respect to their structure and properties. Ferroelectric materials and nanoparticles in particular are highlighted, especially in the case of the barium titanate, and their potential applications are discussed. Different nanocrystal synthetic techniques are discussed. Nanoparticle superlattices, the novel "meta-materials" built from self-assembly at the nanoscale, are introduced. The formation of nanoparticle superlattices and the importance and interest of synthesizing these nanostructures is discussed. Chapter 2. Advanced applications for high k dielectric and ferroelectric materials in the electronics industry continues to demand an understanding of the underlying physics in decreasing dimensions into the nanoscale. The first part of this chapter presents the synthesis, processing, and electrical characterization of nanostructured thin films (thickness ˜100 nm) of barium titanate BaTiO3 built from uniform nanoparticles (alcohols were used to study the effect of size and morphological control over the nanocrystals. Techniques including X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and high-resolution electron microscopy are used to examine crystallinity and morphology. Chapter 3. By investigating the self-assembly of cadmium selenide-gold (CdSe-Au) nanoparticle mixtures by transmission electron microscopy after solvent evaporation, the effect of solvents in the formation process of CdSe-Au binary nanoparticle superlattices (BNSLs) was studied. 1-dodecanethiol was found to be critical in generating conditions necessary for superlattice formation, prior to the other factors that likely determine structure, highlighting the dual role of this organic polar molecule as both ligand and high boiling point/crystallization solvent. The influence of thiol was investigated under various concentrations (and also

  3. Anion binding in covalent and self-assembled molecular capsules. (United States)

    Ballester, Pablo


    This critical review describes selected examples extracted from the extensive literature generated during the past 42 years on the topic of anion binding in molecular capsules. The goal of including anions in molecular capsules emerges from the idea of incorporating the traits exhibited by biological receptors into synthetic ones. At the outset of this research area the capsules were unimolecular. The scaffold of the receptor was designed to covalently link a series of functional groups that could converge into a cavity and to avoid its collapse. The initial examples involved the encapsulation of one monoatomic spherical anion. With time, the cavity size of the receptor was increased and encapsulation of polyatomic anions and co-encapsulation became a reality. Synthetic economy fueled the use of aggregates of self-complementary molecules rather than one large molecule as capsules. The main purpose of this review is to give a general overview of the topic which might be of interest to supramolecular or non supramolecular chemists alike (149 references).

  4. Controlling Photoconductivity in PBI Films by Supramolecular Assembly. (United States)

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


    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.

  5. Supramolecular Chemistry in Microflow Fields: Toward a New Material World of Precise Kinetic Control. (United States)

    Numata, Munenori


    Constructing new and versatile self-assembling systems in supramolecular chemistry is much like the development of new reactions or new catalysts in synthetic organic chemistry. As one such new technology, conventional supramolecular assembly systems have been combined with microflow techniques to control intermolecular or interpolymer interactions through precise regulation of a flowing self-assembly field. The potential of the microflow system has been explored by using various simple model compounds. Uniform solvent diffusion in the microflow leads to rapid activation of molecules in a nonequilibrium state and, thereby, enhanced interactions. All of these self-assembly processes begin from a temporally activated state and proceed in a uniform chemical environment, forming a synchronized cluster and resulting in effective conversion to supramolecules, with precise tuning of molecular (or polymer) interactions. This approach allows the synthesis of a variety of discrete microstructures (e.g., fibers, sheets) and unique supramolecules (e.g., hierarchical assemblies, capped fibers, polymer networks, supramolecules with time-delayed action) that have previously been inaccessible. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Molecular self-assembly for biological investigations and nanoscale lithography (United States)

