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Sample records for self-assembled network formation

  1. A new building block for DNA network formation by self-assembly and polymerase chain reaction.

    Science.gov (United States)

    Bußkamp, Holger; Keller, Sascha; Robotta, Marta; Drescher, Malte; Marx, Andreas

    2014-01-01

    The predictability of DNA self-assembly is exploited in many nanotechnological approaches. Inspired by naturally existing self-assembled DNA architectures, branched DNA has been developed that allows self-assembly to predesigned architectures with dimensions on the nanometer scale. DNA is an attractive material for generation of nanostructures due to a plethora of enzymes which modify DNA with high accuracy, providing a toolbox for many different manipulations to construct nanometer scaled objects. We present a straightforward synthesis of a rigid DNA branching building block successfully used for the generation of DNA networks by self-assembly and network formation by enzymatic DNA synthesis. The Y-shaped 3-armed DNA construct, bearing 3 primer strands is accepted by Taq DNA polymerase. The enzyme uses each arm as primer strand and incorporates the branched construct into large assemblies during PCR. The networks were investigated by agarose gel electrophoresis, atomic force microscopy, dynamic light scattering, and electron paramagnetic resonance spectroscopy. The findings indicate that rather rigid DNA networks were formed. This presents a new bottom-up approach for DNA material formation and might find applications like in the generation of functional hydrogels.

  2. Aggregation and network formation in self-assembly of protein (H3.1) by a coarse-grained Monte Carlo simulation

    Science.gov (United States)

    Pandey, R. B.; Farmer, B. L.

    2014-11-01

    Multi-scale aggregation to network formation of interacting proteins (H3.1) are examined by a knowledge-based coarse-grained Monte Carlo simulation as a function of temperature and the number of protein chains, i.e., the concentration of the protein. Self-assembly of corresponding homo-polymers of constitutive residues (Cys, Thr, and Glu) with extreme residue-residue interactions, i.e., attractive (Cys-Cys), neutral (Thr-Thr), and repulsive (Glu-Glu), are also studied for comparison with the native protein. Visual inspections show contrast and similarity in morphological evolutions of protein assembly, aggregation of small aggregates to a ramified network from low to high temperature with the aggregation of a Cys-polymer, and an entangled network of Glu and Thr polymers. Variations in mobility profiles of residues with the concentration of the protein suggest that the segmental characteristic of proteins is altered considerably by the self-assembly from that in its isolated state. The global motion of proteins and Cys polymer chains is enhanced by their interacting network at the low temperature where isolated chains remain quasi-static. Transition from globular to random coil transition, evidenced by the sharp variation in the radius of gyration, of an isolated protein is smeared due to self-assembly of interacting networks of many proteins. Scaling of the structure factor S(q) with the wave vector q provides estimates of effective dimension D of the mass distribution at multiple length scales in self-assembly. Crossover from solid aggregates (D ˜ 3) at low temperature to a ramified fibrous network (D ˜ 2) at high temperature is observed for the protein H3.1 and Cys polymers in contrast to little changes in mass distribution (D ˜ 1.6) of fibrous Glu- and Thr-chain configurations.

  3. Molecular Gels Materials with Self-Assembled Fibrillar Networks

    CERN Document Server

    Weiss, Richard G

    2006-01-01

    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...

  4. Understanding emergent functions in self-assembled fibrous networks

    Science.gov (United States)

    Sinko, Robert; Keten, Sinan

    2015-09-01

    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.

  5. Directed Formation of DNA Nanoarrays through Orthogonal Self-Assembly

    Directory of Open Access Journals (Sweden)

    Eugen Stulz

    2011-06-01

    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.

  6. Nanoporous network channels from self-assembled triblock copolymer supramolecules.

    Science.gov (United States)

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

    2011-02-16

    Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Formation of mixed and patterned self-assembled films of alkylphosphonates on commercially pure titanium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rudzka, Katarzyna; Sanchez Treviño, Alda Y.; Rodríguez-Valverde, Miguel A., E-mail: marodri@ugr.es; Cabrerizo-Vílchez, Miguel A.

    2016-12-15

    Highlights: • Chemically-tailored titanium surfaces were prepared by self-assembly of alkylphosphonates. • Mixed self-assembled films were prepared with aqueous mixtures of two alkylphosphonates. • Single self-assembled films were altered by laser abrasion. • Mixed and patterned self-assembled films on titanium may guide the bone-like formation. - Abstract: Titanium is extensively employed in biomedical devices, in particular as implant. The self-assembly of alkylphosphonates on titanium surfaces enable the specific adsorption of biomolecules to adapt the implant response against external stimuli. In this work, chemically-tailored cpTi surfaces were prepared by self-assembly of alkylphosphonate molecules. By bringing together attributes of two grafting molecules, aqueous mixtures of two alkylphosphonates were used to obtain mixed self-assembled films. Single self-assembled films were also altered by laser abrasion to produce chemically patterned cpTi surfaces. Both mixed and patterned self-assembled films were confirmed by AFM, ESEM and X-ray photoelectron spectroscopy. Water contact angle measurements also revealed the composition of the self-assembly films. Chemical functionalization with two grafting phosphonate molecules and laser surface engineering may be combined to guide the bone-like formation on cpTi, and the future biological response in the host.

  8. Multifunctional hybrid networks based on self assembling peptide sequences

    Science.gov (United States)

    Sathaye, Sameer

    loose packing can be attributed to the designed wedge and trough shapes of the peptides disturbing formation of a uniform bilayer type structure proposed in the case of MAX1 with each hairpin having a flat hydrophobic surface. Although designed changes in hydrophobic shape of the peptide nanofibril core in the new peptides were found to significantly influence the self-assembled nanostructure and network rheological behavior, a lack of direct morphological and rheological evidence to prove shape specific hydrophobic interactions between wedge and trough shaped beta-hairpins was encountered. In the second approach, peptides with established differences in assembly kinetics and bulk mechanical properties of assembled peptide hydrogels were used to develop composite materials with diverse morphological and mechanical properties by blending with the biopolymer hyaluronic acid. The diverse properties of the composites have been correlated to the specific peptide hydrogels used to develop the composite and the different stages of peptide assembly at which blending with hyaluronic acid was carried out. Finally along with overall conclusions, the new area of co-assembly of peptides in solution has been explored and discussed as potential future work following the research discussed in this dissertation. Strategies such as construction of composite hydrogels from blends of MAX1/MAX8 peptide hydrogels and biologically important anionic species such as heparin biopolymer and DNA have been discussed. Another area of future work discussed is the design and study of peptides that can incorporate chemically crosslinkable functional groups in their hydrophobic amino acid side chains that can be covalently crosslinked after peptide assembly into fibrils. Such covalent crosslinking can potentially lead to stiffer individual peptide fibrils due to additional bond formation at the fibrillar core and therefore much stiffer hydrogels due to a synergistic effect. These enhanced stiffness

  9. Self-assembled interpenetrating networks by orthogonal self assembly of surfactants and hydrogelators

    NARCIS (Netherlands)

    Brizard, Aurelie M.; Stuart, Marc C. A.; van Esch, Jan H.

    2009-01-01

    Interpenetrating networks (IPN) consist of two or more networks of different components which are entangled on a molecular scale and cannot be separated without breaking at least one of the networks. They are of great technological interest because they allow the blending of two or more otherwise

  10. Nanoporous Network Channels from Self-Assembled Triblock Copolymer Supramolecules

    NARCIS (Netherlands)

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

    2011-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Yuan Gao

    2016-10-01

    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.

  12. Formation of self-assembled stripes on the anodic aluminum oxide

    International Nuclear Information System (INIS)

    Liu Hongwen; Guo Haiming; Wang Yeliang; Shen Chengmin; Yang Haitao; Wang Yutian; Wei Long

    2004-01-01

    Non-polished aluminum sheets were anodized and the coexistence of self-assembled stripes and porous arrays on the Al surface was observed. The nanostructures were investigated in details using an atomic force microscope. And the formation mechanism of the stripes was discussed and simulated using Brusselator model in this work. The authors demonstrated that the self-assembled patterns on the Al surface were governed by the competition of formation and dissolution of alumina film during the reaction process. Moreover, this type of ordered structure could only form in certain conditions

  13. Systems and methods for creation of conducting networks of magnetic particles through dynamic self-assembly process

    Science.gov (United States)

    Snezhko, Oleksiy [Woodridge, IL; Aronson, Igor [Darien, IL; Kwok, Wai-Kwong [Downers Grove, IL

    2011-01-25

    Self-assembly of magnetic microparticles in AC magnetic fields. Excitation of the system by an AC magnetic field provides a variety of patterns that can be controlled by adjusting the frequency and the amplitude of the field. At low particle densities the low-frequency magnetic excitation favors cluster phase formation, while high frequency excitation favors chains and netlike structures. For denser configurations, an abrupt transition to the network phase was obtained.

  14. Formation of high-quality self-assembled monolayers of conjugated dithiols on gold : Base matters

    NARCIS (Netherlands)

    Valkenier, Hennie; Huisman, Everardus H.; Hal, Paul A. van; de Leeuw, Dagobert; Chiechi, Ryan C.; Hummelen, Jan C.

    2011-01-01

    This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases

  15. Water ordering controls the dynamic equilibrium of micelle-fibre formation in self-assembly of peptide amphiphiles.

    Science.gov (United States)

    Deshmukh, Sanket A; Solomon, Lee A; Kamath, Ganesh; Fry, H Christopher; Sankaranarayanan, Subramanian K R S

    2016-08-24

    Understanding the role of water in governing the kinetics of the self-assembly processes of amphiphilic peptides remains elusive. Here, we use a multistage atomistic-coarse-grained approach, complemented by circular dichroism/infrared spectroscopy and dynamic light scattering experiments to highlight the dual nature of water in driving the self-assembly of peptide amphiphiles (PAs). We show computationally that water cage formation and breakage near the hydrophobic groups control the fusion dynamics and aggregation of PAs in the micellar stage. Simulations also suggest that enhanced structural ordering of vicinal water near the hydrophilic amino acids shifts the equilibrium towards the fibre phase and stimulates structure and order during the PA assembly into nanofibres. Experiments validate our simulation findings; the measured infrared O-H bond stretching frequency is reminiscent of an ice-like bond which suggests that the solvated water becomes increasingly ordered with time in the assembled peptide network, thus shedding light on the role of water in a self-assembly process.

  16. SWARM-BOT: Pattern Formation in a Swarm of Self-Assembling Mobile Robots

    OpenAIRE

    El Kamel, A.; Mellouli, K.; Borne, P.; Sahin, E.; Labella, T.H.; Trianni, V.; Deneubourg, J.-L.; Rasse, P.; Floreano, D.; Gambardella, L.M.; Mondada, F.; Nolfi, S.; Dorigo, M.

    2002-01-01

    In this paper we introduce a new robotic system, called swarm-bot. The system consists of a swarm of mobile robots with the ability to connect to/disconnect from each other to self-assemble into different kinds of structures. First, we describe our vision and the goals of the project. Then we present preliminary results on the formation of patterns obtained from a grid-world simulation of the system.

  17. Structure formation in binary mixtures of lipids and detergents: self-assembly and vesicle division.

    Science.gov (United States)

    Noguchi, Hiroshi

    2013-01-14

    Self-assembly dynamics in binary surfactant mixtures and structure changes of lipid vesicles induced by detergent solution are studied using coarse-grained molecular simulations. Disk-shaped micelles, the bicelles, are stabilized by detergents surrounding the rim of a bilayer disk of lipids. The self-assembled bicelles are considerably smaller than bicelles formed from vesicle rupture, and their size is determined by the concentrations of lipids and detergents and the interactions between the two species. The detergent-adsorption induces spontaneous curvature of the vesicle bilayer and results in vesicle division into two vesicles or vesicle rupture into worm-like micelles. The division occurs mainly via the inverse pathway of the modified stalk model. For large spontaneous curvature of the monolayers of the detergents, a pore is often opened, thereby leading to vesicle division or worm-like micelle formation.

  18. Formation of the self-assembled structures by the ultrasonic cavitation erosion-corrosion effect on carbon steel

    Directory of Open Access Journals (Sweden)

    Dayun Yan

    2015-11-01

    Full Text Available The cavitation erosion-corrosion effect on the metal surface always forms irregular oxide structures. In this study, we reported the formation of regular self-assembled structures of amorphous nanoparticles around the cavitation erosion pits on carbon steel upon the ultrasonic cavitation in methylene blue solution. Each self-assembled structure was composed of linearly aligned nanoparticles of about 100 nm. The formation of self-assembled structures might be due to the combined effect of corrosion, specific sonochemical reaction in methylene blue solution, and the magnetic domain structures on the carbon steel.

  19. Integration of Self-Assembled Microvascular Networks with Microfabricated PEG-Based Hydrogels.

    Science.gov (United States)

    Cuchiara, Michael P; Gould, Daniel J; McHale, Melissa K; Dickinson, Mary E; West, Jennifer L

    2012-11-07

    Despite tremendous efforts, tissue engineered constructs are restricted to thin, simple tissues sustained only by diffusion. The most significant barrier in tissue engineering is insufficient vascularization to deliver nutrients and metabolites during development in vitro and to facilitate rapid vascular integration in vivo. Tissue engineered constructs can be greatly improved by developing perfusable microvascular networks in vitro in order to provide transport that mimics native vascular organization and function. Here a microfluidic hydrogel is integrated with a self-assembling pro-vasculogenic co-culture in a strategy to perfuse microvascular networks in vitro. This approach allows for control over microvascular network self-assembly and employs an anastomotic interface for integration of self-assembled micro-vascular networks with fabricated microchannels. As a result, transport within the system shifts from simple diffusion to vessel supported convective transport and extra-vessel diffusion, thus improving overall mass transport properties. This work impacts the development of perfusable prevascularized tissues in vitro and ultimately tissue engineering applications in vivo.

  20. Self-assembled three dimensional network designs for soft electronics.

    Science.gov (United States)

    Jang, Kyung-In; Li, Kan; Chung, Ha Uk; Xu, Sheng; Jung, Han Na; Yang, Yiyuan; Kwak, Jean Won; Jung, Han Hee; Song, Juwon; Yang, Ce; Wang, Ao; Liu, Zhuangjian; Lee, Jong Yoon; Kim, Bong Hoon; Kim, Jae-Hwan; Lee, Jungyup; Yu, Yongjoon; Kim, Bum Jun; Jang, Hokyung; Yu, Ki Jun; Kim, Jeonghyun; Lee, Jung Woo; Jeong, Jae-Woong; Song, Young Min; Huang, Yonggang; Zhang, Yihui; Rogers, John A

    2017-06-21

    Low modulus, compliant systems of sensors, circuits and radios designed to intimately interface with the soft tissues of the human body are of growing interest, due to their emerging applications in continuous, clinical-quality health monitors and advanced, bioelectronic therapeutics. Although recent research establishes various materials and mechanics concepts for such technologies, all existing approaches involve simple, two-dimensional (2D) layouts in the constituent micro-components and interconnects. Here we introduce concepts in three-dimensional (3D) architectures that bypass important engineering constraints and performance limitations set by traditional, 2D designs. Specifically, open-mesh, 3D interconnect networks of helical microcoils formed by deterministic compressive buckling establish the basis for systems that can offer exceptional low modulus, elastic mechanics, in compact geometries, with active components and sophisticated levels of functionality. Coupled mechanical and electrical design approaches enable layout optimization, assembly processes and encapsulation schemes to yield 3D configurations that satisfy requirements in demanding, complex systems, such as wireless, skin-compatible electronic sensors.

  1. Self-assembled three dimensional network designs for soft electronics

    Science.gov (United States)

    Jang, Kyung-In; Li, Kan; Chung, Ha Uk; Xu, Sheng; Jung, Han Na; Yang, Yiyuan; Kwak, Jean Won; Jung, Han Hee; Song, Juwon; Yang, Ce; Wang, Ao; Liu, Zhuangjian; Lee, Jong Yoon; Kim, Bong Hoon; Kim, Jae-Hwan; Lee, Jungyup; Yu, Yongjoon; Kim, Bum Jun; Jang, Hokyung; Yu, Ki Jun; Kim, Jeonghyun; Lee, Jung Woo; Jeong, Jae-Woong; Song, Young Min; Huang, Yonggang; Zhang, Yihui; Rogers, John A.

    2017-06-01

    Low modulus, compliant systems of sensors, circuits and radios designed to intimately interface with the soft tissues of the human body are of growing interest, due to their emerging applications in continuous, clinical-quality health monitors and advanced, bioelectronic therapeutics. Although recent research establishes various materials and mechanics concepts for such technologies, all existing approaches involve simple, two-dimensional (2D) layouts in the constituent micro-components and interconnects. Here we introduce concepts in three-dimensional (3D) architectures that bypass important engineering constraints and performance limitations set by traditional, 2D designs. Specifically, open-mesh, 3D interconnect networks of helical microcoils formed by deterministic compressive buckling establish the basis for systems that can offer exceptional low modulus, elastic mechanics, in compact geometries, with active components and sophisticated levels of functionality. Coupled mechanical and electrical design approaches enable layout optimization, assembly processes and encapsulation schemes to yield 3D configurations that satisfy requirements in demanding, complex systems, such as wireless, skin-compatible electronic sensors.

  2. Self-assembly of an electronically conductive network through microporous scaffolds.

    Science.gov (United States)

    Sebastian, H Bri; Bryant, Steven L

    2017-06-15

    Electron transfer spanning significant distances through a microporous structure was established via the self-assembly of an electronically conductive iridium oxide nanowire matrix enveloping the pore walls. Microporous formations were simulated using two scaffold materials of varying physical and chemical properties; paraffin wax beads, and agar gel. Following infiltration into the micropores, iridium nanoparticles self-assembled at the pore wall/ethanol interface. Subsequently, cyclic voltammetry was employed to electrochemically crosslink the metal, erecting an interconnected, and electronically conductive metal oxide nanowire matrix. Electrochemical and spectral characterization techniques confirmed the formation of oxide nanowire matrices encompassing lengths of at least 1.6mm, 400× distances previously achieved using iridium nanoparticles. Nanowire matrices were engaged as biofuel cell anodes, where electrons were donated to the nanowires by a glucose oxidizing enzyme. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Formation of self assembled PbTe quantum dots in CdTe on Si(111)

    Science.gov (United States)

    Felder, F.; Fognini, A.; Rahim, M.; Fill, M.; Müller, E.; Zogg, H.

    2010-01-01

    We describe the growth and formation of self assembled PbTe quantum dots in a CdTe host on a silicon (111) substrate. Annealing yields different photoluminescence spectra depending on initial PbTe layer thickness, thickness of the CdTe cap layer and annealing temperature. Generally two distinct emission peaks at ˜0.3 eV and ˜0.45 eV are visible. Model calculations explaining their temperature dependence are performed. The dot size corresponds well with the estimated sizes from electron microscopy images. The quantum dots may be used as absorber within a mid-infrared detector.

  4. Self-Assembly, Pattern Formation and Growth Phenomena in Nano-Systems

    CERN Document Server

    Nepomnyashchy, Alexander A

    2006-01-01

    Nano-science and nano-technology are rapidly developing scientific and technological areas that deal with physical, chemical and biological processes that occur on nano-meter scale – one millionth of a millimeter. Self-organization and pattern formation play crucial role on nano-scales and promise new, effective routes to control various nano-scales processes. This book contains lecture notes written by the lecturers of the NATO Advanced Study Institute "Self-Assembly, Pattern Formation and Growth Phenomena in Nano-Systems" that took place in St Etienne de Tinee, France, in the fall 2004. They give examples of self-organization phenomena on micro- and nano-scale as well as examples of the interplay between phenomena on nano- and macro-scales leading to complex behavior in various physical, chemical and biological systems. They discuss such fascinating nano-scale self-organization phenomena as self-assembly of quantum dots in thin solid films, pattern formation in liquid crystals caused by light, self-organi...

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

    KAUST Repository

    Chan, Kiat Hwa

    2017-10-04

    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.

  6. Surface self-assembly of fluorosurfactants during film formation of MMA/nBA colloidal dispersions.

    Science.gov (United States)

    Dreher, W R; Urban, M W

    2004-11-23

    These studies focus on the behavior of fluorosurfactants (FS) containing hydrophobic and ionic entities in the presence of methyl methacrylate/n-butyl acrylate (MMA/nBA) colloidal dispersions stabilized by sodium dodecyl sulfate (SDS). The presence of FS significantly not only alters the mobility of SDS in MMA/nBA films, but their hydrophobic and ionic nature results in self-assembly near the film-air (F-A) interface leading to different surface morphologies. Spherical islands and rodlike morphologies are formed which diminish the kinetic coefficient of friction of films by at least 3 orders of magnitude, and the presence of dual hydrophobic tails and an anionic head appears to have the largest effect on the surface friction. Using internal reflection IR imaging, these studies show that structural and chemical features of FS are directly related to their ability to migrate to the F-A interface and self-assemble to form specific morphological features. While the anionic nature of FS allows for SDS migration to the F-A interface and the formation of stable domains across the surface, intermolecular cohesion of nonionic FS allows for the formation of rodlike structures due to inability to form mixed micelles with SDS. These studies also establish the relationship between surface morphologies, kinetic coefficient of friction, and structural features of surfactants in the complex environments.

  7. Bis-naphthalimides self-assembly organogel formation and application in detection of p-phenylenediamine

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xinhua, E-mail: caoxh@xynu.edu.cn [College of Chemistry and Chemical Engineering, Institute for Conservation and Utilization of Agro-bioresources in Dabie Mountains, Xinyang Normal University, Xinyang, Henan, 464000 (China); State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082 (China); Zhao, Na; Gao, Aiping; Lv, Haiting; Jia, Yuling [College of Chemistry and Chemical Engineering, Institute for Conservation and Utilization of Agro-bioresources in Dabie Mountains, Xinyang Normal University, Xinyang, Henan, 464000 (China); Wu, Renmiao [School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi 341000 (China); Wu, Yongquan, E-mail: wyq@gnnu.edu.cn [School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi 341000 (China)

    2017-01-01

    Two new gelators containing bis-naphthalimides group were designed and synthesized. The gelator 1b could form gels in DMF and mixed solvent of DMSO/H{sub 2}O (10/1, v/v). The self-assembly processes of 1b in two kinds of solvents were detailedly investigated by UV–vis, fluorescence, infrared spectroscopy, field emission scanning electron microscope (FE-SEM), X-ray diffraction and contact angle experiments. The experiment results showed the hydrogen bonding was the main force for the gel formation. The gel 1b formed in mixed solvent of DMSO/H{sub 2}O (10/1, v/v) possessed of the ability of distinguishing of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine. At the same time, the gelator 1b could selectively and sensitively detect p-phenylenediamine in solution with the detection limit of 8.961 × 10{sup −8} M L{sup −1}. The detection experiment was also confirmed by DFT theoretical calculations. This research would expand the supramolecular self-assembly materials application in sensor field and offer a new detection method for organic amines. - Highlights: • The self-assembly process of the gelator 1b in mixed solvent of DMSO/H{sub 2}O (10/1, v/v) are studied. • The gel 1b had the ability of distinguishing of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine. • The gelator 1b could selectively and sensitively detect p-phenylenediamine with the detection limit of 8.961 × 10{sup −8} mol L{sup −1}.

  8. In-plane nuclear field formation investigated in single self-assembled quantum dots

    Science.gov (United States)

    Yamamoto, S.; Matsusaki, R.; Kaji, R.; Adachi, S.

    2018-02-01

    We studied the formation mechanism of the in-plane nuclear field in single self-assembled In0.75Al0.25As /Al0.3Ga0.7As quantum dots. The Hanle curves with an anomalously large width and hysteretic behavior at the critical transverse magnetic field were observed in many single quantum dots grown in the same sample. In order to explain the anomalies in the Hanle curve indicating the formation of a large nuclear field perpendicular to the photo-injected electron spin polarization, we propose a new model based on the current phenomenological model for dynamic nuclear spin polarization. The model includes the effects of the nuclear quadrupole interaction and the sign inversion between in-plane and out-of-plane components of nuclear g factors, and the model calculations reproduce successfully the characteristics of the observed anomalies in the Hanle curves.

  9. Rationally Designed, Multifunctional Self-Assembled Nanoparticles for Covalently Networked, Flexible and Self-Healable Superhydrophobic Composite Films.

    Science.gov (United States)

    Lee, Yujin; You, Eun-Ah; Ha, Young-Geun

    2018-03-21

    For constructing bioinspired functional films with various superhydrophobic functions, including self-cleaning, anticorrosion, antibioadhesion, and oil-water separation, hydrophobic nanomaterials have been widely used as crucial structural components. In general, hydrophobic nanomaterials, however, cannot form strong chemical bond networks in organic-inorganic hybrid composite films because of the absence of chemically compatible binding components. Herein, we report the rationally designed, multifunctional self-assembled nanoparticles with tunable functionalities of covalent cross-linking and hydrophobicity for constructing three-dimensionally interconnected superhydrophobic composite films via a facile solution-based fabrication at room temperature. The multifunctional self-assembled nanoparticles allow the systematic control of functionalities of composite films, as well as the stable formation of covalently linked superhydrophobic composite films with excellent flexibility (bending radii of 6.5 and 3.0 mm, 1000 cycles) and self-healing ability (water contact angle > 150°, ≥10 cycles). The presented strategy can be a versatile and effective route to generating other advanced functional films with covalently interconnected composite networks.

  10. Self-assembling peptide semiconductors

    Science.gov (United States)

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

    2017-01-01

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

  11. Formation of active inclusion bodies induced by hydrophobic self-assembling peptide GFIL8.

    Science.gov (United States)

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

    2015-06-16

    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

  12. Pectin-lipid self-assembly: influence on the formation of polyhydroxy fatty acids nanoparticles.

    Directory of Open Access Journals (Sweden)

    Susana Guzman-Puyol

    Full Text Available Nanoparticles, named cutinsomes, have been prepared from aleuritic (9,10,16-trihidroxipalmitic acid and tomato fruit cutin monomers (a mixture of mainly 9(10,16-dihydroxypalmitic acid (85%, w/w and 16-hydroxyhexadecanoic acid (7.5%, w/w with pectin in aqueous solution. The process of formation of the nanoparticles of aleuritic acid plus pectin has been monitored by UV-Vis spectrophotometry, while their chemical and morphological characterization was analyzed by ATR-FTIR, TEM, and non-contact AFM. The structure of these nanoparticles can be described as a lipid core with a pectin shell. Pectin facilitated the formation of nanoparticles, by inducing their aggregation in branched chains and favoring the condensation between lipid monomers. Also, pectin determined the self-assembly of cutinsomes on highly ordered pyrolytic graphite (HOPG surfaces, causing their opening and forming interconnected structures. In the case of cutin monomers, the nanoparticles are fused, and the condensation of the hydroxy fatty acids is strongly affected by the presence of the polysaccharide. The interaction of pectin with polyhydroxylated fatty acids could be related to an initial step in the formation of the plant biopolyester cutin.

  13. Pectin-lipid self-assembly: influence on the formation of polyhydroxy fatty acids nanoparticles.

    Science.gov (United States)

    Guzman-Puyol, Susana; Benítez, José Jesús; Domínguez, Eva; Bayer, Ilker Sefik; Cingolani, Roberto; Athanassiou, Athanassia; Heredia, Antonio; Heredia-Guerrero, José Alejandro

    2015-01-01

    Nanoparticles, named cutinsomes, have been prepared from aleuritic (9,10,16-trihidroxipalmitic) acid and tomato fruit cutin monomers (a mixture of mainly 9(10),16-dihydroxypalmitic acid (85%, w/w) and 16-hydroxyhexadecanoic acid (7.5%, w/w)) with pectin in aqueous solution. The process of formation of the nanoparticles of aleuritic acid plus pectin has been monitored by UV-Vis spectrophotometry, while their chemical and morphological characterization was analyzed by ATR-FTIR, TEM, and non-contact AFM. The structure of these nanoparticles can be described as a lipid core with a pectin shell. Pectin facilitated the formation of nanoparticles, by inducing their aggregation in branched chains and favoring the condensation between lipid monomers. Also, pectin determined the self-assembly of cutinsomes on highly ordered pyrolytic graphite (HOPG) surfaces, causing their opening and forming interconnected structures. In the case of cutin monomers, the nanoparticles are fused, and the condensation of the hydroxy fatty acids is strongly affected by the presence of the polysaccharide. The interaction of pectin with polyhydroxylated fatty acids could be related to an initial step in the formation of the plant biopolyester cutin.

  14. Variable surface composition and radial interface formation in self-assembled free, mixed Ar/Xe clusters

    International Nuclear Information System (INIS)

    Tchaplyguine, M.; Maartensson, N.; Lundwall, M.; Oehrwall, G.; Feifel, R.; Svensson, S.; Bjoerneholm, O.; Gisselbrecht, M.; Sorensen, S.

    2004-01-01

    Using photoelectron spectroscopy, we demonstrate how the self-assembling process of cluster formation in an adiabatic expansion leads to radial segregation and layering as well as to variable surface composition for binary Ar/Xe clusters. The radial structuring can be qualitatively understood from the different interatomic bonding strengths of the two components

  15. Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

    International Nuclear Information System (INIS)

    Berlanga, Isadora; Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo; Gómez, Victoria Alejandra; Aliaga-Alcalde, Núria; Fuenzalida, Victor; Flores, Marcos

    2017-01-01

    Highlights: • Thiophene curcuminoid molecules deposited on a gold surface by immersion. • Molecular dynamic studies of the molecular arrangement approaching the surface. • XPS and STM studies showing different arrangement of the molecules on the surface. • Molecular Interaction with surface depends on the sulfur position in thiophene rings. • Temporal evolution of the molecular arrangement on the surface. - Abstract: We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

  16. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers.

    Science.gov (United States)

    Kruszewski, Kristen M; Nistico, Laura; Longwell, Mark J; Hynes, Matthew J; Maurer, Joshua A; Hall-Stoodley, Luanne; Gawalt, Ellen S

    2013-05-01

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (-CH3) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an "active" antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Berlanga, Isadora [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo [Departamento de Ciencia de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Beaucheff 851, Santiago (Chile); Gómez, Victoria Alejandra [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Aliaga-Alcalde, Núria [ICREA (Institució Catalana de Recerca i Estudis Avançats), Passeig Lluís Companys, 23, 08018, Barcelona (Spain); CSIC-ICMAB (Institut de Ciència dels Materials de Barcelona), Campus de la Universitat Autònoma de Barcelona, 08193 Bellaterra (Spain); Fuenzalida, Victor [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Flores, Marcos, E-mail: mflorescarra@ing.uchile.cl [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); and others

    2017-01-15

    Highlights: • Thiophene curcuminoid molecules deposited on a gold surface by immersion. • Molecular dynamic studies of the molecular arrangement approaching the surface. • XPS and STM studies showing different arrangement of the molecules on the surface. • Molecular Interaction with surface depends on the sulfur position in thiophene rings. • Temporal evolution of the molecular arrangement on the surface. - Abstract: We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

  18. Hierarchical self-assembly of a striped gyroid formed by threaded chiral mesoscale networks

    DEFF Research Database (Denmark)

    Kirkensgaard, Jacob Judas Kain; Evans, Myfanwy; de Campo, Lilliana

    2014-01-01

    Numerical simulations reveal a family of hierarchical and chiral multicontinuous network structures self-assembled from a melt blend of Y-shaped ABC and ABD three-miktoarm star terpolymers, constrained to have equal-sized A/B and C/D chains, respectively. The C and D majority domains within...... components also forming labyrinthine domains whose geometry and topology changes systematically as a function of composition. These smaller labyrinths are well described by a family of patterns that tile the hyperbolic plane by regular degree-three trees mapped onto the gyroid. The labyrinths within......-ridden achiral patterns, containing domains of either hand, due to the achiral terpolymeric starting molecules. These mesostructures are among the most topologically complex morphologies identified to date and represent an example of hierarchical ordering within a hyperbolic pattern, a unique mode of soft...

  19. Formation of clusters composed of C60 molecules via self-assembly in critical fluids

    International Nuclear Information System (INIS)

    Fukuda, Takahiro; Ishii, Koji; Kurosu, Shunji; Whitby, Raymond; Maekawa, Toru

    2007-01-01

    Fullerenes are promising candidates for intelligent, functional nanomaterials because of their unique mechanical, electronic and chemical properties. However, it is necessary to invent some efficient but relatively simple methods of producing structures composed of fullerenes for the development of nanomechatronic, nanoelectronic and biochemical devices and sensors. In this paper, we show that various structures such as straight fibres, networks formed by fibres, wide sheets and helical structures, which are composed of C 60 molecules, are created by placing C 60 -crystals in critical ethane, carbon dioxide and xenon even though C 60 molecules do not dissolve or disperse in the above fluids. It is supposed, judging by the intermolecular potentials between C 60 and C 60 , between C 60 and ethane, and between ethane and ethane, that C 60 -clusters grow with the assistance of solvent molecules, which are trapped between C 60 molecules under critical conditions. This room-temperature self-assembly cluster growth process in critical fluids may open up a new methodology of forming structures built up with fullerenes without the need for any ultra-fine processing technologies

  20. Influence of PEG Stoichiometry on Structure-Tuned Formation of Self-Assembled Submicron Nickel Particles

    Directory of Open Access Journals (Sweden)

    Bingxue Pu

    2018-01-01

    Full Text Available Self-assembled submicron nickel particles were successfully synthesized via the one-step surfactant-assisted solvothermal method. The impact of surfactant and reducing agent stoichiometry is investigated in this manuscript. Different morphologies and structures of Ni particles, including flower-like nanoflakes, hydrangea-like structures, chain structures, sphere-like structures, and hollow structures were prepared through different processing conditions with two parameters such as temperature and time. Based on scanning electron microscopy (SEM, X-ray diffraction (XRD, thermal gravimetric analysis (TGA and vibrating sample magnetometry (VSM, the submicron nickel particles show good saturation magnetization and excellent thermal stabilities with a possible growth mechanism for the variety of the structure-tuned formation. Importantly, the microwave absorption properties of the submicron nickel particles were studied. The lowest reflection loss of Ni-P9/T200/H15 with a thin layer thickness of 1.7 mm can reach −42.6 dB at 17.3 GHz.

  1. Formation of high-quality self-assembled monolayers of conjugated dithiols on gold: base matters.

    Science.gov (United States)

    Valkenier, Hennie; Huisman, Everardus H; van Hal, Paul A; de Leeuw, Dago M; Chiechi, Ryan C; Hummelen, Jan C

    2011-04-06

    This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et(3)N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu(4)NOH) leads to less dense SAMs and the incorporation of Bu(4)N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et(3)N, and Bu(4)NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of β=0.15 Å(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et(3)N was obtained. © 2011 American Chemical Society

  2. Photocatalytic evaluation of self-assembled porous network structure of ferric oxide film fabricated by dry deposition process

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yunchan; Kim, Hyungsub; Lee, Geon-Yong; Pawar, Rajendra C.; Lee, Jai-Sung; Lee, Caroline Sunyong, E-mail: sunyonglee@hanyang.ac.kr

    2016-09-15

    Ferric oxide powder in the alpha phase (α-Fe{sub 2}O{sub 3}) was deposited on an aluminum oxide (Al{sub 2}O{sub 3}) substrate by a nanoparticle deposition system using the dry deposition method. X-ray diffraction (XRD) images confirmed that the phase of the deposited α-Fe{sub 2}O{sub 3} did not change. The deposited α-Fe{sub 2}O{sub 3} was characterized in terms of its microstructure using scanning electron microscopy (SEM). A porous network microstructure formed when small agglomerates of Fe{sub 2}O{sub 3} (SAF) were deposited. The deposition and formation mechanism of the microstructure were investigated using SEM and three-dimensional (3D) profile analysis. First, a dense coating layer formed when the film was thinner than the particle size. After that, as the film thickness increased to over 5 μm, the porous network structure formed by excavating the surface of the coating layer as it was bombarded by particles. Rhodamine B (RhB) was degraded after 6 h of exposure to the Fe{sub 2}O{sub 3} coating layer with SAF, which has good photocatalytic activity and a high porous network structure. The kinetic rate constants of the SAF and large agglomerates of Fe{sub 2}O{sub 3} (LAF) were calculated to be 0.197(h{sup −1}) and 0.128(h{sup −1}), respectively, based on the absorbance results. Using linear sweep voltammetry, we confirmed that the photoelectric effect occurred in the coating layer by measuring the resulting current under illuminated and dark conditions. - Graphical abstract: Self-assembled porous photocatalytic film fabricated by dry deposition method for water purification. - Highlights: • Different sizes of Fe{sub 2}O{sub 3} agglomerates were used to form porous network structure. • Fe{sub 2}O{sub 3} agglomerate particles were deposited using solvent-free process. • Self-assembled porous network microstructure formed better with small agglomerates of Fe{sub 2}O{sub 3}. • Fabricated porous network structure showed its potential to be used

  3. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

    International Nuclear Information System (INIS)

    Kruszewski, Kristen M.; Nistico, Laura; Longwell, Mark J.; Hynes, Matthew J.; Maurer, Joshua A.; Hall-Stoodley, Luanne; Gawalt, Ellen S.

    2013-01-01

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (− CH 3 ) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. - Highlights: ► SS316L was modified with glycol terminated SAMs in order to reduce biofilm growth. ► Antibiotics gentamicin and vancomycin were immobilized on SS316L via SAMs. ► Only the antibiotic modifications reduced biofilm development on SS316L

  4. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Kruszewski, Kristen M., E-mail: kruszewskik@duq.edu [Duquesne University, Department of Chemistry and Biochemistry, 600 Forbes Avenue, Pittsburgh, PA 15282 (United States); Nistico, Laura, E-mail: lnistico@wpahs.org [Allegheny General Hospital, Center for Genomic Sciences, Allegheny-Singer Research Institute, 320 East North Avenue, 11th floor, South Tower, Pittsburgh, PA 15212 (United States); Longwell, Mark J., E-mail: mlongwel@wpahs.org [Allegheny General Hospital, Center for Genomic Sciences, Allegheny-Singer Research Institute, 320 East North Avenue, 11th floor, South Tower, Pittsburgh, PA 15212 (United States); Hynes, Matthew J., E-mail: mjhynes@go.wustl.edu [Washington University in St. Louis, Department of Chemistry, One Brookings Drive, St. Louis, MO 63130 (United States); Maurer, Joshua A., E-mail: maurer@wustl.edu [Washington University in St. Louis, Department of Chemistry, One Brookings Drive, St. Louis, MO 63130 (United States); Hall-Stoodley, Luanne, E-mail: L.Hall-Stoodley@soton.ac.uk [Southampton Wellcome Trust Clinical Research Facility/NIHR Respiratory BRU, University of Southampton Faculty of Medicine, Southampton General Hospital, Tremona Road, Southampton, Hampshire SO16 6YD (United Kingdom); Gawalt, Ellen S., E-mail: gawalte@duq.edu [Duquesne University, Department of Chemistry and Biochemistry, McGowan Institute for Regenerative Medicine, 600 Forbes Avenue, Pittsburgh, PA 15282 (United States)

    2013-05-01

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (− CH{sub 3}) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. - Highlights: ► SS316L was modified with glycol terminated SAMs in order to reduce biofilm growth. ► Antibiotics gentamicin and vancomycin were immobilized on SS316L via SAMs. ► Only the antibiotic modifications reduced biofilm development on SS316L.

  5. Exciplex formation and energy transfer in a self-assembled metal-organic hybrid system.

    Science.gov (United States)

    Haldar, Ritesh; Rao, K Venkata; George, Subi J; Maji, Tapas Kumar

    2012-05-07

    Exciting assemblies: A metal-organic self-assembly of pyrenebutyric acid (PBA), 1,10-phenanthroline (o-phen), and Mg(II) shows solid-state fluorescence originating from a 1:1 PBA-o-phen exciplex. This exciplex fluorescence is sensitized by another residual PBA chromophore through an excited-state energy-transfer process. The solvent polarity modulates the self-assembly and the corresponding exciplex as well as the energy transfer, resulting in tunable emission of the hybrid (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Atomic-scale structure and formation of self-assembled In(Ga)As quantum rings

    NARCIS (Netherlands)

    Offermans, P.; Koenraad, P.M.; Wolter, J.H.; Granados, D.; Garcia, J.M.; Fomin, V.; Gladilin, V.N.; Devreese, J.T.

    2006-01-01

    The authors present an at.-scale anal. of the In distribution of self-assembled (In,Ga)As quantum rings (QRs), which are formed from InAs quantum dots by capping with a thin layer of GaAs and subsequent annealing. The size and shape of QRs as obsd. by cross-sectional scanning tunneling microscopy

  7. De novo centriole formation in human cells is error-prone and does not require SAS-6 self-assembly.

    Science.gov (United States)

    Wang, Won-Jing; Acehan, Devrim; Kao, Chien-Han; Jane, Wann-Neng; Uryu, Kunihiro; Tsou, Meng-Fu Bryan

    2015-11-26

    Vertebrate centrioles normally propagate through duplication, but in the absence of preexisting centrioles, de novo synthesis can occur. Consistently, centriole formation is thought to strictly rely on self-assembly, involving self-oligomerization of the centriolar protein SAS-6. Here, through reconstitution of de novo synthesis in human cells, we surprisingly found that normal looking centrioles capable of duplication and ciliation can arise in the absence of SAS-6 self-oligomerization. Moreover, whereas canonically duplicated centrioles always form correctly, de novo centrioles are prone to structural errors, even in the presence of SAS-6 self-oligomerization. These results indicate that centriole biogenesis does not strictly depend on SAS-6 self-assembly, and may require preexisting centrioles to ensure structural accuracy, fundamentally deviating from the current paradigm.

  8. Modulating the forces between self-assembling molecules to control the shape of vesicles and the mechanics and alignment of nanofiber networks

    Science.gov (United States)

    Greenfield, Megan Ann

    One of the great challenges in supramolecular chemistry is the design of molecules that can self-assemble into functional aggregates with well-defined three-dimensional structures and bulk material properties. Since the self-assembly of nanostructures is greatly influenced by both the nature of the self-assembling components and the environmental conditions in which the components assemble, this work explores how changes in the molecular design and the environment affect the properties of self-assembled structures. We first explore how to control the mechanical properties of self-assembled fibrillar networks by changing environmental conditions. We report here on how changing pH, screening ions, and solution temperature affect the gelation, stiffness, and response to deformation of peptide amphiphile gels. Although the morphology of PA gels formed by charge neutralization and salt-mediated charge screening are similar by electron microscopy, rheological measurements indicate that the calcium-mediated ionic bridges in CaCl2-PA gels form stronger intra- and inter-fiber crosslinks than the hydrogen bonds formed by the protonated carboxylic acid residues in HCl-PA gels. In contrast, the structure of PA gels changes drastically when the PA solution is annealed prior to gel formation. Annealed PA solutions are birefringent and can form viscoelastic strings of aligned nanofibers when manually dragged across a thin film of CaCl2. These aligned arrays of PA nanofibers hold great promise in controlling the orientation of cells in three-dimensions. Separately, we applied the principles of molecular design to create buckled membrane nanostructures that mimic the shape of viruses. When oppositely charged amphiphilic molecules are mixed they can form vesicles with a periodic two-dimensional ionic lattice that opposes the membrane's natural curvature and can result in vesicle buckling. Our results demonstrate that a large +3 to -1 charge imbalance between the cationic and anionic

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

    Directory of Open Access Journals (Sweden)

    Paolo Neviani

    2010-01-01

    Full Text Available Here we investigate the supramolecular polymerizations of two lipophilic guanosine derivatives in chloroform by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties.

  10. Formation Mechanism of Self Assembled Horizontal ErSb Nanowires Embedded in a GaSb(001) Matrix

    Science.gov (United States)

    Wilson, Nathaniel; Kraemer, Stephan; PalmstrøM, Chris

    The ErxGa1-xSb exhibits a variety of self-assembling nanostructures. In order to harness these nanostructures for use in devices and other material systems it is important to understand their formation. We have characterized the growth mechanism of self-assembled horizontal ErSb nanowires in a GaSb(001) matrix through the use of in-situ Scanning Tunneling Microscopy (STM) as well as ex-situ Transmission Electron Microscopy (TEM). We observe large GaSb macrosteps on the growth surface of Er.3Ga.7Sb samples. The areas near the ledge and base of the macrosteps show significant differences in size and distribution of ErSb nanowires. Results suggest that the formation of macrosteps drives the transition from vertical to horizontal nanowires in the ErxGa1-xSb system. We also observe a low temperature growth mode, which results in horizontal nanowire formation under a wide range of flux conditions. This new growth mode does not exhibit the embedded growth observed in the formation of nanowires at higher temperatures and may allow for horizontal nanowire formation without the presence of macrosteps, as well as the formation of smaller nanoparticles which may be useful for achieving smaller nanoparticle dimensions and electron confinement effects. This work was supported by NSF-DMR under 1507875.

  11. Self-assembly of POSS-containing block copolymers: fixing the hierarchical structure in networks

    Czech Academy of Sciences Publication Activity Database

    Matějka, Libor; Janata, Miroslav; Pleštil, Josef; Zhigunov, Alexander; Šlouf, Miroslav

    2014-01-01

    Roč. 55, č. 1 (2014), s. 126-136 ISSN 0032-3861 R&D Projects: GA ČR GAP108/12/1459 Grant - others:AV ČR(CZ) M200500903 Institutional support: RVO:61389013 Keywords : block copolymers * self-assembly * POSS Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.562, year: 2014

  12. Novel mechanisms for self-assembled pattern formation in nanoscopic metal films

    Science.gov (United States)

    Kalyanaraman, R.; Trice, J.; Favazza, C.; Thomas, D.; Sureshkumar, R.

    2007-03-01

    Classical hydrodynamic theory of dewetting of spinodally unstable thin films (Vrij, Disc. farad. Soc. 1966) predicts a monotonic increase in patterning length scales with increasing film thickness. We verified this effect for nanoscopic Co metal films following melting by ns laser pulses for thickness regime hFavazza et al. Nanotechnology, 2006). However, a dramatic change is observed beyond this thickness hc, with length scales decreasing with increasing h. This novel behavior arises from strong thickness dependence of heating by ultrafast laser light resulting in thermocapillary effects, whose magnitude and sign are thickness dependent. We modified the classical theory, according to which the instability occurs when the stabilizing capillary force is overcome by destabilizing attractive long-range interactions, to include thermocapillary effects. The modified theory accurately predicts the experimentally observed trend. This result suggests that a variety of new length scales can be accessed by robust self-assembly via dewetting of metal films under ultrafast light.

  13. Understanding the Formation of the Self-Assembly of Colloidal Copper Nanoparticles by Surfactant: A Molecular Velcro

    Directory of Open Access Journals (Sweden)

    Raquel Kely Bortoleto-Bugs

    2013-01-01

    Full Text Available Self-assembly procedure is employed to synthesize colloidal copper nanoparticles (ccNPs with cationic surfactant in an environmentally friendly method. Scanning electron microscopy images provide a clear view of the ccNPs formed having an approximate size of 15 nm. The X-ray diffraction reveals that the ccNPs have the two types of copper oxide as well as the metallic copper. The new procedure shows that the cationic surfactant CTAB plays an important role in the understanding and development of self-assembly. There is a strong relationship between the ccNPs formation with the critical micelle concentration of the CTAB which influences both shape and size. The outcomes allowed the development of a molecular model for the ccNPs synthesis showing that the CTAB monomer on the surface has the function of a molecular velcro making the linkage of ccNPs to form an agglomerate with size around 600 nm. Finally, with the emerging new technologies, the synthesis of copper oxide takes a new perspective for their applicability in diverse integrated areas such as the flexible electronics and energy.

  14. Mechanism behind the formation of self-assembled nano-sized clusters in diamond-like carbon nanocomposite.

    Science.gov (United States)

    Foong, Yuan Mei; Koh, Angel Ting Ting; Niu, Lifang; Chua, Daniel Hock Chuan

    2011-12-01

    Many studies have shown that Diamond-like carbon (DLC) films with diversified material properties are obtainable through doping process but the presence of the dopants were reported to form independent nanoclusters within the carbon matrix. Using combined analysis from theoretical estimations (Saha's equation and coefficient of absorption, alpha(p)), Transport of Ions In Matter (TRIM) simulation and experimental results, this work examined the mechanism behind the formation of self-assembled nanoclusters in DLC nanocomposite. We showed that the presence of metal dopants increased the heat dissipation on DLC, which allowed the energetic metal species to diffuse and enhance the formation of nanoclusters that increased the surface roughness of the films. In addition, TRIM and X-ray Photoelectron Spectroscopy (XPS) hinted the presence of energetic species may force the carbon ions to react with the interface to form silicon carbide bonds, which may be a more dominant factor compared to internal stress reduction in improving the adhesion strength of DLC.

