Science.gov

Sample records for nanosphere self-assembly initiated

  1. A Solution NMR Investigation into the Early Events of Amelogenin Nanosphere Self-Assembly Initiated with Sodium Chloride or Calcium Chloride

    SciTech Connect

    Buchko, Garry W.; Tarasevich, Barbara J.; Bekhazi, Jacky G.; Snead, Malcolm L.; Shaw, Wendy J.

    2008-12-08

    Using solution-state NMR spectroscopy, new insights into the early intermolecular interactions stabilizing amelogenin supramolecular assembly and the potential role of calcium ions have been discovered. Two-dimensional 1H-15N spectra were recorded for 15N-labeled amelogenin as a function of increasing Ca2+ concentration starting from monomeric conditions. Evidence for protein-protein interactions were observed between residues E18 and E40 in the N-terminus. At higher Ca2+ concentrations there was concurrent involvement of residues in both the N- (Y12-Q56) and the C-terminus (Q144-T171). Neither specific residues nor their stepwise interaction have previously been identified in the initial stages of nanosphere assembly.

  2. One-pot synthesis, optical property and self-assembly of monodisperse silver nanospheres

    SciTech Connect

    Tang Aiwei; Qu Shengchun; Hou Yanbing; Teng Feng; Wang Yongsheng; Wang Zhanguo

    2011-08-15

    High-quality spherical silver (Ag) nanocrystals have been synthesized by using a one-pot approach, in which pre-synthesis of organometallic precursors is not required. This reaction involves the thermolysis of a mixed solution of silver acetate and n-dodecanethiol in a non-coordinating organic solvent. The size of the as-obtained Ag nanospheres can be controlled by adjusting the reaction time, reaction temperature and the amount of silver acetate added. The growth and nucleation process of the resultant Ag nanospheres have been studied by employing UV-vis absorption spectra and transmission electron microscopy (TEM) images. Furthermore, these Ag nanospheres have good self-assembly behaviors, and they are easily self-assembled into two- or three-dimensional superlattice structures due to the bundling and interdigitation of thiolate molecules adsorbed on Ag nanospheres. This one-pot synthetic procedure is simple and highly reproducible, which may be extended to prepare other noble-metal nanocrystals. - Graphical abstract: Different sized and monodisperse silver nanospheres were prepared using a one-pot approach with no pre-synthesis of organometallic precursors, and the silver nanospheres can self-assemble into highly ordered superlattices. Highlights: > Monodisperse silver nanospheres have been synthesized by a one-pot approach. > The synthetic method does not need pre-synthesis of organometallic precursors. > The silver nanospheres can self-assemble into highly ordered superlattices. > This synthetic method can be extended to prepare other metal nanocrystals.

  3. One-pot synthesis, optical property and self-assembly of monodisperse silver nanospheres

    NASA Astrophysics Data System (ADS)

    Tang, Aiwei; Qu, Shengchun; Hou, Yanbing; Teng, Feng; Wang, Yongsheng; Wang, Zhanguo

    2011-08-01

    High-quality spherical silver (Ag) nanocrystals have been synthesized by using a one-pot approach, in which pre-synthesis of organometallic precursors is not required. This reaction involves the thermolysis of a mixed solution of silver acetate and n-dodecanethiol in a non-coordinating organic solvent. The size of the as-obtained Ag nanospheres can be controlled by adjusting the reaction time, reaction temperature and the amount of silver acetate added. The growth and nucleation process of the resultant Ag nanospheres have been studied by employing UV-vis absorption spectra and transmission electron microscopy (TEM) images. Furthermore, these Ag nanospheres have good self-assembly behaviors, and they are easily self-assembled into two- or three-dimensional superlattice structures due to the bundling and interdigitation of thiolate molecules adsorbed on Ag nanospheres. This one-pot synthetic procedure is simple and highly reproducible, which may be extended to prepare other noble-metal nanocrystals.

  4. Hydrophobic drug delivery by self-assembling triblock copolymer-derived nanospheres.

    PubMed

    Sheihet, Larisa; Dubin, Robert A; Devore, David; Kohn, Joachim

    2005-01-01

    We describe the synthesis and characterization of a family of biocompatible ABA-triblock copolymers that comprised of hydrophilic A-blocks of poly(ethylene glycol) and hydrophobic B-blocks of oligomers of suberic acid and desaminotyrosyl-tyrosine esters. The triblock copolymers spontaneously self-assemble in aqueous solution into nanospheres, with hydrodynamic diameters between 40 and 70 nm, that do not dissociate under chromatographic and ultracentrifugation conditions. These nanospheres form strong complexes with hydrophobic molecules, including the fluorescent dye 5-dodecanoylaminofluorescein (DAF) and the antitumor drug, paclitaxel, but not with hydrophilic molecules such as fluorescein and Oregon Green. The nanosphere-paclitaxel complexes retain in vitro the high antiproliferative activity of paclitaxel, demonstrating that these nanospheres may be useful for delivery of the hydrophobic drugs.

  5. Amphiphilic Graft Copolymer Nanospheres: From Colloidal Self-Assembly to CO2 Capture Membranes.

    PubMed

    Jeon, Harim; Kim, Dong Jun; Park, Min Su; Ryu, Du Yeol; Kim, Jong Hak

    2016-04-13

    Colloidal nanosphere self-assembly effectively generates ordered nanostructures, prompting tremendous interest in many applications such as photonic crystals and templates for inverse opal fabrication. Here we report the self-assembly of low-cost, graft copolymer nanospheres for CO2 capture membranes. Specifically, poly(dimethylsiloxane)-graft-poly(4-vinylpyridine) (PDMS-g-P4VP) is synthesized via one-pot, free radical dispersion polymerization to give discrete monodisperse nanospheres. These nanospheres comprise a surface-anchored highly permeable PDMS layer and internal CO2-philic P4VP spherical core. Their diameter is controllable below the submicrometer range by varying grafting ratios. The colloidal dispersion forms a long-range, close-packed hexagonal array on a substrate by inclined deposition and convective assembly. The array shows dispersion medium-dependent packing characteristics. A thermodynamic correlation is determined using different solvents to obtain stable PDMS-g-P4VP dispersions and interpreted in terms of Flory-Huggins interaction parameter. As a proof-of-concept, the implementation of these nanospheres into membranes simultaneously enhances the CO2 permeability and CO2/N2 selectivity of PDMS-based transport matrixes. Upon physical aging of the solution, the CO2/N2 selectivity is improved up to 26, one of the highest values for highly permeable PDMS-based polymeric membranes. PMID:27004536

  6. Initial condition of stochastic self-assembly.

    PubMed

    Davis, Jason K; Sindi, Suzanne S

    2016-02-01

    The formation of a stable protein aggregate is regarded as the rate limiting step in the establishment of prion diseases. In these systems, once aggregates reach a critical size the growth process accelerates and thus the waiting time until the appearance of the first critically sized aggregate is a key determinant of disease onset. In addition to prion diseases, aggregation and nucleation is a central step of many physical, chemical, and biological process. Previous studies have examined the first-arrival time at a critical nucleus size during homogeneous self-assembly under the assumption that at time t=0 the system was in the all-monomer state. However, in order to compare to in vivo biological experiments where protein constituents inherited by a newly born cell likely contain intermediate aggregates, other possibilities must be considered. We consider one such possibility by conditioning the unique ergodic size distribution on subcritical aggregate sizes; this least-informed distribution is then used as an initial condition. We make the claim that this initial condition carries fewer assumptions than an all-monomer one and verify that it can yield significantly different averaged waiting times relative to the all-monomer condition under various models of assembly.

  7. Initial condition of stochastic self-assembly

    NASA Astrophysics Data System (ADS)

    Davis, Jason K.; Sindi, Suzanne S.

    2016-02-01

    The formation of a stable protein aggregate is regarded as the rate limiting step in the establishment of prion diseases. In these systems, once aggregates reach a critical size the growth process accelerates and thus the waiting time until the appearance of the first critically sized aggregate is a key determinant of disease onset. In addition to prion diseases, aggregation and nucleation is a central step of many physical, chemical, and biological process. Previous studies have examined the first-arrival time at a critical nucleus size during homogeneous self-assembly under the assumption that at time t =0 the system was in the all-monomer state. However, in order to compare to in vivo biological experiments where protein constituents inherited by a newly born cell likely contain intermediate aggregates, other possibilities must be considered. We consider one such possibility by conditioning the unique ergodic size distribution on subcritical aggregate sizes; this least-informed distribution is then used as an initial condition. We make the claim that this initial condition carries fewer assumptions than an all-monomer one and verify that it can yield significantly different averaged waiting times relative to the all-monomer condition under various models of assembly.

  8. Hierarchical superhydrophobic/hydrophilic substrates based on nanospheres self-assembly onto micro-pillars

    NASA Astrophysics Data System (ADS)

    Ma, Pengcheng; Wang, Yifei; Feng, Kaijun; Chen, Zhuojie; Wu, Wengang

    2014-12-01

    We report a novel superhydrophobic/hydrophilic substrate with micro-/nano-hierarchical structures by mimicking the lotus effect. Intrinsic hydrophobic polystyrene nanospheres or intrinsic hydrophilic silica nanospheres, via evaporation-induced self-assembly, are deposited on the surfaces of silicon pillars, including on tops as well as sidewalls. The obtained hierarchical structures with the polystyrene nanosphere deposition could amplify its intrinsic hydrophobicity, because gas interstices between both the nanospheres and micro-pillars jointly enhance the liquid-gas contact fraction significantly. Related theoretical analysis indicates that such structures could easily achieve an apparent contact angle (CA) of higher than 150°. In experiments, we measure the apparent CA of such kinds of hierarchical structures with the silicon pillars in different geometries, and find that the maximum value is up to 163.8°, with a 3.2° slide angle. The hierarchical structures with the silica nanosphere deposition could amplify its intrinsic hydrophilicity as well, because the double structures greatly increase the liquid-solid contact area. The corresponding experiment results show that the apparent CA can be as low as 7.6°.

  9. Self-assembly of poly(o-methoxyaniline) hollow nanospheres from a polymeric acid solution

    NASA Astrophysics Data System (ADS)

    Sui, Jing; Zhang, Lijuan; Peng, Hui; Travas-Sejdic, Jadranka; Kilmartin, Paul A.

    2009-10-01

    Self-assembled poly(o-methoxyaniline) (POMA) hollow nanospheres were prepared in a solution of poly(methyl vinyl ether-alt-maleic acid) (PMVEA) by oxidative polymerization using ammonium persulfate as the oxidant. The weight ratio of PMVEA to o-methoxyaniline in the solution had a significant effect on the morphology of the poly(o-methoxyaniline) nanospheres as determined by scanning electron microscopy. The diameter of the hollow nanospheres decreased from 440 to 210 nm with an increase in the PMVEA concentration from 1% to 5%. Freeze-fracture transmission electron microscopy results showed the presence of spherical micelles composed of PMVEA/ o-methoxyaniline prior to polymerization, which also decreased in size as more PMVEA was added to the solution, and can act as soft templates for the formation of the hollow POMA nanospheres. The POMA/PMVEA hollow nanospheres were characterized by means of Fourier transform infrared, UV-visible, x-ray photoelectron spectroscopy, elemental analysis and conductivity measurements.

  10. Self-assembled multifunctional DNA nanospheres for biosensing and drug delivery into specific target cells

    NASA Astrophysics Data System (ADS)

    Bi, Sai; Dong, Ying; Jia, Xiaoqiang; Chen, Min; Zhong, Hua; Ji, Bin

    2015-04-01

    Self-assembly of three dimensional nucleic acid nanostructures is of great significance in nanotechnology, biosensing and biomedicine. Herein we present a novel class of multifunctional and programmable DNA nanostructures, termed nanospheres (NSs), with monodispersity, dense compaction and uniform size (~200 nm) using only four DNAs based on not only Watson-Crick base pair hybridization between single-stranded DNA but also liquid crystallization and dense packing from periodic DNA duplexes. Due to the diversity of the internal structures, the present NSs can easily evolve into other kinds of DNA assemblies, such as DNA spherical structures with a larger size and a rough surface via rolling circle replication (RCR). Importantly, the functional arms incorporated in building units can be readily designed for biosensing and targeted cancer therapy with high payload capacity and excellent biocompatibility. Therefore, the proposed NSs could lead to novel routes for nucleic acid self-assembly, promising versatile applications in biosensing and biomedicine.Self-assembly of three dimensional nucleic acid nanostructures is of great significance in nanotechnology, biosensing and biomedicine. Herein we present a novel class of multifunctional and programmable DNA nanostructures, termed nanospheres (NSs), with monodispersity, dense compaction and uniform size (~200 nm) using only four DNAs based on not only Watson-Crick base pair hybridization between single-stranded DNA but also liquid crystallization and dense packing from periodic DNA duplexes. Due to the diversity of the internal structures, the present NSs can easily evolve into other kinds of DNA assemblies, such as DNA spherical structures with a larger size and a rough surface via rolling circle replication (RCR). Importantly, the functional arms incorporated in building units can be readily designed for biosensing and targeted cancer therapy with high payload capacity and excellent biocompatibility. Therefore, the

  11. Self-assembly and nanosphere lithography for large-area plasmonic patterns on graphene.

    PubMed

    Lotito, Valeria; Zambelli, Tomaso

    2015-06-01

    Plasmonic structures on graphene can tailor its optical properties, which is essential for sensing and optoelectronic applications, e.g. for the enhancement of photoresponsivity of graphene photodetectors. Control over their structural and, hence, spectral properties can be attained by using electron beam lithography, which is not a viable solution for the definition of patterns over large areas. For the fabrication of large-area plasmonic nanostructures, we propose to use self-assembled monolayers of nanospheres as a mask for metal evaporation and etching processes. An optimized approach based on self-assembly at air/water interface with a properly designed apparatus allows the attainment of monolayers of hexagonally closely packed patterns with high long-range order and large area coverage; special strategies are devised in order to protect graphene against damage resulting from surface treatment and further processing steps such as reactive ion etching, which could potentially impair graphene properties. Therefore we demonstrate that nanosphere lithography is a cost-effective solution to create plasmonic patterns on graphene.

  12. Electric field enhancement in a self-assembled 2D array of silver nanospheres

    SciTech Connect

    El-Khoury, Patrick Z. E-mail: wayne.hess@pnnl.gov; Gong, Yu; Joly, Alan G.; Abellan, Patricia; Browning, Nigel D.; Hess, Wayne P. E-mail: wayne.hess@pnnl.gov; Khon, Elena; Hu, Dehong; Zamkov, Mikhail; Evans, James E.

    2014-12-07

    We investigate the plasmonic properties of a self-assembled 2D array of Ag nanospheres (average particle diameter/inter-particle separation distance of 9/3.7 nm). The structures of the individual particles and their assemblies are characterized using high-resolution transmission electron microscopy (HR-TEM). The plasmonic response of the nanoparticle network is probed using two-photon photoemission electron microscopy (TP-PEEM). HR-TEM and TP-PEEM statistics reveal the structure and plasmonic response of the network to be homogeneous on average. This translates into a relatively uniform surface-enhanced Raman scattering (SERS) response from biphenyl,4-4{sup ′}-dithiol (BPDT) molecules adsorbed onto different sites of the network. Reproducible, bright, and low-background SERS spectra are recorded and assigned on the basis of density functional theory calculations in which BPDT is chemisorbed onto the vertex of a finite tetrahedral Ag cluster consisting of 20 Ag atoms. A notable agreement between experiment and theory allows us to rigorously account for the observable vibrational states of BPDT in the ∼200–2200 cm{sup −1} region of the spectrum. Finite difference time domain simulations further reveal that physical enhancement factors on the order of 10{sup 6} are attainable at the nanogaps formed between the silver nanospheres in the 2D array. Combined with modest chemical enhancement factors, this study paves the way for reproducible single molecule signals from an easily self-assembled SERS substrate.

  13. Electric Field Enhancement in a Self-Assembled 2D Array of Silver Nanospheres

    SciTech Connect

    El-Khoury, Patrick Z.; Khon, Elena; Gong, Yu; Joly, Alan G.; Abellan, Patricia; Evans, James E.; Browning, Nigel D.; Hu, Dehong; Zamkov, Mikhail; Hess, Wayne P.

    2014-12-07

    We investigate the plasmonic properties of a self-assembled 2D array of Ag nanospheres (average particle diameter/inter-particle separation distance of ~9/~4 nm). The structures of the individual particles and their assemblies are characterized using high-resolution transmission electron microscopy (HR-TEM). The plasmonic response of the nanoparticle network is probed using two-photon photoemission electron microscopy (TP-PEEM). HR-TEM and TP-PEEM statistics reveal the structure and plasmonic response of the network to be homogeneous on average. This translates into a relatively uniform surface-enhanced Raman scattering (SERS) response from biphenyl,4-4’-dithiol (BPDT) molecules adsorbed onto different sites of the network. Bright and background free SERS spectra are recorded, assigned on the basis of density 2 functional theory calculations in which BPDT is chemisorbed onto the vertex of a finitie tetrahedral Ag cluster consisting of 20 Ag atoms. A remarkable agreement between experiment and theory allows us to rigorously account for the observable vibrational states of BPDT in the ~200-2200 cm-1 region of the spectrum. Finite difference time domain simulations further reveal that physical enhancement factors on the order of 106 are attainable at the nanogaps formed between the silver nanospheres in the 2D array. Combined with modest chemical enhancement factors, this study paves the way for reproducible single molecule signals from an easily self-assembled SERS substrate.

  14. Effect of nanoparticle polydispersity on the self-assembly of polymer tethered nanospheres.

    PubMed

    Phillips, Carolyn L; Glotzer, Sharon C

    2012-09-14

    Recent simulations predict that aggregating nanospheres functionalized with polymer "tethers" can self-assemble to form a cylinder, perforated lamellae, lamellae, and even the double gyroid phase, which are phases also seen in block copolymer and surfactant systems. Nanoparticle size polydispersity is likely to be a characteristic of these systems. If too high, polydispersity may destabilize a phase. Using multiple thermodynamic paths to explore the phase diagram as a function of temperature and polydispersity, we explore the effect of nanosphere size polydispersity on the phase diagram. We show that in the portions of the phase diagram characterized by an icosahedral local nanoparticle packing motif, a low amount of polydispersity lowers the energy and a large amount of polydispersity raises the energy of the system by disrupting the icosahedral packing. In general, regions of the phase diagram characterized by liquid-like icosahedral packing have high terminal polydispersities from 15% to more than 30%. In the regions of the phase diagram characterized by crystalline local packing, polydispersity raises the energy of the system and induces a phase transition from crystalline to liquid-like ordering within the nanosphere rich regions of the microphase. We find the bilayer crystalline lamellae phase has a terminal polydispersity of 6%, but may still be partially crystalline up to 12%. PMID:22979884

  15. Gold(I) catalysis at extreme concentrations inside self-assembled nanospheres.

    PubMed

    Gramage-Doria, Rafael; Hessels, Joeri; Leenders, Stefan H A M; Tröppner, Oliver; Dürr, Maximilian; Ivanović-Burmazović, Ivana; Reek, Joost N H

    2014-12-01

    Homogeneous transition-metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mM or μM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M, inside well-defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mM levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular CO and CC bond-forming cyclization reactions.

  16. Multipole plasmon resonances in self-assembled metal hollow-nanospheres.

    PubMed

    Yin, Jun; Zang, Yashu; Xu, Binbin; Li, Shuping; Kang, Junyong; Fang, Yanyan; Wu, Zhihao; Li, Jing

    2014-04-21

    Recently, multipole plasmonic mode resonances in metal hollow structures, such as dipole, quadrupole, and octupole modes, have been widely investigated by researchers with the aim for potential applications in bio-sensing, fluorescence, nanolasers or nonlinear nano-photonics. Here, in this work, the multipole plasmon resonances in self-assembled metal hollow-nanospheres (HNSs) are theoretically and experimentally demonstrated and the hot spots originating from the higher order mode plasmonic resonance and interparticle coupling effect are proposed to be used for Raman scattering enhancements. Dipole, quadrupole, octupole and hexadecapole mode plasmonic resonances were clearly resolved in the extinction spectra of these Ag HNS arrays showing good agreement with the theoretical simulation results. Strong regular hot spots were obtained around the surface and in the gaps of the Ag HNSs through the higher order mode plasmonic resonances and corresponding interparticle coupling effect between the HNSs. Maximum local field intensity was accomplished by optimizing the size of as well as the coupling distance between the HNSs and then it was applied to SERS sensing. Raman mapping also demonstrated these self-assembled plasmonic cavity arrays to be a stable and uniform SERS-active substrate.

  17. Controllable preparation of multishelled NiO hollow nanospheres via layer-by-layer self-assembly for supercapacitor application

    NASA Astrophysics Data System (ADS)

    Yang, Zeheng; Xu, Feifei; Zhang, Weixin; Mei, Zhousheng; Pei, Bo; Zhu, Xiao

    2014-01-01

    In this work, we demonstrate a facile layer-by-layer (LBL) self-assembly method for controllable preparation of single-, double-, and triple-shelled NiO hollow nanospheres by calcining Ni(OH)2/C precursors formed at different stage. It is observed that the external nanoflakes of the NiO hollow nanospheres are inherited from the Ni(OH)2 precursors organized on the surface of carbon spheres via a self-assembly growth process and the inner shells result from the formation of different Ni(OH)2 layers within the carbon spheres during different preparation cycles. Supercapacitive performance of the three types of NiO hollow nanospheres as active electrode materials has been evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge. The results indicate that double-shelled NiO hollow nanosphere sample with largest surface area (92.99 m2 g-1) exhibits the best electrochemical properties among the three NiO hollow nanosphere samples. It delivers a high capacitance of 612.5 F g-1 at 0.5 A g-1 and demonstrates a superior long-term cyclic stability, with over 90% specific capacitance retention after 1000 charge-discharge cycles. This excellent performance is ascribed to the short diffusion path and large surface area of the unique hollow structure with nanoflake building blocks for bulk accessibility of faradaic reaction.

  18. pH Dependent Molecular Self-Assembly of Octaphosphonate Porphyrin of Nanoscale Dimensions: Nanosphere and Nanorod Aggregates

    PubMed Central

    Bhosale, Sheshanath V.; Kalyankar, Mohan B.; Nalage, Santosh V.; Lalander, Cecilia H.; Bhosale, Sidhanath V.; Langford, Steven J.; Oliver, Ruth F.

    2011-01-01

    Self-assembled nanostructures of zwitterionic octaphosphanatoporphyrin 1, of either nanoparticles or nanorods, depending on small changes in the pH, is demonstrated based on the J-aggregates. Porphyrin 1 self-assembled into nanosphere aggregates with a diameter of about 70–80 nm in the pH range 5–7, and nanorod aggregates were observed at pH 8.5. Hydrogen bonding, π-π stacking and hydrophilic interactions play important roles in the formation of this nanostructure morphology. Nanostructures were characterized by UV/Vis absorbance, fluorescence, atomic force microscopy (AFM) and transmission electron microscopy (TEM). This interesting pH dependent self-assembly phenomenon could provide a basis for development of novel biomaterials. PMID:21673901

  19. Supramolecular self-assembly carbazolyl radicals nanospheres triggered by ultraviolet light for explosives sensing.

    PubMed

    Ma, Hongwei; Li, Feng; Zhang, Yanan; Li, Xiaobai; Li, Tao; Shen, Fangzhong; Zhang, Ming

    2016-11-01

    In this work, we designed and synthesized a carbazole-type molecule that can form carbazolyl radicals in chloroform solution under the irradiation of UV light. The process is accompanied by an obvious change in the emission color from blue to bright green. The radicals and the neutral molecules assemble together and form nanospheres through synergistic effect of π-π stacking, intermolecular hydrogen bonds and charge transfer interaction. High resolution-transmission electron microscopy (HR-TEM) is used to confirm the nanospheres. The radius sizes of the nanospheres are mainly in 80-100nm. Further, these nanospheres act as the fluorescence sensor for explosives detection, and they exhibit high selectivity and sensitivity to 2, 4, 6-trinitrophenol (TNP). The limit of detection for nanospheres is 1.2×10(-7)M. PMID:27591596

  20. GREEN AND CONTROLLED SYNTHESIS OF GOLD AND PLATINUM NANOMATERIALS USING VITAMIN B2: DENSITY-ASSISTED SELF-ASSEMBLY OF NANOSPHERES, WIRES AND RODS

    EPA Science Inventory

    For the first time, we report density-assisted self-assembly and efficient synthesis of gold (Au) and platinum (Pt) nanospheres, nanowires and nanorods using vitamin B2 (riboflavin) without employing any special capping or dispersing agent at room temperature; this env...

  1. Hydrophobic and high transparent honeycomb diamond-like carbon thin film fabricated by facile self-assembled nanosphere lithography

    NASA Astrophysics Data System (ADS)

    Peng, Kai-Yu; Wei, Da-Hua; Lin, Chii-Ruey; Yu, Yueh-Chung; Yao, Yeong-Der; Lin, Hong-Ming

    2014-01-01

    In this paper, we take advantage of a facile fabrication technique called self-assembled nanosphere lithography (SANSL) combining with proper two-step reactive ion etching (RIE) method and radio frequency (RF) sputtering deposition process for manufacturing honeycomb diamond-like carbon (DLC) thin film structures with hydrophobic and high transparent properties. It is found that the DLC thin films deposited on clean glass substrates at the RF power of 100 W with the surface roughness (Ra) of 2.08 nm and the ID/IG ratio of 1.96 are realized. With a fill-factor of 0.691, the honeycomb DLC patterned thin film shows the best transmittance performance of 87% in the wavelength of visible light, and the optimized contact angle measurement is ˜108°. Compared with the pure DLC thin film and original glass substrate, the hydrophobic property of the patterned DLC films is significantly improved by 80 and 160%, respectively.

  2. Nanoparticle Vesicles with Controllable Surface Topographies through Block Copolymer-Mediated Self-Assembly of Silica Nanospheres.

    PubMed

    Zhou, Shujun; Sugawara-Narutaki, Ayae; Tsuboike, Sachio; Wang, Junzheng; Shimojima, Atsushi; Okubo, Tatsuya

    2015-12-01

    Silica nanoparticle vesicles (NPVs) with encapsulating capability and surface permeability are highly attractive in nanocatalysis, biosensing, and drug delivery systems. Herein, we report the facile fabrication of silica NPVs composed of a monolayer of silica nanospheres (SNSs, ca. 15 nm in diameter) through the block copolymer-mediated self-assembly of SNSs. The silica NPVs gain different surface topographies, such as raspberry- and brain coral-like topographies, under controlled heat treatment conditions. The vesicular assembly of SNSs is successful with a series of poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) block copolymers, and the size of NPVs can be tuned by changing their molecular weight. The polymer is easily extracted from the NPVs with their colloidal dispersibility and structural integrity intact. The polymer-free silica NPVs further serve as a reaction vessel and host for functional materials such as tin oxide nanoparticles.

  3. Self-assembled Multilayers of Silica Nanospheres for Defect Reduction in Non- and Semipolar Gallium Nitride Epitaxial Layers

    PubMed Central

    2015-01-01

    Non- and semipolar GaN have great potential to improve the efficiency of light emitting devices due to much reduced internal electric fields. However, heteroepitaxial GaN growth in these crystal orientations suffers from very high dislocation and stacking faults densities. Here, we report a facile method to obtain low defect density non- and semipolar heteroepitaxial GaN via selective area epitaxy using self-assembled multilayers of silica nanospheres (MSN). Nonpolar (11–20) and semipolar (11–22) GaN layers with high crystal quality have been achieved by epitaxial integration of the MSN and a simple one-step overgrowth process, by which both dislocation and basal plane stacking fault densities can be significantly reduced. The underlying defect reduction mechanisms include epitaxial growth through the MSN covered template, island nucleation via nanogaps in the MSN, and lateral overgrowth and coalescence above the MSN. InGaN/GaN multiple quantum wells structures grown on a nonpolar GaN/MSN template show more than 30-fold increase in the luminescence intensity compared to a control sample without the MSN. This self-assembled MSN technique provides a new platform for epitaxial growth of nitride semiconductors and offers unique opportunities for improving the material quality of GaN grown on other orientations and foreign substrates or heteroepitaxial growth of other lattice-mismatched materials. PMID:27065755

  4. Semi-insulating behaviour of self-assembled tin(IV)corrole nanospheres.

    PubMed

    Sinha, Woormileela; Kumar, Mohit; Garai, Antara; Purohit, Chandra Shekhar; Som, Tapobrata; Kar, Sanjib

    2014-09-01

    Three novel tin(iv)corrole complexes have been prepared and characterized by various spectroscopic techniques including single crystal X-ray structural analysis. Packing diagrams of the tin(iv)corroles revealed that corrolato-tin(iv)-chloride molecules are interconnected by intermolecular C-HCl hydrogen bonding interactions. HCl distances are 2.848 Å, 3.051 Å, and 2.915 Å, respectively, for the complexes. In addition, the C-HCl angles are 119.72°, 144.70°, and 147.08°, respectively, for the complexes. It was also observed that in one of the three synthesized complexes dimers were formed, while in the other two cases 1D infinite polymer chains were formed. Well-defined and nicely organized three-dimensional hollow nanospheres (SEM images on silicon wafers) with diameters of ca. 676 nm and 661 nm are obtained in the complexes, forming 1D polymer chains. By applying a thin layer of tin(iv)corrole nanospheres to an ITO surface (AFM height images of ITO films; ∼200 nm in height), a device was fabricated with the following composition: Ag/ITO-coated glass/tin(iv)corrole nanospheres/ITO-coated glass/Ag. The resistivity (ρ) of the nanostructured film was calculated to be ∼2.4 × 10(8) Ω cm, which falls in the range of semi-insulating semiconductors. CAFM current maps at 10 V bias show bright spots with a 10-20 pA intensity and indicate that the nanospheres (∼250 nm in diameter) are the electron-conducting pathway in the device. The semi-insulating behavior arises from the non-facile electron transfer in the HOMOs of the tin(iv)corrole nanospheres.

  5. Magnetic and magnetotransport properties of arrays of nanostructured antidots obtained by self-assembling polystyrene nanosphere lithography

    SciTech Connect

    Tiberto, Paola; Boarino, Luca; Celegato, Federica; Coiesson, Marco; De Leo, Natascia; Vinai, Franco; Allia, Paolo

    2010-05-15

    A well-ordered nanopatterned structure has been obtained in sputtered magnetic thin films by self-assembling of polystyrene nanospheres. Arrays of holes in Co, Ni, and Ni{sub 80}Fe{sub 20} films having a mean size ranging in the interval of 200-400 nm depending on the experimental condition have been prepared. Sample microstructure has been studied by scanning electron microscopy and atomic force microscopy. Room-temperature hysteresis loops have been measured in the parallel and perpendicular configuration (H{sub max}=20 kOe). Magnetoresistance (MR) measurements have been performed by means of a standard four-contact technique at several angles between the current and the magnetic field (H{sub max}=70 kOe) in the temperature interval of 4-200 K. An anisotropic MR effect has been observed in all compositions independent on the hole mean dimension. The role on magnetic and magnetotransport properties of either sample microstructure or composition has been studied in such patterned structures.

  6. Rapid Synthesis of Monodisperse Au Nanospheres through a Laser Irradiation -Induced Shape Conversion, Self-Assembly and Their Electromagnetic Coupling SERS Enhancement

    NASA Astrophysics Data System (ADS)

    Liu, Dilong; Li, Cuncheng; Zhou, Fei; Zhang, Tao; Zhang, Honghua; Li, Xinyang; Duan, Guotao; Cai, Weiping; Li, Yue

    2015-01-01

    We develop a facile and effective strategy to prepare monodispersed Au spherical nanoparticles by two steps. Large-scale monocrystalline Au nanooctahedra with uniform size were synthesized by a polyol-route and subsequently Au nanoparticles were transformed from octahedron to spherical shape in a liquid under ambient atmosphere by non-focused laser irradiation in very short time. High monodipersed, ultra-smooth gold nanospheres can be obtained by simply optimizing the laser fluence and irradiation time. Photothermal melting-evaporation model was employed to get a better understanding of the morphology transformation for the system of nanosecond pulsed-laser excitation. These Au nanoparticles were fabricated into periodic monolayer arrays by self-assembly utilizing their high monodispersity and perfect spherical shape. Importantly, such Au nanospheres arrays demonstrated very good SERS enhancement related to their periodic structure due to existence of many SERS hot spots between neighboring Au nanospheres caused by the electromagnetic coupling in an array. These gold nanospheres and their self-assembled arrays possess distinct physical and chemical properties. It will make them as an excellent and promising candidate for applying in sensing and spectroscopic enhancement, catalysis, energy, and biology.

  7. Rapid Synthesis of Monodisperse Au Nanospheres through a Laser Irradiation -Induced Shape Conversion, Self-Assembly and Their Electromagnetic Coupling SERS Enhancement

    PubMed Central

    Liu, Dilong; Li, Cuncheng; Zhou, Fei; Zhang, Tao; Zhang, Honghua; Li, Xinyang; Duan, Guotao; Cai, Weiping; Li, Yue

    2015-01-01

    We develop a facile and effective strategy to prepare monodispersed Au spherical nanoparticles by two steps. Large-scale monocrystalline Au nanooctahedra with uniform size were synthesized by a polyol-route and subsequently Au nanoparticles were transformed from octahedron to spherical shape in a liquid under ambient atmosphere by non-focused laser irradiation in very short time. High monodipersed, ultra-smooth gold nanospheres can be obtained by simply optimizing the laser fluence and irradiation time. Photothermal melting-evaporation model was employed to get a better understanding of the morphology transformation for the system of nanosecond pulsed-laser excitation. These Au nanoparticles were fabricated into periodic monolayer arrays by self-assembly utilizing their high monodispersity and perfect spherical shape. Importantly, such Au nanospheres arrays demonstrated very good SERS enhancement related to their periodic structure due to existence of many SERS hot spots between neighboring Au nanospheres caused by the electromagnetic coupling in an array. These gold nanospheres and their self-assembled arrays possess distinct physical and chemical properties. It will make them as an excellent and promising candidate for applying in sensing and spectroscopic enhancement, catalysis, energy, and biology. PMID:25566872

  8. Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome’s Facet

    DOE PAGES

    Mahalik, J. P.; Brown, Kirsten A.; Cheng, Xiaolin; Fuentes-Cabrera, Miguel

    2016-02-24

    Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome s function and how it can be modified tomore » create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we explain a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome s facets is driven by a nucleation growth process, which in turn could play an important role in the hierarchical self- assembly of BMC shells in general.« less

  9. Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome's Facet.

    PubMed

    Mahalik, J P; Brown, Kirsten A; Cheng, Xiaolin; Fuentes-Cabrera, Miguel

    2016-06-28

    Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome's function and how it can be modified to create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we describe a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome's facets is driven by a nucleation-growth process, which in turn could play an important role in the hierarchical self-assembly of BMC shells in general. PMID:26906087

  10. Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome's Facet.

    PubMed

    Mahalik, J P; Brown, Kirsten A; Cheng, Xiaolin; Fuentes-Cabrera, Miguel

    2016-06-28

    Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome's function and how it can be modified to create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we describe a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome's facets is driven by a nucleation-growth process, which in turn could play an important role in the hierarchical self-assembly of BMC shells in general.

  11. Ordered silicon nanowire arrays prepared by an improved nanospheres self-assembly in combination with Ag-assisted wet chemical etching

    NASA Astrophysics Data System (ADS)

    Jia, Guobin; Westphalen, Jasper; Drexler, Jan; Plentz, Jonathan; Dellith, Jan; Dellith, Andrea; Andrä, Gudrun; Falk, Fritz

    2016-04-01

    An improved Langmuir-Blodgett self-assembly process combined with Ag-assisted wet chemical etching for the preparation of ordered silicon nanowire arrays is presented in this paper. The new process is independent of the surface conditions (hydrophilic or hydrophobic) of the substrate, allowing for depositing a monolayer of closely packed polystyrene nanospheres onto any flat surface. A full control of the morphology of the silicon nanowire is achieved. Furthermore, it is observed that the formation of porous-Si at the tips of the nanowires is closely related to the release of Ag nanoparticles from the Ag mask during the etching, which subsequently redeposit on the surface initially free of Ag, and these Ag nanoparticles catalyze the etching of the tips and lead to the porous-Si formation. This finding will help to improve the resulting nano- and microstructures to get them free of pores, and renders it a promising technology for low-cost high throughput fabrication of specific optical devices, photonic crystals, sensors, MEMS, and NEMS by substituting the costly BOSCH process. It is shown that ordered nanowire arrays free of porous structures can be produced if all sources of Ag nanoparticles are excluded, and structures with aspect ratio more than 100 can be produced.

  12. SiO2@Au core-shell nanospheres self-assemble to form colloidal crystals that can be sintered and surface modified to produce pH-controlled membranes.

    PubMed

    Ignacio-de Leon, Patricia Anne A; Zharov, Ilya

    2013-03-19

    We prepared colloidal crystals by self-assembly of gold-coated silica nanospheres, and free-standing nanoporous membranes by sintering these colloidal crystals. We modified the nanopore surface with ionizable functional groups, by forming a monolayer of L-cysteine or by surface-initiated polymerization of methacrylic acid. Diffusion experiments for the cationic dye Rhodamine B through L-cysteine-modified membranes showed a decrease in flux upon addition of an acid due to the nanopore surface becoming positively charged. Diffusion experiments for the neutral dye, ferrocenecarboxaldehyde, through the PMAA-modified membranes showed a 13-fold increase in flux upon addition of an acid resulting from the protonated polymer collapsing onto the nanopore surface leading to larger pore size. Our results demonstrate that SiO2@Au core-shell nanospheres can self-assemble into colloidal crystals and that transport through the corresponding surface-modified Au-coated colloidal membranes can be controlled by pH.

  13. Triphenylalanine peptides self-assemble into nanospheres and nanorods that are different from the nanovesicles and nanotubes formed by diphenylalanine peptides.

    PubMed

    Guo, Cong; Luo, Yin; Zhou, Ruhong; Wei, Guanghong

    2014-03-01

    Understanding the nature of the self-assembly of peptide nanostructures at the molecular level is critical for rational design of functional bio-nanomaterials. Recent experimental studies have shown that triphenylalanine(FFF)-based peptides can self-assemble into solid plate-like nanostructures and nanospheres, which are different from the hollow nanovesicles and nanotubes formed by diphenylalanine(FF)-based peptides. In spite of extensive studies, the assembly mechanism and the molecular basis for the structural differences between FFF and FF nanostructures remain poorly understood. In this work, we first investigate the assembly process and the structural features of FFF nanostructures using coarse-grained molecular dynamics simulations, and then compare them with FF nanostructures. We find that FFF peptides spontaneously assemble into solid nanometer-sized nanospheres and nanorods with substantial β-sheet contents, consistent with the structural properties of hundred-nanometer-sized FFF nano-plates characterized by FT-IR spectroscopy. Distinct from the formation mechanism of water-filled FF nanovesicles and nanotubes reported in our previous study, intermediate bilayers are not observed during the self-assembly process of FFF nanospheres and nanorods. The peptides in FFF nanostructures are predominantly anti-parallel-aligned, which can form larger sizes of β-sheet-like structures than the FF counterparts. In contrast, FF peptides exhibit lipid-like assembly behavior and assemble into bilayered nanostructures. Furthermore, although the self-assembly of FF and FFF peptides is mostly driven by side chain-side chain (SC-SC) aromatic stacking interactions, the main chain-main chain (MC-MC) interactions also play an important role in the formation of fine structures of the assemblies. The delicate interplay between MC-MC and SC-SC interactions results in the different nanostructures formed by the two peptides. These findings provide new insights into the structure

  14. Formation and Reversible Morphological Transition of Bicontinuous Nanospheres and Toroidal Micelles by the Self-Assembly of a Crystalline-b-Coil Diblock Copolymer.

    PubMed

    Presa-Soto, David; Carriedo, Gabino A; de la Campa, Raquel; Presa Soto, Alejandro

    2016-08-16

    We herein report the formation of two complex nanostructures, toroidal micelles and bicontinuous nanospheres, by the self-assembly of the single structurally simple crystalline-b-coil diblock copolymer poly[bis(trifluoroethoxy)phosphazene]-b-poly(styrene), PTFEP-b-PS, in one solvent (THF) and without additives. The nature of these nanostructures in solution was confirmed by DLS and cryo-TEM experiments. The two morphologies are related by means of a new type of reversible morphological evolution, bicontinuous-to-toroidal, triggered by changes in the polymer concentration. WAXS experiments showed that the degree of crystallinity of the PTFEP chains located at the core of the toroids was higher than that in the bicontinuous nanospheres, thus indicating that the final morphology of the aggregates is mostly determined by the ordering of the PTFEP core-forming blocks. PMID:27455871

  15. Triphenylalanine peptides self-assemble into nanospheres and nanorods that are different from the nanovesicles and nanotubes formed by diphenylalanine peptides

    NASA Astrophysics Data System (ADS)

    Guo, Cong; Luo, Yin; Zhou, Ruhong; Wei, Guanghong

    2014-02-01

    Understanding the nature of the self-assembly of peptide nanostructures at the molecular level is critical for rational design of functional bio-nanomaterials. Recent experimental studies have shown that triphenylalanine(FFF)-based peptides can self-assemble into solid plate-like nanostructures and nanospheres, which are different from the hollow nanovesicles and nanotubes formed by diphenylalanine(FF)-based peptides. In spite of extensive studies, the assembly mechanism and the molecular basis for the structural differences between FFF and FF nanostructures remain poorly understood. In this work, we first investigate the assembly process and the structural features of FFF nanostructures using coarse-grained molecular dynamics simulations, and then compare them with FF nanostructures. We find that FFF peptides spontaneously assemble into solid nanometer-sized nanospheres and nanorods with substantial β-sheet contents, consistent with the structural properties of hundred-nanometer-sized FFF nano-plates characterized by FT-IR spectroscopy. Distinct from the formation mechanism of water-filled FF nanovesicles and nanotubes reported in our previous study, intermediate bilayers are not observed during the self-assembly process of FFF nanospheres and nanorods. The peptides in FFF nanostructures are predominantly anti-parallel-aligned, which can form larger sizes of β-sheet-like structures than the FF counterparts. In contrast, FF peptides exhibit lipid-like assembly behavior and assemble into bilayered nanostructures. Furthermore, although the self-assembly of FF and FFF peptides is mostly driven by side chain-side chain (SC-SC) aromatic stacking interactions, the main chain-main chain (MC-MC) interactions also play an important role in the formation of fine structures of the assemblies. The delicate interplay between MC-MC and SC-SC interactions results in the different nanostructures formed by the two peptides. These findings provide new insights into the structure

  16. Self-assembled TiO2 nanospheres by using a biopolymer as a template and its optoelectronic application.

    PubMed

    Dutta, Saikat; Patra, Astam K; De, Sudipta; Bhaumik, Asim; Saha, Basudeb

    2012-03-01

    Self-assembled TiO(2) nanoparticulate materials with well-defined spherical morphologies were synthesized by using a biopolymer sodium alginate as a template under different synthesis conditions. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) techniques were used to characterize the TiO(2) nanoparticles. N(2) sorption analysis revealed the moderately good surface area (124.0 m(2) g(-1)) and pore volume (0.44 cm(3) g(-1)) of these TiO(2) nanoparticles. The biopolymer templating pathway leads to good-quality self-assembled TiO(2) nanoparticles with dimensions of ca. 10-12 nm within the synthesis temperature range of 0-60 °C. These porous TiO(2) nanomaterials showed high photogenerated current in the presence of a dye (Rose Bengal), used as a sensitizer for several photo on/off cycles. PMID:22335551

  17. Initiation of Chondrocyte Self-Assembly Requires an Intact Cytoskeletal Network.

    PubMed

    Lee, Jennifer K; Hu, Jerry C Y; Yamada, Soichiro; Athanasiou, Kyriacos A

    2016-02-01

    Self-assembly and self-organization have recently emerged as robust scaffold-free tissue engineering methodologies that can be used to generate various tissues, including cartilage, vessel, and liver. Self-assembly, in particular, is a scaffold-free platform for tissue engineering that does not require the input of exogenous energy to the system. Although self-assembly can generate functional tissues, most notably neocartilage, the mechanisms of self-assembly remain unclear. To study the self-assembling process, we used articular chondrocytes as a model to identify parameters that can affect this process. Specifically, the roles of cell-cell and cell-matrix adhesion molecules, surface-bound collagen, and the actin cytoskeletal network were investigated. Using time-lapse imaging, we analyzed the early stages of chondrocyte self-assembly. Within hours, chondrocytes rapidly coalesced into cell clusters before compacting to form tight cellular structures. Chondrocyte self-assembly was found to depend primarily on integrin function and secondarily on cadherin function. In addition, actin or myosin II inhibitors prevented chondrocyte self-assembly, suggesting that cell adhesion alone is not sufficient, but rather the active contractile actin cytoskeleton is essential for proper chondrocyte self-assembly and the formation of neocartilage. Better understanding of the self-assembly mechanisms allows for the rational modulation of this process toward generating neocartilages with improved properties. These findings are germane to understanding self-assembly, an emerging platform for tissue engineering of a plethora of tissues, especially as these neotissues are poised for translation.

  18. Development of injectable organic/inorganic colloidal composite gels made of self-assembling gelatin nanospheres and calcium phosphate nanocrystals.

    PubMed

    Wang, Huanan; Bongio, Matilde; Farbod, Kambiz; Nijhuis, Arnold W G; van den Beucken, Jeroen; Boerman, Otto C; van Hest, Jan C M; Li, Yubao; Jansen, John A; Leeuwenburgh, Sander C G

    2014-01-01

    Colloidal gels are a particularly attractive class of hydrogels for applications in regenerative medicine, and allow for a "bottom-up" fabrication of multi-functional biomaterials by employing micro- or nanoscale particles as building blocks to assemble into shape-specific bulk scaffolds. So far, however, the synthesis of colloidal composite gels composed of both organic and inorganic particles has hardly been investigated. The current study has focused on the development of injectable colloidal organic-inorganic composite gels using calcium phosphate (CaP) nanoparticles and gelatin (Gel) nanospheres as building blocks. These novel Gel-CaP colloidal composite gels exhibited a strongly enhanced gel elasticity, shear-thinning and self-healing behavior, and gel stability at high ionic strengths, while chemical - potentially cytotoxic - functionalizations were not necessary to introduce sufficiently strong cohesive interactions. Moreover, it was shown in vitro that osteoconductive CaP nanoparticles can be used as an additional tool to reduce the degradation rate of otherwise fast-degradable gelatin nanospheres and fine-tune the control over the release of growth factors. Finally, it was shown that these colloidal composite gels support attachment, spreading and proliferation of cultured stem cells. Based on these results, it can be concluded that proof-of-principle has been obtained for the design of novel advanced composite materials made of nanoscale particulate building blocks which exhibit great potential for use in regenerative medicine.

  19. Self-Assembly of Two- and Three-Dimensional Particle Arrays by Manipulating the Hydrophobicity of Silica Nanospheres

    SciTech Connect

    Wang, Wei; Gu, Baohua

    2005-11-01

    The surface hydrophobicity of colloidal silica (SiO2) nanopheres is manipulated by a chemical graft of alkyl chains with silane coupling agents or by physical adsorption of a cationic surfactant. The surface-modified SiO2 spheres can be transferred from the aqueous phase to organic solvents and readily self-assemble at the water-air interface to form two-dimensional (2D) particle arrays. Closely packed particle monolayers are obtained by adjusting the hydrophilic/hydrophobic balance of the synthesized SiO2 spheres and may further be transferred onto solid substrates layer by layer to form three-dimensional (3D) ordered particle arrays with a hexagonal close-packed (hcp) crystalline structure. The 2D monolayer and 3D multilayer SiO2 films exhibit photonic crystal properties, which were determined by the UV-visible spectroscopic analysis in transmission mode. In the multilayer films, the Bragg diffraction maxima increased with an increase in thickness of the particle layers. The experimentally observed diffraction positions are in good agreement with those that were theoretically calculated.

  20. Immobilization of Aspergillus terreus lipase in self-assembled hollow nanospheres for enantioselective hydrolysis of ketoprofen vinyl ester.

    PubMed

    Hu, Chengli; Wang, Na; Zhang, Weiwei; Zhang, Sheng; Meng, Yanfa; Yu, Xiaoqi

    2015-01-20

    The aim of this study was to improve the ability of Aspergillus terreus lipase to separate the racemic ketoprofen vinyl ester into individual enantiomers using hollow self-assembly alginate-graft-poly(ethylene glycol)/α-cyclodextrins (Alg-g-PEG/α-CD) spheres as enzyme immobilization carriers. The morphology and size of the Alg-g-PEG/α-CD particles were investigated by transmission electron microscopy (TEM) and were found to be nanoscale. To facilitate recycling, calcium alginate (CA) beads were developed to encapsulate Alg-g-PEG/α-CD particles, thereby producing Alg-g-PEG/α-CD/CA composite beads. The influence of buffer pH and enzyme concentration during immobilization was studied along with the biocatalyst's kinetic parameters. When the immobilized enzyme was under optimal conditions in the resolution reaction, maximal conversion (approximately 45.9%) and enantioselectivity (approximately 128.8) were obtained. The immobilized A. terreus lipase maintained excellent performance even after 20 reuses and retained nearly 100% of its original activity after 24 weeks of storage at 4°C.

  1. Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions

    NASA Astrophysics Data System (ADS)

    Wang, Qi-Qiang; Gonell, Sergio; Leenders, Stefan H. A. M.; Dürr, Maximilian; Ivanović-Burmazović, Ivana; Reek, Joost N. H.

    2016-03-01

    Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions the substrate is bound—often by multiple non-covalent interactions—in a well-defined pocket close to the active site of the enzyme; this pre-organization facilitates highly efficient transformations. Here we report an artificial system that co-encapsulates multiple catalysts and substrates within the confined space defined by an M12L24 nanosphere that contains 24 endohedral guanidinium-binding sites. Cooperative binding means that sulfonate guests are bound much more strongly than carboxylates. This difference has been used to fix gold-based catalysts firmly, with the remaining binding sites left to pre-organize substrates. This strategy was applied to a Au(I)-catalysed cyclization of acetylenic acid to enol lactone in which the pre-organization resulted in much higher reaction rates. We also found that the encapsulated sulfonate-containing Au(I) catalysts did not convert neutral (acid) substrates, and so could have potential in the development of substrate-selective catalysis and base-triggered on/off switching of catalysis.

  2. Quantitative Control of Pore Size of Mesoporous Carbon Nanospheres through the Self-Assembly of Diblock Copolymer Micelles in Solution.

    PubMed

    Tian, Hao; Lin, Zhixing; Xu, Fugui; Zheng, Jingxu; Zhuang, Xiaodong; Mai, Yiyong; Feng, Xinliang

    2016-06-01

    This paper reports facile synthesis of nitrogen-doped mesoporous carbon nanospheres (MCNSs) with average diameters of around 300 nm and well-controlled pore sizes ranging from 8 to 38 nm, by employing polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblocks with different PS block lengths as the soft templates and dopamine as the carbon-rich precursor. For the first time, a linear equation is achieved for the quantitative control of the average pore size of MCNSs by simply adjusting a block length of diblock copolymer. The resultant MCNSs possess high surface areas of up to 450 m(2) g(-1) and nitrogen doping contents of up to ≈3 wt%. As electrode materials of supercapacitors, the MCNSs exhibit excellent electrochemical performance with high specific capacitances of up to 350 F g(-1) at 0.1 A g(-1) , superior rate capability, and cycling stability. Interestingly, the specific capacitance of the MCNSs reduces linearly with increasing pore size, whereas the normalized capacitance by specific surface area remains invariable. This represents a new spectrum of the relationship between electrochemical capacitance and pore size (>5 nm) for porous carbons, which makes a complement to the existing spectra focusing on pore diameters of <5 nm. PMID:27120340

  3. Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions.

    PubMed

    Wang, Qi-Qiang; Gonell, Sergio; Leenders, Stefan H A M; Dürr, Maximilian; Ivanović-Burmazović, Ivana; Reek, Joost N H

    2016-03-01

    Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions the substrate is bound-often by multiple non-covalent interactions-in a well-defined pocket close to the active site of the enzyme; this pre-organization facilitates highly efficient transformations. Here we report an artificial system that co-encapsulates multiple catalysts and substrates within the confined space defined by an M12L24 nanosphere that contains 24 endohedral guanidinium-binding sites. Cooperative binding means that sulfonate guests are bound much more strongly than carboxylates. This difference has been used to fix gold-based catalysts firmly, with the remaining binding sites left to pre-organize substrates. This strategy was applied to a Au(I)-catalysed cyclization of acetylenic acid to enol lactone in which the pre-organization resulted in much higher reaction rates. We also found that the encapsulated sulfonate-containing Au(I) catalysts did not convert neutral (acid) substrates, and so could have potential in the development of substrate-selective catalysis and base-triggered on/off switching of catalysis. PMID:26892553

  4. Nanosphere lithography: fabrication of large-area Ag nanoparticle arrays by convective self-assembly and their characterization by scanning UV-visible extinction spectroscopy.

    PubMed

    Ormonde, Anjeanette D; Hicks, Erin C M; Castillo, Jimmy; Van Duyne, Richard P

    2004-08-01

    This work employs UV-visible extinction spectroscopy as a new spectral mapping technique to characterize self-assembled polystyrene microsphere samples produced by convective self-assembly (CSA). This spectroscopic technique was successfully used to analyze the periodic particle arrays produced by the polystyrene template, yielding a detailed characterization of each sample. The CSA-prepared samples proved to be more uniform across a sample as well as more reproducible than previous sample preparation techniques. For the first time, a detailed characterization and quantitative evaluation of the entire sample has been performed by spectroscopic mapping.

  5. Atomic-level elucidation of the initial stages of self-assembled monolayer metallization and nanoparticle formation.

    PubMed

    Keith, John A; Jacob, Timo

    2010-11-01

    The development of high-performance molecular electronics and nanotech applications requires deep understanding of atomic level structural, electronic, and magnetic properties of electrode/molecular interfaces. Recent electrochemical experiments on self-assembled monolayers (SAMs) have identified highly practical means to generate nanoparticles and metal monolayers suspended above substrate surfaces through SAM metallizations. A rational basis why this process is even possible is not yet well-understood. To clarify the initial stages of interface formation during SAM metallization, we used first-principles spin-polarized density functional theory (DFT) calculations to study Pd diffusion on top of 4-mercaptopyridine (4MP) SAMs on Au(111). After distinguishing potential-energy surfaces (PESs) for different spin configurations for transition metal atoms on the SAM, we find adatom diffusion is not possible over the clean 4MP-SAM surface. Pre-adsorption of transition-metal atoms, however, facilitates atomic diffusion that appears to explain multiple reports on experimentally observed island and monolayer formation on top of SAMs. Furthermore, these diffusions most likely occur by moving across low-lying and intersecting PESs of different spin states, opening the possibility of magnetic control over these systems. Vertical diffusion processes were also investigated, and the electrolyte was found to play a key role in preventing metal permeation through the SAM to the substrate.

  6. Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor.

    PubMed

    Kelp, G; Tätte, T; Pikker, S; Mändar, H; Rozhin, A G; Rauwel, P; Vanetsev, A S; Gerst, A; Merisalu, M; Mäeorg, U; Natali, M; Persson, I; Kessler, V G

    2016-04-01

    Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped. PMID:26960813

  7. Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

    NASA Astrophysics Data System (ADS)

    Kelp, G.; Tätte, T.; Pikker, S.; Mändar, H.; Rozhin, A. G.; Rauwel, P.; Vanetsev, A. S.; Gerst, A.; Merisalu, M.; Mäeorg, U.; Natali, M.; Persson, I.; Kessler, V. G.

    2016-03-01

    Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.Tin oxide is considered to be one of the

  8. Initial Development and Characterization of PLGA Nanospheres Containing Ropivacaine

    PubMed Central

    Moraes, Carolina Morales; de Matos, Angélica Prado; de Lima, Renata; Rosa, André Henrique; de Paula, Eneida

    2008-01-01

    Local anesthetics are able to induce pain relief by binding to the sodium channels of excitable membranes, blocking the influx of sodium ions and the propagation of the nervous impulse. Ropivacaine (RVC) is an amino amide, enantiomerically pure, local anesthetic largely used in surgical procedures, which present physico-chemical and therapeutic properties similar to those of bupivacaine but decreased toxicity and motor blockade. The present work focuses on the preparation and characterization of nanospheres containing RVC; 0.25% and 0.50% RVC were incorporated in poly(d,l-lactide-co-glycolide (PLGA) 50:50) nanospheres (PLGA-NS), prepared by the nanoprecipitation method. Characterization of the nanospheres was conducted through the measurement of pH, particle size, and zeta potential. The pH of the nanoparticle system with RVC was 6.58. The average diameters of the RVC-containing nanospheres was 162.7 ± 1.5 nm, and their zeta potentials were negative, with values of about −10.81 ± 1.16 mV, which promoted good stabilization of the particles in solution. The cytotoxicity experiments show that RVC-loaded PLGA-NS generate a less toxic formulation as compared with plain RVC. Since this polymer drug-delivery system can effectively generate an even less toxic RVC formulation, this study is fundamental due to its characterization of a potentially novel pharmaceutical form for the treatment of pain with RVC. PMID:19669531

  9. Controlling self assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wei, Yanhu

    2007-12-01

    rows containing 16. The combination of chain length matching and dipolar complementary provides a potentially powerful strategy for producing controllably self assembled monolayers from multiple components at the liquid solid surface. In monolayers formed from 1,5-substituted-anthracene derivatives, a number of monolayer defects were observed including isolated single and dimer defects, row defects and complicated interface defects. Packing models are proposed to explain the observed monolayer defects. We designed and synthesized a series of 1,5-substituted-triptycene derivatives. We investigated the variation of STM image contrast for monolayers prepared from triptycene and anthracene derivatives with the tip-sample distance (or setpoint current/bias voltage). A model for the STM image contrast was explored. Several triptycene diode molecules with long alkyl chains were designed and synthesized. Initial studies of their rectifying characteristics were performed on HOPG using scanning tunneling spectroscopy. Finally, we designed and synthesized a series of thioester prediode molecules for studies on gold surfaces. Initial studies of self-assembly on gold were performed using a series of related analogs.

  10. Initiator-catalyzed self-assembly of duplex-looped DNA hairpin motif based on strand displacement reaction for logic operations and amplified biosensing.

    PubMed

    Bi, Sai; Yue, Shuzhen; Wu, Qiang; Ye, Jiayan

    2016-09-15

    Here we program an initiator-catalyzed self-assembly of duplex-looped DNA hairpin motif based on strand displacement reaction. Due to the recycling of initiator and performance in a cascade manner, this system is versatilely extended to logic operations, including the construction of concatenated logic circuits with a feedback function and a biocomputing keypad-lock security system. Compared with previously reported molecular security systems, the prominent feature of our keypad lock is that it can be spontaneously reset and recycled with no need of any external stimulus and human intervention. Moreover, through integrating with an isothermal amplification technique of rolling circle amplification (RCA), this programming catalytic DNA self-assembly strategy readily achieves sensitive and selective biosensing of initiator. Importantly, a magnetic graphene oxide (MGO) is introduced to remarkably reduced background, which plays an important role in enhancing the signal-to-noise ratio and improving the detection sensitivity. Therefore, the proposed sophisticated DNA strand displacement-based methodology with engineering dynamic functions may find broad applications in the construction of programming DNA nanostructures, amplification biosensing platform, and large-scale DNA circuits. PMID:27132002

  11. Initiator-catalyzed self-assembly of duplex-looped DNA hairpin motif based on strand displacement reaction for logic operations and amplified biosensing.

