Sample records for solvent evaporation-induced self-assembly

  1. Alcohol solvents evaporation-induced self-assembly synthesis of mesoporous TiO2- x- y C x N y nanoparticles toward visible-light driven photocatalytic activity (United States)

    Liu, Shou-Heng; Syu, Han-Ren; Wu, Chung-Yi


    A one-step solvent evaporation-induced self-assembly (SEISA) process was demonstrated to prepare carbon and nitrogen co-doping mesoporous TiO2 nanoparticles (MesoTiO2- x- y C x N y - S) using an ionic liquid as carbon and nitrogen sources as well as mesoporous template. After the evaporation of different solvents (methanol, ethanol, and isopropanol) and subsequent calcinations at 773 K, the obtained MesoTiO2- x- y C x N y - S samples were systematically characterized by a variety of spectroscopic and analytical techniques, including small- and large-angle X-ray diffraction (XRD), Raman, transmission electron microscopy (TEM), N2 adsorption-desorption isotherms, Fourier transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopies. The results indicate that the solvents play an essential role on the chemical microstructure, doping elemental states, and photocatalytic performance of catalysts. The MesoTiO2- x- y C x N y -I samples have the lowest band gap of ca. 2.75 eV and strongest absorbance of visible light in the range of 400-600 nm. Among the MesoTiO2- x- y C x N y - S photocatalysts, the MesoTiO2- x- y C x N y -M catalysts show superior photocatalytic activity of hydrogen generation in methanol aqueous solution under visible light irradiation as compared to MesoTiO2- x- y C x N y -E, MesoTiO2- x- y C x N y -I, and commercial Degussa TiO2. This result could be attributed to the moderate C,N co-doping amounts on their developed mesoporous texture (pore size = 8.0 nm) and high surface area (107 m2 g-1) of TiO2 (crystallite size = 9.9 nm) in the MesoTiO2- x- y C x N y -M catalysts.

  2. Alcohol solvents evaporation-induced self-assembly synthesis of mesoporous TiO2−x−yCxNy nanoparticles toward visible-light driven photocatalytic activity

    International Nuclear Information System (INIS)

    Liu, Shou-Heng; Syu, Han-Ren; Wu, Chung-Yi


    A one-step solvent evaporation-induced self-assembly (SEISA) process was demonstrated to prepare carbon and nitrogen co-doping mesoporous TiO 2 nanoparticles (MesoTiO 2−x−y C x N y -S) using an ionic liquid as carbon and nitrogen sources as well as mesoporous template. After the evaporation of different solvents (methanol, ethanol, and isopropanol) and subsequent calcinations at 773 K, the obtained MesoTiO 2−x−y C x N y -S samples were systematically characterized by a variety of spectroscopic and analytical techniques, including small- and large-angle X-ray diffraction (XRD), Raman, transmission electron microscopy (TEM), N 2 adsorption–desorption isotherms, Fourier transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopies. The results indicate that the solvents play an essential role on the chemical microstructure, doping elemental states, and photocatalytic performance of catalysts. The MesoTiO 2−x−y C x N y -I samples have the lowest band gap of ca. 2.75 eV and strongest absorbance of visible light in the range of 400–600 nm. Among the MesoTiO 2−x−y C x N y -S photocatalysts, the MesoTiO 2−x−y C x N y -M catalysts show superior photocatalytic activity of hydrogen generation in methanol aqueous solution under visible light irradiation as compared to MesoTiO 2−x−y C x N y -E, MesoTiO 2−x−y C x N y -I, and commercial Degussa TiO 2 . This result could be attributed to the moderate C,N co-doping amounts on their developed mesoporous texture (pore size = 8.0 nm) and high surface area (107 m 2  g −1 ) of TiO 2 (crystallite size = 9.9 nm) in the MesoTiO 2−x−y C x N y -M catalysts

  3. Evaporation induced self-assembly of nanoparticles in realizing hollow microcapsules (United States)

    Sen, D.; Bahadur, J.; Mazumder, S.