  15. Self-assembly formation of palm-based esters nano-emulsion: A molecular dynamics study

    Science.gov (United States)

    Abdul Rahman, Mohd. Basyaruddin; Huan, Qiu-Yi; Tejo, Bimo A.; Basri, Mahiran; Salleh, Abu Bakar; Rahman, Raja Noor Zaliha Abdul

    2009-10-01

    Palm-oil esters (POEs) are unsaturated and non-ionic esters that can be prepared by enzymatic synthesis from palm oil. Their nano-emulsion properties possess great potential to act as drug carrier for transdermal drug delivery system. A ratio of 75:5:20 (water/POEs/Span20) was chosen from homogenous region in the phase diagram of our previous experimental work to undergo molecular dynamics simulation. A 15 ns molecular dynamics simulation of nano-emulsion system (water/POEs/Span20) was carried out using OPLS-AA force field. The aggregations of the oil and surfactant molecules are observed throughout the simulation. After 8 ns of simulation, the molecules start to aggregate to form one spherical micelle where the POEs molecules are surrounded by the non-ionic surfactant (Span20) molecules with an average size of 4.2 ± 0.05 nm. The size of the micelle and the ability of palm-based nano-emulsion to self-assemble suggest that this nano-emulsion can potentially use in transdermal drug delivery system.

  16. Formation of Self-assembled Nanostructure on Noble Metal Islands Based on Anodized Aluminum Oxide

    International Nuclear Information System (INIS)

    Park, Jong Bae; Kim, Young Sic; Kim, Seong Kyu; Lee, Hae Seong

    2004-01-01

    We have developed the methodology to produce nanoscale gold rods using an AAO template. Each gold rod was generated in every AAO pore. This nanoislands array of gold formed over the AAO pores can be used as corner stones for building nanostructures. We demonstrated this by forming a nanostructure on the Au/AAO by binding a self-assembly class of molecules onto the metal islands. Anodized aluminum oxide (AAO) has been considered an attractive template for simple fabrication of highly-ordered nanostructures. It provides a 2-dimensional array of hexagonal cells with pores of uniform diameter and inter-pore distance that are adjustable in the range of a few tens to hundreds of nanometers. It can be easily grown on an aluminum sheet with high purity by a sequence of several electrochemical steps; electro-polishing, the 1st anodization, etching, and the 2nd anodization. The pores are grown vertically with respect to the AAO surface. The regularity of the pore structure is usually limited by the inherent grain domain in the aluminum sheet to a few micrometers, but can be improved to cover many millimeters of monodomain by pre-indenting the aluminum sheet with SiC 7 or Si 3 N 4 molds. Although fabrication of such molds requires elaborate and costly processes with e-beam nanolithography, such potentially superb regularity can be practically applied to fabrication of nanoscale devices in electronics, optics, biosensors, etc

  17. Formation and Characterization of Self-Assembled Phenylboronic Acid Derivative Monolayers toward Developing Monosaccaride Sensing-Interface

    Directory of Open Access Journals (Sweden)

    Kwangnak Koh

    2007-08-01

    Full Text Available We designed and synthesized phenylboronic acid as a molecular recognitionmodel system for saccharide detection. The phenylboronic acid derivatives that haveboronic acid moiety are well known to interact with saccharides in aqueous solution; thus,they can be applied to a functional interface of saccharide sensing through the formation ofself-assembled monolayer (SAM. In this study, self-assembled phenylboronic acidderivative monolayers were formed on Au surface and carefully characterized by atomicforce microscopy (AFM, Fourier transform infrared reflection absorption spectroscopy(FTIR-RAS, surface enhanced Raman spectroscopy (SERS, and surface electrochemicalmeasurements. The saccharide sensing application was investigated using surface plasmonresonance (SPR spectroscopy. The phenylboronic acid monolayers showed goodsensitivity of monosaccharide sensing even at the low concentration range (1.0 × 10-12 M.The SPR angle shift derived from interaction between phenylboronic acid andmonosaccharide was increased with increasing the alkyl spacer length of synthesizedphenylboronic acid derivatives.

  18. Tuning peptide self-assembly by an in-tether chiral center

    Science.gov (United States)

    Hu, Kuan; Xiong, Wei; Li, Hu; Zhang, Pei-Yu; Yin, Feng; Zhang, Qianling; Jiang, Fan; Li, Zigang

    2018-01-01

    The self-assembly of peptides into ordered nanostructures is important for understanding both peptide molecular interactions and nanotechnological applications. However, because of the complexity and various self-assembling pathways of peptide molecules, design of self-assembling helical peptides with high controllability and tunability is challenging. We report a new self-assembling mode that uses in-tether chiral center-induced helical peptides as a platform for tunable peptide self-assembly with good controllability. It was found that self-assembling behavior was governed by in-tether substitutional groups, where chirality determined the formation of helical structures and aromaticity provided the driving force for self-assembly. Both factors were essential for peptide self-assembly to occur. Experiments and theoretical calculations indicate long-range crystal-like packing in the self-assembly, which was stabilized by a synergy of interpeptide π-π and π-sulfur interactions and hydrogen bond networks. In addition, the self-assembled peptide nanomaterials were demonstrated to be promising candidate materials for applications in biocompatible electrochemical supercapacitors.

  19. Formation of physical-gel redox electrolytes through self-assembly of discotic liquid crystals: Applications in dye sensitized solar cells

    International Nuclear Information System (INIS)

    Khan, Ammar A.; Kamarudin, Muhammad A.; Qasim, Malik M.; Wilkinson, Timothy D.

    2017-01-01

    The self-assembly of small molecules into ordered structures is of significant interest in electronic applications due to simpler device fabrication and better performance. Here we present work on the development of self-assembled fibrous networks of thermotropic triphenylene discotic liquid crystals, where 2,3,6,7,10,11-Hexakishexyloxytriphenylene (HAT6) is studied. The formation of interconnected molecular fibres in acetonitrile-based solvents facilitates thermally-reversible physical-gel (non-covalent) preparation, with the HAT6 network providing mechanical support and containment of the solvent. Furthermore, gel formation is also achieved using an acetonitrile-based iodide/tri-iodide redox liquid electrolyte, and the resulting gel mixture is utilised as an electrolyte in dye-sensitized solar cells (DSSCs). Our results show that it is indeed possible to achieve in situ gel formation in DSSCs, allowing for easy cell fabrication and electrolyte filling. In addition, the gel phase is found to increase device lifetime by limiting solvent evaporation. Differential scanning calorimetry (DSC) and polarising optical microscopy (POM) are used to study gel formation, and it is identified that the thermally reversible gels are stable up to working temperatures of 40 °C. It is found that DSSCs filled with gel electrolyte exhibit longer electron lifetime in the TiO 2 photo-anode (≈8.4 ms in the liquid electrolyte to ≈11.4 ms in the gel electrolytes), most likely due to electron screening from the electrolyte by HAT6. Current-Voltage (I–V) and electrochemical impedance spectroscopy (EIS) are used to study the effect of gel formation on conductivity and electrochemical properties, and it is found that confinement of the liquid electrolyte into a gel phase does not significantly reduce ionic conductivity, a problem common with solid-state polymer electrolytes. A 3.8 mM HAT6 gel electrolyte DSSC exhibited a PCE of 6.19% vs. a 5.86% liquid electrolyte reference. Extended

  20. Photocrosslinked PLA-PEO-PLA Hydrogels from Self-Assembled Physical Networks: Mechanical Properties and Influence of Assumed Constitutive Relationships

    Science.gov (United States)

    Sanabria-DeLong, Naomi; Crosby, Alfred J.; Tew, Gregory N.

    2014-01-01

    Poly(lactide) – block – poly(ethylene oxide) – block – poly(lactide) [PLA-PEO-PLA] triblock copolymers are known to form physical hydrogels in water, due to the polymer's amphiphilicity. Their mechanical properties, biocompatibility, and biodegradability have made them attractive for use as soft tissue scaffolds. However, the network junction points are not covalently crosslinked and in a highly aqueous environment these hydrogels adsorb more water, transform from gel to sol, and lose the designed mechanical properties. In this report, a hydrogel was formed by using a novel two step approach. In the first step end-functionalized PLA-PEOPLA triblock was self-assembled into a physical hydrogel through hydrophobic micelle network junctions, and then, in the second step, this self-assembled physical network structure was locked into place by photocrosslinking the terminal acrylate groups. In contrast to physical hydrogels, the photocrosslinked gels remained intact in phosphate buffered solution at body temperature. The swelling, degradation, and mechanical properties were characterized and demonstrated extended degradation time (~ 65 days), exponential decrease in modulus with degradation time, and tunable shear modulus (1.6 – 133 kPa) by varying concentration. We also discuss the various constitutive relationships (Hookean, Neo-Hookean, and Mooney-Rivlin) that can be used to describe the stress-strain behavior of these hydrogels. The chosen model and assumptions used for data fitting influences the obtained modulus values by as much as a factor of 3.5, demonstrating the importance of clearly stating one's data fitting parameters so that accurate comparisons can be made within the literature. PMID:18817440

  1. Directed self-assembly of nanorod networks: bringing the top down to the bottom up

    International Nuclear Information System (INIS)

    Einsle, Joshua F; Scheunert, Gunther; Murphy, Antony; Pollard, Robert; Bowman, Robert M; McPhillips, John; Zayats, Anatoly V

    2012-01-01

    Self-assembled electrodeposited nanorod materials have been shown to offer an exciting landscape for a wide array of research ranging from nanophotonics through to biosensing and magnetics. However, until now, the scope for site-specific preparation of the nanorods on wafers has been limited to local area definition. Further there is little or no lateral control of nanorod height. In this work we present a scalable method for controlling the growth of the nanorods in the vertical direction as well as their lateral position. A focused ion beam pre-patterns the Au cathode layer prior to the creation of the anodized aluminium oxide (AAO) template on top. When the pre-patterning is of the same dimension as the pore spacing of the AAO template, lines of single nanorods are successfully grown. Further, for sub-200 nm wide features, a relationship between the nanorod height and distance from the non-patterned cathode can be seen to follow a quadratic growth rate obeying Faraday’s law of electrodeposition. This facilitates lateral control of nanorod height combined with localized growth of the nanorods. (paper)

  2. Directed self-assembly of nanorod networks: bringing the top down to the bottom up.

    Science.gov (United States)

    Einsle, Joshua F; Scheunert, Gunther; Murphy, Antony; McPhillips, John; Zayats, Anatoly V; Pollard, Robert; Bowman, Robert M

    2012-12-21

    Self-assembled electrodeposited nanorod materials have been shown to offer an exciting landscape for a wide array of research ranging from nanophotonics through to biosensing and magnetics. However, until now, the scope for site-specific preparation of the nanorods on wafers has been limited to local area definition. Further there is little or no lateral control of nanorod height. In this work we present a scalable method for controlling the growth of the nanorods in the vertical direction as well as their lateral position. A focused ion beam pre-patterns the Au cathode layer prior to the creation of the anodized aluminium oxide (AAO) template on top. When the pre-patterning is of the same dimension as the pore spacing of the AAO template, lines of single nanorods are successfully grown. Further, for sub-200 nm wide features, a relationship between the nanorod height and distance from the non-patterned cathode can be seen to follow a quadratic growth rate obeying Faraday's law of electrodeposition. This facilitates lateral control of nanorod height combined with localized growth of the nanorods.

  3. Formation of fractals by the self-assembly of interpolymer adducts of ...

    Indian Academy of Sciences (India)

    Polycarboxylic acids form self-organized poly- ... observation of the formation of fractal patterns in self- organizing polyacrylic acid systems in films driven by hydrogen bonding .... various positions, the SEM and EDX studies are car- ried out.

  4. Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O-O Bond Formation Pathways by Different Aggregation Patterns.

    Science.gov (United States)

    Yang, Bing; Jiang, Xin; Guo, Qing; Lei, Tao; Zhang, Li-Ping; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

    2016-05-17

    The oxidation of water to molecular oxygen is the key step to realize water splitting from both biological and chemical perspective. In an effort to understand how water oxidation occurs on a molecular level, a large number of molecular catalysts have been synthesized to find an easy access to higher oxidation states as well as their capacity to make O-O bond. However, most of them function in a mixture of organic solvent and water and the O-O bond formation pathway is still a subject of intense debate. Herein, we design the first amphiphilic Ru-bda (H2 bda=2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts (WOCs) of formula [Ru(II) (bda)(4-OTEG-pyridine)2 ] (1, OTEG=OCH2 CH2 OCH2 CH2 OCH3 ) and [Ru(II) (bda)(PySO3 Na)2 ] (2, PySO3 (-) =pyridine-3-sulfonate), which possess good solubility in water. Dynamic light scattering (DLS), scanning electron microscope (SEM), critical aggregation concentration (CAC) experiments and product analysis demonstrate that they enable to self-assemble in water and form the O-O bond through different routes even though they have the same bda(2-) backbone. This work illustrates for the first time that the O-O bond formation pathway can be regulated by the interaction of ancillary ligands at supramolecular level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Self-Assembled Gold Nano-Ripple Formation by Gas Cluster Ion Beam Bombardment.

    Science.gov (United States)

    Tilakaratne, Buddhi P; Chen, Quark Y; Chu, Wei-Kan

    2017-09-08

    In this study, we used a 30 keV argon cluster ion beam bombardment to investigate the dynamic processes during nano-ripple formation on gold surfaces. Atomic force microscope analysis shows that the gold surface has maximum roughness at an incident angle of 60° from the surface normal; moreover, at this angle, and for an applied fluence of 3 × 10 16 clusters/cm², the aspect ratio of the nano-ripple pattern is in the range of ~50%. Rutherford backscattering spectrometry analysis reveals a formation of a surface gradient due to prolonged gas cluster ion bombardment, although the surface roughness remains consistent throughout the bombarded surface area. As a result, significant mass redistribution is triggered by gas cluster ion beam bombardment at room temperature. Where mass redistribution is responsible for nano-ripple formation, the surface erosion process refines the formed nano-ripple structures.

  6. Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)

    2016-06-07

    Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

  7. Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

    International Nuclear Information System (INIS)

    Xu, Wen-Sheng; Freed, Karl F.

    2016-01-01

    Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

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

    KAUST Repository

    Chan, Kiat Hwa; Xue, Bo; Robinson, Robert C.; Hauser, Charlotte

    2017-01-01

    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

  9. Extracellular matrix components and culture regimen selectively regulate cartilage formation by self-assembling human mesenchymal stem cells in vitro and in vivo.

    Science.gov (United States)

    Ng, Johnathan; Wei, Yiyong; Zhou, Bin; Burapachaisri, Aonnicha; Guo, Edward; Vunjak-Novakovic, Gordana

    2016-12-09

    Cartilage formation from self-assembling mesenchymal stem cells (MSCs) in vitro recapitulate important cellular events during mesenchymal condensation that precedes native cartilage development. The goal of this study was to investigate the effects of cartilaginous extracellular matrix (ECM) components and culture regimen on cartilage formation by self-assembling human MSCs in vitro and in vivo. Human bone marrow-derived MSCs (hMSCs) were seeded and compacted in 6.5-mm-diameter transwell inserts with coated (type I, type II collagen) or uncoated (vehicle) membranes, at different densities (0.5 × 10 6 , 1.0 × 10 6 , 1.5 × 10 6 per insert). Pellets were formed by aggregating hMSCs (0.25 × 10 6 ) in round-bottomed wells. All tissues were cultured for up to 6 weeks for in vitro analyses. Discs (cultured for 6, 8 or 10 weeks) and pellets (cultured for 10 weeks) were implanted subcutaneously in immunocompromised mice to evaluate the cartilage stability in vivo. Type I and type II collagen coatings enabled cartilage disc formation from self-assembling hMSCs. Without ECM coating, hMSCs formed dome-shaped tissues resembling the pellets. Type I collagen, expressed in the prechondrogenic mesenchyme, improved early chondrogenesis versus type II collagen. High seeding density improved cartilage tissue properties but resulted in a lower yield of disc formation. Discs and pellets exhibited compositional and organizational differences in vitro and in vivo. Prolonged chondrogenic induction of the discs in vitro expedited endochondral ossification in vivo. The outcomes of cartilage tissues formed from self-assembling MSCs in vitro and in vivo can be modulated by the control of culture parameters. These insights could motivate new directions for engineering cartilage and bone via a cartilage template from self-assembling MSCs.

  10. Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

    Directory of Open Access Journals (Sweden)

    Yongfeng Tong

    2016-02-01

    Full Text Available This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon–chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon–chalcogen atom-bond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the π-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

  11. Ionic Liquids As Self-Assembly Guide for the Formation of Nanostructured Block Copolymer Membranes

    KAUST Repository

    Madhavan, Poornima

    2015-04-30

    Nanostructured block copolymer membranes were manufactured by water induced phase inversion, using ionic liquids (ILs) as cosolvents. The effect of ionic liquids on the morphology was investigated, by using polystyrene-b-poly(4-vinyl pyridine) (PS-b-PV4P) diblock as membrane copolymer matrix and imidazolium and pyridinium based ILs. The effect of IL concentration and chemical composition was evident with particular interaction with P4VP blocks. The order of block copolymer/ILs solutions previous to the membrane casting was confirmed by cryo scanning electron microscopy and the morphologies of the manufactured nanostructured membranes were characterized by transmission and scanning electron microscopy. Non-protic ionic liquids facilitate the formation of hexagonal nanoporous block copolymer structure, while protic ILs led to a lamella-structured membrane. The rheology of the IL/block copolymer solutions was investigated, evaluating the storage and loss moduli. Most membranes prepared with ionic liquid had higher water flux than pure block copolymer membranes without additives.

  12. Self-assembly of cyclodextrins

    DEFF Research Database (Denmark)

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

    2012-01-01

    The design of functional cyclodextrin (CD) nanoparticles is a developing area in the field of nanomedicine. CDs can not only help in the formation of drug carriers but also increase the local concentration of drugs at the site of action. CD monomers form aggregates by self-assembly, a tendency...... 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...

  13. Self-Assembled Core-Satellite Gold Nanoparticle Networks for Ultrasensitive Detection of Chiral Molecules by Recognition Tunneling Current.

    Science.gov (United States)

    Zhang, Yuanchao; Liu, Jingquan; Li, Da; Dai, Xing; Yan, Fuhua; Conlan, Xavier A; Zhou, Ruhong; Barrow, Colin J; He, Jin; Wang, Xin; Yang, Wenrong

    2016-05-24

    Chirality sensing is a very challenging task. Here, we report a method for ultrasensitive detection of chiral molecule l/d-carnitine based on changes in the recognition tunneling current across self-assembled core-satellite gold nanoparticle (GNP) networks. The recognition tunneling technique has been demonstrated to work at the single molecule level where the binding between the reader molecules and the analytes in a nanojunction. This process was observed to generate a unique and sensitive change in tunneling current, which can be used to identify the analytes of interest. The molecular recognition mechanism between amino acid l-cysteine and l/d-carnitine has been studied with the aid of SERS. The different binding strength between homo- or heterochiral pairs can be effectively probed by the copper ion replacement fracture. The device resistance was measured before and after the sequential exposures to l/d-carnitine and copper ions. The normalized resistance change was found to be extremely sensitive to the chirality of carnitine molecule. The results suggested that a GNP networks device optimized for recognition tunneling was successfully built and that such a device can be used for ultrasensitive detection of chiral molecules.

  14. Surface-assisted DNA self-assembly: An enzyme-free strategy towards formation of branched DNA lattice

    International Nuclear Information System (INIS)

    Bhanjadeo, Madhabi M.; Nayak, Ashok K.; Subudhi, Umakanta

    2017-01-01

    DNA based self-assembled nanostructures and DNA origami has proven useful for organizing nanomaterials with firm precision. However, for advanced applications like nanoelectronics and photonics, large-scale organization of self-assembled branched DNA (bDNA) into periodic lattices is desired. In this communication for the first time we report a facile method of self-assembly of Y-shaped bDNA nanostructures on the cationic surface of Aluminum (Al) foil to prepare periodic two dimensional (2D) bDNA lattice. Particularly those Y-shaped bDNA structures having smaller overhangs and unable to self-assemble in solution, they are easily assembled on the surface of Al foil in the absence of ligase. Field emission scanning electron microscopy (FESEM) analysis shows homogenous distribution of two-dimensional bDNA lattices across the Al foil. When the assembled bDNA structures were recovered from the Al foil and electrophoresed in nPAGE only higher order polymeric bDNA structures were observed without a trace of monomeric structures which confirms the stability and high yield of the bDNA lattices. Therefore, this enzyme-free economic and efficient strategy for developing bDNA lattices can be utilized in assembling various nanomaterials for functional molecular components towards development of DNA based self-assembled nanodevices. - Highlights: • Al foil surface-assisted self-assembly of monomeric structures into larger branched DNA lattice. • FESEM study confirms the uniform distribution of two-dimensional bDNA lattice structures across the surface of Al foil. • Enzyme-free and economic strategy to prepare higher order structures from simpler DNA nanostructures have been confirmed by recovery assay. • Use of well proven sequences for the preparation of pure Y-shaped monomeric DNA nanostructure with high yield.

  15. Formation of linear and crosslinked polyurethane nanoparticles that self-assemble differently in acetone and in water

    Czech Academy of Sciences Publication Activity Database

    Serkis-Rodzen, Magdalena; Špírková, Milena; Matějíček, P.; Štěpánek, M.

    2017-01-01

    Roč. 106, May (2017), s. 119-127 ISSN 0300-9440 R&D Projects: GA ČR(CZ) GA13-06700S Institutional support: RVO:61389013 Keywords : polyurethane water dispersion * nanoparticles * self-assembly Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 2.858, year: 2016

  16. Elucidating dominant pathways of the nano-particle self-assembly process.

    Science.gov (United States)

    Zeng, Xiangze; Li, Bin; Qiao, Qin; Zhu, Lizhe; Lu, Zhong-Yuan; Huang, Xuhui

    2016-09-14

    Self-assembly processes play a key role in the fabrication of functional nano-structures with widespread application in drug delivery and micro-reactors. In addition to the thermodynamics, the kinetics of the self-assembled nano-structures also play an important role in determining the formed structures. However, as the self-assembly process is often highly heterogeneous, systematic elucidation of the dominant kinetic pathways of self-assembly is challenging. Here, based on mass flow, we developed a new method for the construction of kinetic network models and applied it to identify the dominant kinetic pathways for the self-assembly of star-like block copolymers. We found that the dominant pathways are controlled by two competing kinetic parameters: the encounter time Te, characterizing the frequency of collision and the transition time Tt for the aggregate morphology change from rod to sphere. Interestingly, two distinct self-assembly mechanisms, diffusion of an individual copolymer into the aggregate core and membrane closure, both appear at different stages (with different values of Tt) of a single self-assembly process. In particular, the diffusion mechanism dominates the middle-sized semi-vesicle formation stage (with large Tt), while the membrane closure mechanism dominates the large-sized vesicle formation stage (with small Tt). Through the rational design of the hydrophibicity of the copolymer, we successfully tuned the transition time Tt and altered the dominant self-assembly pathways.

  17. Onset of self-assembly

    International Nuclear Information System (INIS)

    Chitanvis, S.M.

    1998-01-01

    We have formulated a theory of self-assembly based on the notion of local gauge invariance at the mesoscale. Local gauge invariance at the mesoscale generates the required long-range entropic forces responsible for self-assembly in binary systems. Our theory was applied to study the onset of mesostructure formation above a critical temperature in estane, a diblock copolymer. We used diagrammatic methods to transcend the Gaussian approximation and obtain a correlation length ξ∼(c-c * ) -γ , where c * is the minimum concentration below which self-assembly is impossible, c is the current concentration, and γ was found numerically to be fairly close to 2/3. The renormalized diffusion constant vanishes as the critical concentration is approached, indicating the occurrence of critical slowing down, while the correlation function remains finite at the transition point. copyright 1998 The American Physical Society

  18. Polymer-templated self-assembly of a 2-dimensional gold nanoparticle network

    DEFF Research Database (Denmark)

    Hansen, Christian Rein; Westerlund, Fredrik; Moth-Poulsen, Kasper

    2008-01-01

    We here report on the formation of well-ordered 2D gold nanostructures at the air/water interface. Spreading a mixture of alkanethiol-capped gold nanoparticles (AuNPs) and an amphiphilic poly(p-phenylene) on a water surface and compressing the mixture to a surface pressure of 40 mN/m lead...

  19. Layer-by-layer self-assembly of minocycline-loaded chitosan/alginate multilayer on titanium substrates to inhibit biofilm formation.

    Science.gov (United States)

    Lv, Hongbin; Chen, Zhen; Yang, Xiaoping; Cen, Lian; Zhang, Xu; Gao, Ping

    2014-11-01

    Bacteria adhesion and subsequent biofilm formation are primary causes of implant associated infection. The biofilm makes the bacteria highly resistant to the host defense and antimicrobial treatment. Antibacterial coatings on the surface of titanium implant can prevent biofilm formation effectively, but it is still a challenge to accomplish relatively long lasting antibacterial effects before wound healing or formation of biological seal. The purpose of our work was to construct antibacterial multilayer coatings loaded with minocycline on surface of Ti substrates using chitosan and alginate based on layer-by-layer (LbL) self-assembly technique. In this study, the surfaces of Ti substrates were first hydroxylated and then treated with 3-aminopropyltriethoxysilane (ATPES) to obtain amino-functionalized Ti substrates. Next, the precursor layer of chitosan was covalently conjugated to amino-functionalized Ti substrates. The following alternately coating alginate loaded with minocycline and chitosan onto the precursor layer of chitosan was carried out via LbL self-assembly technique to construct the multilayer coatings on Ti substrates. The multilayer coatings loaded more minocycline and improved sustainability of minocycline release to kill planktonic and adherent bacteria. Moreover, surface charge and hydrophilicity of the coatings and antibacterial ability of chitosan itself also played roles in the antibacterial performance, which can keep the antibacterial ability of the multilayer coatings after minocycline release ceases. In conclusion, LbL self-assembly method provides a promising strategy to fabricate long-term antibacterial surfaces, which is especially effective in preventing implant associated infections in the early stage. Loading minocycline on the surface of implants based on LbL self-assembly strategy can endow implants with sustained antibacterial property. This can inhabit the immediate colonization of bacteria onto the surface of implants in the

  20. Self-assembled, nanowire network electrodes for depleted bulk heterojunction solar cells

    KAUST Repository

    Lan, Xinzheng; Bai, Jing; Masala, Silvia; Thon, Susanna; Ren, Yuan; Kramer, Illan J.; Hoogland, Sjoerd H.; Simchi, Arash; Koleilat, Ghada I.; Paz-Soldan, Daniel; Ning, Zhijun; Labelle, André J.; Kim, Jinyoung; Jabbour, Ghassan E.; Sargent, E. H.

    2013-01-01

    Herein, a solution-processed, bottom-up-fabricated, nanowire network electrode is developed. This electrode features a ZnO template which is converted into locally connected, infiltratable, TiO2 nanowires. This new electrode is used to build a depleted bulk heterojunction solar cell employing hybrid-passivated colloidal quantum dots. The new electrode allows the application of a thicker, and thus more light-absorbing, colloidal quantum dot active layer, from which charge extraction of an efficiency comparable to that obtained from a thinner, planar device could be obtained. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Self-assembled, nanowire network electrodes for depleted bulk heterojunction solar cells

    KAUST Repository

    Lan, Xinzheng

    2013-01-06

    Herein, a solution-processed, bottom-up-fabricated, nanowire network electrode is developed. This electrode features a ZnO template which is converted into locally connected, infiltratable, TiO2 nanowires. This new electrode is used to build a depleted bulk heterojunction solar cell employing hybrid-passivated colloidal quantum dots. The new electrode allows the application of a thicker, and thus more light-absorbing, colloidal quantum dot active layer, from which charge extraction of an efficiency comparable to that obtained from a thinner, planar device could be obtained. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Structural signature of a brittle-to-ductile transition in self-assembled networks.

    Science.gov (United States)

    Ramos, Laurence; Laperrousaz, Arnaud; Dieudonné, Philippe; Ligoure, Christian

    2011-09-30

    We study the nonlinear rheology of a novel class of transient networks, made of surfactant micelles of tunable morphology reversibly linked by block copolymers. We couple rheology and time-resolved structural measurements, using synchrotron radiation, to characterize the highly nonlinear viscoelastic regime. We propose the fluctuations of the degree of alignment of the micelles under shear as a probe to identify a fracture process. We show a clear signature of a brittle-to-ductile transition in transient gels, as the morphology of the micelles varies, and provide a parallel between the fracture of solids and the fracture under shear of viscoelastic fluids.

  3. A fluidic device for the controlled formation and real-time monitoring of soft membranes self-assembled at liquid interfaces.

    Science.gov (United States)

    Mendoza-Meinhardt, Arturo; Botto, Lorenzo; Mata, Alvaro

    2018-02-13

    Membrane materials formed at the interface between two liquids have found applications in a large variety of technologies, from sensors to drug-delivery and catalysis. However, studying the formation of these membranes in real-time presents considerable challenges, owing to the difficulty of prescribing the location and instant of formation of the membrane, the difficulty of observing time-dependent membrane shape and thickness, and the poor reproducibility of results obtained using conventional mixing procedures. Here we report a fluidic device that facilitates characterisation of the time-dependent thickness, morphology and mass transport properties of materials self-assembled at fluid-fluid interfaces. In the proposed device the membrane forms from the controlled coalescence of two liquid menisci in a linear open channel. The linear geometry and controlled mixing of the solutions facilitate real-time visualisation, manipulation and improve reproducibility. Because of its small dimensions, the device can be used in conjunction with standard microscopy methods and reduces the required volumes of potentially expensive reagents. As an example application to tissue engineering, we use the device to characterise interfacial membranes formed by supra-molecular self-assembly of peptide-amphiphiles with either an elastin-like-protein or hyaluronic acid. The device can be adapted to study self-assembling membranes for applications that extend beyond bioengineering.

  4. Structure formation of lipid membranes: Membrane self-assembly and vesicle opening-up to octopus-like micelles

    Science.gov (United States)

    Noguchi, Hiroshi

    2013-02-01

    We briefly review our recent studies on self-assembly and vesicle rupture of lipid membranes using coarse-grained molecular simulations. For single component membranes, lipid molecules self-assemble from random gas states to vesicles via disk-shaped clusters. Clusters aggregate into larger clusters, and subsequently the large disks close into vesicles. The size of vesicles are determined by kinetics than by thermodynamics. When a vesicle composed of lipid and detergent types of molecules is ruptured, a disk-shaped micelle called bicelle can be formed. When both surfactants have negligibly low critical micelle concentration, it is found that bicelles connected with worm-like micelles are also formed depending on the surfactant ratio and spontaneous curvature of the membrane monolayer.

  5. Three-Dimensionally Isotropic Negative Refractive Index Materials from Block Copolymer Self-Assembled Chiral Gyroid Networks

    KAUST Repository

    Hur, Kahyun

    2011-10-17

    Metamaterials are engineered artificial materials that offer new functionalities such as super-resolution imaging and cloaking. Calculations of the photonic properties of three-dimensionally isotropic metamaterials with cubic double gyroid and alternating gyroid morphologies from block copolymer self-assembly are presented.

  6. In situ investigation of formation of self-assembled nanodomain structure in lithium niobate after pulse laser irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Shur, V. Ya.; Kuznetsov, D. K.; Mingaliev, E. A.; Yakunina, E. M.; Lobov, A. I.; Ievlev, A. V. [Ferroelectric Laboratory, Institute of Physics and Applied Mathematics, Ural State University, Lenin Ave. 51, Ekaterinburg 620083 (Russian Federation)

    2011-08-22

    The evolution of the self-assembled quasi-regular micro- and nanodomain structures after pulse infrared laser irradiation was studied by in situ optical observation. The average periods of the structures are much less than the sizes of the laser spots. The polarization reversal occurs through covering of the whole irradiated area by the nets of the spatially separated nanodomain chains and microdomain rays--''hatching effect.'' The main stages of the anisotropic nanodomain kinetics: nucleation, growth, and branching, have been singled out. The observed abnormal domain kinetics was attributed to the action of the pyroelectric field arising during cooling after laser heating.

  7. Self-assembly of tetrapod-shaped CdS nanostructures into 3D networks by a transverse growth process

    International Nuclear Information System (INIS)

    Fu Xiuli; Li Dan; Zhang Lei; Xiao Jinghua; Li Jiangyan; Peng Zhijian; Fang Zheyu

    2011-01-01

    Spontaneous formation of 3D tetrapod-shaped CdS nanostructure networks has been achieved for the first time by vapor diffusion-deposition growth from CdS powders. The growth mechanism of the hexagonal and preferentially oriented CdS tetrapod-shaped nanostructures is a combination of the classic vapor-liquid-solid and vapor-solid processes, and the formation of a 3D network results from the spontaneous growths along the longitudinal and across the axial directions of the primarily formed CdS nanorods. Micro-photoluminescence measurements and near-field scanning optical microscopy investigations show that the synthesized CdS tetrapod networks have an excellent luminescence property and can be used as an optical waveguide cavities in which the guided light can be extremely confined.

  8. Self-Assembly of Molecular Threads into Reversible Gels

    Science.gov (United States)

    Sayar, Mehmet; Stupp, Samuel I.

    2001-03-01

    Reversible gels formed by low concentrations of molecular gelators that self-assemble into fibers with molecular width and extremely long length have been studied via Monte Carlo simulations. The gelators of interest have two kinds of interactions, one governs self-assembly into fibers and the other provides inter-fiber connectivity to drive the formation of a network. The off-lattice Monte Carlo simulation presented here is based on a point particle representation of gelators. In this model each particle can form only two strong bonds, that enable linear fiber formation, but a variable number of weak bonds which provide inter-fiber connectivity. The gel formation has been studied as a function of concentration of monomers, the strength of interactions, number of bonding sites per particle for weak interactions, and the stiffness of the fibers. The simulation results are compared with two experimental systems synthesized in our group in order to understand gelation mechanisms.

  9. Self-assembled nanostructures

    CERN Document Server

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

    2003-01-01

    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.

  10. Nanoparticle Surface Specific Adsorption of Zein and Its Self-assembled Behavior of Nanocubes Formation in Relation to On-Off SERS: Understanding Morphology Control of Protein Aggregates.

    Science.gov (United States)

    Navdeep; Banipal, Tarlok Singh; Kaur, Gurinder; Bakshi, Mandeep Singh

    2016-01-27

    Zein, an industrially important protein, is characterized in terms of its food and pharmaceutical coating applications by using surface enhanced Raman spectroscopy (SERS) on Au, Ag, and PbS nanoparticles (NPs). Its specific surface adsorption behavior on Ag NPs produced self-assembled zein nanocubes which demonstrated on and off SERS activity. Both SERS characterization as well as nanocube formation of zein helped us to understand the complex protein aggregation behavior in shape controlled morphologies, a process with significant ramifications in protein crystallization to achieve ordered morphologies. Interestingly, nanocube formation was promoted in the presence of Ag rather than Au or PbS NPs under in situ synthesis and discussed in terms of specific adsorption. Zein fingerprinting was much more clear and enhanced on Au surface in comparison to Ag while PbS did not demonstrate SERS due to its semiconducting nature.

  11. Macroscopic magnetic Self assembly

    NARCIS (Netherlands)

    Löthman, Per Arvid

    2018-01-01

    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

  12. Effect of amino acid sequence and pH on nanofiber formation of self-assembling peptides EAK16-II and EAK16-IV.

    Science.gov (United States)

    Hong, Yooseong; Legge, Raymond L; Zhang, S; Chen, P

    2003-01-01

    Atomic force microscopy (AFM) and axisymmetric drop shape analysis-profile (ASDA-P) were used to investigate the mechanism of self-assembly of peptides. The peptides chosen consisted of 16 alternating hydrophobic and hydrophilic amino acids, where the hydrophilic residues possess alternating negative and positive charges. Two types of peptides, AEAEAKAKAEAEAKAK (EAK16-II) and AEAEAEAEAKAKAKAK (EAK16-IV), were investigated in terms of nanostructure formation through self-assembly. The experimental results, which focused on the effects of the amino acid sequence and pH, show that the nanostructures formed by the peptides are dependent on the amino acid sequence and the pH of the solution. For pH conditions around neutrality, one of the peptides used in this study, EAK16-IV, forms globular assemblies and has lower surface tension at air-water interfaces than another peptide, EAK16-II, which forms fibrillar assemblies at the same pH. When the pH is lowered below 6.5 or raised above 7.5, there is a transition from globular to fibrillar structures for EAK16-IV, but EAK16-II does not show any structural transition. Surface tension measurements using ADSA-P showed different surface activities of peptides at air-water interfaces. EAK16-II does not show a significant difference in surface tension for the pH range between 4 and 9. However, EAK16-IV shows a noticeable decrease in surface tension at pH around neutrality, indicating that the formation of globular assemblies is related to the molecular hydrophobicity.

  13. Fabrication of large-scale one-dimensional Au nanochain and nanowire networks by interfacial self-assembly

    International Nuclear Information System (INIS)

    Wang Minhua; Li Yongjun; Xie Zhaoxiong; Liu Cai; Yeung, Edward S.

    2010-01-01

    By utilizing the strong capillary attraction between interfacial nanoparticles, large-scale one-dimensional Au nanochain networks were fabricated at the n-butanol/water interface, and could be conveniently transferred onto hydrophilic substrates. Furthermore, the length of the nanochains could be adjusted simply by controlling the density of Au nanoparticles (AuNPs) at the n-butanol/water interface. Surprisingly, the resultant Au nanochains could further transform into smooth nanowires by increasing the aging time, forming a nanowire network. Combined characterization by HRTEM and UV-vis spectroscopy indicates that the formation of Au nanochains stemmed from a stochastic assembly of interfacial AuNPs due to strong capillary attraction, and the evolution of nanochains to nanowires follows an Ostwald ripening mechanism rather than an oriented attachment. This method could be utilized to fabricate large-area nanochain or nanowire networks more uniformly on solid substrates than that of evaporating a solution of nanochain colloid, since it eliminates the three-dimensional aggregation behavior.

  14. Photo-cross-linked PLA-PEO-PLA hydrogels from self-assembled physical networks: mechanical properties and influence of assumed constitutive relationships.

    Science.gov (United States)

    Sanabria-DeLong, Naomi; Crosby, Alfred J; Tew, Gregory N

    2008-10-01

    Poly(lactide)-block-poly(ethylene oxide)-block-poly(lactide) (PLA-PEO-PLA) triblock copolymers are known to form physical hydrogels in water as a result of the polymer's amphiphilicity. Their mechanical properties, biocompatibility, and biodegradability have made them attractive for use as soft tissue scaffolds. However, the network junction points are not covalently cross-linked, and in a highly aqueous environment these hydrogels adsorb more water, transform from gel to sol, and lose the designed mechanical properties. In this article, a hydrogel was formed by the use of a novel two-step approach. In the first step, the end-functionalized PLA-PEO-PLA triblock was self-assembled into a physical hydrogel through hydrophobic micelle network junctions, and in the second step, this self-assembled physical network structure was locked into place by photo-cross-linking the terminal acrylate groups. In contrast with physical hydrogels, the photo-cross-linked gels remained intact in phosphate-buffered solution at body temperature. The swelling, degradation, and mechanical properties were characterized, and they demonstrated an extended degradation time (approximately 65 days), an exponential decrease in modulus with degradation time, and a tunable shear modulus (1.6-133 kPa). We also discuss the various constitutive relationships (Hookean, neo-Hookean, and Mooney-Rivlin) that can be used to describe the stress-strain behavior of these hydrogels. The chosen model and assumptions used for data fitting influenced the obtained modulus values by as much as a factor of 3.5, which demonstrates the importance of clearly stating one's data fitting parameters so that accurate comparisons can be made within the literature.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-15

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

  16. Self-Assembled Formation of Well-Aligned Cu-Te Nano-Rods on Heavily Cu-Doped ZnTe Thin Films

    Science.gov (United States)

    Liang, Jing; Cheng, Man Kit; Lai, Ying Hoi; Wei, Guanglu; Yang, Sean Derman; Wang, Gan; Ho, Sut Kam; Tam, Kam Weng; Sou, Iam Keong

    2016-11-01

    Cu doping of ZnTe, which is an important semiconductor for various optoelectronic applications, has been successfully achieved previously by several techniques. However, besides its electrical transport characteristics, other physical and chemical properties of heavily Cu-doped ZnTe have not been reported. We found an interesting self-assembled formation of crystalline well-aligned Cu-Te nano-rods near the surface of heavily Cu-doped ZnTe thin films grown via the molecular beam epitaxy technique. A phenomenological growth model is presented based on the observed crystallographic morphology and measured chemical composition of the nano-rods using various imaging and chemical analysis techniques. When substitutional doping reaches its limit, the extra Cu atoms favor an up-migration toward the surface, leading to a one-dimensional surface modulation and formation of Cu-Te nano-rods, which explain unusual observations on the reflection high energy electron diffraction patterns and apparent resistivity of these thin films. This study provides an insight into some unexpected chemical reactions involved in the heavily Cu-doped ZnTe thin films, which may be applied to other material systems that contain a dopant having strong reactivity with the host matrix.

  17. Self-assembled formation and transformation of In/CdZnTe(110) nano-rings into camel-humps

    International Nuclear Information System (INIS)

    Cohen-Taguri, G.; Ruzin, A.; Goldfarb, I.

    2012-01-01

    We used in situ scanning tunneling microscopy to monitor in real time the formation of nano-rings at the molecular beam epitaxially grown In/CdZnTe(110) surface, and Auger electron spectroscopy to explore the corresponding compositional changes. In-diffusion of In and segregation of Cd to the surface in course of annealing lead to a formation of elliptically distorted nano-rings, elongated along the fast [110] diffusion direction. Exacerbated diffusion anisotropy in the liquid state, at temperatures above the melting point of In, further distorts the nano-rings into a camel-hump shape.

  18. Modelling Polar Self Assembly

    Science.gov (United States)

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

    2001-03-01

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

  19. Self-assembly of the yeast actomyosin contractile ring as an aggregation process: kinetics of formation and instability regimes

    Science.gov (United States)

    Ojkic, Nikola; Vavylonis, Dimitrios

    2009-03-01

    Fission yeast cells assemble an equatorial contractile ring for cytokinesis, the last step of mitosis. The ring assembles from ˜ 65 membrane-bound ``nodes''' containing myosin motors and other proteins. Actin filaments that grow out from the nodes establish transient connections among the nodes and aid in pulling them together in a process that appears as pair-wise attraction (Vavylonis et al. Science 97:319, 2008). We used scaling arguments, coarse grained stability analysis of homogeneous states, and Monte Carlo simulations of simple models, to explore the conditions that yield fast and efficient ring formation, as opposed to formation of isolated clumps. We described our results as a function of: number of nodes, rate of establishing connections, range of node interaction, distance traveled per node interaction and broad band width, w. Uniform cortical 2d distributions of nodes are stable over short times due to randomness of connections among nodes, but become unstable over long times due to fluctuations in the initial node distribution. Successful condensation of nodes into a ring requires sufficiently small w such that lateral contraction occurs faster then clump formation.

  20. 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

    2017-09-01

    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.

  1. Synthetic Self-Assembled Materials in Biological Environments

    NARCIS (Netherlands)

    Versluis, F.; van Esch, J.H.; Eelkema, R.

    2016-01-01

    Synthetic self-assembly has long been recognized as an excellent approach for the formation of ordered structures on the nanoscale. Although the development of synthetic self-assembling materials has often been inspired by principles observed in nature (e.g., the assembly of lipids, DNA,

  2. 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 ...

  3. Self-assembly of nano/micro-structured Fe3O4 microspheres among 3D rGO/CNTs hierarchical networks with superior lithium storage performances

    International Nuclear Information System (INIS)

    Liu, Jinlong; Feng, Haibo; Wang, Xipeng; Qian, Dong; Jiang, Jianbo; Li, Junhua; Peng, Sanjun; Deng, Miao; Liu, Youcai

    2014-01-01

    Nano/micro-structured Fe 3 O 4 microspheres among three-dimensional (3D) reduced graphene oxide (rGO)/carbon nanotubes (CNTs) hierarchical networks (the ternary composite is denoted as rGCFs) have been synthesized using a facile, self-assembled and one-pot hydrothermal approach. The rGCFs composite exhibits superior lithium storage performances: initial discharge and charge capacities of 1452 and 1036 mAh g −1 , respectively, remarkable rate capability at current densities from 100 mA g −1 to 10 A g −1 and outstanding cycling performance up to 200 cycles. The highly enhanced electrochemical performances of rGCFs depend heavily on the robust 3D rGO/CNTs hierarchical networks, the stable nano/microstructures of active Fe 3 O 4 microspheres and the positive synergistic effects of building components. The systematic structure characterizations and electrochemical investigations provide insightful understanding towards the relationship between structure/morphology and lithium storage performances, which may pave the way for the rational design of composite materials with desirable goals. (papers)

  4. Self-assembly of silver nanoparticles and bacteriophage

    Directory of Open Access Journals (Sweden)

    Santi Scibilia

    2016-03-01

    Full Text Available Biohybrid nanostructured materials, composed of both inorganic nanoparticles and biomolecules, offer prospects for many new applications in extremely diverse fields such as chemistry, physics, engineering, medicine and nanobiotechnology. In the recent years, Phage display technique has been extensively used to generate phage clones displaying surface peptides with functionality towards organic materials. Screening and selection of phage displayed material binding peptides has attracted great interest because of their use for development of hybrid materials with multiple functionalities. Here, we present a self-assembly approach for the construction of hybrid nanostructured networks consisting of M13 P9b phage clone, specific for Pseudomonas aeruginosa, selected by Phage display technology, directly assembled with silver nanoparticles (AgNPs, previously prepared by pulsed laser ablation. These networks are characterized by UV–vis optical spectroscopy, scanning/transmission electron microscopies and Raman spectroscopy. We investigated the influence of different ions and medium pH on self-assembly by evaluating different phage suspension buffers. The assembly of these networks is controlled by electrostatic interactions between the phage pVIII major capsid proteins and the AgNPs. The formation of the AgNPs-phage networks was obtained only in two types of tested buffers at a pH value near the isoelectric point of each pVIII proteins displayed on the surface of the clone. This systematic study allowed to optimize the synthesis procedure to assembly AgNPs and bacteriophage. Such networks find application in the biomedical field of advanced biosensing and targeted gene and drug delivery. Keywords: Phage display, Silver nanoparticles, Self-assembly, Hybrid architecture, Raman spectroscopy

  5. Photocrosslinked PLA-PEO-PLA Hydrogels from Self-Assembled Physical Networks: Mechanical Properties and Influence of Assumed Constitutive Relationships

    OpenAIRE

    Sanabria-DeLong, Naomi; Crosby, Alfred J.; Tew, Gregory N.

    2008-01-01

    Poly(lactide) – block – poly(ethylene oxide) – block – poly(lactide) [PLA-PEO-PLA] triblock copolymers are known to form physical hydrogels in water, due to the polymer's amphiphilicity. Their mechanical properties, biocompatibility, and biodegradability have made them attractive for use as soft tissue scaffolds. However, the network junction points are not covalently crosslinked and in a highly aqueous environment these hydrogels adsorb more water, transform from gel to sol, and lose the des...

  6. Large branched self-assembled DNA complexes

    International Nuclear Information System (INIS)

    Tosch, Paul; Waelti, Christoph; Middelberg, Anton P J; Davies, A Giles

    2007-01-01

    Many biological molecules have been demonstrated to self-assemble into complex structures and networks by using their very efficient and selective molecular recognition processes. The use of biological molecules as scaffolds for the construction of functional devices by self-assembling nanoscale complexes onto the scaffolds has recently attracted significant attention and many different applications in this field have emerged. In particular DNA, owing to its inherent sophisticated self-organization and molecular recognition properties, has served widely as a scaffold for various nanotechnological self-assembly applications, with metallic and semiconducting nanoparticles, proteins, macromolecular complexes, inter alia, being assembled onto designed DNA scaffolds. Such scaffolds may typically contain multiple branch-points and comprise a number of DNA molecules selfassembled into the desired configuration. Previously, several studies have used synthetic methods to produce the constituent DNA of the scaffolds, but this typically constrains the size of the complexes. For applications that require larger self-assembling DNA complexes, several tens of nanometers or more, other techniques need to be employed. In this article, we discuss a generic technique to generate large branched DNA macromolecular complexes

  7. Metallic Contact Formation for Molecular Electronics : Interactions between Vapor-Deposited Metals and Self-Assembled Monolayers of Conjugated Mono- and Dithiols

    NARCIS (Netherlands)

    Boer, Bert de; Frank, Martin M.; Chabal, Yves J.; Jiang, Weirong; Garfunkel, Eric; Bao, Zhenan

    2004-01-01

    We present grazing-incidence Fourier transform infrared and AFM data of Au, Al, and Ti vapor-deposited onto self-assembled monolayers (SAMs) of conjugated mono- and dithiols. SAMs of 4,4'''-dimercapto-p-quaterphenyl, 4,4''-dimercapto-p-terphenyl, and 4,4'-dimercapto-p-biphenyl have reactive thiols

  8. Counterions control whether self-assembly leads to formation of stable and well-defined unilamellar nanotubes or nanoribbons and nanorods

    DEFF Research Database (Denmark)

    Shi, Dong; Schwall, Christian; Sfintes, George

    2014-01-01

    Self-assembly of the amphiphilic π-conjugated carbenium ion ATOTA-1(+) in aqueous solution selectively leads to discrete and highly stable nanotubes or nanoribbons and nanorods, depending on the nature of the counterion (Cl(-) vs. PF6(-), respectively). The nanotubes formed by the Cl(-) salt...