    PubMed

    Bi, Sai; Yue, Shuzhen; Wu, Qiang; Ye, Jiayan

    2016-09-15

    Here we program an initiator-catalyzed self-assembly of duplex-looped DNA hairpin motif based on strand displacement reaction. Due to the recycling of initiator and performance in a cascade manner, this system is versatilely extended to logic operations, including the construction of concatenated logic circuits with a feedback function and a biocomputing keypad-lock security system. Compared with previously reported molecular security systems, the prominent feature of our keypad lock is that it can be spontaneously reset and recycled with no need of any external stimulus and human intervention. Moreover, through integrating with an isothermal amplification technique of rolling circle amplification (RCA), this programming catalytic DNA self-assembly strategy readily achieves sensitive and selective biosensing of initiator. Importantly, a magnetic graphene oxide (MGO) is introduced to remarkably reduced background, which plays an important role in enhancing the signal-to-noise ratio and improving the detection sensitivity. Therefore, the proposed sophisticated DNA strand displacement-based methodology with engineering dynamic functions may find broad applications in the construction of programming DNA nanostructures, amplification biosensing platform, and large-scale DNA circuits.

  12. Simulation of metal-ligand self-assembly into spherical complex M6L8.

    PubMed

    Yoneya, Makoto; Yamaguchi, Tomohiko; Sato, Sota; Fujita, Makoto

    2012-09-01

    Molecular dynamics simulations were performed to study the self-assembly of a spherical complex through metal-ligand coordination interactions. M(6)L(8), a nanosphere with six palladium ions and eight pyridine-capped tridentate ligands, was selected as a target system. We successfully observed the spontaneous formation of spherical shaped M(6)L(8) cages over the course of our simulations, starting from random initial placement of the metals and ligands. To simulate spontaneous coordination bond formations and breaks, the cationic dummy atom method was employed to model nonbonded metal-ligand interactions. A coarse-grained solvent model was used to fill the gap between the time scale of the supramolecular self-assembly and that accessible by common molecular dynamics simulation. The simulated formation process occurred in the distinct three-stage (assembly, evolution, fixation) process that is well correlated with the experimental results. We found that the difference of the lifetime (or the ligand exchange rate) between the smaller-sized incomplete clusters and the completed M(6)L(8) nanospheres is crucially important in their supramolecular self-assembly.

  13. Self assembling proteins

    DOEpatents

    Yeates, Todd O.; Padilla, Jennifer; Colovos, Chris

    2004-06-29

    Novel fusion proteins capable of self-assembling into regular structures, as well as nucleic acids encoding the same, are provided. The subject fusion proteins comprise at least two oligomerization domains rigidly linked together, e.g. through an alpha helical linking group. Also provided are regular structures comprising a plurality of self-assembled fusion proteins of the subject invention, and methods for producing the same. The subject fusion proteins find use in the preparation of a variety of nanostructures, where such structures include: cages, shells, double-layer rings, two-dimensional layers, three-dimensional crystals, filaments, and tubes.

  14. Modeling Protein Self Assembly

    ERIC Educational Resources Information Center

    Baker, William P.; Jones, Carleton Buck; Hull, Elizabeth

    2004-01-01

    Understanding the structure and function of proteins is an important part of the standards-based science curriculum. Proteins serve vital roles within the cell and malfunctions in protein self assembly are implicated in degenerative diseases. Experience indicates that this topic is a difficult one for many students. We have found that the concept…

  15. Photovoltaic self-assembly.

    SciTech Connect

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

    2010-10-01

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

  16. Effect of Self-Assembled Monolayer Modification on Indium-Tin Oxide Surface for Surface-Initiated Vapor Deposition Polymerization of Carbazole Thin Films

    NASA Astrophysics Data System (ADS)

    Yuya Umemoto,; Seong-Ho Kim,; Rigoberto C. Advincula,; Kuniaki Tanaka,; Hiroaki Usui,

    2010-04-01

    With the aim of controlling the interface between an inorganic electrode and an organic layer, a surface-initiated vapor deposition polymerization method was employed to prepare carbazole polymer thin films that are chemically bound to an indium-tin oxide (ITO) surface. A self-assembled monolayer (SAM) that has an azo initiator as a terminal group was prepared on an ITO surface, on which carbazole acrylate monomers were evaporated under ultraviolet (UV) irradiation. The surface morphological characteristics of the films prepared with/without UV irradiation and with/without the SAM were compared. It was found that the UV irradiation leads to the polymerization of carbazole monomers irrespective of the type of substrate used. On the other hand, the surface morphological characteristics were largely dependent on the existence of the SAM. Uniform and smooth polymer thin films were obtained only when the monomers were evaporated on the SAM-modified surface under UV irradiation. A comparison of film growth characteristics on a UV-ozone-treated ITO surface suggested that the formation of uniform films was made possible not by the modification of surface energy but by the growth of the polymers chemically bound to the substrate surface.

  17. Microtubule Self- Assembly

    NASA Astrophysics Data System (ADS)

    Jho, Yongseok; Choi, M. C.; Farago, O.; Kim, Mahnwon; Pincus, P. A.

    2008-03-01

    Microtubules are important structural elements for neurons. Microtubles are cylindrical pipes that are self-assembled from tubulin dimers, These structures are intimately related to the neuron transport system. Abnormal microtubule disintegration contributes to neuro-disease. For several decades, experimentalists investigated the structure of the microtubules using TEM and Cryo-EM. However, the detailed structure at a molecular level remain incompletely understood. . In this presentation, we report numerically studies of the self-assembly process using a toy model for tubulin dimers. We investigate the nature of the interactions which are essential to stabilize such the cylindrical assembly of protofilaments. We use Monte Carlo simulations to suggest the pathways for assembly and disassembly of the microtubules.

  18. Adsorption of Amelogenin onto Self-Assembled and Fluoroapatite Surfaces

    SciTech Connect

    Tarasevich, Barbara J.; Lea, Alan S.; Bernt, William; Engelhard, Mark H.; Shaw, Wendy J.

    2009-02-19

    Abstract. The interactions of proteins at surfaces are of great importance to biomineralizaton processes and to the development and function of biomaterials. Amelogenin is a unique biomineralization protein because it self-assembles to form supramolecular structures called “nanospheres,” spherical aggregates of monomers that are 20-60 nm in diameter. Although the nanosphere quaternary structure has been observed in solution, the quaternary structure of amelogenin adsorbed onto surfaces is also of great interest because the surface structure is critical to its function. We report studies of the adsorption of the amelogenin onto self-assembled monolayers (SAMs) with COOH and CH3 end group functionality and single crystal fluoroapatite (FAP). Dynamic light scattering (DLS) experiments showed that the solutions contained nanospheres and aggregates of nanospheres. Protein adsorption onto the various substrates was evidenced by null ellipsometry, x-ray photoelectron spectroscopy (XPS), and external reflectance Fourier transform infrared spectroscopy (ERFTIR). Although only nanospheres were observed in solution, ellipsometry and atomic force microscopy (AFM) indicated that the protein adsorbates were much smaller structures than the original nanospheres, from monomers to small oligomers in size. Monomer adsorption was promoted onto the CH3 surfaces and small oligomer adsorption was promoted onto the COOH and FAP substrates. In some cases, remnants of the original nanospheres adsorbed as multilayers on top of the underlying subnanosphere layers. This work suggests that amelogenin can adsorb by the “shedding” or disassembling of substructures from the nanospheres onto substrates and indicates that amelogenin may have a range of possible quaternary structures depending on whether it is in solution or interacting with surfaces.

  19. Porous nano-structured Co3O4 anode materials generated from coordination-driven self-assembled aggregates for advanced lithium ion batteries.

    PubMed

    Ge, Danhua; Geng, Hongbo; Wang, Jiaqing; Zheng, Junwei; Pan, Yue; Cao, Xueqin; Gu, Hongwei

    2014-08-21

    A simple and scalable coordination-derived method for the synthesis of porous Co3O4 hollow nanospheres is described here. The initially formed coordination-driven self-assembled aggregates (CDSAAs) could act as the precursor followed by calcination treatment. Then the porous hollow Co3O4 nanospheres are obtained, in which the primary Co3O4 nanoparticles are inter-dispersed. When the nanospheres are used as anode materials for lithium storage, they show excellent coulombic efficiency, high lithium storage capacity and superior cycling performance. In view of the facile synthesis and excellent electrochemical performance obtained, this protocol to fabricate special porous hollow frameworks could be further extended to other metal oxides and is expected to improve the practicality of superior cycle life anode materials with large volume excursions for the development of the next generation of LIBs.

  20. Self-assembly of nanocomposite materials

    DOEpatents

    Brinker, C. Jeffrey; Sellinger, Alan; Lu, Yunfeng

    2001-01-01

    A method of making a nanocomposite self-assembly is provided where at least one hydrophilic compound, at least one hydrophobic compound, and at least one amphiphilic surfactant are mixed in an aqueous solvent with the solvent subsequently evaporated to form a self-assembled liquid crystalline mesophase material. Upon polymerization of the hydrophilic and hydrophobic compounds, a robust nanocomposite self-assembled material is formed. Importantly, in the reaction mixture, the amphiphilic surfactant has an initial concentration below the critical micelle concentration to allow formation of the liquid-phase micellar mesophase material. A variety of nanocomposite structures can be formed, depending upon the solvent evaporazation process, including layered mesophases, tubular mesophases, and a hierarchical composite coating composed of an isotropic worm-like micellar overlayer bonded to an oriented, nanolaminated underlayer.

  1. Self-assembling segmented coiled tubing

    DOEpatents

    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.

  2. Nanoparticle induced self-assembly.

    PubMed

    Helgesen, G; Svåsand, E; Skjeltorp, A T

    2008-05-21

    Self-assembly has for the large part focused on the assembly of molecules without guidance or management from an outside source. However, self-assembly is in principle by no means limited to molecules or the nanoscale. A particularly interesting method to the self-assembly of micro- to millimetre sized components is the use of the 'magnetic hole' effect. In this method, nonmagnetic particles can be manipulated by external magnetic fields by immersing them in a dispersion of colloidal, magnetic nanoparticles, denoted ferrofluids. Nonmagnetic particles in magnetized ferrofluids are in many ways ideal model systems to test various forms of particle self-assembly and dynamics. When microspheres are confined to a monolayer between two parallel plates and subjected to static or oscillating magnetic fields they show a variety of dynamical behaviours and assemblages, depending on the frequency and direction of the external fields. A single pair of magnetic holes oscillating in a ferrofluid layer may be used to measure the viscosity of tiny volumes of the fluid. We have also observed ordering of dilute dispersions of macromolecules and nanoparticles in magnetized ferrofluids. The self-assembly at this length scale results from structural correlations between these nanostructures and ferrofluid particles rather than from the macroscopic magnetostatic effect for the magnetic holes.

  3. Self-assembly via microfluidics.

    PubMed

    Wang, Lei; Sánchez, Samuel

    2015-12-01

    The self-assembly of amphiphilic building blocks has attracted extensive interest in myriad fields in recent years, due to their great potential in the nanoscale design of functional hybrid materials. Microfluidic techniques provide an intriguing method to control kinetic aspects of the self-assembly of molecular amphiphiles by the facile adjustment of the hydrodynamics of the fluids. Up to now, there have been several reports about one-step direct self-assembly of different building blocks with versatile and multi-shape products without templates, which demonstrated the advantages of microfluidics. These assemblies with different morphologies have great applications in various areas such as cancer therapy, micromotor fabrication, and controlled drug delivery.

  4. Onset of self-assembly

    SciTech Connect

    Chitanvis, S.M.

    1998-02-01

    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 {xi}{approximately}(c{minus}c{sup {asterisk}}){sup {minus}{gamma}}, where c{sup {asterisk}} is the minimum concentration below which self-assembly is impossible, c is the current concentration, and {gamma} 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} {ital 1998} {ital The American Physical Society}

  5. Self-assembling amphiphilic peptides†

    PubMed Central

    Dehsorkhi, Ashkan; Castelletto, Valeria; Hamley, Ian W

    2014-01-01

    The self-assembly of several classes of amphiphilic peptides is reviewed, and selected applications are discussed. We discuss recent work on the self-assembly of lipopeptides, surfactant-like peptides and amyloid peptides derived from the amyloid-β peptide. The influence of environmental variables such as pH and temperature on aggregate nanostructure is discussed. Enzyme-induced remodelling due to peptide cleavage and nanostructure control through photocleavage or photo-cross-linking are also considered. Lastly, selected applications of amphiphilic peptides in biomedicine and materials science are outlined. © 2014 The Authors. Journal of Peptide Science published by European Peptide Society and John Wiley & Sons, Ltd. PMID:24729276

  6. Final Report for Grant # DE-FG02-02ER46000 Simulations of Self-Assembly of Tethered Nanoparticle Shape Amphiphiles

    SciTech Connect

    Glotzer, Sharon C.

    2014-08-25

    Self-assembly of nanoparticle building blocks including nanospheres, nanorods, nanocubes, nano plates, nanoprisms, etc., may provide a promising means for manipulating these building blocks into functional and useful materials. One increasingly popular method for self-assembly involves functionalizing nanoparticles and nanostructured molecules with “tethers” of organic polymers or biomolecules with specific or nonspecific interactions to facilitate their assembly. However, there is little theory and little understanding of the general principles underlying self-assembly in these complex materials. Using computer simulation to elucidate the principles of self-assembly and develop a predictive theoretical framework was the central goal of this project.

  7. Mussel-inspired bolaamphiphile sticky self-assemblies for the preparation of magnetic nanoparticles.

    PubMed

    Lee, Chaemyeong; Lee, Sang-Yup

    2015-03-01

    Adopting the strong metal binding moiety of a mussel protein, a novel bolaamphiphile molecule was prepared and applied to the fabrication of magnetic core-shell nanoparticles. The novel bolaamphiphile molecule with 3,4-dihydroxyphenylalanine (DOPA) end groups was synthesized and its self-assembly was used as a template to adsorb metal ions and subsequently to produce magnetic nanoparticles. The DOPA bolaamphiphile molecule self-assembled in aqueous solution to produce nanospherical structures that exposed the catechol moiety of DOPA to the outer surface. The catechol groups adsorbed cobalt and iron ions to create magnetic metal oxide clusters on the self-assembly. Spectroscopic analysis showed that the cobalt and iron ions were coordinated with quinone, an oxidized form of the catechol. Exploiting the strong metal-adsorbing and binding properties of DOPA, dense cobalt oxide and iron oxide shell layers were created on the nanospherical self-assembly to produce magnetic core-shell nanoparticles. This study demonstrated a simple method for creating magnetic metal oxide nanoparticles that exploits the molecular binding forces and self-assembly property of DOPA. PMID:25658196

  8. Hierarchical Self-Assembly of Peptide Amphiphiles: Form and Function at Multiple Length Scales

    NASA Astrophysics Data System (ADS)

    Zha, Runye Helen

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

  9. Anisotropic Self-Assembly of Citrate-Coated Gold Nanoparticles on Fluidic Liposomes.

    PubMed

    Sugikawa, Kouta; Kadota, Tatsuya; Yasuhara, Kazuma; Ikeda, Atsushi

    2016-03-14

    The behavior of self-assembly processes of nanoscale particles on plasma membranes can reveal mechanisms of important biofunctions and/or intractable diseases. Self-assembly of citrate-coated gold nanoparticles (cAuNPs) on liposomes was investigated. The adsorbed cAuNPs were initially fixed on the liposome surfaces and did not self-assemble below the phospholipid phase transition temperature (Tm ). In contrast, anisotropic cAuNP self-assembly was observed upon heating of the composite above the Tm, where the phospholipids became fluid. The number of self-assembled NPs is conveniently controlled by the initial mixing ratio of cAuNPs and liposomes. Gold nanoparticle protecting agents strongly affected the self-assembly process on the fluidic membrane.

  10. Multifunctional self-assembled monolayers

    SciTech Connect

    Zawodzinski, T.; Bar, G.; Rubin, S.; Uribe, F.; Ferrais, J.

    1996-06-01

    This is the final report of at three year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The specific goals of this research project were threefold: to develop multifunctional self-assembled monolayers, to understand the role of monolayer structure on the functioning of such systems, and to apply this knowledge to the development of electrochemical enzyme sensors. An array of molecules that can be used to attach electrochemically active biomolecules to gold surfaces has been synthesized. Several members of a class of electroactive compounds have been characterized and the factors controlling surface modification are beginning to be characterized. Enzymes have been attached to self-assembled molecules arranged on the gold surface, a critical step toward the ultimate goal of this project. Several alternative enzyme attachment strategies to achieve robust enzyme- modified surfaces have been explored. Several means of juxtaposing enzymes and mediators, electroactive compounds through which the enzyme can exchange electrons with the electrode surface, have also been investigated. Finally, the development of sensitive biosensors based on films loaded with nanoscale-supported gold particles that have surface modified with the self-assembled enzyme and mediator have been explored.

  11. Self-assembled plasmonic metamaterials

    NASA Astrophysics Data System (ADS)

    Mühlig, Stefan; Cunningham, Alastair; Dintinger, José; Scharf, Toralf; Bürgi, Thomas; Lederer, Falk; Rockstuhl, Carsten

    2013-07-01

    Nowadays for the sake of convenience most plasmonic nanostructures are fabricated by top-down nanofabrication technologies. This offers great degrees of freedom to tailor the geometry with unprecedented precision. However, it often causes disadvantages as well. The structures available are usually planar and periodically arranged. Therefore, bulk plasmonic structures are difficult to fabricate and the periodic arrangement causes undesired effects, e.g., strong spatial dispersion is observed in metamaterials. These limitations can be mitigated by relying on bottom-up nanofabrication technologies. There, self-assembly methods and techniques from the field of colloidal nanochemistry are used to build complex functional unit cells in solution from an ensemble of simple building blocks, i.e., in most cases plasmonic nanoparticles. Achievable structures are characterized by a high degree of nominal order only on a short-range scale. The precise spatial arrangement across larger dimensions is not possible in most cases; leading essentially to amorphous structures. Such self-assembled nanostructures require novel analytical means to describe their properties, innovative designs of functional elements that possess a desired near- and far-field response, and entail genuine nanofabrication and characterization techniques. Eventually, novel applications have to be perceived that are adapted to the specifics of the self-assembled nanostructures. This review shall document recent progress in this field of research. Emphasis is put on bottom-up amorphous metamaterials. We document the state-of-the-art but also critically assess the problems that have to be overcome.

  12. Self-assembly of subwavelength nanostructures with symmetry breaking in solution

    NASA Astrophysics Data System (ADS)

    Tian, Xiang-Dong; Chen, Shu; Zhang, Yue-Jiao; Dong, Jin-Chao; Panneerselvam, Rajapandiyan; Zhang, Yun; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

    2016-01-01

    Nanostructures with symmetry breaking can allow the coupling between dark and bright plasmon modes to induce strong Fano resonance. However, it is still a daunting challenge to prepare bottom-up self-assembled subwavelength asymmetric nanostructures with appropriate gaps between the nanostructures especially below 5 nm in solution. Here we present a viable self-assembly method to prepare symmetry-breaking nanostructures consisting of Ag nanocubes and Au nanospheres both with tunable size (90-250 nm for Au nanospheres; 100-160 nm for Ag nanocubes) and meanwhile control the nanogaps through ultrathin silica shells of 1-5 nm thickness. The Raman tag of 4-mercaptobenzoic acid (MBA) assists the self-assembly process and endows the subwavelength asymmetric nanostructures with surface-enhanced Raman scattering (SERS) activity. Moreover, thick silica shells (above 50 nm thickness) can be coated on the self-assembled nanostructures in situ to stabilize the whole nanostructures, paving the way toward bioapplications. Single particle scattering spectroscopy with a 360° polarization resolution is performed on individual Ag nanocube and Au nanosphere dimers, correlated with high-resolution TEM characterization. The asymmetric dimers exhibit strong configuration and polarization dependence Fano resonance properties. Overall, the solution-based self-assembly method reported here is opening up new opportunities to prepare diverse multicomponent nanomaterials with optimal performance.Nanostructures with symmetry breaking can allow the coupling between dark and bright plasmon modes to induce strong Fano resonance. However, it is still a daunting challenge to prepare bottom-up self-assembled subwavelength asymmetric nanostructures with appropriate gaps between the nanostructures especially below 5 nm in solution. Here we present a viable self-assembly method to prepare symmetry-breaking nanostructures consisting of Ag nanocubes and Au nanospheres both with tunable size (90-250 nm

  13. Structural and optical properties of self-assembled chains of plasmonic nanocubes

    SciTech Connect

    Klinkova, Anna; Gang, Oleg; Therien-Aubin, Heloise; Ahmed, Aftab; Nykypanchuk, Dmytro; Choueiri, Rachelle M.; Gagnon, Brandon; Muntyanu, Anastasiya; Walker, Gilbert C.; Kumacheva, Eugenia

    2014-10-10

    Solution-based linear self-assembly of metal nanoparticles offers a powerful strategy for creating plasmonic polymers, which, so far, have been formed from spherical nanoparticles and nanorods. Here, we report linear solution-based self-assembly of metal nanocubes (NCs), examine the structural characteristics of the NC chains and demonstrate their advanced optical characteristics. Predominant face-to-face assembly of large NCs coated with short polymer ligands led to a larger volume of hot spots in the chains, a nearly uniform E-field enhancement in the gaps between co-linear NCs and a new coupling mode for NC chains, in comparison with chains of nanospheres with similar dimensions, composition and surface chemistry. The NC chains exhibited a stronger surface enhanced Raman scattering (SERS) signal, in comparison with linear assemblies of nanospheres. The experimental results were in agreement with finite difference time domain (FDTD) simulations.

  14. Structural and optical properties of self-assembled chains of plasmonic nanocubes

    DOE PAGES

    Klinkova, Anna; Gang, Oleg; Therien-Aubin, Heloise; Ahmed, Aftab; Nykypanchuk, Dmytro; Choueiri, Rachelle M.; Gagnon, Brandon; Muntyanu, Anastasiya; Walker, Gilbert C.; Kumacheva, Eugenia

    2014-10-10

    Solution-based linear self-assembly of metal nanoparticles offers a powerful strategy for creating plasmonic polymers, which, so far, have been formed from spherical nanoparticles and nanorods. Here, we report linear solution-based self-assembly of metal nanocubes (NCs), examine the structural characteristics of the NC chains and demonstrate their advanced optical characteristics. Predominant face-to-face assembly of large NCs coated with short polymer ligands led to a larger volume of hot spots in the chains, a nearly uniform E-field enhancement in the gaps between co-linear NCs and a new coupling mode for NC chains, in comparison with chains of nanospheres with similar dimensions, compositionmore » and surface chemistry. The NC chains exhibited a stronger surface enhanced Raman scattering (SERS) signal, in comparison with linear assemblies of nanospheres. The experimental results were in agreement with finite difference time domain (FDTD) simulations.« less

  15. A self-assembled ionophore

    NASA Astrophysics Data System (ADS)

    Tirumala, Sampath K.

    1997-11-01

    Ionophores are compounds that bind and transport ions. Ion binding and transport are fundamental to many biological and chemical processes. In this thesis we detail the structural characterization and cation binding properties of a self-assembled ionophore built from an isoguanosine (isoG) derivative, 5sp'-t-butyldimethylsilyl-2sp',3sp'-isopropylidene isoG 30. We begin with a summary of the themes that facilitate ionophore design and the definitions of "self-assembly" and "self-assembled ionophore" in Chapter 1. In Chapter 2, we describe the structural characterization of the isoG 30 self-assembly. IsoG possesses complementary hydrogen bond donor and acceptor sites suitable to form a Csb4-symmetric tetramer, (isoG)sb4 51, that is stable even in high dielectric organic solvents such as CDsb3CN and dsb6-acetone. The isoG tetramer 51 has been characterized by vapor phase osmometry, UV spectroscopy, and by 1D and 2D NMR spectroscopy. The isoG tetramer 51 organizes by hydrogen bonding between the Watson-Crick face of one isoG base and the complementary bottom edge of another purine. The tetramer 51 is stabilized by an inner and outer ring of hydrogen bonds. The inner ring forms between the imino NH1 proton of one monomer and the C2 carbonyl oxygen of an adjacent monomer, while the outer ring is made up of four NH6-N3 hydrogen bonds. The isoG tetramer 51 is thermodynamically stable, with an equilibrium constant (Ksba) of ca. 10sp9-10sp{10} Msp{-3} at room temperature, and a DeltaGsp° of tetramer formation of -12.5 kcal molsp{-1} in dsb6-acetone at 25sp°C. The van't Hoff plots indicated that the thermodynamic parameters for tetramer formation were DeltaHsp° = -18.2 ± 0.87 kcal molsp{-1} and DeltaSsp°sb{298} = -19.1 ± 5.45 eu. In Chapter 3, we describe the cation binding properties of isoG tetramer 51. The isoG tetramer 51 has a central cavity, containing four oxygen atoms, that is suitable for cation coordination. Depending on the cation, the resulting iso

  16. Self-assembling magnetic "snakes"

    SciTech Connect

    2010-01-01

    Nickel particles float peacefully in a liquid medium until a giant snake seems to swim by and snatch several particles up, adding to its own mass. The self-assembled "snakes" act like biological systems, but they are not alive and are driven by a magnetic field. The research may someday offer some insight into the organization of life itself. Read more at Wired: http://www.wired.com/wiredscience/2009/03/snakes/ Research and video by Alex Snezhko and Igor Aronson, Argonne National Laboratory.

  17. Structural simulations of nanomaterials self-assembled from ionic macrocycles.

    SciTech Connect

    van Swol, Frank B.; Medforth, Craig John

    2010-10-01

    Recent research at Sandia has discovered a new class of organic binary ionic solids with tunable optical, electronic, and photochemical properties. These nanomaterials, consisting of a novel class of organic binary ionic solids, are currently being developed at Sandia for applications in batteries, supercapacitors, and solar energy technologies. They are composed of self-assembled oligomeric arrays of very large anions and large cations, but their crucial internal arrangement is thus far unknown. This report describes (a) the development of a relevant model of nonconvex particles decorated with ions interacting through short-ranged Yukawa potentials, and (b) the results of initial Monte Carlo simulations of the self-assembly binary ionic solids.

  18. Self-assembled controllable microswimmers

    NASA Astrophysics Data System (ADS)

    Grosjean, Galien; Lagubeau, Guillaume; Darras, Alexis; Lumay, Geoffroy; Hubert, Maxime; Vandewalle, Nicolas

    2015-11-01

    Because they cause a deformation of the interface, floating particles interact. In particular, identical particles attract each other. To counter this attraction, particles possessing a large magnetic moment m-> are used. When m-> is perpendicular to the surface, dipole-dipole interaction is repulsive. This competition of forces can lead to the spontaneous formation of organized structures. By using submillimetric steel spheres for which m-> ~ B-> , interdistances in the system can be precisely tuned. Here, we deform these self-assemblies by adding a horizontal contribution m-> to the magnetic moment. Time reversal symmetry is broken in the system, leading to locomotion at low Reynolds number. Moreover, swimming direction depends on the orientation of field, meaning that swimming trajectories can be finely controlled. A model allows to understand the breaking of symmetry, while a study of the vibration modes gives further informations on the dynamics of this sytem. Because this system forms by self-assembly, it allows miniaturization with applications such as cargo transport or solvent flows. It is highly versatile, being composed of simple passive particles and controlled by magnetic fields.

  19. Self-assembling RNA square

    SciTech Connect

    Dibrov, Sergey M.; McLean, Jaime; Parsons, Jerod; Hermann, Thomas

    2011-12-22

    The three-dimensional structures of noncoding RNA molecules reveal recurring architectural motifs that have been exploited for the design of artificial RNA nanomaterials. Programmed assembly of RNA nanoobjects from autonomously folding tetraloop-receptor complexes as well as junction motifs has been achieved previously through sequence-directed hybridization of complex sets of long oligonucleotides. Due to size and complexity, structural characterization of artificial RNA nanoobjects has been limited to low-resolution microscopy studies. Here we present the design, construction, and crystal structure determination at 2.2 {angstrom} of the smallest yet square-shaped nanoobject made entirely of double-stranded RNA. The RNA square is comprised of 100 residues and self-assembles from four copies each of two oligonucleotides of 10 and 15 bases length. Despite the high symmetry on the level of secondary structure, the three-dimensional architecture of the square is asymmetric, with all four corners adopting distinct folding patterns. We demonstrate the programmed self-assembly of RNA squares from complex mixtures of corner units and establish a concept to exploit the RNA square as a combinatorial nanoscale platform.

  20. Chemical reactions directed Peptide self-assembly.

    PubMed

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-01-01

    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.

  1. Chemical Reactions Directed Peptide Self-Assembly

    PubMed Central

    Rasale, Dnyaneshwar B.; Das, Apurba K.

    2015-01-01

    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. PMID:25984603

  2. Characterization of electroosmotic flow through nanoporous self-assembled arrays.

    PubMed

    Bell, Kevan; Gomes, Mikel; Nazemifard, Neda

    2015-08-01

    Characterization of EOF mobility for Tris and TBE buffer solutions is performed in nanoporous arrays using the fluorescent marker method to examine the magnitude of EOFs through nanopores with mean diameters close to electric double layer thickness (Debye length). Structures made from solid silica nanospheres with effective pore sizes from 104 nm down to 8 nm are produced within the microchannel using an evaporation self-assembly method. EOF results in nanoporous matrices show higher EOF mobilities for stronger electrolyte solutions, which are drastically different compared to microchannel EOF. The effects of scaling are also examined by comparing the EOF mobility for varying ratios of pore diameters to the Debye length, which shows a surprising consistency across all particle sizes examined. This work demonstrates various factors which must be considered when designing nanofluidic devices, and discusses the causes of these small scale effects. PMID:25964193

  3. Ultrastructure of forming enamel in mouse bearing a transgene that disrupts the amelogenin self-assembly domains.

    PubMed

    Dunglas, C; Septier, D; Paine, M L; Zhu, D H; Snead, M L; Goldberg, M

    2002-08-01

    The mouse X-chromosomal amelogenin gene promoter was used to drive the expression of mutated amelogenin proteins in vivo. Two different transgenic mouse lines based on deletions to either the amino-terminal (A-domain deletions) or to the carboxyl-region (B-domain deletions) were bred. In the molars of newborn A-domain deleted transgenic mice the formation of the initial layer of aprismatic enamel was delayed. There were severe structural alterations in the enamel of incisors of newborn mice bearing the A-domain deletion which were not apparent in animals bearing the B-domain deletion. In the A-domain-deleted animals, stippled material accumulated throughout the entire thickness of the forming enamel apparently causing a disruption of the normal rod-to-inter-rod relationship. This stippled material was likened to and interpreted as being groupings of amelogenin nanospheres. In the B-domain-deleted animals the stippled material was detected only in minute defects of the forming enamel. These data suggest significant differences in nanosphere assembly properties for animals bearing either the A-domain or the B-domain-deleted transgene. The present in vivo experimental approach suggests that at early stages of enamel formation, the A-domain plays a greater role than does the B-domain in amelogenin self-assembly, and consequently in enamel architecture and structure.

  4. Multi-scale modeling for the self-assembly of DNA-functionalized nanoparticle into supperlattice and Wulff polydedra

    NASA Astrophysics Data System (ADS)

    Li, Ting; Auyeung, Evelyn; Mirkin, Chad; Olvera de La Cruz, Monica; Northwestern University Team

    2014-03-01

    Since 1996, DNA hybridization has proven robust for programmable self-assembly of nanoparticles (NPs). Recently, we showed that through a ``slow cooling'' method, DNA functionalized nanospheres or so-called ``programmable atom equivalents'' can assemble into crystals with a specific and uniform habit. Here we perform molecular dynamics simulations on multi-scale models to study and predict the corresponding shapes. Firstly, we use a scale-accurate coarse-grained model with explicit DNA chains to estimate surface energy ratios for different surface orientations, and predict the corresponding Wulff polyhedra based on these values. Secondly, we use a colloidal model in which each DNA coated nanosphere is represented by a single bead to simulate the growth dynamics of the crystals. By this method, we confirm the shape for the body-centered-cubic system to be a (110)-enclosed rhombic dodecahedron. But the face-centered-cubic system does not show any uniform shape yet except triangular features with (111) and (100) facets due to crystallographic defects including twinning and stacking faults. These simulated crystal shapes agrees very well with experiments. Air Force Office of Scientific Research (AFOSR) Multidisciplinary University Research Initiative (MURI) FA9550-11-1-0275.

  5. Self-assembled artificial cilia

    PubMed Central

    Vilfan, Mojca; Potočnik, Anton; Kavčič, Blaž; Osterman, Natan; Poberaj, Igor; Vilfan, Andrej; Babič, Dušan

    2010-01-01

    Due to their small dimensions, microfluidic devices operate in the low Reynolds number regime. In this case, the hydrodynamics is governed by the viscosity rather than inertia and special elements have to be introduced into the system for mixing and pumping of fluids. Here we report on the realization of an effective pumping device that mimics a ciliated surface and imitates its motion to generate fluid flow. The artificial biomimetic cilia are constructed as long chains of spherical superparamagnetic particles, which self-assemble in an external magnetic field. Magnetic field is also used to actuate the cilia in a simple nonreciprocal manner, resulting in a fluid flow. We prove the concept by measuring the velocity of a cilia-pumped fluid as a function of height above the ciliated surface and investigate the influence of the beating asymmetry on the pumping performance. A numerical simulation was carried out that successfully reproduced the experimentally obtained data. PMID:19934055

  6. Self-assembly of 33-mer gliadin peptide oligomers.

    PubMed

    Herrera, M G; Benedini, L A; Lonez, C; Schilardi, P L; Hellweg, T; Ruysschaert, J-M; Dodero, V I

    2015-11-28

    The 33-mer gliadin peptide, LQLQPF(PQPQLPY)3PQPQPF, is a highly immunogenic peptide involved in celiac disease and probably in other immunopathologies associated with gliadin. Herein, dynamic light scattering measurements showed that 33-mer, in the micromolar concentration range, forms polydisperse nano- and micrometer range particles in aqueous media. This behaviour is reminiscent of classical association of colloids and we hypothesized that the 33-mer peptide self-assembles into micelles that could be the precursors of 33-mer oligomers in water. Deposition of 33-mer peptide aqueous solution on bare mica generated nano- and microstructures with different morphologies as revealed by atomic force microscopy. At 6 μM, the 33-mer is organised in isolated and clusters of spherical nanostructures. In the 60 to 250 μM concentration range, the spherical oligomers associated mainly in linear and annular arrangements and structures adopting a "sheet" type morphology appeared. At higher concentrations (610 μM), mainly filaments and plaques immersed in a background of nanospherical structures were detected. The occurrence of different morphologies of oligomers and finally the filaments suggests that the unique specific geometry of the 33-mer oligomers has a crucial role in the subsequent condensation and organization of their fractal structures into the final filaments. The self-assembly process on mica is described qualitatively and quantitatively by a fractal diffusion limited aggregation (DLA) behaviour with the fractal dimension in the range of 1.62 ± 0.02 to 1.73 ± 0.03. Secondary structure evaluation of the oligomers by Attenuated Total Reflection FTIR spectroscopy (ATR-FTIR) revealed the existence of a conformational equilibrium of self-assembled structures, from an extended conformation to a more folded parallel beta elongated structures. Altogether, these findings provide structural and morphological information about supramolecular organization of the 33-mer

  7. Self-assembled nanomaterials for photoacoustic imaging

    NASA Astrophysics Data System (ADS)

    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.

  8. Self-Assembly: How Nature Builds

    ERIC Educational Resources Information Center

    Jones, M. Gail; Falvo, Michael R.; Broadwell, Bethany; Dotger, Sharon

    2006-01-01

    Self-assembly or spontaneous assembly is a process in which materials build themselves without assistance. This process plays a central role in the construction of biological structures and materials such as cells, viruses, and bone, and also in abiotic processes like phase transitions and crystal formation. The principles of self-assembly help…

  9. Developmental self-assembly of a DNA tetrahedron.

    PubMed

    Sadowski, John P; Calvert, Colby R; Zhang, David Yu; Pierce, Niles A; Yin, Peng

    2014-04-22

    Kinetically controlled isothermal growth is fundamental to biological development, yet it remains challenging to rationally design molecular systems that self-assemble isothermally into complex geometries via prescribed assembly and disassembly pathways. By exploiting the programmable chemistry of base pairing, sophisticated spatial and temporal control have been demonstrated in DNA self-assembly, but largely as separate pursuits. By integrating temporal with spatial control, here we demonstrate the "developmental" self-assembly of a DNA tetrahedron, where a prescriptive molecular program orchestrates the kinetic pathways by which DNA molecules isothermally self-assemble into a well-defined three-dimensional wireframe geometry. In this reaction, nine DNA reactants initially coexist metastably, but upon catalysis by a DNA initiator molecule, navigate 24 individually characterizable intermediate states via prescribed assembly pathways, organized both in series and in parallel, to arrive at the tetrahedral final product. In contrast to previous work on dynamic DNA nanotechnology, this developmental program coordinates growth of ringed substructures into a three-dimensional wireframe superstructure, taking a step toward the goal of kinetically controlled isothermal growth of complex three-dimensional geometries.

  10. A Precise Packing Sequence for Self-Assembled Convex Structures

    NASA Astrophysics Data System (ADS)

    Chen, Ting; Zhang, Zhenli; Glotzer, Sharon

    2007-03-01

    We present molecular simulations of the self-assembly of cone-shaped particles with patchy, attractive interactions[1,2]. Upon cooling from random initial conditions, we find that the cones self assemble into clusters and that clusters comprised of particular numbers of cones have a unique and precisely packed structure that is robust over a range of cone angles. These precise clusters form precise packing sequence that for small sizes is identical to that observed in evaporation-driven assembly of colloidal spheres. This sequence is reproduced and extended in simulations of two simple models of spheres self-assembling from random initial conditions subject to convexity constraints, and contains six of the most common virus capsid structures obtained in vivo including large chiral clusters, and a cluster that may correspond to several non- icosahedral, spherical virus capsid structures obtained in vivo. For prolate spheroidal convexity conditions, we demonstrate the formation of several prolate virus structures from self-assembling hard spheres[3]. [1] Chen T, Zhang ZL, Glotzer SC, PNAS, in press (http://xxx.lanl.gov/pdf/cond-mat/ 0608592) [2] Chen T, Zhang ZL, Glotzer SC, http://xxx.lanl.gov/pdf/cond-mat/0608613 [3] Chen T, Glotzer SC http://xxx.lanl.gov/pdf/q-bio.BM/0608040

  11. Self assembled structures for 3D integration

    NASA Astrophysics Data System (ADS)

    Rao, Madhav

    Three dimensional (3D) micro-scale structures attached to a silicon substrate have various applications in microelectronics. However, formation of 3D structures using conventional micro-fabrication techniques are not efficient and require precise control of processing parameters. Self assembly is a method for creating 3D structures that takes advantage of surface area minimization phenomena. Solder based self assembly (SBSA), the subject of this dissertation, uses solder as a facilitator in the formation of 3D structures from 2D patterns. Etching a sacrificial layer underneath a portion of the 2D pattern allows the solder reflow step to pull those areas out of the substrate plane resulting in a folded 3D structure. Initial studies using the SBSA method demonstrated low yields in the formation of five different polyhedra. The failures in folding were primarily attributed to nonuniform solder deposition on the underlying metal pads. The dip soldering method was analyzed and subsequently refined. A modified dip soldering process provided improved yield among the polyhedra. Solder bridging referred as joining of solder deposited on different metal patterns in an entity influenced the folding mechanism. In general, design parameters such as small gap-spacings and thick metal pads were found to favor solder bridging for all patterns studied. Two types of soldering: face and edge soldering were analyzed. Face soldering refers to the application of solder on the entire metal face. Edge soldering indicates application of solder only on the edges of the metal face. Mechanical grinding showed that face soldered SBSA structures were void free and robust in nature. In addition, the face soldered 3D structures provide a consistent heat resistant solder standoff height that serve as attachments in the integration of dissimilar electronic technologies. Face soldered 3D structures were developed on the underlying conducting channel to determine the thermo-electric reliability of

  12. Protein self-assembly via supramolecular strategies.

    PubMed

    Bai, Yushi; Luo, Quan; Liu, Junqiu

    2016-05-21

    Proteins, as the elemental basis of living organisms, mostly execute their biological tasks in the form of supramolecular self-assemblies with subtle architectures, dynamic interactions and versatile functionalities. Inspired by the structural harmony and functional beauty of natural protein self-assemblies to fabricate sophisticated yet highly ordered protein superstructures represents an adventure in the pursuit of nature's supreme wisdom. In this review, we focus on building protein self-assembly systems based on supramolecular strategies and classify recent progress by the types of utilized supramolecular driving forces. Especially, the design strategy, structure control and the thermodynamic/kinetic regulation of the self-assemblies, which will in turn provide insights into the natural biological self-assembly mechanism, are highlighted. In addition, recently, this research field is starting to extend its interest beyond constructing complex morphologies towards the potential applications of the self-assembly systems; several attempts to design functional protein complexes are also discussed. As such, we hope that this review will provide a panoramic sketch of the field and draw a roadmap towards the ultimate construction of advanced protein self-assemblies that even can serve as analogues of their natural counterparts.

  13. Self-assembling nanoparticles into holographic nanopatterns

    NASA Astrophysics Data System (ADS)

    Lee, Seung-Heon; Diana, Frédéric S.; Badolato, Antonio; Petroff, Pierre M.; Kramer, Edward J.

    2004-05-01

    We demonstrate a method to self-assemble metal nanoparticles into two-dimensional lattices. Monodisperse cobalt nanoparticles were synthesized within inverse micelles of polystyrene-block-poly(2-vinylpyridine) copolymer in toluene. A periodic hole pattern of photoresist (PR) was fabricated on a GaAs substrate by holographic lithography. The nanoparticles as prepared above were self-assembled onto the PR nanopatterns by dip or spin casting. They were selectively positioned in the holes due to the capillary forces related to the pattern geometry. Our study reveals that self-assembled nanoparticles in two-dimensional lattices can be obtained with a controllable number of particles per lattice point.

  14. Adaptive soft molecular self-assemblies.

    PubMed

    Wang, Andong; Shi, Wenyue; Huang, Jianbin; Yan, Yun

    2016-01-14

    Adaptive molecular self-assemblies provide possibility of constructing smart and functional materials in a non-covalent bottom-up manner. Exploiting the intrinsic properties of responsiveness of non-covalent interactions, a great number of fancy self-assemblies have been achieved. In this review, we try to highlight the recent advances in this field. The following contents are focused: (1) environmental adaptiveness, including smart self-assemblies adaptive to pH, temperature, pressure, and moisture; (2) special chemical adaptiveness, including nanostructures adaptive to important chemicals, such as enzymes, CO2, metal ions, redox agents, explosives, biomolecules; (3) field adaptiveness, including self-assembled materials that are capable of adapting to external fields such as magnetic field, electric field, light irradiation, and shear forces. PMID:26509717

  15. Self-assembled chitin nanofibers and applications.

    PubMed

    Rolandi, Marco; Rolandi, Ranieri

    2014-05-01

    Self-assembled natural biomaterials offer a variety of ready-made nanostructures available for basic science research and technological applications. Most natural structural materials are made of self-assembled nanofibers with diameters in the nanometer range. Among these materials, chitin is the second most abundant polysaccharide after cellulose and is part of the exoskeleton or arthropods and mollusk shells. Chitin has several desirable properties as a biomaterial including mechanical strength, chemical and thermal stability, and biocompatibility. However, chitin insolubility in most organic solvents has somewhat limited its use. In this research highlight, we describe recent developments in producing biogenic chitin nanofibers using self-assembly from a solution of squid pen β-chitin in hexafluoroisopropanol. With this solution based assembly, we have demonstrated chitin-silk composite self-assembly, chitin nanofiber fabrication across length-scales, and manufacturing of chitin nanofiber substrates for tissue engineering. PMID:24556234

  16. Directed Self-Assembly of Nanodispersions

    SciTech Connect

    Furst, Eric M

    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

  17. From Solvolysis to Self-Assembly*

    PubMed Central

    Stang, Peter J.

    2009-01-01

    My sojourn from classical physical-organic chemistry and solvolysis to self-assembly and supramolecular chemistry, over the last forty years, is described. My contributions to unsaturated reactive intermediates, namely vinyl cations and unsaturated carbenes, along with my decade long involvement with polyvalent iodine chemistry, especially alkynyliodonium salts, as well as my more recent research with metal-ligand, coordination driven and directed self-assembly of finite supramolecular ensembles are discussed. PMID:19111062

  18. Directed Self-Assembly of Colloidal Particles

    NASA Astrophysics Data System (ADS)

    Zeravcic, Zorana; Collins, Jesse; Manoharan, Vinothan; Brenner, Michael

    2011-03-01

    In nature, simple constituents like atoms, molecules and polymer chains, spontaneously organize into larger, higher order structures. Interactions involved in this self-assembly act on a local level. These facts inspire experimental and theoretical engineering of components able to organize into pre-designed complex systems. We perform numerical simulations of collections of DNA coated colloidal particles. We test different design rules for self-assembly with short-range interactions and explore the stability of equilibrium structures.

  19. Silk Reconstitution Disrupts Fibroin Self-Assembly.

    PubMed

    Koebley, Sean R; Thorpe, Daniel; Pang, Pei; Chrisochoides, Panos; Greving, Imke; Vollrath, Fritz; Schniepp, Hannes C

    2015-09-14

    Using atomic force microscopy, we present the first molecular-scale comparison of two of the most important silk dopes, native (NSF) and reconstituted (RSF) silkworm fibroin. We found that both systems depended on shear to show self-assembly. Significant differences in the nature of self-assembly between NSF and RSF were shown. In the highest studied concentration of 1000 mg/L, NSF exhibited assembly into 20-30 nm-wide nanofibrils closely resembling the surface structures found in natural silk fibers. RSF, in contrast, showed no self-assembly whatsoever at the same concentration, which suggests that the reconstitution process significantly disrupts silk's inherent self-assembly capability. At lower concentrations, both RSF and NSF formed fibrils under shear, apparently denatured by the substrate. Using image analysis, we quantified the properties of these self-assembled fibrils as a function of concentration and found low-concentration fibrils of NSF to form larger continuous structures than those of RSF, further supporting NSF's superior self-assembly capabilities. PMID:26284914

  20. Silk Reconstitution Disrupts Fibroin Self-Assembly.

    PubMed

    Koebley, Sean R; Thorpe, Daniel; Pang, Pei; Chrisochoides, Panos; Greving, Imke; Vollrath, Fritz; Schniepp, Hannes C

    2015-09-14

    Using atomic force microscopy, we present the first molecular-scale comparison of two of the most important silk dopes, native (NSF) and reconstituted (RSF) silkworm fibroin. We found that both systems depended on shear to show self-assembly. Significant differences in the nature of self-assembly between NSF and RSF were shown. In the highest studied concentration of 1000 mg/L, NSF exhibited assembly into 20-30 nm-wide nanofibrils closely resembling the surface structures found in natural silk fibers. RSF, in contrast, showed no self-assembly whatsoever at the same concentration, which suggests that the reconstitution process significantly disrupts silk's inherent self-assembly capability. At lower concentrations, both RSF and NSF formed fibrils under shear, apparently denatured by the substrate. Using image analysis, we quantified the properties of these self-assembled fibrils as a function of concentration and found low-concentration fibrils of NSF to form larger continuous structures than those of RSF, further supporting NSF's superior self-assembly capabilities.

  1. Self-assembling holographic biosensors and biocomputers.

    SciTech Connect

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

    2006-05-01

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

  2. Phase behavior and complex crystal structures of self-assembled tethered nanoparticle telechelics.

    PubMed

    Marson, Ryan L; Phillips, Carolyn L; Anderson, Joshua A; Glotzer, Sharon C

    2014-01-01

    Motivated by growing interest in the self-assembly of nanoparticles for applications such as photonics, organic photovoltaics, and DNA-assisted designer crystals, we explore the phase behavior of tethered spherical nanoparticles. Here, a polymer tether is used to geometrically constrain a pair of nanoparticles creating a tethered nanoparticle "telechelic". Using simulation, we examine how varying architectural features, such as the size ratio of the two end-group nanospheres and the length of the flexible tether, affects the self-assembled morphologies. We demonstrate not only that this hybrid building block maintains the same phase diversity as linear triblock copolymers, allowing for a variety of nanoparticle materials to replace polymer blocks, but also that new structures not previously reported are accessible. Our findings imply a robust underlying ordering mechanism is common among these systems, thus allowing flexibility in synthesis approaches to achieve a target morphology.

  3. Self assembled nanoparticle aggregates from line focused femtosecond laser ablation.

    PubMed

    Zuhlke, Craig A; Alexander, Dennis R; Bruce, John C; Ianno, Natale J; Kamler, Chad A; Yang, Weiqing

    2010-03-01

    In this paper we present the use of a line focused femtosecond laser beam that is rastered across a 2024 T3 aluminum surface to produce nanoparticles that self assemble into 5-60 micron diameter domed and in some cases sphere-shaped aggregate structures. Each time the laser is rastered over initial aggregates their diameter increases as new layers of nanoparticles self assemble on the surface. The aggregates are thus composed of layers of particles forming discrete layered shells inside of them. When micron size aggregates are removed, using an ultrasonic bath, rings are revealed that have been permanently formed in the sample surface. These rings appear underneath, and extend beyond the physical boundary of the aggregates. The surface is blackened by the formation of these structures and exhibits high light absorption. PMID:20389444

  4. Strip-Pattern-Spheres Self-Assembled from Polypeptide-Based Polymer Mixtures: Structure and Defect Features

    NASA Astrophysics Data System (ADS)

    Zhu, Xingyu; Guan, Zhou; Lin, Jiaping; Cai, Chunhua

    2016-07-01

    We found that poly(γ-benzyl-L-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) rod-coil block copolymers and polystyrene (PS) homopolymers can cooperatively self-assemble into nano-spheres with striped patterns on their surfaces (strip-pattern-spheres) in aqueous solution. With assistance of dissipative particle dynamics simulation, it is discovered that the PS homopolymers form a spherical template core and the PBLG-b-PEG block copolymers assemble into striped patterns on the spherical surface. The hydrophobic PBLG rods are packed orderly in the strips, while the hydrophilic PEG blocks stabilize the strip-pattern-spheres in solution. Defects such as dislocations and disclinations can be observed in the striped patterns. Self-assembling temperature and sphere radius are found to affect defect densities in the striped patterns. A possible mechanism is proposed to illustrate how PBLG-b-PEG and PS cooperatively self-assemble into hierarchical spheres with striped patterns on surfaces.

  5. Directed self-assembly of performance materials

    NASA Astrophysics Data System (ADS)

    Nealey, Paul

    Directed self-assembly (DSA) is a promising strategy for high-volume cost-effective manufacturing at the nanoscale. Over the past decades, manufacturing techniques have been developed with such remarkable efficiency that it is now possible to engineer complex systems of heterogeneous materials at the scale of a few tens of nanometers. Further evolution of these techniques, however, is faced with difficult challenges not only in feasibility of implementation at scales of 10 nm and below, but also in prohibitively high capital equipment costs. Materials that self-assemble, on the other hand, spontaneously form structures at the mesoscale, but the micrometer areas or volumes over which the materials self-assemble with adequate perfection in structure is incommensurate with the macroscopic dimensions of working devices and systems of devices of industrial relevance. Directed Self-Assembly (DSA) refers to the integration of self-assembling materials with traditional manufacturing processes. Here we will discuss DSA of block copolymers to revolutionize sub 10 nm lithography and the manufacture of integrated circuits and storage media, DSA of ex-situ synthesized nanoparticles for applications in nanophotonics, and DSA of liquid crystals for advanced optics.

  6. Spectral and directional reshaping of fluorescence in large area self-assembled plasmonic-photonic crystals.

    PubMed

    Ding, Boyang; Hrelescu, Calin; Arnold, Nikita; Isic, Goran; Klar, Thomas A

    2013-02-13

    Spectral and directional reshaping of fluorescence from dye molecules embedded in self-assembled hybrid plasmonic-photonic crystals has been examined. The hybrid crystals comprise two-dimensional hexagonal arrays of dye-doped dielectric nanospheres, capped with silver semishells. Comparing the reshaped fluorescence spectra with measured transmission/reflection spectra and numerical calculations reveals that the spectral and directional reshaping of fluorescence is the result of its coupling to photonic crystal Bloch modes and to void plasmons localized inside the silver caps.

  7. Polymerization-Induced Self-Assembly of Galactose-Functionalized Biocompatible Diblock Copolymers for Intracellular Delivery

    PubMed Central

    2013-01-01

    Recent advances in polymer science are enabling substantial progress in nanobiotechnology, particularly in the design of new tools for enhanced understanding of cell biology and for smart drug delivery formulations. Herein, a range of novel galactosylated diblock copolymer nano-objects is prepared directly in concentrated aqueous solution via reversible addition–fragmentation chain transfer polymerization using polymerization-induced self-assembly. The resulting nanospheres, worm-like micelles, or vesicles interact in vitro with galectins as judged by a turbidity assay. In addition, galactosylated vesicles are highly biocompatible and allow intracellular delivery of an encapsulated molecular cargo. PMID:23941545

  8. Vertical zinc oxide nanowires embedded in self-assembled photonic crystal

    NASA Astrophysics Data System (ADS)

    Mastro, Michael A.; Mazeina, Lena; Kim, Byung-Jae; Prokes, Sharka M.; Hite, Jennifer; Eddy, Charles R.; Kim, Jihyun

    2011-02-01

    A dense array of vertical ZnO nanowires was grown on an Al 0.3Ga 0.7N/AlN distributed Bragg reflector. The ZnO nanowires were embedded in a photonic crystal formed by self-assembly of SiO 2 nanospheres into a close-packed fcc structure. The photonic crystal modified the spontaneous emission spectrum of the ZnO nanowires. A calculation confirmed that a close spacing in the ZnO nanowires will lead to coupling in the wire-to-wire electromagnetic fields.

  9. Theory of Programmable Hierarchic Self-Assembly

    NASA Astrophysics Data System (ADS)

    Tkachenko, Alexei V.

    2011-06-01

    We present a theoretical analysis of the inverse problem in self-assembly. A particular scheme is proposed for building an arbitrary desired nanostructure out of self-assembled building blocks (“octopus” nanoparticles). The conditions for robust self-assembly of the target structure are identified. This includes the minimal number of “colors” needed to encode interparticle bonds, which are to be implemented as pairs of complementary DNA sequences. As a part of this analysis, it is demonstrated that a floppy network with thermal fluctuations, in a certain range of coordination numbers ⟨Z⟩, possesses entropic rigidity and can be described as a traditional elastic solid. The onset of the entropic rigidity, ⟨Z⟩=d+1, determines the minimal number of bond types per particle needed to encode the desired structure. Thermodynamic considerations give additional conditions for the implementation of this scheme.

  10. Self-Assembly of Peptides to Nanostructures

    PubMed Central

    Mandal, Dindyal; Shirazi, Amir Nasrolahi; Parang, Keykavous

    2014-01-01

    The formation of well-ordered nanostructures through self-assembly of diverse organic and inorganic building blocks has drawn much attention owing to their potential applications in biology and chemistry. Among all organic building blocks, peptides are one of the most promising platforms due to their biocompatibility, chemical diversity, and resemblance with proteins. Inspired from the protein assembly in biological systems, various self-assembled peptide structures have been constructed using several amino acids and sequences. This review focuses on this emerging area, the recent advances in peptide self-assembly, and formation of different nanostructures, such as tubular, fibers, vesicles, spherical, and rod coil structures. While different peptide nanostructures are discovered, potential applications will be explored in drug delivery, tissue engineering, wound healing, and surfactants. PMID:24756480

  11. Amyloid inspired self-assembled peptide nanofibers.

    PubMed

    Cinar, Goksu; Ceylan, Hakan; Urel, Mustafa; Erkal, Turan S; Deniz Tekin, E; Tekinay, Ayse B; Dâna, Aykutlu; Guler, Mustafa O

    2012-10-01

    Amyloid peptides are important components in many degenerative diseases as well as in maintaining cellular metabolism. Their unique stable structure provides new insights in developing new materials. Designing bioinspired self-assembling peptides is essential to generate new forms of hierarchical nanostructures. Here we present oppositely charged amyloid inspired peptides (AIPs), which rapidly self-assemble into nanofibers at pH 7 upon mixing in water caused by noncovalent interactions. Mechanical properties of the gels formed by self-assembled AIP nanofibers were analyzed with oscillatory rheology. AIP gels exhibited strong mechanical characteristics superior to gels formed by self-assembly of previously reported synthetic short peptides. Rheological studies of gels composed of oppositely charged mixed AIP molecules (AIP-1 + 2) revealed superior mechanical stability compared to individual peptide networks (AIP-1 and AIP-2) formed by neutralization of net charges through pH change. Adhesion and elasticity properties of AIP mixed nanofibers and charge neutralized AIP-1, AIP-2 nanofibers were analyzed by high resolution force-distance mapping using atomic force microscopy (AFM). Nanomechanical characterization of self-assembled AIP-1 + 2, AIP-1, and AIP-2 nanofibers also confirmed macroscopic rheology results, and mechanical stability of AIP mixed nanofibers was higher compared to individual AIP-1 and AIP-2 nanofibers self-assembled at acidic and basic pH, respectively. Experimental results were supported with molecular dynamics simulations by considering potential noncovalent interactions between the amino acid residues and possible aggregate forms. In addition, HUVEC cells were cultured on AIP mixed nanofibers at pH 7 and biocompatibility and collagen mimetic scaffold properties of the nanofibrous system were observed. Encapsulation of a zwitterionic dye (rhodamine B) within AIP nanofiber network was accomplished at physiological conditions to demonstrate that this

  12. Self-assembly of lipopolysaccharide layers on allantoin crystals.

    PubMed

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Jiang, Qiu Zhen; Gagnon, Pete

    2014-08-01

    Self-assembly of lipopolysaccharides (LPS) on solid surfaces is important for the study of bacterial membranes, but has not been possible due to technical difficulties and the lack of suitable solid supports. Recently we found that crystals of the natural compound allantoin selectively bind pure LPS with sub-nanomolar affinity. The physicochemical origins of this selectivity and the adsorption mode of LPS on allantoin crystals remain, however, unknown. In this study we present evidence that LPS adsorption on allantoin crystals is initiated through hydrogen-bond attachment of hydrophilic LPS regions. Hydrophobic interactions between alkyl chains of adjacently adsorbed LPS molecules subsequently promote self-assembly of LPS layers. The essential role of hydrogen-bond interactions is corroborated by our finding that allantoin crystals bind to practically any hydrophilic surface chemistry. Binding contributions of hydrophobic interactions between LPS alkyl chains are evidenced by the endothermic nature of the adsorption process and explain why the binding affinity for LPS is several orders of magnitude higher than for proteins (lysozyme, BSA and IgG) and polysaccharides. Self-assembly of LPS layers via hydrogen-bond attachment on allantoin crystals emerges as a novel binding mechanism and could be considered as a practical method for preparing biomimetic membranes on a solid support.

  13. Intrinsic universality and the computational power of self-assembly.

    PubMed

    Woods, Damien

    2015-07-28

    Molecular self-assembly, the formation of large structures by small pieces of matter sticking together according to simple local interactions, is a ubiquitous phenomenon. A challenging engineering goal is to design a few molecules so that large numbers of them can self-assemble into desired complicated target objects. Indeed, we would like to understand the ultimate capabilities and limitations of this bottom-up fabrication process. We look to theoretical models of algorithmic self-assembly, where small square tiles stick together according to simple local rules in order to carry out a crystal growth process. In this survey, we focus on the use of simulation between such models to classify and separate their computational and expressive powers. Roughly speaking, one model simulates another if they grow the same structures, via the same dynamical growth processes. Our journey begins with the result that there is a single intrinsically universal tile set that, with appropriate initialization and spatial scaling, simulates any instance of Winfree's abstract Tile Assembly Model. This universal tile set exhibits something stronger than Turing universality: it captures the geometry and dynamics of any simulated system in a very direct way. From there we find that there is no such tile set in the more restrictive non-cooperative model, proving it weaker than the full Tile Assembly Model. In the two-handed model, where large structures can bind together in one step, we encounter an infinite set of infinite hierarchies of strictly increasing simulation power. Towards the end of our trip, we find one tile to rule them all: a single rotatable flipable polygonal tile that simulates any tile assembly system. We find another tile that aperiodically tiles the plane (but with small gaps). These and other recent results show that simulation is giving rise to a kind of computational complexity theory for self-assembly. It seems this could be the beginning of a much longer journey

  14. Nondeterministic self-assembly with asymmetric interactions

    NASA Astrophysics Data System (ADS)

    Tesoro, S.; Göpfrich, K.; Kartanas, T.; Keyser, U. F.; Ahnert, S. E.