    Cheunkar, Sarawut

    Small, diffusible molecules when recognized by their binding partners, such as proteins and antibodies, trigger enzymatic activity, cell communication, and immune response. Progress in analytical methods enabling detection, characterization, and visualization of biological dynamics at the molecular level will advance our exploration of complex biological systems. In this dissertation, analytical platforms were fabricated to capture membrane-associated receptors, which are essential proteins in cell signaling pathways. The neurotransmitter serotonin and its biological precursor were immobilized on gold substrates coated with self-assembled monolayers (SAMs) of oligo(ethylene glycol)alkanethiols and their reactive derivatives. The SAM-coated substrates present the biologically selective affinity of immobilized molecules to target native membrane-associated receptors. These substrates were also tested for biospecificity using antibodies. In addition, small-molecule-functionalized platforms, expressing neurotransmitter pharmacophores, were employed to examine kinetic interactions between G-protein-coupled receptors and their associated neurotransmitters. The binding interactions were monitored using a quartz crystal microbalance equipped with liquid-flow injection. The interaction kinetics of G-protein-coupled serotonin 1A receptor and 5-hydroxytyptophan-functionalized surfaces were studied in a real-time, label-free environment. Key binding parameters, such as equilibrium dissociation constants, binding rate constants, and dissociative half-life, were extracted. These parameters are critical for understanding and comparing biomolecular interactions in modern biomedical research. By integrating self-assembly, surface functionalization, and nanofabrication, small-molecule microarrays were created for high-throughput screening. A hybrid soft-lithography, called microcontact insertion printing, was used to pattern small molecules at the dilute scales necessary for highly

  7. Directed self-assembly of mesoscopic components for led applications (United States)

    Tkachenko, Anton

    Light-emitting diodes (LEDs) constitute a rapidly evolving and fast growing technology that promises to replace incandescent bulbs and compact fluorescent lights in many illumination applications. Large-area LED luminaires have a capability to transform lighting by providing a venue for development of smart lighting systems with additional benefits, such as visible light communications, sensing, health and productivity improvement through color temperature control, capability of creating "virtual sky" ceiling, and many others. The objective of this work is to explore directed self-assembly (DSA) approaches suitable for cost-effective assembly of large amount of LEDs and other mesoscopic (i.e. millimeter and sub-millimeter) electronic components and thus to enable manufacturing of smart lighting luminaires. Existing alternative approaches for assembly of semiconductor dies are examined including transfer printing, laser-assisted die transfer, and various directed self-assembly approaches using shape-recognition, magnetic and capillary forces, etc. After comparing their advantages and limitations, we developed two approaches to magnetic force-assisted DSA of LEDs on a large-area substrate in liquid and air medium. The first approach involves pick-up of buoyant and magnetic dies from the liquid surface onto the flexible substrate in a roll-to-roll process. The possibility of high-speed assembly of LED dies is demonstrated, but with a low yield due to the influence of the capillary force of the carrier liquid and the difficulty in ensuring reliable supply of dies to the assembly interface. To overcome the aforementioned challenges this process was modified to assemble the dies by sinking them onto the receiving substrate with a stencil mask on top, demonstrating LED assembly with a very low error rate but at a lower speed. A solder-assisted self-alignment is used to further improve placement precision and to ensure the proper orientation of the dies. The second

  8. Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene Cores on Self-Assembly Behavior. Part 2: Domain Formation by Self-Assembly in Lipid Bilayer Membranes

    Directory of Open Access Journals (Sweden)

    Stefan Werner


    Full Text Available Supramolecular self-assembly of membrane constituents within a phospholipid bilayer creates complex functional platforms in biological cells that operate in intracellular signaling, trafficking and membrane remodeling. Synthetic polyphilic compounds of macromolecular or small size can be incorporated into artificial phospholipid bilayers. Featuring three or four moieties of different philicities, they reach beyond ordinary amphiphilicity and open up avenues to new functions and interaction concepts. Here, we have incorporated a series of X-shaped bolapolyphiles into DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine bilayers of giant unilamellar vesicles. The bolapolyphiles consist of a rod-like oligo(phenylene ethynylene (OPE core, hydrophilic glycerol-based headgroups with or without oligo(ethylene oxide expansions at both ends and two lateral alkyl chains attached near the center of the OPE core. In the absence of DPPC and water, the compounds showed thermotropic liquid-crystalline behavior with a transition between polyphilic and amphiphilic assembly (see part 1 in this issue. In DPPC membranes, various trends in the domain morphologies were observed upon structure variations, which entailed branched alkyl chains of various sizes, alkyl chain semiperfluorination and size expansion of the headgroups. Observed effects on domain morphology are interpreted in the context of the bulk behavior (part 1 and of a model that was previously developed based on spectroscopic and physicochemical data.