  9. Formation of multiple networks

    DEFF Research Database (Denmark)

    Magnani, Matteo; Rossi, Luca

    2013-01-01

    we introduce the first network formation model for multiple networks. Network formation models are among the most popular tools in traditional network studies, because of both their practical and theoretical impact. However, existing models are not sufficient to describe the generation of multiple...

  10. Construction of Supramolecular Architectures via Self-assembly

    Institute of Scientific and Technical Information of China (English)

    Takeharu; Haino

    2007-01-01

    1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).

  11. Colloidal Self-Assembly Driven by Deformability & Near-Critical Phenomena

    NARCIS (Netherlands)

    Evers, C.H.J.|info:eu-repo/dai/nl/338775188

    2016-01-01

    Self-assembly is the spontaneous formation of patterns or structures without human intervention. This thesis aims to increase our understanding of self-assembly. In self-assembly of proteins, the building blocks are very small and complex. Consequently, grasping the basic principles that drive the

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

    KAUST Repository

    Tétreault, Nicolas

    2010-12-28

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

  13. Formation of a stable, three-dimensional porous structure with self-assembled glass spheres using the plasma-induced electromeniscus phenomenon

    International Nuclear Information System (INIS)

    Matsuura, Hiroshi; Tanikawa, Tamio; Ando, Yasuhisa; Miyake, Koji; Sasaki, Shinya

    2006-01-01

    We develop a method for fabricating a stable, three-dimensional porous structure with self-assembled glass spheres. This three-dimensional (3D) self-assembly of glass spheres is achieved using the electromeniscus phenomenon, which is associated with a microscale solution current. The current encloses a group of glass spheres, carries the spheres, and assembles them three dimensionally with its surface tension at the desired site. The assembled glass spheres are fixed using a plasma-induced reaction combined with thermal treatment of the solution. These assembled microscale spheres create a large number of openings with extensive surface areas. This extensive area among 3D porous structures would be particularly useful for fabricating high-performance catalysts and high-resolution hydrogen sensors

  14. Centrioles: Some Self-Assembly Required

    OpenAIRE

    Song, Mi Hye; Miliaras, Nicholas B.; Peel, Nina; O'Connell, Kevin F.

    2008-01-01

    Centrioles play an important role in organizing microtubules and are precisely duplicated once per cell cycle. New (daughter) centrioles typically arise in association with existing (mother) centrioles (canonical assembly), suggesting that mother centrioles direct the formation of daughter centrioles. However, under certain circumstances, centrioles can also self-assemble free of an existing centriole (de novo assembly). Recent work indicates that the canonical and de novo pathways utilize a ...

  15. Self-assembly dynamics for the transition of a globular aggregate to a fibril network of lysozyme proteins via a coarse-grained Monte Carlo simulation

    Directory of Open Access Journals (Sweden)

    R. B. Pandey

    2015-09-01

    Full Text Available The self-organizing dynamics of lysozymes (an amyloid protein with 148 residues with different numbers of protein chains, Nc = 1,5,10, and 15 (concentration 0.004 – 0.063 is studied by a coarse-grained Monte Carlo simulation with knowledge-based residue-residue interactions. The dynamics of an isolated lysozyme (Nc = 1 is ultra-slow (quasi-static at low temperatures and becomes diffusive asymptotically on raising the temperature. In contrast, the presence of interacting proteins leads to concentration induced protein diffusion at low temperatures and concentration-tempering sub-diffusion at high temperatures. Variation of the radius of gyration of the protein with temperature shows a systematic transition from a globular structure (at low T to a random coil (high T conformation when the proteins are isolated. The crossover from globular to random coil becomes sharper upon increasing the protein concentration (i.e. with Nc = 5,10, with larger Rg at higher temperatures and concentration; Rg becomes smaller on adding more protein chains (e.g. Nc = 15 a non-monotonic response to protein concentration. Analysis of the structure factor (S(q provides an estimate of the effective dimension (D ≥ 3, globular conformation at low temperature, and D ∼ 1.7, random coil, at high temperatures of the isolated protein. With many interacting proteins, the morphology of the self-assembly varies with scale, i.e. at the low temperature (T = 0.015, D ∼ 2.9 on the scale comparable to the radius of gyration of the protein, and D ∼ 2.3 at the large scale over the entire sample. The global network of fibrils appears at high temperature (T = 0.021 with D ∼ 1.7 (i.e. a random coil morphology at large scale involving tenuous distribution of micro-globules (at small scales.

  16. Chemical solution route to self-assembled epitaxial oxide nanostructures.

    Science.gov (United States)

    Obradors, X; Puig, T; Gibert, M; Queraltó, A; Zabaleta, J; Mestres, N

    2014-04-07

    Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials.

  17. Unexpected self-sorting self-assembly formation of a [4:4] sulfate:ligand cage from a preorganized tripodal urea ligand.

    Science.gov (United States)

    Pandurangan, Komala; Kitchen, Jonathan A; Blasco, Salvador; Boyle, Elaine M; Fitzpatrick, Bella; Feeney, Martin; Kruger, Paul E; Gunnlaugsson, Thorfinnur

    2015-04-07

    The design and synthesis of tripodal ligands 1-3 based upon the N-methyl-1,3,5-benzenetricarboxamide platform appended with three aryl urea arms is reported. This ligand platform gives rise to highly preorganized structures and is ideally suited for binding SO4 (2-) and H2 PO4 (-) ions through multiple hydrogen-bonding interactions. The solid-state crystal structures of 1-3 with SO4 (2-) show the encapsulation of a single anion within a cage structure, whereas the crystal structure of 1 with H2 PO4 (-) showed that two anions are encapsulated. We further demonstrate that ligand 4, based on the same platform but consisting of two bis-urea moieties and a single ammonium moiety, also recognizes SO4 (2-) to form a self-assembled capsule with [4:4] SO4 (2-) :4 stoichiometry in which the anions are clustered within a cavity formed by the four ligands. This is the first example of a self-sorting self-assembled capsule where four tetrahedrally arranged SO4 (2-) ions are embedded within a hydrophobic cavity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Dynamic stability of nano-fibers self-assembled from short amphiphilic A6D peptides.

    Science.gov (United States)

    Nikoofard, Narges; Maghsoodi, Fahimeh

    2018-04-07

    Self-assembly of A 6 D amphiphilic peptides in explicit water is studied by using coarse-grained molecular dynamics simulations. It is observed that the self-assembly of randomly distributed A 6 D peptides leads to the formation of a network of nano-fibers. Two other simulations with cylindrical nano-fibers as the initial configuration show the dynamic stability of the self-assembled nano-fibers. As a striking feature, notable fluctuations occur along the axes of the nano-fibers. Depending on the number of peptides per unit length of the nano-fiber, flat-shaped bulges or spiral shapes along the nano-fiber axis are observed at the fluctuations. Analysis of the particle distribution around the nano-fiber indicates that the hydrophobic core and the hydrophilic shell of the nano-structure are preserved in both simulations. The size of the deformations and their correlation times are different in the two simulations. This study gives new insights into the dynamics of the self-assembled nano-structures of short amphiphilic peptides.

  19. Dynamic stability of nano-fibers self-assembled from short amphiphilic A6D peptides

    Science.gov (United States)

    Nikoofard, Narges; Maghsoodi, Fahimeh

    2018-04-01

    Self-assembly of A6D amphiphilic peptides in explicit water is studied by using coarse-grained molecular dynamics simulations. It is observed that the self-assembly of randomly distributed A6D peptides leads to the formation of a network of nano-fibers. Two other simulations with cylindrical nano-fibers as the initial configuration show the dynamic stability of the self-assembled nano-fibers. As a striking feature, notable fluctuations occur along the axes of the nano-fibers. Depending on the number of peptides per unit length of the nano-fiber, flat-shaped bulges or spiral shapes along the nano-fiber axis are observed at the fluctuations. Analysis of the particle distribution around the nano-fiber indicates that the hydrophobic core and the hydrophilic shell of the nano-structure are preserved in both simulations. The size of the deformations and their correlation times are different in the two simulations. This study gives new insights into the dynamics of the self-assembled nano-structures of short amphiphilic peptides.

  20. Self-Assembled Hierarchical Formation of Conjugated 3D Cobalt Oxide Nanobead-CNT-Graphene Nanostructure Using Microwaves for High-Performance Supercapacitor Electrode.

    Science.gov (United States)

    Kumar, Rajesh; Singh, Rajesh Kumar; Dubey, Pawan Kumar; Singh, Dinesh Pratap; Yadav, Ram Manohar

    2015-07-15

    Here we report the electrochemical performance of a interesting three-dimensional (3D) structures comprised of zero-dimensional (0D) cobalt oxide nanobeads, one-dimensional (1D) carbon nanotubes and two-dimensional (2D) graphene, stacked hierarchically. We have synthesized 3D self-assembled hierarchical nanostructure comprised of cobalt oxide nanobeads (Co-nb), carbon nanotubes (CNTs), and graphene nanosheets (GNSs) for high-performance supercapacitor electrode application. This 3D self-assembled hierarchical nanostructure Co3O4 nanobeads-CNTs-GNSs (3D:Co-nb@CG) is grown at a large scale (gram) through simple, facile, and ultrafast microwave irradiation (MWI). In 3D:Co-nb@CG nanostructure, Co3O4 nanobeads are attached to the CNT surfaces grown on GNSs. Our ultrafast, one-step approach not only renders simultaneous growth of cobalt oxide and CNTs on graphene nanosheets but also institutes the intrinsic dispersion of carbon nanotubes and cobalt oxide within a highly conductive scaffold. The 3D:Co-nb@CG electrode shows better electrochemical performance with a maximum specific capacitance of 600 F/g at the charge/discharge current density of 0.7A/g in KOH electrolyte, which is 1.56 times higher than that of Co3O4-decorated graphene (Co-np@G) nanostructure. This electrode also shows a long cyclic life, excellent rate capability, and high specific capacitance. It also shows high stability after few cycles (550 cycles) and exhibits high capacitance retention behavior. It was observed that the supercapacitor retained 94.5% of its initial capacitance even after 5000 cycles, indicating its excellent cyclic stability. The synergistic effect of the 3D:Co-nb@CG appears to contribute to the enhanced electrochemical performances.

  1. Surface cleaning and adsorbate layer formation: Dual role of alkylamines in the formation of self-assembled monolayers on cuprate superconductors

    International Nuclear Information System (INIS)

    Ritchie, J.E.; Murray, W.R.; Kershan, K.; Diaz, V.; Tran, L.; McDevitt, J.T.

    1999-01-01

    The development of monolayer adsorption chemistry for superconductor surfaces is particularly important for a number of practical and fundamental reasons. As high-T c superconductors begin to approach the marketplace in areas of communications, power industries, medical applications, and scientific instrumentation, the development of new soft chemistry approaches for the surface modification of these technologically relevant electronic materials becomes increasingly important. Monolayer adsorption chemistry has been developed extensively for electronic materials such as metals, semiconductors, and insulators. These methodologies have been expanded recently to include a variety of high-temperature superconductors (HTSCs). The authors describe a series of new X-ray photoelectron spectroscopy (XPS), four-point conductivity, critical current, atomic absorption spectroscopy (AAS), grazing angle infrared spectroscopy, and GE--MS experiments, which lead the suggestion that an entirely different mechanism is involved in the formation of HTSC-localized monolayers. According to the new model, the amine reagents serve two chemically distinct roles. In the initial phase, the degraded superconductor exteriors is etched away with the help of the amine compounds. The etching process proceeds to the point where fresh YBa 2 Cu 3 O 7 is exposed, and only at this point do the amines adsorb and remain at the YBa 2 Cu 3 O 7 surface. As the adsorption process continues, there is an accumulation of an organized monolayer at the surface, which prevents further etching of the YBa 2 Cu 3 O 7 material

  2. Centrioles: some self-assembly required.

    Science.gov (United States)

    Song, Mi Hye; Miliaras, Nicholas B; Peel, Nina; O'Connell, Kevin F

    2008-12-01

    Centrioles play an important role in organizing microtubules and are precisely duplicated once per cell cycle. New (daughter) centrioles typically arise in association with existing (mother) centrioles (canonical assembly), suggesting that mother centrioles direct the formation of daughter centrioles. However, under certain circumstances, centrioles can also selfassemble free of an existing centriole (de novo assembly). Recent work indicates that the canonical and de novo pathways utilize a common mechanism and that a mother centriole spatially constrains the self-assembly process to occur within its immediate vicinity. Other recently identified mechanisms further regulate canonical assembly so that during each cell cycle, one and only one daughter centriole is assembled per mother centriole.

  3. Biomedical Applications of Self-Assembling Peptides

    NARCIS (Netherlands)

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

    2016-01-01

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

  4. 3D Programmable Micro Self Assembly

    National Research Council Canada - National Science Library

    Bohringer, Karl F; Parviz, Babak A; Klavins, Eric

    2005-01-01

    .... We have developed a "self assembly tool box" consisting of a range of methods for micro-scale self-assembly in 2D and 3D We have shown physical demonstrations of simple 3D self-assemblies which lead...

  5. Investigation of Self-Assembly Processes for Chitosan-Based Coagulant-Flocculant Systems: A Mini-Review

    Directory of Open Access Journals (Sweden)

    Savi Bhalkaran

    2016-09-01

    Full Text Available The presence of contaminants in wastewater poses significant challenges to water treatment processes and environmental remediation. The use of coagulation-flocculation represents a facile and efficient way of removing charged particles from water. The formation of stable colloidal flocs is necessary for floc aggregation and, hence, their subsequent removal. Aggregation occurs when these flocs form extended networks through the self-assembly of polyelectrolytes, such as the amine-based polysaccharide (chitosan, which form polymer “bridges” in a floc network. The aim of this overview is to evaluate how the self-assembly process of chitosan and its derivatives is influenced by factors related to the morphology of chitosan (flocculant and the role of the solution conditions in the flocculation properties of chitosan and its modified forms. Chitosan has been used alone or in conjunction with a salt, such as aluminum sulphate, as an aid for the removal of various waterborne contaminants. Modified chitosan relates to grafted anionic or cationic groups onto the C-6 hydroxyl group or the amine group at C-2 on the glucosamine monomer of chitosan. By varying the parameters, such as molecular weight and the degree of deacetylation of chitosan, pH, reaction and settling time, dosage and temperature, self-assembly can be further investigated. This mini-review places an emphasis on the molecular-level details of the flocculation and the self-assembly processes for the marine-based biopolymer, chitosan.

  6. Combing and self-assembly phenomena in dry films of Taxol-stabilized microtubules

    Directory of Open Access Journals (Sweden)

    Rose Franck

    2007-01-01

    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.

  7. Chemical reactions directed Peptide self-assembly.

    Science.gov (United States)

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-05-13

    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.

  8. Self-assembly of concentric quantum double rings.

    Science.gov (United States)

    Mano, Takaaki; Kuroda, Takashi; Sanguinetti, Stefano; Ochiai, Tetsuyuki; Tateno, Takahiro; Kim, Jongsu; Noda, Takeshi; Kawabe, Mitsuo; Sakoda, Kazuaki; Kido, Giyuu; Koguchi, Nobuyuki

    2005-03-01

    We demonstrate the self-assembled formation of concentric quantum double rings with high uniformity and excellent rotational symmetry using the droplet epitaxy technique. Varying the growth process conditions can control each ring's size. Photoluminescence spectra emitted from an individual quantum ring complex show peculiar quantized levels that are specified by the carriers' orbital trajectories.

  9. Stereochemistry in subcomponent self-assembly.

    Science.gov (United States)

    Castilla, Ana M; Ramsay, William J; Nitschke, Jonathan R

    2014-07-15

    CONSPECTUS: As Pasteur noted more than 150 years ago, asymmetry exists in matter at all organization levels. Biopolymers such as proteins or DNA adopt one-handed conformations, as a result of the chirality of their constituent building blocks. Even at the level of elementary particles, asymmetry exists due to parity violation in the weak nuclear force. While the origin of homochirality in living systems remains obscure, as does the possibility of its connection with broken symmetries at larger or smaller length scales, its centrality to biomolecular structure is clear: the single-handed forms of bio(macro)molecules interlock in ways that depend upon their handednesses. Dynamic artificial systems, such as helical polymers and other supramolecular structures, have provided a means to study the mechanisms of transmission and amplification of stereochemical information, which are key processes to understand in the context of the origins and functions of biological homochirality. Control over stereochemical information transfer in self-assembled systems will also be crucial for the development of new applications in chiral recognition and separation, asymmetric catalysis, and molecular devices. In this Account, we explore different aspects of stereochemistry encountered during the use of subcomponent self-assembly, whereby complex structures are prepared through the simultaneous formation of dynamic coordinative (N → metal) and covalent (N═C) bonds. This technique provides a useful method to study stereochemical information transfer processes within metal-organic assemblies, which may contain different combinations of fixed (carbon) and labile (metal) stereocenters. We start by discussing how simple subcomponents with fixed stereogenic centers can be incorporated in the organic ligands of mononuclear coordination complexes and communicate stereochemical information to the metal center, resulting in diastereomeric enrichment. Enantiopure subcomponents were then

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

    NARCIS (Netherlands)

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

    2016-01-01

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

  11. Phytosterol-based oleogels self-assembled with monoglyceride for controlled volatile release.

    Science.gov (United States)

    Yang, Dan-Xia; Chen, Xiao-Wei; Yang, Xiao-Quan

    2018-01-01

    Oleogels have recently emerged as a subject of growing interest among industrial and academic researchers as an alternative to saturated/trans-fat and delivery of functional ingredients. Phytosterols, comprising plant-derived natural steroid compounds, are preferred for oleogel production because they are both natural and healthy. In the present study, phytosterol-based oleogels self-assembled with monoglyceride were studied with respect to tuning volatile release. Microscopy images of the bicomponent oleogels of β-sitosterol and monoglyceride showed the formation of a new three-dimensional network of entangled crystals and a controllable microstructure. Our analysis from differential scanning calorimetry and small angle X-ray scattering results suggests the self-assembly of β-sitosterol and monoglyceride via intermolecular hydrogen bonds into spherulitic microstructures. The results showed that the release rate (v 0 ), maximum headspace concentrations (C max ) and partition coefficients (k a/o ) for oleogels showed a significantly controlled release and were tunable via the microstructure of phytosterol-based oleogels under both dynamic and static conditions. In addition, the solid-like oleogels had interesting thixotropic and thermoresponsive behaviors, probably as a result of intermolecular hydrogen bonding. The self-assembly of phytosterol-based oleogels with monoglyceride was attributed to intermolecular hydrogen and is demonstrated to be a promising tunable and functional strategy for delivering flavor compounds. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  12. Heterogeneous self-assembled media for biopolymerization

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain

    2011-01-01

    Heterogeneous media, such as micro-structured aqueous environments, could offer an alternative approach to the synthesis of biopolymers with novel functions. Structured media are here defined as specialized, self-assembled structures that are formed, e.g, by amphiphiles, such as liposomes, emulsion...... polymerization, the initial elongation rates clearly depended on the complementarity of the monomers with the templating nucleobases3. However, metal-ion catalyzed reactions deliver RNA analogs with heterogeneous linkages. Moreover, the usefulness of this medium in the form of quasi-compartmentalization extends...... beyond metal-ion catalysis reactions, as we have recently demonstrated the catalytic power of a dipeptide, SerHis, for the regioselective formation of phosphodiester bonds. These results in conjonction with the synthesis of nucleobases at -78˚C, the demonstration of ribozyme activity (RNA ligase ribozyme...

  13. Formation, surface characterization, and electrocatalytic application of self-assembled monolayer films of tetra-substituted manganese, iron, and cobalt benzylthio phthalocyanine complexes

    CSIR Research Space (South Africa)

    Akinbulu, IA

    2011-10-01

    Full Text Available characteristics of the films were interrogated by cyclic voltammetry. Significant passivation of voltammetry processes associated with bare gold surface (gold oxidation and underpotential deposition of copper) confirmed formation of the films. Electrocatalytic...

  14. Self-Assembly of Infinite Structures

    Directory of Open Access Journals (Sweden)

    Scott M. Summers

    2009-06-01

    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. Bola-amphiphile self-assembly

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    2012-01-01

    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...... dynamics simulation of this self-assembly behaviour....

  16. Self-assembled nanomaterials for photoacoustic imaging

    Science.gov (United States)

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

    2016-01-01

    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.

  17. Self-assembled nanomaterials for photoacoustic imaging.

    Science.gov (United States)

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

    2016-02-07

    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.

  18. Molecular self-assembly advances and applications

    CERN Document Server

    Dequan, Alex Li

    2012-01-01

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

  19. Heterojunction nanowires having high activity and stability for the reduction of oxygen: Formation by self-assembly of iron phthalocyanine with single walled carbon nanotubes (FePc/SWNTs)

    KAUST Repository

    Zhu, Jia; Jia, Nana; Yang, Lijun; Su, Dong; Park, Jinseong; Choi, YongMan; Gong, Kuanping

    2014-01-01

    A self-assembly approach to preparing iron phthalocyanine/single-walled carbon nanotube (FePc/SWNT) heterojunction nanowires as a new oxygen reduction reaction (ORR) electrocatalyst has been developed by virtue of water-adjusted dispersing in 1

  20. Formation and Mechanism of Superhydrophobic/Hydrophobic Surfaces Made from Amphiphiles through Droplet-Mediated Evaporation-Induced Self-Assembly.

    Science.gov (United States)

    Dong, Fangyuan; Zhang, Mi; Tang, Wai-Wa; Wang, Yi

    2015-04-23

    Superhydrophobic/hydrophobic surfaces have attracted wide attention because of their broad applications in various regions, including coating, textile, packaging, electronic devices, and bioengineering. Many studies have been focused on the fabrication of superhydrophobic/hydrophobic surfaces using natural materials. In this paper, superhydrophobic/hydrophobic surfaces were formed by an amphiphilic natural protein, zein, using electrospinning. Water contact angle (WCA) and scanning electron microscopy (SEM) were used to characterize the hydrophobicity and surface morphology of the electrospun structures. The highest WCA of the zein electrospun surfaces could reach 155.5 ± 1.4°. To further understand the mechanism of superhydrophobic surface formation from amphiphiles using electrospinning, a synthetic amphiphilic polymer was selected, and also, a method similar to electrospinning, spray drying, was tried. The electrospun amphiphilic polymer surface showed a high hydrophobicity with a WCA of 141.4 ± 0.7°. WCA of the spray-dried zein surface could reach 125.3 ± 2.1°. The secondary structures of the zein in the electrospun film and cast-dried film were studied using ATR-FTIR, showing that α-helix to β-sheet transformation happened during the solvent evaporation in the cast drying process but not in the electrospinning process. A formation mechanism was proposed on the basis of the orientation of the amphiphiles during the solvent evaporation of different fabrication methods. The droplet-based or jet-based evaporation during electrospinning and spray drying led to the formation of the superhydrophobic/hydrophobic surface by the accumulation of the hydrophobic groups of the amphiphiles on the surface, while the surface-based evaporation during cast drying led to the formation of the hydrophilic surface by the accumulation of the hydrophilic groups of the amphiphiles on the surface.

  1. Construction of energy transfer pathways self-assembled from DNA-templated stacks of anthracene.

    Science.gov (United States)

    Iwaura, Rika; Yui, Hiroharu; Someya, Yuu; Ohnishi-Kameyama, Mayumi

    2014-01-05

    We describe optical properties of anthracene stacks formed from single-component self-assembly of thymidylic acid-appended anthracene 2,6-bis[5-(3'-thymidylic acid)pentyloxy] anthracene (TACT) and the binary self-assembly of TACT and complementary 20-meric oligoadenylic acid (TACT/dA20) in an aqueous buffer. UV-Vis and emission spectra for the single-component self-assembly of TACT and the binary self-assembly of TACT/dA20 were very consistent with stacked acene moieties in both self-assemblies. Interestingly, time-resolved fluorescence spectra from anthracene stacks exhibited very different features of the single-component and binary self-assemblies. In the single-component self-assembly of TACT, a dynamic Stokes shift (DSS) and relatively short fluorescence lifetime (τ=0.35ns) observed at around 450nm suggested that the anthracene moieties were flexible. Moreover, a broad emission at 530nm suggested the formation of an excited dimer (excimer). In the binary self-assembly of TACT/dA20, we detected a broad, red-shifted emission component at 534nm with a lifetime (τ=0.4ns) shorter than that observed in the TACT single-component self-assembly. Combining these results with the emission spectrum of the binary self-assembly of TACT/5'-HEX dA20, we concluded that the energy transfer pathway was constructed by columnar anthracene stacks formed from the DNA-templated self-assembly of TACT. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Self-assembled domain structures: From micro- to nanoscale

    Directory of Open Access Journals (Sweden)

    Vladimir Shur

    2015-06-01

    Full Text Available The recent achievements in studying the self-assembled evolution of micro- and nanoscale domain structures in uniaxial single crystalline ferroelectrics lithium niobate and lithium tantalate have been reviewed. The results obtained by visualization of static domain patterns and kinetics of the domain structure by different methods from common optical microscopy to more sophisticated scanning probe microscopy, scanning electron microscopy and confocal Raman microscopy, have been discussed. The kinetic approach based on various nucleation processes similar to the first-order phase transition was used for explanation of the domain structure evolution scenarios. The main mechanisms of self-assembling for nonequilibrium switching conditions caused by screening ineffectiveness including correlated nucleation, domain growth anisotropy, and domain–domain interaction have been considered. The formation of variety of self-assembled domain patterns such as fractal-type, finger and web structures, broad domain boundaries, and dendrites have been revealed at each of all five stages of domain structure evolution during polarization reversal. The possible applications of self-assembling for micro- and nanodomain engineering were reviewed briefly. The review covers mostly the results published by our research group.

  3. Dynamics of self-assembled cytosine nucleobases on graphene

    Science.gov (United States)

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

    2018-05-01

    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.

  4. Surface Patterning of Benzene Carboxylic Acids on Graphite: Influence of structure, solvent, and concentration on molecular self-assembly

    Science.gov (United States)

    Florio, Gina; Stiso, Kimberly; Campanelli, Joseph; Dessources, Kimberly; Folkes, Trudi

    2012-02-01

    Scanning tunneling microscopy (STM) was used to investigate the molecular self-assembly of four different benzene carboxylic acid derivatives at the liquid/graphite interface: pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), and 1,3,5-benzenetriacetic acid. A range of two dimensional networks are observed that depend sensitively on the number of carboxylic acids present, the nature of the solvent, and the solution concentration. We will describe our recent efforts to determine (a) the preferential two-dimensional structure(s) for each benzene carboxylic acid at the liquid/graphite interface, (b) the thermodynamic and kinetic factors influencing self-assembly (or lack thereof), (c) the role solvent plays in the assembly, (e) the effect of in situ versus ex situ dilution on surface packing density, and (f) the temporal evolution of the self-assembled monolayer. Results of computational analysis of analog molecules and model monolayer films will also be presented to aid assignment of network structures and to provide a qualitative picture of surface adsorption and network formation.

  5. New contribution in the study of phase formation in mixed alkanethiol self-assembled monolayers: a powerful tool for transducers design

    International Nuclear Information System (INIS)

    Coelho, Dyovani; Machado, Sergio A.S.

    2014-01-01

    Here, the formation of distinct 3-mercaptopropionic acid (MPA) and 11-mercaptoundecanoic acid (MUA) domains on polycrystalline gold surfaces was investigated by cyclic voltammetry and electrochemical quartz crystal nanobalance. Voltammetric experiments with the [Fe(CN) 6 ] 4-/3− redox couple showed that the MPA SAM allowed electron transference at the same rate as the bare gold surface, while the MUA SAM blocked the entire electrode surface. The chemical nature of mixed SAMs is discussed by evaluating the mass variations and the respective molecular weight in the desorption potential regions for each thiol by electrochemical quartz crystal nanobalance. Different domains containing MUA, MPA and their mixtures were identified in the massograms, thus demonstrating MPA island domains and the electrochemical response obtained for the [Fe(CN) 6 ] 4-/3− redox couple. The modified surfaces, as well as bare Au electrode, were used for electroanalysis of the flavonoid fisetin in Britton-Robinson buffer solution, pH 5. Depending on the modification, detection limits as low as 3.35 ×10 −10 mol L −1 , which attests the possibility of use such surfaces in electroanalysis

  6. Directed Self-Assembly in "Breath Figure" Templating of Melamine-Based Amphiphilic Copolymers: Effect of Hydrophilic End-Chain on Honeycomb Film Formation and Wetting.

    Science.gov (United States)

    Yin, Hongyao; Feng, Yujun; Billon, Laurent

    2018-01-09

    Amphiphilic copolymers are widely used in the fabrication of hierarchically honeycomb-structured films through a "breath figure" (BF) process because the hydrophilic block plays a key role in stabilising water templating. However, the hydrophilic monomers reported are mainly confined to acrylic acid and its derivatives, which largely limits understanding of the formation of BF arrays and the introduction of additional functions on porous films. The relationship between polymer composition, film microstructure and surface properties are also less documented. Herein, a novel melamine-based hydrophilic moiety, N-[3-({3-[(4,6-bis{[3-(dimethylamino)propyl]amino}-1,3,5-triazin-2yl)amino]propyl}(methyl)amino)propyl]methacrylamide (ANME), was incorporated into polystyrene (PS) chains by combining atom-transfer radical polymerisation and post-modification to afford three well-defined end-functionalised PS-PANME derivatives. These polymers were used to fabricate honeycomb films through the BF technique. Both inner and outer microstructures of the films were characterised by optical microscopy, AFM and SEM. Polymer hydrophilicity is enhanced upon increasing the PANME content, which results in variation of the film microstructure and porosity, and provokes a transition from Cassie-Baxter to Wenzel behaviour. Furthermore, the surface wettability of as-prepared honeycomb films and corresponding pillared films is mainly governed by film morphology, rather than by the properties of the polymers. Knowledge of the relationships between polymer composition and film structure, as well as surface wettability, is beneficial to design and prepare hierarchically porous films with desirable structures and properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Building polyhedra by self-assembly: theory and experiment.

    Science.gov (United States)

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

    2014-01-01

    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.

  8. Self-Assembly of Colloidal Particles

    Indian Academy of Sciences (India)

    is self-assembly where one engineers interaction between nanoscopic building blocks so ..... big question in the field how this microscopic chirality of the virus gets translated ... shape emerges due to a competition between the surface tension.

  9. Polymorphism of lipid self-assembly systems

    International Nuclear Information System (INIS)

    Takahashi, Hiroshi

    2002-01-01

    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)

  10. Directed Self-Assembly of Nanodispersions

    Energy Technology Data Exchange (ETDEWEB)

    Furst, Eric M [University of Delaware

    2013-11-15

    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

  11. Anisotropic enhancement of Yb3+ luminescence by disordered plasmonic networks self-assembled on RbTiOPO4 ferroelectric crystals

    DEFF Research Database (Denmark)

    Sánchez-García, Laura; Ramírez, Mariola O; Tserkezis, Christos

    2017-01-01

    Increasing Yb3+ absorption efficiency is currently desired in a number of applications including bio-imaging, photovoltaics, near infrared driven photocatalysis or ultra-short pulsed solid-state lasers. In this work, silver nanoparticles, which are connected forming disordered networks, have been...

  12. Mechanical Self-Assembly Science and Applications

    CERN Document Server

    2013-01-01

    Mechanical Self-Assembly: Science and Applications introduces a novel category of self-assembly driven by mechanical forces. This book discusses self-assembly in various types of small material structures including thin films, surfaces, and micro- and nano-wires, as well as the practice's potential application in micro and nanoelectronics, MEMS/NEMS, and biomedical engineering. The mechanical self-assembly process is inherently quick, simple, and cost-effective, as well as accessible to a large number of materials, such as curved surfaces for forming three-dimensional small structures. Mechanical self-assembly is complementary to, and sometimes offer advantages over, the traditional micro- and nano-fabrication. This book also: Presents a highly original aspect of the science of self-assembly Describes the novel methods of mechanical assembly used to fabricate a variety of new three-dimensional material structures in simple and cost-effective ways Provides simple insights to a number of biological systems and ...

  13. Coevolutionary modeling in network formation

    KAUST Repository

    Al-Shyoukh, Ibrahim

    2014-12-03

    Network coevolution, the process of network topology evolution in feedback with dynamical processes over the network nodes, is a common feature of many engineered and natural networks. In such settings, the change in network topology occurs at a comparable time scale to nodal dynamics. Coevolutionary modeling offers the possibility to better understand how and why network structures emerge. For example, social networks can exhibit a variety of structures, ranging from almost uniform to scale-free degree distributions. While current models of network formation can reproduce these structures, coevolutionary modeling can offer a better understanding of the underlying dynamics. This paper presents an overview of recent work on coevolutionary models of network formation, with an emphasis on the following three settings: (i) dynamic flow of benefits and costs, (ii) transient link establishment costs, and (iii) latent preferential attachment.

  14. Coevolutionary modeling in network formation

    KAUST Repository

    Al-Shyoukh, Ibrahim; Chasparis, Georgios; Shamma, Jeff S.

    2014-01-01

    Network coevolution, the process of network topology evolution in feedback with dynamical processes over the network nodes, is a common feature of many engineered and natural networks. In such settings, the change in network topology occurs at a comparable time scale to nodal dynamics. Coevolutionary modeling offers the possibility to better understand how and why network structures emerge. For example, social networks can exhibit a variety of structures, ranging from almost uniform to scale-free degree distributions. While current models of network formation can reproduce these structures, coevolutionary modeling can offer a better understanding of the underlying dynamics. This paper presents an overview of recent work on coevolutionary models of network formation, with an emphasis on the following three settings: (i) dynamic flow of benefits and costs, (ii) transient link establishment costs, and (iii) latent preferential attachment.

  15. Self-assembling enzymes and the origins of the cytoskeleton

    Science.gov (United States)

    Barry, Rachael; Gitai, Zemer

    2011-01-01

    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

  16. Classification of coordination polygons and polyhedra according to their mode of self-assembly.

    Science.gov (United States)

    Swiegers, G F; Malefetse, T J

    2001-09-03

    This work extends techniques for the controlled formation of synthetic molecular containers by metal-mediated self-assembly. A new classification system based on the self-assembly of such species is proposed. The system: 1) allows a systematic identification of suitable acceptor-donor combinations, 2) widens the variety of design possibilities available, 3) allows a ready comparison of the self-assembly of different compounds, 4) reveals useful commonalities between different compounds, 5) aids in the development of novel architectures, and 6) permits identification of systems capable of being switched back-and-forth between architectures.

  17. Integrating DNA strand-displacement circuitry with DNA tile self-assembly

    Science.gov (United States)

    Zhang, David Yu; Hariadi, Rizal F.; Choi, Harry M.T.; Winfree, Erik

    2013-01-01

    DNA nanotechnology has emerged as a reliable and programmable way of controlling matter at the nanoscale through the specificity of Watson–Crick base pairing, allowing both complex self-assembled structures with nanometer precision and complex reaction networks implementing digital and analog behaviors. Here we show how two well-developed frameworks, DNA tile self-assembly and DNA strand-displacement circuits, can be systematically integrated to provide programmable kinetic control of self-assembly. We demonstrate the triggered and catalytic isothermal self-assembly of DNA nanotubes over 10 μm long from precursor DNA double-crossover tiles activated by an upstream DNA catalyst network. Integrating more sophisticated control circuits and tile systems could enable precise spatial and temporal organization of dynamic molecular structures. PMID:23756381

  18. Synthesis and Self-Assembly of Chiral Cylindrical Molecular Complexes: Functional Heterogeneous Liquid-Solid Materials Formed by Helicene Oligomers

    Directory of Open Access Journals (Sweden)

    Nozomi Saito

    2018-01-01

    Full Text Available Chiral cylindrical molecular complexes of homo- and hetero-double-helices derived from helicene oligomers self-assemble in solution, providing functional heterogeneous liquid-solid materials. Gels and liotropic liquid crystals are formed by fibril self-assembly in solution; molecular monolayers and fibril films are formed by self-assembly on solid surfaces; gels containing gold nanoparticles emit light; silica nanoparticles aggregate and adsorb double-helices. Notable dynamics appears during self-assembly, including multistep self-assembly, solid surface catalyzed double-helix formation, sigmoidal and stairwise kinetics, molecular recognition of nanoparticles, discontinuous self-assembly, materials clocking, chiral symmetry breaking and homogeneous-heterogeneous transitions. These phenomena are derived from strong intercomplex interactions of chiral cylindrical molecular complexes.

  19. Dynamic Self-Assembly Induced Rapid Dissolution of Cellulose at Low Temperatures

    International Nuclear Information System (INIS)

    Cai, J.; Zhang, L.; Liu, S.; Liu, Y.; Xu, X.; Chen, X.; Chu, B.; Guo, X.; Xu, J.

    2008-01-01

    Cellulose can be dissolved in precooled (-12 C) 7 wt % NaOH-12 wt % urea aqueous solution within 2 min. This interesting process, to our knowledge, represents the most rapid dissolution of native cellulose. The results from 13C NMR, 15N NMR, 1H NMR, FT-IR, small-angle neutron scattering (SANS), transmission electron microscopy (TEM), and wide-angle X-ray diffraction (WAXD) suggested that NaOH 'hydrates' could be more easily attracted to cellulose chains through the formation of new hydrogen-bonded networks at low temperatures, while the urea hydrates could not be associated directly with cellulose. However, the urea hydrates could possibly be self-assembled at the surface of the NaOH hydrogen-bonded cellulose to form an inclusion complex (IC), leading to the dissolution of cellulose. Scattering experiments, including dynamic and static light scattering, indicated that most cellulose molecules, with limited amounts of aggregation, could exist as extended rigid chains in dilute solution. Further, the cellulose solution was relatively unstable and could be very sensitive to temperature, polymer concentration, and storage time, leading to additional aggregations. TEM images and WAXD provided experimental evidence on the formation of a wormlike cellulose IC being surrounded with urea. Therefore, we propose that the cellulose dissolution at -12 C could arise as a result of a fast dynamic self-assembly process among solvent small molecules (NaOH, urea, and water) and the cellulose macromolecules.

  20. Self-assembled DNA Structures for Nanoconstruction

    Science.gov (United States)

    Yan, Hao; Yin, Peng; Park, Sung Ha; Li, Hanying; Feng, Liping; Guan, Xiaoju; Liu, Dage; Reif, John H.; LaBean, Thomas H.

    2004-09-01

    In recent years, a number of research groups have begun developing nanofabrication methods based on DNA self-assembly. Here we review our recent experimental progress to utilize novel DNA nanostructures for self-assembly as well as for templates in the fabrication of functional nano-patterned materials. We have prototyped a new DNA nanostructure known as a cross structure. This nanostructure has a 4-fold symmetry which promotes its self-assembly into tetragonal 2D lattices. We have utilized the tetragonal 2D lattices as templates for highly conductive metallic nanowires and periodic 2D protein nano-arrays. We have constructed and characterized a DNA nanotube, a new self-assembling superstructure composed of DNA tiles. We have also demonstrated an aperiodic DNA lattice composed of DNA tiles assembled around a long scaffold strand; the system translates information encoded in the scaffold strand into a specific and reprogrammable barcode pattern. We have achieved metallic nanoparticle linear arrays templated on self-assembled 1D DNA arrays. We have designed and demonstrated a 2-state DNA lattice, which displays expand/contract motion switched by DNA nanoactuators. We have also achieved an autonomous DNA motor executing unidirectional motion along a linear DNA track.

  1. Onset wear in self-assembled monolayers

    International Nuclear Information System (INIS)

    D'Acunto, Mario

    2006-01-01

    Self-assembled monolayers (SAMs) are very useful for the systematic modification of the physical, chemical and structural properties of a surface by varying the chain length, tail group and composition. Many of these properties can be studied making use of atomic force microscopy (AFM), and the interaction between the AFM probe tip and the SAMs can also be considered an excellent reference to study the fundamental properties of dissipation phenomena and onset wear for viscoelastic materials on the nanoscale. We have performed a numerical study showing that the fundamental mechanism for the onset wear is a process of nucleation of domains starting from initial defects. An SAM surface repeatedly sheared by an AFM probe tip with enough applied loads shows the formation of progressive damages nucleating in domains. The AFM induced surface damages involve primarily the formation of radicals from the carbon chain backbones, but the deformations of the chains resulting in changes of period lattice also have to be taken into consideration. The nucleation of the wear domains generally starts at the initial surface defects where the energy cohesion between chains is lower. Moreover, the presence of surface defects is consistent with the changes in lateral force increasing the probability of the activation for the removal of carbon debris from the chain backbone. The quantification of the progressive worn area is performed making use of the Kolmogorov-Johnson-Mehl-Avrami (KJMA) theory for phase transition kinetic processes. The advantage of knowing the general conditions for onset wear on the SAM surfaces can help in studying the fundamental mechanisms for the tribological properties of viscoelastic materials, in solid lubrication applications and biopolymer mechanics

  2. Syntheses and Self-assembling Behaviors of Pentagonal Conjugates of Tryptophane Zipper-Forming Peptide

    Directory of Open Access Journals (Sweden)

    Nobuo Kimizuka

    2011-08-01

    Full Text Available Pentagonal conjugates of tryptophane zipper-forming peptide (CKTWTWTE with a pentaazacyclopentadecane core (Pentagonal-Gly-Trpzip and Pentagonal-Ala-Trpzip were synthesized and their self-assembling behaviors were investigated in water. Pentagonal-Gly-Trpzip self-assembled into nanofibers with the width of about 5 nm in neutral water (pH 7 via formation of tryptophane zipper, which irreversibly converted to nanoribbons by heating. In contrast, Pentagonal-Ala-Trpzip formed irregular aggregates in water.

  3. Self-recognition in the coordination driven self-assembly of 2-D polygons.

    Science.gov (United States)

    Addicott, Chris; Das, Neeladri; Stang, Peter J

    2004-08-23

    Self-recognition in the transition-metal-mediated self-assembly of some 2-D polygons is presented. Prolonged heating of two or three organoplatinum reagents with 4,4'-dipyridyl in aqueous acetone results in the predominant formation of a rectangle, triangle, and/or square. All mixtures are characterized with NMR and electrospray ionization mass spectrometry (ESIMS). Despite the potential for ill-defined oligomeric products, these mixed ligand systems prefer to self-assemble into discrete species.

  4. Chitosan Based Self-Assembled Nanoparticles in Drug Delivery

    Directory of Open Access Journals (Sweden)

    Javier Pérez Quiñones

    2018-02-01

    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.

  5. DNA assisted self-assembly of PAMAM dendrimers.

    Science.gov (United States)

    Mandal, Taraknath; Kumar, Mattaparthi Venkata Satish; Maiti, Prabal K

    2014-10-09

    We report DNA assisted self-assembly of polyamidoamine (PAMAM) dendrimers using all atom Molecular Dynamics (MD) simulations and present a molecular level picture of a DNA-linked PAMAM dendrimer nanocluster, which was first experimentally reported by Choi et al. (Nano Lett., 2004, 4, 391-397). We have used single stranded DNA (ssDNA) to direct the self-assembly process. To explore the effect of pH on this mechanism, we have used both the protonated (low pH) and nonprotonated (high pH) dendrimers. In all cases studied here, we observe that the DNA strand on one dendrimer unit drives self-assembly as it binds to the complementary DNA strand present on the other dendrimer unit, leading to the formation of a DNA-linked dendrimer dimeric complex. However, this binding process strongly depends on the charge of the dendrimer and length of the ssDNA. We observe that the complex with a nonprotonated dendrimer can maintain a DNA length dependent inter-dendrimer distance. In contrast, for complexes with a protonated dendrimer, the inter-dendrimer distance is independent of the DNA length. We attribute this observation to the electrostatic complexation of a negatively charged DNA strand with the positively charged protonated dendrimer.

  6. Self-assembling segmented coiled tubing

    Science.gov (United States)

    Raymond, David W.

    2016-09-27

    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.

  7. Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

    Science.gov (United States)

    Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

    2018-04-11

    A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

  8. Self-assembled peptide-based nanostructures: Smart nanomaterials toward targeted drug delivery.

    Science.gov (United States)

    Habibi, Neda; Kamaly, Nazila; Memic, Adnan; Shafiee, Hadi

    2016-02-01

    Self-assembly of peptides can yield an array of well-defined nanostructures that are highly attractive nanomaterials for many biomedical applications such as drug delivery. Some of the advantages of self-assembled peptide nanostructures over other delivery platforms include their chemical diversity, biocompatibility, high loading capacity for both hydrophobic and hydrophilic drugs, and their ability to target molecular recognition sites. Furthermore, these self-assembled nanostructures could be designed with novel peptide motifs, making them stimuli-responsive and achieving triggered drug delivery at disease sites. The goal of this work is to present a comprehensive review of the most recent studies on self-assembled peptides with a focus on their "smart" activity for formation of targeted and responsive drug-delivery carriers.

  9. Self-assembled Block Copolymer Membranes with Bioinspired Artificial Channels

    KAUST Repository

    Sutisna, Burhannudin

    2018-04-01

    Nature is an excellent design that inspires scientists to develop smart systems. In the realm of separation technology, biological membranes have been an ideal model for synthetic membranes due to their ultrahigh permeability, sharp selectivity, and stimuliresponse. In this research, fabrications of bioinspired membranes from block copolymers were studied. Membranes with isoporous morphology were mainly prepared using selfassembly and non-solvent induced phase separation (SNIPS). An effective method that can dramatically shorten the path for designing new isoporous membranes from block copolymers via SNIPS was first proposed by predetermining a trend line computed from the solvent properties, interactions and copolymer block sizes of previously-obtained successful systems. Application of the method to new copolymer systems and fundamental studies on the block copolymer self-assembly were performed. Furthermore, the manufacture of bioinspired membranes was explored using (1) poly(styrene-b-4-hydroxystyrene-b-styrene) (PS-b-PHS-b-PS), (2) poly(styrene-bbutadiene- b-styrene) (PS-b-PB-b-PS) and (3) poly(styrene-b-γ-benzyl-L-glutamate) (PSb- PBLG) copolymers via SNIPS. The structure formation was investigated using smallangle X-ray scattering (SAXS) and time-resolved grazing-Incidence SAXS. The PS-b- PHS-b-PS membranes showed preferential transport for proteins, presumably due to the hydrogen bond interactions within the channels, electrostatic attraction, and suitable pore dimension. Well-defined nanochannels with pore sizes of around 4 nm based on PS-b- PB-b-PS copolymers could serve as an excellent platform to fabricate bioinspired channels due to the modifiable butadiene blocks. Photolytic addition of thioglycolic acid was demonstrated without sacrificing the self-assembled morphology, which led to a five-fold increase in water permeance compared to that of the unmodified. Membranes with a unique feather-like structure and a lamellar morphology for dialysis and

  10. Predicting Chiral Nanostructures, Lattices and Superlattices in Complex Multicomponent Nanoparticle Self-Assembly

    KAUST Repository

    Hur, Kahyun

    2012-06-13

    "Bottom up" type nanoparticle (NP) self-assembly is expected to provide facile routes to nanostructured materials for various, for example, energy related, applications. Despite progress in simulations and theories, structure prediction of self-assembled materials beyond simple model systems remains challenging. Here we utilize a field theory approach for predicting nanostructure of complex and multicomponent hybrid systems with multiple types of short- and long-range interactions. We propose design criteria for controlling a range of NP based nanomaterial structures. In good agreement with recent experiments, the theory predicts that ABC triblock terpolymer directed assemblies with ligand-stabilized NPs can lead to chiral NP network structures. Furthermore, we predict that long-range Coulomb interactions between NPs leading to simple NP lattices, when applied to NP/block copolymer (BCP) assemblies, induce NP superlattice formation within the phase separated BCP nanostructure, a strategy not yet realized experimentally. We expect such superlattices to be of increasing interest to communities involved in research on, for example, energy generation and storage, metamaterials, as well as microelectronics and information storage. © 2012 American Chemical Society.

  11. Self-assembled nanogaps for molecular electronics.

    Science.gov (United States)

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

    2009-06-17

    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-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 approximately 20 nm, and hence were expected to minimize the screening effect. The ultra-long conducting SnO2: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.

  12. Self-assembled nanogaps for molecular electronics

    DEFF Research Database (Denmark)

    Tang, Qingxin; Tong, Yanhong; Jain, Titoo

    2009-01-01

    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 se...

  13. Self-assembly of patchy colloidal dumbbells

    NARCIS (Netherlands)

    Avvisati, Guido|info:eu-repo/dai/nl/407630198; Vissers, Teun|info:eu-repo/dai/nl/304829943; Dijkstra, Marjolein|info:eu-repo/dai/nl/123538807

    2015-01-01

    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

  14. Inverse Problem in Self-assembly

    Science.gov (United States)

    Tkachenko, Alexei

    2012-02-01

    By decorating colloids and nanoparticles with DNA, one can introduce highly selective key-lock interactions between them. This leads to a new class of systems and problems in soft condensed matter physics. In particular, this opens a possibility to solve inverse problem in self-assembly: how to build an arbitrary desired structure with the bottom-up approach? I will present a theoretical and computational analysis of the hierarchical strategy in attacking this problem. It involves self-assembly of particular building blocks (``octopus particles''), that in turn would assemble into the target structure. On a conceptual level, our approach combines elements of three different brands of programmable self assembly: DNA nanotechnology, nanoparticle-DNA assemblies and patchy colloids. I will discuss the general design principles, theoretical and practical limitations of this approach, and illustrate them with our simulation results. Our crucial result is that not only it is possible to design a system that has a given nanostructure as a ground state, but one can also program and optimize the kinetic pathway for its self-assembly.