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  15. Nondeterministic self-assembly with asymmetric interactions.

    PubMed

    Tesoro, S; Göpfrich, K; Kartanas, T; Keyser, U F; Ahnert, S E

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation. PMID:27627332

  16. Remote control of self-assembled microswimmers

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  17. Nondeterministic self-assembly with asymmetric interactions.

    PubMed

    Tesoro, S; Göpfrich, K; Kartanas, T; Keyser, U F; Ahnert, S E

    2016-08-01

    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  18. Remote control of self-assembled microswimmers

    PubMed Central

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

    2015-01-01

    Physics governing the locomotion of microorganisms and other microsystems is dominated by viscous damping. An effective swimming strategy involves the non-reciprocal and periodic deformations of the considered body. Here, we show that a magnetocapillary-driven self-assembly, composed of three soft ferromagnetic beads, is able to swim along a liquid-air interface when powered by an external magnetic field. More importantly, we demonstrate that trajectories can be fully controlled, opening ways to explore low Reynolds number swimming. This magnetocapillary system spontaneously forms by self-assembly, allowing miniaturization and other possible applications such as cargo transport or solvent flows. PMID:26538006

  19. Self-assembly of lithographically patterned nanoparticles

    PubMed Central

    Cho, Jeong-Hyun; Gracias, David H.

    2009-01-01

    The construction of three dimensional (3D) objects, with any desired surface patterns, is both critical to and easily achieved in macroscale, science and engineering. However, on the nanoscale, 3D fabrication is limited to particles with only very limited surface patterning. Here, we demonstrate a self-assembly strategy that harnesses the strengths of well established 2D nanoscale patterning techniques and additionally enables the construction of stable 3D polyhedral nanoparticles. As a proof of the concept, we self-assembled cubic particles with sizes as small as 100 nm and with specific and lithographically defined surface patterns. PMID:19681638

  20. Computer simulation of nanocube self-assemblies

    NASA Astrophysics Data System (ADS)

    Zhang, Xi

    Self-assembly of nanoscale building blocks and molecules into ordered nanostructures is a promising venue for bottom-up materials design. A wide variety of nanoparticles with unique shapes and uniform sizes have been successfully synthesized. However, organizing these nanoparticles into desired, predefined nanostructures is a formidable challenge now facing the materials community. For example, simple 2-D arrays and 3-D superlattices are the prevalent structures from most nanocube self-assemblies. Two practical strategies to impart anisotropy onto nanocubes, namely, attaching polymer tethers to nanoparticle surfaces and introducing directional dipolar interactions, can be applied to achieve more complex assembled structures. In this dissertation, we conduct computer simulations on nanocube self-assemblies induced by polymer tethers and directional dipole interactions, to examine the various parameters involved in such complicated self-assembly processes, including temperature, concentration, solvent condition, cube size, tether length, tether topology, tether placement, tether number, dipole direction, dipole strength and polydispersity, in order to understand how the packing geometry and interactions between nanocubes can be manipulated to confer precise control over the assembled structures and the phase behavior. First, we simulate monotethered nanocubes and find that the nanocubes favor face-to-face packing in poor solvents, stabilizing the lamellae phases. Next, we simulate different architectures of tethered nanocubes and demonstrate that the steric influence of tether beads can be manipulated to interfere with the face-to-face packing of nanocubes and alter the phase behaviors. We also study the self-assembly of nanocubes with dipoles. We find that the head-to-tail alignment of dipoles, coupled with the face-to-face close packing of nanocubes, dictates the assembled structures. The face-face attraction between nanocubes can also be utilized to control the

  1. Computing by molecular self-assembly

    PubMed Central

    Jonoska, Nataša; Seeman, Nadrian C.

    2012-01-01

    The paper reviews two computing models by DNA self-assembly whose proof of principal have recently been experimentally confirmed. The first model incorporates DNA nano-devices and triple crossover DNA molecules to algorithmically arrange non-DNA species. This is achieved by simulating a finite-state automaton with output where golden nanoparticles are assembled to read-out the result. In the second model, a complex DNA molecule representing a graph emerges as a solution of a computational problem. This supports the idea that in molecular self-assembly computing, it may be necessary to develop the notion of shape processing besides the classical approach through symbol processing. PMID:23919130

  2. Self-assembled supramolecular nanotube yarn.

    PubMed

    Liu, Yaqing; Wang, Tianyu; Huan, Yong; Li, Zhibo; He, Guowei; Liu, Minghua

    2013-11-01

    Metric length supramolecular nanotube yarns are fabricated though a spinning process from the diluted aqueous solution of self-assembled nanotubes, with bolaamphiphiles working as molecular building blocks. These non-covalent bonding based nanotube yarns show outstanding mechanical strength compared with some conventional polymers and could be operated under the macro conditions. PMID:23943418

  3. Self-assembly micro optical filter

    NASA Astrophysics Data System (ADS)

    Zhang, Ping (Cerina); Le, Kevin; Malalur-Nagaraja-Rao, Smitha; Hsu, Lun-Chen; Chiao, J.-C.

    2006-01-01

    Optical communication and sensor industry face critical challenges in manufacturing for system integration. Due to the assembly complexity and integration platform variety, micro optical components require costly alignment and assembly procedures, in which many required manual efforts. Consequently, self-assembly device architectures have become a great interest and could provide major advantages over the conventional optical devices. In this paper, we discussed a self-assembly integration platform for micro optical components. To demonstrate the adaptability and flexibility of the proposed optical device architectures, we chose a commercially available MEMS fabrication foundry service - MUMPs (Multi-User MEMS Process). In this work, polysilicon layers of MUMPS are used as the 3-D structural material for construction of micro component framework and actuators. However, because the polysilicon has high absorption in the visible and near infrared wavelength ranges, it is not suitable for optical interaction. To demonstrate the required optical performance, hybrid integration of materials was proposed and implemented. Organic compound materials were applied on the silicon-based framework to form the required optical interfaces. Organic compounds provide good optical transparency, flexibility to form filters or lens and inexpensive manufacturing procedures. In this paper, we have demonstrated a micro optical filter integrated with self-assembly structures. We will discuss the self-assembly mechanism, optical filter designs, fabrication issues and results.

  4. Self-assembling materials for therapeutic delivery✩

    PubMed Central

    Branco, Monica C.; Schneider, Joel P.

    2009-01-01

    A growing number of medications must be administered through parenteral delivery, i.e., intravenous, intramuscular, or subcutaneous injection, to ensure effectiveness of the therapeutic. For some therapeutics, the use of delivery vehicles in conjunction with this delivery mechanism can improve drug efficacy and patient compliance. Macromolecular self-assembly has been exploited recently to engineer materials for the encapsulation and controlled delivery of therapeutics. Self-assembled materials offer the advantages of conventional crosslinked materials normally used for release, but also provide the ability to tailor specific bulk material properties, such as release profiles, at the molecular level via monomer design. As a result, the design of materials from the “bottom up” approach has generated a variety of supramolecular devices for biomedical applications. This review provides an overview of self-assembling molecules, their resultant structures, and their use in therapeutic delivery. It highlights the current progress in the design of polymer- and peptide-based self-assembled materials. PMID:19010748

  5. [INVITED] Self-assembled optical metamaterials

    NASA Astrophysics Data System (ADS)

    Baron, Alexandre; Aradian, Ashod; Ponsinet, Virginie; Barois, Philippe

    2016-08-01

    Self-assembled metamaterials constitute a promising platform to achieving bulk and homogenous optical materials that exhibit unusual effective medium properties. For many years now, the research community has contemplated lithographically fabricated metasurfaces, with extraordinary optical features. However, achieving large volumes at low cost is still a challenge by top-down fabrication. Bottom-up fabrication, that relies both on nanochemistry and self-assembly, is capable of building such materials while greatly reducing the energy footprint in the formulation of the metamaterial. Self-assembled metamaterials have shown that they are capable of reaching unprecedented values of bulkiness and homogeneity figures of merit. This feat is achieved by synthesizing plasmonic nanoresonators (meta-atoms in the sense of artificial polarizable units) and assembling them into a fully three-dimensional matrix through a variety of methods. Furthermore it has been shown that a wide range of material parameters can be tailored by controlling the geometry and composition of the meta-atoms as well as the volume fraction of the nano-objects in the metamaterial. Here we conduct a non-comprehensive review of some of the recent trends in self-assembled optical metamaterials and illustrate these trends with our recent work.

  6. Inverse Problem in Self-assembly

    NASA Astrophysics Data System (ADS)

    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.

  7. Self-assembled nanolaminate coatings (SV)

    SciTech Connect

    Fan, H.

    2012-03-01

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

  8. Self-assembly of azide containing dipeptides.

    PubMed

    Yuran, Sivan; Razvag, Yair; Das, Priyadip; Reches, Meital

    2014-07-01

    Functional structures and materials are formed spontaneously in nature through the process of self-assembly. Mimicking this process in vitro will lead to the formation of new substances that would impact many areas including energy production and storage, biomaterials and implants, and drug delivery. The considerable structural diversity of peptides makes them appealing building blocks for self-assembly in vitro. This paper describes the self-assembly of three aromatic dipeptides containing an azide moiety: H-Phe(4-azido)-Phe(4-azido)-OH, H-Phe(4-azido)-Phe-OH, and H-Phe-Phe(4-azido)-OH. The peptide H-Phe(4-azido)-Phe(4-azido)-OH self-assembled into porous spherical structures, whereas the peptides H-Phe(4-azido)-Phe-OH and H-Phe-Phe(4-azido)-OH did not form any ordered structures under the examined experimental conditions. The azido group of the peptide can serve as a photo cross-linking agent upon irradiation with UV light. To examine the effect of this group and its activity on the self-assembled structures, we irradiated the assemblies in solution for different time periods. Using electron microscopy, we determined that the porous spherical assemblies formed by the peptide H-Phe(4-azido)-Phe(4-azido)-OH underwent a structural change upon irradiation. In addition, using FT-IR, we detected the chemical change of the peptide azido group. Moreover, using indentation experiments with atomic force microscopy, we showed that the Young's modulus of the spherical assemblies increased after 20 min of irradiation with UV light. Overall, irradiating the solution of the peptide assemblies containing the azido group resulted in a change both in the morphology and mechanical properties of the peptide-based structures. These ordered assemblies or their peptide monomer building blocks can potentially be incorporated into other peptide assemblies to generate stiffer and more stable materials. PMID:24889029

  9. Synthesis and characterization of Fatty acid/amino Acid self-assemblies.

    PubMed

    Gajowy, Joanna; Bolikal, Durgadas; Kohn, Joachim; Fray, Miroslawa El

    2014-01-01

    In this paper, we discuss the synthesis and self-assembling behavior of new copolymers derived from fatty acid/amino acid components, namely dimers of linoleic acid (DLA) and tyrosine derived diphenols containing alkyl ester pendent chains, designated as "R" (DTR). Specific pendent chains were ethyl (E) and hexyl (H). These poly(aliphatic/aromatic-ester-amide)s were further reacted with poly(ethylene glycol) (PEG) and poly(ethylene glycol methyl ether) of different molecular masses, thus resulting in ABA type (hydrophilic-hydrophobic-hydrophilic) triblock copolymers. We used Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies to evaluate the chemical structure of the final materials. The molecular masses were estimated by gel permeation chromatography (GPC) measurements. The self-organization of these new polymeric systems into micellar/nanospheric structures in aqueous environment was evaluated using ultraviolet/visible (UV-VIS) spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The polymers were found to spontaneously self-assemble into nanoparticles with sizes in the range 196-239 nm and critical micelle concentration (CMC) of 0.125-0.250 mg/mL. The results are quite promising and these materials are capable of self-organizing into well-defined micelles/nanospheres encapsulating bioactive molecules, e.g., vitamins or antibacterial peptides for antibacterial coatings on medical devices. PMID:25347356

  10. Structure and dynamics of optically directed self-assembly of nanoparticles.

    PubMed

    Roy, Debjit; Mondal, Dipankar; Goswami, Debabrata

    2016-01-01

    Self-assembly of nanoparticles leading to the formation of colloidal clusters often serves as the representative analogue for understanding molecular assembly. Unravelling the in situ structure and dynamics of such clusters in liquid suspensions is highly challenging. Presently colloidal clusters are first isolated from their generating environment and then their structures are probed by light scattering methods. In order to measure the in situ structure and dynamics of colloidal clusters, we have generated them using the high-repetition-rate femtosecond laser pulse optical tweezer. Since the constituent of our dimer, trimer or tetramer clusters are 250 nm radius two-photon resonant fluorophore coated nanospheres under the optical trap, they inherently produce Two-Photon Fluorescence, which undergo intra-nanosphere Fluorescence Energy Transfer. This unique energy transfer signature, in turn, enables us to visualize structures and orientations of these colloidal clusters during the process of their formation and subsequent dynamics in a liquid suspension. We also show that due to shape-birefringence, orientation and structural control of these colloidal clusters are possible as the polarization of the trapping laser is changed from linear to circular. We thus report important progress in sampling the smallest possible aggregates of nanoparticles, dimers, trimers or tetramers, formed early in the self-assembly process. PMID:27006305

  11. Structure and dynamics of optically directed self-assembly of nanoparticles

    PubMed Central

    Roy, Debjit; Mondal, Dipankar; Goswami, Debabrata

    2016-01-01

    Self-assembly of nanoparticles leading to the formation of colloidal clusters often serves as the representative analogue for understanding molecular assembly. Unravelling the in situ structure and dynamics of such clusters in liquid suspensions is highly challenging. Presently colloidal clusters are first isolated from their generating environment and then their structures are probed by light scattering methods. In order to measure the in situ structure and dynamics of colloidal clusters, we have generated them using the high-repetition-rate femtosecond laser pulse optical tweezer. Since the constituent of our dimer, trimer or tetramer clusters are 250 nm radius two-photon resonant fluorophore coated nanospheres under the optical trap, they inherently produce Two-Photon Fluorescence, which undergo intra-nanosphere Fluorescence Energy Transfer. This unique energy transfer signature, in turn, enables us to visualize structures and orientations of these colloidal clusters during the process of their formation and subsequent dynamics in a liquid suspension. We also show that due to shape-birefringence, orientation and structural control of these colloidal clusters are possible as the polarization of the trapping laser is changed from linear to circular. We thus report important progress in sampling the smallest possible aggregates of nanoparticles, dimers, trimers or tetramers, formed early in the self-assembly process. PMID:27006305

  12. Chemical Functionalization, Self-Assembly, and Applications of Nanomaterials and Nanocomposites

    SciTech Connect

    Jiao, Tifeng; Yan, Xingbin; Balan, Lavinia; Stepanov, Andrey; Chen, Xinqing; Hu, Michael Z.

    2014-01-01

    This special issue addresses the research studies on chemical functionalization, self-assembly, and applications of nanomaterials and nanocomposites. It contains twentyfour articles including two reviews and twenty-two research articles. It is used to create new functional nanomaterials and nanocomposites with a variety of sizes and morphologies such as Zn/Al layered double hydroxide, tin oxide nanowires, FeOOH-modified anion resin, Au nanoclusters silica composite nanospheres, Ti-doped ZnO sol-composite films, TiO2/ZnO composite, graphene oxide nanocomposites, LiFePO4/C nanocomposites, and chitosan nanoparticles. These nanomaterials and nanocomposites have widespread applications in tissue engineering, antitumor, sensors, photoluminescence, electrochemical, and catalytic properties. In addition, this themed issue includes some research articles about self-assembly systems covering organogels and Langmuir films. Furthermore, B. Blasiak et al. performed a literature survey on the recent advances in production, functionalization, toxicity reduction, and application of nanoparticles in cancer diagnosis, treatment, and treatment monitoring. P. Colson et al. performed a literature survey on the recent advances in nanosphere lithography due to its compatibility with wafer-scale processes as well as its potential to manufacture a wide variety of homogeneous one-, two-, or three-dimensional nanostructures.

  13. Synthesis and Characterization of Fatty Acid/Amino Acid Self-Assemblies

    PubMed Central

    Gajowy, Joanna; Bolikal, Durgadas; Kohn, Joachim; El Fray, Miroslawa

    2014-01-01

    In this paper, we discuss the synthesis and self-assembling behavior of new copolymers derived from fatty acid/amino acid components, namely dimers of linoleic acid (DLA) and tyrosine derived diphenols containing alkyl ester pendent chains, designated as “R” (DTR). Specific pendent chains were ethyl (E) and hexyl (H). These poly(aliphatic/aromatic-ester-amide)s were further reacted with poly(ethylene glycol) (PEG) and poly(ethylene glycol methyl ether) of different molecular masses, thus resulting in ABA type (hydrophilic-hydrophobic-hydrophilic) triblock copolymers. We used Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies to evaluate the chemical structure of the final materials. The molecular masses were estimated by gel permeation chromatography (GPC) measurements. The self-organization of these new polymeric systems into micellar/nanospheric structures in aqueous environment was evaluated using ultraviolet/visible (UV-VIS) spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The polymers were found to spontaneously self-assemble into nanoparticles with sizes in the range 196–239 nm and critical micelle concentration (CMC) of 0.125–0.250 mg/mL. The results are quite promising and these materials are capable of self-organizing into well-defined micelles/nanospheres encapsulating bioactive molecules, e.g., vitamins or antibacterial peptides for antibacterial coatings on medical devices. PMID:25347356

  14. Self-Assembling Protein Microarrays

    NASA Astrophysics Data System (ADS)

    Ramachandran, Niroshan; Hainsworth, Eugenie; Bhullar, Bhupinder; Eisenstein, Samuel; Rosen, Benjamin; Lau, Albert Y.; C. Walter, Johannes; LaBaer, Joshua

    2004-07-01

    Protein microarrays provide a powerful tool for the study of protein function. However, they are not widely used, in part because of the challenges in producing proteins to spot on the arrays. We generated protein microarrays by printing complementary DNAs onto glass slides and then translating target proteins with mammalian reticulocyte lysate. Epitope tags fused to the proteins allowed them to be immobilized in situ. This obviated the need to purify proteins, avoided protein stability problems during storage, and captured sufficient protein for functional studies. We used the technology to map pairwise interactions among 29 human DNA replication initiation proteins, recapitulate the regulation of Cdt1 binding to select replication proteins, and map its geminin-binding domain.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Self-assembly approaches to photonic structures

    NASA Astrophysics Data System (ADS)

    Yin, Yadong

    Self-assembly of spherical colloids has been demonstrated as a simple and effective strategy for fabricating a variety of photonic structures that include photonic crystals, arrayed microlenses, and waveguides. Unlike the top-down fabrication techniques, self-assembly approaches can produce functional structures under ambient conditions of pressure and temperature without the need for costly instruments. A confined self-assembly approach was developed to organize spherical colloids into highly ordered three-dimensional photonic crystals. Such colloidal photonic crystals can block the propagation of photons for a range of wavelengths along specific directions. The capability of this method has been demonstrated with monodispersed spherical colloids of various materials and a range of dimensions. The orientation of the crystals can be controlled by assembling the colloids against two-dimensional arrays of templates patterned in the surfaces of substrates. The colloidal crystals were further explored to fabricate inverse opals with complementary structures. Photonic bandgap properties of these crystals have been characterized by measuring their transmission and reflectance spectra. Self-assembly of nonspherical building blocks may lead to the formation of photonic crystals that can prohibit a band of optical frequencies in all directions of propagation. As the first step along this direction, a general approach based on physical confinement and attractive capillary force has been developed to produce nonspherical building blocks with well-defined structures and dimensions. Complex aggregates such as polygonal and polyhedral clusters, zigzag or helical chains have been fabricated using monodispersed polymer or silica colloids. Arrayed microlenses were fabricated by self-assembling monodispersed polymer colloids in two-dimensional arrays of cylindrical holes patterned on substrates. The spherical colloids were subsequently transformed into mushroom-shaped and then

  17. Ultrasmall peptides self-assemble into diverse nanostructures: morphological evaluation and potential implications.

    PubMed

    Lakshmanan, Anupama; Hauser, Charlotte A E

    2011-01-01

    In this study, we perform a morphological evaluation of the diverse nanostructures formed by varying concentration and amino acid sequence of a unique class of ultrasmall self-assembling peptides. We modified these peptides by replacing the aliphatic amino acid at the C-aliphatic terminus with different aromatic amino acids. We tracked the effect of introducing aromatic residues on self-assembly and morphology of resulting nanostructures. Whereas aliphatic peptides formed long, helical fibers that entangle into meshes and entrap >99.9% water, the modified peptides contrastingly formed short, straight fibers with a flat morphology. No helical fibers were observed for the modified peptides. For the aliphatic peptides at low concentrations, different supramolecular assemblies such as hollow nanospheres and membrane blebs were found. Since the ultrasmall peptides are made of simple, aliphatic amino acids, considered to have existed in the primordial soup, study of these supramolecular assemblies could be relevant to understanding chemical evolution leading to the origin of life on Earth. In particular, we propose a variety of potential applications in bioengineering and nanotechnology for the diverse self-assembled nanostructures. PMID:22016623

  18. Ultrasmall peptides self-assemble into diverse nanostructures: morphological evaluation and potential implications.

    PubMed

    Lakshmanan, Anupama; Hauser, Charlotte A E

    2011-01-01

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

  19. Self-assembling membranes and related methods thereof

    DOEpatents

    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).

  20. Integrating nanosphere lithography in device fabrication

    NASA Astrophysics Data System (ADS)

    Laurvick, Tod V.; Coutu, Ronald A.; Lake, Robert A.

    2016-03-01

    This paper discusses the integration of nanosphere lithography (NSL) with other fabrication techniques, allowing for nano-scaled features to be realized within larger microelectromechanical system (MEMS) based devices. Nanosphere self-patterning methods have been researched for over three decades, but typically not for use as a lithography process. Only recently has progress been made towards integrating many of the best practices from these publications and determining a process that yields large areas of coverage, with repeatability and enabled a process for precise placement of nanospheres relative to other features. Discussed are two of the more common self-patterning methods used in NSL (i.e. spin-coating and dip coating) as well as a more recently conceived variation of dip coating. Recent work has suggested the repeatability of any method depends on a number of variables, so to better understand how these variables affect the process a series of test vessels were developed and fabricated. Commercially available 3-D printing technology was used to incrementally alter the test vessels allowing for each variable to be investigated individually. With these deposition vessels, NSL can now be used in conjunction with other fabrication steps to integrate features otherwise unattainable through current methods, within the overall fabrication process of larger MEMS devices. Patterned regions in 1800 series photoresist with a thickness of ~700nm are used to capture regions of self-assembled nanospheres. These regions are roughly 2-5 microns in width, and are able to control the placement of 500nm polystyrene spheres by controlling where monolayer self-assembly occurs. The resulting combination of photoresist and nanospheres can then be used with traditional deposition or etch methods to utilize these fine scale features in the overall design.

  1. Controlling and imaging biomimetic self-assembly.

    PubMed

    Aliprandi, Alessandro; Mauro, Matteo; De Cola, Luisa

    2016-01-01

    The self-assembly of chemical entities represents a very attractive way to create a large variety of ordered functional structures and complex matter. Although much effort has been devoted to the preparation of supramolecular nanostructures based on different chemical building blocks, an understanding of the mechanisms at play and the ability to monitor assembly processes and, in turn, control them are often elusive, which precludes a deep and comprehensive control of the final structures. Here the complex supramolecular landscape of a platinum(II) compound is characterized fully and controlled successfully through a combination of supramolecular and photochemical approaches. The supramolecular assemblies comprise two kinetic assemblies and their thermodynamic counterpart. The monitoring of the different emission properties of the aggregates, used as a fingerprint for each species, allows the real-time visualization of the evolving self-assemblies. The control of multiple supramolecular pathways will help the design of complex systems in and out of their thermodynamic equilibrium.

  2. Self-Assembled Plasmonic Nanoparticle Clusters

    NASA Astrophysics Data System (ADS)

    Fan, Jonathan A.; Wu, Chihhui; Bao, Kui; Bao, Jiming; Bardhan, Rizia; Halas, Naomi J.; Manoharan, Vinothan N.; Nordlander, Peter; Shvets, Gennady; Capasso, Federico

    2010-05-01

    The self-assembly of colloids is an alternative to top-down processing that enables the fabrication of nanostructures. We show that self-assembled clusters of metal-dielectric spheres are the basis for nanophotonic structures. By tailoring the number and position of spheres in close-packed clusters, plasmon modes exhibiting strong magnetic and Fano-like resonances emerge. The use of identical spheres simplifies cluster assembly and facilitates the fabrication of highly symmetric structures. Dielectric spacers are used to tailor the interparticle spacing in these clusters to be approximately 2 nanometers. These types of chemically synthesized nanoparticle clusters can be generalized to other two- and three-dimensional structures and can serve as building blocks for new metamaterials.

  3. Dissipative self-assembly of vesicular nanoreactors.

    PubMed

    Maiti, Subhabrata; Fortunati, Ilaria; Ferrante, Camilla; Scrimin, Paolo; Prins, Leonard J

    2016-07-01

    Dissipative self-assembly is exploited by nature to control important biological functions, such as cell division, motility and signal transduction. The ability to construct synthetic supramolecular assemblies that require the continuous consumption of energy to remain in the functional state is an essential premise for the design of synthetic systems with lifelike properties. Here, we show a new strategy for the dissipative self-assembly of functional supramolecular structures with high structural complexity. It relies on the transient stabilization of vesicles through noncovalent interactions between the surfactants and adenosine triphosphate (ATP), which acts as the chemical fuel. It is shown that the lifetime of the vesicles can be regulated by controlling the hydrolysis rate of ATP. The vesicles sustain a chemical reaction but only as long as chemical fuel is present to keep the system in the out-of-equilibrium state. The lifetime of the vesicles determines the amount of reaction product produced by the system.

  4. Self-assembled microdevices driven by muscle.

    PubMed

    Xi, Jianzhong; Schmidt, Jacob J; Montemagno, Carlo D

    2005-02-01

    Current procedures for manual extraction of mature muscle tissue in micromechanical structures are time consuming and can damage the living components. To overcome these limitations, we have devised a new system for assembling muscle-powered microdevices based on judicious manipulations of materials phases and interfaces. In this system, individual cells grow and self-assemble into muscle bundles that are integrated with micromechanical structures and can be controllably released to enable free movement. Having realized such an assembly with cardiomyocytes we demonstrate two potential applications: a force transducer able to characterize in situ the mechanical properties of muscle and a self-assembled hybrid (biotic/abiotic) microdevice that moves as a consequence of collective cooperative contraction of muscle bundles. Because the fabrication of silicon microdevices is independent of the subsequent assembly of muscle cells, this system is highly versatile and may lead to the integration of cells and tissues with a variety of other microstructures.

  5. Self-assembled Oniontype Multiferroic Nanostructures

    NASA Astrophysics Data System (ADS)

    Ren, Shenqiang; Briber, Robert M.; Wuttig, Manfred

    2009-03-01

    Spontaneously self-assembled oniontype multiferroic nanostructures based on block copolymers as templating materials are reported. Diblock copolymer containing two different magnetoelectric precursors separately segregated to the two microdomains have been shown to form well-ordered templated lamellar structures. Onion-type multilamellar ordered multiferroic (PZT/CoFe2O4) nanostructures have been induced by room temperature solvent annealing in a magnetic field oriented perpendicular to the plane of the film. The evolution of the onion-like microstructure has been characterized by AFM, MFM, and TEM. The structure retains lamellar periodicity observed at zero field. The onion structure is superparamagnetic above and antiferromagnetic below the blocking temperature. This templating process opens a route for nanometer-scale patterning of magnetic toroids by means of self-assembly on length scales that are difficult to obtain by standard lithography techniques.

  6. Templated Self Assemble of Nano-Structures

    SciTech Connect

    Suo, Zhigang

    2013-04-29

    This project will identify and model mechanisms that template the self-assembly of nanostructures. We focus on a class of systems involving a two-phase monolayer of molecules adsorbed on a solid surface. At a suitably elevated temperature, the molecules diffuse on the surface to reduce the combined free energy of mixing, phase boundary, elastic field, and electrostatic field. With no template, the phases may form a pattern of stripes or disks. The feature size is on the order of 1-100 nm, selected to compromise the phase boundary energy and the long-range elastic or electrostatic interaction. Both experimental observations and our theoretical simulations have shown that the pattern resembles a periodic lattice, but has abundant imperfections. To form a perfect periodic pattern, or a designed aperiodic pattern, one must introduce a template to guide the assembly. For example, a coarse-scale pattern, lithographically defined on the substrate, will guide the assembly of the nanoscale pattern. As another example, if the molecules on the substrate surface carry strong electric dipoles, a charged object, placed in the space above the monolayer, will guide the assembly of the molecular dipoles. In particular, the charged object can be a mask with a designed nanoscale topographic pattern. A serial process (e.g., e-beam lithography) is necessary to make the mask, but the pattern transfer to the molecules on the substrate is a parallel process. The technique is potentially a high throughput, low cost process to pattern a monolayer. The monolayer pattern itself may serve as a template to fabricate a functional structure. This project will model fundamental aspects of these processes, including thermodynamics and kinetics of self-assembly, templated self-assembly, and self-assembly on unconventional substrates. It is envisioned that the theory will not only explain the available experimental observations, but also motivate new experiments.

  7. Lipid-like self-assembling peptides.

    PubMed

    Zhang, Shuguang

    2012-12-18

    One important question in prebiotic chemistry is the search for simple structures that might have enclosed biological molecules in a cell-like space. Phospholipids, the components of biological membranes, are highly complex. Instead, we looked for molecules that might have been available on prebiotic Earth. Simple peptides with hydrophobic tails and hydrophilic heads that are made up of merely a combination of these robust, abiotically synthesized amino acids and could self-assemble into nanotubes or nanovesicles fulfilled our initial requirements. These molecules could provide a primitive enclosure for the earliest enzymes based on either RNA or peptides and other molecular structures with a variety of functions. We discovered and designed a class of these simple lipid-like peptides, which we describe in this Account. These peptides consist of natural amino acids (glycine, alanine, valine, isoleucine, leucine, aspartic acid, glutamic acid, lysine, and arginine) and exhibit lipid-like dynamic behaviors. These structures further undergo spontaneous assembly to form ordered arrangements including micelles, nanovesicles, and nanotubes with visible openings. Because of their simplicity and stability in water, such assemblies could provide examples of prebiotic molecular evolution that may predate the RNA world. These short and simple peptides have the potential to self-organize to form simple enclosures that stabilize other fragile molecules, to bring low concentration molecules into a local environment, and to enhance higher local concentration. As a result, these structures plausibly could not only accelerate the dehydration process for new chemical bond formation but also facilitate further self-organization and prebiotic evolution in a dynamic manner. We also expect that this class of lipid-like peptides will likely find a wide range of uses in the real world. Because of their favorable interactions with lipids, these lipid-like peptides have been used to

  8. Meniscus height controlled convective self-assembly

    NASA Astrophysics Data System (ADS)

    Choudhary, Satyan; Crosby, Alfred

    Convective self-assembly techniques based on the 'coffee-ring effect' allow for the fabrication of materials with structural hierarchy and multi-functionality across a wide range of length scales. The coffee-ring effect describes deposition of non-volatiles at the edge of droplet due to capillary flow and pattern formations due to pinning and de-pinning of meniscus with the solvent evaporation. We demonstrate a novel convective self-assembly method which uses a piezo-actuated bending motion for driving the de-pinning step. In this method, a dilute solution of nanoparticles or polymers is trapped by capillary forces between a blade and substrate. As the blade oscillates with a fixed frequency and amplitude and the substrate translates at a fixed velocity, the height of the capillary meniscus oscillates. The meniscus height controls the contact angle of three phase contact line and at a critical angle de-pinning occurs. The combination of convective flux and continuously changing contact angle drives the assembly of the solute and subsequent de-pinning step, providing a direct means for producing linear assemblies. We demonstrate a new method for convective self-assembly at an accelerated rate when compared to other techniques, with control over deposit dimensions. Army Research Office (W911NF-14-1-0185).

  9. Self-Assembly of Nanoparticle Surfactants

    NASA Astrophysics Data System (ADS)

    Lombardo, Michael T.

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

  10. Interparticle Forces Underlying Nanoparticle Self-Assemblies.

    PubMed

    Luo, Dan; Yan, Cong; Wang, Tie

    2015-12-01

    Studies on the self-assembly of nanoparticles have been a hot topic in nanotechnology for decades and still remain relevant for the present and future due to their tunable collective properties as well as their remarkable applications to a wide range of fields. The novel properties of nanoparticle assemblies arise from their internal interactions and assemblies with the desired architecture key to constructing novel nanodevices. Therefore, a comprehensive understanding of the interparticle forces of nanoparticle self-assemblies is a pre-requisite to the design and control of the assembly processes, so as to fabricate the ideal nanomaterial and nanoproducts. Here, different categories of interparticle forces are classified and discussed according to their origins, behaviors and functions during the assembly processes, and the induced collective properties of the corresponding nanoparticle assemblies. Common interparticle forces, such as van der Waals forces, electrostatic interactions, electromagnetic dipole-dipole interactions, hydrogen bonds, solvophonic interactions, and depletion interactions are discussed in detail. In addition, new categories of assembly principles are summarized and introduced. These are termed template-mediated interactions and shape-complementary interactions. A deep understanding of the interactions inside self-assembled nanoparticles, and a broader perspective for the future synthesis and fabrication of these promising nanomaterials is provided.

  11. Symmetry, Equivalence and Self-Assembly

    NASA Astrophysics Data System (ADS)

    Douglas, Jack

    2006-03-01

    Molecular self-assembly at equilibrium is central to the formation of many biological structures and the emulation of this process through the creation of synthetic counterparts offers great promise for nanofabrication. The central problems in this field are an understanding of how the symmetry of the interacting particles encodes the geometrical structure of the organized structure and the nature of the thermodynamic transitions involved. Our approach is inspired by the self-assembly of actin, tubulin and icosahedral structures of plant and animal viruses. We observe chain, membrane,`nanotube' and hollow icosahedron structures using `equivalent' particles exhibiting an interplay between directional (dipolar and multi-polar) interactions and short-range (van der Waals) interactions. Specifically, a dipolar potential (continuous rotational symmetry) gives rise to chain formation, while potentials having discrete rotational symmetries (e.g., square quadrupole or triangular ring of dipoles) led to the self-organization of nanotube and icosahedral structures with some resemblance to tubulin and icosahedral viruses. The simulations are compared to theoretical models of molecular self-assembly, especially in the case of dipolar fluids where the corresponding analytic theory of equilibrium polymerization is well developed. These computations give insights into the design elements required for the development of synthetic systems exhibiting this type of organization.

  12. Designer self-assembling peptide materials.

    PubMed

    Zhao, Xiaojun; Zhang, Shuguang

    2007-01-01

    Understanding of macromolecular materials at the molecular level is becoming increasingly important for a new generation of nanomaterials for nanobiotechnology and other disciplines, namely, the design, synthesis, and fabrication of nanodevices at the molecular scale from bottom up. Basic engineering principles for microfabrication can be learned through fully grasping the molecular self-assembly and programmed assembly phenomena. Self- and programmed-assembly phenomena are ubiquitous in nature. Two key elements in molecular macrobiological material productions are chemical complementarity and structural compatibility, both of which require weak and non-covalent interactions that bring building blocks together during self-assembly. Significant advances have been made during the 1990s at the interface of materials chemistry and biology. They include the design of helical ribbons, peptide nanofiber scaffolds for three-dimensional cell cultures and tissue engineering, peptide surfactants for solubilizing and stabilizing diverse types of membrane proteins and their complexes, and molecular ink peptides for arbitrary printing and coating surfaces as well as coiled-coil helical peptides for multi-length scale fractal structures. These designer self-assembling peptides have far reaching implications in a broad spectrum of applications in biology, medicine, nanobiotechnology, and nanobiomedical technology, some of which are beyond our current imaginations. [image: see text

  13. Polymer Self-assembly on Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Giulianini, Michele; Motta, Nunzio

    This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV-Vis and Raman), we show how the polymer's higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT π-π stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.

  14. Self-assembled biomimetic nanoreactors I: Polymeric template

    NASA Astrophysics Data System (ADS)

    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.

  15. Differential self-assembly behaviors of cyclic and linear peptides.

    PubMed

    Choi, Sung-ju; Jeong, Woo-jin; Kang, Seong-Kyun; Lee, Myongsoo; Kim, Eunhye; Ryu, Du Yeol; Lim, Yong-beom

    2012-07-01

    Here we ask the fundamental questions about the effect of peptide topology on self-assembly. The study revealed that the self-assembling behaviors of cyclic and linear peptides are significantly different in several respects, in addition to sharing several similarities. Their clear differences included the morphological dissimilarities of the self-assembled nanostructures and their thermal stability. The similarities include their analogous critical aggregation concentration values and cytotoxicity profiles, which are in fact closely related. We believe that understanding topology-dependent self-assembly behavior of peptides is important for developing tailor-made self-assembled peptide nanostructures.

  16. Large organized surface domains self-assembled from nonpolar amphiphiles.

    PubMed

    Krafft, Marie Pierre

    2012-04-17

    unambiguously demonstrated the presence of surface micelles in monolayers of diblocks prior to LB transfer for atomic force microscopy imaging. We characterized an almost perfect two-dimensional crystal, with 12 assignable diffraction peaks, which established that self-assembly and regular nanopatterning were not caused by transfer or induced by the solid support. These experiments also provide the first direct identification of surface micelles on water, and the first identification of such large-size domains using GISAXS. Revisiting Langmuir film compression behavior after we realized that it actually was a compression of nanometric objects led to further unanticipated observations. These films could be compressed far beyond the documented film "collapse", eventually leading to the buildup of two superimposed, less-organized bilayers of diblocks on top of the initially formed monolayer of hemimicelles. Remarkably, the latter withstood the final, irreversible collapse of the composite films. "Gemini" tetrablocks, di(FnHm), with two Fn-chains and two Hm-chains, provided two superposed layers of discrete micelles, apparently the first example of thin films made of stacked discrete self-assembled nanoobjects. Decoration of solid surfaces with domains of predetermined size of these small "nonpolar" molecules is straightforward. Initial examples of applications include deposition of metal dots and catalytic oxidation of CO, and nanopatterning of SiO(2) films.

  17. Self-assembly of peptide scaffolds in biosilica formation: computer simulations of a coarse-grained model.

    PubMed

    Lenoci, Leonardo; Camp, Philip J

    2006-08-01

    The self-assembly of model peptides is studied using Brownian dynamics computer simulations. A coarse-grained, bead-spring model is designed to mimic silaffins, small peptides implicated in the biomineralization of certain silica diatom skeletons and observed to promote the formation of amorphous silica nanospheres in vitro. The primary characteristics of the silaffin are a 15 amino acid hydrophilic backbone and two modified lysine residues near the ends of the backbone carrying long polyamine chains. In the simulations, the model peptides self-assemble to form spherical clusters, networks of strands, or bicontinuous structures, depending on the peptide concentration and effective temperature. The results indicate that over a broad range of volume fractions (0.05-25%) the characteristic structural lengthscales fall in the range 12-45 nm. On this basis, we suggest that self-assembled structures act as either nucleation points or scaffolds for the deposition of 10-100 nm silica-peptide building blocks from which diatom skeletons and synthetic nanospheres are constructed.

  18. Bacterial expression of self-assembling peptide hydrogelators

    NASA Astrophysics Data System (ADS)

    Sonmez, Cem

    For tissue regeneration and drug delivery applications, various architectures are explored to serve as biomaterial tools. Via de novo design, functional peptide hydrogel materials have been developed as scaffolds for biomedical applications. The objective of this study is to investigate bacterial expression as an alternative method to chemical synthesis for the recombinant production of self-assembling peptides that can form rigid hydrogels under physiological conditions. The Schneider and Pochan Labs have designed and characterized a 20 amino acid beta-hairpin forming amphiphilic peptide containing a D-residue in its turn region (MAX1). As a result, this peptide must be prepared chemically. Peptide engineering, using the sequence of MAX1 as a template, afforded a small family of peptides for expression (EX peptides) that have different turn sequences consisting of natural amino acids and amenable to bacterial expression. Each sequence was initially chemically synthesized to quickly assess the material properties of its corresponding gel. One model peptide EX1, was chosen to start the bacterial expression studies. DNA constructs facilitating the expression of EX1 were designed in such that the peptide could be expressed with different fusion partners and subsequently cleaved by enzymatic or chemical means to afford the free peptide. Optimization studies were performed to increase the yield of pure peptide that ultimately allowed 50 mg of pure peptide to be harvested from one liter of culture, providing an alternate means to produce this hydrogel-forming peptide. Recombinant production of other self-assembling hairpins with different turn sequences was also successful using this optimized protocol. The studies demonstrate that new beta-hairpin self-assembling peptides that are amenable to bacterial production and form rigid hydrogels at physiological conditions can be designed and produced by fermentation in good yield at significantly reduced cost when compared to

  19. Molecular Self-Assembly of Short Aromatic Peptides: From Biology to Nanotechnology and Material Science

    NASA Astrophysics Data System (ADS)

    Gazit, Ehud

    2013-03-01

    The formation of ordered amyloid fibrils is the hallmark of several diseases of unrelated origin. In spite of grave clinical consequence, the mechanism of amyloid formation is not fully understood. We have suggested, based on experimental and bioinformatic analysis, that aromatic interactions may provide energetic contribution as well as order and directionality in the molecular-recognition and self-association processes that lead to the formation of these assemblies. This is in line with the well-known central role of aromatic-stacking interactions in self-assembly processes. Our works on the mechanism of aromatic peptide self-assembly, lead to the discovery that the diphenylalanine recognition motif self-assembles into peptide nanotubes with a remarkable persistence length. Other aromatic homodipeptides could self-assemble in nano-spheres, nano-plates, nano-fibrils and hydrogels with nano-scale order. We demonstrated that the peptide nanostructures have unique chemical, physical and mechanical properties including ultra-rigidity as aramides, semi-conductive, piezoelectric and non-linear optic properties. We also demonstrated the ability to use these peptide nanostructures as casting mold for the fabrication of metallic nano-wires and coaxial nano-cables. The application of the nanostructures was demonstrated in various fields including electrochemical biosensors, tissue engineering, and molecular imaging. Finally, we had developed ways for depositing of the peptide nanostructures and their organization. We had use inkjet technology as well as vapour deposition methods to coat surface and from the peptide ``nano-forests''. We recently demonstrated that even a single phenylalanine amino-acid can form well-ordered fibrilar assemblies.

  20. Arrangement of C60 via the self-assembly of post-functionalizable polyisocyanate block copolymer.

    PubMed

    Min, Joonkeun; Shah, Priyank N; Chae, Chang-Geun; Lee, Jae-Suk

    2012-12-13

    Poly(furfuryl isocyanate) (PFIC), which includes the reactive furan group, was synthesized by anionic polymerization using a sodium benzhydroxide (Na-BH), self-assembly initiator. We determined the optimum polymerization conditions by varying both the reaction time and the molar ratio of the monomer to the initiator. Block copolymer, poly(furfuryl isocyanate)-b-poly(n-hexyl isocyanate), was synthesized under optimized polymerization conditions. The PFIC was modified by Diels-Alder reactions with C60 for functionalization. Transmission electron microscopy (TEM) was used to study the self-assembly of block copolymers and modified block copolymer with C60. C60 formed highly ordered aggregates on the PFIC domains via self-assembly of the block copolymer.

  1. Self-assembled lipid bilayer materials

    DOEpatents

    Sasaki, Darryl Y.; Waggoner, Tina A.; Last, Julie A.

    2005-11-08

    The present invention is a self-assembling material comprised of stacks of lipid bilayers formed in a columnar structure, where the assembly process is mediated and regulated by chemical recognition events. The material, through the chemical recognition interactions, has a self-regulating system that corrects the radial size of the assembly creating a uniform diameter throughout most of the structure. The materials form and are stable in aqueous solution. These materials are useful as structural elements for the architecture of materials and components in nanotechnology, efficient light harvesting systems for optical sensing, chemical processing centers, and drug delivery vehicles.

  2. Self-assembly of magnetic biofunctional nanoparticles

    NASA Astrophysics Data System (ADS)

    Sun, Xiangcheng; Thode, C. J.; Mabry, J. K.; Harrell, J. W.; Nikles, D. E.; Sun, K.; Wang, L. M.

    2005-05-01

    Spherical, ferromagnetic FePt nanoparticles with a particle size of 3 nm were prepared by the simultaneous polyol reduction of Fe(acac)3 and Pt(acac)2 in phenyl ether in the presence of oleic acid and oleylamine. The oleic acid ligands can be replaced with 11-mercaptoundecanoic acid, giving particles that can be dispersed in water. Both x-ray diffraction and transmission electron microscopy indicated that FePt particles were not affected by ligands replacement. Dispersions of the FePt particles with 11-mercaptoundecanoic acid ligands and ammonium counter ions gave self-assembled films consisting of highly ordered hexagonal arrays of particles.

  3. Self-assembly of Random Copolymers

    PubMed Central

    Li, Longyu; Raghupathi, Kishore; Song, Cunfeng; Prasad, Priyaa; Thayumanavan, S.

    2014-01-01

    Self-assembly of random copolymers has attracted considerable attention recently. In this feature article, we highlight the use of random copolymers to prepare nanostructures with different morphologies and to prepare nanomaterials that are responsive to single or multiple stimuli. The synthesis of single-chain nanoparticles and their potential applications from random copolymers are also discussed in some detail. We aim to draw more attention to these easily accessible copolymers, which are likely to play an important role in translational polymer research. PMID:25036552

  4. A Tunable Terahertz Detector Based On Self Assembled Plasmonic Structure on a GaAs 2DEG

    NASA Astrophysics Data System (ADS)

    Bae, Chejin; George, Deepu; Singh, Rohit; Markelz, Andrea; Department of Physics, University at Buffalo, The State University of New York Team

    2013-03-01

    To improve detector sensitivity, tunability and remove polarization dependence, we develop the gated grid plasmonic structure on 2DEG by using nanosphere self-assembly lithography. The measured transmission clearly is not following Drude response, but rather has three sharp resonances corresponding fundamental, 3rd, and 5th harmonics of plasmon resonance respectively. Measurements at 80K show a large transmission change of 25%. We also confirmed a magneto plasmon dispersion of this device. In this paper we will discuss the radiative damping effect which affects enhanced absorption at the higher harmonics mode relative to fundamental and inductive grid resonance of this self-assembled plasmonic structure by demonstrating an angular dependence of transmission due to 2D plasmon.

  5. Designed post-self-assembly structural and functional modifications of a truncated tetrahedron.

    PubMed

    Zheng, Yao-Rong; Lan, Wen-Jie; Wang, Ming; Cook, Timothy R; Stang, Peter J

    2011-10-26

    Post-self-assembly modifications of a discrete metal-organic supramolecular structure have been developed. Such modifications allow the properties of the self-assembled supramolecular species to be changed in a simple and efficient manner (>90% yield). Initiated by the application of chemical stimuli, the post-self-assembly modifications described herein result in three distinct changes to the supramolecular system: an individual building-block component change, an overall structural modification, and a functional evolution of a [6+4] metal-organic supramolecular structure. The three modifications have been carefully examined by a range of characterization methods, including NMR and UV-vis spectroscopy, electrospray ionization mass spectrometry, pulsed field gradient spin echo NMR measurements, electrochemical analysis, and computational simulations.

  6. Terminal groups control self-assembly of amphiphilic block copolymers in solution.

    PubMed

    Grzelakowski, M; Kita-Tokarczyk, K

    2016-03-28

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. PMID:26948963

  7. Coarse-grained simulation reveals key features of HIV-1 capsid self-assembly

    NASA Astrophysics Data System (ADS)

    Grime, John M. A.; Dama, James F.; Ganser-Pornillos, Barbie K.; Woodward, Cora L.; Jensen, Grant J.; Yeager, Mark; Voth, Gregory A.

    2016-05-01

    The maturation of HIV-1 viral particles is essential for viral infectivity. During maturation, many copies of the capsid protein (CA) self-assemble into a capsid shell to enclose the viral RNA. The mechanistic details of the initiation and early stages of capsid assembly remain to be delineated. We present coarse-grained simulations of capsid assembly under various conditions, considering not only capsid lattice self-assembly but also the potential disassembly of capsid upon delivery to the cytoplasm of a target cell. The effects of CA concentration, molecular crowding, and the conformational variability of CA are described, with results indicating that capsid nucleation and growth is a multi-stage process requiring well-defined metastable intermediates. Generation of the mature capsid lattice is sensitive to local conditions, with relatively subtle changes in CA concentration and molecular crowding influencing self-assembly and the ensemble of structural morphologies.

  8. Coarse-grained simulation reveals key features of HIV-1 capsid self-assembly

    PubMed Central

    Grime, John M. A.; Dama, James F.; Ganser-Pornillos, Barbie K.; Woodward, Cora L.; Jensen, Grant J.; Yeager, Mark; Voth, Gregory A.

    2016-01-01

    The maturation of HIV-1 viral particles is essential for viral infectivity. During maturation, many copies of the capsid protein (CA) self-assemble into a capsid shell to enclose the viral RNA. The mechanistic details of the initiation and early stages of capsid assembly remain to be delineated. We present coarse-grained simulations of capsid assembly under various conditions, considering not only capsid lattice self-assembly but also the potential disassembly of capsid upon delivery to the cytoplasm of a target cell. The effects of CA concentration, molecular crowding, and the conformational variability of CA are described, with results indicating that capsid nucleation and growth is a multi-stage process requiring well-defined metastable intermediates. Generation of the mature capsid lattice is sensitive to local conditions, with relatively subtle changes in CA concentration and molecular crowding influencing self-assembly and the ensemble of structural morphologies. PMID:27174390

  9. Self-Assembly of Gemini Surfactants

    NASA Astrophysics Data System (ADS)

    Yethiraj, Arun; Mondal, Jagannath; Mahanthappa, Mahesh

    2013-03-01

    The self-assembly behavior of Gemini (dimeric or twin-tail) dicarboxylate disodium surfactants is studied using molecular dynamics simulations. This gemini architecture, in which two single tailed surfactants are joined through a flexible hydrophobic linker, has been shown to exhibit concentration-dependent aqueous self-assembly into lyotropic phases including hexagonal, gyroid, and lamellar morphologies. Our simulations reproduce the experimentally observed phases at similar amphiphile concentrations in water, including the unusual ability of these surfactants to form gyroid phases over unprecedentedly large amphiphile concentration windows. We demonstrate quanitative agreement between the predicted and experimentally observed domain spacings of these nanostructured materials. Through careful conformation analyses of the surfactant molecules, we show that the gyroid phase is electrostatically stabilized related to the lamellar phase. By starting with a lamellar phase, we show that decreasing the charge on the surfactant headgroups by carboxylate protonation or use of a bulkier tetramethyl ammonium counterion in place of sodium drives the formation of a gyroid phase.

  10. Directed Self-Assembly: Expectations and Achievements

    PubMed Central

    2010-01-01

    Nanotechnology has been a revolutionary thrust in recent years of development of science and technology for its broad appeal for employing a novel idea for relevant technological applications in particular and for mass-scale production and marketing as common man commodity in general. An interesting aspect of this emergent technology is that it involves scientific research community and relevant industries alike. Top–down and bottom–up approaches are two broad division of production of nanoscale materials in general. However, both the approaches have their own limits as far as large-scale production and cost involved are concerned. Therefore, novel new techniques are desired to be developed to optimize production and cost. Directed self-assembly seems to be a promising technique in this regard; which can work as a bridge between the top–down and bottom–up approaches. This article reviews how directed self-assembly as a technique has grown up and outlines its future prospects. PMID:20730077

  11. Self-assembled virus-membrane complexes

    SciTech Connect

    Yang, Lihua; Liang, Hongjun; Angelini, Thomas; Butler, John; Coridan, Robert; Tang, Jay; Wong, Gerard

    2010-11-16

    Anionic polyelectrolytes and cationic lipid membranes can self-assemble into lamellar structures ranging from alternating layers of membranes and polyelectrolytes to 'missing layer' superlattice structures. We show that these structural differences can be understood in terms of the surface-charge-density mismatch between the polyelectrolyte and membrane components by examining complexes between cationic membranes and highly charged M13 viruses, a system that allowed us to vary the polyelectrolyte diameter independently of the charge density. Such virus-membrane complexes have pore sizes that are about ten times larger in area than DNA-membrane complexes, and can be used to package and organize large functional molecules; correlated arrays of Ru(bpy){sub 3}{sup 2+} macroionic dyes have been directly observed within the virus-membrane complexes using an electron-density reconstruction. These observations elucidate fundamental design rules for rational control of self-assembled polyelectrolyte-membrane structures, which have applications ranging from non-viral gene therapy to biomolecular templates for nanofabrication.

  12. Triggered self-assembly of magnetic nanoparticles

    PubMed Central

    Ye, L.; Pearson, T.; Cordeau, Y.; Mefford, O. T.; Crawford, T. M.

    2016-01-01

    Colloidal magnetic nanoparticles are candidates for application in biology, medicine and nanomanufac-turing. Understanding how these particles interact collectively in fluids, especially how they assemble and aggregate under external magnetic fields, is critical for high quality, safe, and reliable deployment of these particles. Here, by applying magnetic forces that vary strongly over the same length scale as the colloidal stabilizing force and then varying this colloidal repulsion, we can trigger self-assembly of these nanoparticles into parallel line patterns on the surface of a disk drive medium. Localized within nanometers of the medium surface, this effect is strongly dependent on the ionic properties of the colloidal fluid but at a level too small to cause bulk colloidal aggregation. We use real-time optical diffraction to monitor the dynamics of self-assembly, detecting local colloidal changes with greatly enhanced sensitivity compared with conventional light scattering. Simulations predict the triggering but not the dynamics, especially at short measurement times. Beyond using spatially-varying magnetic forces to balance interactions and drive assembly in magnetic nanoparticles, future measurements leveraging the sensitivity of this approach could identify novel colloidal effects that impact real-world applications of these nanoparticles. PMID:26975332

  13. Computational Modeling of Tissue Self-Assembly

    NASA Astrophysics Data System (ADS)

    Neagu, Adrian; Kosztin, Ioan; Jakab, Karoly; Barz, Bogdan; Neagu, Monica; Jamison, Richard; Forgacs, Gabor

    As a theoretical framework for understanding the self-assembly of living cells into tissues, Steinberg proposed the differential adhesion hypothesis (DAH) according to which a specific cell type possesses a specific adhesion apparatus that combined with cell motility leads to cell assemblies of various cell types in the lowest adhesive energy state. Experimental and theoretical efforts of four decades turned the DAH into a fundamental principle of developmental biology that has been validated both in vitro and in vivo. Based on computational models of cell sorting, we have developed a DAH-based lattice model for tissues in interaction with their environment and simulated biological self-assembly using the Monte Carlo method. The present brief review highlights results on specific morphogenetic processes with relevance to tissue engineering applications. Our own work is presented on the background of several decades of theoretical efforts aimed to model morphogenesis in living tissues. Simulations of systems involving about 105 cells have been performed on high-end personal computers with CPU times of the order of days. Studied processes include cell sorting, cell sheet formation, and the development of endothelialized tubes from rings made of spheroids of two randomly intermixed cell types, when the medium in the interior of the tube was different from the external one. We conclude by noting that computer simulations based on mathematical models of living tissues yield useful guidelines for laboratory work and can catalyze the emergence of innovative technologies in tissue engineering.

  14. Triggered self-assembly of magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Ye, L.; Pearson, T.; Cordeau, Y.; Mefford, O. T.; Crawford, T. M.

    2016-03-01

    Colloidal magnetic nanoparticles are candidates for application in biology, medicine and nanomanufac-turing. Understanding how these particles interact collectively in fluids, especially how they assemble and aggregate under external magnetic fields, is critical for high quality, safe, and reliable deployment of these particles. Here, by applying magnetic forces that vary strongly over the same length scale as the colloidal stabilizing force and then varying this colloidal repulsion, we can trigger self-assembly of these nanoparticles into parallel line patterns on the surface of a disk drive medium. Localized within nanometers of the medium surface, this effect is strongly dependent on the ionic properties of the colloidal fluid but at a level too small to cause bulk colloidal aggregation. We use real-time optical diffraction to monitor the dynamics of self-assembly, detecting local colloidal changes with greatly enhanced sensitivity compared with conventional light scattering. Simulations predict the triggering but not the dynamics, especially at short measurement times. Beyond using spatially-varying magnetic forces to balance interactions and drive assembly in magnetic nanoparticles, future measurements leveraging the sensitivity of this approach could identify novel colloidal effects that impact real-world applications of these nanoparticles.

  15. Transmetalation of self-assembled, supramolecular complexes.

    PubMed

    Carnes, Matthew E; Collins, Mary S; Johnson, Darren W

    2014-03-21

    Substituting one metal for another in inorganic and organometallic systems is a proven strategy for synthesizing complex molecules, and in some cases, provides the only route to a particular system. The multivalent nature of the coordination in metal-ligand assemblies lends itself more readily to some types of transmetalation. For instance, a binding site can open up for exchange without greatly effecting the many other interactions holding the structure together. In addition to exchanging the metal and altering the local binding environment, transmetalation in supramolecular systems can also lead to substantial changes in the nature of the secondary and tertiary structure of a larger assembly. In this tutorial review we will cover discrete supramolecular assemblies in which metals are exchanged. First we will address fully formed structures where direct substitution replaces one type of metal for another without changing the overall supramolecular assembly. We will then address systems where the disruptive exchange of one metal for another leads to a larger change in the supramolecular assembly. When possible we have tried to highlight systems that use supramolecular self-assembly in tandem with transmetalation to synthesize new structures not accessible through a more direct approach. At the end of this review, we highlight the use of transmetalation in self-assembled aqueous inorganic clusters and discuss the consequences for material science applications. PMID:24346298

  16. Self-assembled Nanofibrils for Immunomodulation

    NASA Astrophysics Data System (ADS)

    Zhao, Fan

    This thesis has been mainly focused on applying self-assembled nanofibrils as unique depots for controlled release to modulate immune system, with two major chapters on modulation of innate immunity in chapter 2 and adaptive immunity in chapter 3, respectively. There are 5 chapters in the thesis. Chapter 1 gives a detailed review on the discovery, synthesis and application of self-assembled nanofibrils of therapeutic agents (termed as "self-delivery drugs"), including bioactive molecules; Chapter 2 demonstrates the supramolecular hydrogel of chemotactic peptides as a prolonged inflammation model through proper molecular engineering; Chapter 3 reports a suppressive antibody response achieved by encapsulation of antigens by supramolecular hydrogel of glycopeptide; Chapter 4 illustrates an example of supramolecular hydrogel formation of molecules with extremely low solubility, based on the fact that many small organic drugs have poor solubility. Chapter 5 used beta-galatosidase as a model to study glycosidase-instructed supramolecular hydrogel formation, with potential to target cancer cells due to their distinct metabolic profile.

  17. Self-Assemblies of novel molecules, VECAR

    NASA Astrophysics Data System (ADS)

    Shrestha, Bijay; Kim, Hye-Young; Lee, Soojin; Novak, Brian; Moldovan, Dorel

    2015-03-01

    VECAR is a newly synthesized molecule, which is an amphiphilic antioxidant molecule that consists of two molecular groups, vitamin-E and Carnosine, linked by a hydrocarbon chain. The hydrocarbon chain is hydrophobic and both vitamin-E and Carnosine ends are hydrophilic. In the synthesis process, the length of the hydrophobic chain of VECAR molecules can vary from the shortest (n =0) to the longest (n =18), where n indicates the number of carbon atoms in the chain. We conducted MD simulation studies of self-assembly of VECAR molecules in water using GROMACS on LONI HPC resources. Our study shows that there is a strong correlation between the shape and atomistic structure of the self-assembled nano-structures (SANs) and the chain-length (n) of VECAR molecules. We will report the results of data analyses including the atomistic structure of each SANs and the dynamic and energetic mechanisms of their formation as function of time. In summary, both VECAR molecules of chain-length n =18 and 9 form worm-like micelles, which may be used as a drug delivery system. This research is supported by the Louisiana Board of Regents-RCS Grant (LEQSF(2012-15)-RD-A-19).