    Hollow spherical microcapsules are realized using evaporation induced self assembly of silica nanoparticles by spray drying method. Nanoparticles in spray droplets get jammed, during water evaporation, in an anisotropic fashion, at droplet air-water interface by the action of attractive capillary force. Two levels of structural hierarchy of the microcapsules are investigated using small-angle neutron scattering and scanning electron microscopy.

  4. Understanding the synthesis of mesoporous silica particles by evaporation induced self assembly (United States)

    Rathod, Shailendra B.


    Evaporation-induced self-assembly (EISA) of amphiphilic molecules within aerosol droplets is an attractive method for synthesis of mesoporous silica particles. The aim of this research was to demonstrate synthetic methodologies to develop novel particle architectures using this technique, and to understand the influence of the competing dynamics within an evaporating droplet undergoing EISA on the particle morphology and mesostructure. Experiments were conducted to control particle characteristics. Particle size and distribution was varied by varying the size and distribution of starting droplets. The compressed gas atomizer, TSI 3076, gave a roughly micron-sized droplets with a polydisperse population, whereas the vibrating orifice aerosol generator (VOAG), TSI 3450, gave a highly monodisperse droplet population when orifices of diameters 10 mum and 20 mum were used. The mesopore size and mesostructure ordering were varied by employing amphiphiles of different geometry and by the use of 1,2,3-trimethylbenzene, a pore-swelling agent. The extent of ordering was influenced by factors that govern the rates of reactions of the silica precursors relative to the rates of amphiphile self-assembly. These factors included acid concentration, the alkyl group in the tetraalkoxysilane precursor, the time for which the sol was aged before droplet generation, and CTAB/Si ratio in the starting sol. Experiments and simulation studies were carried out for particles made using CTAB as the templating agent and TMB as a pore-swelling agent. Analysis of these experiments was used to get insight into the three main dynamic processes occurring inside these droplets: evaporation of the volatile species, amphiphile self-assembly and phase transformation, and hydrolysis and condensation reactions of the silica precursor species. Pore swelling was observed for particles made using the VOAG. Particles made using the 10 mum orifice retained their hexagonal mesostructure upon addition of TMB in

  5. Evaporation-induced self assembly of nanoparticles in non-buckling regime: volume fraction dependent packing. (United States)

    Bahadur, J; Sen, D; Mazumder, S; Paul, Bhaskar; Khan, Arshad; Ghosh, G


    Hierarchically structured micrometric spheres are synthesized by evaporation-induced self assembly of silica colloids using spray drying technique. Packing of nanoparticles during drying of droplets is an important issue. The motivation of the present work is to investigate the effects of concentration of initial colloidal dispersion on the packing of the nanoparticles in assembled grains in non-buckling regime of drying. It has been observed that the packing of nanoparticles inside the dried grains, even in the non-buckling regime, varies significantly with concentration. Although, the packing of nanoparticles remains uniform in an assembled grain at smaller concentration, the same becomes non-uniform at higher concentration. Further, the average packing fraction of the nanoparticles within the assembled grains, decreases with increasing colloidal concentration. These observations have been attributed to the modification in viscosity of the initial dispersion. Electron microscopy, light scattering measurements have been performed to probe overall morphology of the dried grains, while inter-particle correlation inside the grains has been investigated by small angle neutron scattering. Copyright © 2010 Elsevier Inc. All rights reserved.

  6. Solvent mediated self-assembly of solids

    Energy Technology Data Exchange (ETDEWEB)

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


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

  7. Nanostructured Mesoporous Silica Wires with Intrawire Lamellae via Evaporation-Induced Self-Assembly in Space-Confined Channels

    Directory of Open Access Journals (Sweden)