  15. 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

    2009-01-01

    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.

  16. Fluorescent Self-Assembled Polyphenylene Dendrimer Nanofibers

    NARCIS (Netherlands)

    Liu, Daojun; Feyter, Steven De; Cotlet, Mircea; Wiesler, Uwe-Martin; Weil, Tanja; Herrmann, Andreas; Müllen, Klaus; Schryver, Frans C. De

    2003-01-01

    A second-generation polyphenylene dendrimer 1 self-assembles into nanofibers on various substrates such as HOPG, silicon, glass, and mica from different solvents. The investigation with noncontact atomic force microscopy (NCAFM) and scanning electron microscopy (SEM) shows that the morphology of the

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

    Science.gov (United States)

    Lin, Tao

    derivatives. Firstly, we investigated the coordination self-assembly of a series of peripheral bromo-phenyl and pyridyl substituted porphyrins with Fe. The self-assembly of the porphyrin derivatives in which phenyl groups are substituted by bromo-phenyl results in coordination networks exhibiting identical structures to that of the parent compounds, but contained nanopores that are functionalized by bromine substitutes. Secondly, we studied a two-dimensional coordination networks formed by 5,10,15,20-tetra(4-pyridyl)porphyrin and Fe. We discovered a novel coordination motif in which a pair of vertically aligned Fe atoms is ligated by four equatorial pyridyl groups. Lateral manipulation, vertical manipulation and tunneling spectroscopy were employed to characterize the networks. These novel coordination networks decorated with Br or vertically aligned Fe atoms may provide potential functions as nano-receptor, molecular magnetism or catalyst. Part III addresses the mechanism of on-surface Ullmann coupling reaction. We studied Pd- and Cu-catalyzed Ullmann coupling reactions between phenyl bromide functionalized porphyrin derivatives. We discovered that the reactions catalyzed by Pd or Cu can be described as a two-phase process that involves an initial activation followed by C-C bond formation. Analysis of rate constants of the Pd-catalyzed reactions allowed us to determine its activation energy as (0.41 +/- 0.03) eV. These results provide a quantitative understanding of on-surface Ullmann coupling reaction. Part IV addresses the on-surface self-assembly driven by a combination of coordination bonds and covalent bonds. Firstly, we utilized metal-directed template to control the on-surface polymerization process. Taking advantage of efficient topochemical enhancement owing to the conformation flexibility of the Cu-pyridyl bonds, macromolecular porphyrin structures that exhibit a narrow size distribution were synthesized. The results reveal that the polymerization process profited

  18. A Theoretical and Experimental Study of DNA Self-assembly

    Science.gov (United States)

    Chandran, Harish

    providing detailed designs for local molecular computations that involve spatially contiguous molecules arranged on addressable substrates via enzyme-free DNA hybridization reaction cascades. We use the Visual DSD simulation software in conjunction with localized reaction rates obtained from biophysical modeling to create chemical reaction networks of localized hybridization circuits that are then model checked using the PRISM model checking software. We develop a DNA detection system employing the triggered self-assembly of a novel DNA dendritic nanostructure. Detection begins when a specific, single-stranded target DNA strand triggers a hybridization chain reaction between two distinct DNA hairpins. Each hairpin opens and hybridizes up to two copies of the other, and hence each layer of the growing dendritic nanostructure can in principle accommodate an exponentially increasing number of cognate molecules, generating a nanostructure with high molecular weight. We build linear activatable assemblies employing a novel protection/deprotection strategy to strictly enforce the direction of tiling assembly growth to ensure the robustness of the assembly process. Our system consists of two tiles that can form a linear co-polymer. These tiles, which are initially protected such that they do not react with each other, can be activated to form linear co-polymers via the use of a strand displacing enzyme.

  19. Light-assisted templated self assembly using photonic crystal slabs.

    Science.gov (United States)

    Mejia, Camilo A; Dutt, Avik; Povinelli, Michelle L

    2011-06-06

    We explore a technique which we term light-assisted templated self-assembly. We calculate the optical forces on colloidal particles over a photonic crystal slab. We show that exciting a guided resonance mode of the slab yields a resonantly-enhanced, attractive optical force. We calculate the lateral optical forces above the slab and predict that stably trapped periodic patterns of particles are dependent on wavelength and polarization. Tuning the wavelength or polarization of the light source may thus allow the formation and reconfiguration of patterns. We expect that this technique may be used to design all-optically reconfigurable photonic devices.

  20. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao; Wang, Qingxiao; Yang, Yang; Zhang, Bei; Zhang, Xixiang

    2012-01-01

    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. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao

    2012-12-01

    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.

  2. Surfactant self-assembly in alcohol-rich solutions

    International Nuclear Information System (INIS)

    Bouguerra, N.; Jebari, M.M.; Gomati, R.; Gharbi, A.

    2005-01-01

    Ionic conductivity and viscosity measurements are achieved along alcohol dilution lines of a single-isotropic phase domain, which extends from the alcohol corner to sponge phase domain to brine corner, of an alcohol-surfactant-brine phase diagram. The results are discussed in terms of amphiphilic self-assembly which leads to stable mixtures of the slightly miscible alcohol and brine used. We show the formation of reverse micelles, whose cores are either dry or charged of brine according to the samples composition, and whose sizes remain small near the sponge phase structure

  3. Stages of neuronal network formation

    International Nuclear Information System (INIS)

    Woiterski, Lydia; Käs, Josef A; Claudepierre, Thomas; Luxenhofer, Robert; Jordan, Rainer

    2013-01-01

    Graph theoretical approaches have become a powerful tool for investigating the architecture and dynamics of complex networks. The topology of network graphs revealed small-world properties for very different real systems among these neuronal networks. In this study, we observed the early development of mouse retinal ganglion cell (RGC) networks in vitro using time-lapse video microscopy. By means of a time-resolved graph theoretical analysis of the connectivity, shortest path length and the edge length, we were able to discover the different stages during the network formation. Starting from single cells, at the first stage neurons connected to each other ending up in a network with maximum complexity. In the further course, we observed a simplification of the network which manifested in a change of relevant network parameters such as the minimization of the path length. Moreover, we found that RGC networks self-organized as small-world networks at both stages; however, the optimization occurred only in the second stage. (paper)

  4. Self-assembly of the second-generation of nitroaryl-ended dendrons onto carbon

    International Nuclear Information System (INIS)

    Farías, E.D.; Paez, J.I.; Strumia, M.C.; Baruzzi, A.M.; Passeggi Jr, M.C.G.; Brunetti, V.

    2014-01-01

    Graphical abstract: - Abstract: We report the self-assembly of the second-generation of nitroaryl-ended dendrons onto carbon surfaces. The immobilized layer was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy and atomic force microscopy (AFM). The response was analyzed in comparison to the first-generation dendron behavior. Reduction of both layers generates the hydroxylamine product. The resulting redox-active layer exhibits a well-behaved redox response for the adsorbed nitroso/hydroxylamine couple. The thermodynamic of the adsorption of both dendrons on glassy carbon electrodes was also studied by CV. The Frumkin adsorption isotherm was the best to describe the specific interactions. The AFM images showed a network film formation with embedded aggregates that completely covered the carbon surface. The average height suggests a tilted preferential adsorption for both molecules

  5. 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.

    2014-01-01

    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

  6. 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

    2017-01-01

    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)

  7. Physical principles of filamentous protein self-assembly kinetics

    Science.gov (United States)

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

    2017-04-01

    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.

  8. Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process

    Science.gov (United States)

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

    2018-03-01

    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.

  9. Ternary self-assemblies in water

    DEFF Research Database (Denmark)

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

    2013-01-01

    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...

  10. Self-assembling membranes and related methods thereof

    Science.gov (United States)

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

    2013-08-20

    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).

  11. Self-assembly via anisotropic interactions : Modeling association kinetics of patchy particle systems and self-assembly induced by critical Casimir forces

    NARCIS (Netherlands)

    Newton, A.C.

    2017-01-01

    Self-assembly, the non-dissipative spontaneous formation of structural order spans many length scales, from amphiphilic molecules forming micelles to stars forming galaxies. This thesis mainly deals with systems on the colloidal length scale where the size of a particle is between a nanometer and a

  12. Self-assembled Nanomaterials for Chemotherapeutic Applications

    Science.gov (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

  13. Matrix development in self-assembly of articular cartilage.

    Directory of Open Access Journals (Sweden)

    Gidon Ofek

    2008-07-01

    Full Text Available Articular cartilage is a highly functional tissue which covers the ends of long bones and serves to ensure proper joint movement. A tissue engineering approach that recapitulates the developmental characteristics of articular cartilage can be used to examine the maturation and degeneration of cartilage and produce fully functional neotissue replacements for diseased tissue.This study examined the development of articular cartilage neotissue within a self-assembling process in two phases. In the first phase, articular cartilage constructs were examined at 1, 4, 7, 10, 14, 28, 42, and 56 days immunohistochemically, histologically, and through biochemical analysis for total collagen and glycosaminoglycan (GAG content. Based on statistical changes in GAG and collagen levels, four time points from the first phase (7, 14, 28, and 56 days were chosen to carry into the second phase, where the constructs were studied in terms of their mechanical characteristics, relative amounts of collagen types II and VI, and specific GAG types (chondroitin 4-sulfate, chondroitin 6-sulfate, dermatan sulfate, and hyaluronan. Collagen type VI was present in initial abundance and then localized to a pericellular distribution at 4 wks. N-cadherin activity also spiked at early stages of neotissue development, suggesting that self-assembly is mediated through a minimization of free energy. The percentage of collagen type II to total collagen significantly increased over time, while the proportion of collagen type VI to total collagen decreased between 1 and 2 wks. The chondroitin 6- to 4- sulfate ratio decreased steadily during construct maturation. In addition, the compressive properties reached a plateau and tensile characteristics peaked at 4 wks.The indices of cartilage formation examined in this study suggest that tissue maturation in self-assembled articular cartilage mirrors known developmental processes for native tissue. In terms of tissue engineering, it is

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

    Directory of Open Access Journals (Sweden)

    Yang Yongkun

    2012-10-01

    Full Text Available 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 to encapsulate gold nanoparticles. The protein nanoparticles are formed upon self-assembly of a protein chain that is composed of a pentameric coiled-coil domain at the N-terminus and trimeric coiled-coil domain at the C-terminus. The self-assembling protein nanoparticles form a central cavity of about 10 nm in size, which is ideal for the encapsulation of gold nanoparticles with similar sizes. Results We have used SAPNs to encapsulate several commercially available gold nanoparticles. The hydrodynamic size and the surface coating of gold nanoparticles are two important factors influencing successful encapsulation by the SAPNs. Gold nanoparticles with a hydrodynamic size of less than 15 nm can successfully be encapsulated. Gold nanoparticles with citrate coating appear to have stronger interactions with the proteins, which can interfere with the formation of regular protein nanoparticles. Upon encapsulation gold nanoparticles with polymer coating interfere less strongly with the ability of the SAPNs to assemble into nanoparticles. Although the central cavity of the SAPNs carries an overall charge, the electrostatic interaction appears to be less critical for the efficient encapsulation of gold nanoparticles into the protein nanoparticles. Conclusions The SAPNs can be used to encapsulate gold nanoparticles. The SAPNs can be further functionalized by engineering functional peptides or proteins to either their N- or C-termini. Therefore encapsulation of gold

  15. Self-assembled biomimetic nanoreactors I: Polymeric template

    Science.gov (United States)

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

    2015-09-01

    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.

  16. Self-Assembled PbSe Nanowire:Perovskite Hybrids

    KAUST Repository

    Yang, Zhenyu

    2015-12-02

    © 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.

  17. Self-Assembled PbSe Nanowire:Perovskite Hybrids

    KAUST Repository

    Yang, Zhenyu; Yassitepe, Emre; Voznyy, Oleksandr; Janmohamed, Alyf; Lan, Xinzheng; Levina, Larissa; Comin, Riccardo; Sargent, Edward H.

    2015-01-01

    © 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.

  18. Network Formation under the Threat of Disruption

    NARCIS (Netherlands)

    Hoyer, B.

    2013-01-01

    The studies in this thesis are focused on the impact the presence of a network disruptor has on network formation models. In particular, we build two theoretical models to study the effect of network disruption on network formation and test the effect network disruption has on equilibrium selection

  19. Impact of cationic surfactant on the self-assembly of sodium caseinate.

    Science.gov (United States)

    Vinceković, Marko; Curlin, Marija; Jurašin, Darija

    2014-08-27

    The impact of a cationic surfactant, dodecylammonium chloride (DDACl), on the self-assembly of sodium caseinate (SC) has been investigated by light scattering, zeta potential, and rheological measurements as well as by microscopy (transmission electron and confocal laser scanning microscopy). In SC dilute solutions concentration-dependent self-assembly proceeds through the formation of spherical associates and their aggregation into elongated structures composed of connected spheres. DDACl interacts with SC via its hydrophilic and hydrophobic groups, inducing changes in SC self-assembled structures. These changes strongly depend on the surfactant aggregation states (monomeric or micellar) as well as concentration ratio of both components, leading to the formation of soluble and insoluble complexes of nano- to microdimensions. DDACl monomers interact with SC self-assembled entities in a different way compared to their micelles. Surfactant monomers form soluble complexes (similar to surfactant mixed micelles) at lower SC concentration but insoluble gelatinous complexes at higher SC concentration. At surfactant micellar concentration soluble complexes with casein chains wrapped around surfactant micelles are formed. This study suggests that the use of proper cationic surfactant concentration will allow modification and control of structural changes of SC self-assembled entities.

  20. Self-assembly of silk fibroin under osmotic stress

    Science.gov (United States)

    Sohn, Sungkyun

    stress technique. Microscopic and thermodynamic details of this self-assembly process along the spinline have been assessed. Formation of a needle-shaped molecular lath under appropriate osmotic stress was found. Silk I degree of hydration of silk gland was quantitatively estimated by image analysis of optical micrographs and the numbers varied from 2.2 to 2.7 depending on the region in the gland. Osmotic pressure in the gland was also estimated by equilibration method.

  1. Meso-scale Modeling of Block Copolymers Self-Assembly in Casting Solutions for Membrane Manufacture

    KAUST Repository

    Moreno Chaparro, Nicolas

    2016-05-01

    the swelling of the B-rich domains. The B-C interactions control the curvature of the assemblies in these blends. Finally, we study the self-assembly triblock copolymers used for membranes fabrication. We show that the polymer concentration, the block-copolymer composition, and the swelling of the micelle are responsible for the formation of elongated micelles in the casting solution. The formation of nanoporous membranes arises from the network-like packing of those micelles.

  2. Heterojunction nanowires having high activity and stability for the reduction of oxygen: Formation by self-assembly of iron phthalocyanine with single walled carbon nanotubes (FePc/SWNTs)

    KAUST Repository

    Zhu, Jia

    2014-04-01

    A self-assembly approach to preparing iron phthalocyanine/single-walled carbon nanotube (FePc/SWNT) heterojunction nanowires as a new oxygen reduction reaction (ORR) electrocatalyst has been developed by virtue of water-adjusted dispersing in 1-cyclohexyl-pyrrolidone (CHP) of the two components. The FePc/SWNT nanowires have a higher Fermi level compared to pure FePc (d-band center, DFT. =. -0.69. eV versus -0.87. eV, respectively). Consequently, an efficient channel for transferring electron to the FePc surface is readily created, facilitating the interaction between FePc and oxygen, so enhancing the ORR kinetics. This heterojunction-determined activity in ORR illustrates a new stratagem to preparing non-noble ORR electrocatalysts of significant importance in constructing real-world fuel cells. © 2013 Elsevier Inc.

  3. Structural Diversity of Self-Assembled Iridescent Arthropod Biophotonic Nanostructures

    Science.gov (United States)

    Saranathan, Vinod Kumar; Prum, Richard O.

    2015-03-01

    Many organisms, especially arthropods, produce vivid interference colors using diverse mesoscopic (100-350 nm) integumentary biophotonic nanostructures that are increasingly being investigated for technological applications. Despite a century of interest, we lack precise structural knowledge of many biophotonic nanostructures and mechanisms controlling their development, when such knowledge can open novel biomimetic routes to facilely self-assemble tunable, multi-functional materials. Here, we use synchrotron small angle X-ray scattering and electron microscopy to characterize the photonic nanostructure of 140 iridescent integumentary scales and setae from 127 species of terrestrial arthropods in 85 genera from 5 orders. We report a rich nanostructural diversity, including triply-periodic bicontinuous networks, close-packed spheres, inverse columnar, perforated lamellar, and disordered sponge-like morphologies, commonly observed as stable phases of amphiphilic surfactants, block copolymer, and lyotropic lipid-water systems. Diverse arthropod lineages appear to have independently evolved to utilize the self-assembly of infolding bilayer membranes to develop biophotonic nanostructures that span the phase-space of amphiphilic morphologies, but at optical length scales.

  4. Hierarchical self-assembly of a bow-shaped molecule bearing self-complementary hydrogen bonding sites into extended supramolecular assemblies.

    Science.gov (United States)

    Ikeda, Masato; Nobori, Tadahito; Schmutz, Marc; Lehn, Jean-Marie

    2005-01-07

    The bow-shaped molecule 1 bearing a self-complementary DAAD-ADDA (D=donor A=acceptor) hydrogen-bonding array generates, in hydrocarbon solvents, highly ordered supramolecular sheet aggregates that subsequently give rise to gels by formation of an entangled network. The process of hierarchical self-assembly of compound 1 was investigated by the concentration and temperature dependence of UV-visible and (1)H NMR spectra, fluorescence spectra, and electron microscopy data. The temperature dependence of the UV-visible spectra indicates a highly cooperative process for the self-assembly of compound 1 in decaline. The electron micrograph of the decaline solution of compound 1 (1.0 mM) revealed supramolecular sheet aggregates forming an entangled network. The selected area electronic diffraction patterns of the supramolecular sheet aggregates were typical for single crystals, indicative of a highly ordered assembly. The results exemplify the generation, by hierarchical self-assembly, of highly organized supramolecular materials presenting novel collective properties at each level of organization.

  5. Self-assembled Nano-layering at the Adhesive interface.

    Science.gov (United States)

    Yoshida, Y; Yoshihara, K; Nagaoka, N; Hayakawa, S; Torii, Y; Ogawa, T; Osaka, A; Meerbeek, B Van

    2012-04-01

    According to the 'Adhesion-Decalcification' concept, specific functional monomers within dental adhesives can ionically interact with hydroxyapatite (HAp). Such ionic bonding has been demonstrated for 10-methacryloyloxydecyl dihydrogen phosphate (MDP) to manifest in the form of self-assembled 'nano-layering'. However, it remained to be explored if such nano-layering also occurs on tooth tissue when commercial MDP-containing adhesives (Clearfil SE Bond, Kuraray; Scotchbond Universal, 3M ESPE) were applied following common clinical application protocols. We therefore characterized adhesive-dentin interfaces chemically, using x-ray diffraction (XRD) and energy-dispersive x-ray spectroscopy (EDS), and ultrastructurally, using (scanning) transmission electron microscopy (TEM/STEM). Both adhesives revealed nano-layering at the adhesive interface, not only within the hybrid layer but also, particularly for Clearfil SE Bond (Kuraray), extending into the adhesive layer. Since such self-assembled nano-layering of two 10-MDP molecules, joined by stable MDP-Ca salt formation, must make the adhesive interface more resistant to biodegradation, it may well explain the documented favorable clinical longevity of bonds produced by 10-MDP-based adhesives.

  6. Forces that Drive Nanoscale Self-assembly on Solid Surfaces

    International Nuclear Information System (INIS)

    Suo, Z.; Lu, W.

    2000-01-01

    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

  7. Preparation and self-assembly of nanostructured BaCrO4 from CTAB reverse microemulsions

    International Nuclear Information System (INIS)

    Li Zhonghao; Zhang Jianling; Du Jimin; Han Buxing; Mu Tiancheng; Gao Yanan; Liu Zhimin

    2005-01-01

    Well-defined superstructures of rectangular-shaped BaCrO 4 and extensive network of BaCrO 4 nanoparticles constructed by self-assembly were prepared in cetyltrimethylammonium bromide (CTAB) reverse microemulsions. The effects of aging time and reactant concentrations on the morphology and the self-assemble pattern of the nanostructured BaCrO 4 were investigated. TEM combined with the electron diffraction was used to characterize the morphology and the crystal structure of the prepared nanostructured BaCrO 4 at different conditions

  8. On the stability of surface-confined nanoporous molecular networks

    Energy Technology Data Exchange (ETDEWEB)

    Ghijsens, Elke; Adisoejoso, Jinne, E-mail: Jinne.adisoejoso@chem.kuleuven.be, E-mail: tobe@chem.es.osaka-u.ac.jp, E-mail: Steven.DeFeyter@chem.kuleuven.be; Van Gorp, Hans; Destoop, Iris; Ivasenko, Oleksandr; Van der Auweraer, Mark; De Feyter, Steven, E-mail: Jinne.adisoejoso@chem.kuleuven.be, E-mail: tobe@chem.es.osaka-u.ac.jp, E-mail: Steven.DeFeyter@chem.kuleuven.be [Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven—University of Leuven, Celestijnenlaan 200 F, B-3001 Leuven (Belgium); Noguchi, Aya; Tahara, Kazukuni; Tobe, Yoshito, E-mail: Jinne.adisoejoso@chem.kuleuven.be, E-mail: tobe@chem.es.osaka-u.ac.jp, E-mail: Steven.DeFeyter@chem.kuleuven.be [Graduate School of Engineering Science, Division of Frontier Materials Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan)

    2015-03-14

    Self-assembly of molecular building blocks into two-dimensional nanoporous networks has been a topic of broad interest for many years. However, various factors govern the specific outcome of the self-assembly process, and understanding and controlling these are key to successful creation. In this work, the self-assembly of two alkylated dehydrobenzo[12]annulene building blocks was compared at the liquid-solid interface. It turned out that only a small chemical modification within the building blocks resulted in enhanced domain sizes and stability of the porous packing relative to the dense linear packing. Applying a thermodynamic model for phase transition revealed some key aspects for network formation.

  9. Self-assembled morphologies of an amphiphilic Y-shaped weak polyelectrolyte in a thin film.

    Science.gov (United States)

    Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

    2017-11-29

    Different from the self-assembly of neutral polymers, polyelectrolytes self-assemble into smaller aggregates with a more loosely assembled structure, which results from the repulsive forces acting between similar electrical compositions with the introduction of ions. The Y-shaped weak polyelectrolytes self-assemble into a core-shell type cylindrical structure with a hexagonal arrangement in a thin film, whose thickness is smaller than the gyration radius of the polymer chain. The corresponding formation mechanism consists of enrichment of the same components, adjustment of the shape of the aggregate, and the subsequent separation into individual aggregates. With the increase in the thickness of the thin film until it exceeds the gyration radius of the polymer chain, combined with the greater freedom of movement along the direction of thin film thickness, the self-assembled structure changes into a micellar structure. Under confinement, the repulsive force to the polymeric components is weakened by the repulsive forces among polyelectrolyte components with like charges, and this helps in generating aggregates with more uniform size and density distribution. In particular, when the repulsive force between the walls and the core forming components is greater than that between the walls and the shell forming components, such asymmetric confinement produces a crossed-cylindrical structure with nearly perpendicular arrangement of two cylinder arrays. Similarly, a novel three-crossed cylinder morphology is self-assembled upon removal of confinement.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xinhua, E-mail: caoxhchem@163.com; Gao, Aiping; Zhao, Na; Yuan, Fangyuan; Liu, Chenxi; Li, Ruru

    2016-04-15

    Graphical abstract: - Highlights: • The different structures could be obtained in this self-assembly system. • A water-drop could freely roll on the xerogel film with the sliding angle of 15.0. • The superhydrophobic surface can be obtained via supramolecular self-assembly. - Abstract: A new organogelator based on fluorene derivative (gelator 1) was designed and synthesized. Organogels could be obtained via the self-assembly of the derivative in acetone, toluene, ethyl acetate, hexane, DMSO and petroleum ether. The self-assembly process was thoroughly characterized using field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), UV–vis, FT-IR and the contact angle. Surfaces with different morphologies and wetting properties were formed via the self-assembly of gelator 1 in the six different solvents. Interestingly, a superhydrophobic surface with a contact angle of 150° was obtained from organogel 1 in DMSO and exhibited the lotus-effect. The sliding angle necessary for a water droplet to move on the glass was only 15°. Hydrogen bonding and van der Waals forces were attributed as the main driving forces for gel formation.

  11. Intracellular Peptide Self-Assembly: A Biomimetic Approach for in Situ Nanodrug Preparation.

    Science.gov (United States)

    Du, Wei; Hu, Xiaomu; Wei, Weichen; Liang, Gaolin

    2018-04-18

    Most nanodrugs are preprepared by encapsulating or loading the drugs with nanocarriers (e.g., dendrimers, liposomes, micelles, and polymeric nanoparticles). However, besides the low bioavailability and fast excretion of the nanodrugs in vivo, nanocarriers often exhibit in vitro and in vivo cytotoxicity, oxidative stress, and inflammation. Self-assembly is a ubiquitous process in biology where it plays important roles and underlies the formation of a wide variety of complex biological structures. Inspired by some cellular nanostructures (e.g., actin filaments, microtubules, vesicles, and micelles) in biological systems which are formed via molecular self-assembly, in recent decades, scientists have utilized self-assembly of oligomeric peptide under specific physiological or pathological environments to in situ construct nanodrugs for lesion-targeted therapies. On one hand, peptide-based nanodrugs always have some excellent intrinsic chemical (specificity, intrinsic bioactivity, biodegradability) and physical (small size, conformation) properties. On the other hand, stimuli-regulated intracellular self-assembly of nanodrugs is quite an efficient way to accumulate the drugs in lesion location and can realize an in situ slow release of the drugs. In this review article, we provided an overview on recent design principles for intracellular peptide self-assembly and illustrate how these principles have been applied for the in situ preparation of nanodrugs at the lesion location. In the last part, we list some challenges underlying this strategy and their possible solutions. Moreover, we envision the future possible theranostic applications of this strategy.

  12. Hierarchical self-assembly of telechelic star polymers: from soft patchy particles to gels and diamond crystals

    International Nuclear Information System (INIS)

    Capone, Barbara; Coluzza, Ivan; Blaak, Ronald; Likos, Christos N; Verso, Federica Lo

    2013-01-01

    The design of self-assembling materials in the nanometer scale focuses on the fabrication of a class of organic and inorganic subcomponents that can be reliably produced on a large scale and tailored according to their vast applications for, e.g. electronics, therapeutic vectors and diagnostic imaging agent carriers, or photonics. In a recent publication (Capone et al 2012 Phys. Rev. Lett. 109 238301), diblock copolymer stars have been shown to be a novel system, which is able to hierarchically self-assemble first into soft patchy particles and thereafter into more complex structures, such as the diamond and cubic crystal. The self-aggregating single star patchy behavior is preserved from extremely low up to high densities. Its main control parameters are related to the architecture of the building blocks, which are the number of arms (functionality) and the fraction of attractive end-monomers. By employing a variety of computational and theoretical tools, ranging from the microscopic to the mesoscopic, coarse-grained level in a systematic fashion, we investigate the crossover between the formation of microstructure versus macroscopic phase separation, as well as the formation of gels and networks in these systems. We finally show that telechelic star polymers can be used as building blocks for the fabrication of open crystal structures, such as the diamond or the simple-cubic lattice, taking advantage of the strong correlation between single-particle patchiness and lattice coordination at finite densities. (paper)

  13. Quantifying quality in DNA self-assembly

    Science.gov (United States)

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

    2014-01-01

    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

  14. Oxide nanostructures through self-assembly

    Science.gov (United States)

    Aggarwal, S.; Ogale, S. B.; Ganpule, C. S.; Shinde, S. R.; Novikov, V. A.; Monga, A. P.; Burr, M. R.; Ramesh, R.; Ballarotto, V.; Williams, E. D.

    2001-03-01

    A prominent theme in inorganic materials research is the creation of uniformly flat thin films and heterostructures over large wafers, which can subsequently be lithographically processed into functional devices. This letter proposes an approach that will lead to thin film topographies that are directly counter to the above-mentioned philosophy. Recent years have witnessed considerable research activity in the area of self-assembly of materials, stimulated by observations of self-organized behavior in biological systems. We have fabricated uniform arrays of nonplanar surface features by a spontaneous assembly process involving the oxidation of simple metals, especially under constrained conditions on a variety of substrates, including glass and Si. In this letter we demonstrate the pervasiveness of this process through examples involving the oxidation of Pd, Cu, Fe, and In. The feature sizes can be controlled through the grain size and thickness of the starting metal thin film. Finally, we demonstrate how such submicron scale arrays can serve as templates for the design and development of self-assembled, nanoelectronic devices.

  15. Fabrication of textured SnO2 transparent conductive films using self-assembled Sn nanospheres

    Science.gov (United States)

    Fukumoto, Michitaka; Nakao, Shoichiro; Hirose, Yasushi; Hasegawa, Tetsuya

    2018-06-01

    We present a novel method to fabricate textured surfaces on transparent conductive SnO2 films by processing substrates through a bottom-up technique with potential for industrially scalable production. The substrate processing consists of three steps: deposition of precursor Sn films on glass substrates, formation of a self-assembled Sn nanosphere layer with reductive annealing, and conversion of Sn to SnO2 by oxidative annealing. Ta-doped SnO2 films conformally deposited on the self-assembled nanospherical SnO2 templates exhibited attractive optical and electrical properties, namely, enhanced haze values and low sheet resistances, for applications as transparent electrodes in photovoltaics.

  16. Surface-Assisted Self-Assembly Strategies Leading to Supramolecular Hydrogels.

    Science.gov (United States)

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

    2018-02-05

    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.

  17. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration

    KAUST Repository

    Yu, Haizhou

    2015-09-21

    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol−1 in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux.

  18. Lipid-bilayer-assisted two-dimensional self-assembly of DNA origami nanostructures

    Science.gov (United States)

    Suzuki, Yuki; Endo, Masayuki; Sugiyama, Hiroshi

    2015-08-01

    Self-assembly is a ubiquitous approach to the design and fabrication of novel supermolecular architectures. Here we report a strategy termed `lipid-bilayer-assisted self-assembly' that is used to assemble DNA origami nanostructures into two-dimensional lattices. DNA origami structures are electrostatically adsorbed onto a mica-supported zwitterionic lipid bilayer in the presence of divalent cations. We demonstrate that the bilayer-adsorbed origami units are mobile on the surface and self-assembled into large micrometre-sized lattices in their lateral dimensions. Using high-speed atomic force microscopy imaging, a variety of dynamic processes involved in the formation of the lattice, such as fusion, reorganization and defect filling, are successfully visualized. The surface modifiability of the assembled lattice is also demonstrated by in situ decoration with streptavidin molecules. Our approach provides a new strategy for preparing versatile scaffolds for nanofabrication and paves the way for organizing functional nanodevices in a micrometer space.

  19. Collagen I self-assembly: revealing the developing structures that generate turbidity.

    Science.gov (United States)

    Zhu, Jieling; Kaufman, Laura J

    2014-04-15

    Type I collagen gels are routinely used in biophysical studies and bioengineering applications. The structural and mechanical properties of these fibrillar matrices depend on the conditions under which collagen fibrillogenesis proceeds, and developing a fuller understanding of this process will enhance control over gel properties. Turbidity measurements have long been the method of choice for monitoring developing gels, whereas imaging methods are regularly used to visualize fully developed gels. In this study, turbidity and confocal reflectance microscopy (CRM) were simultaneously employed to track collagen fibrillogenesis and reconcile the information reported by the two techniques, with confocal fluorescence microscopy (CFM) used to supplement information about early events in fibrillogenesis. Time-lapse images of 0.5 mg/ml, 1.0 mg/ml, and 2.0 mg/ml acid-solubilized collagen I gels forming at 27°C, 32°C, and 37°C were collected. It was found that in situ turbidity measured in a scanning transmittance configuration was interchangeable with traditional turbidity measurements using a spectrophotometer. CRM and CFM were employed to reveal the structures responsible for the turbidity that develops during collagen self-assembly. Information from CRM and transmittance images was collapsed into straightforward single variables; total intensity in CRM images tracked turbidity development closely for all collagen gels investigated, and the two techniques were similarly sensitive to fibril number and dimension. Complementary CRM, CFM, and in situ turbidity measurements revealed that fibril and network formation occurred before substantial turbidity was present, and the majority of increasing turbidity during collagen self-assembly was due to increasing fibril thickness. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

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

    KAUST Repository

    Junnila, Susanna; Houbenov, Nikolay; Karatzas, A.; Hadjichristidis, Nikolaos; Hirao, Akira; Iatrou, Hermis; Ikkala, Olli T.

    2012-01-01

    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

  1. The self-assembly of monodisperse nanospheres within microtubes

    International Nuclear Information System (INIS)

    Zheng Yuebing; Juluri, Bala Krishna; Huang, Tony Jun

    2007-01-01

    Self-assembled monodisperse nanospheres within microtubes have been fabricated and characterized. In comparison with colloidal crystals formed on planar substrates, colloidal nanocrystals self-assembled in microtubes demonstrate high spatial symmetry in their optical transmission and reflection properties. The dynamic self-assembly process inside microtubes is investigated by combining temporal- and spatial-spectrophotometric measurements. The understanding of this process is achieved through both experimentally recorded reflection spectra and finite difference time domain (FDTD)-based simulation results

  2. The Relationship between Self-Assembly and Conformal Mappings

    Science.gov (United States)

    Duque, Carlos; Santangelo, Christian

    The isotropic growth of a thin sheet has been used as a way to generate programmed shapes through controlled buckling. We discuss how conformal mappings, which are transformations that locally preserve angles, provide a way to quantify the area growth needed to produce a particular shape. A discrete version of the conformal map can be constructed from circle packings, which are maps between packings of circles whose contact network is preserved. This provides a link to the self-assembly of particles on curved surfaces. We performed simulations of attractive particles on a curved surface using molecular dynamics. The resulting particle configurations were used to generate the corresponding discrete conformal map, allowing us to quantify the degree of area distortion required to produce a particular shape by finding particle configurations that minimize the area distortion.

  3. Magnetic self-assembly of small parts

    Science.gov (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

  4. Multifunctional Materials Based on Self Assembly of Molecular Nanostructures

    National Research Council Canada - National Science Library

    Stupp, Samuel

    2001-01-01

    .... The objective was to integrate self assembly, encoded in the triblock structure, luminescent properties, and the properties characteristic of materials that have macroscopically polar structure...

  5. Self-assembled software and method of overriding software execution

    Science.gov (United States)

    Bouchard, Ann M.; Osbourn, Gordon C.

    2013-01-08

    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.

  6. Electrodynamic tailoring of self-assembled three-dimensional electrospun constructs

    Science.gov (United States)

    Reis, Tiago C.; Correia, Ilídio J.; Aguiar-Ricardo, Ana

    2013-07-01

    The rational design of three-dimensional electrospun constructs (3DECs) can lead to striking topographies and tailored shapes of electrospun materials. This new generation of materials is suppressing some of the current limitations of the usual 2D non-woven electrospun fiber mats, such as small pore sizes or only flat shaped constructs. Herein, we pursued an explanation for the self-assembly of 3DECs based on electrodynamic simulations and experimental validation. We concluded that the self-assembly process is driven by the establishment of attractive electrostatic forces between the positively charged aerial fibers and the already collected ones, which tend to acquire a negatively charged network oriented towards the nozzle. The in situ polarization degree is strengthened by higher amounts of clustered fibers, and therefore the initial high density fibrous regions are the preliminary motifs for the self-assembly mechanism. As such regions increase their in situ polarization electrostatic repulsive forces will appear, favoring a competitive growth of these self-assembled fibrous clusters. Highly polarized regions will evidence higher distances between consecutive micro-assembled fibers (MAFs). Different processing parameters - deposition time, electric field intensity, concentration of polymer solution, environmental temperature and relative humidity - were evaluated in an attempt to control material's design.The rational design of three-dimensional electrospun constructs (3DECs) can lead to striking topographies and tailored shapes of electrospun materials. This new generation of materials is suppressing some of the current limitations of the usual 2D non-woven electrospun fiber mats, such as small pore sizes or only flat shaped constructs. Herein, we pursued an explanation for the self-assembly of 3DECs based on electrodynamic simulations and experimental validation. We concluded that the self-assembly process is driven by the establishment of attractive

  7. Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Vijay, E-mail: cirivijaypilani@gmail.com [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)

    2016-04-13

    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.

  8. Communication: Programmable self-assembly of thin-shell mesostructures

    Science.gov (United States)

    Halverson, Jonathan D.; Tkachenko, Alexei V.

    2017-10-01

    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.

  9. Controlling water evaporation through self-assembly.

    Science.gov (United States)

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

    2016-09-13

    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.

  10. Beam damage of self-assembled monolayers

    International Nuclear Information System (INIS)

    Rieke, P.C.; Baer, D.R.; Fryxell, G.E.; Engelhard, M.H.; Porter, M.S.

    1993-01-01

    X-ray and electron beam damage studies were performed on Br-terminated and methyl-terminated alkylsilane self-assembled monolayers. X-ray beam initiated damage was primarily limited to removal of the labile Br group and did not significantly damage the hydrocarbon chain. Some of the x-ray beam damage could be attributed to low-energy electrons emitted by the non-monochromatic source, but further damage was attributed to secondary electrons produced in the sample by x-ray exposure. Electron beams caused significant damage to the hydrocarbon chains. Maximum damage occurred with a beam energy of 600 eV and a dosage of 6x10 -3 C/cm 2

  11. Self-assembled ordered carbon-nanotube arrays and membranes.

    Energy Technology Data Exchange (ETDEWEB)

    Overmyer, Donald L.; Siegal, Michael P.; Yelton, William Graham

    2004-11-01

    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.

  12. Self-assembling triblock proteins for biofunctional surface modification

    Science.gov (United States)

    Fischer, Stephen E.

    Despite the tremendous promise of cell/tissue engineering, significant challenges remain in engineering functional scaffolds to precisely regulate the complex processes of tissue growth and development. As the point of contact between the cells and the scaffold, the scaffold surface plays a major role in mediating cellular behaviors. In this dissertation, the development and utility of self-assembling, artificial protein hydrogels as biofunctional surface modifiers is described. The design of these recombinant proteins is based on a telechelic triblock motif, in which a disordered polyelectrolyte central domain containing embedded bioactive ligands is flanked by two leucine zipper domains. Under moderate conditions of temperature and pH, the leucine zipper end domains form amphiphilic alpha-helices that reversibly associate into homo-trimeric aggregates, driving hydrogel formation. Moreover, the amphiphilic nature of these helical domains enables surface adsorption to a variety of scaffold materials to form biofunctional protein coatings. The nature and stability of these coatings in various solution conditions, and their interaction with mammalian cells is the primary focus of this dissertation. In particular, triblock protein coatings functionalized with cell recognition sequences are shown to produce well-defined surfaces with precise control over ligand density. The impact of this is demonstrated in multiple cell types through ligand density-dependent cell-substrate interactions. To improve the stability of these physically self-assembled coatings, two covalent crosslinking strategies are described---one in which a zero-length chemical crosslinker (EDC) is utilized and a second in which disulfide bonds are engineered into the recombinant proteins. These targeted crosslinking approaches are shown to increase the stability of surface adsorbed protein layers with minimal effect on the presentation of many bioactive ligands. Finally, to demonstrate the versatility

  13. Opal-like Multicolor Appearance of Self-Assembled Photonic Array.

    Science.gov (United States)

    Arnon, Zohar A; Pinotsi, Dorothea; Schmidt, Matthias; Gilead, Sharon; Guterman, Tom; Sadhanala, Aditya; Ahmad, Shahab; Levin, Aviad; Walther, Paul; Kaminski, Clemens F; Fändrich, Marcus; Kaminski Schierle, Gabriele S; Adler-Abramovich, Lihi; Shimon, Linda J W; Gazit, Ehud

    2018-06-20

    Molecular self-assembly of short peptide building blocks leads to the formation of various material architectures that may possess unique physical properties. Recent studies had confirmed the key role of biaromaticity in peptide self-assembly, with the diphenylalanine (FF) structural family as an archetypal model. Another significant direction in the molecular engineering of peptide building blocks is the use of fluorenylmethoxycarbonyl (Fmoc) modification, which promotes the assembly process and may result in nanostructures with distinctive features and macroscopic hydrogel with supramolecular features and nanoscale order. Here, we explored the self-assembly of the protected, noncoded fluorenylmethoxycarbonyl-β,β-diphenyl-Ala-OH (Fmoc-Dip) amino acid. This process results in the formation of elongated needle-like crystals with notable aromatic continuity. By altering the assembly conditions, arrays of spherical particles were formed that exhibit strong light scattering. These arrays display vivid coloration, strongly resembling the appearance of opal gemstones. However, unlike the Rayleigh scattering effect produced by the arrangement of opal, the described optical phenomenon is attributed to Mie scattering. Moreover, by controlling the solution evaporation rate, i.e., the assembly kinetics, we were able to manipulate the resulting coloration. This work demonstrates a bottom-up approach, utilizing self-assembly of a protected amino acid minimal building block, to create arrays of organic, light-scattering colorful surfaces.

  14. Multicomponent and Dissipative Self-Assembly Approaches : Towards functional materials

    NARCIS (Netherlands)

    Boekhoven, J.

    2012-01-01

    The use of self-assembly has proven to be a powerful approach to create smart and functional materials and has led to a vast variety of successful examples. However, the full potential of self-assembly has not been reached. Despite the number of successful artificial materials based on

  15. Multivalent protein assembly using monovalent self-assembling building blocks

    NARCIS (Netherlands)

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

    2013-01-01

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

  16. Equilibrium polymerization models of re-entrant self-assembly

    Science.gov (United States)

    Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

    2009-04-01

    As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

  17. Self-assembly behaviour of conjugated terthiophene surfactants in water

    NARCIS (Netherlands)

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

    2011-01-01

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

  18. Freezing-induced self-assembly of amphiphilic molecules

    Science.gov (United States)

    Albouy, P. A.; Deville, S.; Fulkar, A.; Hakouk, K.; Impéror-Clerc, M.; Klotz, M.; Liu, Q.; Marcellini, M.; Perez, J.

    The self-assembly of amphiphilic molecules usually takes place in a liquid phase, near room temperature. Here, using small angle X-ray scattering (SAXS) experiments performed in real time, we show that freezing of aqueous solutions of copolymer amphiphilic molecules can induce self-assembly below 0{\\deg}C.

  19. Self-assembling hybrid diamond–biological quantum devices

    International Nuclear Information System (INIS)

    Albrecht, A; B Plenio, M; Koplovitz, G; Yochelis, S; Paltiel, Y; Retzker, A; Nevo, Y; Shoseyov, O; Jelezko, F; Porath, D

    2014-01-01

    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. (papers)

  20. Self-assembling hybrid diamond-biological quantum devices

    Science.gov (United States)

    Albrecht, A.; Koplovitz, G.; Retzker, A.; Jelezko, F.; Yochelis, S.; Porath, D.; Nevo, Y.; Shoseyov, O.; Paltiel, Y.; Plenio, M. B.

    2014-09-01

    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.

  1. Toward a molecular programming language for algorithmic self-assembly

    Science.gov (United States)

    Patitz, Matthew John

    Self-assembly is the process whereby relatively simple components autonomously combine to form more complex objects. Nature exhibits self-assembly to form everything from microscopic crystals to living cells to galaxies. With a desire to both form increasingly sophisticated products and to understand the basic components of living systems, scientists have developed and studied artificial self-assembling systems. One such framework is the Tile Assembly Model introduced by Erik Winfree in 1998. In this model, simple two-dimensional square 'tiles' are designed so that they self-assemble into desired shapes. The work in this thesis consists of a series of results which build toward the future goal of designing an abstracted, high-level programming language for designing the molecular components of self-assembling systems which can perform powerful computations and form into intricate structures. The first two sets of results demonstrate self-assembling systems which perform infinite series of computations that characterize computably enumerable and decidable languages, and exhibit tools for algorithmically generating the necessary sets of tiles. In the next chapter, methods for generating tile sets which self-assemble into complicated shapes, namely a class of discrete self-similar fractal structures, are presented. Next, a software package for graphically designing tile sets, simulating their self-assembly, and debugging designed systems is discussed. Finally, a high-level programming language which abstracts much of the complexity and tedium of designing such systems, while preventing many of the common errors, is presented. The summation of this body of work presents a broad coverage of the spectrum of desired outputs from artificial self-assembling systems and a progression in the sophistication of tools used to design them. By creating a broader and deeper set of modular tools for designing self-assembling systems, we hope to increase the complexity which is

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

    Science.gov (United States)

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

    2017-07-17

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

  3. Self-assembled nanostructures in oxide ceramics

    Science.gov (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

  4. Synthesis of nanocrystals and nanocrystal self-assembly

    Science.gov (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

  5. Hantavirus Gn and Gc glycoproteins self-assemble into virus-like particles.

    Science.gov (United States)

    Acuña, Rodrigo; Cifuentes-Muñoz, Nicolás; Márquez, Chantal L; Bulling, Manuela; Klingström, Jonas; Mancini, Roberta; Lozach, Pierre-Yves; Tischler, Nicole D

    2014-02-01

    How hantaviruses assemble and exit infected cells remains largely unknown. Here, we show that the expression of Andes (ANDV) and Puumala (PUUV) hantavirus Gn and Gc envelope glycoproteins lead to their self-assembly into virus-like particles (VLPs) which were released to cell supernatants. The viral nucleoprotein was not required for particle formation. Further, a Gc endodomain deletion mutant did not abrogate VLP formation. The VLPs were pleomorphic, exposed protrusions and reacted with patient sera.

  6. Signatures of self-assembly in size distributions of wood members in dam structures of Castor canadensis

    Directory of Open Access Journals (Sweden)

    David M. Blersch

    2014-12-01

    Full Text Available Beavers (Castor canadensis construct dams on rivers throughout most of their historical range in North America, and their impact on water patterns in the landscape is considerable. Dam formation by beavers involves two processes: (1 intentional construction through the selection and placement of wood and sediment, which facilitates (2 the passive capture and accretion of suspended wood and sediment. The second process is a self-assembly mechanism that the beavers leverage by utilizing energy subsidies of watershed transport processes. The relative proportion of beaver activity to self-assembly processes in dam construction, however, is unknown. Here we show that lotic self-assembly processes account for a substantial portion of the work expended in beaver dam construction. We found through comprehensive measurement of the stick dimensions that the distributions for diameter, length, and volume are log-normal. By noting evidence of teeth markings, we determined that size distributions skewed significantly larger for wood handled by beavers compared to those that were not. Subsequent mass calculations suggest that beavers perform 50%–70% of the work of wood member placement for dam assembly, with riparian self-assembly processes contributing the remainder. Additionally, our results establish a benchmark for assessing the proportion of self-assembly work in similar riparian structures. Keywords: Beaver dam, Construction, Castor canadensis, Self-assembly, Distribution, Wood

  7. Self-Assembly and Crystallization of Conjugated Block Copolymers

    Science.gov (United States)

    Davidson, Emily Catherine

    . These results emphasize that targeting curved morphologies with majority conjugated polymer - even when the conjugated polymer is fairly flexible, as is the case with P3EHT - will continue to be an important challenge. The detailed balance between the unique properties of conjugated polymer crystallization and diblock copolymer self-assembly in these materials is illuminated by examining the crystallite orientation and the response of microdomains to crystallization. A critical parameter is found to be the P3EHT drive for extended-chain crystals. It is found that under all probed conditions in lamellar P3EHT-b-PMA, P3EHT chains crystallize with their chains perpendicular to the diblock interface. Further, in P3EHT- b-PMA with a deformable amorphous block, P3EHT drives domain expansion during crystallization despite increasing P3EHT density. This expansion corresponds to the formation of extended-chain crystallites. This resulting conformation is not necessarily expected to be favorable, given that it induces a stretching penalty in the coupled amorphous block. However, this expansion appears to be not only preferred but necessary: crystallization in lamellar confinement with a glassy PS matrix suppresses not only domain extension but also P3EHT crystallization. Interestingly, in cylindrical confinement, it is shown that this drive for extended chain crystals results in local deformation of the cylindrical domains themselves. Finally, the relationship between the detailed crystallization process and the diblock structure is examined. The degree of crystalline perfection of P3EHT can be controlled in confinement by controlling the crystallization temperature (Tc) or, alternatively, via re-crystallization at temperatures below the melting temperature. Surprisingly, in P3EHT-b-PMA increasing the crystallization temperature both improves the crystalline perfection and results in less domain extension. By tracking the changes in domain structure during melting, three distinct

  8. Self-assembled biomimetic superhydrophobic hierarchical arrays.

    Science.gov (United States)

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

    2013-09-01

    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.

  9. Cooperative effects of fibronectin matrix assembly and initial cell-substrate adhesion strength in cellular self-assembly.