  18. Terminal groups control self-assembly of amphiphilic block copolymers in solution

    NASA Astrophysics Data System (ADS)

    Grzelakowski, M.; Kita-Tokarczyk, K.

    2016-03-01

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  19. Anisotropic nanocolloids: self-assembly, interfacial adsorption, and electrostatic screening

    NASA Astrophysics Data System (ADS)

    de Graaf, J.

    2012-06-01

    we obtained a fascinating richness in crystal structures. For the octahedron we determined the equation of state and we obtained a liquid, a (metastable) body-centred-cubic rotator phase, and a crystal phase. (3.) - Octapod hierarchical self-assembly. We analysed the recently observed hierarchical self-assembly of octapod-shaped nanocrystals (octapods) into three-dimensional (3D) superstructures. We constructed an empirical simulation model capable of reproducing the initial chain-formation step of the self-assembly. The van-der-Waals (vdW) interactions between octapods suspended in an (a)polar medium were obtained by means of a Hamaker-de-Boer-type integration and the nature of these interactions allowed us to justify elements of our empirical model. We used the theoretical vdW calculation, together with the experimental and simulation results, to formulate a mechanism which explained the observed self-assembly in terms of the solvent-dependence and directionality of the octapod-octapod interactions. (4.) - Ionic screening of charged Janus particles. We studied the screening of charged Janus particles in an electrolyte by primitive-model Monte Carlo (MC) simulations for a wide variety of parameters. We also introduced a method to compare these results to the predictions of nonlinear Poisson-Boltzmann (PB) theory. The comparison of MC and PB results allowed us to probe the range of validity of the PB approximation. This range of validity corresponds well to the range that was predicted by field-theoretical studies of homogeneously charged flat surfaces.

  20. Macromolecular self-assembly and nanotechnology in China.

    PubMed

    Xu, Huaping; Chen, Daoyong; Wang, Shu; Zhou, Yongfeng; Sun, Junqi; Zhang, Wenke; Zhang, Xi

    2013-10-13

    Macromolecular self-assembly refers to the assembly of synthetic polymers, biomacromolecules and supra-molecular polymers. Through macromolecular self-assembly, the fabrication of ordered structures at different scales, the control of the dynamic assembly process and the integrations of advanced functions can be realized. Macromolecular self-assembly and nanotechnology research in China has developed rapidly, from the early periods of follow-up at low to high level and progress into a stage of innovation and creation. This review selects some representative progresses achieved recently, aiming to reflect the current status of macromolecular self-assembly and nanotechnology research in China.

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

    SciTech Connect

    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.

  2. Magnetic self-assembly of small parts

    NASA Astrophysics Data System (ADS)

    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

  3. Influence of self-assembly regenerated silk fibroin nanofibers on the properties of electrospun materials.

    PubMed

    Zhao, Huijing; Ren, Xia; Zhang, Yi; Huang, Lei

    2015-01-01

    In this study, self-assembly regenerated silk fibroin (RSF) nanofibers were prepared and observed by Atomic Force Microscope (AFM). Then RSF films containing nanospheres and nanofibers were prepared and dissolved with poly (L-lactide-co-ε-caprolactone) (PLCL) with a blending ratio of 30/70 in hexafluoro-2-propanol (HFIP). In order to determine whether different nanostructures in the solution influence the morphological, structural, and mechanical properties of the final electrospun materials, flat membranes were prepared and characterized by Scanning Electron Microscope (SEM), Fourier Transform Infrared (FT-IR), and mechanical testing. The secondary structure of as-spun materials with RSF nanofibers were not changed, however, the diameter of electrospun fibers decreased and tensile strength and elongation at breaks increased. Electrospun materials with RSF nanofibers have the potential to be used for skin, cartilage, and blood vessels because of their biocompatibility and improved mechanical properties.

  4. Influence of self-assembly regenerated silk fibroin nanofibers on the properties of electrospun materials.

    PubMed

    Zhao, Huijing; Ren, Xia; Zhang, Yi; Huang, Lei

    2015-01-01

    In this study, self-assembly regenerated silk fibroin (RSF) nanofibers were prepared and observed by Atomic Force Microscope (AFM). Then RSF films containing nanospheres and nanofibers were prepared and dissolved with poly (L-lactide-co-ε-caprolactone) (PLCL) with a blending ratio of 30/70 in hexafluoro-2-propanol (HFIP). In order to determine whether different nanostructures in the solution influence the morphological, structural, and mechanical properties of the final electrospun materials, flat membranes were prepared and characterized by Scanning Electron Microscope (SEM), Fourier Transform Infrared (FT-IR), and mechanical testing. The secondary structure of as-spun materials with RSF nanofibers were not changed, however, the diameter of electrospun fibers decreased and tensile strength and elongation at breaks increased. Electrospun materials with RSF nanofibers have the potential to be used for skin, cartilage, and blood vessels because of their biocompatibility and improved mechanical properties. PMID:26406088

  5. Measurement of molecular length of self-assembled monolayer probed by localized surface plasmon resonance

    NASA Astrophysics Data System (ADS)

    Ito, Juri; Kajikawa, Kotaro

    2016-02-01

    We propose a method to measure the variation of the molecular length of self-assembled monolayers (SAMs) when it is exposed to solutions at different pH conditions. The surface immobilized gold nanospheres (SIGNs) shows strong absorption peak at the wavelengths of 600-800 nm when p-polarized light is illuminated. The peak wavelength depends on the length of the gap distance between the SIGNs and the substrate. The gap is supported by the SAM molecules. According to the analytical calculation based on multiple expansion, the relation between the peak wavelength of the SIGN structures and the gap distance is calculated, to evaluate the molecular length of the SAM through the optical absorption spectroscopy for the SIGN structures. The molecular length of the SIGN structure was measured in air, water, acidic, and basic solutions. It was found that the molecular lengths are longer in acidic solutions.

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

    NASA Astrophysics Data System (ADS)

    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. An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.

    PubMed

    Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang

    2016-08-14

    Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly. PMID:27414465

  8. An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.

    PubMed

    Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang

    2016-08-14

    Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

  9. Controlling water evaporation through self-assembly.

    PubMed

    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. PMID:27573848

  10. Pseudotannins self-assembled into antioxidant complexes.

    PubMed

    Cheng, H A; Drinnan, C T; Pleshko, N; Fisher, O Z

    2015-10-21

    Natural tannins are attractive as building blocks for biomaterials due to their antioxidant properties and ability to form interpolymer complexes (IPCs) with other macromolecules. One of the major challenges to tannin usage in biomedical applications is their instability at physiological conditions and a lack of control over the purity and reactivity. Herein, we report the synthesis and characterization of tannin-like polymers with controlled architecture, reactivity, and size. These pseudotannins were synthesized by substituting linear dextran chains with gallic, resorcylic, and protocatechuic pendant groups to mimic the structure of natural hydrolysable tannins. We demonstrate that these novel materials can self-assemble to form reductive and colloidally stable nanoscale and microscale particles. Specifically, the synthesis, turbidity, particle size, antioxidant power, and cell uptake of IPCs derived from pseudotannins and poly(ethylene glycol) was evaluated. PMID:26313262

  11. Self-assembling multimeric nucleic acid constructs

    DOEpatents

    Cantor, C.R.; Niemeyer, C.M.; Smith, C.L.; Sano, Takeshi; Hnatowich, D.J.; Rusckowski, M.

    1996-10-01

    The invention is directed to constructs and compositions containing multimeric forms of nucleic acid. Multimeric nucleic acids comprise single-stranded nucleic acids attached via biotin to streptavidin and bound with a functional group. These constructs can be utilized in vivo to treat or identify diseased tissue or cells. Repeated administrations of multimeric nucleic acid compositions produce a rapid and specific amplification of nucleic acid constructs and their attached functional groups. For treatment purposes, functional groups may be toxins, radioisotopes, genes or enzymes. Diagnostically, labeled multimeric constructs may be used to identify specific targets in vivo or in vitro. Multimeric nucleic acids may also be used in nanotechnology and to create self-assembling polymeric aggregates such as membranes of defined porosity, microcircuits and many other products. 5 figs.

  12. Self-assembling multimeric nucleic acid constructs

    DOEpatents

    Cantor, Charles R.; Niemeyer, Christof M.; Smith, Cassandra L.; Sano, Takeshi; Hnatowich, Donald J.; Rusckowski, Mary

    1996-01-01

    The invention is directed to constructs and compositions containing multimeric forms of nucleic acid. Multimeric nucleic acids comprise single-stranded nucleic acids attached via biotin to streptavidin and bound with a functional group. These constructs can be utilized in vivo to treat or identify diseased tissue or cells. Repeated administrations of multimeric nucleic acid compositions produce a rapid and specific amplification of nucleic acid constructs and their attached functional groups. For treatment purposes, functional groups may be toxins, radioisotopes, genes or enzymes. Diagnostically, labeled multimeric constructs may be used to identify specific targets in vivo or in vitro. Multimeric nucleic acids may also be used in nanotechnology and to create self-assembling polymeric aggregates such as membranes of defined porosity, microcircuits and many other products.

  13. Self-assembling multimeric nucleic acid constructs

    DOEpatents

    Cantor, Charles R.; Niemeyer, Christof M.; Smith, Cassandra L.; Sano, Takeshi; Hnatowich, Donald J.; Rusckowski, Mary

    1999-10-12

    The invention is directed to constructs and compositions containing multimeric forms of nucleic acid. Multimeric nucleic acids comprise single-stranded nucleic acids attached via biotin to streptavidin and bound with a functional group. These constructs can be utilized in vivo to treat or identify diseased tissue or cells. Repeated administrations of multimeric nucleic acid compositions produce a rapid and specific amplification of nucleic acid constructs and their attached functional groups. For treatment purposes, functional groups may be toxins, radioisotopes, genes or enzymes. Diagnostically, labeled multimeric constructs may be used to identify specific targets in vivo or in vitro. Multimeric nucleic acids may also be used in nanotechnology and to create self-assembling polymeric aggregates such as membranes of defined porosity, microcircuits and many other products.

  14. Molecular Dynamics in Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Bochinski, Jason; Stevens, Derrick; Scott, Mary; Guy, Laura; Dedeugd, Casey; Clarke, Laura

    2007-03-01

    Silane self-assembled monolayers (SAMs) are an important tool for both scientific research and technological applications. Despite their widespread use, few experimental investigations have addressed molecular motion within these films, which offer a unique and useful physical system for fundamental scientific studies, such as observing dipolar and other glass transitions in two-dimensions. In addition, relaxations such as ``rotator'' phases where molecular groups rotate in a plane parallel to the surface have been correlated with film conductivity, adhesive, and wetting properties. We utilize surface-sensitive, dielectric relaxation spectroscopy to probe molecular motion as a function of temperature within silane chemistry-based monolayers formed upon interdigitated electrodes. Our latest results exploring a previously published motion as well as comparisons to linear polymer films will be discussed.

  15. Self Assembly and Elasticity of Nuclear Pasta

    NASA Astrophysics Data System (ADS)

    Caplan, Matthew; Horowitz, Chuck; Berry, Don; da Silva Schneider, Andre

    2015-10-01

    While the outer crust of a neutron star is likely a solid ion lattice, the core consists of uniform nuclear matter at or above saturation density. In between, nuclei adopt exotic non-spherical geometries called ``nuclear pasta'' in order to minimize the nuclear attraction and Coulomb repulsion between protons. These structures have been well studied with both classical and quantum molecular dynamics, and their geometry can be predicted from the density, temperature, and proton fraction. Recent classical molecular dynamics simulations find evidence for a phase transition at T ~ 0 . 5 MeV, where simulations with low proton fractions undergo a solid-liquid phase transition, while simulations with high proton fractions under a glass-rubber phase transition. This is expected to have nontrivial consequences for the elastic properties of the pasta. Additionally, recent observations indicate that the structure of nuclear pasta may be related to structures observed in biophysics, specifically self assembling lipid membranes.

  16. Self-Assembled Magnetic Surface Swimmers

    NASA Astrophysics Data System (ADS)

    Snezhko, A.; Belkin, M.; Aranson, I. S.; Kwok, W.-K.

    2009-03-01

    We report studies of novel self-assembled magnetic surface swimmers (magnetic snakes) formed from a dispersion of magnetic microparticles at a liquid-air interface and energized by an alternating magnetic field. We show that under certain conditions the snakes spontaneously break the symmetry of surface flows and turn into self-propelled objects. Parameters of the driving magnetic field tune the propulsion velocity of these snakelike swimmers. We find that the symmetry of the surface flows can also be broken in a controlled fashion by attaching a large bead to a magnetic snake (bead-snake hybrid), transforming it into a self-locomoting entity. The observed phenomena have been successfully described by a phenomenological model based on the amplitude equation for surface waves coupled to a large-scale hydrodynamic mean flow equation.

  17. Self-assembled magnetic surface swimmers.

    SciTech Connect

    Snezhko, A.; Belkin, M.; Aranson, I. S.; Kwok, W.-K.; Materials Science Division; Illinois Inst. of Tech.

    2009-03-20

    We report studies of novel self-assembled magnetic surface swimmers (magnetic snakes) formed from a dispersion of magnetic microparticles at a liquid-air interface and energized by an alternating magnetic field. We show that under certain conditions the snakes spontaneously break the symmetry of surface flows and turn into self-propelled objects. Parameters of the driving magnetic field tune the propulsion velocity of these snakelike swimmers. We find that the symmetry of the surface flows can also be broken in a controlled fashion by attaching a large bead to a magnetic snake (bead-snake hybrid), transforming it into a self-locomoting entity. The observed phenomena have been successfully described by a phenomenological model based on the amplitude equation for surface waves coupled to a large-scale hydrodynamic mean flow equation.

  18. Smart self-assembled hybrid hydrogel biomaterials.

    PubMed

    Kopeček, Jindřich; Yang, Jiyuan

    2012-07-23

    Hybrid biomaterials are systems created from components of at least two distinct classes of molecules, for example, synthetic macromolecules and proteins or peptide domains. The synergistic combination of two types of structures may produce new materials that possess unprecedented levels of structural organization and novel properties. This Review focuses on biorecognition-driven self-assembly of hybrid macromolecules into functional hydrogel biomaterials. First, basic rules that govern the secondary structure of peptides are discussed, and then approaches to the specific design of hybrid systems with tailor-made properties are evaluated, followed by a discussion on the similarity of design principles of biomaterials and macromolecular therapeutics. Finally, the future of the field is briefly outlined.

  19. Self-assembled multilayers of nanocomponents.

    PubMed

    Krishnan, R S; Mackay, Michael E; Duxbury, Phillip M; Pastor, Alicia; Hawker, Craig J; Van Horn, Brooke; Asokan, Subashini; Wong, Michael S

    2007-02-01

    We show it is possible to assemble nanoparticle-polymer layers in a controllable manner dictated by the difference in nano-object morphology and dielectric properties. A thin (10-100 nm) layer of the two components is spin coated onto a solid substrate and the system thermally aged to activate a cross-linking process between polymer molecules. The nanoparticles segregate to the solid substrate prior to complete cross-linking if entropic forces are dominant or to the air interface if dielectric (surface energy) forces are properly tuned. Subsequent layers are then spin coated onto the layer below, and the process is repeated to create layered structures with nanometer accuracy useful for tandem solar cells, sensors, optical coatings, etc. Unlike other self-assembly techniques the layer thicknesses are dictated by the spin coating conditions and relative concentration of the two components. PMID:17261075

  20. Supramolecular self-assemblies as functional nanomaterials

    NASA Astrophysics Data System (ADS)

    Busseron, Eric; Ruff, Yves; Moulin, Emilie; Giuseppone, Nicolas

    2013-07-01

    In this review, we survey the diversity of structures and functions which are encountered in advanced self-assembled nanomaterials. We highlight their flourishing implementations in three active domains of applications: biomedical sciences, information technologies, and environmental sciences. Our main objective is to provide the reader with a concise and straightforward entry to this broad field by selecting the most recent and important research articles, supported by some more comprehensive reviews to introduce each topic. Overall, this compilation illustrates how, based on the rules of supramolecular chemistry, the bottom-up approach to design functional objects at the nanoscale is currently producing highly sophisticated materials oriented towards a growing number of applications with high societal impact.

  1. Controlling water evaporation through self-assembly.

    PubMed

    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.

  2. Self assembly properties of primitive organic compounds

    NASA Technical Reports Server (NTRS)

    Deamer, D. W.

    1991-01-01

    A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic

  3. Hollow Nanospheres Array Fabrication via Nano-Conglutination Technology.

    PubMed

    Zhang, Man; Deng, Qiling; Xia, Liangping; Shi, Lifang; Cao, Axiu; Pang, Hui; Hu, Song

    2015-09-01

    Hollow nanospheres array is a special nanostructure with great applications in photonics, electronics and biochemistry. The nanofabrication technique with high resolution is crucial to nanosciences and nano-technology. This paper presents a novel nonconventional nano-conglutination technology combining polystyrenes spheres (PSs) self-assembly, conglutination and a lift-off process to fabricate the hollow nanospheres array with nanoholes. A self-assembly monolayer of PSs was stuck off from the quartz wafer by the thiol-ene adhesive material, and then the PSs was removed via a lift-off process and the hollow nanospheres embedded into the thiol-ene substrate was obtained. Thiolene polymer is a UV-curable material via "click chemistry" reaction at ambient conditions without the oxygen inhibition, which has excellent chemical and physical properties to be attractive as the adhesive material in nano-conglutination technology. Using the technique, a hollow nanospheres array with the nanoholes at the diameter of 200 nm embedded into the rigid thiol-ene substrate was fabricated, which has great potential to serve as a reaction container, catalyst and surface enhanced Raman scattering substrate.

  4. Self-Assembly of Micromachining Systems Powered by Janus Micromotors.

    PubMed

    Maggi, Claudio; Simmchen, Juliane; Saglimbeni, Filippo; Katuri, Jaideep; Dipalo, Michele; De Angelis, Francesco; Sanchez, Samuel; Di Leonardo, Roberto

    2016-01-27

    Janus particles can self-assemble around microfabricated gears in reproducible configurations with a high degree of spatial and orientational order. The final configuration maximizes the torque applied on the rotor leading to a unidirectional and steady rotating motion. The interplay between geometry and dynamical behavior leads to the self-assembly of Janus micromotors starting from randomly distributed particles. PMID:26649462

  5. Controlled Fabrication of Si Nanowires with Nanodots Using Nanosphere Lithography.

    PubMed

    Li, Wei; Wang, Shaolei; He, Sufeng; Hu, Mingyue; Ge, Pengpeng; Wang, Jing; Guo, YanYan

    2016-02-01

    In this paper, we introduce an easy method for fabricating Si nanowires with nanodots using nanosphere lithography. First, a self-assembly ordered single layer of polystyrene nanospheres with a diameter of 220 nm was prepared on Si substrate. Secondly, the polystyrene spheres monolayer was etched by 02 with different time from 10 s to 35 s. After this etching process, the polystyrene nanowires between polystyrene spheres were fabrication. If the etching time was longer than 35 s, there were no polystyrene nanowires. Thereafter, the following etching process with carbon fluoride was performanced. The polystyrene nanowires and nanosphers were worked as masks. Finally, the Si nanowires with nanodots were formed. The size and morphology can be controlled by etching process. This technique for forming nanostructure arrays using nanosphere lithography can be applied in many areas of science and technology.

  6. Microwave assisted synthesis of amorphous magnesium phosphate nanospheres.

    PubMed

    Zhou, Huan; Luchini, Timothy J F; Bhaduri, Sarit B

    2012-12-01

    Magnesium phosphate (MgP) materials have been investigated in recent years for tissue engineering applications, attributed to their biocompatibility and biodegradability. This paper describes a novel microwave assisted approach to produce amorphous magnesium phosphate (AMP) in a nanospherical form from an aqueous solution containing Mg(2+) and HPO(4) (2-)/PO(4) (3-). Some synthesis parameters such as pH, Mg/P ratio, solution composition were studied and the mechanism of AMP precursors was also demonstrated. The as-produced AMP nanospheres were characterized and tested in vitro. The results proved these AMP nanospheres can self-assemble into mature MgP materials and support cell proliferation. It is expected such AMP has potential in biomedical applications. PMID:22890518

  7. Anisotropic Packing of DNA-Mediated Colloidal Self-Assembly

    NASA Astrophysics Data System (ADS)

    Vo, Thi; Lu, Fang; Zhang, Yugang; Gang, Oleg; Kumar, Sanat

    The self-assembly of DNA-grafted nanoparticles has garnered considerable interest in recent years. However, many efforts focused on the usage of spherical nanoparticles, which limits us to the formation of only a handful of crystal lattices. Recent advances in the synthesis of non-spherical particles have directed attention towards the usage of these anisotropic particles for self-assembly. Here we combine experiments and theory on a series of DNA-grafted nanocubes. Our studies indicate that anisotropy not only directs where DNA linkers graft onto the particle but also affects how they pack and orient within a lattice, giving rise to both a preferential attachment effect and orientation-directed self-assembly. These results emphasize anisotropic self-assembly as a powerful new tool that allows for precise and directed control of nanoparticle self-assembly.

  8. Self-Assembly of Optical Molecules with Supramolecular Concepts

    PubMed Central

    Okamoto, Ken; Chithra, Parayalil; Richards, Gary J.; Hill, Jonathan P.; Ariga, Katsuhiko

    2009-01-01

    Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces. PMID:19564931

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

    NASA Astrophysics Data System (ADS)

    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

  10. Solvent mediated self-assembly of solids

    SciTech Connect

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

    1997-12-12

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

  11. RNA self-assembly and RNA nanotechnology.

    PubMed

    Grabow, Wade W; Jaeger, Luc

    2014-06-17

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

  12. Strip-Pattern-Spheres Self-Assembled from Polypeptide-Based Polymer Mixtures: Structure and Defect Features.

    PubMed

    Zhu, Xingyu; Guan, Zhou; Lin, Jiaping; Cai, Chunhua

    2016-01-01

    We found that poly(γ-benzyl-L-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) rod-coil block copolymers and polystyrene (PS) homopolymers can cooperatively self-assemble into nano-spheres with striped patterns on their surfaces (strip-pattern-spheres) in aqueous solution. With assistance of dissipative particle dynamics simulation, it is discovered that the PS homopolymers form a spherical template core and the PBLG-b-PEG block copolymers assemble into striped patterns on the spherical surface. The hydrophobic PBLG rods are packed orderly in the strips, while the hydrophilic PEG blocks stabilize the strip-pattern-spheres in solution. Defects such as dislocations and disclinations can be observed in the striped patterns. Self-assembling temperature and sphere radius are found to affect defect densities in the striped patterns. A possible mechanism is proposed to illustrate how PBLG-b-PEG and PS cooperatively self-assemble into hierarchical spheres with striped patterns on surfaces. PMID:27418116

  13. Strip-Pattern-Spheres Self-Assembled from Polypeptide-Based Polymer Mixtures: Structure and Defect Features

    PubMed Central

    Zhu, Xingyu; Guan, Zhou; Lin, Jiaping; Cai, Chunhua

    2016-01-01

    We found that poly(γ-benzyl-L-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) rod-coil block copolymers and polystyrene (PS) homopolymers can cooperatively self-assemble into nano-spheres with striped patterns on their surfaces (strip-pattern-spheres) in aqueous solution. With assistance of dissipative particle dynamics simulation, it is discovered that the PS homopolymers form a spherical template core and the PBLG-b-PEG block copolymers assemble into striped patterns on the spherical surface. The hydrophobic PBLG rods are packed orderly in the strips, while the hydrophilic PEG blocks stabilize the strip-pattern-spheres in solution. Defects such as dislocations and disclinations can be observed in the striped patterns. Self-assembling temperature and sphere radius are found to affect defect densities in the striped patterns. A possible mechanism is proposed to illustrate how PBLG-b-PEG and PS cooperatively self-assemble into hierarchical spheres with striped patterns on surfaces. PMID:27418116

  14. Analysis of Secondary Structure and Self-Assembly of Amelogenin by Variable Temperature Circular Dichroism and Isothermal Titration Calorimetry

    PubMed Central

    Lakshminarayanan, Rajamani; Yoon, Il; Hegde, Balachandra G.; Daming, Fan; Du, Chang; Moradian-Oldak, Janet

    2009-01-01

    Amelogenin is a proline-rich enamel matrix protein known to play an important role in the oriented growth of enamel crystals. Amelogenin self-assembles to form nanospheres and higher order structures mediated by hydrophobic interactions. This study aims to obtain a better insight into the relationship between primary-secondary structure and self-assembly of amelogenin by applying computational and biophysical methods. Variable temperature circular dichroism studies indicated that under physiological pH recombinant full-length porcine amelogenin contains unordered structures in equilibrium with polyproline type II (PPII) structure, the latter being more populated at lower temperatures. Increasing the concentration of rP172 resulted in the promotion of folding to an ordered β-structured assembly. Isothermal titration calorimetry dilution studies revealed that, at all temperatures, self-assembly is entropically driven due to the hydrophobic effect and the molar heat of assembly (ΔHA) decreases with temperature. Using a computational approach, a profile of domains in the amino acid sequence that have a high propensity to assemble and to have PPII structures has been identified. We conclude that the assembly properties of amelogenin are due to complementarity between the hydrophobic and PPII helix prone regions. PMID:19274734

  15. Self-Assembly of Tetraphenylalanine Peptides.

    PubMed

    Mayans, Enric; Ballano, Gema; Casanovas, Jordi; Díaz, Angélica; Pérez-Madrigal, Maria M; Estrany, Francesc; Puiggalí, Jordi; Cativiela, Carlos; Alemán, Carlos

    2015-11-16

    Three different tetraphenylalanine (FFFF) based peptides that differ at the N- and C-termini have been synthesized by using standard procedures to study their ability to form different nanoassemblies under a variety of conditions. The FFFF peptide assembles into nanotubes that show more structural imperfections at the surface than those formed by the diphenylalanine (FF) peptide under the same conditions. Periodic DFT calculations (M06L functional) were used to propose a model that consists of three FFFF molecules defining a ring through head-to-tail NH3(+)⋅⋅⋅(-)OOC interactions, which in turn stack to produce deformed channels with internal diameters between 12 and 16 Å. Depending on the experimental conditions used for the peptide incubation, N-fluorenylmethoxycarbonyl (Fmoc) protected FFFF self-assembles into a variety of polymorphs: ultra-thin nanoplates, fibrils, and star-like submicrometric aggregates. DFT calculations indicate that Fmoc-FFFF prefers a parallel rather than an antiparallel β-sheet assembly. Finally, coexisting multiple assemblies (up to three) were observed for Fmoc-FFFF-OBzl (OBzl = benzyl ester), which incorporates aromatic protecting groups at the two peptide terminals. This unusual and noticeable feature is attributed to the fact that the assemblies obtained by combining the Fmoc and OBzl groups contained in the peptide are isoenergetic.

  16. Self-assembly of smallest magnetic particles

    PubMed Central

    Mehdizadeh Taheri, Sara; Michaelis, Maria; Friedrich, Thomas; Förster, Beate; Drechsler, Markus; Römer, Florian M.; Bösecke, Peter; Narayanan, Theyencheri; Weber, Birgit; Rehberg, Ingo; Rosenfeldt, Sabine; Förster, Stephan

    2015-01-01

    The assembly of tiny magnetic particles in external magnetic fields is important for many applications ranging from data storage to medical technologies. The development of ever smaller magnetic structures is restricted by a size limit, where the particles are just barely magnetic. For such particles we report the discovery of a kind of solution assembly hitherto unobserved, to our knowledge. The fact that the assembly occurs in solution is very relevant for applications, where magnetic nanoparticles are either solution-processed or are used in liquid biological environments. Induced by an external magnetic field, nanocubes spontaneously assemble into 1D chains, 2D monolayer sheets, and large 3D cuboids with almost perfect internal ordering. The self-assembly of the nanocubes can be elucidated considering the dipole–dipole interaction of small superparamagnetic particles. Complex 3D geometrical arrangements of the nanodipoles are obtained under the assumption that the orientation of magnetization is freely adjustable within the superlattice and tends to minimize the binding energy. On that basis the magnetic moment of the cuboids can be explained. PMID:26554000

  17. Dissipative adaptation in driven self-assembly

    NASA Astrophysics Data System (ADS)

    England, Jeremy L.

    2015-11-01

    In a collection of assembling particles that is allowed to reach thermal equilibrium, the energy of a given microscopic arrangement and the probability of observing the system in that arrangement obey a simple exponential relationship known as the Boltzmann distribution. Once the same thermally fluctuating particles are driven away from equilibrium by forces that do work on the system over time, however, it becomes significantly more challenging to relate the likelihood of a given outcome to familiar thermodynamic quantities. Nonetheless, it has long been appreciated that developing a sound and general understanding of the thermodynamics of such non-equilibrium scenarios could ultimately enable us to control and imitate the marvellous successes that living things achieve in driven self-assembly. Here, I suggest that such a theoretical understanding may at last be emerging, and trace its development from historic first steps to more recent discoveries. Focusing on these newer results, I propose that they imply a general thermodynamic mechanism for self-organization via dissipation of absorbed work that may be applicable in a broad class of driven many-body systems.

  18. Polymer blends for directed self-assembly

    NASA Astrophysics Data System (ADS)

    Namie, Yuuji; Anno, Yusuke; Naruoka, Takehiko; Minegishi, Shinya; Nagai, Tomoki; Hishiro, Yoshi; Yamaguchi, Yoshikazu

    2013-03-01

    The advantage of blend DSA (Directed Self Assembly) is milder anneal condition than PS-b-PMMA BCP DSA materials and availability of conventional instruments. In this paper, blend type DSA was applied for hole patterning. Target patterns were contact hole and oval hole. Polymer phase separation behavior has been studied from the point of χN. In the case of polymer blend, χN needs to be more than 2 to give phase separation. At first the effect of polymer size was studied. When the polymer weight was low, the shrunk hole was not clean because of low χN. Furthermore, the correlation of shrink amount and χN was studied. Higher χN polymer blend system gave higher shrink amount. High χN polymer systems give clear interface, then the intermixing area would be reduced, then the attached polymer blend part became larger. The polymer blend ratio effect was also investigated. The blend ratio was varied for polymer A/ polymer B=70/30-50/50. The shrink amount of oval hole was reduced with increasing the ratio of polymer B. However, the shrink amount ratio of CDY/CDX was almost constant (~3).

  19. Surfactant mediated polyelectrolyte self-assembly

    DOE PAGES

    Goswami, Monojoy; Borreguero Calvo, Jose M.; Pincus, Phillip A.; Sumpter, Bobby G.

    2015-11-25

    Self-assembly and dynamics of polyelectrolyte (PE) surfactant complex (PES) is investigated using molecular dynamics simulations. The complexation is systematically studied for five different PE backbone charge densities. At a fixed surfactant concentration the PES complexation exhibits pearl-necklace to agglomerated double spherical structures with a PE chain decorating the surfactant micelles. The counterions do not condense on the complex, but are released in the medium with a random distribution. The relaxation dynamics for three different length scales, polymer chain, segmental and monomer, show distinct features of the charge and neutral species; the counterions are fastest followed by the PE chain andmore » surfactants. The surfactant heads and tails have the slowest relaxation due to their restricted movement inside the agglomerated structure. At the shortest length scale, all the charge and neutral species show similar relaxation dynamics confirming Rouse behavior at monomer length scales. Overall, the present study highlights the structure-property relationship for polymer-surfactant complexation. These results will help improve the understanding of PES complex and should aid in the design of better materials for future applications.« less

  20. What promotes derected self assembly (DSA)?

    NASA Astrophysics Data System (ADS)

    Nakagawa, S. T.

    2016-09-01

    A low-energy electron beam (EB) can create self-interstitial atoms (SIA) in a solid and can cause directed self-assembly (DSA), e.g. {3 1 1}SIA platelets in c-Si. The crystalline structure of this planar defect is known from experiment to be made up of SIAs that form well aligned <1 1 0> atomic rows on each (3 1 1) plane. To simulate the experiment we distributed Frenkel pairs (FP) randomly in bulk c-Si. Then making use of a molecular dynamic (MD) simulation, we have reproduced the experimental result, where SIAs are trapped at metastable sites in bulk. With increasing pre-doped FP concentration, the number of SIAs that participate in DSA tends to be increased but soon slightly supressed. On the other hand, when the FP concentration is less than 3%, a cooperative motion of target atoms was characterized from the long-range-order (LRO) parameter. Here we investigated the correlation between DSA and that cooperative motion, by adding a case of intrinsic c-Si. We confirmed that the cooperative motion slightly promote DSA by assisting migration of SIAs toward metastable sites as long as the FP concentration is less than 3%, however, it is essentially independent of DSA.

  1. Surfactant mediated polyelectrolyte self-assembly

    SciTech Connect

    Goswami, Monojoy; Borreguero Calvo, Jose M.; Pincus, Phillip A.; Sumpter, Bobby G.

    2015-11-25

    Self-assembly and dynamics of polyelectrolyte (PE) surfactant complex (PES) is investigated using molecular dynamics simulations. The complexation is systematically studied for five different PE backbone charge densities. At a fixed surfactant concentration the PES complexation exhibits pearl-necklace to agglomerated double spherical structures with a PE chain decorating the surfactant micelles. The counterions do not condense on the complex, but are released in the medium with a random distribution. The relaxation dynamics for three different length scales, polymer chain, segmental and monomer, show distinct features of the charge and neutral species; the counterions are fastest followed by the PE chain and surfactants. The surfactant heads and tails have the slowest relaxation due to their restricted movement inside the agglomerated structure. At the shortest length scale, all the charge and neutral species show similar relaxation dynamics confirming Rouse behavior at monomer length scales. Overall, the present study highlights the structure-property relationship for polymer-surfactant complexation. These results will help improve the understanding of PES complex and should aid in the design of better materials for future applications.

  2. Self-assembly programming of DNA polyominoes.

    PubMed

    Ong, Hui San; Syafiq-Rahim, Mohd; Kasim, Noor Hayaty Abu; Firdaus-Raih, Mohd; Ramlan, Effirul Ikhwan

    2016-10-20

    Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously. PMID:27569553

  3. Self-assembly programming of DNA polyominoes.

    PubMed

    Ong, Hui San; Syafiq-Rahim, Mohd; Kasim, Noor Hayaty Abu; Firdaus-Raih, Mohd; Ramlan, Effirul Ikhwan

    2016-10-20

    Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously.

  4. Self-assembly of smallest magnetic particles.

    PubMed

    Mehdizadeh Taheri, Sara; Michaelis, Maria; Friedrich, Thomas; Förster, Beate; Drechsler, Markus; Römer, Florian M; Bösecke, Peter; Narayanan, Theyencheri; Weber, Birgit; Rehberg, Ingo; Rosenfeldt, Sabine; Förster, Stephan

    2015-11-24

    The assembly of tiny magnetic particles in external magnetic fields is important for many applications ranging from data storage to medical technologies. The development of ever smaller magnetic structures is restricted by a size limit, where the particles are just barely magnetic. For such particles we report the discovery of a kind of solution assembly hitherto unobserved, to our knowledge. The fact that the assembly occurs in solution is very relevant for applications, where magnetic nanoparticles are either solution-processed or are used in liquid biological environments. Induced by an external magnetic field, nanocubes spontaneously assemble into 1D chains, 2D monolayer sheets, and large 3D cuboids with almost perfect internal ordering. The self-assembly of the nanocubes can be elucidated considering the dipole-dipole interaction of small superparamagnetic particles. Complex 3D geometrical arrangements of the nanodipoles are obtained under the assumption that the orientation of magnetization is freely adjustable within the superlattice and tends to minimize the binding energy. On that basis the magnetic moment of the cuboids can be explained.

  5. Stochastic self-assembly of incommensurate clusters

    NASA Astrophysics Data System (ADS)

    D'Orsogna, M. R.; Lakatos, G.; Chou, T.

    2012-02-01

    Nucleation and molecular aggregation are important processes in numerous physical and biological systems. In many applications, these processes often take place in confined spaces, involving a finite number of particles. Analogous to treatments of stochastic chemical reactions, we examine the classic problem of homogeneous nucleation and self-assembly by deriving and analyzing a fully discrete stochastic master equation. We enumerate the highest probability steady states, and derive exact analytical formulae for quenched and equilibrium mean cluster size distributions. Upon comparison with results obtained from the associated mass-action Becker-Döring equations, we find striking differences between the two corresponding equilibrium mean cluster concentrations. These differences depend primarily on the divisibility of the total available mass by the maximum allowed cluster size, and the remainder. When such mass "incommensurability" arises, a single remainder particle can "emulsify" the system by significantly broadening the equilibrium mean cluster size distribution. This discreteness-induced broadening effect is periodic in the total mass of the system but arises even when the system size is asymptotically large, provided the ratio of the total mass to the maximum cluster size is finite. Ironically, classic mass-action equations are fairly accurate in the coarsening regime, before equilibrium is reached, despite the presence of large stochastic fluctuations found via kinetic Monte-Carlo simulations. Our findings define a new scaling regime in which results from classic mass-action theories are qualitatively inaccurate, even in the limit of large total system size.

  6. Enzyme-assisted self-assembly under thermodynamic control

    NASA Astrophysics Data System (ADS)

    Williams, Richard J.; Smith, Andrew M.; Collins, Richard; Hodson, Nigel; Das, Apurba K.; Ulijn, Rein V.

    2009-01-01

    The production of functional molecular architectures through self-assembly is commonplace in biology, but despite advances, it is still a major challenge to achieve similar complexity in the laboratory. Self-assembled structures that are reproducible and virtually defect free are of interest for applications in three-dimensional cell culture, templating, biosensing and supramolecular electronics. Here, we report the use of reversible enzyme-catalysed reactions to drive self-assembly. In this approach, the self-assembly of aromatic short peptide derivatives provides a driving force that enables a protease enzyme to produce building blocks in a reversible and spatially confined manner. We demonstrate that this system combines three features: (i) self-correction-fully reversible self-assembly under thermodynamic control; (ii) component-selection-the ability to amplify the most stable molecular self-assembly structures in dynamic combinatorial libraries; and (iii) spatiotemporal confinement of nucleation and structure growth. Enzyme-assisted self-assembly therefore provides control in bottom-up fabrication of nanomaterials that could ultimately lead to functional nanostructures with enhanced complexities and fewer defects.

  7. Colloidosome like structures: self-assembly of silica microrods

    DOE PAGES

    Datskos, P.; Polizos, G.; Bhandari, M.; Cullen, D. A.; Sharma, J.

    2016-03-07

    Self-assembly of one-dimensional structures is attracting a great deal of interest because assembled structures can provide better properties compared to individual building blocks. We demonstrate silica microrod self-assembly by exploiting Pickering emulsion based strategy. Micron-sized silica rods were synthesized employing previously reported methods based on polyvinylpyrrolidone/ pentanol emulsion droplets. Moreover, rods self-assembled to make structures in the range of z10 40 mm. Smooth rods assembled better than segmented rods. Finally, the assembled structures were bonded by weak van der Waals forces.

  8. Bio-inspired supramolecular self-assembly towards soft nanomaterials

    PubMed Central

    LIN, Yiyang; MAO, Chuanbin

    2011-01-01

    Supramolecular self-assembly has proven to be a reliable approach towards versatile nanomaterials based on multiple weak intermolecular forces. In this review, the development of bio-inspired supramolecular self-assembly into soft materials and their applications are summarized. Molecular systems used in bio-inspired “bottom-up self-assembly” involve small organic molecules, peptides or proteins, nucleic acids, and viruses. Self-assembled soft nanomaterials have been exploited in various applications such as inorganic nanomaterial synthesis, drug or gene delivery, tissue engineering, and so on. PMID:21980594

  9. Magnetic manipulation of self-assembled colloidal asters

    NASA Astrophysics Data System (ADS)

    Snezhko, Alexey; Aranson, Igor S.

    2011-09-01

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

  10. Magnetic manipulation of self-assembled colloidal asters.

    SciTech Connect

    Snezhko, A.; Aranson, I. S.

    2011-09-01

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

  11. Predicting self-assembled patterns on spheres with multicomponent coatings.

    PubMed

    Edlund, Erik; Lindgren, Oskar; Jacobi, Martin Nilsson

    2014-05-01

    Patchy colloids are promising candidates for building blocks in directed self-assembly, but large scale synthesis of colloids with controlled surface patterns remains challenging. One potential fabrication method is to self-assemble the surface patterns themselves, allowing complex morphologies to organize spontaneously. For this approach to be competitive, prediction and control of the pattern formation process are necessary. However, structure formation in many-body systems is fundamentally hard to understand, and new theoretical methods are needed. Here we present a theory for self-assembling pattern formation in multi-component systems on the surfaces of colloidal particles, formulated as an analytic technique that predicts morphologies directly from the interactions in an effective model. As a demonstration we formulate an isotropic model of alkanethiols on gold, a suggested system for directed self-assembly, and predict its morphologies and transitions as a function of the interaction parameters.

  12. Directed flexibility: self-assembly of a supramolecular tetrahedron.

    PubMed

    Ludlow, James M; Xie, Tingzheng; Guo, Zaihong; Guo, Kai; Saunders, Mary Jane; Moorefield, Charles N; Wesdemiotis, Chrys; Newkome, George R

    2015-03-01

    Self-assembly of a tribenzo-27-crown-9 ether functionalized with six terpyridines generated (85%) an expanded tetrahedral structure comprised of four independent triangular surfaces interlinked by crown ether vertices.

  13. Directed self-assembly of proteins into discrete radial patterns

    PubMed Central

    Thakur, Garima; Prashanthi, Kovur; Thundat, Thomas

    2013-01-01

    Unlike physical patterning of materials at nanometer scale, manipulating soft matter such as biomolecules into patterns is still in its infancy. Self-assembled monolayer (SAM) with surface density gradient has the capability to drive biomolecules in specific directions to create hierarchical and discrete structures. Here, we report on a two-step process of self-assembly of the human serum albumin (HSA) protein into discrete ring structures based on density gradient of SAM. The methodology involves first creating a 2-dimensional (2D) polyethylene glycol (PEG) islands with responsive carboxyl functionalities. Incubation of proteins on such pre-patterned surfaces results in direct self-assembly of protein molecules around PEG islands. Immobilization and adsorption of protein on such structures over time evolve into the self-assembled patterns. PMID:23719678

  14. Converting molecular information of redox coenzymes via self-assembly.

    PubMed

    Morikawa, Masa-aki; Kimizuka, Nobuo

    2012-11-21

    β-Nicotinamide adenine dinucleotide (NAD(+)) and its reduced form NADH specifically interact with a cyanine dye in aqueous media, giving distinct spectral and nanostructural characteristics to which molecular information of constituent coenzymes are converted via self-assembly.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

  16. Liquid crystal organization of self-assembling cyclic peptides.

    PubMed

    Amorín, Manuel; Pérez, Ana; Barberá, Joaquín; Ozores, Haxel Lionel; Serrano, José Luis; Granja, Juan R; Sierra, Teresa

    2014-01-21

    Self-assembling cyclic peptides decorated with mesogens form porous columnar mesophases in which, depending on the number of hydrocarbon chains, double or single channels are formed along each column. PMID:24281818

  17. Self-Assembly of Structures with Addressable Complexity.

    PubMed

    Jacobs, William M; Frenkel, Daan

    2016-03-01

    The self-assembly of structures with "addressable complexity", where every component is distinct and is programmed to occupy a specific location within a target structure, is a promising route to engineering materials with precisely defined morphologies. Because systems with many components are inherently complicated, one might assume that the chances of successful self-assembly are extraordinarily small. Yet recent advances suggest otherwise: addressable structures with hundreds of distinct building blocks have been designed and assembled with nanometer precision. Despite this remarkable success, it is often challenging to optimize a self-assembly reaction to ensure that the intended structure is kinetically accessible. In this Perspective, we focus on the prediction of kinetic pathways for self-assembly and implications for the design of robust experimental protocols. The development of general principles to predict these pathways will enable the engineering of complex materials using a much wider range of building blocks than is currently possible. PMID:26862684

  18. Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properities

    PubMed Central

    Sun, Xiang; Lai, Guoqiao; Li, Zhifang; Ma, Yuwen; Yuan, Xiao; Shen, Yongjia

    2015-01-01

    Summary This paper reports the self-assembly of two new tetrathiafulvalene (TTF) derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron microscopy (SEM) and X-ray diffraction (XRD), which showed that the self-assembly ability of T 1 was better than that of T 2. The results revealed that more urethane groups in a molecule did not necessarily instigate self-assembly. UV–vis and FTIR spectra were measured to explore noncovalent interactions. The driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T 1 and T 2 films was tested by a four-probe method. PMID:26734083

  19. Activity-assisted self-assembly of colloidal particles.

    PubMed

    Mallory, S A; Cacciuto, A

    2016-08-01

    We outline a basic strategy of how self-propulsion can be used to improve the yield of a typical colloidal self-assembly process. The success of this approach is predicated on the thoughtful design of the colloidal building block as well as how self-propulsion is endowed to the particle. As long as a set of criteria are satisfied, it is possible to significantly increase the rate of self-assembly, and greatly expand the window in parameter space where self-assembly can occur. In addition, we show that by tuning the relative on-off time of the self-propelling force it is possible to modulate the effective speed of the colloids allowing for further optimization of the self-assembly process.

  20. Modeling the Kinetics of Open Self-Assembly.

    PubMed

    Verdier, Timothée; Foret, Lionel; Castelnovo, Martin

    2016-07-01

    In this work, we explore theoretically the kinetics of molecular self-assembly in the presence of constant monomer flux as an input, and a maximal size. The proposed model is supposed to reproduce the dynamics of viral self-assembly for enveloped virus. It turns out that the kinetics of open self-assembly is rather quantitatively different from the kinetics of similar closed assembly. In particular, our results show that the convergence toward the stationary state is reached through assembly waves. Interestingly, we show that the production of complete clusters is much more efficient in the presence of a constant input flux, rather than providing all monomers at the beginning of the self-assembly.

  1. Activity-assisted self-assembly of colloidal particles

    NASA Astrophysics Data System (ADS)

    Mallory, S. A.; Cacciuto, A.

    2016-08-01

    We outline a basic strategy of how self-propulsion can be used to improve the yield of a typical colloidal self-assembly process. The success of this approach is predicated on the thoughtful design of the colloidal building block as well as how self-propulsion is endowed to the particle. As long as a set of criteria are satisfied, it is possible to significantly increase the rate of self-assembly, and greatly expand the window in parameter space where self-assembly can occur. In addition, we show that by tuning the relative on-off time of the self-propelling force it is possible to modulate the effective speed of the colloids allowing for further optimization of the self-assembly process.

  2. Self-assembled peptide nanostructures for functional materials

    NASA Astrophysics Data System (ADS)

    Sardan Ekiz, Melis; Cinar, Goksu; Aref Khalily, Mohammad; Guler, Mustafa O.

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.

  3. Activity-assisted self-assembly of colloidal particles.

    PubMed

    Mallory, S A; Cacciuto, A

    2016-08-01

    We outline a basic strategy of how self-propulsion can be used to improve the yield of a typical colloidal self-assembly process. The success of this approach is predicated on the thoughtful design of the colloidal building block as well as how self-propulsion is endowed to the particle. As long as a set of criteria are satisfied, it is possible to significantly increase the rate of self-assembly, and greatly expand the window in parameter space where self-assembly can occur. In addition, we show that by tuning the relative on-off time of the self-propelling force it is possible to modulate the effective speed of the colloids allowing for further optimization of the self-assembly process. PMID:27627360

  4. Differentially photo-crosslinked polymers enable self-assembling microfluidics

    PubMed Central

    Jamal, Mustapha; Zarafshar, Aasiyeh M.; Gracias, David H.

    2012-01-01

    An important feature of naturally self-assembled systems such as leaves and tissues is that they are curved and have embedded fluidic channels that enable the transport of nutrients to, or removal of waste from, specific three-dimensional (3D) regions. Here, we report the self-assembly of photopatterned polymers, and consequently microfluidic devices, into curved geometries. We discovered that differentially photo-crosslinked SU-8 films spontaneously and reversibly curved upon film de-solvation and re-solvation. Photolithographic patterning of the SU-8 films enabled the self-assembly of cylinders, cubes, and bidirectionally folded sheets. We integrated polydimethylsiloxane (PDMS) microfluidic channels with these SU-8 films to self-assemble curved microfluidic networks. PMID:22068594

  5. Supramolecular chirality in self-assembled peptide amphiphile nanostructures.

    PubMed

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

    Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound. PMID:26146021

  6. Self-assembly drugs: from micelles to nanomedicine.

    PubMed

    Messina, Paula V; Besada-Porto, Jose Miguel; Ruso, Juan M

    2014-03-01

    Self-assembly has fascinated many scientists over the past few decades. Rapid advances and widespread interest in the study of this subject has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nano- and mesoscopic dimensions. Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries for scientists seeking to design novel molecular materials exhibiting unusual properties, and for researchers investigating the structure and function of biomolecules. Consequently, self-assembly transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field including nanotechnology and nanomedicine. Basically, self-assembly focuses on a wide range of discrete molecules or molecular assemblies and uses physical transformations to achieve its goals. In this Review, we present a comprehensive overview of the advances in the field of drug self-assembly and discuss in detail the synthesis, self-assembly behavior, and physical properties as well as applications. We refer the reader to past reviews dealing with colloidal molecules and colloidal self-assembly. In the first part, we will discuss, compare, and link the various bioinformatic procedures: Molecular Dynamics and Quantitative Structure Activity Relationship. The second section deals with the self-assembly behavior in more detail, in which we focus on several experimental techniques, selected according to the depth of knowledge obtained. The last part will review the advances in drug-protein assembly. Nature provides many examples of proteins that form their substrate binding sites by bringing together the component pieces in a process of self-assembly. We will focus in the understanding of physical properties and applications developing thereof.

  7. Self-assembly drugs: from micelles to nanomedicine.

    PubMed

    Messina, Paula V; Besada-Porto, Jose Miguel; Ruso, Juan M

    2014-03-01

    Self-assembly has fascinated many scientists over the past few decades. Rapid advances and widespread interest in the study of this subject has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nano- and mesoscopic dimensions. Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries for scientists seeking to design novel molecular materials exhibiting unusual properties, and for researchers investigating the structure and function of biomolecules. Consequently, self-assembly transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field including nanotechnology and nanomedicine. Basically, self-assembly focuses on a wide range of discrete molecules or molecular assemblies and uses physical transformations to achieve its goals. In this Review, we present a comprehensive overview of the advances in the field of drug self-assembly and discuss in detail the synthesis, self-assembly behavior, and physical properties as well as applications. We refer the reader to past reviews dealing with colloidal molecules and colloidal self-assembly. In the first part, we will discuss, compare, and link the various bioinformatic procedures: Molecular Dynamics and Quantitative Structure Activity Relationship. The second section deals with the self-assembly behavior in more detail, in which we focus on several experimental techniques, selected according to the depth of knowledge obtained. The last part will review the advances in drug-protein assembly. Nature provides many examples of proteins that form their substrate binding sites by bringing together the component pieces in a process of self-assembly. We will focus in the understanding of physical properties and applications developing thereof. PMID:24444168

  8. DYNAMIC SHEAR-INFLUENCED COLLAGEN SELF-ASSEMBLY

    PubMed Central

    Saeidi, Nima; Sander, Edward A.

    2011-01-01

    The ability to influence the direction of polymerization of a self-assembling biomolecular system has the potential to generate materials with extremely high anisotropy. In biological systems where highly-oriented cellular populations give rise to aligned and often load-bearing tissue such organized molecular scaffolds could aid in the contact guidance of cells for engineered tissue constructs (e.g cornea and tendon). In this investigation we examine the detailed dynamics of pepsin-extracted type I bovine collagen assembly on a glass surface under the influence of flow between two plates. Differential Interference Contrast (DIC) imaging (60x-1.4NA) with focal plane stabilization was used to resolve and track the growth of collagen aggregates on borosilicate glass for 4 different shear rates (500, 80, 20, and 9 s-1). The detailed morphology of the collagen fibrils/aggregates was examined using Quick Freeze Deep Etch electron microscopy. Nucleation of fibrils on the glass was observed to occur rapidly (~2 min) followed by continued growth of the fibrils. The growth rates were dependent on flow in a complex manner with the highest rate of axial growth (0.1 microns/sec) occurring at a shear rate of 9 s-1. The lowest growth rate occurred at the highest shear. Fibrils were observed to both branch and join during the experiments. The best alignment of fibrils was observed at intermediate shear rates of 20 and 80s-1. However, the investigation revealed that fibril directional growth was not stable. At high shear rates, fibrils would often turn downstream forming what we term “hooks” which are likely the combined result of monomer interaction with the initial collagen layer or “mat” and the high shear rate. Further, QFDE examination of fibril morphology demonstrated that the assembled fibrillar structure did not possess native D-periodicity. Instead, fibrils comprised a collection of generally aligned, monomers which were self-assembled to form a fibril

  9. Born-Haber cycle for monolayer self-assembly at the liquid-solid interface: assessing the enthalpic driving force.

    PubMed

    Song, Wentao; Martsinovich, Natalia; Heckl, Wolfgang M; Lackinger, Markus

    2013-10-01

    The driving force for self-assembly is the associated gain in free energy with decisive contributions from both enthalpy and entropy differences between final and initial state. For monolayer self-assembly at the liquid-solid interface, solute molecules are initially dissolved in the liquid phase and then become incorporated into an adsorbed monolayer. In this work, we present an adapted Born-Haber cycle for obtaining precise enthalpy values for self-assembly at the liquid-solid interface, a key ingredient for a profound thermodynamic understanding of this process. By choosing terephthalic acid as a model system, it is demonstrated that all required enthalpy differences between well-defined reference states can be independently and consistently assessed by both experimental and theoretical methods, giving in the end a reliable value of the overall enthalpy gain for self-assembly of interfacial monolayers. A quantitative comparison of enthalpy gain and entropy cost reveals essential contributions from solvation and dewetting, which lower the entropic cost and render monolayer self-assembly a thermodynamically favored process.

  10. Electric Field Controlled Self-Assembly of Hierarchically Ordered Membranes.

    PubMed

    Velichko, Yuri S; Mantei, Jason R; Bitton, Ronit; Carvajal, Daniel; Shull, Kenneth R; Stupp, Samuel I

    2012-01-25

    Self-assembly in the presence of external forces is an adaptive, directed organization of molecular components under nonequilibrium conditions. While forces may be generated as a result of spontaneous interactions among components of a system, intervention with external forces can significantly alter the final outcome of self-assembly. Superimposing these intrinsic and extrinsic forces provides greater degrees of freedom to control the structure and function of self-assembling materials. In this work we investigate the role of electric fields during the dynamic self-assembly of a negatively charged polyelectrolyte and a positively charged peptide amphiphile in water leading to the formation of an ordered membrane. In the absence of electric fields, contact between the two solutions of oppositely charged molecules triggers the growth of closed membranes with vertically oriented fibrils that encapsulate the polyelectrolyte solution. This process of self-assembly is intrinsically driven by excess osmotic pressure of counterions, and the electric field is found to modify the kinetics of membrane formation, and also its morphology and properties. Depending on the strength and orientation of the field we observe a significant increase or decrease of up to nearly 100% in membrane thickness, as well as the controlled rotation of nanofiber growth direction by 90 degrees, resulting in a significant increase in mechanical stiffness. These results suggest the possibility of using electric fields to control structure in self-assembly processes involving diffusion of oppositely charged molecules. PMID:23166533

  11. DNA-based self-assembly for functional nanomaterials.

    PubMed

    Wang, Zhen-Gang; Ding, Baoquan

    2013-07-26

    The unprecedented development of DNA nanotechnology has caused DNA self-assembly to attract close attention in many disciplines. In this research news article, the employment of DNA self-assembly in the fields of materials science and nanotechnology is described. DNA self-assembly can be used to prepare bulk-scale hydrogels and 3D macroscopic crystals with nanoscale internal structures, to induce the crystallization of nanoparticles, to template the fabrication of organic conductive nanomaterials, and to act as drug delivery vehicles for therapeutic agents. The properties and functions are fully tunable because of the designability and specificity of DNA assembly. Moreover, because of the intrinsic dynamics, DNA self-assembly can act as a program switch and can efficiently control stimuli responsiveness. We highlight the power of DNA self-assembly in the preparation and function regulation of materials, aiming to motivate future multidisciplinary and interdisciplinary research. Finally, we describe some of the challenges currently faced by DNA assembly that may affect the functional evolution of such materials, and we provide our insights into the future directions of several DNA self-assembly-based nanomaterials. PMID:24048977

  12. Design strategies for self-assembly of discrete targets

    SciTech Connect

    Madge, Jim; Miller, Mark A.

    2015-07-28

    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.

  13. Structures Self-Assembled Through Directional Solidification

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.; Sayir, Ali

    2005-01-01

    dry plasma etch. The wet chemical etches the silicon away, exposing the TiSi2 rods, whereas plasma etching preferentially etches the Si-TiSi2 interface to form a crater. The porous architectures are applicable to fabricating microdevices or creating templates for part fabrication. The porous rod structure can serve as a platform for fabricating microplasma devices for propulsion or microheat exchangers and for fabricating microfilters for miniatured chemical reactors. Although more work is required, self-assembly from DSE can have a role in microdevice fabrication.

  14. Synthesis of nanocrystals and nanocrystal self-assembly

    NASA Astrophysics Data System (ADS)

    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 (<20 nm in diameter) in diameter. Essential to our approach is an understanding of the nanoparticle as a building block, combined with an ability to integrate them into thin films that have uniform and characteristic electrical properties. We observe the BaTiO3 nanocrystals crystallize with evidence of tetragonality. Electric field dependent polarization measurements show spontaneous polarization and hysteresis, indicating ferroelectric behavior for the BaTiO 3 nanocrystalline films with grain sizes in the range of 10--30 nm. Dielectric measurements of the films show dielectic constants in the range of 85--90 over the 1 kHz--100 kHz, with low loss. We present nanocrystals as initial building blocks for the preparation of thin films which exhibit uniform nanostructured morphologies and grain sizes. In the second part of this chapter, a nonhydrolytic alcoholysis route to study the preparation of well-crystallized size-tunable BaTiO3

  15. The Self-Assembly of Nanogold for Optical Metamaterials

    NASA Astrophysics Data System (ADS)

    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

  16. Self-Assembling Peptide Amphiphiles for Targeted Drug Delivery

    NASA Astrophysics Data System (ADS)

    Moyer, Tyson

    The systemic delivery of therapeutics is currently limited by off-target side effects and poor drug uptake into the cells that need to be treated. One way to circumvent these issues is to target the delivery and release of therapeutics to the desired location while limiting systemic toxicity. Using self-assembling peptide amphiphiles (PAs), this work has investigated supramolecular nanostructures for the development of targeted therapies. Specifically, the research has focused on the interrelationships between presentation of targeting moeities and the control of nanostructure morphology in the context of systemic delivery for targeting cancer and vascular injuries. The self-assembly region of the PA was systematically altered to achieve control of nanostructure widths, from 100 nm to 10 nm, by the addition of valine-glutamic acid dimers into the chemical structure, subsequently increasing the degree of nanostructure twist. For the targeting of tumors, a homing PA was synthesized to include a dimeric, cyclic peptide sequence known to target the cancer-specific, death receptor 5 (DR5) and initiate apoptosis through the oligomerization of DR5. This PA presented a multivalent display of DR5-binding peptides, resulting in improved binding affinity measured by surface plasmon resonance. The DR5-targeting PA also showed enhanced efficacy in both in vitro and in vivo tumor models relative to non-targeted controls. Alternative modifications to the PA-based antitumor therapies included the use of a cytotoxic, membrane-lytic PA coassembled with a pegylated PA, which showed enhanced biodistribution and in vivo activity after coassembly. The functionalization of the hydrophobic core was also accomplished through the encapsulation of the chemotherapy camptothecin, which was shown to be an effective treatment in vivo. Additionally, a targeted PA nanostructure was designed to bind to the site of vascular intervention by targeting collagen IV. Following balloon angioplasty

  17. Electric Field Driven Self-Assembly of Colloidal Rods

    NASA Astrophysics Data System (ADS)

    Juarez, Jaime; Chaudhary, Kundan; Chen, Qian; Granick, Steve; Lewis, Jennifer

    2012-02-01

    The ability to assemble anisotropic colloidal building blocks into ordered configurations is of both scientific and technological importance. We are studying how electric field-induced interactions guide the self-assembly of these blocks into well aligned microstructures. Specifically, we present observations of the assembly of colloidal silica rods (L/D ˜ 4) within planar electrode cells as a function of different electric field parameters. Results from video microscopy and image analysis demonstrate that aligned microstructures form due to the competition between equilibrium interactions of induced dipoles and non-equilibrium processes (i.e., electro-osmosis). Under the appropriate electric field conditions (˜ kHZ AC fields), aligned colloidal rod fluids form over large areas on the electrode surface. The superposition of a DC electric field to this aligned colloidal rod fluid initiates their condensation into a vertically oriented crystalline phase. Ongoing work is now focused on exploring how temporal changes to electric fields influence colloidal rod dynamics and, hence, the assembly kinetics of aligned colloidal monolayers.