  9. Intraligand Charge Transfer Sensitization on Self-Assembled Europium Tetrahedral Cage Leads to Dual-Selective Luminescent Sensing toward Anion and Cation. (United States)

    Liu, Cui-Lian; Zhang, Rui-Ling; Lin, Chen-Sheng; Zhou, Li-Peng; Cai, Li-Xuan; Kong, Jin-Tao; Yang, Song-Qiu; Han, Ke-Li; Sun, Qing-Fu


    Luminescent supramolecular lanthanide edifices have many potential applications in biology, environments, and materials science. However, it is still a big challenge to improve the luminescent performance of multinuclear lanthanide assemblies in contrast to their mononuclear counterparts. Herein, we demonstrate that combination of intraligand charge transfer (ILCT) sensitization and coordination-driven self-assembly gives birth to bright Eu III tetrahedral cages with a record emission quantum yield of 23.1%. The ILCT sensitization mechanism has been unambiguously confirmed by both time-dependent density functional theory calculation and femtosecond transient absorption studies. Meanwhile, dual-responsive sensing toward both anions and cations has been demonstrated making use of the ILCT transition on the ligand. Without introduction of additional recognition units, high sensitivity and selectivity are revealed for the cage in both turn-off luminescent sensing toward I - and turn-on sensing toward Cu 2+ . This study offers important design principles for the future development of luminescent lanthanide molecular materials.

  10. Anandamide and analogous endocannabinoids: a lipid self-assembly study

    Energy Technology Data Exchange (ETDEWEB)

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Mulet, Xavier; Drummond, Calum J.


    Anandamide, the endogenous agonist of the cannabinoid receptors, has been widely studied for its interesting biological and medicinal properties and is recognized as a highly significant lipid signaling molecule within the nervous system. Few studies have, however, examined the effect of the physical conformation of anandamide on its function. The study presented herein has focused on characterizing the self-assembly behaviour of anandamide and four other endocannabinoid analogues of anandamide, viz., 2-arachidonyl glycerol, arachidonyl dopamine, 2-arachidonyl glycerol ether (noladin ether), and o-arachidonyl ethanolamide (virodhamine). Molecular modeling of the five endocannabinoid lipids indicates that the highly unsaturated arachidonyl chain has a preference for a U or J shaped conformation. Thermal phase studies of the neat amphiphiles showed that a glass transition was observed for all of the endocannabinoids at {approx} -110 C with the exception of anandamide, with a second glass transition occurring for 2-arachidonyl glycerol, 2-arachidonyl glycerol ether, and virodhamine (-86 C, -95 C, -46 C respectively). Both anandamide and arachidonyl dopamine displayed a crystal-isotropic melting point (-4.8 and -20.4 C respectively), while a liquid crystal-isotropic melting transition was seen for 2-arachidonyl glycerol (-40.7 C) and 2-arachidonyl glycerol ether (-71.2 C). No additional transitions were observed for virodhamine. Small angle X-ray scattering and cross polarized optical microscopy studies as a function of temperature indicated that in the presence of excess water, both 2-arachidonyl glycerol and anandamide form co-existing Q{sub II}{sup G} (gyroid) and Q{sub II}{sup D} (diamond) bicontinuous cubic phases from 0 C to 20 C, which are kinetically stable over a period of weeks but may not represent true thermodynamic equilibrium. Similarly, 2-arachidonyl glycerol ether acquired an inverse hexagonal (HII) phase in excess water from 0 C to 40 C, while

  11. Folate mediated self-assembled phytosterol-alginate nanoparticles for targeted intracellular anticancer drug delivery. (United States)

    Wang, Jianting; Wang, Ming; Zheng, Mingming; Guo, Qiong; Wang, Yafan; Wang, Heqing; Xie, Xiangrong; Huang, Fenghong; Gong, Renmin