    Science.gov (United States)

    Brennan, James R; Hocking, Denise C

    2016-03-01

    organize cells into modular building blocks for artificial tissue fabrication. Fibronectin is an ECM protein that plays a key role in tissue formation during embryonic development. Additionally, the cell-mediated process of converting soluble fibronectin into insoluble, ECM-associated fibrils has been shown to initiate cellular self-assembly in vitro. In this study, we examine the relationship between the strength of cell-substrate adhesions and the ability of fibronectin fibril assembly to induce cellular self-assembly. Our results indicate that substrate composition and density play cooperative roles with cell-mediated fibronectin matrix assembly to control the transition of cells from 2D monolayers into 3D multicellular aggregates. Results of this study provide a quantitative approach to build predictive models of cellular self-assembly, as well as a simple cell-culture platform to produce biomimetic units for modular tissue engineering. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2018-07-13

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

  11. Nondeterministic self-assembly of two tile types on a lattice.

    Science.gov (United States)

    Tesoro, S; Ahnert, S E

    2016-04-01

    Self-assembly is ubiquitous in nature, particularly in biology, where it underlies the formation of protein quaternary structure and protein aggregation. Quaternary structure assembles deterministically and performs a wide range of important functions in the cell, whereas protein aggregation is the hallmark of a number of diseases and represents a nondeterministic self-assembly process. Here we build on previous work on a lattice model of deterministic self-assembly to investigate nondeterministic self-assembly of single lattice tiles and mixtures of two tiles at varying relative concentrations. Despite limiting the simplicity of the model to two interface types, which results in 13 topologically distinct single tiles and 106 topologically distinct sets of two tiles, we observe a wide variety of concentration-dependent behaviors. Several two-tile sets display critical behaviors in the form of a sharp transition from bound to unbound structures as the relative concentration of one tile to another increases. Other sets exhibit gradual monotonic changes in structural density, or nonmonotonic changes, while again others show no concentration dependence at all. We catalog this extensive range of behaviors and present a model that provides a reasonably good estimate of the critical concentrations for a subset of the critical transitions. In addition, we show that the structures resulting from these tile sets are fractal, with one of two different fractal dimensions.

  12. Self-Organization and the Self-Assembling Process in Tissue Engineering

    Science.gov (United States)

    Eswaramoorthy, Rajalakshmanan; Hadidi, Pasha; Hu, Jerry C.

    2015-01-01

    In recent years, the tissue engineering paradigm has shifted to include a new and growing subfield of scaffoldless techniques which generate self-organizing and self-assembling tissues. This review aims to provide a cogent description of this relatively new research area, with special emphasis on applications toward clinical use and research models. Particular emphasis is placed on providing clear definitions of self-organization and the self-assembling process, as delineated from other scaffoldless techniques in tissue engineering and regenerative medicine. Significantly, during formation, self-organizing and self-assembling tissues display biological processes similar to those that occur in vivo. These help lead to the recapitulation of native tissue morphological structure and organization. Notably, functional properties of these tissues also approach native tissue values; some of these engineered tissues are already in clinical trials. This review aims to provide a cohesive summary of work in this field, and to highlight the potential of self-organization and the self-assembling process to provide cogent solutions to current intractable problems in tissue engineering. PMID:23701238

  13. Self-Assembly of Telechelic Tyrosine End-Capped PEO Star Polymers in Aqueous Solution.

    Science.gov (United States)

    Edwards-Gayle, Charlotte J C; Greco, Francesca; Hamley, Ian W; Rambo, Robert P; Reza, Mehedi; Ruokolainen, Janne; Skoulas, Dimitrios; Iatrou, Hermis

    2018-01-08

    We investigate the self-assembly of two telechelic star polymer-peptide conjugates based on poly(ethylene oxide) (PEO) four-arm star polymers capped with oligotyrosine. The conjugates were prepared via N-carboxy anhydride-mediated ring-opening polymerization from PEO star polymer macroinitiators. Self-assembly occurs above a critical aggregation concentration determined via fluorescence probe assays. Peptide conformation was examined using circular dichroism spectroscopy. The structure of self-assembled aggregates was probed using small-angle X-ray scattering and cryogenic transmission electron microscopy. In contrast to previous studies on linear telechelic PEO-oligotyrosine conjugates that show self-assembly into β-sheet fibrils, the star architecture suppresses fibril formation and micelles are generally observed instead, a small population of fibrils only being observed upon pH adjustment. Hydrogelation is also suppressed by the polymer star architecture. These peptide-functionalized star polymer solutions are cytocompatible at sufficiently low concentration. These systems present tyrosine at high density and may be useful in the development of future enzyme or pH-responsive biomaterials.

  14. Kinetics of directed self-assembly of block copolymers on chemically patterned substrates

    International Nuclear Information System (INIS)

    Müller, Marcus; Li, Weihua; Rey, Juan Carlos Orozco; Welling, Ulrich

    2015-01-01

    Chemically patterned surfaces have been successfully employed to direct the kinetics of self-assembly of block copolymers into dense, periodic morphologies (”chemoepitaxy”). Significant efforts have been directed towards understanding the kinetics of structure formation and, particularly, the formation and annihilation of defects. In the present manuscript we use computer simulations of a soft, coarse-grained polymer model to study the kinetics of structure formation of lamellar-forming block copolymer thin films on a chemical pattern of lines and spaces. The case where the copolymer material replicates the surface pattern and the more subtle scenario of sparse guiding patterns are considered. Our simulation results highlight (1) the importance of the early stages of pattern-directed self-assembly that template the subsequent morphology and (2) the dependence of the free-energy landscape on the incompatibility between the two blocks of the copolymer. (paper)

  15. Functional self-assembled lipidic systems derived from renewable resources.

    Science.gov (United States)

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

    2016-01-01

    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.

  16. Equation of State for Phospholipid Self-Assembly

    DEFF Research Database (Denmark)

    Marsh, Derek

    2016-01-01

    Phospholipid self-assembly is the basis of biomembrane stability. The entropy of transfer from water to self-assembled micelles of lysophosphatidylcholines and diacyl phosphatidylcholines with different chain lengths converges to a common value at a temperature of 44°C. The corresponding enthalpies...... 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...

  17. Templated Biomineralization on Self-Assembled Protein Fibers

    Energy Technology Data Exchange (ETDEWEB)

    Subburaman,K.; Pernodet, N.; Kwak, S.; DiMasi, E.; Ge, S.; Zaitsev, V.; Ba, X.; Yang, N.; Rafailovich, M.

    2006-01-01

    Biological mineralization of tissues in living organisms relies on proteins that preferentially nucleate minerals and control their growth. This process is often referred to as 'templating', but this term has become generic, denoting various proposed mineral-organic interactions including both chemical and structural affinities. Here, we present an approach using self-assembled networks of elastin and fibronectin fibers, similar to the extracellular matrix. When induced onto negatively charged sulfonated polystyrene surfaces, these proteins form fiber networks of {approx}10-{mu}m spacing, leaving open regions of disorganized protein between them. We introduce an atomic force microscopy-based technique to measure the elastic modulus of both structured and disorganized protein before and during calcium carbonate mineralization. Mineral-induced thickening and stiffening of the protein fibers during early stages of mineralization is clearly demonstrated, well before discrete mineral crystals are large enough to image by atomic force microscopy. Calcium carbonate stiffens the protein fibers selectively without affecting the regions between them, emphasizing interactions between the mineral and the organized protein fibers. Late-stage observations by optical microscopy and secondary ion mass spectroscopy reveal that Ca is concentrated along the protein fibers and that crystals form preferentially on the fiber crossings. We demonstrate that organized versus unstructured proteins can be assembled mere nanometers apart and probed in identical environments, where mineralization is proved to require the structural organization imposed by fibrillogenesis of the extracellular matrix.

  18. Optical orientation in self assembled quantum dots

    International Nuclear Information System (INIS)

    Stevens, Gregory C.

    2002-01-01

    We examined Zeeman splitting in a series of ln x Ga (1-x) As/GaAs self assembled quantum dots (SAQD's) with different pump polarisations. All these measurements were made in very low external magnetic fields where direct determination of the Zeeman splitting energy is impossible due to its small value in comparison to the photoluminescence linewidths. The use of a technique developed by M. J. Snelling allowed us to obtain the Zeeman splitting and hence the excitonic g-factors indirectly. We observed a linear low field splitting, becoming increasingly non-linear at higher fields. We attribute this non-linearity to field induced level mixing. It is believed these are the first low field measurements in these structures. A number of apparent nuclear effects in the Zeeman splitting measurements led us onto the examination of nuclear effects in these structures. The transverse and oblique Hanie effects then allowed us to obtain the sign of the electronic g-factors in two of our samples, for one sample, a (311) grown In 0.5 Ga 0.5 As/GaAs SAQD sample, we were able to ascertain the spin relaxation time, the maximum value of the nuclear field, and provide evidence of the existence of nuclear spin freezing in at least one of our samples. We have then used a novel technique investigated by D. J. Guerrier, to examine optically detected nuclear magnetic resonance in our samples. We believe this is the first such study on these structures. We could not ascertain the dipolar indium resonance signal, even though all other isotopes were seen. We have therefore suggested a number of possible mechanisms that may be responsible for the lack of an indium resonance signal. (author)

  19. Self-assembly strategies for the synthesis of functional nanostructured materials

    Science.gov (United States)

    Perego, M.; Seguini, G.

    2016-06-01

    Self-assembly is the autonomous organization of components into patterns or structures without human intervention. This is the approach followed by nature to generate living cells and represents one of the practical strategies to fabricate ensembles of nanostructures. In static self-assembly the formation of ordered structures could require energy but once formed the structures are stable. The introduction of additional regular features in the environment could be used to template the self-assembly guiding the organization of the components and determining the final structure they form. In this regard self-assembly of block copolymers represents a potent platform for fundamental studies at the nanoscale and for application-driven investigation as a tool to fabricate functional nanostructured materials. Block copolymers can hierarchically assemble into chemically distinct domains with size and periodicity on the order of 10nm or below, offering a potentially inexpensive route to generate large-area nanostructured materials. The final structure characteristics of these materials are dictated by the properties of the elementary block copolymers, like chain length, volume fraction or degree of block incompatibility. Modern synthetic chemistry offers the possibility to design these macromolecules with very specific length scales and geometries, directly embodying in the block copolymers the code that drives their self- assembling process. The understanding of the kinetics and thermodynamics of the block copolymer self-assembly process in the bulk phase as well as in thin films represents a fundamental prerequisite toward the exploitation of these materials. Incorporating block copolymer into device fabrication procedures or directly into devices, as active elements, will lead to the development of a new generation of devices fabricated using the fundamental law of nature to our advantage in order to minimize cost and power consumption in the fabrication process

  20. Ultrathin self-assembled anionic polymer membranes for superfast size-selective separation

    Science.gov (United States)

    Deng, Chao; Zhang, Qiu Gen; Han, Guang Lu; Gong, Yi; Zhu, Ai Mei; Liu, Qing Lin

    2013-10-01

    commercial membranes, and can highly efficiently separate 5 and 15 nm gold nanoparticles from their mixtures. The newly developed nanoporous membranes have a wide application in separation and purification of biomacromolecules and nanoparticles. Electronic supplementary information (ESI) available: Synthesis and characterization of SPEK-C; effect of the sulfonation degree on membrane formation; structure and properties of the self-assembled membranes; separation of cyt.c by the self-assembled membranes; size-selective separation of gold nanoparticles by the self-assembled membranes; comparison with commercial flat sheet ultrafiltration membranes. See DOI: 10.1039/c3nr03362g

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

    KAUST Repository

    Junnila, Susanna

    2012-03-27

    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.

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

    KAUST Repository

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

    2016-01-01

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

  3. Silica biomineralization via the self-assembly of helical biomolecules.

    Science.gov (United States)

    Liu, Ben; Cao, Yuanyuan; Huang, Zhehao; Duan, Yingying; Che, Shunai

    2015-01-21

    The biomimetic synthesis of relevant silica materials using biological macromolecules as templates via silica biomineralization processes attract rapidly rising attention toward natural and artificial materials. Biomimetic synthesis studies are useful for improving the understanding of the formation mechanism of the hierarchical structures found in living organisms (such as diatoms and sponges) and for promoting significant developments in the biotechnology, nanotechnology and materials chemistry fields. Chirality is a ubiquitous phenomenon in nature and is an inherent feature of biomolecular components in organisms. Helical biomolecules, one of the most important types of chiral macromolecules, can self-assemble into multiple liquid-crystal structures and be used as biotemplates for silica biomineralization, which renders them particularly useful for fabricating complex silica materials under ambient conditions. Over the past two decades, many new silica materials with hierarchical structures and complex morphologies have been created using helical biomolecules. In this review, the developments in this field are described and the recent progress in silica biomineralization templating using several classes of helical biomolecules, including DNA, polypeptides, cellulose and rod-like viruses is summarized. Particular focus is placed on the formation mechanism of biomolecule-silica materials (BSMs) with hierarchical structures. Finally, current research challenges and future developments are discussed in the conclusion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Lipid dip-pen nanolithography on self-assembled monolayers

    International Nuclear Information System (INIS)

    Gavutis, Martynas; Navikas, Vytautas; Rakickas, Tomas; Vaitekonis, Šarūnas; Valiokas, Ramūnas

    2016-01-01

    Dip-pen nanolithography (DPN) with lipids as an ink enables functional micro/nanopatterning on different substrates at high process speeds. However, only a few studies have addressed the influence of the physicochemical properties of the surface on the structure and phase behavior of DPN-printed lipid assemblies. Therefore, by combining the scanning probe and optical imaging techniques in this work we have analyzed lipid microdomain formation on the self-assembled monolayers (SAMs) on gold as well-defined model surfaces that displayed hydrophilic (protein-repellent) or hydrophobic (protein-adhesive) characteristics. We have found that on the tri(ethylene glycol)-terminated SAM the lipid ink transfer was fast (∼10 –1 μm 3 s −1 ), quasi-linear and it yielded unstable, sparsely packed lipid microspots. Contrary to this, on the methyl-terminated SAM the lipid transfer was ∼20 times slower, nonlinear, and the obtained stable dots of ∼1 μm in diameter consisted of lipid multilayers. Our comparative analysis indicated that the measured lipid transfer was consistent with the previously reported so-called polymer transfer model (Felts et al 2012, Nanotechnology 23 215301). Further on, by employing the observed distinct contrast in the DPN ink behavior we constructed confined lipid microdomains on pre-patterned SAMs, in which the lipids assembled either into monolayer or multilamellar phases. Such microdomains can be further utilized for lipid membrane mimetics in microarray and lab-on-a-chip device formats. (paper)

  5. Self-Assembled Nanostructured Health Monitoring Sensors, Phase I

    Data.gov (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...

  6. Self-Assembling Wireless Autonomous Reconfigurable Modules (SWARM), Phase I

    Data.gov (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...

  7. Self-Assembly of Rod-Coil Block Copolymers

    National Research Council Canada - National Science Library

    Jenekhe, S

    1999-01-01

    ... the self-assembly of new rod-coil diblock, rod- coil-rod triblock, and coil-rod-coil triblock copolymers from solution and the resulting discrete and periodic mesostmctares with sizes in the 100...

  8. Preparation and self-assembly of amphiphilic polylysine dendrons

    DEFF Research Database (Denmark)

    Mirsharghi, Sahar; Knudsen, Kenneth D.; Bagherifam, Shahla

    2016-01-01

    Polylysine dendrons with lipid tails prepared by divergent solid-phase synthesis showed self-assembling properties in aqueous solutions., Herein, we present the synthesis of new amphiphilic polylysine dendrons with variable alkyl chain lengths (C1–C18) at the C-terminal. The dendrons were...... synthesized in moderate to quantitative yields by divergent solid-phase synthesis (SPS) employing an aldehyde linker. The self-assembling properties of the dendrons in aqueous solutions were studied by small angle neutron scattering (SANS) and dynamic light scattering (DLS). The self-assembling properties...... were influenced by the length of the alkyl chain and the generation number (Gn). Increasing the temperature and concentration did not have significant impact on the hydrodynamic diameter, but the self-assembling properties were influenced by the pH value. This demonstrated the need for positively...

  9. Enabling complex nanoscale pattern customization using directed self-assembly.

    Science.gov (United States)

    Doerk, Gregory S; Cheng, Joy Y; Singh, Gurpreet; Rettner, Charles T; Pitera, Jed W; Balakrishnan, Srinivasan; Arellano, Noel; Sanders, Daniel P

    2014-12-16

    Block copolymer directed self-assembly is an attractive method to fabricate highly uniform nanoscale features for various technological applications, but the dense periodicity of block copolymer features limits the complexity of the resulting patterns and their potential utility. Therefore, customizability of nanoscale patterns has been a long-standing goal for using directed self-assembly in device fabrication. Here we show that a hybrid organic/inorganic chemical pattern serves as a guiding pattern for self-assembly as well as a self-aligned mask for pattern customization through cotransfer of aligned block copolymer features and an inorganic prepattern. As informed by a phenomenological model, deliberate process engineering is implemented to maintain global alignment of block copolymer features over arbitrarily shaped, 'masking' features incorporated into the chemical patterns. These hybrid chemical patterns with embedded customization information enable deterministic, complex two-dimensional nanoscale pattern customization through directed self-assembly.

  10. Synthesis and self-assembly of complex hollow materials

    KAUST Repository

    Zeng, Hua Chun

    2011-01-01

    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

  11. Time lapse microscopy of temperature control during self-assembly of 3D DNA crystals

    Science.gov (United States)

    Conn, Fiona W.; Jong, Michael Alexander; Tan, Andre; Tseng, Robert; Park, Eunice; Ohayon, Yoel P.; Sha, Ruojie; Mao, Chengde; Seeman, Nadrian C.

    2017-10-01

    DNA nanostructures are created by exploiting the high fidelity base-pairing interactions of double-stranded branched DNA molecules. These structures present a convenient medium for the self-assembly of macroscopic 3D crystals. In some self-assemblies in this system, crystals can be formed by lowering the temperature, and they can be dissolved by raising it. The ability to monitor the formation and melting of these crystals yields information that can be used to monitor crystal formation and growth. Here, we describe the development of an inexpensive tool that enables direct observation of the crystal growth process as a function of both time and temperature. Using the hanging-drop crystallization of the well-characterized 2-turn DNA tensegrity triangle motif for our model system, its response to temperature has been characterized visually.

  12. Fabrication and Operation of Microfluidic Hanging-Drop Networks.

    Science.gov (United States)

    Misun, Patrick M; Birchler, Axel K; Lang, Moritz; Hierlemann, Andreas; Frey, Olivier

    2018-01-01

    The hanging-drop network (HDN) is a technology platform based on a completely open microfluidic network at the bottom of an inverted, surface-patterned substrate. The platform is predominantly used for the formation, culturing, and interaction of self-assembled spherical microtissues (spheroids) under precisely controlled flow conditions. Here, we describe design, fabrication, and operation of microfluidic hanging-drop networks.

  13. Zinc-Triggered Hydrogelation of Self-assembled Small Molecules to Inhibit Bacterial Growth

    Science.gov (United States)

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

    2015-01-01

    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.

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

    DEFF Research Database (Denmark)

    Canning, John; Lindoy, Lachlan; Huyang, George

    2013-01-01

    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. Mesoscopic Self-Assembly: A Shift to Complexity

    Directory of Open Access Journals (Sweden)

    Massimo eMastrangeli

    2015-06-01

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

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

    OpenAIRE

    El Idrissi, Mohamed

    2017-01-01

    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...

  17. Directed self-assembled crystalline oligomer domains on graphene and graphite

    DEFF Research Database (Denmark)

    Balzer, Frank; Henrichsen, Henrik Hartmann; Klarskov, Mikkel Buster

    2014-01-01

    We observe the formation of thin films of fibre-like aggregates from the prototypical organic semiconductor molecule para-hexaphenylene (p-6P) on graphite thin flakes and on monolayer graphene. Using atomic force microscopy, scanning electron microscopy, x-ray diffraction, polarized fluorescence...... show that the graphene surface can be used as a growth substrate to direct the self-assembly of organic molecular thin films and nanofibres, both with and without lithographical processing....

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

    Science.gov (United States)

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

    2011-04-27

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

  19. Triazolobithiophene Light Absorbing Self-Assembled Monolayers: Synthesis and Mass Spectrometry Applications

    Directory of Open Access Journals (Sweden)

    Denis Séraphin

    2011-10-01

    Full Text Available The synthesis of five light absorbing triazolobithiophenic thiols, which were utilized for producing self-assembled monolayers (SAMs on gold surfaces, is presented. The monolayer formation was monitored by cyclic voltammetry, indicating excellent surface coverage. The new triazolobithiophenic compounds exhibited an absorption maximum around 340 nm, which is close to the emission wavelength of a standard nitrogen laser. Consequently these compounds could be used to aid ionization in laser desorption mass spectrometry (MS.

  20. Design strategies for self-assembly of discrete targets

    International Nuclear Information System (INIS)

    Madge, Jim; Miller, Mark A.

    2015-01-01

    Both biological and artificial self-assembly processes can take place by a range of different schemes, from the successive addition of identical building blocks to hierarchical sequences of intermediates, all the way to the fully addressable limit in which each component is unique. In this paper, we introduce an idealized model of cubic particles with patterned faces that allows self-assembly strategies to be compared and tested. We consider a simple octameric target, starting with the minimal requirements for successful self-assembly and comparing the benefits and limitations of more sophisticated hierarchical and addressable schemes. Simulations are performed using a hybrid dynamical Monte Carlo protocol that allows self-assembling clusters to rearrange internally while still providing Stokes-Einstein-like diffusion of aggregates of different sizes. Our simulations explicitly capture the thermodynamic, dynamic, and steric challenges typically faced by self-assembly processes, including competition between multiple partially completed structures. Self-assembly pathways are extracted from the simulation trajectories by a fully extendable scheme for identifying structural fragments, which are then assembled into history diagrams for successfully completed target structures. For the simple target, a one-component assembly scheme is most efficient and robust overall, but hierarchical and addressable strategies can have an advantage under some conditions if high yield is a priority

  1. In Situ Atomic Force Microscopy Studies on Nucleation and Self-Assembly of Biogenic and Bio-Inspired Materials

    Directory of Open Access Journals (Sweden)

    Cheng Zeng

    2017-08-01

    Full Text Available Through billions of years of evolution, nature has been able to create highly sophisticated and ordered structures in living systems, including cells, cellular components and viruses. The formation of these structures involves nucleation and self-assembly, which are fundamental physical processes associated with the formation of any ordered structure. It is important to understand how biogenic materials self-assemble into functional and highly ordered structures in order to determine the mechanisms of biological systems, as well as design and produce new classes of materials which are inspired by nature but equipped with better physiochemical properties for our purposes. An ideal tool for the study of nucleation and self-assembly is in situ atomic force microscopy (AFM, which has been widely used in this field and further developed for different applications in recent years. The main aim of this work is to review the latest contributions that have been reported on studies of nucleation and self-assembly of biogenic and bio-inspired materials using in situ AFM. We will address this topic by introducing the background of AFM, and discussing recent in situ AFM studies on nucleation and self-assembly of soft biogenic, soft bioinspired and hard materials.

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

    Science.gov (United States)

    Roy, Debmalya; Shastri, Babita; Mukhopadhyay, K

    2012-07-12

    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. Surface Mediated Self-Assembly of Amyloid Peptides

    Science.gov (United States)

    Fakhraai, Zahra

    2015-03-01

    Amyloid fibrils have been considered as causative agents in many neurodegenerative diseases, including Alzheimer's disease, Parkinson's disease, type II diabetes and amyloidosis. Amyloid fibrils form when proteins or peptides misfold into one dimensional crystals of stacked beta-sheets. In solution, amyloid fibrils form through a nucleation and growth mechanism. The rate limiting nucleation step requires a critical concentration much larger than those measured in physiological conditions. As such the exact origins of the seeds or oligomers that result in the formation of fully mature fibrils in the body remain topic intense studies. It has been suggested that surfaces and interfaces can enhance the fibrillization rate. However, studies of the mechanism and kinetics of the surface-mediated fibrillization are technologically challenging due to the small size of the oligomer and protofibril species. Using smart sample preparation technique to dry the samples after various incubation times we are able to study the kinetics of fibril formation both in solution and in the vicinity of various surfaces using high-resolution atomic force microscopy. These studies elucidate the role of surfaces in catalyzing amyloid peptide formation through a nucleation-free process. The nucleation free self-assembly is rapid and requires much smaller concentrations of peptides or proteins. We show that this process resembles diffusion limited aggregation and is governed by the peptide adhesion rate, two -dimensional diffusion of the peptides on the surface, and preferential interactions between the peptides. These studies suggest an alternative pathway for amyloid formation may exist, which could lead to new criteria for disease prevention and alternative therapies. Research was partially supported by a seed grant from the National Institute of Aging of the National Institutes of Health (NIH) under Award Number P30AG010124 (PI: John Trojanowski) and the University of Pennsylvania.

  4. Self-Assembly of Protein Nanostructures to Enhance Biosensor Sensitivity

    Science.gov (United States)

    Olsen, Bradley; Dong, Xuehui; Obermeyer, Allie

    The Langmuir adsorption isotherm predicts that the number of bound species on a surface at a given concentration will be directly proportional to the number of binding sites on the surface. Therefore, the number of binding events in a biosensor may be increased at a given analyte concentration if the surface density of binding domains is increased. Here, we demonstrate the formation of block copolymers where one block is a human IgG antibody or a nanobody and self-assemble these molecules into nanostructured films with a high density of binding sites. The type of nanostructure formed and the rate of transport through the protein-polymer layers are explored as a function of coil fraction of the protein-polymer conjugate block copolymers, showing optima for transport and assembly that depend upon the identity of the protein. For small enough analytes, binding to the antibodies and nanobodies is linear with film thickness, indicating that the entire film is accessible. Consistent with the enhanced number of binding sites and the prediction of the Langmuir isotherm, the films improve sensitivity by several orders of magnitude relative to chemisorbed protein layers used in current sensor designs. Current research is integrating this new material technology into prototype sensors. Work supported by the Air Force Office of Scientific Reesearch (AFOSR).

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

    Directory of Open Access Journals (Sweden)

    Tatiana N. Pashirova

    2017-02-01

    Full Text Available Over the last decade isoindigo derivatives have attracted much attention due to their high potential in pharmacy and in the chemistry of materials. In addition, isoindigo derivatives can be modified to form supramolecular structures with tunable morphologies for the use in drug delivery. Amphiphilic long-chain dialkylated isoindigos have the ability to form stable solid nanoparticles via a simple nanoprecipitation technique. Their self-assembly was investigated using tensiometry, dynamic light scattering, spectrophotometry, and fluorometry. The critical association concentrations and aggregate sizes were measured. The hydrophilic–lipophilic balance of alkylated isoindigo derivatives strongly influences aggregate morphology. In the case of short-chain dialkylated isoindigo derivatives, supramolecular polymers of 200 to 700 nm were formed. For long-chain dialkylated isoindigo derivatives, micellar aggregates of 100 to 200 nm were observed. Using micellar surfactant water-soluble forms of monosubstituted 1-hexadecylisoindigo as well as 1,1′-dimethylisoindigo were prepared for the first time. The formation of mixed micellar structures of different types in micellar anionic surfactant solutions (sodium dodecyl sulfate was determined. These findings are of practical importance and are of potential interest for the design of drug delivery systems and new nanomaterials.

  6. Fatigue crack propagation in self-assembling nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Klingler, Andreas; Wetzel, Bernd [Institute for Composite Materials (IVW GmbH) Technical University of Kaiserslautern, 67633 Kaiserslautern (Germany)

    2016-05-18

    Self-assembling block-copolymers allow the easy manufacturing of nanocomposites due to the thermodynamically driven in situ formation of nanosized phases in thermosetting resins during the curing process. Complex mechanical dispersion processes can be avoided. The current study investigates the effect of a block-copolymer on the fatigue crack propagation resistance of a cycloaliphatic amine cured epoxy resin. It was found that a small amount of MAM triblock-copolymer significantly increases the resistance to fatigue crack propagation of epoxy. Crack growth rate and the Paris law exponent for fatigue-crack growth were considerably reduced from m=15.5 of the neat epoxy to m=8.1 of the nanocomposite. To identify the related reinforcing and fracture mechanisms structural analyses of the fractured surfaces were performed by scanning electron microscope. Characteristic features were identified to be deformation, debonding and fracture of the nano-phases as well as crack pinning. However, the highest resistance against fatigue crack propagation was achieved in a bi-continuous microstructure that consisted of an epoxy-rich phase with embedded submicron sized MAM inclusions, and which was surrounded by a block-copolymer-rich phase that showed rupture and plastic deformation.

  7. Modeling the self-assembly of ordered nanoporous materials

    Energy Technology Data Exchange (ETDEWEB)

    Monson, Peter [Univ. of Massachusetts, Amherst, MA (United States); Auerbach, Scott [Univ. of Massachusetts, Amherst, MA (United States)

    2017-11-13

    This report describes progress on a collaborative project on the multiscale modeling of the assembly processes in the synthesis of nanoporous materials. Such materials are of enormous importance in modern technology with application in the chemical process industries, biomedicine and biotechnology as well as microelectronics. The project focuses on two important classes of materials: i) microporous crystalline materials, such as zeolites, and ii) ordered mesoporous materials. In the first case the pores are part of the crystalline structure, while in the second the structures are amorphous on the atomistic length scale but where surfactant templating gives rise to order on the length scale of 2 - 20 nm. We have developed a modeling framework that encompasses both these kinds of materials. Our models focus on the assembly of corner sharing silica tetrahedra in the presence of structure directing agents. We emphasize a balance between sufficient realism in the models and computational tractibility given the complex many-body phenomena. We use both on-lattice and off-lattice models and the primary computational tools are Monte Carlo simulations with sampling techniques and ensembles appropriate to specific situations. Our modeling approach is the first to capture silica polymerization, nanopore crystallization, and mesopore formation through computer-simulated self assembly.

  8. Fatigue crack propagation in self-assembling nanocomposites

    Science.gov (United States)

    Klingler, Andreas; Wetzel, Bernd

    2016-05-01

    Self-assembling block-copolymers allow the easy manufacturing of nanocomposites due to the thermodynamically driven in situ formation of nanosized phases in thermosetting resins during the curing process. Complex mechanical dispersion processes can be avoided. The current study investigates the effect of a block-copolymer on the fatigue crack propagation resistance of a cycloaliphatic amine cured epoxy resin. It was found that a small amount of MAM triblock-copolymer significantly increases the resistance to fatigue crack propagation of epoxy. Crack growth rate and the Paris law exponent for fatigue-crack growth were considerably reduced from m=15.5 of the neat epoxy to m=8.1 of the nanocomposite. To identify the related reinforcing and fracture mechanisms structural analyses of the fractured surfaces were performed by scanning electron microscope. Characteristic features were identified to be deformation, debonding and fracture of the nano-phases as well as crack pinning. However, the highest resistance against fatigue crack propagation was achieved in a bi-continuous microstructure that consisted of an epoxy-rich phase with embedded submicron sized MAM inclusions, and which was surrounded by a block-copolymer-rich phase that showed rupture and plastic deformation.

  9. Fatigue crack propagation in self-assembling nanocomposites

    International Nuclear Information System (INIS)

    Klingler, Andreas; Wetzel, Bernd

    2016-01-01

    Self-assembling block-copolymers allow the easy manufacturing of nanocomposites due to the thermodynamically driven in situ formation of nanosized phases in thermosetting resins during the curing process. Complex mechanical dispersion processes can be avoided. The current study investigates the effect of a block-copolymer on the fatigue crack propagation resistance of a cycloaliphatic amine cured epoxy resin. It was found that a small amount of MAM triblock-copolymer significantly increases the resistance to fatigue crack propagation of epoxy. Crack growth rate and the Paris law exponent for fatigue-crack growth were considerably reduced from m=15.5 of the neat epoxy to m=8.1 of the nanocomposite. To identify the related reinforcing and fracture mechanisms structural analyses of the fractured surfaces were performed by scanning electron microscope. Characteristic features were identified to be deformation, debonding and fracture of the nano-phases as well as crack pinning. However, the highest resistance against fatigue crack propagation was achieved in a bi-continuous microstructure that consisted of an epoxy-rich phase with embedded submicron sized MAM inclusions, and which was surrounded by a block-copolymer-rich phase that showed rupture and plastic deformation.

  10. Anisotropic Self-Assembly of Organic–Inorganic Hybrid Microtoroids

    KAUST Repository

    Al-Rehili, Safa’a

    2016-10-24

    Toroidal structures based on self-assembly of predesigned building blocks are well-established in the literature, but spontaneous self-organization to prepare such structures has not been reported to date. Here, organic–inorganic hybrid microtoroids synthesized by simultaneous coordination-driven assembly of amphiphilic molecules and hydrophilic polymers are reported. Mixing amphiphilic molecules with iron(III) chloride and hydrophilic polymers in water leads, within minutes, to the formation of starlike nanostructures. A spontaneous self-organization of these nanostructures is then triggered to form stable hybrid microtoroids. Interestingly, the toroids exhibit anisotropic hierarchical growth, giving rise to a layered toroidal framework. These microstructures are mechanically robust and can act as templates to host metallic nanoparticles such as gold and silver. Understanding the nature of spontaneous assembly driven by coordination multiple non-covalent interactions can help explain the well-ordered complexity of many biological organisms in addition to expanding the available tools to mimic such structures at a molecular level.

  11. The Self-Assembly of Nanogold for Optical Metamaterials

    Science.gov (United States)

    Nidetz, Robert A.

    2011-12-01

    Optical metamaterials are an emerging field that enables manipulation of light like never before. Producing optical metamaterials requires sub-wavelength building blocks. The focus here was to develop methods to produce building blocks for metamaterials from nanogold. Electron-beam lithography was used to define an aminosilane patterned chemical template in order to electrostatically self-assemble citrate-capped gold nanoparticles. Equilibrium self-assembly was achieved in 20 minutes by immersing chemical templates into gold nanoparticle solutions. The number of nanoparticles that self-assembled on an aminosilane dot was controlled by manipulating the diameters of the dots and nanoparticles. Adding salt to the nanoparticle solution enabled the nanoparticles to self-assemble in greater numbers on the same sized dot. However, the preparation of the nanoparticle solution containing salt was sensitive to spikes in the salt concentration which led to aggregation of the nanoparticles and non-specific deposition. Gold nanorods were also electrostatically self-assembled. Polyelectrolyte-coated gold nanorods were patterned with limited success. A polyelectrolyte chemical template also patterned gold nanorods, but the gold nanorods preferred to pattern on the edges of the pattern. Ligand-exchanged gold nanorods displayed the best self-assembly, but suffered from slow kinetics. Self-assembled gold nanoparticles were cross-linked with poly(diallyldimethylammonium chloride). The poly(diallyldimethylammonium chloride) allowed additional nanoparticles to pattern on top of the already patterned nanoparticles. Cross-linked nanoparticles were lifted-off of the substrate by sonication in a sodium hydroxide solution. The presence of van der Waals forces and/or amine bonding prevent the nanogold from lifting-off without sonication. A good-solvent evaporation process was used to self-assemble poly(styrene) coated gold nanoparticles into spherical microbead assemblies. The use of larger

  12. Continuum Modeling of Biological Network Formation

    KAUST Repository

    Albi, Giacomo; Burger, Martin; Haskovec, Jan; Markowich, Peter A.; Schlottbom, Matthias

    2017-01-01

    We present an overview of recent analytical and numerical results for the elliptic–parabolic system of partial differential equations proposed by Hu and Cai, which models the formation of biological transportation networks. The model describes

  13. Fluid-Mediated Stochastic Self-Assembly at Centimetric and Sub-Millimetric Scales: Design, Modeling, and Control

    Directory of Open Access Journals (Sweden)

    Bahar Haghighat

    2016-08-01

    Full Text Available Stochastic self-assembly provides promising means for building micro-/nano-structures with a variety of properties and functionalities. Numerous studies have been conducted on the control and modeling of the process in engineered self-assembling systems constituted of modules with varied capabilities ranging from completely reactive nano-/micro-particles to intelligent miniaturized robots. Depending on the capabilities of the constituting modules, different approaches have been utilized for controlling and modeling these systems. In the quest of a unifying control and modeling framework and within the broader perspective of investigating how stochastic control strategies can be adapted from the centimeter-scale down to the (sub-millimeter-scale, as well as from mechatronic to MEMS-based technology, this work presents the outcomes of our research on self-assembly during the past few years. As the first step, we leverage an experimental platform to study self-assembly of water-floating passive modules at the centimeter scale. A dedicated computational framework is developed for real-time tracking, modeling and control of the formation of specific structures. Using a similar approach, we then demonstrate controlled self-assembly of microparticles into clusters of a preset dimension in a microfluidic chamber, where the control loop is closed again through real-time tracking customized for a much faster system dynamics. Finally, with the aim of distributing the intelligence and realizing programmable self-assembly, we present a novel experimental system for fluid-mediated programmable stochastic self-assembly of active modules at the centimeter scale. The system is built around the water-floating 3-cm-sized Lily robots specifically designed to be operative in large swarms and allows for exploring the whole range of fully-centralized to fully-distributed control strategies. The outcomes of our research efforts extend the state-of-the-art methodologies

  14. Self-assembled tethered bimolecular lipid membranes.

    Science.gov (United States)

    Sinner, Eva-Kathrin; Ritz, Sandra; Naumann, Renate; Schiller, Stefan; Knoll, Wolfgang

    2009-01-01

    This chapter describes some of the strategies developed in our group for designing, constructing and structurally and functionally characterizing tethered bimolecular lipid membranes (tBLM). We introduce this platform as a novel model membrane system that complements the existing ones, for example, Langmuir monolayers, vesicular liposomal dispersions and bimolecular ("black") lipid membranes. Moreover, it offers the additional advantage of allowing for studies of the influence of membrane structure and order on the function of integral proteins, for example, on how the composition and organization of lipids in a mixed membrane influence the ion translocation activity of integral channel proteins. The first strategy that we introduce concerns the preparation of tethered monolayers by the self-assembly of telechelics. Their molecular architecture with a headgroup, a spacer unit (the "tether") and the amphiphile that mimics the lipid molecule allows them to bind specifically to the solid support thus forming the proximal layer of the final architecture. After fusion of vesicles that could contain reconstituted proteins from a liposomal dispersion in contact to this monolayer the tethered bimolecular lipid membrane is obtained. This can then be characterized by a broad range of surface analytical techniques, including surface plasmon spectroscopies, the quartz crystal microbalance, fluorescence and IR spectroscopies, and electrochemical techniques, to mention a few. It is shown that this concept allows for the construction of tethered lipid bilayers with outstanding electrical properties including resistivities in excess of 10 MOmega cm2. A modified strategy uses the assembly of peptides as spacers that couple covalently via their engineered sulfhydryl or lipoic acid groups at the N-terminus to the employed gold substrate, while their C-terminus is being activated afterward for the coupling of, for example, dimyristoylphosphatidylethanol amine (DMPE) lipid molecules

  15. Spectro-microscopic study of the formation of supramolecular networks

    Science.gov (United States)

    Sadowski, Jerzy T.

    2015-03-01

    Metal-organic frameworks (MOFs) are emerging as a new class of materials for CO2 capture. There are many fundamental questions, including the optimum pore size and arrangement of the molecules in the structure to achieve highest CO2 uptake. As only the surface is of interest for potential applications such as heterogeneous catalysis, nano-templating, and sensing, 2D analogs of MOFs can serve as good model systems. Utilizing capabilities of LEEM/PEEM for non-destructive interrogation of the real-time molecular self-assembly, we investigated supramolecular systems based on carboxylic acid-metal complexes, such as trimesic and mellitic acid, doped with transition metals. Such 2D networks act as host systems for transition-metal phthalocyanines (MPc; M = Fe, Ti, Sc) and the electrostatic interactions of CO2 molecules with transition metal ions, can be tuned by controlling the type of TM ion and the size of the pore in the host network. The understanding of directed self-assembly by controlling the molecule-substrate interaction can enable us to engineer the pore size and density, and thus tune the host's chemical activity. Research carried out at the Center for Functional Nanomaterials and National Synchrotron Light Source, Brookhaven National Laboratory, which are supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10.

  16. Directed networks, allocation properties and hierarchy formation

    NARCIS (Netherlands)

    Slikker, M.; Gilles, R.P.; Norde, H.W.; Tijs, S.H.

    2005-01-01

    We investigate properties for allocation rules on directed communication networks and the formation of such networks under these payoff properties. We study allocation rules satisfying two appealing properties, Component Efficiency (CE) and the Hierarchical Payoff Property (HPP). We show that such

  17. Novel alternating polymer adsorption/surface activation self-assembled film based on hydrogen bond

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Yongjun; Yang Shuguang; Guan Ying; Miao Xiaopeng; Cao Weixiao; Xu Jian

    2003-08-01

    By combining hydrogen bonding layer-by-layer self-assembly and the stepwise chemisorption method, a new alternating polymer adsorption/surface activation self-assembly method was developed. First a layer of diphenylamine-4-diazonium-formaldehyde resin (diazo resin or DR) is deposited on a substrate. In the following surface activation step, the diazonium groups on the surface couple with resorcin in the outside solution. The deposition of another layer of DR is feasible due to the formation of hydrogen bond between the diazonium group of DR and the hydroxy group of the resorcin moieties. The resulting film is photosensitive. After UV irradiation, the film becomes very stable towards polar organic solvents.

  18. Block copolymer self-assembly-directed synthesis of mesoporous gyroidal superconductors.

    Science.gov (United States)

    Robbins, Spencer W; Beaucage, Peter A; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G; Sethna, James P; DiSalvo, Francis J; Gruner, Sol M; Van Dover, Robert B; Wiesner, Ulrich

    2016-01-01

    Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly-directed sol-gel-derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (T c) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (J c) of 440 A cm(-2) at 100 Oe and 2.5 K. We expect block copolymer self-assembly-directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies.

  19. Self-assembling chimeric polypeptide-doxorubicin conjugate nanoparticles that abolish tumours after a single injection

    Science.gov (United States)

    Andrew Mackay, J.; Chen, Mingnan; McDaniel, Jonathan R.; Liu, Wenge; Simnick, Andrew J.; Chilkoti, Ashutosh

    2009-12-01

    New strategies to self-assemble biocompatible materials into nanoscale, drug-loaded packages with improved therapeutic efficacy are needed for nanomedicine. To address this need, we developed artificial recombinant chimeric polypeptides (CPs) that spontaneously self-assemble into sub-100-nm-sized, near-monodisperse nanoparticles on conjugation of diverse hydrophobic molecules, including chemotherapeutics. These CPs consist of a biodegradable polypeptide that is attached to a short Cys-rich segment. Covalent modification of the Cys residues with a structurally diverse set of hydrophobic small molecules, including chemotherapeutics, leads to spontaneous formation of nanoparticles over a range of CP compositions and molecular weights. When used to deliver chemotherapeutics to a murine cancer model, CP nanoparticles have a fourfold higher maximum tolerated dose than free drug, and induce nearly complete tumour regression after a single dose. This simple strategy can promote co-assembly of drugs, imaging agents and targeting moieties into multifunctional nanomedicines.

  20. Biomineralization of a Self-assembled, Soft-Matrix Precursor: Enamel

    Science.gov (United States)

    Snead, Malcolm L.

    2015-04-01

    Enamel is the bioceramic covering of teeth, a composite tissue composed of hierarchical organized hydroxyapatite crystallites fabricated by cells under physiologic pH and temperature. Enamel material properties resist wear and fracture to serve a lifetime of chewing. Understanding the cellular and molecular mechanisms for enamel formation may allow a biology-inspired approach to material fabrication based on self-assembling proteins that control form and function. A genetic understanding of human diseases exposes insight from nature's errors by exposing critical fabrication events that can be validated experimentally and duplicated in mice using genetic engineering to phenocopy the human disease so that it can be explored in detail. This approach led to an assessment of amelogenin protein self-assembly that, when altered, disrupts fabrication of the soft enamel protein matrix. A misassembled protein matrix precursor results in loss of cell-to-matrix contacts essential to fabrication and mineralization.

  1. Exploring single chain amphiphile self-assembly and their possible roles in light transduction

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain

    2011-01-01

    Self-assembled structures of single-chain amphiphiles have been used as hosts for biochemical, and chemical reactions. Their use as models for protocells (i.e., precursors to the first biological cells) has been extensively researched by various groups because the availability of single chain......: the medium composition in terms of ionic strengths and the medium physical parameters, such as temperature, significantly influence the formation of structures, as well as their subsequent stability. In addition, membranes composed of a single amphiphile type seem to be implausible as no potential amphiphile...... source studied to date can supply one single type of amphiphile at concentrations conducive to self-assembly. Mixtures of single-chain amphiphiles were therefore proposed to better model primitive membranes and potentially enhance their structural integrity1-3. Recently, we have established that complex...

  2. Influence of topographically patterned angled guidelines on directed self-assembly of block copolymers

    Science.gov (United States)

    Rebello, Nathan; Sethuraman, Vaidyanathan; Blachut, Gregory; Ellison, Christopher J.; Willson, C. Grant; Ganesan, Venkat

    2017-11-01

    Single chain in mean-field Monte Carlo simulations were employed to study the self-assembly of block copolymers (BCP) in thin films that use trapezoidal guidelines to direct the orientation and alignment of lamellar patterns. The present study explored the influence of sidewall interactions and geometry of the trapezoidal guidelines on the self-assembly of perpendicularly oriented lamellar morphologies. When both the sidewall and the top surface exhibit preferential interactions to the same block of the BCP, trapezoidal guidelines with intermediate taper angles were found to result in less defective perpendicularly orientated morphologies. Similarly, when the sidewall and top surface are preferential to distinct blocks of the BCP, intermediate tapering angles were found to be optimal in promoting defect free structures. Such results are rationalized based on the energetics arising in the formation of perpendicularly oriented lamella on patterned substrates.

  3. Self-assembled bilayers based on organothiol and organotrimethoxysilane on zinc platform

    International Nuclear Information System (INIS)

    Berger, Francois; Delhalle, Joseph; Mekhalif, Zineb

    2010-01-01

    This study describes the formation of a bilayer system developed on electrodeposited zinc. In a first step, a monolayer of 11-mercapto-1-undecanol is grafted on zinc, optimization of the conditions of elaboration have been performed. In a second step, organotrimethoxysilane have been grafted on the zinc modified with the hydroxyl terminated self-assembled monolayer (SAM) to finalize the bilayer system. X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS) and contact angle measurements are used to characterize each step of modification. An electrochemical evaluation of the different created systems is carried out by linear sweep voltammetry (LSV), cyclic voltammetry (CV) and scanning vibrating electrode technique (SVET). The impact of the modification of zinc using SAM and self-assembled bilayer (SAB) on the electrochemical activity of the surface is highlighted.

  4. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    Science.gov (United States)

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

  5. Designing spatial correlation of quantum dots: towards self-assembled three-dimensional structures

    International Nuclear Information System (INIS)

    Bortoleto, J R R; Zelcovit, J G; Gutierrez, H R; Bettini, J; Cotta, M A

    2008-01-01

    Buried two-dimensional arrays of InP dots were used as a template for the lateral ordering of self-assembled quantum dots. The template strain field can laterally organize compressive (InAs) as well as tensile (GaP) self-assembled nanostructures in a highly ordered square lattice. High-resolution transmission electron microscopy measurements show that the InAs dots are vertically correlated to the InP template, while the GaP dots are vertically anti-correlated, nucleating in the position between two buried InP dots. Finite InP dot size effects are observed to originate InAs clustering but do not affect GaP dot nucleation. The possibility of bilayer formation with different vertical correlations suggests a new path for obtaining three-dimensional pseudocrystals

  6. New Strategies for Constructing Polymeric Micelles and Hollow Spheres Via Self-Assembly

    Institute of Scientific and Technical Information of China (English)

    Ming Jiang

    2005-01-01

    @@ 1Introduction In recent years, self-assembly of block copolymers leading to micelles in selective solvents, which dissolve only one of the blocks, has developed rapidly because the micelles are very strong candidates for potential applications in advanced technologies. The micelles usually have core-shell structure which are connected by covalent bonds. Based on our long-term research on interpolymer complexation due to hydrogen bonding, where we noticed that the complexation often led to the formation of irregular aggregates, we succeeded recently in developing a series of new approaches to polymeric micelles and hollow spheres via specific intermolecular interactions. As in these approaches, a variety of polymers with interacting groups i.e. homopolymers, random copolymers, graft copolymers as well as low mass compounds (LMC), can be used as building blocks, our research strategies have substantially extended the field of self-assembly.

  7. Organic molecules deposited on graphene: A computational investigation of self-assembly and electronic structure

    International Nuclear Information System (INIS)

    Oliveira, I. S. S. de; Miwa, R. H.