  18. Cationic polymers and their self-assembly for antibacterial applications.

    PubMed

    Deka, Smriti Rekha; Sharma, Ashwani Kumar; Kumar, Pradee

    2015-01-01

    The present article focuses on the amphiphilic cationic polymers as antibacterial agents. These polymers undergo self-assembly in aqueous conditions and impart biological activity by efficiently interacting with the bacterial cell wall, hence, used in preparing chemical disinfectants and biocides. Both cationic charge as well as hydrophobic segments facilitate interactions with the bacterial cell surface and initiate its disruption. The perturbation in transmembrane potential causes leakage of cytosolic contents followed by cell death. Out of two categories of macromolecules, peptide oligomers and cationic polymers, which have extensively been used as antibacterials, we have elaborated on the current advances made in the area of cationic polymer-based (naturally occurring and commonly employed synthetic polymers and their modified analogs) antibacterial agents. The development of polymer-based antibacterials has helped in addressing challenges posed by the drug-resistant bacterial infections. These polymers provide a new platform to combat such infections in the most efficient manner. This review presents concise discussion on the amphiphilic cationic polymers and their modified analogs having low hemolytic activity and excellent antibacterial activity against array of fungi, bacteria and other microorganisms.

  19. Differential hydrophobicity drives self-assembly in Huntington's disease.

    PubMed

    Burke, Martin G; Woscholski, Rüdiger; Yaliraki, S N

    2003-11-25

    Identifying the driving forces and the mechanism of association of huntingtin-exon1, a close marker for the progress of Huntington's disease, is an important prerequisite to finding potential drug targets and, ultimately, a cure. We introduce here a modeling framework based on a key analogy of the physicochemical properties of the exon1 fragment to block copolymers. We use a systematic mesoscale methodology, based on dissipative particle dynamics, which is capable of overcoming kinetic barriers, thus capturing the dynamics of significantly larger systems over longer times than considered before. Our results reveal that the relative hydrophobicity of the poly(glutamine) block as compared with the rest of the (proline-based) exon1 fragment, ignored to date, constitutes a major factor in the initiation of the self-assembly process. We find that the assembly is governed by both the concentration of exon1 and the length of the poly(glutamine) stretch, with a low-length threshold for association, even at the lowest volume fractions we considered. Moreover, this self-association occurs irrespective of whether the glutamine stretch is in random-coil or hairpin configuration, leading to spherical or cylindrical assemblies, respectively. We discuss the implications of these results for reinterpretation of existing research within this context, including that the routes toward aggregation of exon1 may be distinct from those of the widely studied homopolymeric poly(glutamine) peptides.

  20. Directed self-assembly cut mask assignment for unidirectional design

    NASA Astrophysics Data System (ADS)

    Ou, Jiaojiao; Yu, Bei; Gao, Jhih-Rong; Pan, David Z.

    2015-07-01

    Recently, directed self-assembly (DSA) has emerged as a promising lithography solution for cut manufacturing. We perform a comprehensive study on the DSA aware mask optimization problem to provide a DSA friendly design on cut layers. We first formulate the problem as an integer linear programming (ILP) to assign cuts to different guiding templates, targeting both conflict minimization and line-end extension minimization. As ILP may not be scalable for very large size problems, we then propose two speed-up strategies. The first one is to decompose the initial problem into smaller ones and solve them separately, followed by solution merging without much loss of quality. The second one is using the set cover algorithm to decide the DSA guiding pattern assignment, and then legalize the template placement. Our approaches can be naturally extended to handle arbitrary DSA guiding template patterns with complicated shapes. Experimental results show that our methodologies can significantly improve the DSA friendly, i.e., both the unresolved pattern number and the line-end extensions can be reduced.

  1. Kinetics of self-assembled monolayer formation on individual nanoparticles.

    PubMed

    Smith, Jeremy G; Jain, Prashant K

    2016-08-24

    Self-assembled monolayer (SAM) formation of alkanethiols on nanoparticle surfaces is an extensively studied surface reaction. But the nanoscale aspects of the rich microscopic kinetics of this reaction may remain hidden due to ensemble-averaging in colloidal samples, which is why we investigated in real-time how alkanethiol SAMs form on a single Ag nanoparticle. From single-nanoparticle trajectories obtained using in situ optical spectroscopy, the kinetics of SAM formation appears to be limited by the growth of the layer across the nanoparticle surface. A significant spread in the growth kinetics is seen between nanoparticles. The single-nanoparticle rate distributions suggest two distinct modes for SAM growth: spillover of adsorbed thiols from the initial binding sites on the nanoparticle and direct adsorption of thiol from solution. At low concentrations, wherein direct adsorption from solution is not prevalent and growth takes place primarily by adsorbate migration, the SAM formation rate was less variable from one nanoparticle to another. On the other hand, at higher thiol concentrations, when both modes of growth were operative, the population of nanoparticles with inherent variations in surface conditions and/or morphology exhibited a heterogeneous distribution of rates. These new insights into the complex dynamics of SAM formation may inform synthetic strategies for ligand passivation and functionalization of nanoparticles and models of reactive adsorption and catalysis on nanoparticles. PMID:27523488

  2. Tunable two dimensional protein patterns through self-assembly nanosphere template

    NASA Astrophysics Data System (ADS)

    Li, Zhishi; Ruan, Weidong; Shen, Shanshan; Wang, Haiyang; Guo, Zhinan; Xue, Xiangxin; Mao, Zhu; Ji, Wei; Wang, Xu; Song, Wei; Zhao, Bing

    2012-10-01

    By the aim of constructing surfaces for multi-component and multifunctional bioassay, a microsphere lithography technique was employed to control the surface morphology. Two kinds of protein molecules (antibodies) were used as building blocks. As a result, dual-component biocompatible surfaces with alternate immunoglobulin micropatterns were fabricated. The employed antibodies included human Immunoglobulin G (IgG) and rabbit IgG, which composed nanometer scale surface arrays on the surfaces. The antibodies were identified specially by immunoreactions with labeled antigens of fluorescein isothiocyanate (FITC)-antihuman IgG and tetramethylrhodamine-5-(and 6)-isothiocyanate (TRITC)-antirabbit IgG. The immune responses were confirmed by confocal fluorescence (FL) microscopy. A study on the sensitivity and quantification was done by using surface-enhanced resonance Raman scattering (SERRS) spectroscopy. The obtained SERRS spectra showed satisfactory resolution in the multi-component detection objects. No interference was observed from inner- or interactions of detecting molecules. The detection limits for both of the antigens reached to as low as 1 ng/mL, which was comparable to FL method. Meanwhile, a good linear relationship between SERRS peak intensity and the logarithm of antigens' concentrations (from 1 ng/mL to 1 mg/mL) were observed. The results demonstrated that SERRS is a very promising detection technique for multi-component immunoassay, and has great potential applications in biotechnology and biochemistry.

  3. Dynamic, Directed Self-Assembly of Nanoparticles via Toggled Interactions.

    PubMed

    Sherman, Zachary M; Swan, James W

    2016-05-24

    Crystals self-assembled from nanoparticles have useful properties such as optical activity and sensing capability. During fabrication, however, gelation and glassification often leave these materials arrested in defective or disordered metastable states. This is a key difficulty preventing adoption of self-assembled nanoparticle materials at scale. Processes which suppress kinetic arrest and defect formation while accelerating growth of ordered materials are essential for bottom-up approaches to creating nanomaterials. Dynamic, directed self-assembly processes in which the interactions between self-assembling components are actuated temporally offer one promising methodology for accelerating and controlling bottom-up growth of nanostructures. In this article, we show through simulation and theory how time-dependent, periodically toggled interparticle attractions can avoid kinetic barriers and yield well-ordered crystalline domains for a dispersion of nanoparticles interacting via a short-ranged, isotropic potential. The growth mechanism and terminal structure of the dispersion are controlled by parameters of the toggling protocol. This control allows for selection of processes that yield rapid self-assembled, low defect crystals. Although self-assembly via periodically toggled attractions is inherently unsteady and out-of-equilibrium, its outcome is predicted by a first-principles theory of nonequilibrium thermodynamics. The theory necessitates equality of the time average of pressure and chemical potential in coexisting phases of the dispersion. These quantities are evaluated using well known equations of state. The phase behavior predicted by this theory agrees well with measurements made in Brownian dynamics simulations of sedimentation equilibrium and homogeneous nucleation. The theory can easily be extended to model dynamic self-assembly directed by other toggled conservative force fields.

  4. Flexible minerals: self-assembled calcite spicules with extreme bending strength.

    PubMed

    Natalio, Filipe; Corrales, Tomas P; Panthöfer, Martin; Schollmeyer, Dieter; Lieberwirth, Ingo; Müller, Werner E G; Kappl, Michael; Butt, Hans-Jürgen; Tremel, Wolfgang

    2013-03-15

    Silicatein-α is responsible for the biomineralization of silicates in sponges. We used silicatein-α to guide the self-assembly of calcite "spicules" similar to the spicules of the calcareous sponge Sycon sp. The self-assembled spicules, 10 to 300 micrometers (μm) in length and 5 to 10 μm in diameter, are composed of aligned calcite nanocrystals. The spicules are initially amorphous but transform into calcite within months, exhibiting unusual growth along [100]. They scatter x-rays like twinned calcite crystals. Whereas natural spicules evidence brittle failure, the synthetic spicules show an elastic response, which greatly enhances bending strength. This remarkable feature is linked to a high protein content. With nano-thermogravimetric analysis, we measured the organic content of a single spicule to be 10 to 16%. In addition, the spicules exhibit waveguiding properties even when they are bent.

  5. Light-controlled morphologies of self-assembled triarylamine-fullerene conjugates.

    PubMed

    Busseron, Eric; Cid, Juan-José; Wolf, Adrian; Du, Guangyan; Moulin, Emilie; Fuks, Gad; Maaloum, Mounir; Polavarapu, Prasad; Ruff, Adrian; Saur, Ann-Kathrin; Ludwigs, Sabine; Giuseppone, Nicolas

    2015-03-24

    A family of triarylamine-fullerene conjugates has been synthesized and shown to self-assemble upon light stimulation in chlorinated solvents. This light-induced process primarily involves excitation of triarylamine derivatives, which then oxidize and stack with their neutral counterparts to form charge transfer complexes in the form of p-conducting channels, while fullerenes are consequently enforced in coaxial n-conducting columnar arrangements. These supramolecular heterojunctions can be organized over very long distances in micrometric fibers when a controlled amount of photons is provided from a white light source to initiate the process. Surprisingly, when sunlight or UV light is used instead, the nanostructuration leads to monodisperse spherical objects due to the nature of the nucleation-growth process involved in the stacks formation. This control over the supramolecular morphology of organic self-assemblies using the nature of light is of general interest for the design of functional responsive materials. PMID:25734231

  6. Self-Assembled Quantum Dots of Indium

    NASA Astrophysics Data System (ADS)

    Leonard, Devin Blaine

    1995-01-01

    The deposition of InAs or In_ xGa_{1-x}As upon GaAs substrates by molecular beam epitaxy (MBE) generally proceeds via the mode first described by Stranski and von Krastanow (SK). After the deposition of a certain thickness of this material, small islands of the deposited material nucleate on the surface. The island formation is attributed not to a large epitaxial surface energies, but to an elastic (dislocation free) relaxation of the mismatch strain (a _{InAs}=1.07cdot a_{GaAs}). I present a detailed study of the nucleation and growth of these InAs islands using atomic force microscopy (AFM) and transmission electron microscopy (TEM). The islands are found to be lens-shaped, coherently-strained and remarkably uniform in their size. Embedding these 4 nm tall, 25 nm diameter InAs islands in GaAs confines injected carriers in three dimensions. The islands thus formed fulfill the requirements of a quantum dot (or box), which behave as "artificial atoms" whose allowed energy eigenstates are discrete. Quantum dots have been the "holy grail" for many scientists because of the advantages these discrete energy levels provide in electronic and optical devices, such as semiconductor lasers. Self-assembled quantum dots (SAQD), presented in this dissertation, surmount the fabrication difficulties typical for quantum dots, reducing efforts to more fundamental problems of size uniformity and control. SAQDs have distinct advantages over quantum dots formed with other methods. For instance, no processing is required before or after growth. In addition, layers of SAQDs can be easily integrated into GaAs/AlGaAs devices. Contrary to quantum dots formed with other techniques, a strong light emission is observed from the SAQD at ~1.2 eV. Further photoluminescence (PL) experiments reveal emission linewidths less than.5 meV from individual SAQD, but a ~50 meV linewidth from larger arrays due to small SAQD thickness fluctuations. PL excitation (PLE) spectra reveal a large shift between

  7. AFM characterization of spin coated carboxylated polystyrene nanospheres/xyloglucan layers on mica and silicon.

    PubMed

    Lubambo, Adriana F; Lucyszyn, Neoli; Petzhold, Cesar L; Sierakowski, Maria-R; Schreiner, Wido H; Saul, Cyro K

    2013-03-01

    Self-assembled nano-arrays have a potential application as solid-phase diagnostics in many biomedical devices. The easiness of its production is directly connected to manufacture cost reduction. In this work, we present self-assembled structures starting from spin coated thin films of carboxylated polystyrene (PSC) and xyloglucan (XG) mixtures on both mica and silicon substrates. AFM images showed PSC nanospheres on top of a homogeneous layer of XG, for both substrates. The average nanosphere diameter fluctuated for a constant speed and it was likely to be independent of the component proportions on the mixture within a range of 30-50% (v/v) PSC. It was also observed that the largest diameters were found at the center of the sample and the smallest at the border. The detected nanospheres were also more numerous at the border. This behavior presents a similarity to spin coated colloidal dispersions. We observed that the average nanosphere diameter on mica substrates was bigger than the nanosphere diameters obtained on top of silicon substrates, under the same conditions. This result seems to be possibly connected to different mixture-surface interactions. PMID:23465925

  8. Interface-induced disassembly of a self-assembled two-component nanoparticle system.

    PubMed

    Gao, Yan; Duc, Le T; Ali, Affira; Liang, Beverly; Liang, Jenn-Tai; Dhar, Prajnaparamita

    2013-03-19

    We present a study of static and dynamic interfacial properties of self-assembled polyelectrolyte complex nanoparticles (size 110-120 nm) containing entrapped surfactant molecules at a fluid/fluid interface. Surface tension vs time measurements of an aqueous solution of these polyelectrolyte complex nanoparticles (PCNs) show a concentration-dependent biphasic adsorption to the air/water interface while interfacial microrheology data show a concentration-dependent initial increase in the surface viscosity (up to 10(-7) N·m/s), followed by a sharp decrease (10(-9) N·m/s). Direct visualization of the air/water interface shows disappearance of particles from the interface over time. On the basis of these observations, we propose that the PCNs at fluid/fluid interfaces exist in two states: initial accumulation of PCNs at the air/water interface as nanoparticles, followed by interface induced disassembly of the accumulated PCNs into their components. The lack of change in particle size, charge, and viscosity of the bulk aqueous solution of PCNs with time indicates that this disintegration of the self-assembled PCNs is an interfacial phenomenon. Changes in energy encountered by the PCNs at the interface lead to instability of the self-assembled system and dissociation into its components. Such systems can be used for applications requiring directed delivery and triggered release of entrapped surfactants or macromolecules at fluid/fluid interfaces.

  9. One-step electrodeposition of self-assembled colloidal particles: a novel strategy for biomedical coating.

    PubMed

    Sun, Jiadi; Liu, Xiaoya; Meng, Long; Wei, Wei; Zheng, Yufeng

    2014-09-23

    A novel biomedical coating was prepared from self-assembled colloidal particles through direct electrodeposition. The particles, which are photo-cross-linkable and nanoscaled with a high specific surface area, were obtained via self-assembly of amphiphilic poly(γ-glutamic acid)-g-7-amino-4-methylcoumarin (γ-PGA-g-AMC). The size, morphology, and surface charge of the resulting colloidal particles and their dependence on pH, initial concentrations, and UV irradiation were successfully studied. A nanostructured coating was formed in situ on the surface of magnesium alloys by electrodeposition of colloidal particles. The composition, morphology, and phase of the coating were monitored using Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and X-ray diffraction. The corrosion test showed that the formation of the nanostructured coating on magnesium alloys effectively improved their initial anticorrosion properties. More importantly, the corrosion resistance was further enhanced by chemical photo-cross-linking. In addition, the low cytotoxicity of the coated samples was confirmed by MTT assay against NIH-3T3 normal cells. The contribution of our work lies in the creation of a novel strategy to fabricate a biomedical coating in view of the versatility of self-assembled colloidal particles and the controllability of the electrodeposition process. It is believed that our work provides new ideas and reliable data to design novel functional biomedical coatings.

  10. Hydrogels constructed via self-assembly of beta-hairpin molecules

    NASA Astrophysics Data System (ADS)

    Ozbas, Bulent

    There is a recent and growing interest in hydrogel materials that are formed via peptide self-assembly for tissue engineering applications. Peptide based materials are excellent candidates for diverse applications in biomedical field due to their responsive behavior and complex self-assembled structures. However, there is very limited information on the self-assembly and resultant network and mechanical properties of these types of hydrogels. The main goal of this dissertation is to investigate the self-assembly mechanism and viscoelastic properties of hydrogels that can be altered by changing solution conditions as well as the primary structure of the peptide. These hydrogels are formed via intramolecular folding and consequent self-assembly of 20 amino acid long beta-hairpin peptide molecules (Max1). The peptide molecules are locally amphiphilic with two linear strands of alternating hydrophobic valine and hydrophilic lysine amino acids connected with a Dproline-LProline turn sequence. Circular dichroism and FTIR spectroscopy show that at physiological conditions peptides are unfolded in the absence of salt. By raising the ionic strength of the solution electrostatic interactions between charged lysines are screened and the peptide arms are forced into a beta-sheet secondary structure stabilized by the turn sequence. These folded molecules intermolecularly assemble via hydrophobic collapse and hydrogen bonding into a three dimensional network. Folding and self-assembly of these molecules can also be triggered by increasing temperature and/or pH of the peptide solution. In addition, the random-coil to beta-sheet transition of the beta-hairpin peptides is pH and, with proper changes in the peptide sequence, thermally reversible. Rheological measurements demonstrate that the resultant supramolecular structure forms an elastic material, whose structure, and thus modulus, can be tuned by magnitude of the stimulus. Hydrogels recover their initial viscoelastic

  11. Cooperative thermodynamic control of selectivity in the self-assembly of rare earth metal-ligand helices.

    PubMed

    Johnson, Amber M; Young, Michael C; Zhang, Xing; Julian, Ryan R; Hooley, Richard J

    2013-11-27

    Metal-selective self-assembly with rare-earth cations is possible with suitable rigid, symmetrical bis-tridentate ligands. Kinetically controlled formation is initially observed, with smaller cations preferentially incorporated. Over time, the more thermodynamically favorable complexes with larger metals are formed. This thermodynamic control is a cooperative supramolecular phenomenon and only occurs upon multiple-metal-based self-assembly: single-metal ML3 analogues do not show reversible selectivity. The selectivity is dependent on small variations in lanthanide ionic radius and occurs despite identical coordination-ligand coordination geometries and minor size differences in the rare-earth metals.

  12. Semiconducting nanowires from hairpin-shaped self-assembling sexithiophenes.

    PubMed

    Tsai, Wei-Wen; Tevis, Ian D; Tayi, Alok S; Cui, Honggang; Stupp, Samuel I

    2010-11-18

    Conjugated organic molecules can be designed to self-assemble from solution into nanostructures for functions such as charge transport, light emission, or light harvesting. We report here the design and synthesis of a novel hairpin-shaped self-assembling molecule containing electronically active sexithiophene moieties. In several nonpolar organic solvents, such as toluene or chlorocyclohexane, this compound was found to form organogels composed of nanofibers with uniform diameters of 3.0 (±0.3) nm. NMR analysis and spectroscopic measurements revealed that the self-assembly is driven by π-π interactions of the sexithiophene moieties and hydrogen bonding among the amide groups at the head of the hairpin. Field effect transistors built with this molecule revealed p-type semiconducting behavior and higher hole mobilities when films were cast from solvents that promote self-assembly. We propose that hydrogen bonding and π-π stacking act synergistically to create ordered stacking of sexithiophene moieties, thus providing an efficient pathway for charge carriers within the nanowires. The nanostructures formed exhibit unusually broad absorbance in their UV-vis spectrum, which we attribute to the coexistence of both H and J aggregates from face-to-face π-π stacking of sexithiophene moieties and hierarchical bundling of the nanowires. The large absorption range associated with self-assembly of the hairpin molecules makes them potentially useful in light harvesting for energy applications. PMID:20698523

  13. Sequential programmable self-assembly: Role of cooperative interactions.

    PubMed

    Halverson, Jonathan D; Tkachenko, Alexei V

    2016-03-01

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

  14. Sequential programmable self-assembly: Role of cooperative interactions

    NASA Astrophysics Data System (ADS)

    Halverson, Jonathan D.; Tkachenko, Alexei V.

    2016-03-01

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

  15. Core-shell self-assembly triggered via a thiol-disulfide exchange reaction for reduced glutathione detection and single cells monitoring

    PubMed Central

    Zhang, Zhen; Jiao, Yuting; Wang, Yuanyuan; Zhang, Shusheng

    2016-01-01

    A novel core-shell DNA self-assembly catalyzed by thiol-disulfide exchange reactions was proposed, which could realize GSH-initiated hybridization chain reaction (HCR) for signal amplification and molecules gathering. Significantly, these self-assembled products via electrostatic interaction could accumulate into prominent and clustered fluorescence-bright spots in single cancer cells for reduced glutathione monitoring, which will effectively drive cell monitoring into a new era. PMID:27412605

  16. Nano-scale characterization of binary self-assembled monolayers under an ambient condition with STM and TERS.

    PubMed

    Horimoto, Noriko N; Tomizawa, Shigeru; Fujita, Yasuhiko; Kajimoto, Shinji; Fukumura, Hiroshi

    2014-09-01

    Gold surfaces were modified by benzyl-mercaptan (BM) and then partly replaced with benzenethiol (BT), which formed binary self-assembled monolayers (SAM). Initially BT randomly replaced BM in the monolayer, but at long exchange times >15 nm radius domains were observed with specific relative composition of BT and BM.

  17. Guided and magnetic self-assembly of tunable magnetoceptive gels

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  18. Cell Environment-Differentiated Self-Assembly of Nanofibers.

    PubMed

    Zheng, Zhen; Chen, Peiyao; Xie, Maolin; Wu, Chengfan; Luo, Yufeng; Wang, Wentao; Jiang, Jun; Liang, Gaolin

    2016-09-01

    Employing cellular environment for the self-assembly of supramolecular nanofibers for biological applications has been widely explored. But using one precursor to differentiate the extra- and intracellular environments to self-assemble into two different nanofibers remains challenging. With the knowledge that the extracellualr environment of some cancer cells contains large amounts of alkaline phosphatase (ALP) while their intracellular environment is glutathione (GSH)-abundant in mind, we rationally designed a precursor Cys(SEt)-Glu-Tyr(H2PO3)-Phe-Phe-Gly-CBT (1) that can efficiently yield amphiphilic 2 and 2-D to self-assemble into two different nanofibers in hydrogels under the sequential treatment of ALP and GSH. We envision that, by employing a click condensation reaction, this work offers a platform for facilely postmodulation of supramolecular nanofibers, and the versatile precursor 1 could be used to kill two birds with one stone. PMID:27532322

  19. Self-Assembly of DNA-coated colloids

    NASA Astrophysics Data System (ADS)

    Pine, David

    DNA-coated particles have emerged as a powerful tool for programming the self-assembly of colloids and nanoparticles. The power of this approach lies in the highly specific molecular recognition properties of DNA and in the thermal reversibility of the interactions between DNA strands attached to different particles. These two properties taken together can, in principle, direct the bottom-up self-assembly of different materials into almost any desired structure. Here we discuss the self-assembly of single and multi-component crystals of DNA-coated colloids. This work is supported by the Army Research Office under MURI Grant Award Number W911NF-10-1-0518 and the MRSEC Program of the NSF under Award Number DMR-1420073.

  20. Guided and magnetic self-assembly of tunable magnetoceptive gels

    PubMed Central

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

    2014-01-01

    Self-assembly of components into complex functional patterns at microscale is common in nature, and used increasingly in numerous disciplines such as optoelectronics, microfabrication, sensors, tissue engineering and computation. Here, we describe the use of stable radicals to guide the self-assembly of magnetically tunable gels, which we call ‘magnetoceptive’ materials at the scale of hundreds of microns to a millimeter, each can be programmed by shape and composition, into heterogeneous complex structures. Using paramagnetism of free radicals as a driving mechanism, complex heterogeneous structures are built in the magnetic field generated by permanent magnets. The overall magnetic signature of final structure is erased via an antioxidant vitamin E, subsequent to guided self-assembly. We demonstrate unique capabilities of radicals and antioxidants in fabrication of soft systems with heterogeneity in material properties, such as porosity, elastic modulus and mass density; then in bottom-up tissue engineering and finally, levitational and selective assembly of microcomponents. PMID:25175148

  1. Self-assembly: mastering photonic processes at nanoscale

    NASA Astrophysics Data System (ADS)

    Fiorini, C.; Charra, F.

    2010-12-01

    Supramolecular ordering happens as an important parameter for the control of light emission processes. In this review paper, we discuss several examples of application of self-assembly to the realization of nano-structures designed in view of mastering specific photonic processes. This comprises the formation of highly localized plasmon modes in self-organized 2D assemblies of metal nanoparticles, the immobilization of dyes inside highly homogeneous 2D alveolar self-assembled molecular matrices and molecular 3D building blocks designed to combine in-plane periodicity and off-plane π-conjugated protrusions. Finally, we will discuss 3D self-assembly in solution with the example of fluorescent labelling of DNA.

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

    PubMed Central

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

    2015-01-01

    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. PMID:26766923

  3. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    PubMed

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    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 oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  4. Multivalent Protein Assembly Using Monovalent Self-Assembling Building Blocks

    PubMed Central

    Petkau-Milroy, Katja; Sonntag, Michael H.; Colditz, Alexander; Brunsveld, Luc

    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 to streptavidin. Next to tetravalent streptavidin, monovalent streptavidin was used to study the protein assembly along the supramolecular polymer in detail without the interference of cross-linking. Upon self-assembly of the monovalent biotinylated discotics, multivalent proteins can be assembled along the supramolecular polymer. The concentration of discotics, which influences the length of the final polymers at the same time dictates the amount of assembled proteins. PMID:24152447

  5. Self-assembled tunable networks of sticky colloidal particles

    NASA Astrophysics Data System (ADS)

    Demortière, Arnaud; Snezhko, Alexey; Sapozhnikov, Maksim V.; Becker, Nicholas; Proslier, Thomas; Aranson, Igor S.

    2014-01-01

    Surfaces decorated with dense arrays of microscopic fibres exhibit unique materials properties, including superhydrophobicity and low friction. Nature relies on ‘hairy’ surfaces to protect blood capillaries from wear and infection (endothelial glycocalyx). Here we report on the discovery of self-assembled tunable networks of microscopic polymer fibres ranging from wavy colloidal ‘fur’ to highly interconnected networks. The networks emerge via dynamic self-assembly in an alternating electric field from a non-aqueous suspension of ‘sticky’ polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles. We demonstrate, using atomic layer deposition, that the networks can serve as a template for a transparent conductor. These self-assembled tunable materials are promising candidates for large surface area electrodes in batteries and organic photovoltaic cells, as well as for microfluidic sensors and filters.

  6. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    PubMed

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    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 oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented. PMID:15787373

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

    SciTech Connect

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

    2005-03-01

    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.

  8. Scanning tunneling microscopy studies of mixed self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette Fernandez

    This thesis examines the formation of multicomponent self-assembled mono-layers (SAMs) on the Au(111) surface using scanning tunneling microscopy. Two methods, sequential adsorption and coadsorption, are used to create these mixed SAMs. In the sequential adsorption experiments, a clean Au(111)-on-mica sub-strate is exposed to the first molecular species and then this adsorbate-covered sample is exposed to the second molecular species. Alternately, in the coadsorption experiments, a gold surface is exposed to both adsorbates simultaneously. Exposing a coronene- or dithiocarbamate-covered surface to excess thiol in the vapor phase results in a drastic restructuring of the initial surface. This is primarily driven by the kinetics of the octanethiol monolayer formation process, but the extent to which this happens is dependent on the molecule-molecule and molecule-surface interactions of the adsorbate due to the initial coverage and order of the monolayer. An octanethiolate monolayer is also substantially modified when immersed in a solution containing dithiocarbamate (DTC). Defects in the octanethiol monolayer are prime sites for molecular exchange. A surplus of DTC in the solution drives substitution that can lead to the complete removal of thiol from the surface. When a Au(111) surface is exposed to solutions containing both octanethiol and dithiocarbamate (DTC), both molecular species compete for available ad- sorption sites. At equal octanethiol-to-DTC ratios, molecular exchange hinders octanethiol monolayer formation. Higher octanethiol concentration in solution results in the incorporation of thiol into the resulting monolayer, with a strong dependence on the chain length of the DTC molecules.

  9. Self-assembly of copper nanoparticles (cubes, rods and spherical nanostructures): Significant role of morphology on hydrogen and oxygen evolution efficiencies

    NASA Astrophysics Data System (ADS)

    Ahmed, Jahangeer; Trinh, Phong; Mugweru, Amos M.; Ganguli, Ashok K.

    2011-05-01

    Nanocrystalline copper nanoparticles with varying morphology, nanocubes (˜50 nm), nanorods (diameter of ˜3 nm and length of ˜50 nm) and nanospheres (5 nm) have been synthesized using the microemulsion method and subsequent treatment at 400 °C in hydrogen atmosphere. The role of concentration in the self-assembly of nanoparticles in varying dimensionality has been brought out in this study. Copper nanoparticles are known to be efficient electro-catalysts for a variety of reactions. In addition, the ability of copper catalyst to generate hydrogen and oxygen in electrochemical reactions provided the impetus to understand size and shape dependence of such electro-catalytic reactions of copper in nanocrystalline form. Cube-shaped nanoparticles show significantly high hydrogen and oxygen evolution efficiencies compared to the nanorods and spherical nanoparticles. The nanospheres show higher hydrogen and oxygen evolution efficiencies than the nanorods.

  10. Interfacial and mechanical properties of self-assembling systems

    NASA Astrophysics Data System (ADS)

    Carvajal, Daniel

    Self-assembly is a fascinating phenomena where interactions between small subunits allow them to aggregate and form complex structures that can span many length scales. These self-assembled structures are especially important in biology where they are necessary for life as we know it. This dissertation is a study of three very different self-assembling systems, all of which have important connections to biology and biological systems. Drop shape analysis was used to study the interfacial assembly of amphiphilic block copolymers at the oil/water interface. When biologically functionalyzed copolymers are used, this system can serve as a model for receptor-ligand interactions that are used by cells to perform many activities, such as interact with their surroundings. The physical properties of a self-assembling membrane system were quantified using membrane inflation and swelling experiments. These types of membranes may have important applications in medicine such as drug eluting (growth factor eluting) scaffolds to aid in wound healing. The factors affecting the properties of bis(leucine) oxalamide gels were also explored. We believe that this particular system will serve as an appropriate model for biological gels that are made up of fiber-like and/or rod-like structures. During the course of the research presented in this dissertation, many new techniques were developed specifically to allow/aid the study of these distinct self-assembling systems. For example, numerical methods were used to predict drop stability for drop shape analysis experiments and the methods used to create reproducibly create self-assembling membranes were developed specifically for this purpose. The development of these new techniques is an integral part of the thesis and should aid future students who work on these projects. A number ongoing projects and interesting research directions for each one of the projects is also presented.

  11. Self-Assembled DNA Templated Nano-wires and Circuits

    NASA Astrophysics Data System (ADS)

    Braun, Erez

    2000-03-01

    The realization that conventional microelectronics is approaching its miniaturization limits has motivated the search for an alternative route based on self-assembled nanometer-scale electronics. We have recently proposed a new approach based on the hybridization of biological and electronic materials (Braun E., Eichen Y., Sivan U. and Ben-Yoseph G., Nature 391, 775 (1998)). The concept relies on a two-step self-assembly process. The inherent molecular recognition capabilities of DNA molecules are first utilized to construct a network that serves as a template for the subsequent assembly of electronic materials into a circuit. The utilization of DNA and its associated enzymatic machinery enables: (a) self-assembly of complex substrates, (b) specific molecular addresses for the localization of electronic materials (e.g., gold colloids) by standard molecular biology techniques, (c) interdevice wiring and (d) bridging the microscopic structures to the macroscopic world. The self-assembly of nanometer scale electronics relies on two complementary developments. First, the ability to convert DNA molecules into thin conductive wires and second, the self-assembly of complex extended DNA templates. Our progress in these two directions will be presented. Regarding the first issue, a physical process resulting in condensation of gold colloids onto DNA molecules enables the assembly of thin gold wires (around 100-200 A wide) having, in principle, unlimited extensions. The second issue is developed in the context of recombinant DNA which allows the self-assembly of precise molecular junctions and networks. Specifically, we use RecA protein, which is the main protein responsible for genetic recombination in E. Coli bacteria, to construct DNA junctions at pre-designed addresses (sequences) on the molecules. The integration of these processes allows advancing nanometer-scale electronics. A realistic fabrication scheme for a room-temperature single-electron transistor

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

    PubMed

    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.

  13. Self-assembly of bis(phthalocyaninato)terbium on metal surfaces

    NASA Astrophysics Data System (ADS)

    Deng, Zhitao; Rauschenbach, Stephan; Stepanow, Sebastian; Klyatskaya, Svetlana; Ruben, Mario; Kern, Klaus

    2015-09-01

    Single-molecule magnets represent the smallest stable magnetic entities available to technology, with promising applications in data storage and quantum computation in sight. Therefore, an interface between devices and single-molecule magnets must be developed, for which the self-assembly behavior at surfaces is highly relevant. The molecular magnet bis(phthalocyaninato)terbium (TbPc2) represents a molecular system with interesting magnetic properties. In order to fabricate low dimensional nanostructures based on TbPc2, the self-assembly behavior on Cu(100), Cu(111) and Au(111) substrates is studied in ultra-high vacuum (UHV). On Cu(100), TbPc2 does not aggregate even at high coverage, which yields a good zero-dimensional system. On Cu(111), the TbPc2 molecules self-assemble into ribbon-like islands with a high aspect ratio, or an isotropically growing phase, depending on the coverage. On Au(111), TbPc2 molecules form two-dimensional domains from the initial growth stage and extend to highly ordered films, which cover entire terraces at high coverage. The molecular ordering of TbPc2 can be understood based on the behavior of single Pc adlayers, taking into account the molecular double-decker structure. The freedom in the dihedral angle between top and bottom Pc ligands allows one to optimize the molecular ordering through a flexible conformation.

  14. Surface Effects Mediate Self-Assembly of Amyloid-β Peptides

    PubMed Central

    2015-01-01

    Here we present a label-free method for studying the mechanism of surface effects on amyloid aggregation. In this method, spin-coating is used to rapidly dry samples, in a homogeneous manner, after various incubation times. This technique allows the control of important parameters for self-assembly, such as the surface concentration. Atomic force microscopy is then used to obtain high-resolution images of the morphology. While imaging under dry conditions, we show that the morphologies of self-assembled aggregates of a model amyloid-β peptide, Aβ12–28, are strongly influenced by the local surface concentration. On mica surfaces, where the peptides can freely diffuse, homogeneous, self-assembled protofibrils formed spontaneously and grew longer with longer subsequent incubation. The surface fibrillization rate was much faster than the rates of fibril formation observed in solution, with initiation occurring at much lower concentrations. These data suggest an alternative pathway for amyloid formation on surfaces where the nucleation stage is either bypassed entirely or too fast to measure. This simple preparation procedure for high-resolution atomic force microscopy imaging of amyloid oligomers and protofibrils should be applicable to any amyloidogenic protein species. PMID:25229233

  15. Self-Assembly of Octopus Nanoparticles into Pre-Programmed Finite Clusters

    NASA Astrophysics Data System (ADS)

    Halverson, Jonathan; Tkachenko, Alexei

    2012-02-01

    The precise control of the spatial arrangement of nanoparticles (NP) is often required to take full advantage of their novel optical and electronic properties. NPs have been shown to self-assemble into crystalline structures using either patchy surface regions or complementary DNA strands to direct the assembly. Due to a lack of specificity of the interactions these methods lead to only a limited number of structures. An emerging approach is to bind ssDNA at specific sites on the particle surface making so-called octopus NPs. Using octopus NPs we investigate the inverse problem of the self-assembly of finite clusters. That is, for a given target cluster (e.g., arranging the NPs on the vertices of a dodecahedron) what are the minimum number of complementary DNA strands needed for the robust self-assembly of the cluster from an initially homogeneous NP solution? Based on the results of Brownian dynamics simulations we have compiled a set of design rules for various target clusters including cubes, pyramids, dodecahedrons and truncated icosahedrons. Our approach leads to control over the kinetic pathway and has demonstrated nearly perfect yield of the target.

  16. Nanoscale self-assembly of starch: Phase relations, formation, and structure

    NASA Astrophysics Data System (ADS)

    Creek, John A.

    This project has been undertaken to develop a fundamental understanding of the spherulitic self-assembly of starch polymers from aqueous solution, both as a model for starch granule initiation in vivo and as a biologically-inspired material with applications in the food and pharmaceutical industries. Botanical starches were observed to form semi-crystalline spherulites from aqueous solution when cooled after a high temperature treatment, and the processes resulting in spherulite formation were investigated. Based on the influence of cooling rate on spherulite formation from a botanical starch, liquid-liquid demixing in competition with crystallization was proposed as the mechanism leading to spherulite formation (summarized in a hypothetical phase diagram). Study of amylose and amylopectin self-assembly demonstrated that the linear polymer plays the primary role in forming spherulites. As a result, the roles of degree of polymerization, concentration, and thermal processing conditions on amylose self-assembly were explored. Thermal properties, final system morphology, and crystalline allomorph were characterized. In all cases the experimental findings supported the proposed phase diagram. Finally, the crystalline nanostructure of the spherulites was probed using atomic force microscopy (AFM), revealing a seemingly universal level of structure in crystalline starch materials. This was compared to an existing model of crystallization for synthetic polymers involving a transitional liquid crystalline-like ordering---a comparison that makes sense in light of the known helical structure of starch.

  17. Composition and method for self-assembly and mineralization of peptide amphiphiles

    DOEpatents

    Stupp, Samuel I.; Beniash, Elia; Hartgerink, Jeffrey D.

    2009-06-30

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

  18. Composition and method for self-assembly and mineralization of peptide-amphiphiles

    DOEpatents

    Stupp, Samuel I.; Beniash, Elia; Hartgerink, Jeffrey D.

    2012-02-28

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

  19. Design of Self-Assembling Peptide Hydrogelators Amenable to Bacterial Expression

    PubMed Central

    Sonmez, Cem; Nagy, Katelyn J.; Schneider, Joel P.

    2014-01-01

    Hydrogels formed from self-assembling peptides are finding use in tissue engineering and drug delivery applications. Given the notorious difficulties associated with producing self-assembling peptides by recombinant expression, most are typically prepared by chemical synthesis. Herein, we report the design of a family of self-assembling β-hairpin peptides amenable to efficient production using an optimized bacterial expression system. Expressing peptides, EX1, EX2 and EX3 contain identical eight-residue amphiphilic β-strands connected by varying turn sequences that are responsible for ensuring chain reversal and the proper intramolecular folding and consequent self-assembly of the peptide into a hydrogel network under physiological conditions. EX1 was initially used to establish and optimize the bacterial expression system by which all the peptides could be eventually individually expressed. Expression clones were designed to allow exploration of possible fusion partners and investigate both enzymatic and chemical cleavage as means to liberate the target peptide. A systematic analysis of possible expression systems followed by fermentation optimization lead to a system in which all three peptides could be expressed as fusions with BAD-BH3, the BH3 domain of the proapoptotic BAD (Bcl-2 Associated Death) Protein. CNBr cleavage followed by purification afforded 50, 31, and 15 mg/L yields of pure EX1, EX2 and EX3, respectively. CD spectroscopy, TEM, and rheological analysis indicate that these peptides fold and assembled into well-defined fibrils that constitute hydrogels having shear-thin/recovery properties. PMID:25453938

  20. Nanofibers Self-assembled from Structural Complementary Borono-decapeptides.

    PubMed

    Chen, Chang-Sheng; Ji, Tian-Jiao; Xu, Xiao-Ding; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2010-11-01

    A series of structural complementary decapeptides with phenyl boronic acid tails or borono-decapeptides (BPs) were designed and synthesized for supramolecular self-assembly. After dissolving these borono-decapeptides in deionized (DI) water, well-defined nanofibers were formed in BP1 (B(OH)(2) VEKELVKEKL-OH) and BP3 (B(OH)(2) AELELARARL-OH). It was found that the self-assembled borono-decapeptide BP1 and BP3 have a parallel β-sheet conformation in the formed nanofibers. The strategy demonstrated here shows a great prospect in preparation of well-ordered nanofibers via rationally designing the molecular structures of peptides.

  1. Self-Assembled Organic Nanocrystals with Strong Nonlinear Optical Response.

    PubMed

    Rosenne, Shaked; Grinvald, Eran; Shirman, Elijah; Neeman, Lior; Dutta, Sounak; Bar-Elli, Omri; Ben-Zvi, Regev; Oksenberg, Eitan; Milko, Petr; Kalchenko, Vyacheslav; Weissman, Haim; Oron, Dan; Rybtchinski, Boris

    2015-11-11

    Facile molecular self-assembly affords a new family of organic nanocrystals that, unintuitively, exhibit a significant nonlinear optical response (second harmonic generation, SHG) despite the relatively small molecular dipole moment of the constituent molecules. The nanocrystals are self-assembled in aqueous media from simple monosubstituted perylenediimide (PDI) molecular building blocks. Control over the crystal dimensions can be achieved via modification of the assembly conditions. The combination of a simple fabrication process with the ability to generate soluble SHG nanocrystals with tunable sizes may open new avenues in the area of organic SHG materials.

  2. Molecular beam epitaxy grown indium self-assembled plasmonic nanostructures

    NASA Astrophysics Data System (ADS)

    Gibson, Ricky; Gehl, Michael; Sears, Jasmine; Zandbergen, Sander; Nader, Nima; Keiffer, Patrick; Hendrickson, Joshua; Arnoult, Alexandre; Khitrova, Galina

    2015-09-01

    We describe molecular beam epitaxy (MBE) growth conditions for self-assembled indium nanostructures, or islands, which allow for the tuning of the density and size of the indium nanostructures. How the plasmonic resonance of indium nanostructures is affected by the island density, size, distribution in sizes, and indium purity of the nanostructures is explored. These self-assembled nanostructures provide a platform for integration of resonant and non-resonant plasmonic structures within a few nm of quantum wells (QWs) or quantum dots (QDs) in a single process. A 4× increase in peak photoluminescence intensity is demonstrated for near-surface QDs resonantly coupled to indium nanostructures.

  3. Nano-engineering by optically directed self-assembly.

    SciTech Connect

    Furst, Eric; Dunn, Elissa; Park, Jin-Gyu; Brinker, C. Jeffrey; Sainis, Sunil; Merrill, Jason; Dufresne, Eric; Reichert, Matthew D.; Brotherton, Christopher M.; Bogart, Katherine Huderle Andersen; Molecke, Ryan A.; Koehler, Timothy P.; Bell, Nelson Simmons; Grillet, Anne Mary; Gorby, Allen D.; Singh, John; Lele, Pushkar; Mittal, Manish

    2009-09-01

    Lack of robust manufacturing capabilities have limited our ability to make tailored materials with useful optical and thermal properties. For example, traditional methods such as spontaneous self-assembly of spheres cannot generate the complex structures required to produce a full bandgap photonic crystals. The goal of this work was to develop and demonstrate novel methods of directed self-assembly of nanomaterials using optical and electric fields. To achieve this aim, our work employed laser tweezers, a technology that enables non-invasive optical manipulation of particles, from glass microspheres to gold nanoparticles. Laser tweezers were used to create ordered materials with either complex crystal structures or using aspherical building blocks.

  4. Scanning tunneling microscopy of self-assembled viral nanostructures

    NASA Astrophysics Data System (ADS)

    Anacleto, Benjamin; Steinsultz, Nat; Sharma, Prashant

    2010-03-01

    We use scanning tunneling microscopy to investigate self-assembled monolayers of M13 bacteriophages on graphite surface. The bacteriophages we use have gold binding peptide motifs on their outer protein coat (˜1μm long, ˜10 nm diameter) allowing us to self-assemble gold nanoparticles on graphite. Using scanning tunneling microscopy we are able to resolve sub-molecular structure of the protein coat of M13 bacteriophage. Scanning tunneling spectroscopy allows us to study the binding of gold nanoparticles to the peptide motif on the bacteriophage.

  5. Self-assembly of flagellin on Au(111) surfaces.

    PubMed

    González Orive, Alejandro; Pissinis, Diego E; Diaz, Carolina; Miñán, Alejandro; Benítez, Guillermo A; Rubert, Aldo; Daza Millone, Antonieta; Rumbo, Martin; Hernández Creus, Alberto; Salvarezza, Roberto C; Schilardi, Patricia L

    2014-11-01

    The adsorption of flagellin monomers from Pseudomonas fluorescens on Au(111) has been studied by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Surface Plasmon Resonance (SPR), and electrochemical techniques. Results show that flagellin monomers spontaneously self-assemble forming a monolayer thick protein film bounded to the Au surface by the more hydrophobic subunit and exposed to the environment the hydrophilic subunit. The films are conductive and allow allocation of electrochemically active cytochrome C. The self-assembled films could be used as biological platforms to build 3D complex molecular structures on planar metal surfaces and to functionalize metal nanoparticles.

  6. Self-assembly of flagellin on Au(111) surfaces.

    PubMed

    González Orive, Alejandro; Pissinis, Diego E; Diaz, Carolina; Miñán, Alejandro; Benítez, Guillermo A; Rubert, Aldo; Daza Millone, Antonieta; Rumbo, Martin; Hernández Creus, Alberto; Salvarezza, Roberto C; Schilardi, Patricia L

    2014-11-01

    The adsorption of flagellin monomers from Pseudomonas fluorescens on Au(111) has been studied by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Surface Plasmon Resonance (SPR), and electrochemical techniques. Results show that flagellin monomers spontaneously self-assemble forming a monolayer thick protein film bounded to the Au surface by the more hydrophobic subunit and exposed to the environment the hydrophilic subunit. The films are conductive and allow allocation of electrochemically active cytochrome C. The self-assembled films could be used as biological platforms to build 3D complex molecular structures on planar metal surfaces and to functionalize metal nanoparticles. PMID:25112916

  7. Morphological Control of Anisotropic Self-Assemblies from Alternating Poly(p-dioxanone)-poly(ethylene glycol) Multiblock Copolymer Depending on the Combination Effect of Crystallization and Micellization.

    PubMed

    Wang, Mei-Jia; Wang, Hao; Chen, Si-Chong; Chen, Cheng; Liu, Ya

    2015-06-30

    A novel and facile method was developed for morphological controlling of self-assemblies prepared by crystallization induced self-assembly of crystalline-coil copolymer depending on the combination effect of crystallization and micellization. The morphological evolution of the self-assemblies of alternating poly(p-dioxanone)-block-poly(ethylene glycol) (PPDO-PEG) multiblock copolymer prepared by different solvent mixing methods in aqueous solution were investigated. "Chrysanthemum"-like and "star anise"-like self-assemblies were obtained at different rates of solvent mixing. The results suggested gradually change in solvent quality (slowly dropping water into DMF solution) leaded to a hierarchical micellization-crystallization process of core-forming PPDO blocks, and flake-like particles were formed at the initial stage of crystallization. Meanwhile, crystallization induced micellization process occurred when solvent quality changed drastically. Shuttle-like particles, which have much smaller size than those of flake-like particles, were formed at the initial stage of crystallization when quickly injecting water into DMF solution of the copolymer. Therefore, owing to the different changing rate of solvent quality, which may result in different combination effect of crystallization and micellization during self-assembly of the copolymer, PPDO-PEG self-assemblies with different hierarchical morphology in nano scale could be obtained. PMID:26061590

  8. Stability of antibacterial self-assembled monolayers on hydroxyapatite.

    PubMed

    Torres, Nelson; Oh, Sunho; Appleford, Mark; Dean, David D; Jorgensen, James H; Ong, Joo L; Agrawal, C Mauli; Mani, Gopinath

    2010-08-01

    Open fractures are common in battlefields, motor vehicle accidents, gunshot wounds, sports injuries, and high-energy falls. Such fractures are treated using hydroxyapatite (HA)-based bone graft substitutes. However, open fracture wounds are highly susceptible to bacterial infections. Hence, this study was focused on incorporating antibacterial properties to HA using silver (Ag) carrying self-assembled monolayers (SAMs). Also, the stability of Ag carrying SAMs on HA was investigated under sterilization and physiological conditions. Initially, the -COOH terminated phosphonic acid SAMs of two different chain lengths (11 carbon atoms - shorter chain and 16 carbon atoms - longer chain) were deposited on HA. Antibacterial SAMs (ASAMs) were prepared by chemically attaching Ag to shorter and longer chain SAMs coated HA. X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle goniometry collectively confirmed the attachment of Ag onto SAMs coated HA. The bacterial adhesion study showed that the adherence of Staphylococcus aureus was significantly reduced on ASAMs coated HA when compared to control-HA. The stability studies showed that gas plasma, dry heat and autoclave degraded most of the ASAMs on HA. UV irradiation did not damage the shorter chain ASAMs as vigorously as other treatments, while it degraded the longer chain ASAMs completely. Ethylene oxide treatment did not degrade the longer chain ASAMs unlike all other treatments but it severely damaged the shorter chain ASAMs. Both shorter and longer chain ASAMs significantly desorbed from the HA surfaces under physiological conditions although longer chain ASAMs exhibited better stability than shorter chain ASAMs. This study demonstrated the potential for using ASAMs to provide antibacterial properties to HA and the need for developing techniques to improve stability of SAMs under sterilization and physiological conditions. PMID:20188873

  9. Alkanethiols on platinum: multicomponent self-assembled monolayers.

    PubMed

    Petrovykh, Dmitri Y; Kimura-Suda, Hiromi; Opdahl, Aric; Richter, Lee J; Tarlov, Michael J; Whitman, Lloyd J

    2006-03-14

    We have studied the formation of self-assembled monolayers (SAMs) of n-alkanethiols on platinum thin films using X-ray photoelectron spectroscopy (XPS), reflection-absorption infrared spectroscopy (RAIRS), spectroscopic ellipsometry (SE), and contact angle (CA) measurements. Specifically, SAMs of 1-hexanethiol, 1-dodecanethiol, and 1-octadecanethiol were grown on polycrystalline Pt films, and the effects of Pt surface preparation, deposition conditions, and solvent treatments on the initial quality and stability of the monolayer in air were investigated. The SAMs prepared under ambient conditions on piranha-cleaned and UV/ozone-cleaned substrates were compared to monolayers formed on template-stripped Pt in an inert atmosphere. We found that alkanethiols deposited from 1 mM ethanolic solutions on piranha-cleaned Pt formed densely packed monolayers in which alkyl chains were oriented close to the surface normal. Stored in the laboratory ambient, these monolayers were unchanged over about 1 week but were largely oxidized in about 1 month. No evidence was found of molecules being weakly bound within the monolayer or having undergone C-S bond scission; however, three distinct sulfur states were observed for all samples in the XPS of the S 2p region. The lowest- and highest-binding-energy components are assigned to alkylthiolate and partially oxidized alkylthiolate species, respectively. The remaining S 2p component (approximately one-third of the sulfur layer), intermediate in binding energy between the other two components, is attributed to a chemisorbed species with a S binding configuration distinct from the majority alkylthiolate: for example, S bound to Pt bound to O, S with a different Pt coordination number, or S in an adsorbed disulfide.

  10. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine-phenylalanine motif.

    PubMed

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K; Anson, Christopher E; Powell, Annie K; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N; Coles, Simon J; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G; Balaban, Teodor Silviu

    2016-01-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence. PMID:27582363

  11. Self-Assembly of Nano Hydroxyapatite or Aragonite Induced by Molecular Recognition to Soy Globulin 7S or 11S.

    PubMed

    Liu, Dagang; Tian, Huafeng; Kumar, Rakesh; Zhang, Lina

    2009-09-01

    Molecular self-assembly is emerging as a viable 'bottom-up' approach to build stable organic/inorganic nanometer-scale blocks. Herein, under the conditions of appropriate pH and ionic strength, soy globulin 7S or 11S were coprecipitated with hydroxyapatite (HAp) or aragonite (Arag), respectively, to fabricate two organic/inorganic hybrids: 7S/HAp and 11S/Arag. Results from high-resolution transmission electron microscopy show that the hybrids exhibit a nanosized core-shell structure with globulin monomer 7S or 11S as core and HAp or Arag as shells. 7S/HAp and 11S/Arag present a disk and hexagon shape, respectively. After calcinations, monodispersed HAp without support from globulins existed as nanospheres. It was revealed that the globulin as host induces the self-assembly and growth layer by layer of HAp or Arag nanocrystals. The factors of molecular recognition and surface potential definitely affected the size and shape of the hierarchical blocks. This work provided a novel pathway to controllably synthesize a wide variety of precise plant protein/biomineral hybrid biomaterials.

  12. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine-phenylalanine motif

    NASA Astrophysics Data System (ADS)

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K.; Anson, Christopher E.; Powell, Annie K.; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N.; Coles, Simon J.; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G.; Balaban, Teodor Silviu

    2016-09-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence.

  13. A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif

    PubMed Central

    Charalambidis, Georgios; Georgilis, Evangelos; Panda, Manas K.; Anson, Christopher E.; Powell, Annie K.; Doyle, Stephen; Moss, David; Jochum, Tobias; Horton, Peter N.; Coles, Simon J.; Linares, Mathieu; Beljonne, David; Naubron, Jean-Valère; Conradt, Jonas; Kalt, Heinz; Mitraki, Anna; Coutsolelos, Athanassios G.; Balaban, Teodor Silviu

    2016-01-01

    Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence. PMID:27582363

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

    NASA Astrophysics Data System (ADS)

    Di Stasio, Francesco; Berti, Luca; McDonnell, Shane O.; Robbiano, Valentina; Anderson, Harry L.; Comoretto, Davide; Cacialli, Franco

    2013-10-01

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

  15. Cooperative Self-Assembly of Peptide Gelators and Proteins

    PubMed Central

    2014-01-01

    Molecular self-assembly provides a versatile route for the production of nanoscale materials for medical and technological applications. Herein, we demonstrate that the cooperative self-assembly of amphiphilic small molecules and proteins can have drastic effects on supramolecular nanostructuring of resulting materials. We report that mesoscale, fractal-like clusters of proteins form at concentrations that are orders of magnitude lower compared to those usually associated with molecular crowding at room temperature. These protein clusters have pronounced effects on the molecular self-assembly of aromatic peptide amphiphiles (fluorenylmethoxycarbonyl- dipeptides), resulting in a reversal of chiral organization and enhanced order through templating and binding. Moreover, the morphological and mechanical properties of the resultant nanostructured gels can be controlled by the cooperative self-assembly of peptides and protein fractal clusters, having implications for biomedical applications where proteins and peptides are both present. In addition, fundamental insights into cooperative interplay of molecular interactions and confinement by clusters of chiral macromolecules is relevant to gaining understanding of the molecular mechanisms of relevance to the origin of life and development of synthetic mimics of living systems. PMID:24256076

  16. Self-assembling multidomain peptide fibers with aromatic cores

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Self-assembling multidomain peptides have been shown to have desirable properties, such as the ability to form hydrogels that rapidly recover following shear-thinning and the potential to be tailored by amino acid selection to vary their elasticity and encapsulate and deliver proteins and cells. Her...

  17. Nano-imaging enabled via self-assembly

    PubMed Central

    McLeod, Euan; Ozcan, Aydogan

    2014-01-01

    SUMMARY Imaging object details with length scales below approximately 200 nm has been historically difficult for conventional microscope objective lenses because of their inability to resolve features smaller than one-half the optical wavelength. Here we review some of the recent approaches to surpass this limit by harnessing self-assembly as a fabrication mechanism. Self-assembly can be used to form individual nano- and micro-lenses, as well as to form extended arrays of such lenses. These lenses have been shown to enable imaging with resolutions as small as 50 nm half-pitch using visible light, which is well below the Abbe diffraction limit. Furthermore, self-assembled nano-lenses can be used to boost contrast and signal levels from small nano-particles, enabling them to be detected relative to background noise. Finally, alternative nano-imaging applications of self-assembly are discussed, including three-dimensional imaging, enhanced coupling from light-emitting diodes, and the fabrication of contrast agents such as quantum dots and nanoparticles. PMID:25506387

  18. Self-assembling biomolecular catalysts for hydrogen production

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  19. Photoresponsive self-assemblies based on fatty acids.

    PubMed

    Fameau, A-L; Arnould, A; Lehmann, M; von Klitzing, R

    2015-02-18

    Photoresponsive surfactant system based on fatty acids has been developed by the introduction in aqueous solution of a photoacid generator (PAG). Self-assembly transitions are triggered by UV irradiation due to a pH change induced by the presence of PAG.

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

    PubMed Central

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

    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. PMID:20209016

  1. Directed intermixing in multi-component self-assembling biomaterials

    PubMed Central

    Gasiorowski, Joshua Z.; Collier, Joel H.

    2011-01-01

    The non-covalent co-assembly of multiple different peptides can be a useful route for producing multifunctional biomaterials. However, to date such materials have almost exclusively been investigated as homogeneous self-assemblies, having functional components uniformly distributed throughout their supramolecular structures. Here we illustrate control over the intermixing of multiple different self-assembling peptides, in turn providing a simple but powerful means for modulating these materials’ mechanical and biological properties. In beta-sheet fibrillizing hydrogels, significant increases in stiffening could be achieved using heterobifunctional cross-linkers by sequestering peptides bearing different reactive groups into distinct populations of fibrils, thus favoring inter-fibril cross-linking. Further, by specifying the intermixing of RGD-bearing peptides in 2-D and 3-D self-assemblies, the growth of HUVECs and NIH 3T3 cells could be significantly modulated. This approach may be immediately applicable towards a wide variety of self-assembling systems that form stable supramolecular structures. PMID:21863894

  2. Soft self-assembled nanoparticles with temperature-dependent properties

    NASA Astrophysics Data System (ADS)

    Rovigatti, Lorenzo; Capone, Barbara; Likos, Christos N.