    Self-assembled core/shell nanoparticles (NPs) were synthesized from water-soluble alginate substituted by hydrophobic phytosterols. Folate, a cancer-cell-specific ligand, was conjugated to the phytosterol-alginate (PA) NPs for targeting folate-receptor-overexpressing cancer cells. The physicochemical properties of folate-phytosterol-alginate (FPA) NPs were characterized by nuclear magnetic resonance, transmission electron microscopy, dynamic light scattering, electrophoretic light scattering, and fluorescence spectroscopy. Doxorubicin (DOX), an anticancer drug, was entrapped inside prepared NPs by dialysis method. The identification of prepared FPA NPs to folate-receptor-overexpressing cancer cells (KB cells) was confirmed by cytotoxicity and folate competition assays. Compared to the pure DOX and DOX/PA NPs, the DOX/FPA NPs had lower IC50 value to KB cells because of folate-receptor-mediated endocytosis process and the cytotoxicity of DOX/FPA NPs to KB cells could be competitively inhibited by free folate. The cellular uptake and internalization of pure DOX and DOX/FPA NPs was confirmed by confocal laser scanning microscopy image and the higher intracellular uptake of drug for DOX/FPA NPs over pure DOX was observed. The FPA NPs had the potential as a promising carrier to target drugs to cancer cells overexpressing folate receptors and avoid cytotoxicity to normal tissues. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. VP6-SUMO Self-Assembly as Nanocarriers for Gastrointestinal Delivery

    Directory of Open Access Journals (Sweden)

    V. Palmieri


    Full Text Available High proteolytic degradation and poor absorption through epithelial barriers are major challenges to successful oral delivery of therapeutics. Nanoparticle platforms can enhance drug stability and extend the residence time in gastrointestinal (GI tract. However, drug delivery systems are often inactivated in acidic environment of stomach or suffer poor absorption from intestinal cells due to the mucus layer. To overcome these issues we developed a drug delivery system constituted by a protein construct made by a Rotavirus capsid protein (VP6 and the small ubiquitin-like modifier SUMO. This chimeric construct allows specificity towards intestinal cells, the Rotavirus natural target, combined by an enhanced stability given by the eukaryotic protein transporter SUMO. Furthermore SUMO can act as a molecular switch that facilitates import/export of its ligand to the nucleus, the hypersensitive subcellular site target of many cell killing therapies. In this paper we show that SUMO-VP6 constructs self-assembly into stable nanocarriers. SUMO-VP6 nanocarriers display ideal features for drug delivery: a small size and high monodispersity, a high stability in different pH conditions and a high uptake in the nuclear and cytoplasmic compartment of intestinal cells. These features make SUMO-VP6 nanocarriers a promising novel system for oral delivery of poorly soluble drugs.

  13. Vertical Conducting Nanodomains Self-Assembled from Poly(3-hexylthiophene)-Based Diblock Copolymer Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Y Lee; S Kim; H Yang; M Jang; S Hwang; H Lee; K Baek


    We have synthesized {pi}-conjugated poly(3-hexyl thiophene)-block-poly(methyl methacrylate) (P3HT-b-PMMA) with a P3HT molecular weight of 11 kDa and a PMMA volume fraction of 0.53, which potentially has several organic electronic applications. Its phase-separation behavior was investigated for various thicknesses cast from organic solvents. When cast onto 300 nm thick SiO{sub 2} dielectrics from toluene, in which the P3HT segments have limited solubility, the P3HT-b-PMMA films consist of nanofibrillar self-assemblies of laterally {pi}-stacked P3HT chains. In contrast, the P3HT segments were found to be highly mobile in chlorobenzene, generating a typical phase-separation morphology consisting of vertically conducting P3HT nanodomains on these dielectrics. As the thickness of the cast films increased, however, the topmost surface becomes covered with {pi}-conjugated nanofibrils that are laterally oriented with respect to the surface. Due to the anisotropic domain orientations of P3HT, top-gate organic field-effect transistors (OFETs) containing the P3HT-b-PMMA films exhibited enhanced electrical performance compared to bottom-gate OFETs.

  14. Synthesis and self-assembling of responsive polysaccharide-based copolymers in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Nivia do N.; Balaban, Rosangela de C. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Halila, Sami; Borsali, Redouane, E-mail:, E-mail: [Centre de Recherche sur les Macromolecules Vegetales (CERMAV), Grenoble (France)