    2015-01-01

    We use ab initio simulations to investigate the adsorption and the self-assembly processes of tetracyanoquinodimethane (TCNQ), tetrafluoro-tetracyanoquinodimethane (F4-TCNQ), and tetrasodium 1,3,6,8-pyrenetetrasulfonic acid (TPA) on the graphene surface. We find that there are no chemical bonds at the molecule–graphene interface, even at the presence of grain boundaries on the graphene surface. The molecules bond to graphene through van der Waals interactions. In addition to the molecule–graphene interaction, we performed a detailed study of the role played by the (lateral) molecule–molecule interaction in the formation of the, experimentally verified, self-assembled layers of TCNQ and TPA on graphene. Regarding the electronic properties, we calculate the electronic charge transfer from the graphene sheet to the TCNQ and F4-TCNQ molecules, leading to a p-doping of graphene. Meanwhile, such charge transfer is reduced by an order of magnitude for TPA molecules on graphene. In this case, it is not expected a significant doping process upon the formation of self-assembled layer of TPA molecules on the graphene sheet

  8. Surface self-assembled hybrid nanocomposites with electroactive nanoparticles and enzymes confined in a polymer matrix for controlled electrocatalysis

    DEFF Research Database (Denmark)

    Zhu, Nan; Ulstrup, Jens; Chi, Qijin

    2015-01-01

    A three-dimensional network of highly branched poly(ethyleneimine) (PEI) is designed and synthesized on gold electrode surfaces. A self-assembled monolayer (SAM) of dithiobis(succinimidyl propionate) (DTSP) on a gold electrode was first prepared, which is confirmed by the reductive desorption of ...

  9. Temperature-dependent self-assembly and rheological behavior of a thermoreversible pmma-P n BA-PMMA triblock copolymer gel

    Energy Technology Data Exchange (ETDEWEB)

    Zabet, Mahla; Mishra, Satish; Boy, Ramiz; Walters, Keisha B.; Naskar, Amit K.; Kundu, Santanu (UO); (ORNL); (MSSU)

    2017-03-25

    Self-assembly and mechanical properties of triblock copolymers in a mid-block selective solvent are of interest in many applications. Herein, we report physical assembly of an ABA triblock copolymer, [PMMA–PnBA–PMMA] in two different mid-block selective solvents, n-butanol and 2-ethyl-1-hexanol. Gel formation resulting from end-block associations and the corresponding changes in mechanical properties have been investigated over a temperature range of -80 °C to 60 °C, from near the solvent melting points to above the gelation temperature. Shear-rheometry, thermal analysis, and small-angle neutron scattering data reveal formation and transition of structure in these systems from a liquid state to a gel state to a percolated cluster network with decrease in temperature. The aggregated PMMA end-blocks display a glass transition temperature. Our results provide new understanding into the structural changes of a self-assembled triblock copolymer gel over a large length scale and wide temperature range.

  10. Limited farsightedness in network formation

    NARCIS (Netherlands)

    Morbitzer, D.T.

    2013-01-01

    Social relationships can be beneficial for various reasons. For example, people find jobs through their social contacts, and researchers connect with each other to cooperate on projects. Within these networks of relations, actors maintain different positions, which can influence their outcomes.

  11. Self-assembly strategies for the synthesis of functional nanostructured materials

    International Nuclear Information System (INIS)

    Perego, M.; Seguini, G.

    2016-01-01

    Self-assembly is the autonomous organization of components into patterns or structures without human intervention. This is the approach followed by nature to generate living cells and represents one of the practical strategies to fabricate ensembles of nanostructures. In static self-assembly the formation of ordered structures could require energy but once formed the structures are stable. The introduction of additional regular features in the environment could be used to template the self-assembly guiding the organization of the components and determining the final structure they form. In this regard self-assembly of block copolymers represents a potent platform for fundamental studies at the nanoscale and for application-driven investigation as a tool to fabricate functional nanostructured materials. Block copolymers can hierarchically assemble into chemically distinct domains with size and periodicity on the order of 10 nm or below, offering a potentially inexpensive route to generate large-area nanostructured materials. The final structure characteristics of these materials are dictated by the properties of the elementary block copolymers, like chain length, volume fraction or degree of block incompatibility. Modern synthetic chemistry offers the possibility to design these macromolecules with very specific length scales and geometries, directly embodying in the block copolymers the code that drives their self- assembling process. The understanding of the kinetics and thermodynamics of the block copolymer selfassembly process in the bulk phase as well as in thin films represents a fundamental prerequisite toward the exploitation of these materials. Incorporating block copolymer into device fabrication procedures or directly into devices, as active elements, will lead to the development of a new generation of devices fabricated using the fundamental law of nature to our advantage in order to minimize cost and power consumption in the fabrication process

  12. Self-assembling peptide nanofiber hydrogels in tissue engineering and regenerative medicine: Progress, design guidelines, and applications.

    Science.gov (United States)

    Koutsopoulos, Sotirios

    2016-04-01

    Until the mid-1980s, mainly biologists were conducting peptide research. This changed with discoveries that opened new paths of research involving the use of peptides in bioengineering, biotechnology, biomedicine, nanotechnology, and bioelectronics. Peptide engineering and rational design of novel peptide sequences with unique and tailor-made properties further expanded the field. The discovery of short self-assembling peptides, which upon association form well-defined supramolecular architectures, created new and exciting areas of research. Depending on the amino acid sequence, the pH, and the type of the electrolyte in the medium, peptide self-assembly leads to the formation of nanofibers, which are further organized to form a hydrogel. In this review, the application of ionic complementary peptides which self-assemble to form nanofiber hydrogels for tissue engineering and regenerative medicine will be discussed through a selective presentation of the most important work performed during the last 25 years. © 2016 Wiley Periodicals, Inc.

  13. Three-Dimensional Self-Assembled Photonic Crystal Waveguide

    Science.gov (United States)

    Baek, Kang-Hyun

    Photonic crystals (PCs), two- or three-dimensionally periodic, artificial, and dielectric structures, have a specific forbidden band for electromagnetic waves, referred to as photonic bandgap (PBG). The PBG is analogous to the electronic bandgap in natural crystal structures with periodic atomic arrangement. A well-defined and embedded planar, line, or point defect within the PCs causes a break in its structural periodicity, and introduces a state in the PBG for light localization. It offers various applications in integrated optics and photonics including optical filters, sharp bending light guides and very low threshold lasers. Using nanofabrication processes, PCs of the 2-D slab-type and 3-D layer-by-layer structures have been investigated widely. Alternatively, simple and low-cost self-assembled PCs with full 3-D PBG, inverse opals, have been suggested. A template with face centered cubic closed packed structure, opal, may initially be built by self-assembly of colloidal spheres, and is selectively removed after infiltrating high refractive index materials into the interstitials of spheres. In this dissertation, the optical waveguides utilizing the 3-D self-assembled PCs are discussed. The waveguides were fabricated by microfabrication technology. For high-quality colloidal silica spheres and PCs, reliable synthesis, self-assembly, and characterization techniques were developed. Its theoretical and experimental demonstrations are provided and correlated. They suggest that the self-assembled PCs with PBG are feasible for the applications in integrated optics and photonics.

  14. Physical principles for DNA tile self-assembly.

    Science.gov (United States)

    Evans, Constantine G; Winfree, Erik

    2017-06-19

    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.

  15. pH-dependent and pH-independent self-assembling behavior of surfactant-like peptides

    DEFF Research Database (Denmark)

    Gurevich, Leonid; Fojan, Peter

    2012-01-01

    formation of ordered aggregates with well-defined secondary structure from short unstructured peptides and provide a simple system where factors responsible for self-assembly can be singled out and studied one by one. The ability to control the shape and structure of peptide aggregates can provide basis...

  16. Self-Assembly of Ureido-Pyrimidinone Dimers into One-Dimensional Stacks by Lateral Hydrogen Bonding

    NARCIS (Netherlands)

    Nieuwenhuizen, Marko M.L.; de Greef, Tom F.A.; van der Bruggen, Rob L.J.; Paulusse, Jos Marie Johannes; Appel, Wilco P.J.; Smulders, Maarten M.J.; Sijbesma, Rint P.; Meijer, E.W.

    2010-01-01

    Ureido-pyrimidinone (UPy) dimers substituted with an additional urea functionality self-assemble into one-dimensional stacks in various solvents through lateral non-covalent interactions. 1H NMR and DOSY studies in CDCl3 suggest the formation of short stacks (<10), whereas temperature-dependent

  17. Self-Assembly of Diblock Molecular Polymer Brushes in the Spherical Confinement of Nanoemulsion Droplets.

    Science.gov (United States)

    Steinhaus, Andrea; Pelras, Théophile; Chakroun, Ramzi; Gröschel, André H; Müllner, Markus

    2018-05-02

    Understanding the self-assembly behavior of polymers of various topologies is key to a reliable design of functional polymer materials. Self-assembly under confinement conditions emerges as a versatile avenue to design polymer particles with complex internal morphologies while simultaneously facilitating scale-up. However, only linear block copolymers have been studied to date, despite the increasing control over macromolecule composition and architecture available. This study extends the investigation of polymer self-assembly in confinement from regular diblock copolymers to diblock molecular polymer brushes (MPBs). Block-type MPBs with polystyrene (PS) and polylactide (PLA) compartments of different sizes are incorporated into surfactant-stabilized oil-in-water (chloroform/water) emulsions. The increasing confinement in the nanoemulsion droplets during solvent evaporation directs the MPBs to form solid nano/microparticles. Microscopy studies reveal an intricate internal particle structure, including interpenetrating networks and axially stacked lamellae of PS and PLA, depending on the PS/PLA ratio of the brushes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Loo, Yihua; Hauser, Charlotte A E

    2016-01-01

    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)

  19. Regulating DNA Self-assembly by DNA-Surface Interactions.

    Science.gov (United States)

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

    2017-12-14

    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.

  20. Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports

    International Nuclear Information System (INIS)

    Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandra K.; Birnbaum, Jerome C.; Wu, Hong; Kemner, K. M.; Kelly, Shelley

    2005-01-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents, whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometallate anions and radionuclides. Details addressing the design, synthesis and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental clean-up necessary after 40 years of weapons grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented

  1. Network Configuration Analysis for Formation Flying Satellites

    Science.gov (United States)

    Knoblock, Eric J.; Wallett, Thomas M.; Konangi, Vijay K.; Bhasin, Kul B.

    2001-01-01

    The performance of two networks to support autonomous multi-spacecraft formation flying systems is presented. Both systems are comprised of a ten-satellite formation, with one of the satellites designated as the central or 'mother ship.' All data is routed through the mother ship to the terrestrial network. The first system uses a TCP/EP over ATM protocol architecture within the formation, and the second system uses the IEEE 802.11 protocol architecture within the formation. The simulations consist of file transfers using either the File Transfer Protocol (FTP) or the Simple Automatic File Exchange (SAFE) Protocol. The results compare the IP queuing delay, IP queue size and IP processing delay at the mother ship as well as end-to-end delay for both systems. In all cases, using IEEE 802.11 within the formation yields less delay. Also, the throughput exhibited by SAFE is better than FTP.

  2. Hydrazine-mediated construction of nanocrystal self-assembly materials.

    Science.gov (United States)

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

    2014-10-28

    Self-assembly is the basic feature of supramolecular chemistry, which permits to integrate and enhance the functionalities of nano-objects. However, the conversion of self-assembled structures to practical materials is still laborious. In this work, on the basis of studying one-pot synthesis, spontaneous assembly, and in situ polymerization of aqueous semiconductor nanocrystals (NCs), NC self-assembly materials are produced and applied to design high performance white light-emitting diode (WLED). In producing self-assembly materials, the additive hydrazine (N2H4) is curial, which acts as the promoter to achieve room-temperature synthesis of aqueous NCs by favoring a reaction-controlled growth, as the polyelectrolyte to weaken inter-NC electrostatic repulsion and therewith facilitate the one-dimensional self-assembly, and in particular as the bifunctional monomers to polymerize with mercapto carboxylic acid-modified NCs via in situ amidation reaction. This strategy is versatile for mercapto carboxylic acid-modified aqueous NCs, for example CdS, CdSe, CdTe, CdSe(x)Te(1-x), and Cd(y)Hg(1-y)Te. Because of the multisite modification with carboxyl, the NCs act as macromonomers, thus producing cross-linked self-assembly materials with excellent thermal, solvent, and photostability. The assembled NCs preserve strong luminescence and avoid unpredictable fluorescent resonance energy transfer, the main problem in design WLED from multiple NC components. These advantages allow the fabrication of NC-based WLED with high color rendering index (86), high luminous efficacy (41 lm/W), and controllable color temperature.

  3. Micelles versus Ribbons: How Congeners Drive the Self-Assembly of Acidic Sophorolipid Biosurfactants.

    Science.gov (United States)

    Dhasaiyan, Prabhu; Le Griel, Patrick; Roelants, Sophie; Redant, Emile; Van Bogaert, Inge N A; Prevost, Sylvain; Prasad, B L V; Baccile, Niki

    2017-03-17

    Sophorolipids (SLs), a class of microbially derived biosurfactants, are reported by different research groups to have different self-assembled structures (either micelles or giant ribbons) under the same conditions. Here we explore the reasons behind these contradictory results and attribute these differences to the role of specific congeners that are present in minute quantities. We show that a sample composed of a majority of oleic acid (C18:1) sophorolipid in the presence of only 0.5 % (or more) of congeners with stearic acid (C18:0) or linoleic acid (C18:2) results in the formation of micelles that are stable over long periods of time. Conversely, the presence of only 10 to 15 % of congeners with a stearic acid chain gives fibrillar structures instead of micelles. To study the mechanisms responsible, oleic acid SLs devoid of any other congeners were prepared. Very interestingly, this sample can self-assemble into either micelles or fibers depending on minute modifications to the self-assembly conditions. The findings are supported by light scattering, small-angle X-ray scattering, transmission electron microscopy under cryogenic conditions, high-pressure liquid chromatography, and NMR spectroscopy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Disassembly of Bacterial Biofilms by the Self-Assembled Glycolipids Derived from Renewable Resources.

    Science.gov (United States)

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

    2017-11-22

    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.

  5. Lipid-bilayer-assisted two-dimensional self-assembly of DNA origami nanostructures

    Science.gov (United States)

    Endo, Masayuki; Sugiyama, Hiroshi

    2015-01-01

    Self-assembly is a ubiquitous approach to the design and fabrication of novel supermolecular architectures. Here we report a strategy termed ‘lipid-bilayer-assisted self-assembly' that is used to assemble DNA origami nanostructures into two-dimensional lattices. DNA origami structures are electrostatically adsorbed onto a mica-supported zwitterionic lipid bilayer in the presence of divalent cations. We demonstrate that the bilayer-adsorbed origami units are mobile on the surface and self-assembled into large micrometre-sized lattices in their lateral dimensions. Using high-speed atomic force microscopy imaging, a variety of dynamic processes involved in the formation of the lattice, such as fusion, reorganization and defect filling, are successfully visualized. The surface modifiability of the assembled lattice is also demonstrated by in situ decoration with streptavidin molecules. Our approach provides a new strategy for preparing versatile scaffolds for nanofabrication and paves the way for organizing functional nanodevices in a micrometer space. PMID:26310995

  6. Self-assembly of diphenylalanine backbone homologues and their combination with functionalized carbon nanotubes.

    Science.gov (United States)

    Dinesh, Bhimareddy; Squillaci, Marco A; Ménard-Moyon, Cécilia; Samorì, Paolo; Bianco, Alberto

    2015-10-14

    The integration of carbon nanotubes (CNTs) into organized nanostructures is of great interest for applications in materials science and biomedicine. In this work we studied the self-assembly of β and γ homologues of diphenylalanine peptides under different solvent and pH conditions. We aimed to investigate the role of peptide backbone in tuning the formation of different types of nanostructures alone or in combination with carbon nanotubes. In spite of having the same side chain, β and γ peptides formed distinctively different nanofibers, a clear indication of the role played by the backbone homologation on the self-assembly. The variation of the pH allowed to transform the nanofibers into spherical structures. Moreover, the co-assembly of β and γ peptides with carbon nanotubes covalently functionalized with the same peptide generated unique dendritic assemblies. This comparative study on self-assembly using diphenylalanine backbone homologues and of the co-assembly with CNT covalent conjugates is the first example exploring the capacity of β and γ peptides to adopt precise nanostructures, particularly in combination with carbon nanotubes. The dendritic organization obtained by mixing carbon nanotubes and peptides might find interesting applications in tissue engineering and neuronal interfacing.

  7. Controllable self-assembly of sodium caseinate with a zwitterionic vitamin-derived bolaamphiphile.

    Science.gov (United States)

    Sun, Li-Hui; Sun, Yu-Long; Yang, Li-Jun; Zhang, Jian; Chen, Zhong-Xiu

    2013-11-06

    The control of self-assembly of sodium caseinate (SC) including the formation of mixed layers, microspheres, or nanoparticles is highly relevant to the microstructure of food and the design of promising drug delivery systems. In this paper, we designed a structure-switchable zwitterionic bolaamphiphile, 1,12-diaminododecanediorotate (DDO), from orotic acid, which has special binding sites and can guide the self-assembly of SC. Complexation between SC and DDO was investigated using dynamic light scattering, transmission electron microscopy, differential scanning calorimetry, and fluorescence spectra measurements. Monomeric DDO was bound to the negatively charged sites on the SC micelle and made the structure of SC more compact with decreased electrostatic repulsion between the head groups. Vesicular DDO led to reassociation of vesicles with enlarged size via preferable hydrophobic interactions. Moreover, the aggregation between SC and DDO was found to be temperature-dependent and reversible. This research provides an effective way to control the reversible self-assembly of SC by the zwitterionic vitamin-derived bolaamphiphile.

  8. Enhancing Self-Assembly in Cellulose Nanocrystal Suspensions Using High-Permittivity Solvents.

    Science.gov (United States)

    Bruckner, Johanna R; Kuhnhold, Anja; Honorato-Rios, Camila; Schilling, Tanja; Lagerwall, Jan P F

    2016-09-27

    Helical liquid crystal self-assembly in suspensions of cellulose nanocrystals (CNCs), bioderived nanorods exhibiting excellent mechanical and optical properties, opens attractive routes to sustainable production of advanced functional materials. For convenience, in most studies until now, the CNCs were suspended in water, leaving a knowledge gap concerning the influence of the solvent. Using a novel approach for aggregation-free solvent exchange in CNC suspensions, here we show that protic solvents with a high dielectric permittivity εr significantly speed up self-assembly (from days to hours) at high CNC mass fraction and reduce the concentration dependence of the helix period (variation reducing from more than 30 μm to less than 1 μm). Moreover, our computer simulations indicate that the degree of order at constant CNC content increases with increasing εr, leading to a shorter pitch and a reduced threshold for liquid crystallinity. In low-εr solvents, the onset of long-range orientational order is coupled to kinetic arrest, preventing the formation of a helical superstructure. Our results show that the choice of solvent is a powerful parameter for tuning the behavior of CNC suspensions, enhancing our ability to control the self-assembly and thereby harvesting valuable novel cellulose-based materials.

  9. Lipid self-assembly and lectin-induced reorganization of the plasma membrane.

    Science.gov (United States)

    Sych, Taras; Mély, Yves; Römer, Winfried

    2018-05-26

    The plasma membrane represents an outstanding example of self-organization in biology. It plays a vital role in protecting the integrity of the cell interior and regulates meticulously the import and export of diverse substances. Its major building blocks are proteins and lipids, which self-assemble to a fluid lipid bilayer driven mainly by hydrophobic forces. Even if the plasma membrane appears-globally speaking-homogeneous at physiological temperatures, the existence of specialized nano- to micrometre-sized domains of raft-type character within cellular and synthetic membrane systems has been reported. It is hypothesized that these domains are the origin of a plethora of cellular processes, such as signalling or vesicular trafficking. This review intends to highlight the driving forces of lipid self-assembly into a bilayer membrane and the formation of small, transient domains within the plasma membrane. The mechanisms of self-assembly depend on several factors, such as the lipid composition of the membrane and the geometry of lipids. Moreover, the dynamics and organization of glycosphingolipids into nanometre-sized clusters will be discussed, also in the context of multivalent lectins, which cluster several glycosphingolipid receptor molecules and thus create an asymmetric stress between the two membrane leaflets, leading to tubular plasma membrane invaginations.This article is part of the theme issue 'Self-organization in cell biology'. © 2018 The Author(s).

  10. Multi-scale ordering of self-assembled InAs/GaAs(001 quantum dots

    Directory of Open Access Journals (Sweden)

    Kiravittaya S

    2006-01-01

    Full Text Available AbstractOrdering phenomena related to the self-assembly of InAs quantum dots (QD grown on GaAs(001 substrates are experimentally investigated on different length scales. On the shortest length-scale studied here, we examine the QD morphology and observe two types of QD shapes, i.e., pyramids and domes. Pyramids are elongated along the 12345678910 directions and are bounded by {137} facets, while domes have a multi-facetted shape. By changing the growth rates, we are able to control the size and size homogeneity of freestanding QDs. QDs grown by using low growth rate are characterized by larger sizes and a narrower size distribution. The homogeneity of buried QDs is measured by photoluminescence spectroscopy and can be improved by low temperature overgrowth. The overgrowth induces the formation of nanostructures on the surface. The fabrication of self-assembled nanoholes, which are used as a template to induce short-range positioning of QDs, is also investigated. The growth of closely spaced QDs (QD molecules containing 2–6 QDs per QD molecule is discussed. Finally, the long-range positioning of self-assembled QDs, which can be achieved by the growth on patterned substrates, is demonstrated. Lateral QD replication observed during growth of three-dimensional QD crystals is reported.

  11. Preparation and characterization of self-assembly hydrogels with exfoliated montmorillonite nanosheets and chitosan

    Science.gov (United States)

    Wang, Wei; Zhao, Yunliang; Yi, Hao; Chen, Tianxing; Kang, Shichang; Li, Hongqiang; Song, Shaoxian

    2018-01-01

    Novel montmorillonite-nanosheet/chitosan (MMTNS/CS) hydrogels fabricated via the self-assembly of exfoliated MMTNS and CS chains were investigated. The exfoliation of MMTNS, self-assembly mechanism and structure of MMTNS/CS hydrogels were characterized by an atomic force microscope, scanning electron microscope, transmission electron microscope, Fourier transform infrared spectroscope, energy-dispersive x-ray spectroscope and Brunauer-Emmett-Teller analyzer, respectively. The results indicated that MMT could be easily exfoliated to nanosheets with a thickness of 1 ˜ 5 nm in aqueous solution by an ultrasonic base upon interlayer hydration. The formation mechanism of the self-assembly hydrogels was due to the hydrogen bond (-OH ··· +NH3-) and electrostatic interaction between the MMTNS and CS. The MMTNSs were connected consecutively by CS in-plane to form a huge slice. The porous structure of the hydrogels was controllable by adjusting the MMTNS/CS mass ratio. The hydrogels could be used as adsorbents for sewage treatments, carriers for drugs, microorganisms and catalyzers due to their controllable porous structure and tremendous specific surface area which were derived from the completely exfoliated MMTNS.

  12. In-situ visualization and order quantification of symmetric diblock copolymer directed self-assembly

    International Nuclear Information System (INIS)

    Salaün, M.; Le Gallic, M.; Picard, E.; Zelsmann, M.

    2013-01-01

    In this work, atomic force microscopy (AFM) investigations of lamellar PS-b-PMMA block copolymer layers are performed during the self-assembly process. These in-situ experiments are made on both un-patterned planar substrates and topographical substrates (graphoepitaxy experiments) at different temperatures and for different durations. Image processing software is used to produce AFM movies of the same location on the sample and to measure polymer micro-phase domain lengths versus annealing time. We observed that micro-domain formation starts after only a few minutes of heating. On planar substrates, the micro-domain length evolution with time (t) is in accordance with the literature, following a power law ∼ t 0.29 . On the other hand, in substrate channels and in conditions used, we show that the domain length dependence follows a two-step process. Initially, the system adopts a similar kinetic dependence as that of the planar substrate, but at longer times, drastically reduced time dependence is observed due to the topographical confinement of the domains. - Highlights: ► Live atomic force microscopy of block copolymer directed self-assembly is performed. ► Values of polymer self-assembly kinetic in topographical trenches are measured. ► Opens the way to a better understanding of graphoepitaxy order nucleation and growth

  13. Neural stem cells encapsulated in a functionalized self-assembling peptide hydrogel for brain tissue engineering.

    Science.gov (United States)

    Cheng, Tzu-Yun; Chen, Ming-Hong; Chang, Wen-Han; Huang, Ming-Yuan; Wang, Tzu-Wei

    2013-03-01

    Brain injury is almost irreparable due to the poor regenerative capability of neural tissue. Nowadays, new therapeutic strategies have been focused on stem cell therapy and supplying an appropriate three dimensional (3D) matrix for the repair of injured brain tissue. In this study, we specifically linked laminin-derived IKVAV motif on the C-terminal to enrich self-assembling peptide RADA(16) as a functional peptide-based scaffold. Our purpose is providing a functional self-assembling peptide 3D hydrogel with encapsulated neural stem cells to enhance the reconstruction of the injured brain. The physiochemical properties reported that RADA(16)-IKVAV can self-assemble into nanofibrous morphology with bilayer β-sheet structure and become gelationed hydrogel with mechanical stiffness similar to brain tissue. The in vitro results showed that the extended IKVAV sequence can serve as a signal or guiding cue to direct the encapsulated neural stem cells (NSCs) adhesion and then towards neuronal differentiation. Animal study was conducted in a rat brain surgery model to demonstrate the damage in cerebral neocortex/neopallium loss. The results showed that the injected peptide solution immediately in situ formed the 3D hydrogel filling up the cavity and bridging the gaps. The histological analyses revealed the RADA(16)-IKVAV self-assembling peptide hydrogel not only enhanced survival of encapsulated NSCs but also reduced the formation of glial astrocytes. The peptide hydrogel with IKVAV extended motifs also showed the support of encapsulated NSCs in neuronal differentiation and the improvement in brain tissue regeneration after 6 weeks post-transplantation. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Surface Modification of Self-Assembled Graphene Oxide for Cell Culture Studies

    Science.gov (United States)

    Swain, John E., III

    Thin films show great promise for biological applications, from in situ monitoring to pharmaceutical testing. In this study, a graphene oxide (GO) thin film is prepared with the aim to further functionalize the film for pharmaceutical toxicity screening applications. GO was selected due to its capability to be reduced into an optically transparent and electrically conductive thin film. In addition, GO is derived from carbon, a widely abundant element, in contrast to many other thin films that rely on resource-limited precious metals. Special care was taken to select GO and GO film synthesis methods that minimize the amount of organic-based solvents, maintain reactions at atmospheric pressure and moderate temperatures, and are scalable for manufacturing. Chemical oxidation of graphite flakes was carried out via a modified Hummer's Method with a pre-oxidation step. The resulting GO flakes were self-assembled using commercially available 4-sulfocalix[4]arene. Analytical characterizations (e.g., elemental analysis, XRD, FTIR, Raman, SEM, AFM) were performed to evaluate the success of graphite oxidation and formation of the self-assembled thin film. In order to gain a better understanding of the interactions between GO and sulfocalix (SCX), equilibrium conformations of the SCX molecule and truncated GO were calculated using Spartan'16 Parallels. This study demonstrates that the interaction between the GO and the SCX molecule to create a self-assembled thin film is the result of pi-pi stacking, as hypothesized by Sundramoorthy et al. (2015). The self-assembled GO film was successfully deposited on a polyethylene terephthalate (PET) substrate and functionalized with 3-aminopropyl triethoxysilane (APTES), which renders the film capable of further functionalization with proteins for yielding a three-dimensional cell culture or co-culture platform for different applications.

  15. Sambot II: A self-assembly modular swarm robot

    Science.gov (United States)

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

    2018-04-01

    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.

  16. Self-assembled three-dimensional chiral colloidal architecture

    Science.gov (United States)

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

    2017-11-01

    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.

  17. Ultrafine luminescent structures through nanoparticle self-assembly

    International Nuclear Information System (INIS)

    Prabhakaran, K; Goetzinger, S; Shafi, K V P M; Mazzei, A; Schietinger, S; Benson, O

    2006-01-01

    We report the fabrication of ultrafine structures consisting of regular arrays of nanoemitters through the self-assembly of luminescent nanoparticles on a silicon wafer. Nanoparticles of yttrium aluminium garnet (YAG) doped with Eu 3+ ions were synthesized by a sonochemical technique. These particles, suspended in ethanol, are introduced onto a pre-patterned silicon wafer, covered with a thin oxide layer. On annealing the sample in an ultrahigh-vacuum chamber, the nanoparticles self-assemble along the pattern. We demonstrate this 'chemical lithography' by assembling the nanoparticles along a variety of patterns. We believe that such self-organized nanopatterning of functional structures is important for the realization of nanodevices

  18. Self-assembly of active amphiphilic Janus particles

    Science.gov (United States)

    Mallory, S. A.; Alarcon, F.; Cacciuto, A.; Valeriani, C.

    2017-12-01

    In this article, we study the phenomenology of a two dimensional dilute suspension of active amphiphilic Janus particles. We analyze how the morphology of the aggregates emerging from their self-assembly depends on the strength and the direction of the active forces. We systematically explore and contrast the phenomenologies resulting from particles with a range of attractive patch coverages. Finally, we illustrate how the geometry of the colloids and the directionality of their interactions can be used to control the physical properties of the assembled active aggregates and suggest possible strategies to exploit self-propulsion as a tunable driving force for self-assembly.

  19. Electrostatic Force Microscopy of Self Assembled Peptide Structures

    DEFF Research Database (Denmark)

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

    2011-01-01

    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......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...

  20. Self-Assembled Hydrogel Nanoparticles for Drug Delivery Applications

    Directory of Open Access Journals (Sweden)

    Miguel Gama

    2010-02-01

    Full Text Available Hydrogel nanoparticles—also referred to as polymeric nanogels or macromolecular micelles—are emerging as promising drug carriers for therapeutic applications. These nanostructures hold versatility and properties suitable for the delivery of bioactive molecules, namely of biopharmaceuticals. This article reviews the latest developments in the use of self-assembled polymeric nanogels for drug delivery applications, including small molecular weight drugs, proteins, peptides, oligosaccharides, vaccines and nucleic acids. The materials and techniques used in the development of self-assembling nanogels are also described.

  1. Consensus formation on coevolving networks: groups' formation and structure

    International Nuclear Information System (INIS)

    Kozma, Balazs; Barrat, Alain

    2008-01-01

    We study the effect of adaptivity on a social model of opinion dynamics and consensus formation. We analyse how the adaptivity of the network of contacts between agents to the underlying social dynamics affects the size and topological properties of groups and the convergence time to the stable final state. We find that, while on static networks these properties are determined by percolation phenomena, on adaptive networks the rewiring process leads to different behaviors: adaptive rewiring fosters group formation by enhancing communication between agents of similar opinion, though it also makes possible the division of clusters. We show how the convergence time is determined by the characteristic time of link rearrangement. We finally investigate how the adaptivity yields nontrivial correlations between the internal topology and the size of the groups of agreeing agents

  2. Self-assembled electrical materials from contorted aromatics

    Science.gov (United States)

    Xiao, Shengxiong

    This thesis describes the design, synthesis, self-assembly and electrical properties of new types of contorted polycyclic aromatic hydrocarbons. These topologically interesting contorted aromatics show promising transistor characteristics as new building blocks for organic field-effect transistors (OFETs) at different length scales. In chapter 2, a class of pentacenes that are substituted along their long edges with aromatic rings were synthesized. Their solid-state assemblies were studied by X-ray crystallography. Their performance as thin film transistors (TFTs) and single crystal field effect transistors (SCFETs) were systematically evaluated. A structure-property relationship between these highly phenylated pentacenes was found. Chapter 3 explores the new concept of whether a non-planar aromatic core could yield efficacious electronic materials, as the ultimate success in the organic electronics will require a holistic approach to creating new building blocks. Synthesis, functionalization and assembly of a new type of contorted hexabenzocoronene (HBC) whose aromatic core is heavily distorted away from planarity due to the steric congestion around its proximal carbons were discussed. Structural studies by X-ray crystallography showed that these HBC molecules stack into columnar structures in the solid state, which are ideal for conduction. Chapter 4 describes that microscale liquid crystalline thin film OFETs of tetradodecyloxy HBC showed the best transistor properties of all discotic columnar materials. Chapter 5 details the fabrication and characterization of nanoscale single crystalline fiber OFETs of octadodecyloxyl HBC. In Chapter 6 we show that a molecular scale monolayer of HBC acid chlorides could be self-assembled on SiO2 insulating layer and could be organized laterally between the ends of 2 nm carbon nanotube gaps to form high quality FETs that act as environmental and chemical sensors. Chapter 7 details the enforced one-dimensional photoconductivity

  3. Low temperature self-assembled growth of rutile TiO2/manganese oxide nanocrystalline films

    Science.gov (United States)

    Sun, Zhenya; Zhou, Daokun; Du, Jianhua; Xie, Yuxing

    2017-10-01

    We report formation of rutile TiO2 nanocrystal at low temperature range in the presence of α-MnO2 which self-assembled onto sulfanyl radical activated silicon oxide substrate. SEM, HRTEM, XPS and Raman spectroscopy were used to study the morphology and oxidation state of synthesised crystals. The results showed that when the α-MnO2 was reduced to Mn3O4, it induced the formation of rutile instead of anatase phase in the TiCl4-HCl aqueous system. The finding will promote the understanding of phase transformation mechanism when manganese oxide and titanium oxide co-exist in soil and water environment.

  4. Evaporation, diffusion and self-assembly at drying interfaces.

    Science.gov (United States)

    Roger, K; Sparr, E; Wennerström, H

    2018-04-18

    Water evaporation from complex aqueous solutions leads to the build-up of structure and composition gradients at their interface with air. We recently introduced an experimental setup for quantitatively studying such gradients and discussed how structure formation can lead to a self-regulation mechanism for controlling water evaporation through self-assembly. Here, we provide a detailed theoretical analysis using an advection/diffusion transport equation that takes into account thermodynamically non-ideal conditions and we directly relate the theoretical description to quantitative experimental data. We derive that the concentration profile develops according to a general square root of time scaling law, which fully agrees with experimental observations. The evaporation rate notably decreases with time as t-1/2, which shows that diffusion in the liquid phase is the rate limiting step for this system, in contrast to pure water evaporation. For the particular binary system that was investigated experimentally, which is composed of water and a sugar-based surfactant (α-dodecylmaltoside), the interfacial layer consists in a sequence of liquid crystalline phases of different mesostructures. We extract values for mutual diffusion coefficients of lamellar, hexagonal and micellar cubic phases, which are consistent with previously reported values and simple models. We thus provide a method to estimate the transport properties of oriented mesophases. The macroscopic humidity-independence of the evaporation rate up to 85% relative humidities is shown to result from both an extremely low mutual diffusion coefficient and the large range of water activities corresponding to relative humidities below 85%, at which the lamellar phase exists. Such a humidity self-regulation mechanism is expected for a large variety of complex system.

  5. Non-equilibrium magnetic colloidal dispersions at liquid-air interfaces: dynamic patterns, magnetic order and self-assembled swimmers

    International Nuclear Information System (INIS)

    Snezhko, Alexey

    2011-01-01

    Colloidal dispersions of interacting particles subjected to an external periodic forcing often develop nontrivial self-assembled patterns and complex collective behavior. A fundamental issue is how collective ordering in such non-equilibrium systems arises from the dynamics of discrete interacting components. In addition, from a practical viewpoint, by working in regimes far from equilibrium new self-organized structures which are generally not available through equilibrium thermodynamics can be created. In this review spontaneous self-assembly phenomena in magnetic colloidal dispersions suspended at liquid-air interfaces and driven out of equilibrium by an alternating magnetic field are presented. Experiments reveal a new type of nontrivially ordered self-assembled structures emerging in such systems in a certain range of excitation parameters. These dynamic structures emerge as a result of the competition between magnetic and hydrodynamic forces and have complex unconventional magnetic ordering. Nontrivial self-induced hydrodynamic fields accompany each out-of-equilibrium pattern. Spontaneous symmetry breaking of the self-induced surface flows leading to a formation of self-propelled microstructures has been discovered. Some features of the self-localized structures can be understood in the framework of the amplitude equation (Ginzburg-Landau type equation) for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density and the Navier-Stokes equation for hydrodynamic flows. To understand the fundamental microscopic mechanisms governing self-assembly processes in magnetic colloidal dispersions at liquid-air interfaces a first-principle model for a non-equilibrium self-assembly is presented. The latter model allows us to capture in detail the entire process of out-of-equilibrium self-assembly in the system and reproduces most of the observed phenomenology. (topical review)

  6. Protocol for Communication Networking for Formation Flying

    Science.gov (United States)

    Jennings, Esther; Okino, Clayton; Gao, Jay; Clare, Loren

    2009-01-01

    An application-layer protocol and a network architecture have been proposed for data communications among multiple autonomous spacecraft that are required to fly in a precise formation in order to perform scientific observations. The protocol could also be applied to other autonomous vehicles operating in formation, including robotic aircraft, robotic land vehicles, and robotic underwater vehicles. A group of spacecraft or other vehicles to which the protocol applies could be characterized as a precision-formation- flying (PFF) network, and each vehicle could be characterized as a node in the PFF network. In order to support precise formation flying, it would be necessary to establish a corresponding communication network, through which the vehicles could exchange position and orientation data and formation-control commands. The communication network must enable communication during early phases of a mission, when little positional knowledge is available. Particularly during early mission phases, the distances among vehicles may be so large that communication could be achieved only by relaying across multiple links. The large distances and need for omnidirectional coverage would limit communication links to operation at low bandwidth during these mission phases. Once the vehicles were in formation and distances were shorter, the communication network would be required to provide high-bandwidth, low-jitter service to support tight formation-control loops. The proposed protocol and architecture, intended to satisfy the aforementioned and other requirements, are based on a standard layered-reference-model concept. The proposed application protocol would be used in conjunction with conventional network, data-link, and physical-layer protocols. The proposed protocol includes the ubiquitous Institute of Electrical and Electronics Engineers (IEEE) 802.11 medium access control (MAC) protocol to be used in the datalink layer. In addition to its widespread and proven use in

  7. Spectromicroscopy of self-assembled protein clusters

    Energy Technology Data Exchange (ETDEWEB)

    Schonschek, O.; Hormes, J.; Herzog, V. [Univ. of Bonn (Germany)

    1997-04-01

    The aim of this project is to use synchrotron radiation as a tool to study biomedical questions concerned with the thyroid glands. The biological background is outlined in a recent paper. In short, Thyroglobulin (TG), the precursor protein of the hormone thyroxine, forms large (20 - 500 microns in diameter) clusters in the extracellular lumen of thyrocytes. The process of the cluster formation is still not well understood but is thought to be a main storage mechanism of TG and therefore thyroxine inside the thyroid glands. For human thyroids, the interconnections of the proteins inside the clusters are mainly disulfide bondings. Normally, sulfur bridges are catalyzed by an enzyme called Protein Disulfide Bridge Isomerase (PDI). While this enzyme is supposed to be not present in any extracellular space, the cluster formation of TG takes place in the lumen between the thyrocytes. A possible explanation is the autocatalysis of TG.

  8. Networks for Autonomous Formation Flying Satellite Systems

    Science.gov (United States)

    Knoblock, Eric J.; Konangi, Vijay K.; Wallett, Thomas M.; Bhasin, Kul B.

    2001-01-01

    The performance of three communications networks to support autonomous multi-spacecraft formation flying systems is presented. All systems are comprised of a ten-satellite formation arranged in a star topology, with one of the satellites designated as the central or "mother ship." All data is routed through the mother ship to the terrestrial network. The first system uses a TCP/lP over ATM protocol architecture within the formation the second system uses the IEEE 802.11 protocol architecture within the formation and the last system uses both of the previous architectures with a constellation of geosynchronous satellites serving as an intermediate point-of-contact between the formation and the terrestrial network. The simulations consist of file transfers using either the File Transfer Protocol (FTP) or the Simple Automatic File Exchange (SAFE) Protocol. The results compare the IF queuing delay, and IP processing delay at the mother ship as well as application-level round-trip time for both systems, In all cases, using IEEE 802.11 within the formation yields less delay. Also, the throughput exhibited by SAFE is better than FTP.

  9. Self-assembly from milli- to nanoscales: methods and applications

    International Nuclear Information System (INIS)

    Mastrangeli, M; Celis, J-P; Abbasi, S; Varel, C; Böhringer, K F; Van Hoof, C

    2009-01-01

    The design and fabrication techniques for microelectromechanical systems (MEMS) and nanodevices are progressing rapidly. However, due to material and process flow incompatibilities in the fabrication of sensors, actuators and electronic circuitry, a final packaging step is often necessary to integrate all components of a heterogeneous microsystem on a common substrate. Robotic pick-and-place, although accurate and reliable at larger scales, is a serial process that downscales unfavorably due to stiction problems, fragility and sheer number of components. Self-assembly, on the other hand, is parallel and can be used for device sizes ranging from millimeters to nanometers. In this review, the state-of-the-art in methods and applications for self-assembly is reviewed. Methods for assembling three-dimensional (3D) MEMS structures out of two-dimensional (2D) ones are described. The use of capillary forces for folding 2D plates into 3D structures, as well as assembling parts onto a common substrate or aggregating parts to each other into 2D or 3D structures, is discussed. Shape matching and guided assembly by magnetic forces and electric fields are also reviewed. Finally, colloidal self-assembly and DNA-based self-assembly, mainly used at the nanoscale, are surveyed, and aspects of theoretical modeling of stochastic assembly processes are discussed. (topical review)

  10. Tuning of metal work functions with self-assembled monolayers

    NARCIS (Netherlands)

    de Boer, B; Hadipour, A; Mandoc, MM; van Woudenbergh, T; Blom, PWM

    2005-01-01

    Work functions of gold and silver are varied by over 1.4 and 1.7 eV, respectively, by using self-assembled monolayers. Using these modified electrodes, the hole current in a poly(2-methoxy-5-(2'-ethylhexyloxy)- 1,4-phenylene vinylene) light-emitting diode is tuned by more than six orders of

  11. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)

    Unknown

    Physical and Materials Chemistry Division, National Chemical Laboratory,. Pune 411 008, India e-mail: viji@ems.ncl.res.in. 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 ...

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

    Indian Academy of Sciences (India)

    Administrator

    characterization and self-assembly with gold nanoparticles. JUN-BO LI. 1, ... gold surface lead to the enhancement of device prop- erties. 36,37 ... Reactions were monitored by thin-layer ..... plasmon (SP) absorption band (figure 5) of TOAB-.

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

    NARCIS (Netherlands)

    Vutukuri, H.R.

    2012-01-01

    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

  14. Characterization of self-assembled monolayers on a ruthenium surface

    NARCIS (Netherlands)

    Shaheen, Amrozia; Sturm, Jacobus Marinus; Ricciardi, R.; Huskens, Jurriaan; Lee, Christopher James; Bijkerk, Frederik

    2017-01-01

    We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on

  15. Self-assembled fluorescent organic nanoparticles for live cell imaging

    NARCIS (Netherlands)

    Fischer, I.; Petkau, K.; Dorland, Y.L.; Schenning, A.P.H.J.; Brunsveld, L.

    2013-01-01

    Fluorescent, cell-permeable, organic nanoparticles based on self-assembled p-conjugated oligomers with high absorption cross-sections and high quantum yields have been developed. The nanoparticles are generated with a tuneable density of amino groups for charge-mediated cellular uptake by a

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

    OpenAIRE

    Yang Yongkun; Burkhard Peter

    2012-01-01

    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...

  17. Oscillatory persistent currents in self-assembled quantum rings

    NARCIS (Netherlands)

    Kleemans, N.A.J.M.; Bominaar-Silkens, I.M.A.; Fomin, V.; Gladilin, V.N.; Granados, D.; Taboada, A.G.; Garcia, J.M.; Offermans, P.; Zeitler, U.; Christianen, P.C.M.; Maan, J.C.; Devreese, J.T.; Koenraad, P.M.

    2007-01-01

    We report the direct measurement of the persistent current carried by a single electron by means of magnetization experiments on self-assembled InAs/GaAs quantum rings. We measured the first Aharonov-Bohm oscillation at a field of 14 T, in perfect agreement with our model based on the structural

  18. Long lived coherence in self-assembled quantum dots

    DEFF Research Database (Denmark)

    Birkedal, Dan; Leosson, Kristjan; Hvam, Jørn Märcher

    2001-01-01

    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...

  19. Multiphonon capture processes in self-assembled quantum dots

    DEFF Research Database (Denmark)

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

    2001-01-01

    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...

  20. Coherence and dephasing in self-assembled quantum dots

    DEFF Research Database (Denmark)

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

    2003-01-01

    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...

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

    NARCIS (Netherlands)

    Robson Marsden, Hana

    2009-01-01

    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

  2. Electrostatic Self-Assembly of Polysaccharides into Nanofibers

    DEFF Research Database (Denmark)

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

    2017-01-01

    In this study, the anionic polysaccharide Xanthan gum (X) was mixed with positively charged Chitosan oligomers (ChO), and used as building blocks, to generate novel nanofibers by electrostatic self-assembly in aqueous conditions. Different concentrations, ionic strength and order of mixing of both...

  3. Self-assembly of hydrofluorinated Janus graphene monolayer

    DEFF Research Database (Denmark)

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei

    2016-01-01

    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...

  4. Self-assembling bilayers of palladiumthiolates in organic media

    Indian Academy of Sciences (India)

    Unknown

    applications in catalytic systems, solubalizing agents and drug delivery matrices. Following the pioneering efforts of ... In this context, self-assembly of amphipiles in nonpolar organic media assumes significance 8 since .... structures in clear contrast to lamellar phases formed by the higher members. We sought to image the ...

  5. 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: f.ladouceur@unsw.edu.a [School of Chemistry, University of NSW, Sydney, NSW, 2052 (Australia)

    2010-12-15

    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.

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

    NARCIS (Netherlands)

    Yildirim, O.

    2010-01-01

    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

  7. Self-assembling electroactive hydrogels for flexible display technology

    International Nuclear Information System (INIS)

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

    2010-01-01

    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.

  8. Self-assembling peptide hydrogels immobilized on silicon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Franchi, Stefano; Battocchio, Chiara; Galluzzi, Martina; Navisse, Emanuele [Department of Sciences, University “Roma Tre”, Via della Vasca Navale 79, Roma, 00146 (Italy); Zamuner, Annj; Dettin, Monica [Department of Industrial Engineering, University of Padua, Via Marzolo, 9, Padua, 35131 (Italy); Iucci, Giovanna, E-mail: giovanna.iucci@uniroma3.it [Department of Sciences, University “Roma Tre”, Via della Vasca Navale 79, Roma, 00146 (Italy)

    2016-12-01

    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. 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

    2016-01-01

    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

  10. Molecular Electronics of Self-Assembled Monolayers

    DEFF Research Database (Denmark)

    Wang, Xintai

    This thesis deals withmolecular electronic investigations on self-assembledmonolayers. The thesis is divided into seven chapters, as outlined below.Chapter 1 is a general introduction of the history of molecular electronics and its current state.Chapter 2 is separated into three parts. Part I...... providesa brief introduction toself-assembledmonolayers(SAMs), includingits structure, formation, and its role in molecular electronic investigations. Part II is an introduction of different molecular functions, which are interesting for designing real devices. Part III is an introduction of a novel carbon...... material: graphene, and how such material can be incorporated intothe field of molecular electronics.Chapter 3 is a brief introduction of important instruments used in this thesis.Chapter 4, 5 and 6 describe the major experimental work in this thesis. Chapter 4 introduces two novel anchoring...

  11. Supracolloidal Architectures Self-Assembled in Microdroplets.

    Science.gov (United States)

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

    2015-10-26

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

  12. Synthesis, electrochemistry, STM investigation of oligothiophene self-assemblies with superior structural order and electronic properties

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, Cheng-Yu [C-PCS, Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Liu, Yinghao; Yarotski, Dmitry [Center of Integrated Nanotechnologies, Materials Physics and Application Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Li, Hao [Theory Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Xu, Ping; Yen, Hung-Ju [C-PCS, Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Tretiak, Sergei, E-mail: serg@lanl.gov [Theory Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Wang, Hsing-Lin, E-mail: hwang@lanl.gov [C-PCS, Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2016-12-20

    Graphical abstract: STM imaging reveals differently oriented domains of self-assembled tetrathiophene molecules. - Highlights: • Optical and redox properties of oligothiophene derivatives are studied. • Packing pattern of self-assembly monolayer depends on the conjugation length. • Strong electronic coupling and three redox couples in cyclic voltamogram are observed in the hierarchical self-assembly. - Abstract: Three oligothiophene (terthiophene, tetrathiophene and pentathiophene) derivatives are synthesized and their monolayer self-assemblies on gold (Au) are prepared via Au–S covalent bond. Our UV–Vis experimental characterization of solution reveals the dependence of the optical properties on the conjugation length of the oligothiophenes, which compares well with Time-Dependent Density Functional Theory (TDDFT) simulations of spectra of individual chromophores. Photoluminescent spectra of thin films show pronounced red shifts compared to that of solutions, suggesting strong inter-oligomer interactions. The comparative studies of cyclic voltammograms of tetrathiophene from solution, cast film and self-assembled monolayer (SAM) indicate presence of one, two, and three oxidized species in these samples, respectively, suggesting a very strong electronic coupling between tetrathiophene molecules in the SAM. Scanning tunneling microscopy (STM) imaging of SAMs of the tetrathiophene on an atomically flat Au surface exhibits formation of monolayer assemblies with molecular order, and the molecular packing appears to show an overlay of oligothiophene molecules on top of another one. In contrast, the trimer and pentamer images show only aggregated species lacking long-range order on the molecular level. Such trends in going from disordered–ordered–disordered monolayer assemblies are mainly due to a delicate balance between inter-chromophore π–π couplings, hydrophobic interaction and the propensity to form Au–S covalent bond. Such hypothesis has been

  13. Photoconductivity of nanowires that are self-assembled from chiral porphyrins

    Science.gov (United States)

    Menko, J. G.; Smith, W. F.; Lu, Y.; Johnson, A. T.; Iavicoli, P.