    2016-02-01

    The fabrication of versatile building blocks that reliably self-assemble into desired ordered and disordered phases is amongst the hottest topics in contemporary materials science. To this end, microscopic units of varying complexity, aimed at assembling the target phases, have been thought, designed, investigated and built. Such a path usually requires laborious fabrication techniques, especially when specific functionalisation of the building blocks is required. Telechelic star polymers, i.e., star polymers made of a number of f di-block copolymers consisting of solvophobic and solvophilic monomers grafted on a central anchoring point, spontaneously self-assemble into soft patchy particles featuring attractive spots (patches) on the surface. Here we show that the tunability of such a system can be widely extended by controlling the physical and chemical parameters of the solution. Indeed, under fixed external conditions the self-assembly behaviour depends only on the number of arms and on the ratio of solvophobic to solvophilic monomers. However, changes in temperature and/or solvent quality make it possible to reliably change the number and size of the attractive patches. This allows the steering of the mesoscopic self-assembly behaviour without modifying the microscopic constituents. Interestingly, we also demonstrate that diverse combinations of the parameters can generate stars with the same number of patches but different radial and angular stiffness. This mechanism could provide a neat way of further fine-tuning the elastic properties of the supramolecular network without changing its topology.

  3. Self-assembled peptide nanostructures for functional materials.

    PubMed

    Ekiz, Melis Sardan; Cinar, Goksu; Khalily, Mohammad Aref; Guler, Mustafa O

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies. PMID:27578525

  4. An exactly solvable model of hierarchical self-assembly.

    PubMed

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

    2009-06-14

    Many living and nonliving structures in the natural world form by hierarchical organization, but physical theories that describe this type of organization are scarce. To address this problem, a model of equilibrium self-assembly is formulated in which dynamically associating species organize into hierarchical structures that preserve their shape at each stage of assembly. In particular, we consider symmetric m-gons that associate at their vertices into Sierpinski gasket structures involving the hierarchical association of triangles, squares, hexagons, etc., at their corner vertices, thereby leading to fractal structures after many generations of assembly. This rather idealized model of hierarchical assembly yields an infinite sequence of self-assembly transitions as the morphology progressively organizes to higher levels of the hierarchy, and these structures coexists at dynamic equilibrium, as found in real hierarchically self-assembling systems such as amyloid fiber forming proteins. Moreover, the transition sharpness progressively grows with increasing m, corresponding to larger and larger loops in the assembled structures. Calculations are provided for several basic thermodynamic properties (including the order parameters for assembly for each stage of the hierarchy, average mass of clusters, specific heat, transition sharpness, etc.) that are required for characterizing the interaction parameters governing this type of self-assembly and for elucidating other basic qualitative aspects of these systems. Our idealized model of hierarchical assembly gives many insights into this ubiquitous type of self-organization process. PMID:19530788

  5. An exactly solvable model of hierarchical self-assembly

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

    Many living and nonliving structures in the natural world form by hierarchical organization, but physical theories that describe this type of organization are scarce. To address this problem, a model of equilibrium self-assembly is formulated in which dynamically associating species organize into hierarchical structures that preserve their shape at each stage of assembly. In particular, we consider symmetric m-gons that associate at their vertices into Sierpinski gasket structures involving the hierarchical association of triangles, squares, hexagons, etc., at their corner vertices, thereby leading to fractal structures after many generations of assembly. This rather idealized model of hierarchical assembly yields an infinite sequence of self-assembly transitions as the morphology progressively organizes to higher levels of the hierarchy, and these structures coexists at dynamic equilibrium, as found in real hierarchically self-assembling systems such as amyloid fiber forming proteins. Moreover, the transition sharpness progressively grows with increasing m, corresponding to larger and larger loops in the assembled structures. Calculations are provided for several basic thermodynamic properties (including the order parameters for assembly for each stage of the hierarchy, average mass of clusters, specific heat, transition sharpness, etc.) that are required for characterizing the interaction parameters governing this type of self-assembly and for elucidating other basic qualitative aspects of these systems. Our idealized model of hierarchical assembly gives many insights into this ubiquitous type of self-organization process.

  6. Amphiphilic self-assembly of alkanols in protic ionic liquids.

    PubMed

    Jiang, Haihui Joy; FitzGerald, Paul A; Dolan, Andrew; Atkin, Rob; Warr, Gregory G

    2014-08-21

    Strong cohesive forces in protic ionic liquids (PILs) can induce a liquid nanostructure consisting of segregated polar and apolar domains. Small-angle X-ray scattering has shown that these forces can also induce medium chain length n-alkanols to self-assemble into micelle- and microemulsion-like structures in ethylammonium (EA(+)) and propylammonium (PA(+)) PILs, in contrast to their immiscibility with both water and ethanolammonium (EtA(+)) PILs. These binary mixtures are structured on two distinct length scales: one associated with the self-assembled n-alkanol aggregates and the other with the underlying liquid nanostructure. This suggests that EA(+) and PA(+) enable n-alkanol aggregation by acting as cosurfactants, which EtA(+) cannot do because its terminating hydroxyl renders the cation nonamphiphilic. The primary determining factor for miscibility and self-assembly is the ratio of alkyl chain lengths of the alkanol and PIL cation, modulated by the anion type. These results show how ILs can support the self-assembly of nontraditional amphiphiles and enable the creation of new forms of soft matter. PMID:25068766

  7. Self-assembled peptide nanostructures for functional materials.

    PubMed

    Ekiz, Melis Sardan; Cinar, Goksu; Khalily, Mohammad Aref; Guler, Mustafa O

    2016-10-01

    Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.

  8. Multistep hierarchical self-assembly of chiral nanopore arrays

    PubMed Central

    Kim, Hanim; Lee, Sunhee; Shin, Tae Joo; Korblova, Eva; Walba, David M.; Clark, Noel A.; Lee, Sang Bok; Yoon, Dong Ki

    2014-01-01

    A series of simple hierarchical self-assembly steps achieve self-organization from the centimeter to the subnanometer-length scales in the form of square-centimeter arrays of linear nanopores, each one having a single chiral helical nanofilament of large internal surface area and interfacial interactions based on chiral crystalline molecular arrangements. PMID:25246585

  9. Clustering and self-assembly in colloidal systems

    NASA Astrophysics Data System (ADS)

    Smallenburg, F.

    2012-01-01

    A colloidal dispersion consists of small particles called colloids, typically tens of nanometers to a few micrometers in size, suspended in a solvent. Due to collisions with the much smaller particles in the solvent, colloids perform Brownian motion: randomly directed movements that cause the particles to diffuse through the system. In principle, this motion allow the system of particles to explore all configurations available to them, sampling all of phase space according to the Boltzmann distribution. Analogous to molecular and atomic systems, colloidal systems can form disordered gas and liquid phases, as well as more ordered phases such as crystals, liquid crystals, or finite-sized aggregates. Since the particles form these phases based purely on their interactions and the Brownian motion that results from thermal fluctuations in their solvent, the process of forming these ordered structures is called self-assembly. In this thesis, we study the self-assembly of a variety of colloidal systems. We attempt to determine what structures can be expected to form, investigate the order and stability of these phases, and examine the nucleation of self-assembled crystals. To do this, we make use of computers to simulate the behavior of colloidal particles in suspension. Depending on the system under consideration, we perform either Monte Carlo simulations or event-driven molecular dynamics. In particular, we study the self-assembly of particles of several shapes in external electric or magnetic fields, the phase behavior of hard colloidal cubes, and the phase diagrams of charged colloidal spheres with a constant surface potential. Furthermore, we investigate the nucleation of binary hard sphere mixtures, the self-assembly of colloidal particles in evaporating emulsion droplets, and the formation of colloidal micelles. Where possible, we compare our results with experimental findings in similar systems.

  10. Probabilistic Analysis of Pattern Formation in Monotonic Self-Assembly.

    PubMed

    Moore, Tyler G; Garzon, Max H; Deaton, Russell J

    2015-01-01

    Inspired by biological systems, self-assembly aims to construct complex structures. It functions through piece-wise, local interactions among component parts and has the potential to produce novel materials and devices at the nanoscale. Algorithmic self-assembly models the product of self-assembly as the output of some computational process, and attempts to control the process of assembly algorithmically. Though providing fundamental insights, these computational models have yet to fully account for the randomness that is inherent in experimental realizations, which tend to be based on trial and error methods. In order to develop a method of analysis that addresses experimental parameters, such as error and yield, this work focuses on the capability of assembly systems to produce a pre-determined set of target patterns, either accurately or perhaps only approximately. Self-assembly systems that assemble patterns that are similar to the targets in a significant percentage are "strong" assemblers. In addition, assemblers should predominantly produce target patterns, with a small percentage of errors or junk. These definitions approximate notions of yield and purity in chemistry and manufacturing. By combining these definitions, a criterion for efficient assembly is developed that can be used to compare the ability of different assembly systems to produce a given target set. Efficiency is a composite measure of the accuracy and purity of an assembler. Typical examples in algorithmic assembly are assessed in the context of these metrics. In addition to validating the method, they also provide some insight that might be used to guide experimentation. Finally, some general results are established that, for efficient assembly, imply that every target pattern is guaranteed to be assembled with a minimum common positive probability, regardless of its size, and that a trichotomy exists to characterize the global behavior of typical efficient, monotonic self-assembly systems

  11. Probabilistic Analysis of Pattern Formation in Monotonic Self-Assembly

    PubMed Central

    Moore, Tyler G.; Garzon, Max H.; Deaton, Russell J.

    2015-01-01

    Inspired by biological systems, self-assembly aims to construct complex structures. It functions through piece-wise, local interactions among component parts and has the potential to produce novel materials and devices at the nanoscale. Algorithmic self-assembly models the product of self-assembly as the output of some computational process, and attempts to control the process of assembly algorithmically. Though providing fundamental insights, these computational models have yet to fully account for the randomness that is inherent in experimental realizations, which tend to be based on trial and error methods. In order to develop a method of analysis that addresses experimental parameters, such as error and yield, this work focuses on the capability of assembly systems to produce a pre-determined set of target patterns, either accurately or perhaps only approximately. Self-assembly systems that assemble patterns that are similar to the targets in a significant percentage are “strong” assemblers. In addition, assemblers should predominantly produce target patterns, with a small percentage of errors or junk. These definitions approximate notions of yield and purity in chemistry and manufacturing. By combining these definitions, a criterion for efficient assembly is developed that can be used to compare the ability of different assembly systems to produce a given target set. Efficiency is a composite measure of the accuracy and purity of an assembler. Typical examples in algorithmic assembly are assessed in the context of these metrics. In addition to validating the method, they also provide some insight that might be used to guide experimentation. Finally, some general results are established that, for efficient assembly, imply that every target pattern is guaranteed to be assembled with a minimum common positive probability, regardless of its size, and that a trichotomy exists to characterize the global behavior of typical efficient, monotonic self-assembly

  12. Direct Synthesis of Controlled-Size Nanospheres inside Nanocavities of Self-Organized Photopolymerizing Soft Oxometalates [PW12 O40 ]n (n=1100-7500).

    PubMed

    Das, Kousik; Roy, Soumyajit

    2015-09-01

    The unusual self-assembly of {(BMIm)2 (DMIm)[PW12 O40 ]}n (n=1100-7500) (BMIm=1-butyl-3-methylimidazolium, DMIm=3,3'-dimethyl-1,1'-diimidazolium) soft oxometalates (SOMs) with controlled size and a hollow nanocavity was exploited for the photochemical synthesis of polymeric nanospheres within the nanocavity of the SOM. The SOM vesicle has been characterized by using several techniques, including dynamic light scattering (DLS), static light scattering (SLS), attenuated total reflection (ATR) IR spectroscopy, Raman spectroscopy, microscopy, and zeta-potential analysis. The self-assembly and stabilization of this soft-oxometalate vesicle has been shown by means of counter-ion condensation. The immediate implication of such stabilization-the variation of the dielectric constant with the hydrodynamic radius of the vesicle-has been used to synthesize vesicles of controlled size. Such vesicles of varying size have been used as templates for polymerization reactions that produce polymeric spheres of controlled size. Direct evidence shows that the SOM behaves as a model heterogeneous catalytic system. Such surfactant- and initiator-free photochemical synthetic routes for obtaining uniform latex spheres could be used in the making of optical bandgap materials, inverse opals, and paints. PMID:26185037

  13. The impact of substrate interaction in directed self-assembly of symmetric diblock copolymer thin films

    NASA Astrophysics Data System (ADS)

    Seidel, Robert

    ) and size of process window. It also introduces an analysis technique for evaluating assembly kinetics with an emphasis on defect annihilation. The fifth chapter seeks to identify more thoroughly the root causes of LER in BCP line/space DSA by investigating a number of factors. The sixth and final full chapter describes initial success in the effort to extend the concepts of BCP DSA on patterned planar substrates to flexible or three-dimensional substrates (for roll-to-roll applications) by using functional layer-by-layer deposited films. Our final conclusion touches on the ideas of nucleation of self-assembled BCP structures and how they relate to kinetic pathways and timescales of assembly.

  14. Hierarchical self-assembly: Self-organized nanostructures in a nematically ordered matrix of self-assembled polymeric chains

    NASA Astrophysics Data System (ADS)

    Mubeena, Shaikh; Chatterji, Apratim

    2015-03-01

    We report many different nanostructures which are formed when model nanoparticles of different sizes (diameter σn) are allowed to aggregate in a background matrix of semiflexible self-assembled polymeric wormlike micellar chains. The different nanostructures are formed by the dynamical arrest of phase-separating mixtures of micellar monomers and nanoparticles. The different morphologies obtained are the result of an interplay of the available free volume, the elastic energy of deformation of polymers, the density (chemical potential) of the nanoparticles in the polymer matrix, and, of course, the ratio of the size of self-assembling nanoparticles and self-avoidance diameter of polymeric chains. We have used a hybrid semi-grand-canonical Monte Carlo simulation scheme to obtain the (nonequilibrium) phase diagram of the self-assembled nanostructures. We observe rodlike structures of nanoparticles which get self-assembled in the gaps between the nematically ordered chains, as well as percolating gel-like network of conjoined nanotubes. We also find a totally unexpected interlocked crystalline phase of nanoparticles and monomers, in which each crystal plane of nanoparticles is separated by planes of perfectly organized polymer chains. We identified the condition which leads to such interlocked crystal structure. We suggest experimental possibilities of how the results presented in this paper could be used to obtain different nanostructures in the laboratory.

  15. A Case Study of the Likes and Dislikes of DNA and RNA in Self-Assembly.

    PubMed

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

    2015-12-01

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

  16. Synthetic Molecular Machines for Active Self-Assembly: Prototype Algorithms, Designs, and Experimental Study

    NASA Astrophysics Data System (ADS)

    Dabby, Nadine L.

    behaviors. This class of behaviors includes any behavior where a passive physical system simply does not have enough physical energy to perform the specified tasks in the requisite amount of time. As we will demonstrate and prove, a sufficiently expressive implementation of an "active" molecular self-assembly approach can achieve these behaviors. Using an external source of fuel solves part of the problem, so the system is not "energetically incomplete." But the programmable system also needs to have sufficient expressive power to achieve the specified behaviors. Perhaps surprisingly, some of these systems do not even require Turing completeness to be sufficiently expressive. Building on a large variety of work by other scientists in the fields of DNA nanotechnology, chemistry and reconfigurable robotics, this thesis introduces several research contributions in the context of active self-assembly. We show that simple primitives such as insertion and deletion are able to generate complex and interesting results such as the growth of a linear polymer in logarithmic time and the ability of a linear polymer to treadmill. To this end we developed a formal model for active-self assembly that is directly implementable with DNA molecules. We show that this model is computationally equivalent to a machine capable of producing strings that are stronger than regular languages and, at most, as strong as context-free grammars. This is a great advance in the theory of active self-assembly as prior models were either entirely theoretical or only implementable in the context of macro-scale robotics. We developed a chain reaction method for the autonomous exponential growth of a linear DNA polymer. Our method is based on the insertion of molecules into the assembly, which generates two new insertion sites for every initial one employed. The building of a line in logarithmic time is a first step toward building a shape in logarithmic time. We demonstrate the first construction of a synthetic

  17. Switching in the self-assembly of tobacco mosaic virus.

    PubMed

    Caspar, D L; Namba, K

    1990-01-01

    Experimental observations on the structure and physicochemical properties of TMV protein assemblies have led to a fundamental switch in the model of the self-assembly process: rather than being nucleated by the hypothetical two-layer disk, virus assembly appears to be initiated by interaction of the specific RNA sequence with a short helical aggregate of the coat protein arranged as in the virus. Formation of the 20s nucleating aggregate involves the binding of an average of half a proton per protein subunit. This proton-binding site can be identified with the carboxyl-carboxylate pair that is formed between top and bottom protein surfaces at a radius of 58 A in the virus helix. Because the 20s aggregate consists of about two helical turns, only one carboxyl-carboxylate pair will be formed between each top-bottom pair of protein subunits. Limitation of the length of the 20s helical aggregate at neutral pH can be accounted for by disorder of the inner loop of the protein chain, due to electrostatic repulsion among the carboxyl groups that form the anomalous proton-binding site at 25 A radius in the ordered virus structure. To grow beyond two to three turns, inner loops of the protein at the interior of the helix must be ordered in the close-packed arrangement. The electrostatic repulsion opposing this ordering can be overcome by binding of the viral RNA at neutral pH, by calcium binding, or by proton binding in slightly acid solution. Virus disassembly upon infection appears to result from the low intracellular calcium and proton concentration compared to the extracellular environment, which increases the electrostatic repulsion among the negatively charged groups involved in calcium and proton binding, thereby allowing cellular ribosomes to competitively bind the viral RNA. Disk aggregates of TMV protein, which form at high ionic strength in alkaline solution, do not appear to be involved in virus assembly. The stacked-disc aggregate, which was previously presumed

  18. Self-assembly of hybrid structures on nano templates

    NASA Astrophysics Data System (ADS)

    Wang, Ruomiao

    This dissertation describes the investigation on the synthesis of hybrid structures on nano-templates. Fabrication of molecular nano-patterns of organic amphiphiles (e.g. fatty acids) by self-assembly has been discussed here, and their application as templates for two-dimensional in situ synthesis of metal soap molecular pattern has been demonstrated. The synthesis of nanoparticle---nanorod hybrid structure represents another effort to achieve hybrid materials. Therefore, methods to create complex inorganic---organic nano---hybrid are provided by this work. AFM disclosed the pattern structures of the self-assembled monolayers as designed nanoscaled patterns. It is observed two pattern periodicities reflecting the head-to-head and head-to-tail molecular assembly tendencies of the fatty acids and their dependence on the molecular structure and chain length, which exhibits a linear increase in the periodicity with an increasing molecular chain length. The investigation on molecular patterns of self-assembled monolayers of metal arachidates on graphite by AFM and FTIR is described. Metal arachidate self-assemblies show similar stripe pattern and periodicities as those of arachidic acid. The monolayer structure is mainly dictated by graphite, while the type of metal ions mainly affects the domain size, shape and regularity. The results of AFM and FTIR are correlated to the Irving-Williams Series, which predicts bond strength of the metal ions to ligands. The spin coated films from binary solutions of nanoparticles and fatty acids with different chain lengths (Even number of carbon, C18--C26), have been used to study the effect of nanoparticles on self-assemble pattern of fatty acids. C18--C22 acids formed uniform nanorods attached and induced by nanoparticles, while the self-assembled stripe patterns of C24 and C26 were unaffected by the presence of nanoparticles. The nanoparticles were aligned on C26 monolayer. The seeded nucleation mechanism has been studied by AFM

  19. Controlled fabrication of silicon nanowires via nanosphere lithograph and metal assisted chemical etching.

    PubMed

    Sun, Bo; Shi, Tielin; Sheng, Wenjun; Liao, Guanglan

    2013-08-01

    We investigated the controlled fabrication of uniform vertical aligned silicon nanowires with desired length, diameter and location by combining nanosphere lithograph and metal assisted chemical etching techniques. The close-packed polystyrene nanospheres array was obtained by self-assemble technique, followed by reactive ion etching to acquire a non-close-packed monolayer template. Subsequently, the template was used to create a metal film with nanoholes array, which enable the controlled fabrication of ordered silicon nanowires via metal assisted chemical etching technique. By adjusting the monolayer of polystyrene nanospheres and the conditions for the metal assisted chemical etching, we obtained uniform distributed silicon nanowires with desired morphology. The aspect ratio of the silicon nanowires can reach to about 86:1. Furthermore, we have obtained the double-layer silicon nanowires by slight modifying the process. The influences of various conditions during etching were also discussed for improving the controlled fabrication.

  20. An information-bearing seed for nucleating algorithmic self-assembly.

    PubMed

    Barish, Robert D; Schulman, Rebecca; Rothemund, Paul W K; Winfree, Erik

    2009-04-14

    Self-assembly creates natural mineral, chemical, and biological structures of great complexity. Often, the same starting materials have the potential to form an infinite variety of distinct structures; information in a seed molecule can determine which form is grown as well as where and when. These phenomena can be exploited to program the growth of complex supramolecular structures, as demonstrated by the algorithmic self-assembly of DNA tiles. However, the lack of effective seeds has limited the reliability and yield of algorithmic crystals. Here, we present a programmable DNA origami seed that can display up to 32 distinct binding sites and demonstrate the use of seeds to nucleate three types of algorithmic crystals. In the simplest case, the starting materials are a set of tiles that can form crystalline ribbons of any width; the seed directs assembly of a chosen width with >90% yield. Increased structural diversity is obtained by using tiles that copy a binary string from layer to layer; the seed specifies the initial string and triggers growth under near-optimal conditions where the bit copying error rate is <0.2%. Increased structural complexity is achieved by using tiles that generate a binary counting pattern; the seed specifies the initial value for the counter. Self-assembly proceeds in a one-pot annealing reaction involving up to 300 DNA strands containing >17 kb of sequence information. In sum, this work demonstrates how DNA origami seeds enable the easy, high-yield, low-error-rate growth of algorithmic crystals as a route toward programmable bottom-up fabrication.

  1. Self Assembled Structures by Directional Solidification of Eutectics

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.; Sayir, Ali

    2004-01-01

    Interest in ordered porous structures has grown because of there unique properties such as photonic bandgaps, high backing packing density and high surface to volume ratio. Inspired by nature, biometric strategies using self assembled organic molecules dominate the development of hierarchical inorganic structures. Directional solidification of eutectics (DSE) also exhibit self assembly characteristics to form hierarchical metallic and inorganic structures. Crystallization of diphasic materials by DSE can produce two dimensional ordered structures consisting of rods or lamella. By selective removal of phases, DSE is capable to fabricate ordered pore arrays or ordered pin arrays. Criteria and limitations to fabricate hierarchical structures will be presented. Porous structures in silicon base alloys and ceramic systems will be reported.

  2. Stable doping of carbon nanotubes via molecular self assembly

    SciTech Connect

    Lee, B.; Chen, Y.; Podzorov, V.; Cook, A.; Zakhidov, A.

    2014-10-14

    We report a novel method for stable doping of carbon nanotubes (CNT) based on methods of molecular self assembly. A conformal growth of a self-assembled monolayer of fluoroalkyl trichloro-silane (FTS) at CNT surfaces results in a strong increase of the sheet conductivity of CNT electrodes by 60–300%, depending on the CNT chirality and composition. The charge carrier mobility of undoped partially aligned CNT films was independently estimated in a field-effect transistor geometry (~100 cm²V⁻¹s⁻¹). The hole density induced by the FTS monolayer in CNT sheets is estimated to be ~1.8 ×10¹⁴cm⁻². We also show that FTS doping of CNT anodes greatly improves the performance of organic solar cells. This large and stable doping effect, easily achieved in large-area samples, makes this approach very attractive for applications of CNTs in transparent and flexible electronics.

  3. Protein-directed self-assembly of a fullerene crystal.

    PubMed

    Kim, Kook-Han; Ko, Dong-Kyun; Kim, Yong-Tae; Kim, Nam Hyeong; Paul, Jaydeep; Zhang, Shao-Qing; Murray, Christopher B; Acharya, Rudresh; DeGrado, William F; Kim, Yong Ho; Grigoryan, Gevorg

    2016-04-26

    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design.

  4. Directed self-assembly of nanoparticles for nanomotors.

    PubMed

    Dong, Bin; Zhou, Tian; Zhang, Hui; Li, Christopher Y

    2013-06-25

    We report, for the first time, the design and fabrication of a nanoparticle-based nanomotor system by directly self-assembling nanoparticles onto functional, nanometer-thin lamellae, such as polymer single crystals. Tens of thousands of judiciously selected nanoparticles (gold, iron oxide, and platinum nanoparticles) with sizes ranging from <5 to a few tens of nanometers have been introduced into a single nanomotor via directed self-assembly. The resulting nanomotor realizes functions such as autonomous movement, remote control, and cargo transportation by utilizing the advantages offered by nanoparticles, such as the small size, surface plasmon resonance, catalytic and magnetic properties. Because of the structural and functional versatility of nanoparticles, the facile fabricating procedure, and the potential for mass production, our strategy shows a key step toward the development of next generation multifunctional nanomotors.

  5. Self-assembly of amorphous calcium carbonate microlens arrays

    PubMed Central

    Lee, Kyubock; Wagermaier, Wolfgang; Masic, Admir; Kommareddy, Krishna P.; Bennet, Mathieu; Manjubala, Inderchand; Lee, Seung-Woo; Park, Seung B.; Cölfen, Helmut; Fratzl, Peter

    2012-01-01

    Biological materials are often based on simple constituents and grown by the principle of self-assembly under ambient conditions. In particular, biomineralization approaches exploit efficient pathways of inorganic material synthesis. There is still a large gap between the complexity of natural systems and the practical utilization of bioinspired formation mechanisms. Here we describe a simple self-assembly route leading to a CaCO3 microlens array, somewhat reminiscent of the brittlestars' microlenses, with uniform size and focal length, by using a minimum number of components and equipment at ambient conditions. The formation mechanism of the amorphous CaCO3 microlens arrays was elucidated by confocal Raman spectroscopic imaging to be a two-step growth process mediated by the organic surfactant. CaCO3 microlens arrays are easy to fabricate, biocompatible and functional in amorphous or more stable crystalline forms. This shows that advanced optical materials can be generated by a simple mineral precipitation. PMID:22395616

  6. Environmental and Sensing Applications of Molecular Self-Assembly

    SciTech Connect

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

    2004-03-31

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

  7. Amphipathicity and self-assembly behavior of amphiphilic alginate esters.

    PubMed

    Yang, Ji Sheng; Zhou, Qi Quan; He, Wen

    2013-01-30

    Amphiphilic alginate esters (Alg-C(n)) with different degree of substitution (DS) and hydrophobic alkyl length were synthesized by the reaction between partially protonated sodium alginate and aliphatic alcohols (octanol, dodecanol or hexadecanol) and characterized by conventional methods. The critical micelles concentration (CMC) of Alg-C(n) was determined by measuring the fluorescence intensity of pyrene as a fluorescent probe, conductance and surface tension (SFT). Formation and characteristics of the self-assembly micelles of Alg-C(n) were studied by transmission electron microscopy (TEM) and Zetasizer Nano Series method. The results indicate that CMC value and the self-assembled micelle size decreased with the increasing of the hydrophobic alkyl chain length, as the DS of Alg-C(n) is similar.

  8. Self-Assembly of Graphene on Carbon Nanotube Surfaces

    PubMed Central

    Li, Kaiyuan; Eres, Gyula; Howe, Jane; Chuang, Yen-Jun; Li, Xufan; Gu, Zhanjun; Zhang, Litong; Xie, Sishen; Pan, Zhengwei

    2013-01-01

    The rolling up of a graphene sheet into a tube is a standard visualization tool for illustrating carbon nanotube (CNT) formation. However, the actual processes of rolling up graphene sheets into CNTs in laboratory syntheses have never been demonstrated. Here we report conformal growth of graphene by carbon self-assembly on single-wall and multi-wall CNTs using chemical vapor deposition (CVD) of methane without the presence of metal catalysts. The new graphene layers roll up into seamless coaxial cylinders encapsulating the existing CNTs, but their adhesion to the primary CNTs is weak due to the existence of lattice misorientation. Our study shows that graphene nucleation and growth by self-assembly of carbon on the inactive carbon basal plane of CNTs occurs by a new mechanism that is markedly different from epitaxial growth on metal surfaces, opening up the possibility of graphene growth on many other non-metal substrates by simple methane CVD. PMID:23912638

  9. Self-assembled and nanostructured siRNA delivery systems.

    PubMed

    Jeong, Ji Hoon; Park, Tae Gwan; Kim, Sun Hwa

    2011-09-01

    A wide range of organic and inorganic materials have been used in the development of nano-scale self-assembling gene delivery systems to improve the therapeutic efficacy of nucleic acid drugs. Small interfering RNA (siRNA) has recently been recognized as a promising and potent nucleic acid medicine for the treatment of incurable genetic disorders including cancer; however, siRNA-based therapeutics suffer from the same delivery problems as conventional nucleic acid drugs such as plasmid DNA and antisense oligonucleotides. Many of the delivery strategies developed for nucleic acid drugs have been applied to siRNA therapeutics, but they have not produced satisfactory in vivo gene silencing efficiencies to warrant clinical trials. This review discusses recent progress in the development of self-assembled and nanostructured delivery systems for efficient siRNA-induced gene silencing and their potential application in clinical settings. PMID:21424157

  10. Self-Assembled Magnetic Surface Swimmers: Theoretical Model

    NASA Astrophysics Data System (ADS)

    Aranson, Igor; Belkin, Maxim; Snezhko, Alexey

    2009-03-01

    The mechanisms of self-propulsion of living microorganisms are a fascinating phenomenon attracting enormous attention in the physics community. A new type of self-assembled micro-swimmers, magnetic snakes, is an excellent tool to model locomotion in a simple table-top experiment. The snakes self-assemble from a dispersion of magnetic microparticles suspended on the liquid-air interface and subjected to an alternating magnetic field. Formation and dynamics of these swimmers are captured in the framework of theoretical model coupling paradigm equation for the amplitude of surface waves, conservation law for the density of particles, and the Navier-Stokes equation for hydrodynamic flows. The results of continuum modeling are supported by hybrid molecular dynamics simulations of magnetic particles floating on the surface of fluid.

  11. Protein-directed self-assembly of a fullerene crystal

    NASA Astrophysics Data System (ADS)

    Kim, Kook-Han; Ko, Dong-Kyun; Kim, Yong-Tae; Kim, Nam Hyeong; Paul, Jaydeep; Zhang, Shao-Qing; Murray, Christopher B.; Acharya, Rudresh; Degrado, William F.; Kim, Yong Ho; Grigoryan, Gevorg

    2016-04-01

    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design.

  12. Calixarene-encapsulated nanoparticles: self-assembly into functional nanomaterials†

    PubMed Central

    Wei, Alexander

    2007-01-01

    Calixarenes are excellent surfactants for enhancing the dispersion and self-assembly of metal nanoparticles into well-defined structures, particularly those with unit length scales in the 10–100 nm size range. Particles within these ensembles are strongly coupled, giving rise to unique collective optical or magnetic properties. The self-assembled nanostructures described in this feature article include 2D arrays of colloidal Au nanoparticles with size-dependent plasmonic responses, and sub-100 nm Co nanoparticle rings with chiral magnetic states. These nanoparticle assemblies may be further developed for applications in chemical sensing based on surface-enhanced Raman scattering (SERS) and as binary elements for nonvolatile memory, respectively. PMID:16582988

  13. Electrostatically Directed Self-Assembly of Ultrathin Supramolecular Polymer Microcapsules

    PubMed Central

    Parker, Richard M; Zhang, Jing; Zheng, Yu; Coulston, Roger J; Smith, Clive A; Salmon, Andrew R; Yu, Ziyi; Scherman, Oren A; Abell, Chris

    2015-01-01

    Supramolecular self-assembly offers routes to challenging architectures on the molecular and macroscopic scale. Coupled with microfluidics it has been used to make microcapsules—where a 2D sheet is shaped in 3D, encapsulating the volume within. In this paper, a versatile methodology to direct the accumulation of capsule-forming components to the droplet interface using electrostatic interactions is described. In this approach, charged copolymers are selectively partitioned to the microdroplet interface by a complementary charged surfactant for subsequent supramolecular cross-linking via cucurbit[8]uril. This dynamic assembly process is employed to selectively form both hollow, ultrathin microcapsules and solid microparticles from a single solution. The ability to dictate the distribution of a mixture of charged copolymers within the microdroplet, as demonstrated by the single-step fabrication of distinct core–shell microcapsules, gives access to a new generation of innovative self-assembled constructs. PMID:26213532

  14. Self-Assembled Silicon Nanotubes under Supercritically Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Tang, Y. H.; Pei, L. Z.; Chen, Y. W.; Guo, C.

    2005-09-01

    Self-assembled silicon nanotubes with one-dimensional structure have been synthesized from silicon monoxide powder under supercritically hydrothermal conditions with a temperature of 470 °C and a pressure of 6.8 MPa. The silicon nanotubes were identified by transmission electron microscopy and high-resolution transmission electron microscopy. The results show that the silicon nanotubes (SiNT) have closed caps. The structures of the silicon nanotubes are hollow inner pore, crystalline silicon wall layers with a 0.31 nm interplanar spacing and 2-3 nm amorphous silica outer layers. Pure crystalline silicon nanotubes survive after etching the silicon nanotubes with 5% HF acid for enough time to imply that the self-assembled silicon nanotubes are stable. A possible theoretical reason for the growth of SiNTs from SiO under supercritically hydrothermal conditions was also proposed.

  15. Transport and photodetection in self-assembled semiconductor quantum dots.

    PubMed

    Razeghi, M; Lim, H; Tsao, S; Szafraniec, J; Zhang, W; Mi, K; Movaghar, B

    2005-02-01

    A great step forward in science and technology was made when it was discovered that lattice mismatch can be used to grow highly ordered, artificial atom-like structures called self-assembled quantum dots. Several groups have in the meantime successfully demonstrated useful infrared photodetection devices which are based on this technology. The new physics is fascinating, and there is no doubt that many new applications will be found when we have developed a better understanding of the underlying physical processes, and in particular when we have learned how to integrate the exciting new developments made in nanoscopic addressing and molecular self-assembly methods with semiconducting dots. In this paper we examine the scientific and technical questions encountered in current state of the art infrared detector technology and suggest ways of overcoming these difficulties. Promoting simple physical pictures, we focus in particular on the problem of high temperature detector operation and discuss the origin of dark current, noise, and photoresponse.

  16. Linker-Mediated Self-Assembly Dynamics of Charged Nanoparticles.

    PubMed

    Lin, Guanhua; Chee, See Wee; Raj, Sanoj; Král, Petr; Mirsaidov, Utkur

    2016-08-23

    Using in situ liquid cell transmission electron microscopy (TEM), we visualized a stepwise self-assembly of surfactant-coated and hydrated gold nanoparticles (NPs) into linear chains or branched networks. The NP binding is facilitated by linker molecules, ethylenediammonium, which form hydrogen bonds with surfactant molecules of neighboring NPs. The observed spacing between bound neighboring NPs, ∼15 Å, matches the combined length of two surfactants and one linker molecule. Molecular dynamics simulations reveal that for lower concentrations of linkers, NPs with charged surfactants cannot be fully neutralized by strongly binding divalent linkers, so that NPs carry higher effective charges and tend to form chains, due to poor screening. The highly polar NP surfaces polarize and partly immobilize nearby water molecules, which promotes NPs binding. The presented experimental and theoretical approach allows for detail observation and explanation of self-assembly processes in colloidal nanosystems. PMID:27494560

  17. Self-assembled photonic crystals for a chemical sensing

    NASA Astrophysics Data System (ADS)

    Bourdillon, C.; Gam Derouich, S.; Daney de Marcillac, W.; Coolen, L.; Maître, A.; Mangeney, C.; Schwob, C.

    2016-03-01

    As they allow the control of light propagation, photonic crystals find many fields of application. Among them, self-assembled 3D-photonic crystals are ordered at the nanometric scale over centrimetric areas. Furthermore, self-assembly allows the design of complexes structures leading, for example, to the controlled disruption of the crystal periodicity (called defect) and the appearance of permitted optical frequency bands within the photonic bandgap. Light frequencies included in the corresponding passband are then localized in the defect allowing manipulation of nano-emitters fluorescence. We present the fabrication and the optical characterization of a heterostructure composed of a sputtered silica layer sandwiched between two silica opals. We show by photoluminescence measurements than this structure strongly modifies the transmitted fluorescence of nanocrystals.

  18. Biomolecular decision-making process for self assembly.

    SciTech Connect

    Osbourn, Gordon Cecil

    2005-01-01

    The brain is often identified with decision-making processes in the biological world. In fact, single cells, single macromolecules (proteins) and populations of molecules also make simple decisions. These decision processes are essential to survival and to the biological self-assembly and self-repair processes that we seek to emulate. How do these tiny systems make effective decisions? How do they make decisions in concert with a cooperative network of other molecules or cells? How can we emulate the decision-making behaviors of small-scale biological systems to program and self-assemble microsystems? This LDRD supported research to answer these questions. Our work included modeling and simulation of protein populations to help us understand, mimic, and categorize molecular decision-making mechanisms that nonequilibrium systems can exhibit. This work is an early step towards mimicking such nanoscale and microscale biomolecular decision-making processes in inorganic systems.

  19. Self-assembly of nanomaterials at fluid interfaces.

    PubMed

    Toor, Anju; Feng, Tao; Russell, Thomas P

    2016-05-01

    Recent developments in the field of the self-assembly of nanoscale materials such as nanoparticles, nanorods and nanosheets at liquid/liquid interfaces are reviewed. Self-assembly behavior of both biological and synthetic particles is discussed. For biological nanoparticles, the nanoparticle assembly at fluid interfaces provides a simple route for directing nanoparticles into 2D or 3D constructs with hierarchical ordering. The interfacial assembly of single-walled carbon nanotubes (SWCNTs) at liquid interfaces would play a key role in applications such as nanotube fractionation, flexible electronic thin-film fabrication and synthesis of porous SWCNT/polymer composites foams. Liquids can be structured by the jamming of nanoparticle surfactants at fluid interfaces. By controlling the interfacial packing of nanoparticle surfactants using external triggers, a new class of materials can be generated that combines the desirable characteristics of fluids such as rapid transport of energy carriers with the structural stability of a solid. PMID:27233643

  20. Self-assembly of graphene on carbon nanotube surfaces.

    PubMed

    Li, Kaiyuan; Eres, Gyula; Howe, Jane; Chuang, Yen-Jun; Li, Xufan; Gu, Zhanjun; Zhang, Litong; Xie, Sishen; Pan, Zhengwei

    2013-01-01

    The rolling up of a graphene sheet into a tube is a standard visualization tool for illustrating carbon nanotube (CNT) formation. However, the actual processes of rolling up graphene sheets into CNTs in laboratory syntheses have never been demonstrated. Here we report conformal growth of graphene by carbon self-assembly on single-wall and multi-wall CNTs using chemical vapor deposition (CVD) of methane without the presence of metal catalysts. The new graphene layers roll up into seamless coaxial cylinders encapsulating the existing CNTs, but their adhesion to the primary CNTs is weak due to the existence of lattice misorientation. Our study shows that graphene nucleation and growth by self-assembly of carbon on the inactive carbon basal plane of CNTs occurs by a new mechanism that is markedly different from epitaxial growth on metal surfaces, opening up the possibility of graphene growth on many other non-metal substrates by simple methane CVD. PMID:23912638

  1. Increase in stability of cellulase immobilized on functionalized magnetic nanospheres

    NASA Astrophysics Data System (ADS)

    Zhang, Wenjuan; Qiu, Jianhui; Feng, Huixia; Zang, Limin; Sakai, Eiichi

    2015-02-01

    Functionalized magnetic nanospheres were prepared by co-condensation of tetraethylorthosilicate with three different amino-silanes: 3-(2-aminoethylamino propyl)-triethoxysilane (AEAPTES), 3-(2-aminoethylamino propyl)-trimethoxysilane (AEAPTMES) and 3-aminopropyltriethoxysilane (APTES). Then three functionalized magnetic nanospheres were used as supports for immobilization of cellulase. The three functionalized magnetic nanospheres with core-shell morphologies exhibited higher capacity for cellulase immobilization than unfunctionalized magnetic nanospheres. The increasing of surface charge of functionalized magnetic nanospheres leads to an enhancement of the capacity of cellulase immobilization. Particularly, AEAPTMES with methoxy groups was favored to be hydrolyzed and grafted on unfunctionalized magnetic nanospheres than the others. AEAPTMES functionalized magnetic nanospheres with the highest zeta potential (29 mV) exhibited 87% activity recovery and the maximum amount of immobilized cellulase was 112 mg/g support at concentration of initial cellulase of 8 mg/mL. Immobilized cellulase on AEAPTMES functionalized magnetic nanospheres had higher temperature stability and broader pH stability than other immobilized cellulases and free cellulase. In particular, it can be used in about 40 °C, demonstrating the potential of biofuel production using this immobilized cellulase.

  2. Lighting up cells with lanthanide self-assembled helicates

    PubMed Central

    Bünzli, Jean-Claude G.

    2013-01-01

    Lanthanide bioprobes and bioconjugates are ideal luminescent stains in view of their low propensity to photobleaching, sharp emission lines and long excited state lifetimes permitting time-resolved detection for enhanced sensitivity. We show here how the interplay between physical, chemical and biochemical properties allied to microfluidics engineering leads to self-assembled dinuclear lanthanide luminescent probes illuminating live cells and selectively detecting biomarkers expressed by cancerous human breast cells. PMID:24511387

  3. Sequential programmable self-assembly: Role of cooperative interactions

    DOE PAGES

    Jonathan D. Halverson; Tkachenko, Alexei V.

    2016-03-04

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

  4. Design of Controllable Bio-Inspired Chiroptic Self-Assemblies.

    PubMed

    Tao, Kai; Jacoby, Guy; Burlaka, Luba; Beck, Roy; Gazit, Ehud

    2016-09-12

    Modulation of chiroptics, chiral phenomena of the optical properties, is pivotal in a variety of advanced applications, including chirality-specific biosensing and photonic switches. One of the most effective methods for achieving this control is assembly of the optical moieties into chiral nanostructures. Lipopeptide self-assemblies have been extensively employed as soft templates to organize composites into low-dimensional superstructures due to their rigidity and ease of functionalization. Therefore, an appealing approach is to provide chiroptical control by using lipopeptide self-assemblies as templates to assemble chromophores. Herein, two lipopeptidic molecules, namely, C14-FFK and C14-FK, composed of phenylalanine and lysine residues conjugated to a myristic acid chain, were custom-designed. Spectroscopic and microscopic characterizations indicated that C14-FFK self-assembled to wide, slightly left-handed nanoribbons, while C14-FK formed narrow, intensely right-handed nanofibers. The different chirality was derived from the distinct self-assembly driving forces, especially the molecular bending dimensions. These superstructures presented an ideal capability to serve as soft templates to assemble porphyrin (ZnTPyP) through noncovalent electrostatic attractive interactions, or assemble the phenolic groups through covalent conjugation to peptide backbones. The distinct exciton coupling of the chromophores allowed their achiral optics to become chiral, showing negative Cotton effect when templated by nanoribbons and positive Cotton effect with nanofibers as templates. Following replacement of the lipopeptides with their d-type enantiomers, the handedness of the superstructures and the associated chiroptics were reversed and presented "mirror" symmetric CD signals to their l-type counterparts. These findings may pave the way to the formation of morphologically and chioptically controllable nanomaterials. PMID:27461453

  5. Recent progress on patchy colloids and their self-assembly

    NASA Astrophysics Data System (ADS)

    Yi, Gi-Ra; Pine, David J.; Sacanna, Stefano

    2013-05-01

    ‘Patchy colloids’ is a term that has been recently introduced to indicate specially engineered particles with directional interactions. Based on this concept, a ‘bottom-up’ process for fabricating functional materials and devices has been envisioned, which employs colloidal building blocks and mimics molecular bonding. This article reviews recent progress which has been made in the synthesis and self-assembly of patchy colloids and discusses future directions as well as unresolved challenges.

  6. Controlling guest-host interactions in self-assembled materials

    NASA Astrophysics Data System (ADS)

    Steinbeck, Christian Alexander

    Aqueous solutions of self-assembling macromolecules can be found in many industrial formulations, as well as in many living organisms. Regardless of the specific system, the self-assembling macromolecules are rarely found in the absence of other solutes or guest species. Such components may include fragrance molecules incorporated into block-copolymer micelles for use in detergents, dyes included in micellar precursor solutions for the synthesis of mesostructured silica-block copolymer composites, or specifically designed additives for controlling protein folding and activity. A detailed understanding of the structures and dynamic molecular interactions among the various species in solution and their influences on macromolecule aggregation and phase behaviors is of paramount importance for designing systems with improved properties and performance. Unambiguous measurements of the loci of interaction and solubilization of small molecule species (e.g., dyes or surfactants) within self-assembling block-copolymer species or proteins in aqueous solutions have been established. This has been achieved by exploiting powerful correlative multidimensional nuclear magnetic resonance (NMR) spectroscopy techniques, including pulsed-field-gradient diffusion measurements, which provide detailed molecular insights into a variety of heterogeneous self-assembled systems. Furthermore, these insights and measurements enable the solution conditions to be established that permit the control and release of such guest molecules from association with macromolecular carrier species into the surrounding solution. Specifically, the use of temperature to control the distribution of porphyrin guest-species in a block-copolymer host and the light-dependent folding and unfolding of bovine serum albumin through varying interactions with an azo-benzene functionalized surfactant are demonstrated. In the absence of long-range order in these complex systems, advanced NMR spectroscopy methods provide

  7. The position of hydrophobic residues tunes peptide self-assembly.

    PubMed

    Bortolini, Christian; Liu, Lei; Gronewold, Thomas M A; Wang, Chen; Besenbacher, Flemming; Dong, Mingdong

    2014-08-21

    The final structure and properties of synthetic peptides mainly depend on their sequence composition and experimental conditions. This work demonstrates that a variation in the positions of hydrophobic residues within a peptide sequence can tune the self-assembly. Techniques employed are atomic force microscopy, transmission electron microscopy and an innovative method based on surface acoustic waves. In addition, a systematic investigation on pH dependence was carried out by utilizing constant experimental parameters. PMID:24995505

  8. Self-assembly of double helical nanostructures inside carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Lv, Cheng; Xue, Qingzhong; Shan, Meixia; Jing, Nuannuan; Ling, Cuicui; Zhou, Xiaoyan; Jiao, Zhiyong; Xing, Wei; Yan, Zifeng

    2013-05-01

    We use molecular dynamics (MD) simulations to show that a DNA-like double helix of two poly(acetylene) (PA) chains can form inside single-walled carbon nanotubes (SWNTs). The computational results indicate that SWNTs can activate and guide the self-assembly of polymer chains, allowing them to adopt a helical configuration in a SWNT through the combined action of the van der Waals potential well and the π-π stacking interaction between the polymer and the inner surface of SWNTs. Meanwhile both the SWNT size and polymer chain stiffness determine the outcome of the nanostructure. Furthermore, we also found that water clusters encourage the self-assembly of PA helical structures in the tube. This molecular model may lead to a better understanding of the formation of a double helix biological molecule inside SWNTs. Alternatively, it could form the basis of a novel nanoscale material by utilizing the `empty' spaces of SWNTs.We use molecular dynamics (MD) simulations to show that a DNA-like double helix of two poly(acetylene) (PA) chains can form inside single-walled carbon nanotubes (SWNTs). The computational results indicate that SWNTs can activate and guide the self-assembly of polymer chains, allowing them to adopt a helical configuration in a SWNT through the combined action of the van der Waals potential well and the π-π stacking interaction between the polymer and the inner surface of SWNTs. Meanwhile both the SWNT size and polymer chain stiffness determine the outcome of the nanostructure. Furthermore, we also found that water clusters encourage the self-assembly of PA helical structures in the tube. This molecular model may lead to a better understanding of the formation of a double helix biological molecule inside SWNTs. Alternatively, it could form the basis of a novel nanoscale material by utilizing the `empty' spaces of SWNTs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33157h

  9. Nucleation of apatite crystals in vitro by self-assembled dentin matrix protein 1

    NASA Astrophysics Data System (ADS)

    He, Gen; Dahl, Tom; Veis, Arthur; George, Anne

    2003-08-01

    Bones and teeth are biocomposites that require controlled mineral deposition during their self-assembly to form tissues with unique mechanical properties. Acidic extracellular matrix proteins play a pivotal role during biomineral formation. However, the mechanisms of protein-mediated mineral initiation are far from understood. Here we report that dentin matrix protein 1 (DMP1), an acidic protein, can nucleate the formation of hydroxyapatite in vitro in a multistep process that begins by DMP1 binding calcium ions and initiating mineral deposition. The nucleated amorphous calcium phosphate precipitates ripen and nanocrystals form. Subsequently, these expand and coalesce into microscale crystals elongated in the c-axis direction. Characterization of the functional domains in DMP1 demonstrated that intermolecular assembly of acidic clusters into a β-sheet template was essential for the observed mineral nucleation. Protein-mediated initiation of nanocrystals, as discussed here, might provide a new methodology for constructing nanoscale composites by self-assembly of polypeptides with tailor-made peptide sequences.

  10. Self-assembled amyloid fibrils with controllable conformational heterogeneity

    PubMed Central

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-01-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled. PMID:26592772

  11. Self-assembled amyloid fibrils with controllable conformational heterogeneity.

    PubMed

    Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Lee, Chang Young; Eom, Kilho; Kwon, Taeyun

    2015-01-01

    Amyloid fibrils are a hallmark of neurodegenerative diseases and exhibit a conformational diversity that governs their pathological functions. Despite recent findings concerning the pathological role of their conformational diversity, the way in which the heterogeneous conformations of amyloid fibrils can be formed has remained elusive. Here, we show that microwave-assisted chemistry affects the self-assembly process of amyloid fibril formation, which results in their conformational heterogeneity. In particular, microwave-assisted chemistry allows for delicate control of the thermodynamics of the self-assembly process, which enabled us to tune the molecular structure of β-lactoglobulin amyloid fibrils. The heterogeneous conformations of amyloid fibrils, which can be tuned with microwave-assisted chemistry, are attributed to the microwave-driven thermal energy affecting the electrostatic interaction during the self-assembly process. Our study demonstrates how microwave-assisted chemistry can be used to gain insight into the origin of conformational heterogeneity of amyloid fibrils as well as the design principles showing how the molecular structures of amyloid fibrils can be controlled. PMID:26592772

  12. Self-assembled magnetic filter for highly efficient immunomagnetic separation.

    PubMed

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

    2011-01-01

    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. PMID:20949198

  13. Self-assembled polymer nanocomposites and their networks

    NASA Astrophysics Data System (ADS)

    Patil, Nitin Vikas

    This dissertation describes new routes to synthesize polymer nanocomposite networks via self-assembly. Polymerizable structure directing agents (referred to as surfmers) obtained by end-group functionalization preserves the structure-directing capabilities of the surfactant for templating ordered mesoporous silica particle growth, while simultaneously generating a reactive matrix for polymer network formation through reactive end groups in the presence of intimately mixed mesoporous silicates. A combination of small angle X-ray scattering, surface area, and microscopy experiments on mesoporous silica indicated the structure directing capabilities of surfmers. Free-radical polymerization of the surfmer leads to novel crosslinked nanocomposites networks. Multiple experiments, including gel permeation chromatography, swelling, and solid state NMR experiments on polymer nanocomposites gave evidence of the polymerization of surfmer leading to formation of crosslink networks. Polymer nanocomposites with varied silica content were prepared. Effects of silica content on polymer nanocomposites were studied on rheometer. Results obtained from rheological experiments indicate that the storage (G') and loss modulus (G") increases with increase in the content of mesoporous silica. In this way, the nanocomposites networks obtained via self-assembly shows independent behavior with respect to frequency in rheological experiments. Additionally, this self-assembled route was extended to synthesize biodegradable and biocompatible polymer nanocomposites networks. The nanocomposite networks obtained with 15% of silica content showed the increase in storage modulus by two orders of magnitude in rheological experiments.

  14. Engineering hierarchical nanostructures by elastocapillary self-assembly.

    PubMed

    De Volder, Michaël; Hart, A John

    2013-02-25

    Surfaces coated with nanoscale filaments such as silicon nanowires and carbon nanotubes are potentially compelling for high-performance battery and capacitor electrodes, photovoltaics, electrical interconnects, substrates for engineered cell growth, dry adhesives, and other smart materials. However, many of these applications require a wet environment or involve wet processing during their synthesis. The capillary forces introduced by these wet environments can lead to undesirable aggregation of nanoscale filaments, but control of capillary forces can enable manipulation of the filaments into discrete aggregates and novel hierarchical structures. Recent studies suggest that the elastocapillary self-assembly of nanofilaments can be a versatile and scalable means to build complex and robust surface architectures. To enable a wider understanding and use of elastocapillary self-assembly as a fabrication technology, we give an overview of the underlying fundamentals and classify typical implementations and surface designs for nanowires, nanotubes, and nanopillars made from a wide variety of materials. Finally, we discuss exemplary applications and future opportunities to realize new engineered surfaces by the elastocapillary self-assembly of nanofilaments. PMID:23339106

  15. Evolutionary dynamics in a simple model of self-assembly

    NASA Astrophysics Data System (ADS)

    Johnston, Iain G.; Ahnert, Sebastian E.; Doye, Jonathan P. K.; Louis, Ard A.

    2011-06-01

    We investigate the evolutionary dynamics of an idealized model for the robust self-assembly of two-dimensional structures called polyominoes. The model includes rules that encode interactions between sets of square tiles that drive the self-assembly process. The relationship between the model’s rule set and its resulting self-assembled structure can be viewed as a genotype-phenotype map and incorporated into a genetic algorithm. The rule sets evolve under selection for specified target structures. The corresponding complex fitness landscape generates rich evolutionary dynamics as a function of parameters such as the population size, search space size, mutation rate, and method of recombination. Furthermore, these systems are simple enough that in some cases the associated model genome space can be completely characterized, shedding light on how the evolutionary dynamics depends on the detailed structure of the fitness landscape. Finally, we apply the model to study the emergence of the preference for dihedral over cyclic symmetry observed for homomeric protein tetramers.

  16. Size-controlled self-assembly of superparamagnetic polymersomes.

    PubMed

    Hickey, Robert J; Koski, Jason; Meng, Xin; Riggleman, Robert A; Zhang, Peijun; Park, So-Jung

    2014-01-28

    We report the size-controlled self-assembly of polymersomes through the cooperative self-assembly of nanoparticles and amphiphilic polymers. Polymersomes densely packed with magnetic nanoparticles in the polymersome membrane (magneto-polymersome) were fabricated with a series of different sized iron oxide nanoparticles. The distribution of nanoparticles in a polymersome membrane was size-dependent; while small nanoparticles were dispersed in a polymer bilayer, large particles formed a well-ordered superstructure at the interface between the inner and outer layer of a bilayer membrane. The yield of magneto-polymersomes increased with increasing the diameter of incorporated nanoparticles. Moreover, the size of the polymersomes was effectively controlled by varying the size of incorporated nanoparticles. This size-dependent self-assembly was attributed to the polymer chain entropy effect and the size-dependent localization of nanoparticles in polymersome bilayers. The transverse relaxation rates (r2) of magneto-polymersomes increased with increasing the nanoparticle diameter and decreasing the size of polymersomes, reaching 555 ± 24 s(-1) mM(-1) for 241 ± 16 nm polymersomes, which is the highest value reported to date for superparamagnetic iron oxide nanoparticles.

  17. Polymer adsorption-driven self-assembly of nanostructures.

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

    Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context.

  18. Patterning self-assembled FePt nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Min; Nikles, David E.; Yin, Huaqin; Wang, Shoutao; Harrell, J. W.; Majetich, Sara A.

    2003-10-01

    We describe a potential way to extend the ordered domain of self-assembled FePt nanoparticles. The FePt particles, with an average diameter of 3 nm, were prepared by simultaneous thermal decomposition of Fe(CO) 5 and chemical reduction of Pt(acac) 2 and then were dispersed in a mixture of hexane and octane. When self-assembling on a plain silicon wafer, FePt nanoparticles formed ordered hexagonal arrays in a range of tens to a few hundred nanometers. A silicon wafer with patterned holes of a photoresist film, made using UV-lithographing technique, was used as a template to direct the stacking direction of the FePt nanoparticles. The FePt dispersion was dropped on the patterned holes of the photoresist film. After being heat-treated at 100°C for 30 min under vacuum condition, the photoresist was stripped out by dipping the sample in acetone. The patterned disks, with an average diameter of 2.0 μm and a height of 250 nm, of self-assembled FePt nanoparticles were examined using SEM and Auger mapping. Their magnetic properties were measured using AGM. The Auger electrons of neither Fe LMM nor Pt MNN could be detected from the sample, which indicated the adsorption of oleic acid and oleylamine on the surface of FePt nanoparticles. The coercivity of patterned FePt significantly increased with the annealing temperature above 600°C.

  19. Dynamic self-assembly and control of microfluidic particle crystals

    PubMed Central

    Lee, Wonhee; Amini, Hamed; Stone, Howard A.; Di Carlo, Dino

    2010-01-01

    Engineered two-phase microfluidic systems have recently shown promise for computation, encryption, and biological processing. For many of these systems, complex control of dispersed-phase frequency and switching is enabled by nonlinearities associated with interfacial stresses. Introducing nonlinearity associated with fluid inertia has recently been identified as an easy to implement strategy to control two-phase (solid-liquid) microscale flows. By taking advantage of inertial effects we demonstrate controllable self-assembling particle systems, uncover dynamics suggesting a unique mechanism of dynamic self-assembly, and establish a framework for engineering microfluidic structures with the possibility of spatial frequency filtering. Focusing on the dynamics of the particle–particle interactions reveals a mechanism for the dynamic self-assembly process; inertial lift forces and a parabolic flow field act together to stabilize interparticle spacings that otherwise would diverge to infinity due to viscous disturbance flows. The interplay of the repulsive viscous interaction and inertial lift also allow us to design and implement microfluidic structures that irreversibly change interparticle spacing, similar to a low-pass filter. Although often not considered at the microscale, nonlinearity due to inertia can provide a platform for high-throughput passive control of particle positions in all directions, which will be useful for applications in flow cytometry, tissue engineering, and metamaterial synthesis. PMID:21149674

  20. Molecular pathways for defect annihilation in directed self-assembly.

    PubMed

    Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo; Khaira, Gurdaman; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A; Li, Weihua; Müller, Marcus; Nealey, Paul F; de Pablo, Juan J

    2015-11-17

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm(2). In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales-a handful of nanometers-and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail. PMID:26515095

  1. Equilibrium self-assembly of small RNA viruses

    NASA Astrophysics Data System (ADS)

    Bruinsma, R. F.; Comas-Garcia, M.; Garmann, R. F.; Grosberg, A. Y.

    2016-03-01

    We propose a description for the quasiequilibrium self-assembly of small, single-stranded (ss) RNA viruses whose capsid proteins (CPs) have flexible, positively charged, disordered tails that associate with the negatively charged RNA genome molecules. We describe the assembly of such viruses as the interplay between two coupled phase-transition-like events: the formation of the protein shell (the capsid) by CPs and the condensation of a large ss viral RNA molecule. Electrostatic repulsion between the CPs competes with attractive hydrophobic interactions and attractive interaction between neutralized RNA segments mediated by the tail groups. An assembly diagram is derived in terms of the strength of attractive interactions between CPs and between CPs and the RNA molecules. It is compared with the results of recent studies of viral assembly. We demonstrate that the conventional theory of self-assembly, which does describe the assembly of empty capsids, is in general not applicable to the self-assembly of RNA-encapsidating virions.

  2. Equilibrium self-assembly of small RNA viruses.

    PubMed

    Bruinsma, R F; Comas-Garcia, M; Garmann, R F; Grosberg, A Y

    2016-03-01

    We propose a description for the quasiequilibrium self-assembly of small, single-stranded (ss) RNA viruses whose capsid proteins (CPs) have flexible, positively charged, disordered tails that associate with the negatively charged RNA genome molecules. We describe the assembly of such viruses as the interplay between two coupled phase-transition-like events: the formation of the protein shell (the capsid) by CPs and the condensation of a large ss viral RNA molecule. Electrostatic repulsion between the CPs competes with attractive hydrophobic interactions and attractive interaction between neutralized RNA segments mediated by the tail groups. An assembly diagram is derived in terms of the strength of attractive interactions between CPs and between CPs and the RNA molecules. It is compared with the results of recent studies of viral assembly. We demonstrate that the conventional theory of self-assembly, which does describe the assembly of empty capsids, is in general not applicable to the self-assembly of RNA-encapsidating virions.