    This work reports the synthesis and the thermoresponsive self-assembly behavior of carboxymethylcellulose-g-JeffamineM2070 and carboxymethylcellulose-g-JeffamineM600 copolymers in aqueous media. They were prepared through the grafting of two different types of amino-terminated poly(ethylene oxide-co-propylene oxide) chains onto the carboxylate groups of carboxymethylcellulose, by using water-soluble carbodiimide derivative and N-hydroxysuccinimide as coupling reagents. The grafting efficiency was confirmed by infrared and the degree of substitution by {sup 1}H NMR integrations. The salt effect on cloud point temperature was evaluated into different solvents (Milli-Q water, 0.5M NaCl, synthetic sea water (SSW) and 0.5M K{sub 2}CO{sub 3}) by UV-Vis and dynamic light scattering (DLS) measurements. Both copolymers showed lower cloud point temperature in 0.5M K2CO3 than in 0.5M NaCl and in SSW, which was attributed to the higher ionic strength for K{sub 2}CO{sub 3} combined to the ability of CO{sub 3}{sup 2-} to decrease polymer-water interactions. Copolymers chains displayed higher hydrodynamic radii than CMC precursor at 25 and 60 °C in saline solutions, and self-associations changed as a function of the environment and copolymer composition. (author)

  15. Self-assembly of left- and right-handed molecular screws. (United States)

    Xu, Fei; Khan, I John; McGuinness, Kenneth; Parmar, Avanish S; Silva, Teresita; Murthy, N Sanjeeva; Nanda, Vikas


    Stereoselectivity is a hallmark of biomolecular processes from catalysis to self-assembly, which predominantly occur between homochiral species. However, both homochiral and heterochiral complexes of synthetic polypeptides have been observed where stereoselectivity hinges on details of intermolecular interactions. This raises the question whether general rules governing stereoselectivity exist. A geometric ridges-in-grooves model of interacting helices indicates that heterochiral associations should generally be favored in this class of structures. We tested this principle using a simplified molecular screw, a collagen peptide triple-helix composed of either l- or d-proline with a cyclic aliphatic side chain. Calculated stabilities of like- and opposite-handed triple-helical pairings indicated a preference for heterospecific associations. Mixing left- and right-handed helices drastically lowered solubility, resulting in micrometer-scale sheet-like assemblies that were one peptide-length thick as characterized with atomic force microscopy. X-ray scattering measurements of interhelical spacing in these sheets support a tight ridges-in-grooves packing of left- and right-handed triple helices.

  16. Study of polymorphism using patterned self-assembled monolayers approach on metal substrates (United States)

    Quiñones, Rosalynn; Brown, Ryanne T.; Searls, Noah; Richards-Waugh, Lauren


    Polymorphism is a molecule's ability to possess altered physical crystalline structures and has become an active interest in pharmaceuticals due to its ability to influence a drug's physical and chemical properties. Crystal stability and solubility are crucial in determining a drug's pharmacokinetics and pharmacodynamics. Changes in these properties due to polymorphisms have contributed to recalls and modifications in industrial production. For this study, the effects of surface interactions with pharmaceuticals were examined through surface modification methodology using organic phosphonic and sulfonic acid self-assembled monolayers (SAMs) developed on a nickel or zinc oxide metal substrate. Drugs analyzed included carbamazepine, cimetidine, tolfenamic acid, and flufenamic acid. All drugs were thermodynamically applied to the reformed surface to aid in recrystallization. It was hypothesized and confirmed that intermolecular bonds, especially hydrogen bonds between the SAMs and pharmaceutical drugs, were the force that assisted in polymorph development. The study was successful in revealing multiple forms for each drug, including their commercial form and at least one additional form using micro FT-IR, Raman spectroscopy, and PXRD. Visual comparisons of crystal polymorphisms were performed with IR microscopy.

  17. Electrostatic self-assembly in polyelectrolyte-neutral block copolymers and oppositely charged surfactant solutions

    International Nuclear Information System (INIS)

    Berret, J.-F.Jean-Francois; Oberdisse, Julian


    We report on small-angle neutron scattering (SANS) of colloidal complexes resulting from the electrostatic self-assembly of polyelectrolyte-neutral copolymers and oppositely charged surfactants. The polymers are double hydrophilic block copolymers of low molecular weight (between 5000 and 50 000 g/mol). One block is a polyelectrolyte chain, which can be either positively or negatively charged, whereas the second block is neutral and in good solvent conditions. In aqueous solutions, surfactants with an opposite charge to that of the polyelectrolyte interact strongly with these copolymers. The two species associate into stable 100 nm-colloidal complexes which exhibit a core-shell microstructure. For different polymer/surfactant couples, we have shown that the core is constituted from densely packed surfactant micelles connected by the polyelectrolyte chains. The outer part of the complex is a corona formed by the neutral soluble chains. Using a model of aggregation based on a Monte-Carlo algorithm, we have simulated the internal structure of the aggregates. The model assumes spherical cages containing one to several hundreds of micelles in a closely packed state. The agreement between the model and the data is remarkable