    2010-03-01

    Recently synthesized chiral porphyrin moleculesfootnotetextM. Linares, P. Iavicoli, K. Psychogyiopoulou, D. Beljonne, S. De Feyter, D. B. Amabilino, and R. Lazzaroni, Langmuir 2008, 24, 9566-9574. in a methlocyclohexane solvent self-assemble into aggregates which appear as a network of nanoscale filaments when deposited onto oxidized silicon. We have shown in preliminary experiments conducted in air that the aggregates are photoconductive, with an action spectrum (photoconductivity vs. wavelength) that matches the in-solution absorbance curve. We discuss these results, and also experiments conducted in a dry nitrogen environment.

  14. Morphology-tunable and photoresponsive properties in a self-assembled two-component gel system.

    Science.gov (United States)

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

    2007-01-02

    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.

  15. Self-assembled structural color in nature

    Science.gov (United States)

    Parnell, Andrew

    The vibrancy and variety of structural color found in nature has long been well-known; what has only recently been discovered is the sophistication of the physics that underlies these effects. In the talk I will discuss some of our recent studies of the structures responsible for color in bird feathers and beetle elytra, based on structural characterization using small angle x-ray scattering, x-ray tomography and optical modeling. These have enabled us to study a large number of structural color exhibiting materials and look for trends in the structures nature uses to provide these optical effects. In terms of creating the optical structure responsible for the color of the Eurasian Jay feathers (Garrulus glandarius) the nanostructure is produced by a phase-separation process that is arrested at a late stage; mastery of the color is achieved by control over the duration of this phase-separation process. Our analysis shows that nanostructure in single bird feather barbs can be varied continuously by controlling the time the keratin network is allowed to phase separate before mobility in the system is arrested. Dynamic scaling analysis of the single barb scattering data implies that the phase separation arrest mechanism is rapid and also distinct from the spinodal phase separation mechanism i.e. it is not gelation or intermolecular re-association. Any growing lengthscale using this spinodal phase separation approach must first traverse the UV and blue wavelength regions, growing the structure by coarsening, resulting in a broad distribution of domain sizes. AJP acknowledges financial support via the APS/DPOLY exchange lectureship 2017.

  16. Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions

    Science.gov (United States)

    Mann, Stephen

    2009-10-01

    Understanding how chemically derived processes control the construction and organization of matter across extended and multiple length scales is of growing interest in many areas of materials research. Here we review present equilibrium and non-equilibrium self-assembly approaches to the synthetic construction of discrete hybrid (inorganic-organic) nano-objects and higher-level nanostructured networks. We examine a range of synthetic modalities under equilibrium conditions that give rise to integrative self-assembly (supramolecular wrapping, nanoscale incarceration and nanostructure templating) or higher-order self-assembly (programmed/directed aggregation). We contrast these strategies with processes of transformative self-assembly that use self-organizing media, reaction-diffusion systems and coupled mesophases to produce higher-level hybrid structures under non-equilibrium conditions. Key elements of the constructional codes associated with these processes are identified with regard to existing theoretical knowledge, and presented as a heuristic guideline for the rational design of hybrid nano-objects and nanomaterials.

  17. Self-assembled metallic nanoparticle template — a new approach of surface nanostructuring at nanometer scale

    Directory of Open Access Journals (Sweden)

    A. Taleb

    2017-09-01

    Full Text Available In the present work, the formation of silver and copper nanostructures on highly oriented pyrolytic graphite (HOPG modified with self-assembled gold nanoparticles (Au NPs is demonstrated. Surface patterning with nanometer resolution was achieved. Different methods such as field emission scanning electron microscopy (FEGSEM, energy dispersive spectrometry (EDS and X-ray photoelectron spectroscopy (XPS were used to illustrate a selective deposition of silver and copper on Au NPs. The mechanism of silver and copper ions reduction on Au NP with n-dodecanethiol coating is discussed.

  18. Controlled modification of octadecyltrichlorosilane self-assembled monolayer by CO2 plasma

    International Nuclear Information System (INIS)

    Delorme, Nicolas; Bardeau, Jean-Francois; Bulou, Alain; Poncin-Epaillard, Fabienne

    2006-01-01

    CO 2 -plasma is used to introduce functional groups on the uppermost surface of an alkoxy silane self-assembled monolayer (Sam). The structural and chemical modifications of the material surface were monitored by X-ray reflectometry, atomic force microscopy, X-ray photoelectrons spectroscopy and water contact angle measurements. Optimization of the plasma parameters is performed in order to achieve a maximum functionalization and to prevent degradation of the SAM. Finally, the ability of grafting organic compounds onto the plasma modified SAMS was demonstrated by the formation of an alkoxysilane bilayer

  19. Optical Properties of GaAs Quantum Dots Fabricated by Filling of Self-Assembled Nanoholes

    Directory of Open Access Journals (Sweden)

    Heyn Ch

    2009-01-01

    Full Text Available Abstract Experimental results of the local droplet etching technique for the self-assembled formation of nanoholes and quantum rings on semiconductor surfaces are discussed. Dependent on the sample design and the process parameters, filling of nanoholes in AlGaAs generates strain-free GaAs quantum dots with either broadband optical emission or sharp photoluminescence (PL lines. Broadband emission is found for samples with completely filled flat holes, which have a very broad depth distribution. On the other hand, partly filling of deep holes yield highly uniform quantum dots with very sharp PL lines.

  20. Narcissistic self-sorting in self-assembled cages of rare Earth metals and rigid ligands.

    Science.gov (United States)

    Johnson, Amber M; Wiley, Calvin A; Young, Michael C; Zhang, Xing; Lyon, Yana; Julian, Ryan R; Hooley, Richard J

    2015-05-04

    Highly selective, narcissistic self-sorting can be achieved in the formation of self-assembled cages of rare earth metals with multianionic salicylhydrazone ligands. The assembly process is highly sensitive to the length of the ligand and the coordination geometry. Most surprisingly, high-fidelity sorting is possible between ligands of identical coordination angle and geometry, differing only in a single functional group on the ligand core, which is not involved in the coordination. Supramolecular effects allow discrimination between pendant functions as similar as carbonyl or methylene groups in a complex assembly process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Photoligation of self-assembled DNA constructs containing anthracene-functionalized 2'-amino-LNA monomers

    DEFF Research Database (Denmark)

    Pasternak, Karol; Pasternak, Anna; Gupta, Pankaj

    2011-01-01

    Efficient synthesis of a novel anthracene-functionalized 2'-amino-LNA phosphoramidite derivative is described together with its incorporation into oligodeoxynucleotides. Two DNA strands with the novel 2'-N-anthracenylmethyl-2'-amino-LNA monomers can be effectively cross-linked by photoligation...... at 366nm in various types of DNA constructs. Successful application of three differently functionalized 2'-amino-LNA monomers in self-assembled higher ordered structures for simultaneous cross-linking and monitoring of assembly formation is furthermore demonstrated....

  2. Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

    Science.gov (United States)

    Velayutham, T. S.; Ng, B. K.; Gan, W. C.; Majid, W. H. Abd.; Hashim, R.; Zahid, N. I.; Chaiprapa, Jitrin

    2014-08-01

    Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10-2-106 Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.

  3. Predicting supramolecular self-assembly on reconstructed metal surfaces

    Science.gov (United States)

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

    2014-06-01

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

  4. Real-time analysis of self-assembled nucleobases by Venturi easy ambient sonic-spray ionization mass spectrometry.

    Science.gov (United States)

    Na, Na; Shi, Ruixia; Long, Zi; Lu, Xin; Jiang, Fubin; Ouyang, Jin

    2014-10-01

    In this study, the real-time analysis of self-assembled nucleobases was employed by Venturi easy ambient sonic-spray ionization mass spectrometry (V-EASI-MS). With the analysis of three nucleobases including 6-methyluracil (6MU), uracil (U) and thymine (T) as examples, different orders of clusters centered with different metal ions were recorded in both positive and negative modes. Compared with the results obtained by traditional electrospray ionization mass spectrometry (ESI-MS) under the same condition, more clusters with high orders, such as [6MU7+Na](+), [6MU15+2NH4](2+), [6MU10+Na](+), [T7+Na](+), and [T15+2NH4](2+) were detected by V-EASI-MS, which demonstrated the soft ionization ability of V-EASI for studying the non-covalent interaction in a self-assembly process. Furthermore, with the injection of K(+) to the system by a syringe pumping, the real-time monitoring of the formation of nucleobases clusters was achieved by the direct extraction of samples from the system under the Venturi effect. Therefore, the effect of cations on the formation of clusters during self-assembly of nucleobases was demonstrated, which was in accordance with the reports. Free of high voltage, heating or radiation during the ionization, this technique is much soft and suitable for obtaining the real-time information of the self-assembly system, which also makes it quite convenient for extraction samples from the reaction system. This "easy and soft" ionization technique has provided a potential pathway for monitoring and controlling the self-assembly processes. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Role of Achiral Nucleobases in Multicomponent Chiral Self-Assembly: Purine-Triggered Helix and Chirality Transfer.

    Science.gov (United States)

    Deng, Ming; Zhang, Li; Jiang, Yuqian; Liu, Minghua

    2016-11-21

    Chiral self-assembly is a basic process in biological systems, where many chiral biomolecules such as amino acids and sugars play important roles. Achiral nucleobases usually covalently bond to saccharides and play a significant role in the formation of the double helix structure. However, it remains unclear how the achiral nucleobases can function in chiral self-assembly without the sugar modification. Herein, we have clarified that purine nucleobases could trigger N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to self-assemble into helical nanostructures. Moreover, the helical nanostructure could serve as a matrix and transfer the chirality to an achiral fluorescence probe, thioflavin T (ThT). Upon chirality transfer, the ThT showed not only supramolecular chirality but also circular polarized fluorescence (CPL). Without the nucleobase, the self-assembly processes cannot happen, thus providing an example where achiral molecules played an essential role in the expression and transfer of the chirality. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Sequence Identification, Recombinant Production, and Analysis of the Self-Assembly of Egg Stalk Silk Proteins from Lacewing Chrysoperla carnea.

    Science.gov (United States)

    Neuenfeldt, Martin; Scheibel, Thomas

    2017-06-13

    Egg stalk silks of the common green lacewing Chrysoperla carnea likely comprise at least three different silk proteins. Based on the natural spinning process, it was hypothesized that these proteins self-assemble without shear stress, as adult lacewings do not use a spinneret. To examine this, the first sequence identification and determination of the gene expression profile of several silk proteins and various transcript variants thereof was conducted, and then the three major proteins were recombinantly produced in Escherichia coli encoded by their native complementary DNA (cDNA) sequences. Circular dichroism measurements indicated that the silk proteins in aqueous solutions had a mainly intrinsically disordered structure. The largest silk protein, which we named ChryC1, exhibited a lower critical solution temperature (LCST) behavior and self-assembled into fibers or film morphologies, depending on the conditions used. The second silk protein, ChryC2, self-assembled into nanofibrils and subsequently formed hydrogels. Circular dichroism and Fourier transform infrared spectroscopy confirmed conformational changes of both proteins into beta sheet rich structures upon assembly. ChryC3 did not self-assemble into any morphology under the tested conditions. Thereby, through this work, it could be shown that recombinant lacewing silk proteins can be produced and further used for studying the fiber formation of lacewing egg stalks.

  7. Synthesis and characterization of designed BMHP1-derived self-assembling peptides for tissue engineering applications.

    Science.gov (United States)

    Silva, Diego; Natalello, Antonino; Sanii, Babak; Vasita, Rajesh; Saracino, Gloria; Zuckermann, Ronald N; Doglia, Silvia Maria; Gelain, Fabrizio

    2013-01-21

    The importance of self-assembling peptides (SAPs) in regenerative medicine is becoming increasingly recognized. The propensity of SAPs to form nanostructured fibers is governed by multiple forces including hydrogen bonds, hydrophobic interactions and π-π aromatic interactions among side chains of the amino acids. Single residue modifications in SAP sequences can significantly affect these forces. BMHP1-derived SAPs is a class of biotinylated oligopeptides, which self-assemble in β-structured fibers to form a self-healing hydrogel. In the current study, selected modifications in previously described BMHP1-derived SAPs were designed in order to investigate the influence of modified residues on self-assembly kinetics and scaffold formation properties. The Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis demonstrated the secondary structure (β-sheet) formation in all modified SAP sequences, whereas atomic force microscopy (AFM) analysis further confirmed the presence of nanofibers. Furthermore, the fiber shape and dimension analysis by AFM showed flattened and twisted fiber morphology ranging from ∼8 nm to ∼70 nm. The mechanical properties of the pre-assembled and post assembled solution were investigated by rheometry. The shear-thinning behavior and rapid re-healing properties of the pre-assembled solutions make them a preferable choice for injectable scaffolds. The wide range of stiffnesses (G')--from ∼1000 to ∼27,000 Pa--exhibited by the post-assembled scaffolds demonstrated their potential for a variety of tissue engineering applications. The extra cellular matrix (ECM) mimicking (physically and chemically) properties of SAP scaffolds enhanced cell adhesion and proliferation. The capability of the scaffold to facilitate murine neural stem cell (mNSC) proliferation was evaluated in vitro: the increased mNSCs adhesion and proliferation demonstrated the potential of newly synthesized SAPs for regenerative medicine

  8. Structural and thermodynamic analysis of modified nucleosides in self-assembled DNA cross-tiles.

    Science.gov (United States)

    Hakker, Lauren; Marchi, Alexandria N; Harris, Kimberly A; LaBean, Thomas H; Agris, Paul F

    2014-01-01

    DNA Holliday junctions are important natural strand-exchange structures that form during homologous recombination. Immobile four-arm junctions, analogs to Holliday junctions, have been designed to self-assemble into cross-tile structures by maximizing Watson-Crick base pairing and fixed crossover points. The cross-tiles, self-assembled from base pair recognition between designed single-stranded DNAs, form higher order lattice structures through cohesion of self-associating sticky ends. These cross-tiles have 16 unpaired nucleosides in the central loop at the junction of the four duplex stems. The importance of the centralized unpaired nucleosides to the structure's thermodynamic stability and self-assembly is unknown. Cross-tile DNA nanostructures were designed and constructed from nine single-stranded DNAs with four shell strands, four arms, and a central loop containing 16 unpaired bases. The 16 unpaired bases were either 2'-deoxyribothymidines, 2'-O-methylribouridines, or abasic 1',2'-dideoxyribonucleosides. Thermodynamic profiles and structural base-stacking contributions were assessed using UV absorption spectroscopy during thermal denaturation and circular dichroism spectroscopy, respectively, and the resulting structures were observed by atomic force microscopy. There were surprisingly significant changes in the thermodynamic and structural properties of lattice formation as a result of altering only the 16 unpaired, centralized nucleosides. The 16 unpaired 2'-O-methyluridines were stabilizing and produced uniform tubular structures. In contrast, the abasic nucleosides were destabilizing producing a mixture of structures. These results strongly indicate the importance of a small number of centrally located unpaired nucleosides within the structures. Since minor modifications lead to palpable changes in lattice formation, DNA cross-tiles present an easily manipulated structure convenient for applications in biomedical and biosensing devices.

  9. DNA Self-Assembly: From Chirality to Evolution

    Directory of Open Access Journals (Sweden)

    Youri Timsit

    2013-04-01

    Full Text Available Transient or long-term DNA self-assembly participates in essential genetic functions. The present review focuses on tight DNA-DNA interactions that have recently been found to play important roles in both controlling DNA higher-order structures and their topology. Due to their chirality, double helices are tightly packed into stable right-handed crossovers. Simple packing rules that are imposed by DNA geometry and sequence dictate the overall architecture of higher order DNA structures. Close DNA-DNA interactions also provide the missing link between local interactions and DNA topology, thus explaining how type II DNA topoisomerases may sense locally the global topology. Finally this paper proposes that through its influence on DNA self-assembled structures, DNA chirality played a critical role during the early steps of evolution.

  10. 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

    2017-07-21

    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.

  11. DNA-Based Self-Assembly of Fluorescent Nanodiamonds.

    Science.gov (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

    2015-08-12

    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.

  12. The self-assembling process and applications in tissue engineering

    Science.gov (United States)

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

    2018-01-01

    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

  13. Quantitative self-assembly prediction yields targeted nanomedicines

    Science.gov (United States)

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

    2018-02-01

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

  14. Understanding the self-assembly of TCNQ on Cu(111)

    DEFF Research Database (Denmark)

    Stradi, Daniele; Borca, Bogdana; Barja, Sara

    2016-01-01

    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......-assembled molecular layer can be controlled by tuning of the experimental conditions under which the deposition is carried out. When the Cu(111) substrate is held above room temperature (T-Cu(111) = 350 K) during deposition, a structure is formed in which the two molecules in the unit cell are oriented one...... 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...

  15. Self-Assembled Monolayers of CdSe Nanocrystals on Doped GaAs Substrates

    DEFF Research Database (Denmark)

    Marx, E.; Ginger, D.S.; Walzer, Karsten

    2002-01-01

    This letter reports the self-assembly and analysis of CdSe nanocrystal monolayers on both p- and a-doped GaAs substrates. The self-assembly was performed using a 1,6-hexanedithiol self-assembled monolayer (SAM) to link CdSe nanocrystals to GaAs substrates. Attenuated total reflection Fourier tran...

  16. Dispersion of nanoparticulate suspensions using self-assembled surfactant aggregates

    Science.gov (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

  17. Microtubule dynamics. II. Kinetics of self-assembly

    DEFF Research Database (Denmark)

    Flyvbjerg, H.; Jobs, E.

    1997-01-01

    Inverse scattering theory describes the conditions necessary and sufficient to determine an unknown potential from known scattering data. No similar theory exists for when and how one may deduce the kinetics of an unknown chemical reaction from quantitative information about its final state and i...... to analyze the self-assembly of microtubules from tubulin are general, and many other reactions and processes may be studied as inverse problems with these methods when enough experimental data are available....

  18. Fabrication of Nanostructures Using Self-Assembled Peptides as Templates

    DEFF Research Database (Denmark)

    Castillo, Jaime

    2015-01-01

    the advantages of diphenylalanine are explained step by step offering new alternatives to fabricate nanostructures in a simple and rapid way. The chapter is complemented with techniques to manipulate the self-assembled diphenylalanine nanostructures without changing its properties during the manipulation process.......This chapter evaluates the use of a short-aromatic dipeptide, diphenylalanine, as a template in the fabrication of new nanostructures (nanowires, coaxial nanocables, nanochannels) using materials such as silicon, conducting and non-conducting polymers. Diphenylalanine self...

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

    Science.gov (United States)

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

    2016-03-02

    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.

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

    OpenAIRE

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

    2016-01-01

    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...

  1. 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.

    2017-01-01

    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 http://journal.frontiersin.org/article/10.3389/fphys.2017.00531/full

  2. Self-assembled containers based on extended tetrathiafulvalene.

    Science.gov (United States)

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

    2013-07-10

    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.

  3. Self-assembly and speed distributions of active granular particles

    Science.gov (United States)

    Sánchez, R.; Díaz-Leyva, P.

    2018-06-01

    The relationship between the dynamics of self-propelled systems and the self-assembly of structured clusters are studied via the experimental speed distributions of submonolayers of self-propelled granular particles. A distribution developed for non-self-propelled granular particles describes the speed distributions remarkably well, despite some of the assumptions behind its original derivation not being applicable. This is explained in terms of clustering and dissipation being the key phenomena governing this regime.

  4. Biocompatible and Biomimetic Self-Assembly of Functional Nanostructures

    Science.gov (United States)

    2010-02-28

    evaporation induced self-assembly of aqueous silica precursors with a biologically compatible surfactant, glycerol monooleate ( GMO ) via dip-coating...film 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

  5. Continuum Modeling of Biological Network Formation

    KAUST Repository

    Albi, Giacomo

    2017-04-10

    We present an overview of recent analytical and numerical results for the elliptic–parabolic system of partial differential equations proposed by Hu and Cai, which models the formation of biological transportation networks. The model describes the pressure field using a Darcy type equation and the dynamics of the conductance network under pressure force effects. Randomness in the material structure is represented by a linear diffusion term and conductance relaxation by an algebraic decay term. We first introduce micro- and mesoscopic models and show how they are connected to the macroscopic PDE system. Then, we provide an overview of analytical results for the PDE model, focusing mainly on the existence of weak and mild solutions and analysis of the steady states. The analytical part is complemented by extensive numerical simulations. We propose a discretization based on finite elements and study the qualitative properties of network structures for various parameter values.

  6. Self-assembly of inorganic nanoparticles: Ab ovo

    Science.gov (United States)

    Kotov, Nicholas A.

    2017-09-01

    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.

  7. Supramolecular ribbons from amphiphilic trisamides self-assembly.

    Science.gov (United States)

    García, Fátima; Buendía, Julia; Sánchez, Luis

    2011-08-05

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

  8. Molecular Motions in Functional Self-Assembled Nanostructures

    Directory of Open Access Journals (Sweden)

    Jean-Marc Saiter

    2013-01-01

    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.

  9. Self-assembled magnetic filter for highly efficient immunomagnetic separation.

    Science.gov (United States)

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

    2011-01-07

    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.

  10. Controlling Self-Assembly in Al(110) Homoepitaxy

    Science.gov (United States)

    Tiwary, Yogesh; Fichthorn, Kristen

    2010-03-01

    Homoepitaxial growth on Al(110) exhibits nanoscale self-assembly into huts with well-defined (100) and (111) facets [1]. Although some of the diffusion mechanisms underlying this kinetic self-assembly were identified and incorporated into a two-dimensional model [2], we used density-functional theory (DFT) to identify many other mechanisms that are needed to describe the three-dimensional assembly seen experimentally [3]. We developed a three-dimensional kinetic Monte Carlo (KMC) model of Al(110) homoepitaxy. The inputs to the model were obtained from DFT [3,4]. Our model is in agreement with experimentally observed trends for this system. We used KMC to predict self-assembly under various growth conditions. To achieve precise placement of Al nanohuts, we simulated thermal-field-directed assembly [5]. Our results indicate that this technique can be used to create uniform arrays of nanostructures. [1] F. Buatier de Mongeot, W. Zhu, A. Molle, R. Buzio, C. Boragno, U. Valbusa, E. Wang, and Z. Zhang, Phys. Rev. Lett. 91, 016102 (2003). [2] W. Zhu, F. Buatier de Mongeot, U. Valbusa, E. G. Wang, and Z. Y. Zhang, Phys. Rev. Lett. 92, 106102 (2004). [3] Y. Tiwary and K. A. Fichthorn, submitted to Phys. Rev. B. [4] Y. Tiwary and K. A. Fichthorn, Phys. Rev. B 78, 205418 (2008). [5] C. Zhang and R. Kalyanaraman, Appl. Phys. Lett. 83, 4827 (2003).

  11. Toward tunable doping in graphene FETs by molecular self-assembled monolayers

    Science.gov (United States)

    Li, Bing; Klekachev, Alexander V.; Cantoro, Mirco; Huyghebaert, Cedric; Stesmans, André; Asselberghs, Inge; de Gendt, Stefan; de Feyter, Steven

    2013-09-01

    In this paper, we report the formation of self-assembled monolayers (SAMs) of oleylamine (OA) on highly oriented pyrolytic graphite (HOPG) and graphene surfaces and demonstrate the potential of using such organic SAMs to tailor the electronic properties of graphene. Molecular resolution Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) images reveal the detailed molecular ordering. The electrical measurements show that OA strongly interacts with graphene leading to n-doping effects in graphene devices. The doping levels are tunable by varying the OA deposition conditions. Importantly, neither hole nor electron mobilities are decreased by the OA modification. As a benefit from this noncovalent modification strategy, the pristine characteristics of the device are recoverable upon OA removal. From this study, one can envision the possibility to correlate the graphene-based device performance with the molecular structure and supramolecular ordering of the organic dopant.In this paper, we report the formation of self-assembled monolayers (SAMs) of oleylamine (OA) on highly oriented pyrolytic graphite (HOPG) and graphene surfaces and demonstrate the potential of using such organic SAMs to tailor the electronic properties of graphene. Molecular resolution Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) images reveal the detailed molecular ordering. The electrical measurements show that OA strongly interacts with graphene leading to n-doping effects in graphene devices. The doping levels are tunable by varying the OA deposition conditions. Importantly, neither hole nor electron mobilities are decreased by the OA modification. As a benefit from this noncovalent modification strategy, the pristine characteristics of the device are recoverable upon OA removal. From this study, one can envision the possibility to correlate the graphene-based device performance with the molecular structure and supramolecular ordering of the organic

  12. Self-assembly of micelles into designed networks

    Directory of Open Access Journals (Sweden)

    Pyatenko Alexander

    2007-01-01

    Full Text Available AbstractThe EO20PO70EO20(molecular weight 5800 amphiphile as a template is to form dispersed micelle structures. Silver nanoparticles, as inorganic precursors synthesized by a laser ablation method in pure water, are able to produce the highly ordered vesicles detected by TEM micrography. The thickness of the outer layer of a micelle, formed by the silver nanoparticles interacting preferentially with the more hydrophilic EO20block, was around 3.5 nm. The vesicular structure ensembled from micelles is due to proceeding to the mixture of cubic and hexagonal phases.

  13. Topographic characterization of the self-assembled nanostructures of chitosan on mica surface by atomic force microscopy

    International Nuclear Information System (INIS)

    Wang, Li; Wu, Jiafeng; Guo, Yan; Gong, Coucong; Song, Yonghai

    2015-01-01

    Graphical abstract: - Highlights: • Nanocomposites of chitosan film were prepared by simple self-assembly from solvent media. • Chitosan molecules assembled on mica surface of nanoparticles, fibril and membrane with varied chitosan concentration. • Chitosan molecules assembled with different nanostructure under varied pH. • The optimum drying temperature for forming chitosan membrane is about 65 °C. - Abstract: In this work, the self-assembled nanostructures of chitosan on mica surface formed from various solvents were investigated by using atomic force microscopy. The effects of various factors on the self-assembled nanostructures of chitosan on mica surface, including solvents, the concentration of chitosan, the pH of solution and the drying temperature, were explored in detail. Our experimental data resulted in the conclusion that chitosan molecules could self-assemble on mica surface to form various nanostructures such as nanoparticles, fibril and film. Nanoparticles were always formed on mica surface from CCl_4, C_6H_6, CH_2Cl_2 solution, fibril preferred to form on mica surface from CH_3CH_2OH and CH_3OH solution and the optimal solvent to form film was found to be CH_3CN. Low concentration, pH and temperature were helpful for the formation of nanoparticles, medium concentration, pH and temperature resulted in fibril and high concentration, pH and temperature were often beneficial to forming chitosan films. The study of self-assembled nanostructures of chitosan on mica surface would provide new insight into the development of chitosan-based load-bearing materials.

  14. Self-assembled nanomaterials based on beta (β"3) tetrapeptides

    International Nuclear Information System (INIS)

    Seoudi, Rania S; Hinds, Mark G; Wilson, David J D; Adda, Christopher G; Mechler, Adam; Del Borgo, Mark; Aguilar, Marie-Isabel; Perlmutter, Patrick

    2016-01-01

    β "3-amino acid based polypeptides offer a unique starting material for the design of self-assembled nanostructures such as fibres and hierarchical dendritic assemblies, due to their well-defined helical geometry in which the peptide side chains align at 120° due to the 3.0–3.1 residue pitch of the helix. In a previous work we have described the head-to-tail self-assembly of N-terminal acetylated β "3-peptides into infinite helical nanorods that was achieved by designing a bioinspired supramolecular self-assembly motif. Here we describe the effect of consecutively more polar side chains on the self-assembly characteristics of β "3-tetrapeptides Ac-β "3Ala-β "3Leu-β "3Ile-β "3Ala (Ac-β"3[ALIA]), Ac-β "3Ser-β "3Leu-β "3Ile-β "3Ala (Ac-β"3[SLIA]) and Ac-β "3Lys-β "3Leu-β "3Ile-β "3Glu (Ac-β"3[KLIE]). β "3-tetrapeptides complete 1 1/3 turns of the helix: thus in the oligomeric form the side chain positions shift 120° with each added monomer, forming a regular periodic pattern along the nanorod. Dynamic light scattering (DLS) measurements confirmed that these peptides self-assemble even in highly polar solvents such as water and DMSO, while diffusion-ordered NMR spectroscopy revealed the presence of a substantial monomeric population. Temperature dependence of the size distribution in DLS measurements suggests a dynamic equilibrium between monomers and oligomers. Solution casting produced distinct fibrillar deposits after evaporating the solvent. In the case of the apolar Ac-β "3[ALIA] the longitudinal helix morphology gives rise to geometrically defined (∼70°) junctions between fibres, forming a mesh that opens up possibilities for applications e.g. in tissue scaffolding. The deposits of polar Ac-β "3[SLIA] and Ac-β "3[KLIE] exhibit fibres in regular parallel alignment over surface areas in the order of 10 μm. (paper)

  15. Nanospheres Prepared by Self-Assembly of Random Copolymers in Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Eri Yoshida

    2012-01-01

    Full Text Available The synthesis of spherical particles was attained by the direct self-assembly of poly[2-(perfluorooctylethyl acrylate-random-acrylic acid], P(POA-r-AA, and by the indirect self-assembly poly[POA-random-2-(dimethylaminoethyl acrylate], P(POA-r-DAA, with dicarboxylic acids in supercritical carbon dioxide (scCO2. The copolymers formed spherical particles with hundreds of nanometer diameters in a heterogeneous state at pressures lower than the cloud point pressure. The formation of spherical particles was also dependent on the temperature. The formation of spherical particles could be optimized through varying the solvent quality by the manipulation of the CO2 pressure and temperature for the different copolymer compositions. The dynamic light scattering and 1H NMR studies demonstrated that the nanospheres had the micellar structures consisting of the CO2-philic POA shells and the CO2-phobic AA or DAA cores including the main chain cores. The nanospheres produced the superhydrophobic surfaces based on the water-proof shells of the POA units.

  16. Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly

    Science.gov (United States)

    Boott, Charlotte E.; Gwyther, Jessica; Harniman, Robert L.; Hayward, Dominic W.; Manners, Ian

    2017-08-01

    The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles—which are promising for many applications—are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach—starting from monomers—that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres.

  17. Self-assembly model, hepatocytes attachment and inflammatory response for silk fibroin/chitosan scaffolds

    International Nuclear Information System (INIS)

    She Zhending; Feng Qingling; Liu Weiqiang

    2009-01-01

    Silk fibroin is an attractive natural fibrous protein for biomedical application due to its good biocompatibility and high tensile strength. Silk fibroin is apt to form a sheet-like structure during the freeze-drying process, which is not suitable for the scaffold of tissue engineering. In our former study, the adding of chitosan promoted the self-assembly of silk fibroin/chitosan (SFCS) into a three-dimensional (3D) homogeneous porous structure. In this study, a model of the self-assembly is proposed; furthermore, hepatocytes attachment and inflammatory response for the SFCS scaffold were examined. The rigid chain of chitosan may be used as a template for β-sheet formation of silk fibroin, and this may break the sheet structure of the silk fibroin scaffold and promote the formation of a 3D porous structure of the SFCS scaffold. Compared with the polylactic glycolic acid scaffold, the SFCS scaffold further facilitates the attachment of hepatocytes. To investigate the inflammatory response, SFCS scaffolds were implanted into the greater omentum of rats. From the results of implantation, we could demonstrate in vivo that the implantation of SFCS scaffolds resulted in only slight inflammation. Keeping the good histocompatibility and combining the advantages of both fibroin and chitosan, the SFCS scaffold could be a prominent candidate for soft tissue engineering, for example, in the liver.

  18. Self-assembly model, hepatocytes attachment and inflammatory response for silk fibroin/chitosan scaffolds

    Energy Technology Data Exchange (ETDEWEB)

    She Zhending; Feng Qingling [State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Liu Weiqiang, E-mail: biomater@mail.tsinghua.edu.c [Center for Advanced Materials and Biotechnology, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China)

    2009-08-15

    Silk fibroin is an attractive natural fibrous protein for biomedical application due to its good biocompatibility and high tensile strength. Silk fibroin is apt to form a sheet-like structure during the freeze-drying process, which is not suitable for the scaffold of tissue engineering. In our former study, the adding of chitosan promoted the self-assembly of silk fibroin/chitosan (SFCS) into a three-dimensional (3D) homogeneous porous structure. In this study, a model of the self-assembly is proposed; furthermore, hepatocytes attachment and inflammatory response for the SFCS scaffold were examined. The rigid chain of chitosan may be used as a template for beta-sheet formation of silk fibroin, and this may break the sheet structure of the silk fibroin scaffold and promote the formation of a 3D porous structure of the SFCS scaffold. Compared with the polylactic glycolic acid scaffold, the SFCS scaffold further facilitates the attachment of hepatocytes. To investigate the inflammatory response, SFCS scaffolds were implanted into the greater omentum of rats. From the results of implantation, we could demonstrate in vivo that the implantation of SFCS scaffolds resulted in only slight inflammation. Keeping the good histocompatibility and combining the advantages of both fibroin and chitosan, the SFCS scaffold could be a prominent candidate for soft tissue engineering, for example, in the liver.

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

    Science.gov (United States)

    Shah, Vivek B; Biswas, Pratim

    2014-02-25

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

  20. Novel self-assembled mesalamine-sucralfate complexes: preparation, characterization, and formulation aspects.

    Science.gov (United States)

    Ispas-Szabo, Pompilia; Friciu, Mihaela Maria; Nguyen, Phuong; Dumoulin, Yves; Mateescu, Mircea Alexandru

    2016-01-01

    Two well-known active agents, mesalamine (MES) and sucralfate (SUC), were investigated for possible utilization as fixed-dose combination product. The anti-inflammatory action of MES in association with bioadhesiveness and mucosal healing properties of SUC were considered promising for the development of a new compound containing both molecules, aimed as an improved treatment of ulcerative colitis. The present study investigates the capacity of the two active agents to interact and generate a new and stable entity via self-assembling. Spray-drying was used to co-process the two active principles from an aqueous mixture where the ratio MES:SUC was in the range 25:75, 50:50, and 75:25. The structural data (X-Ray, FTIR, SEM, DSC, and (1)H NMR) have shown that MES and SUC are interacting leading to complexes with properties differing from those of each separate active agent and from their physical blends. (1)H NMR results indicated that complexation occurred when the aqueous suspensions of drugs were mixed, prior to spray-drying. Drug-drug self-assembling was the driving mechanism in the formation of the new entity. Based on the structural data, a hypothetical structure of the complex was proposed. Co-processing of MES and SUC represents a simple and useful procedure to prepare new self-assembled compounds by valorizing the ionic interactions between the two entities. Preliminary studies with oral solid dosage forms based on MES-SUC complexes tested in vitro have shown a controlled MES release, opening the perspective of a new colon-targeted delivery system and a novel class of compounds with therapeutic application in inflammatory bowel diseases.

  1. Engineering Plasmonic Nanocrystal Coupling through Template-Assisted Self-Assembly

    Science.gov (United States)

    Greybush, Nicholas J.

    The construction of materials from nanocrystal building blocks represents a powerful new paradigm for materials design. Just as nature's materials orchestrate intricate combinations of atoms from the library of the periodic table, nanocrystal "metamaterials" integrate individual nanocrystals into larger architectures with emergent collective properties. The individual nanocrystal "meta-atoms" that make up these materials are themselves each a nanoscale atomic system with tailorable size, shape, and elemental composition, enabling the creation of hierarchical materials with predesigned structure at multiple length scales. However, an improved fundamental understanding of the interactions among individual nanocrystals is needed in order to translate this structural control into enhanced functionality. The ability to form precise arrangements of nanocrystals and measure their collective properties is therefore essential for the continued development of nanocrystal metamaterials. In this dissertation, we utilize template-assisted self-assembly and spatially-resolved spectroscopy to form and characterize individual nanocrystal oligomers. At the intersection of "top-down" and "bottom-up" nanoscale patterning schemes, template-assisted self-assembly combines the design freedom of lithography with the chemical control of colloidal synthesis to achieve unique nanocrystal configurations. Here, we employ shape-selective templates to assemble new plasmonic structures, including heterodimers of Au nanorods and upconversion phosphors, a series of hexagonally-packed Au nanocrystal oligomers, and triangular formations of Au nanorods. Through experimental analysis and numerical simulation, we elucidate the means through which inter-nanocrystal coupling imparts collective optical properties to the plasmonic assemblies. Our self-assembly and measurement strategy offers a versatile platform for exploring optical interactions in a wide range of material systems and application areas.

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

    Science.gov (United States)

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

    2009-08-24

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

  3. Isolated self-assembled InAs/InP(001) quantum wires obtained by controlling the growth front evolution

    International Nuclear Information System (INIS)

    Fuster, David; Alen, Benito; Gonzalez, Luisa; Gonzalez, Yolanda; Martinez-Pastor, Juan; Gonzalez, Maria Ujue; GarcIa, Jorge M

    2007-01-01

    In this work we explore the first stages of quantum wire (QWR) formation studying the evolution of the growth front for InAs coverages below the critical thickness, θ c , determined by reflection high energy electron diffraction (RHEED). Our results obtained by in situ measurement of the accumulated stress evolution during InAs growth on InP(001) show that the relaxation process starts at a certain InAs coverage θ R c . At this θ R , the spontaneous formation of isolated quantum wires takes place. For θ>θ R this ensemble of isolated nanostructures progressively evolves towards QWRs that cover the whole surface for θ θ c . These results allow for a better understanding of the self-assembling process of QWRs and enable the study of the individual properties of InAs/InP self-assembled single quantum wires

  4. Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat

    Science.gov (United States)

    Suh, Hyo Seon; Kim, Do Han; Moni, Priya; Xiong, Shisheng; Ocola, Leonidas E.; Zaluzec, Nestor J.; Gleason, Karen K.; Nealey, Paul F.

    2017-07-01

    Directed self-assembly (DSA) of the domain structure in block copolymer (BCP) thin films is a promising approach for sub-10-nm surface patterning. DSA requires the control of interfacial properties on both interfaces of a BCP film to induce the formation of domains that traverse the entire film with a perpendicular orientation. Here we show a methodology to control the interfacial properties of BCP films that uses a polymer topcoat deposited by initiated chemical vapour deposition (iCVD). The iCVD topcoat forms a crosslinked network that grafts to and immobilizes BCP chains to create an interface that is equally attractive to both blocks of the underlying copolymer. The topcoat, in conjunction with a chemically patterned substrate, directs the assembly of the grating structures in BCP films with a half-pitch dimension of 9.3 nm. As the iCVD topcoat can be as thin as 7 nm, it is amenable to pattern transfer without removal. The ease of vapour-phase deposition, applicability to high-resolution BCP systems and integration with pattern-transfer schemes are attractive properties of iCVD topcoats for industrial applications.

  5. Indirect amperometric sensing of dopamine using a redox-switchable naphthoquinone-terminated self-assembled monolayer on gold electrode

    International Nuclear Information System (INIS)

    Hammami, Asma; Raouafi, Noureddine; Sahli, Rihab

    2016-01-01

    We report on the design of a simple yet sensitive and selective electrode for amperometric determination of dopamine at a cathodic potential as low as −0.30 V vs. Ag/AgCl. The electrode was obtained by self-assembly of ω-mercaptopropyl naphthoquinone (NQ-SAM) on the surface of a polycrystalline gold electrode. The presence of dopamine induces an increase of the reduction current peak at −0.30 V corresponding to the reduction of naphthoquinone to hydronaphthoquinone. Dopamine and dopamine-quinone accumulate on the surface to form a 3D network linked by hydrogen bonds. Raman and infrared spectroscopy as well as atomic force microscopy confirmed the multilayer formation. The method allows dopamine to be indirectly detected at a working potential that is lower by 0.50 V than the standard oxidation potential at a bare gold electrode. The sensor shows distinct oxidation potentials for dopamine (120 mV), ascorbic acid (280 mV) and uric acid (520 mV) which makes the method fairly selective. The analytical range extends from 1 to 100 μM concentrations of dopamine, and the limits of detection and quantification are 0.040 and 0.134 μM, respectively. (author)

  6. Borax mediated layer-by-layer self-assembly of neutral poly(vinyl alcohol) and chitosan.

    Science.gov (United States)

    Manna, Uttam; Patil, Satish

    2009-07-09

    We report a multilayer film of poly(vinyl alcohol) (PVA)-borate complex and chitosan by using a layer-by-layer approach. PVA is an uncharged polymer, but hydroxyl functional groups of PVA can be cross-linked by using borax as a cross-linking agent. As a result electrostatic charges and intra- and interchain cross-links are introduced in the PVA chain and provide physically cross-linked networks. The PVA-borate was then deposited on a flat substrate as well as on colloidal particles with chitosan as an oppositely charged polyelectrolyte. Quartz crystal microbalance, scanning electron microscopy, and atomic force microscopy were used to follow the growth of thin film on flat substrate. Analogous experiments were performed on melamine formaldehyde colloidal particles (3-3.5 microm) to quantify the process for the preparation of hollow microcapsules. Removal of the core in 0.1 N HCl results in hollow microcapsules. Characterization of microcapsules by transmission electron microscopy revealed formation of stable microcapsules. Further, self-assembly of PVA-borate/chitosan was loaded with the anticancer drug doxorubicin, and release rates were determined at different pH values to highlight the drug delivery potential of this system.

  7. SM50 repeat-polypeptides self-assemble into discrete matrix subunits and promote appositional calcium carbonate crystal growth during sea urchin tooth biomineralization.

    Science.gov (United States)

    Mao, Yelin; Satchell, Paul G; Luan, Xianghong; Diekwisch, Thomas G H

    2016-01-01

    The two major proteins involved in vertebrate enamel formation and echinoderm sea urchin tooth biomineralization, amelogenin and SM50, are both characterized by elongated polyproline repeat domains in the center of the macromolecule. To determine the role of polyproline repeat polypeptides in basal deuterostome biomineralization, we have mapped the localization of SM50 as it relates to crystal growth, conducted self-assembly studies of SM50 repeat polypeptides, and examined their effect on calcium carbonate and apatite crystal growth. Electron micrographs of the growth zone of Strongylocentrotus purpuratus sea urchin teeth documented a series of successive events from intravesicular mineral nucleation to mineral deposition at the interface between tooth surface and odontoblast syncytium. Using immunohistochemistry, SM50 was detected within the cytoplasm of cells associated with the developing tooth mineral, at the mineral secreting front, and adjacent to initial mineral deposits, but not in muscles and ligaments. Polypeptides derived from the SM50 polyproline alternating hexa- and hepta-peptide repeat region (SM50P6P7) formed highly discrete, donut-shaped self-assembly patterns. In calcium carbonate crystal growth studies, SM50P6P7 repeat peptides triggered the growth of expansive networks of fused calcium carbonate crystals while in apatite growth studies, SM50P6P7 peptides facilitated the growth of needle-shaped and parallel arranged crystals resembling those found in developing vertebrate enamel. In comparison, SM50P6P7 surpassed the PXX24 polypeptide repeat region derived from the vertebrate enamel protein amelogenin in its ability to promote crystal nucleation and appositional crystal growth. Together, these studies establish the SM50P6P7 polyproline repeat region as a potent regulator in the protein-guided appositional crystal growth that occurs during continuous tooth mineralization and eruption. In addition, our studies highlight the role of species

  8. Encapsulation of Curcumin in Self-Assembling Peptide Hydrogels as Injectable Drug Delivery Vehicles

    Science.gov (United States)

    Altunbas, Aysegul; Lee, Seung Joon; Rajasekaran, Sigrid A.; Schneider, Joel P.; Pochan, Darrin J.

    2011-01-01

    Curcumin, a hydrophobic polyphenol, is an extract of turmeric root with antioxidant, anti-inflammatory and anti-tumorigenic properties. Its lack of water solubility and relatively low bioavailability set major limitations for its therapeutic use. In this study, a self-assembling peptide hydrogel is demonstrated to be an effective vehicle for the localized delivery of curcumin over sustained periods of time. The curcumin-hydrogel is prepared in-situ where curcumin encapsulation within the hydrogel network is accomplished concurrently with peptide self-assembly. Physical and in vitro biological studies were used to demonstrate the effectiveness of curcumin-loaded β-hairpin hydrogels as injectable agents for localized curcumin delivery. Notably, rheological characterization of the curcumin loaded hydrogel before and after shear flow have indicated solid-like properties even at high curcumin payloads. In vitro experiments with a medulloblastoma cell line confirm that the encapsulation of the curcumin within the hydrogel does not have an adverse effect on its bioactivity. Most importantly, the rate of curcumin release and its consequent therapeutic efficacy can be conveniently modulated as a function of the concentration of the MAX8 peptide. PMID:21601921

  9. Evolving self-assembly in autonomous homogeneous robots: experiments with two physical robots.

    Science.gov (United States)

    Ampatzis, Christos; Tuci, Elio; Trianni, Vito; Christensen, Anders Lyhne; Dorigo, Marco

    2009-01-01

    This research work illustrates an approach to the design of controllers for self-assembling robots in which the self-assembly is initiated and regulated by perceptual cues that are brought forth by the physical robots through their dynamical interactions. More specifically, we present a homogeneous control system that can achieve assembly between two modules (two fully autonomous robots) of a mobile self-reconfigurable system without a priori introduced behavioral or morphological heterogeneities. The controllers are dynamic neural networks evolved in simulation that directly control all the actuators of the two robots. The neurocontrollers cause the dynamic specialization of the robots by allocating roles between them based solely on their interaction. We show that the best evolved controller proves to be successful when tested on a real hardware platform, the swarm-bot. The performance achieved is similar to the one achieved by existing modular or behavior-based approaches, also due to the effect of an emergent recovery mechanism that was neither explicitly rewarded by the fitness function, nor observed during the evolutionary simulation. Our results suggest that direct access to the orientations or intentions of the other agents is not a necessary condition for robot coordination: Our robots coordinate without direct or explicit communication, contrary to what is assumed by most research works in collective robotics. This work also contributes to strengthening the evidence that evolutionary robotics is a design methodology that can tackle real-world tasks demanding fine sensory-motor coordination.

  10. 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)

    2009-04-23

    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.

  11. Particle self-assembly at ionic liquid-based interfaces.

    Science.gov (United States)

    Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

    2014-04-01

    This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-03-15

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

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  14. Self-assembly of single "square" quantum rings in gold-free GaAs nanowires.

    Science.gov (United States)

    Zha, Guowei; Shang, Xiangjun; Su, Dan; Yu, Ying; Wei, Bin; Wang, Li; Li, Mifeng; Wang, Lijuan; Xu, Jianxing; Ni, Haiqiao; Ji, Yuan; Sun, Baoquan; Niu, Zhichuan

    2014-03-21

    Single nanostructures embedded within nanowires (NWs) represent one of the most promising technologies for applications in quantum photonics. However, fabrication imperfections and etching-induced defects are inevitable for top-down fabrications, whereas self-assembly bottom-up approaches cannot avoid the difficulties of its stochastic nature and are limited to restricted heterogeneous material systems. Here we demonstrate the versatile self-assembly of single "square" quantum rings (QR) on the sidewalls of gold-free GaAs NWs for the first time. By tuning the deposition temperature, As overpressure and amount of gallium-droplets, we were able to control the density and morphology of the structure, yielding novel single quantum dots, QR, coupled QRs, and nano-antidots. A proposed model based on a strain-driven, transport-dependent nucleation of gallium droplets at high temperature accounts for the formation mechanism of these structures. We achieved a single-QR-in-NW structure, of which the optical properties were analyzed using micro-photoluminescence at 10 K and a spatially resolved cathodoluminescence technique at 77 K. The spectra show sharp discrete peaks; of these peaks, the narrowest linewidth (separation) was 578 μeV (1-3 meV), reflecting the quantized nature of the ring-type electronic states.

  15. Block copolymer templated self-assembly of disk-shaped molecules

    Science.gov (United States)

    Aragones, J. L.; Alexander-Katz, A.

    2017-08-01

    Stacking of disk-shaped organic molecules is a promising strategy to develop electronic and photovoltaic devices. Here, we investigate the capability of a soft block copolymer matrix that microphase separates into a cylindrical phase to direct the self-assembly of disk-shaped molecules by means of molecular simulations. We show that two disk molecules confined in the cylinder domain experience a depletion force, induced by the polymer chains, which results in the formation of stacks of disks. This entropic interaction and the soft confinement provided by the matrix are both responsible for the structures that can be self-assembled, which include slanted or columnar stacks. In addition, we evidence the transmission of stresses between the different minority domains of the microphase, which results in the establishment of a long-ranged interaction between disk molecules embedded in different domains; this interaction is of the order of the microphase periodicity and may be exploited to direct assembly of disks at larger scales.