  3. Molecular pathways for defect annihilation in directed self-assembly.

    DOE PAGES

    Hur, Su-Mi; Thapar, Vikram; Ramirez-Hernandez, Abelardo; Khaira, Gurdaman S.; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Muller, Marcus; Nealey, Paul F.; de Pablo, Juan J.

    2015-11-17

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free-energymore » barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers, how they depend on material characteristics, and we propose strategies designed to over-come them. The validity of our conclusions for industrially-relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales - a handful of nanometers -, and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail.« less

  4. Molecular pathways for defect annihilation in directed self-assembly.

    SciTech Connect

    Hur, Su-Mi; Thapar, Vikram; Ramirez-Hernandez, Abelardo; Khaira, Gurdaman S.; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Muller, Marcus; Nealey, Paul F.; de Pablo, Juan J.

    2015-11-17

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free-energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers, how they depend on material characteristics, and we propose strategies designed to over-come them. The validity of our conclusions for industrially-relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales - a handful of nanometers -, and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail.

  5. Directed self-assembly of a colloidal kagome lattice.

    PubMed

    Chen, Qian; Bae, Sung Chul; Granick, Steve

    2011-01-20

    A challenging goal in materials chemistry and physics is spontaneously to form intended superstructures from designed building blocks. In fields such as crystal engineering and the design of porous materials, this typically involves building blocks of organic molecules, sometimes operating together with metallic ions or clusters. The translation of such ideas to nanoparticles and colloidal-sized building blocks would potentially open doors to new materials and new properties, but the pathways to achieve this goal are still undetermined. Here we show how colloidal spheres can be induced to self-assemble into a complex predetermined colloidal crystal-in this case a colloidal kagome lattice-through decoration of their surfaces with a simple pattern of hydrophobic domains. The building blocks are simple micrometre-sized spheres with interactions (electrostatic repulsion in the middle, hydrophobic attraction at the poles, which we call 'triblock Janus') that are also simple, but the self-assembly of the spheres into an open kagome structure contrasts with previously known close-packed periodic arrangements of spheres. This open network is of interest for several theoretical reasons. With a view to possible enhanced functionality, the resulting lattice structure possesses two families of pores, one that is hydrophobic on the rims of the pores and another that is hydrophilic. This strategy of 'convergent' self-assembly from easily fabricated colloidal building blocks encodes the target supracolloidal architecture, not in localized attractive spots but instead in large redundantly attractive regions, and can be extended to form other supracolloidal networks.

  6. Spectroscopic critical dimension technology (SCD) for directed self assembly

    NASA Astrophysics Data System (ADS)

    Nishibe, Senichi; Dziura, Thaddeus; Nagaswami, Venkat; Gronheid, Roel

    2014-04-01

    Directed self-assembly (DSA) is being actively investigated as a potential patterning solution for future generation devices. While SEM based CD measurement is currently used in research and development, scatterometry-based techniques like spectroscopic CD (SCD) are preferred for high volume manufacturing. SCD can offer information about sub-surface features that are not available from CD-SEM measurement. Besides, SCD is a non-destructive, high throughput technique already adopted in HVM in several advanced nodes. The directed self assembly CD measurement can be challenging because of small dimensions and extremely thin layers in the DSA stack. In this study, the SCD technology was investigated for a 14 nm resolution PS-b-PMMA chemical epitaxy UW process optimized by imec. The DSA stack involves new materials such as cross-linkable polysterene (XPS) of thickness approximately 5 nm, ArF immersion resist (subsequently removed), -OH terminated neutral brush layer, and BCP material (Polystyrene-blockmethyl methacrylate of thickness roughly 20 to 30 nm). The mask contains a large CD and pitch matrix, for studying the quality of self-assembly as a function of the guide pattern dimensions. We report on the ability of SCD to characterize the dimensional variation in these targets and hence provide a viable process control solution.

  7. Molecular pathways for defect annihilation in directed self-assembly

    PubMed Central

    Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo; Khaira, Gurdaman; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Müller, Marcus; Nealey, Paul F.; de Pablo, Juan J.

    2015-01-01

    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales—a handful of nanometers—and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail. PMID:26515095

  8. Chiral Perylene Materials by Ionic Self-Assembly.

    PubMed

    Echue, Geraldine; Hamley, Ian; Lloyd Jones, Guy C; Faul, Charl F J

    2016-09-01

    Two chiral complexes (1-SDS and 1-SDBS) were prepared via the ionic self-assembly of a chiral perylene diimide tecton with oppositely charged surfactants. The effect of surfactant tail architecture on the self-assembly properties and supramolecular structure was investigated in detail using UV-vis, IR, circular dichroism, light microscopy, X-ray diffraction studies, and electron microscopy. The results obtained revealed the molecular chirality of the parent perylene tecton could be translated into supramolecular helical chirality of the resulting complexes via primary ionic interactions through careful choice of solvent and concentration. Differing solvent-dependent aggregation behavior was observed for these complexes as a result of the different possible noncovalent interactions via the surfactant alkyl tails. The results presented in this study demonstrate that ionic self-assembly (ISA) is a facile strategy for the production of chiral supramolecular materials based on perylene diimides. The structure-function relationship is easily explored here due to the wide selection and easy availability of common surfactants. PMID:27486788

  9. Self-assembly of strongly dipolar molecules on metal surfaces

    NASA Astrophysics Data System (ADS)

    Kunkel, Donna A.; Hooper, James; Simpson, Scott; Miller, Daniel P.; Routaboul, Lucie; Braunstein, Pierre; Doudin, Bernard; Beniwal, Sumit; Dowben, Peter; Skomski, Ralph; Zurek, Eva; Enders, Axel

    2015-03-01

    The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C6H2(⋯ NHR)2(⋯ O)2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings.

  10. Enhanced photoluminescence by tyrosine-containing bolaamphiphile self-assembly.

    PubMed

    Kwak, Jinyoung; Lee, Sang-Yup

    2013-04-01

    Photoluminescent spherical nanostructures were prepared through the self-assembly of a tyrosine-containing bolaamphiphilic molecule, and their antenna effect was examined. The photoluminescent spherical nanostructures were simply prepared by self-assembly of bolaamphiphile molecules in an aqueous solution in which water-soluble photosensitizers and lanthanide ions were dissolved. The photosensitizers and lanthanide cations were incorporated with the phenol group and the carboxyl end of the tyrosine moiety, respectively. Through fluorescence microscopy and photoluminescence spectroscopy analyses, the various combinations of two lanthanide ions (Eu and Tb) and four photosensitizers were screened for synergetic photoluminescence with bolaamphiphile self-assembly. The bolaamphiphile assembly enhanced the photoluminescence intensity by a factor of around 2 when it was associated with Tb and salicylic acid. This enhancement is driven by the phosphorescence enhancement of the photosensitizer induced by the π-π interactions with the phenol group in tyrosine. These results indicate that the tyrosine-containing bolaamphiphile is a promising molecule that can easily produce a soft nanoscaled host matrix with an antenna effect for photoluminescence.

  11. Three dimensional self-assembly at the nanoscale

    NASA Astrophysics Data System (ADS)

    Gracias, D. H.

    2013-05-01

    At the nanoscale, three dimensional manipulation and assembly becomes extremely challenging and also cost prohibitive. Self-assembly provides an attractive and possibly the only highly parallel methodology to structure truly three dimensional patterned materials and devices at this size scale for applications in electronics, optics, robotics and medicine. This is a concise review along with a perspective of an important and exciting field in nanotechnology and is related to a Nanoengineering Pioneer Award that I received at this SPIE symposium for my contributions to the 3D selfassembly of nanostructures. I detail a historical account of 3D self-assembly and outline important developments in this area which is put into context with the larger research areas of 3D nanofabrication, assembly and nanomanufacturing. A focus in this review is on our work as it relates to the self-assembly with lithographically patterned units; this approach provides a means for heterogeneous integration of periodic, curved and angled nanostructures with precisely defined three dimensional patterns.

  12. Polymer adsorption-driven self-assembly of nanostructures.

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

    Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context. PMID:11326074

  13. Multilayer block copolymer meshes by orthogonal self-assembly

    PubMed Central

    Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R.; Alexander-Katz, Alfredo; Ross, Caroline A.; Berggren, Karl K.

    2016-01-01

    Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders. PMID:26796218

  14. Algorithmic Self-Assembly of DNA Sierpinski Triangles

    PubMed Central

    2004-01-01

    Algorithms and information, fundamental to technological and biological organization, are also an essential aspect of many elementary physical phenomena, such as molecular self-assembly. Here we report the molecular realization, using two-dimensional self-assembly of DNA tiles, of a cellular automaton whose update rule computes the binary function XOR and thus fabricates a fractal pattern—a Sierpinski triangle—as it grows. To achieve this, abstract tiles were translated into DNA tiles based on double-crossover motifs. Serving as input for the computation, long single-stranded DNA molecules were used to nucleate growth of tiles into algorithmic crystals. For both of two independent molecular realizations, atomic force microscopy revealed recognizable Sierpinski triangles containing 100–200 correct tiles. Error rates during assembly appear to range from 1% to 10%. Although imperfect, the growth of Sierpinski triangles demonstrates all the necessary mechanisms for the molecular implementation of arbitrary cellular automata. This shows that engineered DNA self-assembly can be treated as a Turing-universal biomolecular system, capable of implementing any desired algorithm for computation or construction tasks. PMID:15583715

  15. Molecular Motions in Functional Self-Assembled Nanostructures

    PubMed Central

    Dhotel, Alexandre; Chen, Ziguang; Delbreilh, Laurent; Youssef, Boulos; Saiter, Jean-Marc; Tan, Li

    2013-01-01

    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. PMID:23348927

  16. Large-scale dissipative particle dynamics simulations of self-assembly amphiphilic systems†

    PubMed Central

    Li, Xuejin; Tang, Yu-Hang

    2014-01-01

    We present large-scale simulation results on the self-assembly of amphiphilic systems in bulk solution and under soft confinement. Self-assembled unilamellar and multilamellar vesicles are formed from amphiphilic molecules in bulk solution. The system is simulated by placing amphiphilic molecules inside large unilamellar vesicles (LUVs) and the dynamic soft confinement-induced self-assembled vesicles are investigated. Moreover, the self-assembly of sickle hemoglobin (HbS) is simulated in a crowded and fluctuating intracellular space and our results demonstrate that the HbS self-assemble into polymer fibers causing the LUV shape to be distorted. PMID:24938634

  17. Phonon line emission revealed by self-assembly of colloidal nanoplatelets.

    PubMed

    Tessier, Mickaël D; Biadala, Louis; Bouet, Cécile; Ithurria, Sandrine; Abecassis, Benjamin; Dubertret, Benoit

    2013-04-23

    We show that colloidal nanoplatelets can self-assemble to form a 1D superlattice. When self-assembled, an additional emission line appears in the photoluminescence spectrum at low temperatures. This emission line is a collective effect, greatly enhanced when the NPLs are self-assembled. It is attributed to the longitudinal optical (LO) phonon replica of the band-edge exciton, and its presence in self-assembled nanoplatelets is explained using a model based on an efficient photons reabsorption between neighboring nanoplatelets. The presence of phonon replica at low temperatures in ensemble measurements suggests the possibility to design a laser, based on self-assembled nanoplatelets.

  18. Molecular Self-Assembly into One-Dimensional Nanostructures

    PubMed Central

    PALMER, LIAM C.; STUPP, SAMUEL I.

    2008-01-01

    CONSPECTUS Self-assembly of small molecules into one-dimensional nanostructures offers many potential applications in electronically and biologically active materials. The recent advances discussed in this Account demonstrate how researchers can use the fundamental principles of supramolecular chemistry to craft the size, shape, and internal structure of nanoscale objects. In each system described here, we used atomic force microscopy (AFM) and transmission electron microscopy (TEM) to study the assembly morphology. Circular dichroism, nuclear magnetic resonance, infrared, and optical spectroscopy provided additional information about the self-assembly behavior in solution at the molecular level. Dendron rod–coil molecules self-assemble into flat or helical ribbons. They can incorporate electronically conductive groups and can be mineralized with inorganic semiconductors. To understand the relative importance of each segment in forming the supramolecular structure, we synthetically modified the dendron, rod, and coil portions. The self-assembly depended on the generation number of the dendron, the number of hydrogen-bonding functions, and the length of the rod and coil segments. We formed chiral helices using a dendron–rod–coil molecule prepared from an enantiomerically enriched coil. Because helical nanostructures are important targets for use in biomaterials, nonlinear optics, and stereoselective catalysis, researchers would like to precisely control their shape and size. Tripeptide-containing peptide lipid molecules assemble into straight or twisted nanofibers in organic solvents. As seen by AFM, the sterics of bulky end groups can tune the helical pitch of these peptide lipid nanofibers in organic solvents. Furthermore, we demonstrated the potential for pitch control using trans-to-cis photoisomerization of a terminal azobenzene group. Other molecules called peptide amphiphiles (PAs) are known to assemble in water into cylindrical nanostructures that

  19. Simulation of macromolecule self-assembly in solution: A multiscale approach

    SciTech Connect

    Lavino, Alessio D. Barresi, Antonello A. Marchisio, Daniele L.; Pasquale, Nicodemo di; Carbone, Paola

    2015-12-17

    One of the most common processes to produce polymer nanoparticles is to induce self-assembly by using the solvent-displacement method, in which the polymer is dissolved in a “good” solvent and the solution is then mixed with an “anti-solvent”. The polymer ability to self-assemble in solution is therefore determined by its structural and transport properties in solutions of the pure solvents and at the intermediate compositions. In this work, we focus on poly-ε-caprolactone (PCL) which is a biocompatible polymer that finds widespread application in the pharmaceutical and biomedical fields, performing simulation at three different scales using three different computational tools: full atomistic molecular dynamics (MD), population balance modeling (PBM) and computational fluid dynamics (CFD). Simulations consider PCL chains of different molecular weight in solution of pure acetone (good solvent), of pure water (anti-solvent) and their mixtures, and mixing at different rates and initial concentrations in a confined impinging jets mixer (CIJM). Our MD simulations reveal that the nano-structuring of one of the solvents in the mixture leads to an unexpected identical polymer structure irrespectively of the concentration of the two solvents. In particular, although in pure solvents the behavior of the polymer is, as expected, very different, at intermediate compositions, the PCL chain shows properties very similar to those found in pure acetone as a result of the clustering of the acetone molecules in the vicinity of the polymer chain. We derive an analytical expression to predict the polymer structural properties in solution at different solvent compositions and use it to formulate an aggregation kernel to describe the self-assembly in the CIJM via PBM and CFD. Simulations are eventually validated against experiments.

  20. Simulation of macromolecule self-assembly in solution: A multiscale approach

    NASA Astrophysics Data System (ADS)

    Lavino, Alessio D.; di Pasquale, Nicodemo; Carbone, Paola; Barresi, Antonello A.; Marchisio, Daniele L.

    2015-12-01

    One of the most common processes to produce polymer nanoparticles is to induce self-assembly by using the solvent-displacement method, in which the polymer is dissolved in a "good" solvent and the solution is then mixed with an "anti-solvent". The polymer ability to self-assemble in solution is therefore determined by its structural and transport properties in solutions of the pure solvents and at the intermediate compositions. In this work, we focus on poly-ɛ-caprolactone (PCL) which is a biocompatible polymer that finds widespread application in the pharmaceutical and biomedical fields, performing simulation at three different scales using three different computational tools: full atomistic molecular dynamics (MD), population balance modeling (PBM) and computational fluid dynamics (CFD). Simulations consider PCL chains of different molecular weight in solution of pure acetone (good solvent), of pure water (anti-solvent) and their mixtures, and mixing at different rates and initial concentrations in a confined impinging jets mixer (CIJM). Our MD simulations reveal that the nano-structuring of one of the solvents in the mixture leads to an unexpected identical polymer structure irrespectively of the concentration of the two solvents. In particular, although in pure solvents the behavior of the polymer is, as expected, very different, at intermediate compositions, the PCL chain shows properties very similar to those found in pure acetone as a result of the clustering of the acetone molecules in the vicinity of the polymer chain. We derive an analytical expression to predict the polymer structural properties in solution at different solvent compositions and use it to formulate an aggregation kernel to describe the self-assembly in the CIJM via PBM and CFD. Simulations are eventually validated against experiments.

  1. Recent Advances on Carbon Nanospheres. Synthetic Routes and Applications

    DOE PAGES

    Zhang, Pengfei; Qiao, Zhenan; Dai, Sheng

    2015-04-02

    Carbon-based materials are the most popular material types in both fundamental research and industrial applications, partly because of their well-controlled nano-morphologies. In the past two decades, we have witnessed a number of breakthroughs in carbon research: fullerenes, carbon nanotubes, and more recently graphene. Nowadays, carbon nanospheres are attracting more and more attention worldwide due to their excellent performance in various fields: drug delivery, heterogeneous catalysis, encapsulation of support and electrode materials. Actually, spherical carbon is an old material, whereas controlling carbon spheres in the nanometer range is a recent story. In the past 5 years, it has become possible tomore » precisely control the particle size, surface area, pore size, chemical composition, and dispersity of carbon nanospheres. Toward this end, a number of synthetic strategies are emerging, such as hydrothermal carbonization of biomass-based resources, extended Stöber synthesis, and organic–organic self-assembly via different binding methods. In this feature article, we summarize recent routes for carbon nanospheres and briefly touch on their applications to shed light on the potential of this field. Throughout this article, a special emphasis is placed on the possible modulation of spherical structures at the nanoscale, and we wish to inspire many more designs and applications of carbon nanostructures in the near future.« less

  2. Recent Advances on Carbon Nanospheres. Synthetic Routes and Applications

    SciTech Connect

    Zhang, Pengfei; Qiao, Zhenan; Dai, Sheng

    2015-04-02

    Carbon-based materials are the most popular material types in both fundamental research and industrial applications, partly because of their well-controlled nano-morphologies. In the past two decades, we have witnessed a number of breakthroughs in carbon research: fullerenes, carbon nanotubes, and more recently graphene. Nowadays, carbon nanospheres are attracting more and more attention worldwide due to their excellent performance in various fields: drug delivery, heterogeneous catalysis, encapsulation of support and electrode materials. Actually, spherical carbon is an old material, whereas controlling carbon spheres in the nanometer range is a recent story. In the past 5 years, it has become possible to precisely control the particle size, surface area, pore size, chemical composition, and dispersity of carbon nanospheres. Toward this end, a number of synthetic strategies are emerging, such as hydrothermal carbonization of biomass-based resources, extended Stöber synthesis, and organic–organic self-assembly via different binding methods. In this feature article, we summarize recent routes for carbon nanospheres and briefly touch on their applications to shed light on the potential of this field. Throughout this article, a special emphasis is placed on the possible modulation of spherical structures at the nanoscale, and we wish to inspire many more designs and applications of carbon nanostructures in the near future.

  3. Surface-enhanced Raman scattering of 4-mercaptobenzoic acid and hemoglobin adsorbed on self-assembled Ag monolayer films with different shapes

    NASA Astrophysics Data System (ADS)

    Zhu, Shuangmei; Fan, Chunzhen; Wang, Junqiao; He, Jinna; Liang, Erjun

    2014-06-01

    Polyvinylpyrrolidone (PVP)-protected silver nanostructures of various shapes, including nanocubes, nanospheres, and hybrid shapes with nanospheres and nanorods, on the surface of glass or Si substrates (PVP-Ag films) are prepared by using electrostatic self-assembly. With 4-mercaptobenzoic acid (4-MBA) as a probe molecule, it is demonstrated that the PVP-protected silver nanocubes films (PVP-Ag NCs) have better surface-enhanced Raman scattering (SERS) activity with an order of magnitude larger enhancement factors (EF) than the PVP-protected silver nanospheres films and the PVP-protected silver hybrid shapes films, which is confirmed by our numerical simulations. The EF of 4-MBA on the PVP-Ag NCs film are up to ~5.38 × 106, and the detection limit is at least down to ~10-8 M. The uniformity and reproducibility of the SERS signals on PVP-Ag NCs film are tested by point-to-point and batch-to-batch measurements. Meanwhile, the PVP-Ag films are also shown to be an excellent SERS substrate with good biocompatibility for hemoglobin detection. It is shown that the PVP-Ag NCs films can be used as excellent SERS substrate with good activity, uniformity, reproducibility, and biocompatibility and are promising for a myriad of chemical and biochemical sensing applications.

  4. Self-assembled multicompartment liquid crystalline lipid carriers for protein, peptide, and nucleic acid drug delivery.

    PubMed

    Angelova, Angelina; Angelov, Borislav; Mutafchieva, Rada; Lesieur, Sylviane; Couvreur, Patrick

    2011-02-15

    Lipids and lipopolymers self-assembled into biocompatible nano- and mesostructured functional materials offer many potential applications in medicine and diagnostics. In this Account, we demonstrate how high-resolution structural investigations of bicontinuous cubic templates made from lyotropic thermosensitive liquid-crystalline (LC) materials have initiated the development of innovative lipidopolymeric self-assembled nanocarriers. Such structures have tunable nanochannel sizes, morphologies, and hierarchical inner organizations and provide potential vehicles for the predictable loading and release of therapeutic proteins, peptides, or nucleic acids. This Account shows that structural studies of swelling of bicontinuous cubic lipid/water phases are essential for overcoming the nanoscale constraints for encapsulation of large therapeutic molecules in multicompartment lipid carriers. For the systems described here, we have employed time-resolved small-angle X-ray scattering (SAXS) and high-resolution freeze-fracture electronic microscopy (FF-EM) to study the morphology and the dynamic topological transitions of these nanostructured multicomponent amphiphilic assemblies. Quasi-elastic light scattering and circular dichroism spectroscopy can provide additional information at the nanoscale about the behavior of lipid/protein self-assemblies under conditions that approximate physiological hydration. We wanted to generalize these findings to control the stability and the hydration of the water nanochannels in liquid-crystalline lipid nanovehicles and confine therapeutic biomolecules within these structures. Therefore we analyzed the influence of amphiphilic and soluble additives (e.g. poly(ethylene glycol)monooleate (MO-PEG), octyl glucoside (OG), proteins) on the nanochannels' size in a diamond (D)-type bicontinuous cubic phase of the lipid glycerol monooleate (MO). At body temperature, we can stabilize long-living swollen states, corresponding to a diamond cubic phase

  5. Self-assembled multicompartment liquid crystalline lipid carriers for protein, peptide, and nucleic acid drug delivery.

    PubMed

    Angelova, Angelina; Angelov, Borislav; Mutafchieva, Rada; Lesieur, Sylviane; Couvreur, Patrick

    2011-02-15

    Lipids and lipopolymers self-assembled into biocompatible nano- and mesostructured functional materials offer many potential applications in medicine and diagnostics. In this Account, we demonstrate how high-resolution structural investigations of bicontinuous cubic templates made from lyotropic thermosensitive liquid-crystalline (LC) materials have initiated the development of innovative lipidopolymeric self-assembled nanocarriers. Such structures have tunable nanochannel sizes, morphologies, and hierarchical inner organizations and provide potential vehicles for the predictable loading and release of therapeutic proteins, peptides, or nucleic acids. This Account shows that structural studies of swelling of bicontinuous cubic lipid/water phases are essential for overcoming the nanoscale constraints for encapsulation of large therapeutic molecules in multicompartment lipid carriers. For the systems described here, we have employed time-resolved small-angle X-ray scattering (SAXS) and high-resolution freeze-fracture electronic microscopy (FF-EM) to study the morphology and the dynamic topological transitions of these nanostructured multicomponent amphiphilic assemblies. Quasi-elastic light scattering and circular dichroism spectroscopy can provide additional information at the nanoscale about the behavior of lipid/protein self-assemblies under conditions that approximate physiological hydration. We wanted to generalize these findings to control the stability and the hydration of the water nanochannels in liquid-crystalline lipid nanovehicles and confine therapeutic biomolecules within these structures. Therefore we analyzed the influence of amphiphilic and soluble additives (e.g. poly(ethylene glycol)monooleate (MO-PEG), octyl glucoside (OG), proteins) on the nanochannels' size in a diamond (D)-type bicontinuous cubic phase of the lipid glycerol monooleate (MO). At body temperature, we can stabilize long-living swollen states, corresponding to a diamond cubic phase

  6. Combustion and self-assembly of nanoenergetic materials

    NASA Astrophysics Data System (ADS)

    Malchi, Jonathan Yaniv

    The recent worldwide interest in nanotechnology spans a wide variety of scientific fields such as electronics, biology, materials science and medicine. Because of their extremely small dimensions, nanoparticles demonstrate properties different from matter at larger scales. Understanding these unusual properties and utilizing them for macroscale devices is an overall goal for nanotechnology. Moreover, manipulating these small particles into organized structures is crucial for taking full advantage of what nanotechnology has to offer, however it has proven to be a difficult task. Recent work utilizing electrostatic forces shows great potential for the self-assembly of nanoparticles into organized two-dimensional and three-dimensional structures. Overall, this work examines how nanotechnology and self-assembly can benefit the field of energetic materials. Because of aluminum's high energy density and low cost, it has been used in the field of energetic materials for several decades. In order to achieve sufficient energy release rates, aluminum is typically manufactured as a powder having spherical particles with diameters on the micron scale. It is well-known that decreasing the original particle diameter of a fuel particle will increase the burning time and, thus, energy release rate. Therefore, aluminum particles have recently been made to have diameters on the nanoscale, and shown to be advantageous for several applications. The combustion of nanoaluminum (nAl) in various systems is the primary focus of this study. A progression of experiments is used to analyze the combustion of nAl: (1) a fully heterogeneous flame spread system, (2) a semi-homogeneous sonicated thermite system and (3) a quasi-homogeneous self-assembled thermite system. The flame spread experiment physically separates the nAl from the gaseous oxidizer allowing for a well-understood convective, diffusive, reactive system to be analyzed. Because of the simplicity of the experimental setup, variables

  7. Self-assembly based nanometer-scale patterning for nanowire growth

    NASA Astrophysics Data System (ADS)

    Chandramohan, Abhishek; Sibirev, Nikolai; Dubrovskii, Vladimir G.; Mendis, Budhika; Petty, Mike C.; Gallant, Andrew J.; Zeze, Dagou A.

    2015-08-01

    Periodic nanostructure arrays have been ubiquitously exploited lately due to their properties and prospective applications in production of templates for self-induced and gold (Au)-catalysed nanowires (NWs), because this approach is relatively cheap, time-efficient and do not require electron beam lithography. The technique consists creating nanoholes in SiO2 to expose the silicon Si (111) beneath where self-induced NWs can nucleate, while nanodots deposited onto the Si (111) surface serve as catalyst seeds. For Au-catalysed NWs, a monolayer of self-assembled polystyrene nanospheres (PNS 300nm) was created on a 2 inch Si wafer by spin coating and later etched for a short time before a very thin Au-catalyst layer was deposited. In turn, for self-induced, PNS monolayer was created onto a SiO2-Si substrate. A longer etch was required to reduce PNS diameter significantly to leave relatively larger spacing where chromium is blanket deposited. PNS were lifted off by sonicating the samples in toluene produce the periodic arrays of nanodots and nanoholes, respectively. The underlying SiO2 was etched further through the nanoholes to uncover the Si below. 200 nm holes and 30-70 nm dots were demonstrated through the bespoke methods. The patterned substrates served as master templates, subsequently copied using polydimethylsiloxane (PDMS) to produce a flexible stamp for nanoimprint lithography. A bilayer resist lift off process was developed to print the replicated nanodots or nanoholes on large-area substrates onto which III-V NWs can be grown.

  8. Anion-exchange nanospheres as titration reagents for anionic analytes.

    PubMed

    Zhai, Jingying; Xie, Xiaojiang; Bakker, Eric

    2015-08-18

    We present here anion-exchange nanospheres as novel titration reagents for anions. The nanospheres contain a lipophilic cation for which the counterion is initially Cl(-). Ion exchange takes place between Cl(-) in the nanospheres and a more lipophilic anion in the sample, such as ClO4(-) and NO3(-). Consecutive titration in the same sample solution for ClO4(-) and NO3(-) were demonstrated. As an application, the concentration of NO3(-) in spinach was successfully determined using this method.

  9. Platelets self-assemble into porous nacre during freeze casting.

    PubMed

    Hunger, Philipp M; Donius, Amalie E; Wegst, Ulrike G K

    2013-03-01

    Nacre possesses a remarkable combination of mechanical properties. Its high stiffness, strength and toughness are attributed to a highly aligned structure of aragonite platelets "glued" together by a small fraction (∼5vol%) of polymer; theoretically it can be described by a shear-lag model of staggered tensile elements between which loads are transferred via shear. Despite extensive research, it has not been possible yet to manufacture this aligned structure as a bulk material of considerable volume with a fast and easy production process. Particularly porous materials would benefit from enhanced wall material properties to compensate for performance loss due to their high porosity. An important application for such porous materials are tissue scaffolds for bone substitution. Bone, like nacre, exhibits excellent mechanical properties, particularly an exceptionally high toughness, because of its composite structure of hydroxyapatite platelets aligned in a ∼35vol% polymer matrix. Through the freeze casting process, which results in a fast and straightforward self-assembly of platelet-shaped particles during directional solidification, highly porous bulk materials with nacre-like cell walls can now be created. This porous nacre outperforms by a factor of 1.5-4 in terms of stiffness, strength and toughness materials that have the same amount of porosity but do not exhibit the nacre-like microarchitecture. The self-assembly process presented in this study thus has tremendous potential for the creation of highly porous, yet mechanically strong tissue scaffolds for low or medium load bearing bone substitute materials. Due to the versatility of the freeze casting process, materials with a self-assembled cell wall structure can be created from high-aspect ratio particles of all material classes. This enables material optimization for a great variety of applications such as impact protection, filtration, catalysis, energy generation and storage, in addition to those with

  10. Self-assembly of amorphous biophotonic nanostructures by phase separation

    SciTech Connect

    Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar; Mochrie, Simon G.J.; Cao, Hui; Prum, Richard O.

    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. A Programmable Transducer Self-Assembled from DNA

    PubMed Central

    Chakraborty, Banani; Jonoska, Natasha; Seeman, Nadrian C.

    2012-01-01

    A transducer consists of an input/output alphabet, a finite set of states, and a transition function. From an input symbol applied to a given state, the transition function determines the next state, and an output symbol. Using DNA, we have constructed a transducer that divides a number by 3. The input consists of a series of individually addressable 2-state DNA nanomechanical devices that control the orientations of a group of flat 6-helix DNA motifs; these motifs have edge domains tailed in sticky ends corresponding to the numbers 0 and 1. Three-domain DNA molecules (TX tiles) act as computational tiles that correspond to the transitions that the transducer can undergo. The output domain of these TX tiles contains sticky ends that also correspond to 0 or 1. Two different DNA tiles can chelate these output domains: A 5 nm gold nanoparticle is attached to the chelating tile that binds to 0-domains and a 10 nm gold nanoparticle is attached to the chelating tile that binds to 1-domains. The answer to the division is represented by the series of gold nanoparticles, which can be interpreted as a binary number. The answers of the computation are read out by examination of the transducer complexes under a transmission electron microscope. The start or end points of the output sequence can be indicated by the presence of a 15 nm gold nanoparticle. This work demonstrates two previously unreported features integrated in a single framework: [1] a system that combines DNA algorithmic self-assembly with DNA nanomechanical devices that control that input, and [2] the arrangement of non-DNA species, here metallic nanoparticles, through DNA algorithmic self-assembly. The nanomechanical devices are controlled by single-stranded DNA strands, allowing multiple input sequences to be applied to the rest of the system, thus guiding the algorithmic self-assembly to a variety of outputs. PMID:23139854

  12. Self-assembling SAS-6 multimer is a core centriole building block.

    PubMed

    Gopalakrishnan, Jayachandran; Guichard, Paul; Smith, Andrew H; Schwarz, Heinz; Agard, David A; Marco, Sergio; Avidor-Reiss, Tomer

    2010-03-19

    Centrioles are conserved microtubule-based organelles with 9-fold symmetry that are essential for cilia and mitotic spindle formation. A conserved structure at the onset of centriole assembly is a "cartwheel" with 9-fold radial symmetry and a central tubule in its core. It remains unclear how the cartwheel is formed. The conserved centriole protein, SAS-6, is a cartwheel component that functions early in centriole formation. Here, combining biochemistry and electron microscopy, we characterize SAS-6 and show that it self-assembles into stable tetramers, which serve as building blocks for the central tubule. These results suggest that SAS-6 self-assembly may be an initial step in the formation of the cartwheel that provides the 9-fold symmetry. Electron microscopy of centrosomes identified 25-nm central tubules with repeating subunits and show that SAS-6 concentrates at the core of the cartwheel. Recombinant and native SAS-6 self-oligomerizes into tetramers with approximately 6-nm subunits, and these tetramers are components of the centrosome, suggesting that tetramers are the building blocks of the central tubule. This is further supported by the observation that elevated levels of SAS-6 in Drosophila cells resulted in higher order structures resembling central tubule morphology. Finally, in the presence of embryonic extract, SAS-6 tetramers assembled into high density complexes, providing a starting point for the eventual in vitro reconstruction of centrioles.

  13. Evolving self-assembly in autonomous homogeneous robots: experiments with two physical robots.

    PubMed

    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. PMID:19463056

  14. Toward reliable algorithmic self-assembly of DNA tiles: a fixed-width cellular automaton pattern.

    PubMed

    Fujibayashi, Kenichi; Hariadi, Rizal; Park, Sung Ha; Winfree, Erik; Murata, Satoshi

    2008-07-01

    Bottom-up fabrication of nanoscale structures relies on chemical processes to direct self-assembly. The complexity, precision, and yield achievable by a one-pot reaction are limited by our ability to encode assembly instructions into the molecules themselves. Nucleic acids provide a platform for investigating these issues, as molecular structure and intramolecular interactions can encode growth rules. Here, we use DNA tiles and DNA origami to grow crystals containing a cellular automaton pattern. In a one-pot annealing reaction, 250 DNA strands first assemble into a set of 10 free tile types and a seed structure, then the free tiles grow algorithmically from the seed according to the automaton rules. In our experiments, crystals grew to approximately 300 nm long, containing approximately 300 tiles with an initial assembly error rate of approximately 1.4% per tile. This work provides evidence that programmable molecular self-assembly may be sufficient to create a wide range of complex objects in one-pot reactions.

  15. Localized dealloying corrosion mediated by self-assembled monolayers used as an inhibitor system.

    PubMed

    Shrestha, B R; Bashir, A; Ankah, G N; Valtiner, M; Renner, F U

    2015-01-01

    The structure and chemistry of thiol or selenol self-assembled organic monolayers have been frequently addressed due to the unique opportunities in functionalization of materials. Such organic films can also act as effective inhibition layers to mitigate oxidation or corrosion. Cu-Au alloy substrates covered by self-assembled monolayers show a different dealloying mechanism compared to bare surfaces. The organic surface layer inhibits dealloying of noble metal alloys by a suppression of surface diffusion at lower potentials but at higher applied potentials dealloying proceeds in localized regions due to passivity breakdown. We present an in situ atomic force microscopy study of a patterned thiol layer applied on Cu-Au alloy surfaces and further explore approaches to change the local composition of the surface layers by exchange of molecules. The pattern for the in situ experiment has been applied by micro-contact printing. This allows the study of corrosion protection with its dependence on different molecule densities at different sites. Low-density thiol areas surrounding the high-density patterns are completely protected and initiation of dealloying proceeds only along the areas with the lowest inhibitor concentration. Dealloying patterns are highly influenced and controlled by molecular thiol to selenol exchange and are also affected by introducing structural defects such as scratches or polishing defects. PMID:25920488

  16. Control over nanostructures and associated mesomorphic properties of doped self-assembled triarylamine liquid crystals.

    PubMed

    Domoto, Yuya; Busseron, Eric; Maaloum, Mounir; Moulin, Emilie; Giuseppone, Nicolas

    2015-01-26

    We have synthesized a series of triarylamine-cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by (1) H NMR and UV/Vis spectroscopy that their supramolecular self-assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable-temperature polarizing optical microscopy (VT-POM), variable-temperature X-ray diffraction (VT-XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar- or columnar-packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self-assemblies as electroactive materials from solution to mesophases. PMID:25483214

  17. Counterion-mediated hierarchical self-assembly of an ABC miktoarm star terpolymer.

    PubMed

    Hanisch, Andreas; Gröschel, André H; Förtsch, Melanie; Drechsler, Markus; Jinnai, Hiroshi; Ruhland, Thomas M; Schacher, Felix H; Müller, Axel H E

    2013-05-28

    Directed self-assembly processes of polymeric systems represent a powerful approach for the generation of structural hierarchy in analogy to biological systems. Herein, we utilize triiodide as a strongly polarizable counterion to induce hierarchical self-assembly of an ABC miktoarm star terpolymer comprising a polybutadiene (PB), a poly(tert-butyl methacrylate) (PtBMA), and a poly(N-methyl-2-vinylpyridinium) (P2VPq) segment. Hereby, the miktoarm architecture in conjunction with an increasing ratio of triiodide versus iodide counterions allows for a stepwise assembly of spherical micelles as initial building blocks into cylindrical structures and superstructures thereof. Finally, micrometer-sized multicompartment particles with a periodic lamellar fine structure are observed, for which we introduce the term "woodlouse". The counterion-mediated decrease in hydrophilicity of the corona-forming P2VPq block is the underlying trigger to induce this hierarchical structure formation. All individual steps and the corresponding intermediates toward these well-defined superstructures were intensively studied by scattering and electron microscopic techniques, including transmission electron microtomography. PMID:23544750

  18. Molecular Design of Bioinspired Nanostructures for Biomedical Applications: Synthesis, Self-Assembly and Functional Properties

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  19. Directed Self-Assembly of Diblock Copolymer Thin Films on Prepatterned Metal Nanoarrays.

    PubMed

    Chang, Tongxin; Huang, Haiying; He, Tianbai

    2016-01-01

    The sequential layer by layer self-assembly of block copolymer (BCP) nanopatterns is an effective approach to construct 3D nanostructures. Here large-scale highly ordered metal nano-arrays prepared from solvent annealed thin films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer are used to direct the assembly of the same BCP. The influence of initial loading concentration of metal precursor, the type of metal nanoparticle (gold, platinum, and silver), and the nanoparticle-substrate interaction on the directed assembly behavior of the upper BCP layer have been focused. It is found that the upper BCP film can be completely directed by the gold nanoarray with P2VP domain exclusively located between two adjacent gold nanowires or nanodots, which behaves the same way as on the platinum nanoarray. While the silver nanoarray can be destroyed during the upper BCP self-assembly with the silver nanoparticles assembled into the P2VP domain. Based on the discussions of the surface energy of nanoparticles and the interplay between nanoparticle-substrate interaction and nanoparticle-polymer interaction, it is concluded that the effect of immobilization of nanoparticles on the substrate, together with entropy effect to minimize the energetically unfavorable chain stretching contributes to the most effective alignment between each layer. PMID:26513110

  20. Surface modification and functionalization through the self-assembled monolayer and graft polymerization.

    PubMed

    Ruckenstein, E; Li, Z F

    2005-03-17

    The modification of a surface at the molecular level with precise control of the building blocks generates an integrated molecular system. This field has progressed rapidly in recent years through the use of self-assembled monolayer (SAM) interfaces. Recent developments on surface-initiated chemical reactions, functionalization, and graft polymerization on SAM interfaces are emphasized in the present review. A number of surface modifications by grafting are reviewed. The grafting of polyaniline on a glass surface, previously modified with a silane self-assembled monolayer (SAM), is examined in detail for both planar and 3-D systems, such as fibers, nanoparticles, and even polymer patterned surfaces. We also discuss the graft polymerization of water-soluble polymers on the surface of silicon nanoparticles, which generate stable aqueous colloidal solutions and have numerous applications. Finally, we compare and review some surface-modification techniques on the surfaces of polymers, such as two-solvent entrapment, polymer blending, and chemical grafting, which improve their biocompatibility.

  1. Energy levels in self-assembled quantum arbitrarily shaped dots.

    PubMed

    Tablero, C

    2005-02-01

    A model to determine the electronic structure of self-assembled quantum arbitrarily shaped dots is applied. This model is based principally on constant effective mass and constant potentials of the barrier and quantum dot material. An analysis of the different parameters of this model is done and compared with those which take into account the variation of confining potentials, bands, and effective masses due to strain. The results are compared with several spectra reported in literature. By considering the symmetry, the computational cost is reduced with respect to other methods in literature. In addition, this model is not limited by the geometry of the quantum dot. PMID:15740390

  2. Rapid self-assembly of block copolymers to photonic crystals

    DOEpatents

    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.

  3. Buckling instability of self-assembled colloidal columns.

    PubMed

    Swan, James W; Vasquez, Paula A; Furst, Eric M

    2014-09-26

    Suspended, slender self-assembled domains of magnetically responsive colloids are observed to buckle in microgravity. Upon cessation of the magnetic field that drives their assembly, these columns expand axially and buckle laterally. This phenomenon resembles the buckling of long beams due to thermal expansion; however, linear stability analysis predicts that the colloidal columns are inherently susceptible to buckling because they are freely suspended in a Newtonian fluid. The dominant buckling wavelength increases linearly with column thickness and is quantitatively described using an elastohydrodynamic model and the suspension thermodynamic equation of state. PMID:25302919

  4. Buckling Instability of Self-Assembled Colloidal Columns

    NASA Astrophysics Data System (ADS)

    Swan, James W.; Vasquez, Paula A.; Furst, Eric M.

    2014-09-01

    Suspended, slender self-assembled domains of magnetically responsive colloids are observed to buckle in microgravity. Upon cessation of the magnetic field that drives their assembly, these columns expand axially and buckle laterally. This phenomenon resembles the buckling of long beams due to thermal expansion; however, linear stability analysis predicts that the colloidal columns are inherently susceptible to buckling because they are freely suspended in a Newtonian fluid. The dominant buckling wavelength increases linearly with column thickness and is quantitatively described using an elastohydrodynamic model and the suspension thermodynamic equation of state.

  5. Surfactant Two-Dimensional Self-Assembly under Confinement

    SciTech Connect

    Sushko, Maria L.; Liu, Jun

    2011-03-28

    Confinement-induced structural rearrangements in supported self-assembled surfactant layers in aqueous salt solutions are investigated using classical Density Functional Theory. The systematic study of the influence of the nature of electrolyte revealed that 2:1 electrolyte stabilizes the hemicylindrical configuration of ionic surfactant layers, while a confinement-induced transition to a tilted monolayer configuration was found in symmetric 1:1 and 2:2 electrolytes. On the basis of this study we formulate a general model for the energetics of structural rearrangements in supported surfactant layers.

  6. Simulations of calcite crystallization on self-assembled monolayers.

    PubMed

    Freeman, Colin L; Harding, John H; Duffy, Dorothy M

    2008-09-01

    This paper presents simulations of calcium carbonate ordering in contact with self-assembled monolayers. The calculations use potential-based molecular dynamics to model the crystallization of calcium carbonate to calcite expressing both the (00.1) and (01.2) surfaces. The effect of monolayer properties: ionization; epitaxial matching; charge density; and headgroup orientation on the crystallization process are examined in detail. The results demonstrate that highly charged surfaces are vital to stimulate ordering and crystallization. Template directed crystallization requires charge epitaxy between both the crystal surface and the monolayer. The orientation of the headgroup appears to make no contribution to the selection of the crystal surface.

  7. Directed self-assembly graphoepitaxy template generation with immersion lithography

    NASA Astrophysics Data System (ADS)

    Ma, Yuansheng; Lei, Junjiang; Andres Torres, J.; Hong, Le; Word, James; Fenger, Germain; Tritchkov, Alexander; Lippincott, George; Gupta, Rachit; Lafferty, Neal; He, Yuan; Bekaert, Joost; Vanderberghe, Geert

    2015-07-01

    We present an optimization methodology for the template designs of subresolution contacts using directed self-assembly (DSA) with graphoepitaxy and immersion lithography. We demonstrate the flow using a 60-nm-pitch contact design in doublet with Monte Carlo simulations for DSA. We introduce the notion of template error enhancement factor (TEEF) to gauge the sensitivity of DSA printing infidelity to template printing infidelity and evaluate optimized template designs with TEEF metrics. Our data show that source mask optimization and inverse lithography technology are critical to achieve sub-80 nm non-L0 pitches for DSA patterns using 193i.

  8. Development of self-assembling nanowires containing electronically active oligothiophenes

    NASA Astrophysics Data System (ADS)

    Tsai, Wei-Wen

    This dissertation discusses the development of conductive one-dimensional nanowires from self-assembling oligothiophene molecules. Self-assembly has been demonstrated to be a promising alternative approach towards high performance, solution processable, and low-cost organic electronics. One of the many challenges in this field is the control of supramolecular morphologies of ordered structures containing pi-conjugated moieties. This research demonstrated several successful strategies to achieve self assembly of conductive nanowires using synergistic interactions combining pi stacking and hydrogen bonding. The first approach used was to develop a hairpin-shaped sexithiophene molecule, which features two arms of the conjugated structure. The diamidocyclohexyl headgroup of this molecule successfully directs the self-assembly from hydrogen bonding among the amides, forming high-aspect-ratio one-dimensional nanowires with well-defined diameters of 3.0 +/- 0.3 nm. The molecular orientation in the nanostructures promotes formation of sexithiophene H and J aggregates that facilitate efficient charge transport. Organic field-effect transistors were fabricated to reveal improved intrinsic hole mobility from films of the nanostructures, 3.46 x 10-6 cm2V-1s-1, which is one order of magnitude higher than films cast from unassembled molecules. Bulk heterojunction solar cells were developed from this molecule and fullerenes utilizing solution-phase fabrication methods. Intimate mix of the molecule and phenyl-C61-butyric acid methyl ester creates structured interfaces for efficient exciton splitting. The charge carrier mobilities of each material are improved by self-assembly in solution and thermal-energy assisted phase separation.The photovoltaic devices achieved the highest open-circuit voltage of 0.62 V, short-circuit current of 1.79 mA/cm2, fill factor of 35%, and power conversion efficiency of 0.48%. Another strategy to one-dimensional nanowires studied here involved the

  9. Electronic instabilities in self-assembled atom wires

    SciTech Connect

    Snijders, Paul C; Weitering, Harm H

    2010-01-01

    Low dimensional systems have fascinated physicists for a long time due to their unusual properties such as charge fractionalization, semionic statistics, and Luttinger liquid behavior among others. In nature, however, low dimensional systems often suffer from thermal fluctuations that can make these systems structurally unstable. Human beings, however, can trick nature by producing artificial structures which are not naturally produced. This Colloquium reviews the problem of self-assembled atomic wires on solid surfaces from an experimental and theoretical point of view. These materials represent a class of one-dimensional systems with very unusual properties that can open doors to the study of exotic physics that cannot be studied otherwise.

  10. Self-assembling peptide amphiphile nanostructures for cancer therapy

    NASA Astrophysics Data System (ADS)

    Soukasene, Stephen

    The application of nanotechnology to cancer therapy shows great promise for reducing the burden of the disease. By virtue of their size, nanoscale objects preferentially accumulate in tumor tissue through an enhanced permeability and retention (EPR) effect. However, to fully overcome the issues that limit current cancer treatments, viable nanostructures must also impart multifunctionality and be fully compatible with their biological surrounds. The self-assembling peptide amphiphile (PA) materials studied extensively in the Stupp Research Group form very biocompatible high aspect ratio nanostructures that meet these criteria. This thesis investigates the development of PA nanostructures designed to treat cancer. We first look to use the PA as a drug delivery vehicle by entrapping a small hydrophobic anti-cancer drug, camptothecin, in the core of the nanostructures. Using a solvent evaporation technique to load the drug into the PA nanofibers, we are able to improve the aqueous solubility of the molecule by nearly 30-fold. TEM and AFM studies show that entrapment of drug molecules does not disrupt the self-assembled morphology of the nanofiber. In vitro and in vivo studies are also conducted to demonstrate the bioactivity of the drug after its entrapment. As a potential platform for novel therapeutics, we next develop techniques for using light irradiation to trigger self-assembly inside the confined space of liposomes. We encapsulate PA monomers that assemble under acidic conditions along with a photoacid generator inside liposomes. Upon exposure to 254 nm light, the PA monomers self assemble inside the liposome to form nanostructures, which we observe through a quick freeze/deep etch technique that allows us to look inside the liposomes by SEM and TEM. Last of all, the development and discovery of epitopes for targeting PA nanostructures to tumors are explored. Using phage display technology we generate two groups of peptide sequences, one of which can potentially

  11. Self-assembly of silk fibroin under osmotic stress

    NASA Astrophysics Data System (ADS)

    Sohn, Sungkyun

    The supramolecular self-assembly behavior of silk fibroin was investigated using osmotic stress technique. In Chapter 2, a ternary phase diagram of water-silk-LiBr was constructed based on X-ray results on the osmotically stressed regenerated silk fibroin of Bombyx mori silkworm. Microscopic data indicated that silk I is a hydrated structure and a rough estimate of the number of water molecules lost by the structure upon converting from silk I to silk II has been made, and found to be about 2.2 per [GAGAGS] hexapeptide. In Chapter 3, wet-spinning of osmotically stressed, regenerated silk fibroin was performed, based on the prediction that the enhanced control over structure and phase behavior using osmotic stress method helps improve the physical properties of wet-spun regenerated silk fibroin fibers. The osmotic stress was applied in order to pre-structure the regenerated silk fibroin molecule from its original random coil state to more oriented state, manipulating the phase of the silk solution in the phase diagram before the start of spinning. Monofilament fiber with a diameter of 20 microm was produced. In Chapter 4, we investigated if there is a noticeable synergistic osmotic pressure increase between co-existing polymeric osmolyte and salt when extremely highly concentrated salt molecules are present both at sample subphase and stressing subphase, as is the case of silk fibroin self-assembly. The equilibration method that measures osmotic pressure relative to a reference with known osmotic pressure was introduced. Osmotic pressure of aqueous LiBr solution up to 2.75M was measured and it was found that the synergistic effect was insignificant up to this salt concentration. Solution parameters of stressing solutions and Arrhenius kinetics based on time-temperature relationship for the equilibration process were derived as well. In Chapter 5, self-assembly behavior of natural silk fibroin within the gland of Bombyx mori silkworm was investigated using osmotic

  12. Model for dynamic self-assembled magnetic surface structures

    NASA Astrophysics Data System (ADS)

    Belkin, M.; Glatz, A.; Snezhko, A.; Aranson, I. S.

    2010-07-01

    We propose a first-principles model for the dynamic self-assembly of magnetic structures at a water-air interface reported in earlier experiments. The model is based on the Navier-Stokes equation for liquids in shallow water approximation coupled to Newton equations for interacting magnetic particles suspended at a water-air interface. The model reproduces most of the observed phenomenology, including spontaneous formation of magnetic snakelike structures, generation of large-scale vortex flows, complex ferromagnetic-antiferromagnetic ordering of the snake, and self-propulsion of bead-snake hybrids.

  13. Customizing mesoscale self-assembly with three-dimensional printing

    NASA Astrophysics Data System (ADS)

    Poty, M.; Lumay, G.; Vandewalle, N.

    2014-02-01

    Self-assembly due to capillary forces is a common method for generating two-dimensional mesoscale structures from identical floating particles at the liquid-air interface. Designing building blocks to obtain a desired mesoscopic structure is a scientific challenge. We show herein that it is possible to shape the particles with a low cost three-dimensional printer, for composing specific mesoscopic structures. Our method is based on the creation of capillary multipoles inducing either attractive or repulsive forces. Since capillary interactions can be downscaled, our method opens new paths toward low cost microfabrication.

  14. Guided Self-Assembly of Nano-Precipitates into Mesocrystals

    PubMed Central

    Liu, H.; Gao, Y.; Xu, Z.; Zhu, Y.M.; Wang, Y.; Nie, J.F.

    2015-01-01

    We show by a combination of computer simulation and experimental characterization guided self-assembly of coherent nano-precipitates into a mesocrystal having a honeycomb structure in bulk materials. The structure consists of different orientation variants of a product phase precipitated out of the parent phase by heterogeneous nucleation on a hexagonal dislocation network. The predicted honeycomb mesocrystal has been confirmed by experimental observations in an Mg-Y-Nd alloy. The structure and lattice parameters of the mesocrystal and the size of the nano-precipitates are readily tuneable, offering ample opportunities to tailor its properties for a wide range of technological applications. PMID:26559002

  15. Preface: Special Topic on Supramolecular Self-Assembly at Surfaces

    SciTech Connect

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

    2015-03-14

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

  16. Rapid Self-Assembly of Uranyl Polyhedra into Crown Clusters

    SciTech Connect

    Sigmon, Ginger E.; Burns, Peter C.

    2011-06-22

    Clusters built from 32 uranyl peroxide polyhedra self-assemble and crystallize within 15 min after combining uranyl nitrate, ammonium hydroxide, and hydrogen peroxide in aqueous solution under ambient conditions. These novel crown-shaped clusters are remarkable in that they form so quickly, have extraordinarily low aqueous solubility, form with at least two distinct peroxide to hydroxyl ratios, and form in very high yield. The clusters, which have outer diameters of 23 Å, topologically consist of eight pentagons and four hexagons. Their rapid formation and low solubility in aqueous systems may be useful properties at various stages in an advanced nuclear energy system.

  17. Purification of ethanol for highly sensitive self-assembly experiments

    PubMed Central

    Barbe, Kathrin; Kind, Martin; Pfeiffer, Christian

    2014-01-01

    Summary Ethanol is the preferred solvent for the formation of self-assembled monolayers (SAMs) of thiolates on gold. By applying a thin film sensor system, we could demonstrate that even the best commercial qualities of ethanol contain surface-active contaminants, which can compete with the desired thiolates for surface sites. Here we present that gold nanoparticles deposited onto zeolite X can be used to remove these contaminants by chemisorption. This nanoparticle-impregnated zeolite does not only show high capacities for surface-active contaminants, such as thiols, but can be fully regenerated via a simple pyrolysis protocol. PMID:25161861

  18. Model for dynamic self-assembled magnetic surface structures.

    SciTech Connect

    Belkin, M.; Glatz, A.; Snezhko, A.; Aranson, I. S.; Materials Science Division; Northwestern Univ.

    2010-07-07

    We propose a first-principles model for the dynamic self-assembly of magnetic structures at a water-air interface reported in earlier experiments. The model is based on the Navier-Stokes equation for liquids in shallow water approximation coupled to Newton equations for interacting magnetic particles suspended at a water-air interface. The model reproduces most of the observed phenomenology, including spontaneous formation of magnetic snakelike structures, generation of large-scale vortex flows, complex ferromagnetic-antiferromagnetic ordering of the snake, and self-propulsion of bead-snake hybrids.

  19. Out of the cleanroom, self-assembled magnetic artificial cilia.

    PubMed

    Wang, Ye; Gao, Yang; Wyss, Hans; Anderson, Patrick; den Toonder, Jaap

    2013-09-01

    Micro-sized hair-like structures, such as cilia, are abundant in nature and have various functionalities. Many efforts have been made to mimic the fluid pumping function of cilia, but most of the fabrication processes for these "artificial cilia" are tedious and expensive, hindering their practical application. In this paper a cost-effective in situ fabrication technique for artificial cilia is demonstrated. The cilia are constructed by self-assembly of micron sized magnetic beads and encapsulated with soft polymer coatings. Actuation of the cilia induces an effective fluid flow, and the cilia lengths and distribution can be adjusted by varying the magnetic bead concentration and fabrication parameters.

  20. Directed self-assembly defectivity assessment. Part II

    NASA Astrophysics Data System (ADS)

    Bencher, Chris; Yi, He; Zhou, Jessica; Cai, Manping; Smith, Jeffrey; Miao, Liyan; Montal, Ofir; Blitshtein, Shiran; Lavi, Alon; Dotan, Kfir; Dai, Huixiong; Cheng, Joy Y.; Sanders, Daniel P.; Tjio, Melia; Holmes, Steven

    2012-03-01

    The main concern for the commercialization of directed self-assembly (DSA) for semiconductor manufacturing continues to be the uncertainty in capability and control of defect density. Our research investigates the defect densities of various DSA process applications in the context of a 300mm wafer fab cleanroom environment; this paper expands substantially on the previously published DSA defectivity study by reporting a defect density process window relative to chemical epitaxial pre-pattern registration lines; as well as investigated DSA based contact hole shrinking and report critical dimension statistics for the phase separated polymers before and after etch, along with positional accuracy measurements and missing via defect density.

  1. Programmed self-assembly of complex DNA nanostructures

    NASA Astrophysics Data System (ADS)

    Tian, Cheng

    DNA has served as an excellent building block to self-assemble into a wide range of one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) structures with the bottom-up method. Due to the specificity of base pairing, the DNA assembly system is predictable and robust. These DNA structures with higher diversity and complexity have potential applications as templates to organize guest molecules or nanoparticles for the nanofabrication, as biosensors for the genetic diagnosis and environmental detection, and as nanocarriers to deliver and release drugs for the therapy. My major researches focus on designing a novel building block and assembly strategies to self-assemble DNA into complex nanostructures to increase the diversity and complexity. A novel building block was first constructed, which is a parallel, left-handed DNA helix containing multiple domains of half-turn-long standard B-DNA. Such a structure can be used to introduce left-handed crossings in order to increase the diversity and complexity of DNA nanostructures, and can be taken into consideration when predicting the secondary structure of DNA/RNA molecules in cells. In addition, a tile-based directed self-assembly strategy was developed to construct DNA nanocages. In this strategy, directing building blocks were employed to control the self-assembly process of assembly building blocks. This strategy greatly expands the scope of accessible DNA nanostructures and would facilitate technological applications such as nano-guest encapsulation, drug delivery, and nanoparticle organization. As the complexity of DNA nanostructures increases, more errors might be involved in the assembly process. Therefore, a simplified design system based on T-junction was designed to build DNA arrays and minimize the assembly errors. In such system, due to the sequence symmetry, only one DNA single strand is employed and assembled into predesigned 1D and 2D arrays. This design system can be applied to assemble a

  2. Passivation effects in B doped self-assembled Si nanocrystals

    SciTech Connect

    Puthen Veettil, B. Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Zhang, Tian; Yang, Terry; Johnson, Craig; Conibeer, Gavin; Perez-Würfl, Ivan; McCamey, Dane

    2014-12-01

    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. Kinetics of the self-assembly of nanocrystal superlattices measured by real-time in situ X-ray scattering.

    PubMed

    Weidman, Mark C; Smilgies, Detlef-M; Tisdale, William A

    2016-07-01

    On solvent evaporation, non-interacting monodisperse colloidal particles self-assemble into a close-packed superlattice. Although the initial and final states can be readily characterized, little is known about the dynamic transformation from colloid to superlattice. Here, by using in situ grazing-incidence X-ray scattering, we tracked the self-assembly of lead sulfide nanocrystals in real time. Following the first appearance of an ordered arrangement, the superlattice underwent uniaxial contraction and collective rotation as it approached its final body-centred cubic structure. The nanocrystals became crystallographically aligned early in the overall self-assembly process, showing that nanocrystal ordering occurs on a faster timescale than superlattice densification. Our findings demonstrate that synchrotron X-ray scattering is a viable method for studying self-assembly in its native environment, with ample time resolution to extract kinetic rates and observe intermediate configurations. The method could be used for real-time direction of self-assembly processes and to better understand the forces governing self-organization of soft materials.