  18. Self-Assembly of Grafted Nanoparticles for Transport Channels in Membranes (United States)

    Bilchak, Connor; Buenning, Ellie; Durning, Christopher; Kumar, Sanat


    Polymer membranes have seen increased application for vapor separations, particularly for natural gas processing and purification. The addition of nanoparticles to such membranes has led to conflicting findings; conventional (Maxwell) composite theory predicts the addition of inert filler to hinder membrane transport properties. However, our research using silica nanoparticles grafted with Poly (Methacrylate) has shown these grafted systems to possess permeabilities similar to those of a pure polymer system increasing penetrant solubility without compromising diffusivity. This is counterintuitive to Maxwell theory. We propose that the grafted nanoparticles self-assemble into an ordered crystal lattice containing low-density ``channels'' which facilitate penetrant uptake. Atomic force microscopy and small-angle neutron scattering experiments appear to confirm this theory. Varying polymer grafting density and chain length is also predicted to alter transport properties, allowing for the fabrication of membrane with tunable diffusivity and selectivity. These grafted nanocomposite systems therefore represent a means of creating robust membranes with transport properties similar to those of conventional polymeric films that may be easily adapted for various separations processes. Corresponding author.

  19. Synthesis and self-assembling of responsive polysaccharide-based copolymers in aqueous media

    International Nuclear Information System (INIS)

    Marques, Nivia do N.; Balaban, Rosangela de C.; Halila, Sami; Borsali, Redouane


    This work reports the synthesis and the thermoresponsive self-assembly behavior of carboxymethylcellulose-g-JeffamineM2070 and carboxymethylcellulose-g-JeffamineM600 copolymers in aqueous media. They were prepared through the grafting of two different types of amino-terminated poly(ethylene oxide-co-propylene oxide) chains onto the carboxylate groups of carboxymethylcellulose, by using water-soluble carbodiimide derivative and N-hydroxysuccinimide as coupling reagents. The grafting efficiency was confirmed by infrared and the degree of substitution by 1 H NMR integrations. The salt effect on cloud point temperature was evaluated into different solvents (Milli-Q water, 0.5M NaCl, synthetic sea water (SSW) and 0.5M K 2 CO 3 ) by UV-Vis and dynamic light scattering (DLS) measurements. Both copolymers showed lower cloud point temperature in 0.5M K2CO3 than in 0.5M NaCl and in SSW, which was attributed to the higher ionic strength for K 2 CO 3 combined to the ability of CO 3 2- to decrease polymer-water interactions. Copolymers chains displayed higher hydrodynamic radii than CMC precursor at 25 and 60 °C in saline solutions, and self-associations changed as a function of the environment and copolymer composition. (author)

  20. High-resolution noncontact AFM and Kelvin probe force microscopy investigations of self-assembled photovoltaic donor-acceptor dyads. (United States)

    Grévin, Benjamin; Schwartz, Pierre-Olivier; Biniek, Laure; Brinkmann, Martin; Leclerc, Nicolas; Zaborova, Elena; Méry, Stéphane


    Self-assembled donor-acceptor dyads are used as model nanostructured heterojunctions for local investigations by noncontact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). With the aim to probe the photo-induced charge carrier generation, thin films deposited on transparent indium tin oxide substrates are investigated in dark conditions and upon illumination. The topographic and contact potential difference (CPD) images taken under dark conditions are analysed in view of the results of complementary transmission electron microscopy (TEM) experiments. After in situ annealing, it is shown that the dyads with longer donor blocks essentially lead to standing acceptor-donor lamellae, where the acceptor and donor groups are π-stacked in an edge-on configuration. The existence of strong CPD and surface photo-voltage (SPV) contrasts shows that structural variations occur within the bulk of the edge-on stacks. SPV images with a very high lateral resolution are achieved, which allows for the resolution of local photo-charging contrasts at the scale of single edge-on lamella. This work paves the way for local investigations of the optoelectronic properties of donor-acceptor supramolecular architectures down to the elementary building block level.