  16. Directed self-assembly of large scaffold-free multi-cellular honeycomb structures

    International Nuclear Information System (INIS)

    Tejavibulya, Nalin; Youssef, Jacquelyn; Bao, Brian; Ferruccio, Toni-Marie; Morgan, Jeffrey R

    2011-01-01

    A significant challenge to the field of biofabrication is the rapid construction of large three-dimensional (3D) living tissues and organs. Multi-cellular spheroids have been used as building blocks. In this paper, we create large multi-cellular honeycomb building blocks using directed self-assembly, whereby cell-to-cell adhesion, in the context of the shape and obstacles of a micro-mold, drives the formation of a 3D structure. Computer-aided design, rapid prototyping and replica molding were used to fabricate honeycomb-shaped micro-molds. Nonadhesive hydrogels cast from these micro-molds were equilibrated in the cell culture medium and seeded with two types of mammalian cells. The cells settled into the honeycomb recess were unable to attach to the nonadhesive hydrogel and so cell-to-cell adhesion drove the self-assembly of a large multi-cellular honeycomb within 24 h. Distinct morphological changes occurred to the honeycomb and its cells indicating the presence of significant cell-mediated tension. Unlike the spheroid, whose size is constrained by a critical diffusion distance needed to maintain cell viability, the overall size of the honeycomb is not limited. The rapid production of the honeycomb building unit, with its multiple rings of high-density cells and open lumen spaces, offers interesting new possibilities for biofabrication strategies.

  17. Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

    KAUST Repository

    Musteata, Valentina-Elena; Sutisna, Burhannudin; Polymeropoulos, Georgios; Avgeropoulos, Apostolos; Meneau, Florian; Peinemann, Klaus-Viktor; Hadjichristidis, Nikolaos; Nunes, Suzana Pereira

    2017-01-01

    Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

  18. Self-assembled H-aggregation induced high performance poly (3-hexylthiophene) Schottky diode

    Science.gov (United States)

    Chaudhary, Vivek; Pandey, Rajiv K.; Prakash, Rajiv; Singh, Arun Kumar

    2017-12-01

    The investigation of size confinement and chain orientation within the microstructure of a polymer thin film is very important for electronic device applications and fundamental research. Here, we present single step methodology for the synthesis of solution-processable poly (3-hexylthiophene) (P3HT) nanofibers via a self-assembly process. The formation of P3HT nanofibers is confirmed by atomic force microscopy. The synthesized nanofibers are characterized by UV-visible absorption, photoluminescence, and Raman spectroscopy. The aggregation type of self-assembled P3HT is studied by both UV-visible absorbance and photoluminescence spectroscopy. The exciton bandwidth in polymer films is calculated by following the Spano's H-aggregate model and found to be 28 meV. Raman spectroscopy is used to identify the various stretching modes present in nanofibers. The structural investigation using grazing angle X-ray diffraction of nanofibers reveals the presence of alkyl chain ordering. We have fabricated organic Schottky diodes with P3HT nanofibers on indium tin oxide (ITO) coated glass with configuration Al/P3HT/ITO, and current density-voltage characteristics are subsequently used for extracting the electronic parameters of the device. We have also discussed the charge transport mechanism at the metal/polymer interface.

  19. Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

    KAUST Repository

    Musteata, Valentina-Elena

    2017-11-08

    Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

  20. Biomimetic self-assembly of a functional asymmetrical electronic device.

    Science.gov (United States)

    Boncheva, Mila; Gracias, David H; Jacobs, Heiko O; Whitesides, George M

    2002-04-16

    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.

  1. Self-assembly of heterogeneous supramolecular structures with uniaxial anisotropy.

    Science.gov (United States)

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

    2006-12-28

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

  2. Passivation effects in B doped self-assembled Si nanocrystals

    International Nuclear Information System (INIS)

    Puthen Veettil, B.; Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Zhang, Tian; Yang, Terry; Johnson, Craig; Conibeer, Gavin; Perez-Würfl, Ivan; McCamey, Dane

    2014-01-01

    Doping of semiconductor nanocrystals has enabled their widespread technological application in optoelectronics and micro/nano-electronics. In this work, boron-doped self-assembled silicon nanocrystal samples have been grown and characterised using Electron Spin Resonance and photoluminescence spectroscopy. The passivation effects of boron on the interface dangling bonds have been investigated. Addition of boron dopants is found to compensate the active dangling bonds at the interface, and this is confirmed by an increase in photoluminescence intensity. Further addition of dopants is found to reduce the photoluminescence intensity by decreasing the minority carrier lifetime as a result of the increased number of non-radiative processes

  3. A 3D Optical Metamaterial Made by Self-Assembly

    KAUST Repository

    Vignolini, Silvia

    2011-10-24

    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.

  4. A 3D Optical Metamaterial Made by Self-Assembly

    KAUST Repository

    Vignolini, Silvia; Yufa, Nataliya A.; Cunha, Pedro S.; Guldin, Stefan; Rushkin, Ilia; Stefik, Morgan; Hur, Kahyun; Wiesner, Ulrich; Baumberg, Jeremy J.; Steiner, Ullrich

    2011-01-01

    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.

  5. Oscillatory persistent currents in self-assembled quantum rings.

    Science.gov (United States)

    Kleemans, N A J M; Bominaar-Silkens, I M A; Fomin, V M; Gladilin, V N; Granados, D; Taboada, A G; García, J M; Offermans, P; Zeitler, U; Christianen, P C M; Maan, J C; Devreese, J T; Koenraad, P M

    2007-10-05

    We report the direct measurement of the persistent current carried by a single electron by means of magnetization experiments on self-assembled InAs/GaAs quantum rings. We measured the first Aharonov-Bohm oscillation at a field of 14 T, in perfect agreement with our model based on the structural properties determined by cross-sectional scanning tunneling microscopy measurements. The observed oscillation magnitude of the magnetic moment per electron is remarkably large for the topology of our nanostructures, which are singly connected and exhibit a pronounced shape asymmetry.

  6. Microcolumns with self-assembled particle frits for proteomics

    DEFF Research Database (Denmark)

    Ishihama, Yasushi; Rappsilber, Juri; Andersen, Jens S

    2002-01-01

    LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size...... of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles...

  7. Rapid self-assembly of block copolymers to photonic crystals

    Science.gov (United States)

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  8. Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

    CERN Document Server

    Garti, Nissim

    2012-01-01

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

  9. Exploring the properties and possibilities of self-assembling

    DEFF Research Database (Denmark)

    Andersen, Karsten Brandt; Castillo, Jaime

    2013-01-01

    structures ranging from piezo electricity over semi conductance to fluorescence. If such peptide nanotubes could be controlled and incorporated in sensors such as a biological field effect transistor it would greatly reduce the fabrication costs while at the same time providing researchers with new...... and exciting possibilities. The major driving forces supporting the interest in the peptide nanotubes is the fast and simple assembly process combined with their remarkable stability towards alcohols, organic solvents, and biological analytes that was presented shortly after the self-assembling properties...... and illustrated their potential use as sensitive temperature sensor....

  10. Biomimetic engineering: towards a self-assembled nanotechnology

    International Nuclear Information System (INIS)

    Braach-Maksvytis, V.

    2002-01-01

    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

  11. Simultaneous synthesis and self-assembly of inorganic nanomaterials towards active and stable nanocatalysts

    Science.gov (United States)

    Yao, Zhou

    The synthetic process in which the formation of nanoparticles and the self-assembly of those nanoparticles as building blocks are coupled together represents an efficient strategy towards stable nanostructures with relatively large geometric dimensions, well-defined shapes, structural hierarchicy and desirable porosities. In this dissertation, through employing appropriate soft/hard templates and controlling the reaction kinetics and thermodynamics, a series of novel physicochemical processes were developed to generate a wide variety of hierarchical 1D, 2D and 3D nanostructures with complex chemical compositions, structural integrities and/or porosities, which were then evaluated as electrocatalysts, heterogeneous catalysts and adsorbents. Based on the properties of their chemical compositions and potential applications, two types of inorganic nanostructures were obtained, including the noble metal-based nanostructures which could be employed as electrocatalysts and the Al-silicate-based hierarchical nanocomposites which could be used for preparation of supported nanocatalysts. The formation mechanisms underlying different processes are also well investigated.

  12. Self-assembly of nanosize coordination cages on si(100) surfaces.

    Science.gov (United States)

    Busi, Marco; Laurenti, Marco; Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Fragalà, Ignazio L; Montalti, Marco; Prodi, Luca; Dalcanale, Enrico

    2007-01-01

    Bottom-up fabrication of 3D organic nanostructures on Si(100) surfaces has been achieved by a two-step procedure. Tetradentate cavitand 1 was grafted on the Si surface together with 1-octene (Oct) as a spatial spectator by photochemical hydrosilylation. Ligand exchange between grafted cavitand 1 and self-assembled homocage 2, derived from cavitand 5 bearing a fluorescence marker, led to the formation of coordination cages on Si(100). Formation, quantification, and distribution of the nanoscale molecular containers on a silicon surface was assessed by using three complementary analytical techniques (AFM, XPS, and fluorescence) and validated by control experiments on cavitand-free silicon surfaces. Interestingly, the fluorescence of pyrene at approximately 4 nm above the Si(100) surface can be clearly observed.

  13. Crystalline mono- and multilayer self-assemblies of oligothiophenes at the air-water interface

    DEFF Research Database (Denmark)

    Isz, S.; Weissbuch, I.; Kjær, K.

    1997-01-01

    The formation of Langmuir monolayers at the air-water interface has long been believed to be limited to amphiphilic molecules containing a hydrophobic chain and a hydrophilic headgroup. Here we report the formation of crystalline mono- and multilayer self-assemblies of oligothiophenes, a class...... of aromatic nonamphiphilic molecules, self-aggregated at the air-water interface. As model systems we have examined the deposition of quaterthiophene (S-4), quinquethiophene (S-5). and sexithiophene (S-6) from chloroform solutions on the water surface. The structures of the films were determined by surface...... surface. S-5 self-ageregates at the water surface to form mixtures of monolayers and bilayers of the beta polymorph; S-6 forms primarily crystalline monolayers of both alpha and beta forms. The crystalline assemblies preserve their integrity during transfer from the water surface onto solid supports...

  14. Self-assembled epitaxial NiSi2 nanowires on Si(001) by reactive deposition epitaxy

    International Nuclear Information System (INIS)

    Chen, S.Y.; Chen, L.J.

    2006-01-01

    Self-assembled epitaxial NiSi 2 nanowires have been fabricated on Si(001) by reactive deposition epitaxy (RDE). The RDE method promoted nanowire growth since it provides deposited atoms sufficient kinetic energy for movement on the Si surface during the growth of silicide islands. The twin-related interface between NiSi 2 and Si is directly related to the nanowire formation since it breaks the symmetry of the surface and leads to the asymmetric growth. The temperature of RDE was found to greatly influence the formation of nanowires. By RDE at 750 deg. C, a high density of NiSi 2 nanowires was formed with an average aspect ratio of 30

  15. Self-assembly of silica microparticles in magnetic multiphase flows: Experiment and simulation

    Science.gov (United States)

    Li, Xiang; Niu, Xiao-Dong; Li, You; Chen, Mu-Feng

    2018-04-01

    Dynamic self-assembly, especially self-assembly under magnetic field, is vital not only for its marvelous phenomenon but also for its mechanisms. Revealing the underlying mechanisms is crucial for a deeper understanding of self-assembly. In this paper, several magnetic induced self-assembly experiments by using the mixed magnetic multiphase fluids comprised of silica microspheres were carried out. The relations of the strength of external magnetic field, the inverse magnetorheological effect, and the structures of self-assembled particles were investigated. In addition, a momentum-exchanged immersed boundary-based lattice Boltzmann method (MEIB-LBM) for modeling multi-physical coupling multiphase flows was employed to numerically study the magnetic induced self-assembly process in detail. The present work showed that the external magnetic field can be used to control the form of self-assembly of nonmagnetic microparticles in a chain-like structure, and the self-assembly process can be classified into four stages with magnetic hysteresis, magnetization of nonmagnetic microparticles, self-assembly in chain-like structures, and the stable chain state. The combination of experimental and numerical results could offer a method to control the self-assembled nonmagnetic microparticles, which can provide the technical and theoretical support for the design and fabrication of micro/nanomaterials.

  16. Molecular dynamics simulations of peptide adsorption on self-assembled monolayers

    International Nuclear Information System (INIS)

    Xie Yun; Liu Meifeng; Zhou Jian

    2012-01-01

    All-atom molecular dynamics simulations are performed to investigate the neuromedin-B peptide adsorption on the self-assembled monolayers (SAMs) of SH(CH 2 ) 10 N + (CH 3 ) 2 CH 2 CH(OH)CH 2 SO 3 - (SBT), SH(CH 2 ) 10 OH and SH(CH 2 ) 10 CH 3 . The force-distance profiles show that the surface resistance to peptide adsorption is mainly generated by the water molecules tightly bound to surfaces via hydrogen bonds (hydration water molecules); but surfaces themselves may also set an energy barrier for the approaching peptide. For the SBT-SAM, the surface first exerts a relatively high repulsive force and then a rather week attractive force on the approaching peptide; meanwhile the hydration water molecules exert a strong repulsive force on the peptide. Therefore, SBT-SAM has an excellent performance on resisting protein adsorption. For the OH-SAM and CH 3 -SAM, surfaces show low or little energy barrier but strong affinity to the peptide; and the hydration water molecules apply merely a repulsive force within a much narrower range and with lower intensity compared with the case for the SBT-SAM. The analysis of structural and dynamical properties of the peptide, surface and water indicates that possible factors contributing to surface resistance include the hydrogen-bond formation capability of surfaces, mobility of water molecules near surfaces, surface packing density and chain flexibility of SAMs. There are a large number of hydrogen bonds formed between the hydration water molecules and the functional groups of the SBT-SAM, which greatly lowers the mobility of water molecules near the surface. This tightly-bound water layer effectively reduces the direct contact between the surface and the peptide. Furthermore, the SBT-SAM also has a high flexibility and a low surface packing density, which allows water molecules to penetrate into the surface to form tightly-bound networks and therefore reduces the affinity between the peptide and the surface. The results show that

  17. The influence of the type of oil phase on the self-assembly process of ¿-oryzanol + ß-sitosterol tubules in organogel systems

    NARCIS (Netherlands)

    Sawalha, H.I.M.; Margry, G.; Adel, den R.; Venema, P.; Bot, A.; Flöter, E.; Linden, van der E.

    2013-01-01

    Mixtures of ¿-oryzanol and ß-sitosterol were used to structure different oils (decane, limonene, sunflower oil, castor oil and eugenol). The ¿-oryzanol and ß-sitosterol mixtures self-assemble into double-walled hollow tubules (~10 nm in diameter) in the oil phase, which aggregate to form a network

  18. Solvent-mediated self-assembly of hexadecanethiol on GaAs (0 0 1)

    International Nuclear Information System (INIS)

    Huang, Xiaohuan; Dubowski, Jan J.

    2014-01-01

    Graphical abstract: - Highlights: • Outstanding quality hexadecanethiol self-assembled monolayers (HDT SAM) produced on GaAs (0 0 1) due to the mediated role of water in an alcoholic environment. • HDT SAM formed in chloroform exhibit excellent electronic passivation properties in contrast to their structural characteristics. • Low dielectric constant solvents do not necessary provide conditions advantageous for the formation of high quality alkanethiol SAM. • Photoluminescence emitting materials allow to investigate the mechanisms of both electronic and chemical passivation and, thus, they are an excellent platform for studying the mechanisms of SAM formation on solid substrates. - Abstract: We have investigated the influence of solvents on the quality of hexadecanethiol (HDT) self-assembled monolayers (SAM) formed on GaAs (0 0 1) in chloroform, ethanol and ethanol/water 1:1 characterized by their increasing dielectric constants from 4.8 (chloroform) to 24.5 (ethanol) and water (80.1). Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) data show that the incubation in ethanol/water 1:1 solution creates conditions favouring inter-molecular interaction leading to the formation of an outstanding quality HDT SAM on GaAs (0 0 1). Incubation in low-dielectric constant solvents is not offering advantageous conditions for growing HDT SAM on GaAs. The chloroform environment, while weakening the thiol–thiol interaction, induces the oxidation of the GaAs surface and, in particular, formation of Ga 2 O 3 . This reduces the concentration of surface defects responsible for non-radiative recombination and leads to an enhanced photoluminescence emission, despite the fact that HDT SAM formed in chloroform are highly disordered, exhibiting the worst chemical passivation among the investigated samples

  19. Spontaneous Self-Assembly of Fully Protected Ester 1:1 [α/α-Nα-Bn-hydrazino] Pseudodipeptides into a Twisted Parallel β-Sheet in the Crystal State.

    Science.gov (United States)

    Romero, Eugénie; Moussodia, Ralph-Olivier; Kriznik, Alexandre; Wenger, Emmanuel; Acherar, Samir; Jamart-Grégoire, Brigitte

    2016-10-07

    Previous studies have demonstrated that amidic α/β-pseudodipeptides, 1:1 [α/α-N α -Bn-hydrazino], have the ability to fold via a succession of γ-turn (C 7 pseudocycle) and hydrazinoturn in CDCl 3 solution, their amide terminals enabling the formation of an intramolecular H-bond network. Despite their lack of a primary amide terminals allowing the formation of the hydrazinoturn, their ester counterparts 1-4 were proven to self-assemble into C 6 and C 7 pseudocycles by intramolecular H-bonds in solution state and into an uncommon twisted parallel β-sheet through intermolecular H-bonding in the crystal state to form a supramolecular helix, with eight molecules needed to complete a full 360° rotation. Such self-organization (with eight molecules) has only been observed in a specific α/α-pseudodipeptide, depsipeptide (Boc-Leu-Lac-OEt). Relying on IR absorption, NMR, X-ray diffraction, and CD analyses, the aim of this study was to demonstrate that stereoisomers of ester 1:1 [α/α-N α -Bn-hydrazino] pseudodipeptides 1-4 are able to self-assemble into this β-helical structure. The absolute configuration of the asymmetric C α -atom of the α-amino acid residue influences the left- or right-handed twist without changing the pitch of the formed helix.

  20. Self-assembling layers created by membrane proteins on gold.

    Science.gov (United States)

    Shah, D S; Thomas, M B; Phillips, S; Cisneros, D A; Le Brun, A P; Holt, S A; Lakey, J H

    2007-06-01

    Membrane systems are based on several types of organization. First, amphiphilic lipids are able to create monolayer and bilayer structures which may be flat, vesicular or micellar. Into these structures membrane proteins can be inserted which use the membrane to provide signals for lateral and orientational organization. Furthermore, the proteins are the product of highly specific self-assembly otherwise known as folding, which mostly places individual atoms at precise places in three dimensions. These structures all have dimensions in the nanoscale, except for the size of membrane planes which may extend for millimetres in large liposomes or centimetres on planar surfaces such as monolayers at the air/water interface. Membrane systems can be assembled on to surfaces to create supported bilayers and these have uses in biosensors and in electrical measurements using modified ion channels. The supported systems also allow for measurements using spectroscopy, surface plasmon resonance and atomic force microscopy. By combining the roles of lipids and proteins, highly ordered and specific structures can be self-assembled in aqueous solution at the nanoscale.

  1. New self-assembly strategies for next generation lithography

    Science.gov (United States)

    Schwartz, Evan L.; Bosworth, Joan K.; Paik, Marvin Y.; Ober, Christopher K.

    2010-04-01

    Future demands of the semiconductor industry call for robust patterning strategies for critical dimensions below twenty nanometers. The self assembly of block copolymers stands out as a promising, potentially lower cost alternative to other technologies such as e-beam or nanoimprint lithography. One approach is to use block copolymers that can be lithographically patterned by incorporating a negative-tone photoresist as the majority (matrix) phase of the block copolymer, paired with photoacid generator and a crosslinker moiety. In this system, poly(α-methylstyrene-block-hydroxystyrene)(PαMS-b-PHOST), the block copolymer is spin-coated as a thin film, processed to a desired microdomain orientation with long-range order, and then photopatterned. Therefore, selfassembly of the block copolymer only occurs in select areas due to the crosslinking of the matrix phase, and the minority phase polymer can be removed to produce a nanoporous template. Using bulk TEM analysis, we demonstrate how the critical dimension of this block copolymer is shown to scale with polymer molecular weight using a simple power law relation. Enthalpic interactions such as hydrogen bonding are used to blend inorganic additives in order to enhance the etch resistance of the PHOST block. We demonstrate how lithographically patternable block copolymers might fit in to future processing strategies to produce etch-resistant self-assembled features at length scales impossible with conventional lithography.

  2. Self-assembled rosette nanotubes encapsulate and slowly release dexamethasone

    Directory of Open Access Journals (Sweden)

    Chen Y

    2011-05-01

    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

  3. Silver nanoprisms self-assembly on differently functionalized silica surface

    International Nuclear Information System (INIS)

    Pilipavicius, J; Chodosovskaja, A; Beganskiene, A; Kareiva, A

    2015-01-01

    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

  4. Stochastic lag time in nucleated linear self-assembly

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, Nitin S. [Group Theory of Polymers and Soft Matter, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Schoot, Paul van der [Group Theory of Polymers and Soft Matter, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Institute for Theoretical Physics, Utrecht University, Leuvenlaan 4, 3584 CE Utrecht (Netherlands)

    2016-06-21

    Protein aggregation is of great importance in biology, e.g., in amyloid fibrillation. The aggregation processes that occur at the cellular scale must be highly stochastic in nature because of the statistical number fluctuations that arise on account of the small system size at the cellular scale. We study the nucleated reversible self-assembly of monomeric building blocks into polymer-like aggregates using the method of kinetic Monte Carlo. Kinetic Monte Carlo, being inherently stochastic, allows us to study the impact of fluctuations on the polymerization reactions. One of the most important characteristic features in this kind of problem is the existence of a lag phase before self-assembly takes off, which is what we focus attention on. We study the associated lag time as a function of system size and kinetic pathway. We find that the leading order stochastic contribution to the lag time before polymerization commences is inversely proportional to the system volume for large-enough system size for all nine reaction pathways tested. Finite-size corrections to this do depend on the kinetic pathway.

  5. Probabilistic Performance Guarantees for Distributed Self-Assembly

    KAUST Repository

    Fox, Michael J.

    2015-04-01

    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.

  6. Self-Assembling Multifunctional Peptide Dimers for Gene Delivery Systems

    Directory of Open Access Journals (Sweden)

    Kitae Ryu

    2015-01-01

    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.

  7. Self-assembly of colloids with magnetic caps

    Energy Technology Data Exchange (ETDEWEB)

    Novak, E.V., E-mail: ekaterina.novak@urfu.ru [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)

    2017-06-01

    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.

  8. Managing lifelike behavior in a dynamic self-assembled system

    Science.gov (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.

  9. Synthesis and self-assembly of complex hollow materials

    KAUST Repository

    Zeng, Hua Chun

    2011-01-01

    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.

  10. Self-assembled cellulose materials for biomedicine: A review.

    Science.gov (United States)

    Yang, Jisheng; Li, Jinfeng

    2018-02-01

    Cellulose-based materials have reached a growing interest for the improvement of biomedicine, due to their good biocompatibility, biodegradability, and low toxicity. Self-assembly is a spontaneous process by which organized structures with particular functions and properties could be obtained without additional complicated processing steps. This article describes the modifications, properties and applications of cellulose and its derivatives, which including a detailed review of representative types of solvents such as NMMO, DMAc/LiCl, some molten salt hydrates, some aqueous solutions of metal complexes, ionic liquids and NaOH-water system etc. The modifications were frequently performed by esterification, etherification, ATRP, RAFT, ROP and other novel methods. Stimuli-responsive cellulose-based materials, such as temperature-, pH-, light- and redox-responsive, were synthesized for their superior performance. Additionally, the applications of cellulose-based materials which can self-assemble into micelles, vesicles and other aggregates, for drug/gene delivery, bioimaging, biosensor, are also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Self-assembly of dodecaphenyl POSS thin films

    Science.gov (United States)

    Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor

    2017-12-01

    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.

  12. Proteins evolve on the edge of supramolecular self-assembly

    Science.gov (United States)

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

    2017-08-01

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

  13. Self-assembled single-phase perovskite nanocomposite thin films.

    Science.gov (United States)

    Kim, Hyun-Suk; Bi, Lei; Paik, Hanjong; Yang, Dae-Jin; Park, Yun Chang; Dionne, Gerald F; Ross, Caroline A

    2010-02-10

    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.

  14. Liposomes self-assembled from electrosprayed composite microparticles

    International Nuclear Information System (INIS)

    Yu Dengguang; Yang Junhe; Wang Xia; Tian Feng

    2012-01-01

    Composite microparticles, consisting of polyvinylpyrrolidone (PVP), naproxen (NAP) and lecithin (PC), have been successfully prepared using an electrospraying process and exploited as templates to manipulate molecular self-assembly for the synthesis of liposomes in situ. Field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) observations demonstrate that the microparticles have an average diameter of 960 ± 140 nm and a homogeneous structure. X-ray diffraction (XRD) patterns, differential scanning calorimetry (DSC) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) results verify that the building blocks NAP and PC are scattered in the polymer matrix in a molecular way owing to the very fast drying of the electrospraying process and the favorable secondary interactions among the components. FESEM, scanning probe microscope (SPM) and TEM observations demonstrate that the liposomes can be achieved through molecular self-assembly in situ when the microparticles contact water thanks to ‘like prefers like’ and by means of the confinement effect of the microparticles. The liposomes have an encapsulation rate of 91.3%, and 80.7% of the drug in the liposomes can be freed into the dissolution medium in a sustained way and by a diffusion mechanism over a period of 24 h. The developed strategy not only provides a new, facile, and effective method to assemble and organize molecules of multiple components into liposomes with electrosprayed microparticles as templates, but also opens a new avenue for nanofabrication in a step-by-step and controllable way. (paper)

  15. Mixed carboranethiol self-assembled monolayers on gold surfaces

    Science.gov (United States)

    Yavuz, Adem; Sohrabnia, Nima; Yilmaz, Ayşen; Danışman, M. Fatih

    2017-08-01

    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.

  16. PageRank model of opinion formation on Ulam networks

    Science.gov (United States)

    Chakhmakhchyan, L.; Shepelyansky, D.

    2013-12-01

    We consider a PageRank model of opinion formation on Ulam networks, generated by the intermittency map and the typical Chirikov map. The Ulam networks generated by these maps have certain similarities with such scale-free networks as the World Wide Web (WWW), showing an algebraic decay of the PageRank probability. We find that the opinion formation process on Ulam networks has certain similarities but also distinct features comparing to the WWW. We attribute these distinctions to internal differences in network structure of the Ulam and WWW networks. We also analyze the process of opinion formation in the frame of generalized Sznajd model which protects opinion of small communities.

  17. The Role of Trust in Costly Network Formation

    NARCIS (Netherlands)

    Gilles, R.P.; Sarangi, S.

    2003-01-01

    We consider game theoretic models of social network formation.In this paper we limit our investigation to game theoretic models of network formation that are based on individual actions only.Our approach is based on three simple and realistic principles: (1) Link formation is a binary process of

  18. Morphology and Pattern Control of Diphenylalanine Self-Assembly via Evaporative Dewetting.

    Science.gov (United States)

    Chen, Jiarui; Qin, Shuyu; Wu, Xinglong; Chu, And Paul K

    2016-01-26

    Self-assembled peptide nanostructures have unique physical and biological properties and promising applications in electrical devices and functional molecular recognition. Although solution-based peptide molecules can self-assemble into different morphologies, it is challenging to control the self-assembly process. Herein, controllable self-assembly of diphenylalanine (FF) in an evaporative dewetting solution is reported. The fluid mechanical dimensionless numbers, namely Rayleigh, Marangoni, and capillary numbers, are introduced to control the interaction between the solution and FF molecules in the self-assembly process. The difference in the film thickness reflects the effects of Rayleigh and Marangoni convection, and the water vapor flow rate reveals the role of viscous fingering in the emergence of aligned FF flakes. By employing dewetting, various FF self-assembled patterns, like concentric and spokelike, and morphologies, like strips and hexagonal tubes/rods, can be produced, and there are no significant lattice structural changes in the FF nanostructures.

  19. Unknown Aspects of Self-Assembly of PbS Microscale Superstructures

    Science.gov (United States)

    Querejeta-Fernández, Ana; Hernández-Garrido, Juan C.; Yang, Hengxi; Zhou, Yunlong; Varela, Aurea; Parras, Marina; Calvino-Gámez, José J.; González-Calbet, Jose M.; Green, Peter F.; Kotov, Nicholas A.

    2012-01-01

    A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints this field requires advancements in three principle directions: a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and micro-levels of organization; b) understanding of disassembly/deconstruction processes; and c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: 1) nucleation of early PbS NPs with an average diameter of 31 nm; 2) assembly into 100–500 nm octahedral mesocrystals; 3) assembly into 1000–2500 nm hyperbranched stars; 4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; 5) deconstruction into rods and cubooctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern–determining forces that include vander Waals and electrostatic (charge-charge, dipole-dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy harvesting devices which require organization of PbS components at multiple scales. PMID:22515512

  20. Real time monitoring of superparamagnetic nanoparticle self-assembly on surfaces of magnetic recording media

    International Nuclear Information System (INIS)

    Ye, L.; Pearson, T.; Crawford, T. M.; Qi, B.; Cordeau, Y.; Mefford, O. T.

    2014-01-01

    Nanoparticle self-assembly dynamics are monitored in real-time by detecting optical diffraction from an all-nanoparticle grating as it self-assembles on a grating pattern recorded on a magnetic medium. The diffraction efficiency strongly depends on concentration, pH, and colloidal stability of nanoparticle suspensions, demonstrating the nanoparticle self-assembly process is highly tunable. This metrology could provide an alternative for detecting nanoparticle properties such as colloidal stability

  1. Crops: a green approach toward self-assembled soft materials.

    Science.gov (United States)

    Vemula, Praveen Kumar; John, George

    2008-06-01

    To date, a wide range of industrial materials such as solvents, fuels, synthetic fibers, and chemical products are being manufactured from petroleum resources. However, rapid depletion of fossil and petroleum resources is encouraging current and future chemists to orient their research toward designing safer chemicals, products, and processes from renewable feedstock with an increased awareness of environmental and industrial impact. Advances in genetics, biotechnology, process chemistry, and engineering are leading to a new manufacturing concept for converting renewable biomass to valuable fuels and products, generally known as the biorefinery concept. The swift integration of crop-based materials synthesis and biorefinery manufacturing technologies offers the potential for new advances in sustainable energy alternatives and biomaterials that will lead to a new manufacturing paradigm. This Account presents a novel and emerging concept of generating various forms of soft materials from crops (an alternate feedstock). In future research, developing biobased soft materials will be a fascinating yet demanding practice, which will have direct impact on industrial applications as an economically viable alternative. Here we discuss some remarkable examples of glycolipids generated from industrial byproducts such as cashew nut shell liquid, which upon self-assembly produced soft nanoarchitectures including lipid nanotubes, twisted/helical nanofibers, low-molecular-weight gels, and liquid crystals. Synthetic methods applied to a "chiral pool" of carbohydrates using the selectivity of enzyme catalysis yield amphiphilic products derived from biobased feedstock including amygdalin, trehalose, and vitamin C. This has been achieved with a lipase-mediated regioselective synthetic procedure to obtain such amphiphiles in quantitative yields. Amygdalin amphiphiles showed unique gelation behavior in a broad range of solvents such as nonpolar hexanes to polar aqueous solutions

  2. A promising routine to fabricate GeSi nanowires via self-assembly on miscut Si (001) substrates.

    Science.gov (United States)

    Zhong, Zhenyang; Gong, Hua; Ma, Yingjie; Fan, Yongliang; Jiang, Zuimin

    2011-04-11

    : Very small and compactly arranged GeSi nanowires could self-assembled on vicinal Si (001) substrates with ~8° off toward ⟨110⟩ during Ge deposition. The nanowires were all oriented along the miscut direction. The small ration of height over width of the nanowire indicated that the nanowires were bordered partly with {1 0 5} facets. These self-assembled small nanowires were remarkably influenced by the growth conditions and the miscut angle of substrates in comparison with large dome-like islands obtained after sufficient Ge deposition. These results proposed that the formation of the nanowire was energetically driven under growth kinetic assistance. Three-dimensionally self-assembled GeSi nanowires were first realized via multilayer Ge growth separated with Si spacers. These GeSi nanowires were readily embedded in Si matrix and compatible with the sophisticated Si technology, which suggested a feasible strategy to fabricate nanowires for fundamental studies and a wide variety of applications.PACS: 81.07.Gf, 81.16.Dn, 68.65.-k, 68.37.Ps.

  3. A promising routine to fabricate GeSi nanowires via self-assembly on miscut Si (001 substrates

    Directory of Open Access Journals (Sweden)

    Zhong Zhenyang

    2011-01-01

    Full Text Available Abstract Very small and compactly arranged GeSi nanowires could self-assembled on vicinal Si (001 substrates with ~8° off toward ⟨110⟩ during Ge deposition. The nanowires were all oriented along the miscut direction. The small ration of height over width of the nanowire indicated that the nanowires were bordered partly with {1 0 5} facets. These self-assembled small nanowires were remarkably influenced by the growth conditions and the miscut angle of substrates in comparison with large dome-like islands obtained after sufficient Ge deposition. These results proposed that the formation of the nanowire was energetically driven under growth kinetic assistance. Three-dimensionally self-assembled GeSi nanowires were first realized via multilayer Ge growth separated with Si spacers. These GeSi nanowires were readily embedded in Si matrix and compatible with the sophisticated Si technology, which suggested a feasible strategy to fabricate nanowires for fundamental studies and a wide variety of applications. PACS: 81.07.Gf, 81.16.Dn, 68.65.-k, 68.37.Ps

  4. Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

    Energy Technology Data Exchange (ETDEWEB)

    Tuccitto, N. [Dipartimento di Scienze Chimiche Universita degli Studi di Catania, v.le A. Doria 6, 95125, Catania (Italy)], E-mail: n.tuccitto@unict.it; Torrisi, V.; Delfanti, I.; Licciardello, A. [Dipartimento di Scienze Chimiche Universita degli Studi di Catania, v.le A. Doria 6, 95125, Catania (Italy)

    2008-12-15

    Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au{sub n}{sup -}) in comparison with the molecular ions (M{sup -}) and clusters (M{sub x}Au{sub y}{sup -}) by using Bi{sup +}, Bi{sub 3}{sup +}, Bi{sub 5}{sup +} beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.

  5. Fabrication of Cu{sub 2}S nanoneedles by self-assembly of nanoparticles via simple wet chemical route

    Energy Technology Data Exchange (ETDEWEB)

    Kumarakuru, Haridas, E-mail: haridas.kumarakuru@nmmu.ac.za; Coombes, Matthew J.; Neethling, Johannes H.; Westraadt, Johan E.

    2014-03-15

    Highlights: • An inexpensive wet chemical method was used at room temperature to grow Cu{sub 2}S. • Growth of Cu{sub 2}S nanostructures influences by the Cl{sup −} ion concentration. • Thioglycerol and Cl{sup −} ions are used as a blend capping agents. • Cu{sub 2}S nanoneedles were formed via self-assembly of nanoparticles. • We can propose a growth model for Cu{sub 2}S nanoneedles based on our observations. -- Abstract: Cu{sub 2}S nanoneedles, fabricated by self-assembly of Cu{sub 2}S nanoparticles via wet chemical method are investigated. Crystallinity and surface morphologies of the as-grown needles are examined using X-ray diffraction and scanning and transmission electron microscopy. It is observed that the nanoparticle formation is controlled by the blend concentration of capping agents, thioglycerol, added during the synthesis and the Cl{sup −} ions delivered by the CuCl source. The likely reasons for the elongated structure of the nanoparticle self-assembly are also discussed.

  6. Tailoring the self-assembly of linear alkyl chains for the design of advanced materials with technological applications.

    Science.gov (United States)

    Hoppe, Cristina E; Williams, Roberto J J

    2018-03-01

    The self-assembly of n-alkyl chains at the bulk or at the interface of different types of materials and substrates has been extensively studied in the past. The packing of alkyl chains is driven by Van der Waals interactions and can generate crystalline or disordered domains, at the bulk of the material, or self-assembled monolayers at an interface. This natural property of alkyl chains has been employed in recent years to develop a new generation of materials for technological applications. These studies are dispersed in a variety of journals. The purpose of this article was to discuss some selected examples where these advanced properties arise from a process involving the self-assembly of alkyl chains. We included a description of electronic devices and new-generation catalysts with properties derived from a controlled two-dimensional (2D) or three-dimensional (3D) self-assembly of alkyl chains at an interface. Then, we showed that controlling the crystallization of alkyl chains at the bulk can be used to generate a variety of advanced materials such as superhydrophobic coatings, shape memory hydrogels, hot-melt adhesives, thermally reversible light scattering (TRLS) films for intelligent windows and form-stable phase change materials (FS-PCMs) for the storage of thermal energy. Finally, we discussed two examples where advanced properties derive from the formation of disordered domains by physical association of alkyl chains. This was the case of photoluminescent nanocomposites and materials used for reversible optical storage. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Redox-Active Carbohydrate-Coated Nanoparticles: Self-Assembly of a Cyclodextrin-Polystyrene Glycopolymer with Tetrazine-Naphthalimide.

    Science.gov (United States)

    Gross, Andrew J; Haddad, Raoudha; Travelet, Christophe; Reynaud, Eric; Audebert, Pierre; Borsali, Redouane; Cosnier, Serge

    2016-11-15

    The controlled self-assembly of precise and well-defined photochemically and electrochemically active carbohydrate-coated nanoparticles offers the exciting prospect of biocompatible catalysts for energy storage/conversion and biolabeling applications. Here an aqueous nanoparticle system has been developed with a versatile outer layer for host-guest molecule encapsulation via β-cyclodextrin inclusion complexes. A β-cyclodextrin-modified polystyrene polymer was first obtained by copper nanopowder click chemistry. The glycopolymer enables self-assembly and controlled encapsulation of tetrazine-naphthalimide, as a model redox-active agent, into nanoparticles via nanoprecipitation. Cyclodextrin host-guest interactions permit encapsulation and internanoparticle cross-linking for the formation of fluorescent compound and clustered self-assemblies with chemically reversible electroactivity in aqueous solution. Light scattering experiments revealed stable particles with hydrodynamic diameters of 138 and 654 nm for nanoparticles prepared with tetrazine, of which 95% of the nanoparticles represent the smaller objects by number. Dynamic light scattering revealed differences as a function of preparation method in terms of size, 3-month stability, polydispersity, radius of gyration, and shape factor. Individual self-assemblies were visualized by atomic force microscopy and fluorescence microscopy and monitored in real-time by nanoparticle tracking analysis. UV-vis and fluorescence spectra provided insight into the optical properties and critical evidence for host-guest encapsulation as evidenced by solvachromatism and enhanced tetrazine uptake. Cyclic voltammetry was used to investigate the electrochemical properties and provided further support for encapsulation and an estimate of the tetrazine loading capacity in tandem with light scattering data.

  8. Self-assembly of fatty acids on hydroxylated Al surface and effects of their stability on wettability and nanoscale organization.

    Science.gov (United States)

    Liascukiene, Irma; Steffenhagen, Marie; Asadauskas, Svajus J; Lambert, Jean-François; Landoulsi, Jessem

    2014-05-27

    The self-assembly of fatty acids (FA) on the surfaces of inorganic materials is a relevant way to control their wetting properties. While the mechanism of adsorption on model flat substrate is well described in the literature, interfacial processes remain poorly documented on nanostructured surfaces. In this study, we report the self-assembly of a variety of FA on a hydroxylated Al surface which exhibits a random nanoscale organization. Our results revealed a peculiar fingerprint due to the FA self-assembly which consists in the formation of aligned nanopatterns in a state of hierarchical nanostructuration, regardless of the molecular structure of the FA (chain length, level of unsaturation). After a significant removal of adsorbed FA using UV/O3 treatment, a complete wetting was reached, and a noticeable disturbance of the surface morphology was observed, evidencing the pivotal role of FA molecules to maintain these nanostructures. The origin of wetting properties was investigated prior to and after conditioning of FA-modified samples taking into account key parameters, namely the surface roughness and its composition. For this purpose, the Wenzel roughness, defined as the third moment of power spectral density, was used, as it is sensitive to high spatial frequency and thus to the obtained hierarchical level of nanostructuration. Our results revealed that no correlation can be made between water contact angles (θ(w)) and the Wenzel roughness. By contrast, θ(w) strongly increased with the amount of -CHx- groups exhibited by adsorbed FA. These findings suggest that the main origin of hydrophobization is the presence of self-assembled molecules and that the surface roughness has only a small contribution to the wettability.

  9. Self-assembled patches in PtSi/n-Si (111) diodes

    Science.gov (United States)

    Afandiyeva, I. M.; Altιndal, Ş.; Abdullayeva, L. K.; Bayramova, A. İ.

    2018-05-01

    Using the effect of the temperature on the capacitance–voltage (C–V) and conductance–voltage (G/ω–V) characteristics of PtSi/n-Si (111) Schottky diodes the profile of apparent doping concentration (N Dapp), the potential difference between the Fermi energy level and the bottom of the conduction band (V n), apparent barrier height (Φ Bapp), series resistance (R s) and the interface state density N ss have been investigated. From the temperature dependence of (C–V) it was found that these parameters are non-uniformly changed with increasing temperature in a wide temperature range of 79–360 K. The voltage and temperature dependences of apparent carrier distribution we attributed to the existence of self-assembled patches similar the quantum wells, which formed due to the process of PtSi formation on semiconductor and the presence of hexagonal voids of Si (111).

  10. Fabrication of self-assembled photonic-crystal structures by centrifugation and spin coating

    Science.gov (United States)

    Xu, Yan; Schneider, Garrett J.; Wetzel, Eric D.; Prather, Dennis W.

    2003-11-01

    We have developed a simple, low-cost process for the fabrication of high-quality three-dimensional artificial-opal and inverse-opal photonic crystals. The process is based on the self-assembly of a template from a uniform suspension of polystyrene microspheres, which is sintered for added strength and subsequently back-filled with high-index material. The template formation is assisted by a combination of centrifugation and spin-annealing, which requires relatively short process times and inexpensive laboratory equipment. The process has been used to fabricate polycrystalline photonic crystals with photonic stop gaps in the mid-IR portion of the spectrum. Details of the fabrication process and fabricated samples will be presented. In addition, Fourier-transform IR reflection spectroscopy has been used to characterize the samples; the results are shown to be in excellent agreement with band structure diffraction calculations.

  11. Intracellular targeting of CD44+ cells with self-assembling, protein only nanoparticles.

    Science.gov (United States)

    Pesarrodona, Mireia; Ferrer-Miralles, Neus; Unzueta, Ugutz; Gener, Petra; Tatkiewicz, Witold; Abasolo, Ibane; Ratera, Imma; Veciana, Jaume; Schwartz, Simó; Villaverde, Antonio; Vazquez, Esther

    2014-10-01

    CD44 is a multifunctional cell surface protein involved in proliferation and differentiation, angiogenesis and signaling. The expression of CD44 is up-regulated in several types of human tumors and particularly in cancer stem cells, representing an appealing target for drug delivery in the treatment of cancer. We have explored here several protein ligands of CD44 for the construction of self-assembling modular proteins designed to bind and internalize target cells. Among five tested ligands, two of them (A5G27 and FNI/II/V) drive the formation of protein-only, ring-shaped nanoparticles of about 14 nm that efficiently bind and penetrate CD44(+) cells by an endosomal route. The potential of these newly designed nanoparticles is evaluated regarding the need of biocompatible nanostructured materials for drug delivery in CD44-linked conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-10-15

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

  13. 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

    2011-01-01

    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.

  14. Structural features of anodic oxide films formed on aluminum substrate coated with self-assembled microspheres

    International Nuclear Information System (INIS)

    Asoh, Hidetaka; Uchibori, Kota; Ono, Sachiko

    2009-01-01

    The structural features of anodic oxide films formed on an aluminum substrate coated with self-assembled microspheres were investigated by scanning electron microscopy and atomic force microscopy. In the first anodization in neutral solution, the growth of a barrier-type film was partially suppressed in the contact area between the spheres and the underlying aluminum substrate, resulting in the formation of ordered dimple arrays in an anodic oxide film. After the subsequent second anodization in acid solution at a voltage lower than that of the first anodization, nanopores were generated only within each dimple. The nanoporous region could be removed selectively by post-chemical etching using the difference in structural dimensions between the porous region and the surrounding barrier region. The mechanism of anodic oxide growth on the aluminum substrate coated with microspheres through multistep anodization is discussed.

  15. Structural features of anodic oxide films formed on aluminum substrate coated with self-assembled microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Asoh, Hidetaka [Department of Applied Chemistry, Faculty of Engineering, Kogakuin University, 2665-1 Nakano, Hachioji, Tokyo 192-0015 (Japan)], E-mail: asoh@cc.kogakuin.ac.jp; Uchibori, Kota; Ono, Sachiko [Department of Applied Chemistry, Faculty of Engineering, Kogakuin University, 2665-1 Nakano, Hachioji, Tokyo 192-0015 (Japan)

    2009-07-15

    The structural features of anodic oxide films formed on an aluminum substrate coated with self-assembled microspheres were investigated by scanning electron microscopy and atomic force microscopy. In the first anodization in neutral solution, the growth of a barrier-type film was partially suppressed in the contact area between the spheres and the underlying aluminum substrate, resulting in the formation of ordered dimple arrays in an anodic oxide film. After the subsequent second anodization in acid solution at a voltage lower than that of the first anodization, nanopores were generated only within each dimple. The nanoporous region could be removed selectively by post-chemical etching using the difference in structural dimensions between the porous region and the surrounding barrier region. The mechanism of anodic oxide growth on the aluminum substrate coated with microspheres through multistep anodization is discussed.

  16. Self-assembled colloidal PbS quantum dots on GaAs substrates

    International Nuclear Information System (INIS)

    Lue, Wei; Yamada, Fumihiko; Kamiya, Itaru

    2010-01-01

    We report the fabrication and analysis of self-assembled monolayer and bilayer films of colloidal PbS quantum dots (QDs) on GaAs (001) substrates. 1,6-hexanedithiol is used as link molecule between QDs and GaAs substrates. Atomic force microscopy (AFM) and photoluminescence (PL) measurements confirm the formation of PbS QD film on GaAs. For the monolayer PbS QD film, the temperature-dependent PL shows a feature typical of close-packed film. For the bilayer PbS QD film fabricated from two different mean-sized PbS QDs, we find that the stacking sequence of QDs with different size affects the quantum yield and emission wavelength of the film.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  18. Synthesis of Photocrosslinkable and Amine Containing Multifunctional Nanoparticles via Polymerization-Induced Self-Assembly.

    Science.gov (United States)

    Huang, Jianbing; Li, Decai; Liang, Hui; Lu, Jiang

    2017-08-01

    Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained. Since cinnamate groups can easily undergo a [2 + 2] cycloaddition of the carbon-carbon double bonds upon UV irradiation, the as-prepared block copolymer nanoparticles are readily stabilized by photo-crosslinking to produce anisotropic nanoparticles. The crosslinked block copolymer nanoparticles can be used as templates for in situ formation polymer/gold hybrid nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Light-assisted, templated self-assembly of gold nanoparticle chains.

    Science.gov (United States)

    Jaquay, Eric; Martínez, Luis Javier; Huang, Ningfeng; Mejia, Camilo A; Sarkar, Debarghya; Povinelli, Michelle L

    2014-09-10

    We experimentally demonstrate the technique of light-assisted, templated self-assembly (LATS) to trap and assemble 200 nm diameter gold nanoparticles. We excite a guided-resonance mode of a photonic-crystal slab with 1.55 μm laser light to create an array of optical traps. Unlike our previous demonstration of LATS with polystyrene particles, we find that the interparticle interactions play a significant role in the resulting particle patterns. Despite a two-dimensionally periodic intensity profile in the slab, the particles form one-dimensional chains whose orientations can be controlled by the incident polarization of the light. The formation of chains can be understood in terms of a competition between the gradient force due to the excitation of the mode in the slab and optical binding between particles.

  20. DNA-mediated self-assembly of carbon nanotubes on gold

    International Nuclear Information System (INIS)

    Sanchez-Pomales, Germarie; Rivera-Velez, Nelson E; Cabrera, Carlos R

    2007-01-01

    This report presents the use of disulfide-modified single-stranded DNA (ssDNA) to form DNA self-assembled monolayers (SAMs) and mixed DNA-carbon nanotube (CNT) hybrids SAMs on gold substrates. Mixed DNA-CNT SAMs are composed of DNA, mercaptohexanol (MCH) and DNA-CNT aggregates. Both, DNA-CNT and DNA areas of the mixed SAMs were analyzed and compared to traditional DNA SAMs. The results suggest the formation of a more compact and densely packed monolayer of DNA-CNT in comparison with DNA. The use of DNA-CNT hybrids to form SAMs on gold substrates might represent a new approach to improve the immobilization of DNA strands on gold, and might therefore help with the development of enhanced DNA sensors