    Michael Z. Hu


    Full Text Available Evaporation-induced self-assembly (EISA of silica sol-gel ethanol-water solution mixtures with block-copolymer were studied inside uniform micro/nano-channels. Nanostructured mesoporous silica wires, with various intrawire self-assembly structures including lamellae, were prepared via EISA process but in space-confined channels with the diameter ranging from 50 nm to 200 nm. Membranes made of anodized aluminum oxide (AAO and track-etched polycarbonate (EPC were utilized as the arrays of space-confined channels (i.e., 50, 100, and 200 nm EPC and 200 nm AAO for infiltration and drying of mixture solutions; these substrate membranes were submerged in mixture solutions consisting of a silica precursor, a structure-directing agent, ethanol, and water. After the substrate channels were filled with the solution under vacuum impregnation, the membrane was removed from the solution and dried in air. The silica precursor used was tetraethyl othosilicate (TEOS, and the structure-directing agent employed was triblock copolymer Pluronic-123 (P123. It was found that the formation of the mesoporous nanostructures in silica wires within uniform channels were significantly affected by the synthesis conditions including (1 preassemble TEOS aging time, (2 the evaporation rate during the vacuum impregnation, and (3 the air-dry temperature. The obtained intrawire structures, including 2D hexagonal rods and lamellae, were studied by scanning transmission electron microscopy (STEM. A steric hindrance effect seems to explain well the observed polymer-silica mesophase formation tailored by TEOS aging time. The evaporation effect, air-drying effect, and AAO versus EPC substrate effect on the mesoporous structure of the formed silica wires were also presented and discussed.

  8. Effect of surfactant concentration on characteristics of mesoporous bioactive glass prepared by evaporation induced self-assembly process

    International Nuclear Information System (INIS)

    Shih, Chi-Chung; Chien, Chi-Sheng; Kung, Jung-Chang; Chen, Jian-Chih; Chang, Shy-Shin; Lu, Pei-Shan; Shih, Chi-Jen


    Highlights: ► All the unwanted organic contents were removed completely at temperatures above 600 °C. ► Specific surface area and pore volume of Mesoporous bioactive glasses reached maximum at the critical surfactant concentration. ► SAED pattern suggests that some glassy structures in the Bioactive Glasses became crystalline due to the heat treatment. ► The MBGs can induce the formation of an apatite-like layer on their surface in SBF, even after short soaking periods. - Abstract: Mesoporous bioactive glasses were prepared by the evaporation-induced self-assembly method. The main objective of the present study is to determine the effect of surfactant concentration on the synthesis of SiO 2 –CaO–P 2 O 5 mesoporous bioactive glasses; the characterization techniques used include X-ray diffraction, scanning electron microscopy and nitrogen adsorption and desorption isotherms. The results show that the specific surface area initially increased with increasing surfactant concentrations in the range of 2.1–9.1 wt% and significantly decreased from 328.7 to 204.0 m 2 /g in the concentration range of 9.1–12.5 wt%. For texture evaluation, the selected area electron diffraction patterns of the mesoporous bioactive glass precursor gels (9.1 wt% F127) calcined at different temperatures were analyzed; these patterns support the notion that some glassy structures in bioactive glasses become crystalline following heat treatment. The scanning electron microscopy images and X-ray diffraction patterns obtained agree with the inductively coupled plasma with atomic emission spectroscopy results as the mesoporous bioactive glasses can induce the formation of an apatite-like layer on their surface in SBF, even after short soaking periods.

  9. Effect of surfactant concentration on characteristics of mesoporous bioactive glass prepared by evaporation induced self-assembly process

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    Shih, Chi-Chung [Department of Emergency Medicine, Chang Gung Memorial Hospital, Keelung, and Chang Gung University College of Medicine, Taoyuan, Taiwan (China); Department of Family Medicine, Chang Gung Memorial Hospital, Keelung, and Chang Gung University College of Medicine, Taoyuan, Taiwan (China); Chien, Chi-Sheng [Department of Biomedical Engineering, National Cheng Kung University, Tainan, Taiwan (China); Department of Orthopaedics, Chi Mei Foundation Hospital, Tainan, Taiwan (China); Department of Electrical Engineering, Southern Taiwan University of Science and Technology, Tainan, Taiwan (China); Kung, Jung-Chang [Department of Family Dentistry, Chung-Ho Memorial Hospital, Kaohsiung Medical University, Kaohsiung 807, Taiwan (China); Chen, Jian-Chih [Department of Orthopaedics, Kaohsiung Medical University Hospital, Kaohsiung Medical University, Kaohsiung 807, Taiwan (China); Chang, Shy-Shin [Department of Emergency Medicine, Chang Gung Memorial Hospital, Taoyuan, and Chang Gung University College of Medicine, Taoyuan, Taiwan (China); Department of Family Medicine, Chang Gung Memorial Hospital, Taoyuan, and Chang Gung University College of Medicine, Taoyuan, Taiwan (China); Lu, Pei-Shan [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Shih, Chi-Jen, E-mail: [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 80708, Taiwan (China)