  4. Kinetics of the self-assembly of nanocrystal superlattices measured by real-time in situ X-ray scattering.

    PubMed

    Weidman, Mark C; Smilgies, Detlef-M; Tisdale, William A

    2016-07-01

    On solvent evaporation, non-interacting monodisperse colloidal particles self-assemble into a close-packed superlattice. Although the initial and final states can be readily characterized, little is known about the dynamic transformation from colloid to superlattice. Here, by using in situ grazing-incidence X-ray scattering, we tracked the self-assembly of lead sulfide nanocrystals in real time. Following the first appearance of an ordered arrangement, the superlattice underwent uniaxial contraction and collective rotation as it approached its final body-centred cubic structure. The nanocrystals became crystallographically aligned early in the overall self-assembly process, showing that nanocrystal ordering occurs on a faster timescale than superlattice densification. Our findings demonstrate that synchrotron X-ray scattering is a viable method for studying self-assembly in its native environment, with ample time resolution to extract kinetic rates and observe intermediate configurations. The method could be used for real-time direction of self-assembly processes and to better understand the forces governing self-organization of soft materials. PMID:26998914

  5. Early-time, beta-hairpin peptide self-assembly and hydrogelation: Structure, kinetics, and shear-recovery

    NASA Astrophysics Data System (ADS)

    Yucel, Tuna

    Recently, there has been growing interest in the supramolecular self-assembly and hydrogelation of peptides for potential biomaterials applications. However, there has been limited work on the physicochemical characterization of these systems that will be crucial for the development of these materials for future applications. The main objective of this dissertation was to provide a solid understanding of the self-assembly kinetics, hydrogelation pathways and the physical origins of the shear-recovery behavior of a self-assembled, peptidic hydrogel system. The MAX1 peptide, (VK)4-VDPPT-(KV)4-NH 2 is unfolded, and completely soluble in acidic to neutral aqueous solution. Increasing the pH or ionic strength of the solution triggers intramolecular peptide folding into beta-hairpins and concomitant intermolecular self-assembly into bilayered nanofibrils. Combined static and dynamic light scattering experiments revealed a direct transition from the initial, monomeric state to self-assembled nanofibrils, without an intermediate self-assembly step. The energy barrier associated with MAX1 self-assembly suggested that the self-assembly process involved intramolecular peptide folding events and cluster reorganization to facilitate intermolecular self-assembly. The assembly kinetics could be modeled using Smoluchowski's equation which indicated an essentially diffusion-limited assembly process. The analysis of early-stage dependence of apparent mass on size and the concentration dependence of assembly kinetics gave different fractal dimension values: The former indicated that the nanofibrils behaved locally as rigid rods, while the latter analysis suggested an increase in the apparent fractal dimension at larger length scales. Cryogenic transmission electron microscopy indicated that the increase in the apparent fractal dimension could be attributed to the formation of branched clusters of well-defined (uniform, 3 nm cross section), semi-flexible, beta-sheet-rich nanofibrils

  6. How chain plasmons govern the optical response in strongly interacting self-assembled metallic clusters of nanoparticles.

    PubMed

    Esteban, Ruben; Taylor, Richard W; Baumberg, Jeremy J; Aizpurua, Javier

    2012-06-19

    Self-assembled clusters of metallic nanoparticles separated by nanometric gaps generate strong plasmonic modes that support both intense and localized near fields. These find use in many ultrasensitive chemical and biological sensing applications through surface enhanced Raman scattering (SERS). The inability to control at the nanoscale the structure of the clusters on which the optical response crucially depends, has led to the development of general descriptions to model the various morphologies fabricated. Here, we use rigorous electrodynamic calculations to study clusters formed by a hundred nanospheres that are separated by ∼1 nm distance, set by the dimensions of the macrocyclic molecular linker employed experimentally. Three-dimensional (3D) cluster structures of moderate compactness are of special interest since they resemble self-assembled clusters grown under typical diffusion-limited aggregation conditions. We find very good agreement between the simulated and measured far-field extinction spectra, supporting the equivalence of the assumed and experimental morphologies. From these results we argue that the main features of the optical response of two- and three-dimensional clusters can be understood in terms of the excitation of simple units composed of different length resonant chains. Notably, we observe a qualitative difference between short- and long-chain modes in both spectral response and spatial distribution: dimer and short-chain modes are observed in the periphery of the cluster at higher energies, whereas inside the structure longer chain excitation occurs at lower energies. We study in detail different configurations of isolated one-dimensional chains as prototypical building blocks for large clusters, showing that the optical response of the chains is robust to disorder. This study provides an intuitive understanding of the behavior of very complex aggregates and may be generalized to other types of aggregates and systems formed by large

  7. A facile and green approach for the controlled synthesis of porous SnO₂ nanospheres: application as an efficient photocatalyst and an excellent gas sensing material.

    PubMed

    Manjula, P; Boppella, Ramireddy; Manorama, Sunkara V

    2012-11-01

    A facile and elegant methodology invoking the principles of Green Chemistry for the synthesis of porous tin dioxide nanospheres has been described. The low-temperature (∼50 °C) synthesis of SnO₂ nanoparticles and their self-assembly into organized, uniform, and monodispersed porous nanospheres with high surface area is facilitated by controlling the concentration of glucose, which acts as a stabilizing as well as structure-directing agent. A systematic control on the stannate to glucose molar concentration ratio determines the exact conditions to obtain monodispersed nanospheres, preferentially over random aggregation. Detailed characterization of the structure, morphology, and chemical composition reveals that the synthesized material, 50 nm SnO₂ porous nanospheres possess BET surface area of about 160 m²/g. Each porous nanosphere consists of a few hundred nanoparticles ∼2-3 nm in diameter with tetragonal cassiterite crystal structure. The SnO₂ nanospheres exhibit elevated photocatalytic activity toward methyl orange with good recyclability. Because of the high activity and stability of this photocatalyst, the material is ideal for applications in environmental remediation. Moreover, SnO₂ nanospheres display excellent gas sensing capabilities toward hydrogen. Surface modification of the nanospheres with Pd transforms this sensing material into a highly sensitive and selective room-temperature hydrogen sensor.

  8. Molecular self-assembly: Design, synthesis, and characterization of peptidic materials for bio- and nano-technologies

    NASA Astrophysics Data System (ADS)

    Lamm, Matthew S.

    The research presented in this dissertation focuses on the design, synthesis, and characterization of amphiphilic peptides capable of self-assembling into beta-sheet fibrils under specific aqueous solution conditions. The peptide design consists of two beta-sheet forming strands of alternating valine and lysine residues, flanking a central tetrapeptide sequence that contains a diproline. Depending on the chirality of the prolines the peptide can assume either an intramolecularly folded or an extended conformation in the self-assembled state. For the peptide where intramolecular folding is designed against, the self-assembled nanostructure was found to exhibit a unique, nontwisted laminated morphology. Experimental techniques including transmission electron microscopy, atomic force microscopy, circular dichroism spectroscopy, Fourier transform infra-red spectroscopy and x-ray diffraction were employed to characterize the self-assembled structure and kinetics. With the understanding of the self-assembly process gained from these first peptides, other peptide sequences were rationally designed to assemble with a desired nanostructure. For example, the effect of peptide strand length in conserving the laminated morphology and controlling the fibril height was investigated. In addition, other peptides were designed so as to affect the self-assembled nanostructure by enforcing a parallel versus anti-parallel beta-sheet or by disrupting the registry of laminating beta-sheet filaments. In some cases, the peptides assembled into structures predicted by the initial design while other peptides assembled into unexpected fibril morphologies. The major conclusions from the research on these peptides is that the diproline sequence plays an important role in disrupting the beta-strand twist thereby resulting in a nontwisted laminated morphology. However, when the flanking beta-strands become long enough, the effect of the diproline sequence becomes diminished and the fibrils do

  9. Moiré nanosphere lithography: use colloidal moiré patterns as masks

    NASA Astrophysics Data System (ADS)

    Chen, Kai; Rajeeva, Bharath B.; Wu, Zilong; Rukavina, Michael; Dao, Thang Duy; Ishii, Satoshi; Aono, Masakazu; Nagao, Tadaaki; Zheng, Yuebing

    2015-08-01

    Nanosphere lithography (NSL) uses self-assembled layers of monodisperse micro-/nano-spheres as masks to fabricate plasmonic metal nanoparticles. Different variants of NSL have been proposed with the combination with dry etching and/or angled-deposition. These techniques have employed to fabricate a wide variety of plasmonic nanoparticles or nanostructures. Here we report another promising extension - moiré nanosphere lithography (MNSL), which incorporates in-plane twisting between neighboring monolayers, to extend the patterning capability of conventional NSL. In conventional NSL, the masks, either a monolayer or bilayer, are formed by spontaneous self-assembly. Therefore, the resulted colloidal crystal configurations are limited. In this work we used sequential stacking of polystyrene nanosphere monolayers to form a bilayer crystal at the air/water interfaces. During this layer-by-layer stacking process, a crystal domain in the top layer gains the freedom to positon itself in a relative angle to that in the bottom layer allowing for the formation of moiré patterns. Subsequent O2 plasma etching results in a variety of complex nanostructures that have not been reported before. Using etched moiré patterns as masks, we further fabricated the corresponding gold nanostructures and characterized their scattering optical properties. We believe this facile technique provides a new strategy to fabricate novel and complex plasmonic nanostructures or metasurfaces.

  10. Cyclization and Catenation Directed by Molecular Self-Assembly

    SciTech Connect

    Wang, Wei; Wang, Li Q; Palmer, Bruce J; Exarhos, Gregory J; Li, Alexander D

    2006-08-30

    We report here that molecular self-assembly can effectively direct and enhance specific reaction pathways. Using perylene π-π stacking weak attractive forces, we succeeded in synthesizing perylene bisimide macrocyclic dimer and a concatenated dimer-dimer ring from dynamic self-assembly of monomeric bis-N, N’-(2-(2-(2-(2-thioacetyl ethoxy) ethoxy) ethoxy) ethyl) perylene tetracarboxylic diimide. The monocyclic ring closure and the dimer-dimer ring concatenation were accomplished through formation of disulfide bonds, which was readily triggered by air oxidization under basic deacetylation conditions. The perylene cyclic dimer and its concatenated tetramer were characterized using both structural methods (NMR, mass spectroscopy) and photophysical measurements (UV-vis spectroscopy). Kinetic analyses offer informative insights about reaction pathways and possible mechanisms, which lead to the formation of fascinating concatenated rings. Molecular dynamic behaviors of both the monocyclic dimer and the concatenated dimer-dimer ring were modeled with the NWChem molecular dynamics software module, which shows distinct stacking activities for the monocyclic dimer and the concatenated tetramer.

  11. Designing self-assembling 3D structures of microcapsules

    NASA Astrophysics Data System (ADS)

    Li, Like; Shum, Henry; Shklyaev, Oleg; Yashin, Victor; Balazs, Anna

    Self-assembly of complex, three-dimensional structures is commonly achieved by biological cells but difficult to realize in synthetic systems with micron-scale or larger components. Some previous modeling studies have considered only the planar self-assembly of microcapsules on a substrate. In this work, nanoparticles released from the capsules bind to the substrate and to the shells of nearby capsules. The non-uniform nanoparticle deposition on a capsule's surface leads to adhesion gradients, which drive the capsules to effectively ``climb'' on top of one another and self-organize in the vertical direction. We determine conditions that favor this structural organization. In particular, we study how the vertical structuring depends on the background fluid flow, the topography of the microcapsules and the underlying surface, the capsule-capsule interaction and that between the capsules and the substrate. The findings can provide design rules for the autonomous creation of novel nanocomposites, where the layers are formed from nanoparticle-containing and nanoparticle-decorated microcapsules.

  12. Self-assembly of organic films on a liquid metal

    NASA Astrophysics Data System (ADS)

    Magnussen, Olaf M.; Ocko, Benjamin M.; Deutsch, Moshe; Regan, Michael J.; Pershan, Peter S.; Abernathy, Douglas; Grübel, Gerhard; Legrand, Jean-François

    1996-11-01

    THE structure and phase behaviour of organic thin films result from the subtle interplay of intermolecular Van der Waals interactions, which promote self-assembly and long-ranged order, and the more complex interactions between the end groups of the organic chains and the substrate. The structure of molecular films of amphiphiles has been extensively studied on subphases of dielectric liquids, notably water (Langmuir mono-layers) and on solid surfaces (self-assembled monolayers, SAMs)1-4. Here we report structural studies, by synchrotron X-ray scattering, of an intermediate case: densely packed alka-nethiol films on the surface of liquid mercury. While, like SAMs, these films form strong chemical bonds to the subphase, this subphase is smooth and unstructured, as in the case of Langmuir monolayers. But unlike either of these1,2,5-7, our films have no in-plane long-range order. We suggest that the strong interaction of the thiol group with the underlying disordered liquid dominates here over the order-promoting interactions of the alkyl chains.

  13. Molecular Self-Assembly at Metal-Electrolyte Interfaces

    PubMed Central

    Phan, Thanh Hai; Wandelt, Klaus

    2013-01-01

    The self-assembly of molecular layers has become an important strategy in modern design of functional materials. However, in particular, large organic molecules may no longer be sufficiently volatile to be deposited by vapor deposition. In this case, deposition from solution may be a promising route; in ionic form, these molecules may even be soluble in water. In this contribution, we present and discuss results on the electrochemical deposition of viologen- and porphyrin molecules as well as their co-adsorption on chloride modified Cu(100) and Cu(111) single crystal electrode surfaces from aqueous acidic solutions. Using in situ techniques like cyclic voltametry and high resolution scanning tunneling microscopy, as well as ex-situ photoelectron spectroscopy data the highly ordered self-assembled organic layers are characterized with respect to their electrochemical behavior, lateral order and inner conformation as well as phase transitions thereof as a function of their redox-state and the symmetry of the substrate. As a result, detailed structure models are derived and are discussed in terms of the prevailing interactions. PMID:23439555

  14. Self-assembling and self-limiting monolayer deposition

    NASA Astrophysics Data System (ADS)

    Foest, Rüdiger; Schmidt, Martin; Gargouri, Hassan

    2014-02-01

    Effects of spatial ordering of molecules on surfaces are commonly utilized to deposit ultra-thin films with a thickness of a few nm. In this review paper, several methods are discussed, that are distinguished from other thin film deposition processes by exactly these effects that lead to self-assembling and self-limiting layer growth and eventually to coatings with unique and fascinating properties and applications in micro-electronics, optics, chemistry, or biology. Traditional methods for the formation of self-assembled films of ordered organic molecules, such as the Langmuir-Blodgett technique along with thermal atomic layer deposition (ALD) of inorganic molecules are evaluated. The overview is complemented by more recent developments for the deposition of organic or hybrid films by molecular layer deposition. Particular attention is given to plasma assisted techniques, either as a preparative, supplementary step or as inherent part of the deposition as in plasma enhanced ALD or plasma assisted, repeated grafting deposition. The different methods are compared and their film formation mechanisms along with their advantages are presented from the perspective of a plasma scientist. The paper contains lists of established film compounds and a collection of the relevant literature is provided for further reading.

  15. Self-assembled octapeptide scaffolds for in vitro chondrocyte culture.

    PubMed

    Mujeeb, Ayeesha; Miller, Aline F; Saiani, Alberto; Gough, Julie E

    2013-01-01

    Nature has evolved a variety of creative approaches to many aspects of materials synthesis and microstructural control. Molecular self-assembly is a simple and efficient way to fabricate complex nanostructures such as hydrogels. We have recently investigated the gelation properties of a series of ionic-complementary peptides based on the alternation of non-polar hydrophobic and polar hydrophilic residues. In this work we focus on one specific octapeptide, FEFEFKFK (F, phenylalanine; E, glutamic acid; K, lysine). This peptide was shown to self-assemble in solution and form β-sheet-rich nanofibres which, above a critical gelation concentration, entangle to form a self-supporting hydrogel. The fibre morphology of the hydrogel was analysed using transmission electron microscopy and cryo-scanning electron microscopy illustrating a dense fibrillar network of nanometer size fibres. Oscillatory rheology results show that the hydrogel possesses visco-elastic properties. Bovine chondrocytes were used to assess the biocompatibility of the scaffolds over 21 days under two-dimensional (2-D) and three-dimensional (3-D) cell culture conditions, particularly looking at cell morphology, proliferation and matrix deposition. 2-D culture resulted in cell viability and collagen type I deposition. In 3-D culture the mechanically stable gel was shown to support the viability of cells, the retention of cell morphology and collagen type II deposition. Subsequently the scaffold may serve as a template for cartilage tissue engineering.

  16. Simulation of self-assembly of polyzwitterions into vesicles

    DOE PAGES

    Mahalik, Jyoti P.; Muthukumar, Murugappan

    2016-08-19

    Using the Langevin dynamics method and a coarse-grained model, we have researched the formation of vesicles by hydrophobic polymers consisting of periodically placed zwitterion side groups in dilute salt-free aqueous solutions. The zwitterions, being permanent charge dipoles, provide long-range electrostatic correlations which are interfered by the conformational entropy of the polymer. Our simulations are geared towards gaining conceptual understanding in these correlated dipolar systems, where theoretical calculations are at present formidable. A competition between hydrophobic interactions and dipole-dipole interactions leads to a series of self-assembled structures. As the spacing d between the successive zwitterion side groups decreases, single chains undergomore » globule → disk → worm-like structures. We have calculated the Flory-Huggins χ parameter for these systems in terms of d and monitored the radius of gyration, hydrodynamic radius, spatial correlations among hydrophobic and dipole monomers, and dipole-dipole orientational correlation functions. During the subsequent stages of self-assembly, these structures lead to larger globules and vesicles as d is decreased up to a threshold value, below which no large scale morphology forms. Finally the vesicles form via a polynucleation mechanism whereby disk-like structures form first, followed by their subsequent merger.« less

  17. Molecular Self-Assembly Driven by London Dispersion Forces

    SciTech Connect

    Li, Guo; Cooper, Valentino R; Cho, Jun-Hyung; Du, Shixuan; Gao, Hongjun; Zhang, Zhenyu

    2011-01-01

    The nature and strength of intermolecular interactions are crucial to a variety of kinetic and dynamic processes at surfaces. Whereas strong chemisorption bonds are known to facilitate molecular binding, the importance of the weaker yet ubiquitous van der Waals (vdW) interactions remains elusive in most cases. Here we use first-principles calculations combined with kinetic Monte Carlo simulations to unambiguously demonstrate the vital role that vdW interactions play in molecular self-assembly, using styrene nanowire growth on silicon as a prototypical example. We find that, only when the London dispersion forces are included, accounting for the attractive parts of vdW interactions, can the effective intermolecular interaction be reversed from being repulsive to attractive. Such attractive interactions, in turn, ensure the preferred growth of long wires under physically realistic conditions as observed experimentally. We further propose a cooperative scheme, invoking the application of an electric field and the selective creation of Si dangling bonds, to drastically improve the ordered arrangement of the molecular structures. The present study represents a significant step forward in the fundamental understanding and precise control of molecular self-assembly guided by London dispersion forces.

  18. Self-assembled single-phase perovskite nanocomposite thin films.

    PubMed

    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.

  19. A coarse-grained model of microtubule self-assembly

    NASA Astrophysics Data System (ADS)

    Regmi, Chola; Cheng, Shengfeng

    Microtubules play critical roles in cell structures and functions. They also serve as a model system to stimulate the next-generation smart, dynamic materials. A deep understanding of their self-assembly process and biomechanical properties will not only help elucidate how microtubules perform biological functions, but also lead to exciting insight on how microtubule dynamics can be altered or even controlled for specific purposes such as suppressing the division of cancer cells. Combining all-atom molecular dynamics (MD) simulations and the essential dynamics coarse-graining method, we construct a coarse-grained (CG) model of the tubulin protein, which is the building block of microtubules. In the CG model a tubulin dimer is represented as an elastic network of CG sites, the locations of which are determined by examining the protein dynamics of the tubulin and identifying the essential dynamic domains. Atomistic MD modeling is employed to directly compute the tubulin bond energies in the surface lattice of a microtubule, which are used to parameterize the interactions between CG building blocks. The CG model is then used to study the self-assembly pathways, kinetics, dynamics, and nanomechanics of microtubules.

  20. Self-assembly of active colloidal molecules with dynamic function

    NASA Astrophysics Data System (ADS)

    Soto, Rodrigo; Golestanian, Ramin

    Catalytically active colloids maintain non-equilibrium conditions in which they produce and deplete chemicals at their surface. While individual colloids that are symmetrically coated do not exhibit dynamical activity, the concentration fields resulting from their chemical activity decay as 1/r and produce gradients that attract or repel other colloids depending on their surface chemistry and ambient variables. This results in a non-equilibrium analogue of ionic systems, but with the remarkable novel feature of action-reaction symmetry breaking. In dilute conditions these active colloids join up to form molecules via generalized ionic bonds. Colloids are found to join up to form self-assembled molecules that could be inert or have spontaneous activity in the form of net translational velocity and spin depending on their symmetry properties and their constituents. As the interactions do not satisfy detailed-balance, it is possible to achieve structures with time dependent functionality. We study a molecule that adopts spontaneous oscillations and another that exhibits a run-and-tumble dynamics similar to bacteria. Our study shows that catalytically active colloids could be used for designing self-assembled structures that posses dynamical functionalities.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

    NASA Astrophysics Data System (ADS)

    Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

    2016-06-01

    Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.

  3. Stochastic lag time in nucleated linear self-assembly

    NASA Astrophysics Data System (ADS)

    Tiwari, Nitin S.; van der Schoot, Paul

    2016-06-01

    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.

  4. Compositional Inheritance: Comparison of Self-assembly and Catalysis

    NASA Astrophysics Data System (ADS)

    Wu, Meng; Higgs, Paul G.

    2008-10-01

    Genetic inheritance in modern cells is due to template-directed replication of nucleic acids. However, the difficulty of prebiotic synthesis of long information-carrying polymers like RNA raises the question of whether some other form of heredity is possible without polymers. As an alternative, the lipid world theory has been proposed, which considers non-covalent assemblies of lipids, such as micelles and vesicles. Assemblies store information in the form of a non-random molecular composition, and this information is passed on when the assemblies divide, i.e . the assemblies show compositional inheritance. Here, we vary several important assumptions of previous lipid world models and show that compositional inheritance is relevant more generally than the context in which it was originally proposed. Our models assume that interaction occurs between nearest neighbour molecules only, and account for spatial segregation of molecules of different types within the assembly. We also draw a distinction between a self-assembly model, in which the composition is determined by mutually favourable interaction energies between the molecules, and a catalytic model, in which the composition is determined by mutually favourable catalysis. We show that compositional inheritance occurs in both models, although the self-assembly case seems more relevant if the molecules are simple lipids. In the case where the assemblies are composed of just two types of molecules, there is a strong analogy with the classic two-allele Moran model from population genetics. This highlights the parallel between compositional inheritance and genetic inheritance.

  5. Synthesis and simultaneous self-assembly of novel antibacterial polyurethanes

    NASA Astrophysics Data System (ADS)

    Duan, J. H.; Yin, F.; Jiang, G. C.

    2016-07-01

    Novel physically crosslinked polyurethane (PUII) based on isophorone diisocyanates (IPDI) was prepared by a conventional two step method. The chemical structures of the PUII were characterized by fourier transform infrared (FTIR), proton nuclear magnetic resonance (1H-NMR), gel permeation chromatography (GPC) and scanning electron microscopy (SEM). The PUII hydrogels were subjected to solvent-induced self-assembly in THF + water to construct a variety of morphologies. The self-assembly morphology of the PUII was observed by scanning electron microscopy (SEM). Different amounts (0.2%, 0.4%, 0.6%, 0.8%, 1.0%) of 1,3,5-Tris(2-hydroxyethyl)hexahydro-1,3,5-triazine (TNO) was added as antibacterial agent to the polyurethane prepolymers. The inhibiting capacity of the antibacterial films to the Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Gray mold has been studied. The inhibiting capacity of films for each strain effect became obvious with the increase of content of antibacterial agent and the sensitive degree to all kind of bacterial species was different.

  6. Modeling the Self-assembly of the Cellulosome Enzyme Complex*

    PubMed Central

    Bomble, Yannick J.; Beckham, Gregg T.; Matthews, James F.; Nimlos, Mark R.; Himmel, Michael E.; Crowley, Michael F.

    2011-01-01

    Most bacteria use free enzymes to degrade plant cell walls in nature. However, some bacteria have adopted a different strategy wherein enzymes can either be free or tethered on a protein scaffold forming a complex called a cellulosome. The study of the structure and mechanism of these large macromolecular complexes is an active and ongoing research topic, with the goal of finding ways to improve biomass conversion using cellulosomes. Several mechanisms involved in cellulosome formation remain unknown, including how cellulosomal enzymes assemble on the scaffoldin and what governs the population of cellulosomes created during self-assembly. Here, we present a coarse-grained model to study the self-assembly of cellulosomes. The model captures most of the physical characteristics of three cellulosomal enzymes (Cel5B, CelS, and CbhA) and the scaffoldin (CipA) from Clostridium thermocellum. The protein structures are represented by beads connected by restraints to mimic the flexibility and shapes of these proteins. From a large simulation set, the assembly of cellulosomal enzyme complexes is shown to be dominated by their shape and modularity. The multimodular enzyme, CbhA, binds statistically more frequently to the scaffoldin than CelS or Cel5B. The enhanced binding is attributed to the flexible nature and multimodularity of this enzyme, providing a longer residence time around the scaffoldin. The characterization of the factors influencing the cellulosome assembly process may enable new strategies to create designers cellulosomes. PMID:21098021

  7. Structure of self - assembled two-dimensional spherical crystals

    NASA Astrophysics Data System (ADS)

    Bausch, Andreas R.

    2004-03-01

    Dense spherical particles on a flat surface usually pack into a simple triangular lattice, similar to billiard balls at the start of a game. The minimum energy configuration for interacting particles on the curved surface of a sphere, however, presents special difficulties, as recognized already by J.J. Thomson. We describe experimental investigations of the structure of two-dimensional spherical crystals. The crystals, formed by beads self-assembled on water droplets in oil, serve as model systems for exploring very general theories about the minimum energy configurations of particles with arbitrary repulsive interactions on curved surfaces. Above a critical system size we find that crystals develop distinctive high-angle grain boundaries or "scars" not found in planar crystals. The number of excess defects in a scar is shown to grow linearly with the dimensionless system size. First experiments where the melting of the crystal structure was observable will be discussed. Dynamic triangulation methods allow the analysis of the dynamics of the defects. Possible modifications towards mechanically stabilized self assembly structures result in so called Colloidosomes, which are promising for many different encapsulation purposes.

  8. Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

    PubMed Central

    Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

    2016-01-01

    Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations. PMID:27279329

  9. Free surface BCP self-assembly process characterization with CDSEM

    NASA Astrophysics Data System (ADS)

    Levi, Shimon; Weinberg, Yakov; Adan, Ofer; Klinov, Michael; Argoud, Maxime; Claveau, Guillaume; Tiron, Raluca

    2016-03-01

    A simple and common practice to evaluate Block copolymers (BCP) self-assembly performances, is on a free surface wafer. With no guiding pattern the BCP designed to form line space pattern for example, spontaneously rearranges to form a random fingerprint type of a pattern. The nature of the rearrangement is dictated by the physical properties of the BCP moieties, wafer surface treatment and the self-assembly process parameters. Traditional CDSEM metrology algorithms are designed to measure pattern with predefined structure, like linespace or oval via holes. Measurement of pattern with expected geometry can reduce measurement uncertainty. Fingerprint type of structure explored in this dissertation, poses a challenge for CD-SEM measurement uncertainty and offers an opportunity to explore 2D metrology capabilities. To measure this fingerprints we developed a new metrology approach that combines image segmentation and edge detection to measure 2D pattern with arbitrary rearrangement. The segmentation approach enabled to quantify the quality of the BCP material and process, detecting 2D attributes such as: CD and CDU at one axis, and number of intersections, length and number of PS fragments, etched PMMA spaces and donut shapes numbers on the second axis. In this paper we propose a 2D metrology to measure arbitrary BCP pattern on a free surface wafer. We demonstrate experimental results demonstrating precision data, and characterization of PS-b-PMMA BCP, intrinsic period L0 = 38nm (Arkema), processed at different bake time and temperatures.

  10. The surface plasmon modes of self-assembled gold nanocrystals

    NASA Astrophysics Data System (ADS)

    Barrow, Steven J.; Wei, Xingzhan; Baldauf, Julia S.; Funston, Alison M.; Mulvaney, Paul

    2012-12-01

    The three-dimensional (3D) self-assembly of nanocrystals constitutes one of the most important challenges in materials science. A key milestone is the synthesis of simple, regular structures, such as platonic solids, composed of nanocrystal building blocks. Such objects are predicted to have unique optical and electronic properties such as polarization-independent light-scattering and intense local fields. Here we present a two-stage process for fabricating well-defined and highly symmetric, 3D gold nanocrystal structures, including tetrahedra, 3D pentamers and 3D hexamers. Polarized scattering spectra are used to elucidate the plasmon modes present in each structure, and these are compared with computational models. We conclude that self-assembly of highly symmetric, polarization-independent structures with interparticle spacings of order 0.5 nm can now be fabricated. Drastically, enhanced local fields, 1000 times higher than the incident field strength, are produced within the interstices. Fano resonances are generated if the symmetry is broken.

  11. Simulation of self-assembly of polyzwitterions into vesicles

    NASA Astrophysics Data System (ADS)

    Mahalik, J. P.; Muthukumar, M.

    2016-08-01

    Using the Langevin dynamics method and a coarse-grained model, we have studied the formation of vesicles by hydrophobic polymers consisting of periodically placed zwitterion side groups in dilute salt-free aqueous solutions. The zwitterions, being permanent charge dipoles, provide long-range electrostatic correlations which are interfered by the conformational entropy of the polymer. Our simulations are geared towards gaining conceptual understanding in these correlated dipolar systems, where theoretical calculations are at present formidable. A competition between hydrophobic interactions and dipole-dipole interactions leads to a series of self-assembled structures. As the spacing d between the successive zwitterion side groups decreases, single chains undergo globule → disk → worm-like structures. We have calculated the Flory-Huggins χ parameter for these systems in terms of d and monitored the radius of gyration, hydrodynamic radius, spatial correlations among hydrophobic and dipole monomers, and dipole-dipole orientational correlation functions. During the subsequent stages of self-assembly, these structures lead to larger globules and vesicles as d is decreased up to a threshold value, below which no large scale morphology forms. The vesicles form via a polynucleation mechanism whereby disk-like structures form first, followed by their subsequent merger.

  12. Compositional inheritance: comparison of self-assembly and catalysis.

    PubMed

    Wu, Meng; Higgs, Paul G

    2008-10-01

    Genetic inheritance in modern cells is due to template-directed replication of nucleic acids. However, the difficulty of prebiotic synthesis of long information-carrying polymers like RNA raises the question of whether some other form of heredity is possible without polymers. As an alternative, the lipid world theory has been proposed, which considers non-covalent assemblies of lipids, such as micelles and vesicles. Assemblies store information in the form of a non-random molecular composition, and this information is passed on when the assemblies divide, i.e. the assemblies show compositional inheritance. Here, we vary several important assumptions of previous lipid world models and show that compositional inheritance is relevant more generally than the context in which it was originally proposed. Our models assume that interaction occurs between nearest neighbour molecules only, and account for spatial segregation of molecules of different types within the assembly. We also draw a distinction between a self-assembly model, in which the composition is determined by mutually favourable interaction energies between the molecules, and a catalytic model, in which the composition is determined by mutually favourable catalysis. We show that compositional inheritance occurs in both models, although the self-assembly case seems more relevant if the molecules are simple lipids. In the case where the assemblies are composed of just two types of molecules, there is a strong analogy with the classic two-allele Moran model from population genetics. This highlights the parallel between compositional inheritance and genetic inheritance. PMID:18636340

  13. Protein-directed self-assembly of a fullerene crystal

    PubMed Central

    Kim, Kook-Han; Ko, Dong-Kyun; Kim, Yong-Tae; Kim, Nam Hyeong; Paul, Jaydeep; Zhang, Shao-Qing; Murray, Christopher B.; Acharya, Rudresh; DeGrado, William F.; Kim, Yong Ho; Grigoryan, Gevorg

    2016-01-01

    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design. PMID:27113637

  14. Self-assembly of ordered, conjugated polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    McCaughey, Byron

    This research aims to control the configuration and properties of functional, conjugated polymer systems by tuning the composite nanostructure and molecular interactions. This is accomplished by self-assembly of specific organic and inorganic building blocks. New nanocomposite synthesis schemes are demonstrated for poly(2,5-thienylene ethynylene) (PTE) and polydiacetylene (PDA) that focus on the combination of amphiphiles with hydrophobic and hydrophilic components. The weak molecular interactions between these building blocks result in spontaneous organization into highly ordered amorphous and crystalline structures. Emulsion polymerization, simultaneous monomer incorporation during self-assembly, and PDA supramolecular assembly synthesis paradigms will be discussed. By controlling the interactions, synthesis conditions, and building blocks; this research tunes the structure, molecular conformation, and therefore the optical properties of the resultant composites. Notable results include control of PTE particle size; direction of PTE/silica nanocomposite mesostructure; synthesis of free-standing mesoporous PTE; completely reversible thermochromatic and structural transitions in PDA assemblies; chemical and solvent sensing with PDA; and tunable mechanochromatic response with PDA composites. The synthesis schemes developed in this dissertation research program provide a general route to prepare functional materials with beneficial properties such as thermally controlled optical adsorption, self-healing mesostructure, molecular recognition, and mechanically induced color changes for the detection of damage in plastic composites.

  15. Turn nucleation perturbs amyloid β self-assembly and cytotoxicity.

    PubMed

    Doran, Todd M; Anderson, Elizabeth A; Latchney, Sarah E; Opanashuk, Lisa A; Nilsson, Bradley L

    2012-08-10

    The accumulation of senile plaques composed of amyloid β (Aβ) fibrils is a hallmark of Alzheimer's disease, although prefibrillar oligomeric species are believed to be the primary neurotoxic congeners in the pathogenesis of Alzheimer's disease. Uncertainty regarding the mechanistic relationship between Aβ oligomer and fibril formation and the cytotoxicity of these aggregate species persists. β-Turn formation has been proposed to be a potential rate-limiting step during Aβ fibrillogenesis. The effect of turn nucleation on Aβ self-assembly was probed by systematically replacing amino acid pairs in the putative turn region of Aβ (residues 24-27) with d-ProGly ((D)PG), an effective turn-nucleating motif. The kinetic, thermodynamic, and cytotoxic effects of these mutations were characterized. It was found that turn formation dramatically accelerated Aβ fibril self-assembly dependent on the site of turn nucleation. The cytotoxicity of the three (D)PG-containing Aβ variants was significantly lower than that of wild-type Aβ40, presumably due to decreased oligomer populations as a function of a more rapid progression to mature fibrils; oligomer populations were not eliminated, however, suggesting that turn formation is also a feature of oligomer structures. These results indicate that turn nucleation is a critical step in Aβ40 fibril formation.

  16. Template-mediated self-assembly of ordered magnetic nanoarrays

    NASA Astrophysics Data System (ADS)

    Sui, Yucheng

    2005-03-01

    Creation of magnetic nanostrctures is a very important research topic in nanoscience and nanotechnology. Among the popular bottom-up methods, self-assembly of magnetic nanostructures by chemical synthesis is favorable over others because it represents a low-cost and highly effective approach [1]. In this study, a novel technique template-mediated self-assembly is employed, that is the manipulation of magnetic clusters through both an external magnetic field and an ordered alumina template in order to fabricate ordered magnetic patterns with anisotropic properties [2]. This experiment consists of three parts. First, the synthesis and selection of FePt L10 clusters by hydrogen reduction and their capping by surfactants. Second, the fabrication of ordered alumina template by two-step anodization. Third, the insertion and assembly of clusters in nanopores under external magnetic field. Ordered magnetic dots were created with a coercivity of 13.4 kOe. The interactions between the scanning magnetic tips of MFM and the dots array were studied. This research is supported by DOE, NSF-MRSEC, W.M. Keck Foundation, ARO, and CMRA. 1. Y.C. Sui, R. Skomski, K. D. Sorge, and D. J. Sellmyer. Appl. Phys. Lett. 84, 1525 (2004). 2. Y.C. Sui, W. Liu, L. Yue, X.Z. Li, J. Zhou, R. Skomski and D. J. Sellmyer, J. Appl. Phys. (in press).

  17. Aerosol-Assisted Self-Assembly of Mesostructured Spherical Nanoparticles

    SciTech Connect

    Brinker, C.J.; Fan,; H.; Lu, Y.; Rieker, T.; Stump, A.; Ward, T.L.

    1999-03-23

    Nanostructured particles exhibiting well-defined pore sizes and pore connectivities (1-, 2-, or 3-dimensional) are of interest for catalysis, chromatography, controlled release, low dielectric constant fillers, and custom-designed pigments and optical hosts. During the last several years considerable progress has been made on controlling the macroscopic forms of mesoporous silicas prepared by surfactant and block copolymer liquid crystalline templating procedures. Typically interfacial phenomena are used to control the macroscopic form (particles, fibers, or films), while self-assembly of amphiphilic surfactants or polymers is used to control the mesostructure. To date, although a variety of spherical or nearly-spherical particles have been prepared, their extent of order is limited as is the range of attainable mesostructures. They report a rapid, aerosol process that results in solid, completely ordered spherical particles with stable hexagonal, cubic, or vesicular mesostructures. The process relies on evaporation-induced interfacial self-assembly (EISA) confined to a spherical aerosol droplet. The process is simple and generalizable to a variety of materials combinations. Additionally, it can be modified to provide the first aerosol route to the formation of ordered mesostructured films.

  18. Protein-directed self-assembly of a fullerene crystal.

    PubMed

    Kim, Kook-Han; Ko, Dong-Kyun; Kim, Yong-Tae; Kim, Nam Hyeong; Paul, Jaydeep; Zhang, Shao-Qing; Murray, Christopher B; Acharya, Rudresh; DeGrado, William F; Kim, Yong Ho; Grigoryan, Gevorg

    2016-01-01

    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design. PMID:27113637

  19. Precise hierarchical self-assembly of multicompartment micelles

    PubMed Central

    Gröschel, André H.; Schacher, Felix H.; Schmalz, Holger; Borisov, Oleg V.; Zhulina, Ekaterina B.; Walther, Andreas; Müller, Axel H.E.

    2012-01-01

    Hierarchical self-assembly offers elegant and energy-efficient bottom-up strategies for the structuring of complex materials. For block copolymers, the last decade witnessed great progress in diversifying the structural complexity of solution-based assemblies into multicompartment micelles. However, a general understanding of what governs multicompartment micelle morphologies and polydispersity, and how to manipulate their hierarchical superstructures using straightforward concepts and readily accessible polymers remains unreached. Here we demonstrate how to create homogeneous multicompartment micelles with unprecedented structural control via the intermediate pre-assembly of subunits. This directed self-assembly leads to a step-wise reduction of the degree of conformational freedom and dynamics and avoids undesirable kinetic obstacles during the structure build-up. It yields a general concept for homogeneous populations of well-defined multicompartment micelles with precisely tunable patchiness, while using simple linear ABC triblock terpolymers. We further demonstrate control over the hierarchical step-growth polymerization of multicompartment micelles into micron-scale segmented supracolloidal polymers as an example of programmable mesoscale colloidal hierarchies via well-defined patchy nanoobjects. PMID:22426231

  20. Self assembly of highly-ordered nanoparticle monolayers.

    SciTech Connect

    Bigioni, T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.; Univ. of Chicago

    2006-01-01

    When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

  1. Simulation of self-assembly of polyzwitterions into vesicles.

    PubMed

    Mahalik, J P; Muthukumar, M

    2016-08-21

    Using the Langevin dynamics method and a coarse-grained model, we have studied the formation of vesicles by hydrophobic polymers consisting of periodically placed zwitterion side groups in dilute salt-free aqueous solutions. The zwitterions, being permanent charge dipoles, provide long-range electrostatic correlations which are interfered by the conformational entropy of the polymer. Our simulations are geared towards gaining conceptual understanding in these correlated dipolar systems, where theoretical calculations are at present formidable. A competition between hydrophobic interactions and dipole-dipole interactions leads to a series of self-assembled structures. As the spacing d between the successive zwitterion side groups decreases, single chains undergo globule → disk → worm-like structures. We have calculated the Flory-Huggins χ parameter for these systems in terms of d and monitored the radius of gyration, hydrodynamic radius, spatial correlations among hydrophobic and dipole monomers, and dipole-dipole orientational correlation functions. During the subsequent stages of self-assembly, these structures lead to larger globules and vesicles as d is decreased up to a threshold value, below which no large scale morphology forms. The vesicles form via a polynucleation mechanism whereby disk-like structures form first, followed by their subsequent merger. PMID:27544126

  2. Self-Assembly of Channel Type β-CD Dimers Induced by Dodecane

    PubMed Central

    Zhou, Chengcheng; Cheng, Xinhao; Zhao, Qiang; Yan, Yun; Wang, Jide; Huang, Jianbin

    2014-01-01

    Cyclodextrins (CDs) can hardly self-assemble into well-defined structures. Here we report if they preassemble into channel type dimers assisted by dodecane, well-defined vesicles and bricks can be formed. Unlike the traditional self-assembly of amphiphilic molecules driven by hydrophobic effect, the self-assembly of the channel type dodecane@2β-CD supramolecular building block is predoninantly driven by hydrogen-bonds. More water molecules are found in the lyophilized vesicles than in the bricks, suggesting water molecules play an important role in the self-assembly of the channel-type dimers of β-CD. The amount of structural water in the self-assembly is closely related to the curvature of the final self-assembled structures. Our work reveals that the channel-type dimer of β-CD may represent a new sort of building block for advanced structures. PMID:25532046

  3. Self-Assembly of Channel Type β-CD Dimers Induced by Dodecane

    NASA Astrophysics Data System (ADS)

    Zhou, Chengcheng; Cheng, Xinhao; Zhao, Qiang; Yan, Yun; Wang, Jide; Huang, Jianbin

    2014-12-01

    Cyclodextrins (CDs) can hardly self-assemble into well-defined structures. Here we report if they preassemble into channel type dimers assisted by dodecane, well-defined vesicles and bricks can be formed. Unlike the traditional self-assembly of amphiphilic molecules driven by hydrophobic effect, the self-assembly of the channel type dodecane@2β-CD supramolecular building block is predoninantly driven by hydrogen-bonds. More water molecules are found in the lyophilized vesicles than in the bricks, suggesting water molecules play an important role in the self-assembly of the channel-type dimers of β-CD. The amount of structural water in the self-assembly is closely related to the curvature of the final self-assembled structures. Our work reveals that the channel-type dimer of β-CD may represent a new sort of building block for advanced structures.

  4. Molecular self-assembly routes to optically functional thin films: Electroluminescent multilayer structures

    SciTech Connect

    Li, W.; Malinsky, J.E.; Chou, H.

    1998-07-01

    This contribution describes the use of layer-by-layer self-limiting siloxane chemisorption processes to self-assemble structurally regular multilayer organic LED (OLED) devices. Topics discussed include: (1) the synthesis of silyl-functionalized precursor molecules for hole transport layer (HTL), emissive layer (EML), and electron transport layer (ETL) self-assembly, (2) the use of layer-by-layer self-assembly for ITO electrode modification/passivation/hole-electron balancing in a vapor-deposited device, (3) the microstructure/chemical characterization of HTL self-assembly using a prototype triarylamine precursor, (4) fabrication and properties of a hybrid self-assembled + vapor deposited two-layer LED, and (5) fabrication and properties of a fully self-assembled two-layer OLED.

  5. Self-assembly of channel type β-CD dimers induced by dodecane.

    PubMed

    Zhou, Chengcheng; Cheng, Xinhao; Zhao, Qiang; Yan, Yun; Wang, Jide; Huang, Jianbin

    2014-01-01

    Cyclodextrins (CDs) can hardly self-assemble into well-defined structures. Here we report if they preassemble into channel type dimers assisted by dodecane, well-defined vesicles and bricks can be formed. Unlike the traditional self-assembly of amphiphilic molecules driven by hydrophobic effect, the self-assembly of the channel type dodecane@2β-CD supramolecular building block is predoninantly driven by hydrogen-bonds. More water molecules are found in the lyophilized vesicles than in the bricks, suggesting water molecules play an important role in the self-assembly of the channel-type dimers of β-CD. The amount of structural water in the self-assembly is closely related to the curvature of the final self-assembled structures. Our work reveals that the channel-type dimer of β-CD may represent a new sort of building block for advanced structures. PMID:25532046

  6. Morphology and Pattern Control of Diphenylalanine Self-Assembly via Evaporative Dewetting.

    PubMed

    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.

  7. Self-assembly of PEGylated gold nanoparticles with satellite structures as seeds.

    PubMed

    Bachelet, Marie; Chen, Rongjun

    2016-07-21

    We report a very simple method for the self-assembly of spherical gold nanoparticles (AuNPs), coated with poly(ethylene glycol) (PEG), through a slow evaporation process at room temperature. Clusters of particles forming satellite structures may act as seeds for the self-assembly in a crystallization-like process. Based on the transmission electron microscopy (TEM) images obtained a mechanism for the self-assembly was suggested.

  8. Real time monitoring of superparamagnetic nanoparticle self-assembly on surfaces of magnetic recording media

    SciTech Connect

    Ye, L.; Pearson, T.; Crawford, T. M.; Qi, B.; Cordeau, Y.; Mefford, O. T.

    2014-05-07

    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.

  9. Self-assembly of patterned nanoparticles on cellular membranes: effect of charge distribution.

    PubMed

    Li, Ye; Zhang, Xianren; Cao, Dapeng

    2013-06-01

    Nanoparticle-assisted drug delivery has been emerging as an active research area. Achieving high drug loading is only one facet of drug delivery issues; it is also important to investigate the effect of surface charge distribution on self-assembly of nanoparticles on cellular membranes. By considering the electrostatic distribution of patterned nanoparticles, we used dissipative particle dynamics simulations to investigate the self-assembly of pattern charged nanoparticles with five different surface charged patterns. It is found that both surface charged pattern and nanoparticle size significantly affect the self-assembly of nanoparticles on cellular membranes. Results indicate that 1/2 pattern charged small nanoparticles can self-assemble into dendritic structures, while those with a 1/4 pattern self-assemble into clusters. As the nanoparticle size increases, 1/2 pattern charged medium nanoparticles can self-assemble into linear structures, while those with a 1/4 pattern self-assemble into clusters. For very large nanoparticles, both 1/2 pattern and 1/4 pattern charged nanoparticles self-assemble into flaky structures with different connections. By considering the effects of surface charged pattern and nanoparticle size on self-assembly, we found that nanoparticle self-assembly requires a minimum effective charged area. When the local charged area of nanoparticles is less than the threshold, surface charge cannot induce nanoparticle self-assembly; that is, the surface charged pattern of a nanoparticle would determine effectively the self-assembly structure. It is expected that this work will provide guidance for nanoparticle-assisted drug delivery.

  10. Nanoparticle fabrication by geometrically confined nanosphere lithography

    NASA Astrophysics Data System (ADS)

    Denomme, Ryan C.; Iyer, Krishna; Kreder, Michael; Smith, Brendan; Nieva, Patricia M.

    2013-07-01

    Arrays of metal nanoparticles, typically gold or silver, exhibit localized surface plasmon resonance, a phenomenon that has many applications, such as chemical and biological sensing. However, fabrication of metal nanoparticle arrays with high uniformity and repeatability, at a reasonable cost, is difficult. Nanosphere lithography (NSL) has been used before to produce inexpensive nanoparticle arrays through the use of monolayers of self-assembled microspheres as a deposition mask. However, control over the size and location of the arrays, as well as uniformity over large areas is poor, thus limiting its use to research purposes. In this paper, a new NSL method, called here geometrically confined NSL (GCNSL), is presented. In GCNSL, microsphere assembly is confined to geometric patterns defined in photoresist, allowing high-precision and large-scale nanoparticle patterning while still remaining low cost. Using this new method, it is demonstrated that 400 nm polystyrene microspheres can be assembled inside of large arrays of photoresist patterns. Results show that optimal microsphere assembly is achieved with long and narrow rectangular photoresist patterns. The combination of microsphere monolayers and photoresist patterns is then used as a deposition mask to produce silver nanoparticles at precise locations on the substrate with high uniformity, repeatability, and quality.

  11. Persistence Length Control of the Polyelectrolyte Layer-by-Layer Self-Assembly on Carbon Nanotubes

    SciTech Connect

    Huang, S J; Artyukhin, A B; Wang, Y; Ju, J; Stroeve, P; Noy, A

    2005-04-30

    One-dimensional inorganic materials such as carbon nanotubes1 and semiconductor nanowires have been central to important advances in materials science in the last decade. Unique mechanical and electronic properties of these molecular-scale wires enabled a variety of applications ranging from novel composite materials, to electronic circuits, to new sensors. Often, these applications require non-covalent modification of carbon nanotubes with organic compounds, DNA and biomolecules, and polymers to change nanotube properties or to add new functionality. We recently demonstrated a versatile and flexible strategy for non-covalent modification of carbon nanotubes using layer-by-layer self-assembly of polyelectrolytes. Researchers used this technique extensively for modification of flat surfaces, micro-, and nano-particles; however, little is known about the mechanism and the factors influencing layer-by-layer self-assembly in one-dimensional nanostructures. The exact conformation of polyelectrolyte chains deposited on single-walled carbon nanotubes (SWNT) is still unknown. There are two possible configurations: flexible polymers wrapping around the nanotube and stretched, rigid chains stacked parallel to the nanotube axis. Several factors, such as polymer rigidity, surface curvature, and strength of polymer-surface interactions, can determine the nature of assembly. Persistence length of the polymer chain should be one of the critical parameters, since it determines the chain's ability to wrap around the nanotube. Indeed, computer simulations for spherical substrates show that polymer rigidity and substrate surface curvature can influence the deposition process. Computational models also show that the persistence length of the polymer must fall below the threshold values determined by target surface curvature in order to initiate polyelectrolyte deposition process. Although these models described the effects of salt concentration and target surface curvature, they

  12. Kinetic trapping - a strategy for directing the self-assembly of unique functional nanostructures.

    PubMed

    Yan, Yun; Huang, Jianbin; Tang, Ben Zhong

    2016-10-14

    Supramolecular self-assembly into various nano- or microscopic structures based on non-covalent interactions between molecules has been recognized as a very efficient approach that leads to functional materials. Since most non-covalent interactions are relatively weak and form and break without significant activation barriers, the thermodynamic equilibrium of many supramolecular systems can be easily influenced by processing pathways that allow the system to stay in a kinetically trapped state. Thus far, kinetic traps have been found to be very important in producing more elaborate structural and functional diversity of self-assembled systems. In this review, we try to summarize the approaches that can produce kinetically trapped self-assemblies based on examples made by us. We focus on the following subjects: (1) supramolecular pathway dependent self-assembly, including kinetically trapped self-assemblies facilitated by host-guest chemistry, coordination chemistry, and electrostatic interactions; (2) physical processing pathway dependent self-assembly, including solvent quality controlled self-assembly, evaporation induced self-assembly and crystallization induced self-assembly.

  13. Proteolysis Triggers Self-Assembly and Unmasks Innate Immune Function of a Human α-Defensin Peptide

    PubMed Central

    Chairatana, Phoom; Shen, Bo; Bevins, Charles L.; Nolan, Elizabeth M.

    2015-01-01

    Human α-defensin 6 (HD6) is a unique peptide of the defensin family that provides innate immunity in the intestine by self-assembling to form high-order oligomers that entrap bacteria and prevent host cell invasion. Here, we report critical steps in the self-assembly pathway of HD6. We demonstrate that HD6 is localized in secretory granules of small intestinal Paneth cells. HD6 is stored in these granules as an 81-residue propeptide (proHD6), and is recovered from ileal lumen as a 32-residue mature peptide. The propeptide neither forms higher-order oligomers, nor agglutinates bacteria, nor prevents Listeria monocytogenes invasion into epithelial cells. The Paneth cell granules also contain the protease trypsin, and trypsin-catalyzed hydrolysis of proHD6 liberates mature HD6, unmasking its latent activities. This work illustrates a remarkable example of how nature utilizes a propeptide strategy to spatially and temporally control peptide self-assembly, and thereby initiates innate immune function in the human intestine. PMID:27076903

  14. Insight into fractal self-assembly of poly(diallyldimethylammonium chloride)/sodium carboxymethyl cellulose polyelectrolyte complex nanoparticles.

    PubMed

    Zhao, Qiang; An, Quanfu; Qian, Jinwen; Wang, Xuesan; Zhou, Yang

    2011-12-22

    Poly(diallyldimethylammonium chloride)-sodium carboxymethyl cellulose polyelectrolyte complexes (PDDA-CMCNa PECs) solids were prepared and dispersed in NaOH aqueous solution. Self-assembly of PECs nanoparticles during the solvent evaporation was examined by field emission electron microscopy (FESEM), atomic force microscopy (AFM), and fractal dimension analysis. It was found that tree-shaped fractal patterns formed after the solvent (water) was dried at ambient temperatures, and the fractal pattern is composed of needle-shaped PEC aggregate (PECA) nanoparticles. Time-dependent FESEM observation revealed that the fractal pattern started with the formation of initial nucleon and it is growing, during which the diffusion limited aggregation (DLA) mechanism revealed and made the pattern branched. Physical insight into the DLA mechanism was discussed in detail. Effects of PEC concentrations, PEC compositions, solvent evaporation temperatures, pH of PEC dispersion, and chemical structures of PECs on the formation of self-assembled fractal pattern were studied. Generally, it was found that the morphologies, charge characters of PEC particles, and the solvent evaporation conditions play important roles during the fractal self-assembly process. PMID:22098094

  15. Self-assembly modified-mushroom nanocomposite for rapid removal of hexavalent chromium from aqueous solution with bubbling fluidized bed

    PubMed Central

    Xu, Fei; Liu, Xu; Chen, Yijiao; Zhang, Ke; Xu, Heng

    2016-01-01

    A self-assembled modified Pleurotus Cornucopiae material (SMPM) combined with improved Intermittent Bubbling Fluidized Bed (IBFB) was investigated to remove the hexavalent chromium ions in aqueous solution. After the modification, the powder-like raw material gradually self-assembled together to SMPM, which had crinkly porous structure, improved the Cr-accommodation ability in a sound manner. Optimized by Taguchi method, Cr(VI) removal efficiency was up to 75.91% and 48.01% for 100 mg/L and 500 mg/L initial concentration of Cr(VI), respectively. Results indicated that the metal removal was dependent on dosage of adsorbent, particle diameter and treatment time. The experimental data obtained from the biosorption process was successfully correlated with Freundlich isotherm model. Thermodynamic study indicated the endothermic nature of the process. The results confirmed that self-assembly modified Pleurotus Cornucopiae material could be applied for the removal of heavy metal from wastewater in continuous fluidized bed process. PMID:27188258

  16. Creating Sub-50 Nm Nanofluidic Junctions in PDMS Microfluidic Chip via Self-Assembly Process of Colloidal Particles.

    PubMed

    Wei, Xi; Syed, Abeer; Mao, Pan; Han, Jongyoon; Song, Yong-Ak

    2016-03-13

    Polydimethylsiloxane (PDMS) is the prevailing building material to make microfluidic devices due to its ease of molding and bonding as well as its transparency. Due to the softness of the PDMS material, however, it is challenging to use PDMS for building nanochannels. The channels tend to collapse easily during plasma bonding. In this paper, we present an evaporation-driven self-assembly method of silica colloidal nanoparticles to create nanofluidic junctions with sub-50 nm pores between two microchannels. The pore size as well as the surface charge of the nanofluidic junction is tunable simply by changing the colloidal silica bead size and surface functionalization outside of the assembled microfluidic device in a vial before the self-assembly process. Using the self-assembly of nanoparticles with a bead size of 300 nm, 500 nm, and 900 nm, it was possible to fabricate a porous membrane with a pore size of ~45 nm, ~75 nm and ~135 nm, respectively. Under electrical potential, this nanoporous membrane initiated ion concentration polarization (ICP) acting as a cation-selective membrane to concentrate DNA by ~1,700 times within 15 min. This non-lithographic nanofabrication process opens up a new opportunity to build a tunable nanofluidic junction for the study of nanoscale transport processes of ions and molecules inside a PDMS microfluidic chip.

  17. Self-assembly modified-mushroom nanocomposite for rapid removal of hexavalent chromium from aqueous solution with bubbling fluidized bed

    NASA Astrophysics Data System (ADS)

    Xu, Fei; Liu, Xu; Chen, Yijiao; Zhang, Ke; Xu, Heng

    2016-05-01

    A self-assembled modified Pleurotus Cornucopiae material (SMPM) combined with improved Intermittent Bubbling Fluidized Bed (IBFB) was investigated to remove the hexavalent chromium ions in aqueous solution. After the modification, the powder-like raw material gradually self-assembled together to SMPM, which had crinkly porous structure, improved the Cr-accommodation ability in a sound manner. Optimized by Taguchi method, Cr(VI) removal efficiency was up to 75.91% and 48.01% for 100 mg/L and 500 mg/L initial concentration of Cr(VI), respectively. Results indicated that the metal removal was dependent on dosage of adsorbent, particle diameter and treatment time. The experimental data obtained from the biosorption process was successfully correlated with Freundlich isotherm model. Thermodynamic study indicated the endothermic nature of the process. The results confirmed that self-assembly modified Pleurotus Cornucopiae material could be applied for the removal of heavy metal from wastewater in continuous fluidized bed process.

  18. Application of capillary forces and stiction for lateral displacement, alignment, suspension and locking of self-assembled microcantilevers

    NASA Astrophysics Data System (ADS)

    Rose, F.; Hattori, M.; Kobayashi, D.; Toshiyoshi, H.; Fujita, H.; Kawakatsu, H.

    2006-10-01

    We report the surface-tension-powered self-assembly (displacement, alignment, pulling down and locking) of microcantilevers. Capillary forces-assisted displacement is realized by compression of four arrays of springs linked to the opposite lateral sides of the cantilevers. After in-plane translation along the initial cantilever orientation, the microstructure is pulled down and locked on the substrate by stiction. Spring and capillary forces are described with a simple analytical model. Complete self-assembly occurs when the layout of the whole system (the cantilever with its traveling spring structure, the surrounding area and the local distribution of the liquid) is well designed. We show that the presence of a water meniscus trapped at a step edge in the vicinity of the tip end of a microcantilever could lead to stiction failure before traveling of the structure. Small beams (6 µm long) protruding over step edges were fabricated by adding a mechanically assisted displacement step (with a microneedle) to the self-assembly experiment.

  19. Designing functional materials using the hydrophobic face of a self-assembling amphiphilic beta-hairpin peptide

    NASA Astrophysics Data System (ADS)

    Micklitsch, Christopher M.

    The ability of proteins to adopt discrete structures, as well as the ability of folded proteins to undergo supramolecular assembly, is based on the display of chemical functionality of the protein. Proteins fold and assemble according to the influence of intra- and intermolecular forces that act upon it to form ordered structures. By identifying these forces and how they influence assembly, they, in turn, can be exploited to design and synthesize materials from protein-based building blocks. By fabricating materials in this manner, the bulk material properties can be tuned by engineering at the molecular level. This study explores how modulation of the hydrophobic face of a de novo designed self-assembling beta-hairpin peptide affects its ability to fold and self-assemble to form a hydrogel, as well as on the resulting hydrogel's nanoscale structure and bulk properties. Initially, sequence modifications using amino acids of varying hydrophobicity were used to modify the hydrophobic face of the amphiphilic peptide. These modifications demonstrate how important hydrophobic regions of the peptide are to its ability to fold, self-assemble and form a hydrogel. The knowledge acquired from these studies was then used in the de novo design of a zinc-triggered peptide hydrogel, employing a nonnatural metal-binding amino acid on the hydrophobic face to instill metal-sensitivity in the peptide. Finally, aromatic interactions were incorporated on the topologically smooth hydrophobic face to direct self-assembly so as to impede the formation of interfibril junctions that lead to crosslinking of the fibrils that comprise the hydrogel scaffold.

  20. From self-assembly fundamental knowledge to nanomedicine developments.

    PubMed

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

    2014-03-01

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