    Highlights: Black-Right-Pointing-Pointer All the unwanted organic contents were removed completely at temperatures above 600 Degree-Sign C. Black-Right-Pointing-Pointer Specific surface area and pore volume of Mesoporous bioactive glasses reached maximum at the critical surfactant concentration. Black-Right-Pointing-Pointer SAED pattern suggests that some glassy structures in the Bioactive Glasses became crystalline due to the heat treatment. Black-Right-Pointing-Pointer The MBGs can induce the formation of an apatite-like layer on their surface in SBF, even after short soaking periods. - Abstract: Mesoporous bioactive glasses were prepared by the evaporation-induced self-assembly method. The main objective of the present study is to determine the effect of surfactant concentration on the synthesis of SiO{sub 2}-CaO-P{sub 2}O{sub 5} mesoporous bioactive glasses; the characterization techniques used include X-ray diffraction, scanning electron microscopy and nitrogen adsorption and desorption isotherms. The results show that the specific surface area initially increased with increasing surfactant concentrations in the range of 2.1-9.1 wt% and significantly decreased from 328.7 to 204.0 m{sup 2}/g in the concentration range of 9.1-12.5 wt%. For texture evaluation, the selected area electron diffraction patterns of the mesoporous bioactive glass precursor gels (9.1 wt% F127) calcined at different temperatures were analyzed; these patterns support the notion that some glassy structures in bioactive glasses become crystalline following heat treatment. The scanning electron microscopy images and X-ray diffraction patterns obtained agree with the inductively coupled plasma with atomic emission spectroscopy results as the mesoporous bioactive glasses can induce the formation of an apatite-like layer on their surface in SBF, even after short soaking periods.

  10. Synthesis of magnetic mesoporous titania colloidal crystals through evaporation induced self-assembly in emulsion as effective and recyclable photocatalysts. (United States)

    Chen, Jeffrey E; Lian, Hong-Yuan; Dutta, Saikat; Alshehri, Saad M; Yamauchi, Yusuke; Nguyen, Mai Thanh; Yonezawa, Tetsu; Wu, Kevin C-W


    This study illustrates the directed self-assembly of mesoporous TiO2 with magnetic properties due to its colloidal crystal structure with Fe3O4. The Fe3O4 nanoparticles were synthesized using co-precipitation techniques to a size of 28.2 nm and a magnetic saturation of 66.9 emu g(-1). Meanwhile, mesoporous titania nanoparticles (MTNs) with a particle diameter of 373 nm, a specific surface area of 236.3 m(2) g(-1), and a pore size of 2.8 nm were prepared by controlling the rate of hydrolysis. Magnetic colloidal crystals (a diameter of 10.2 μm) were formed by the aggregation of Fe3O4 and MTNs caused by the interface phenomena during solvent evaporation in emulsion. Even the anatase octahedrite produced from the colloidal crystal after a hydrothermal reaction retained a magnetic saturation of 2.8 emu g(-1). This study also investigates the photodegradation activity of our synthesized material as a photocatalyst, while utilizing its capability for magnetic separation to prove its usefulness in catalyst recycling.

  11. Facile Synthesis of Wormhole-Like Mesoporous Tin Oxide via Evaporation-Induced Self-Assembly and the Enhanced Gas-Sensing Properties (United States)

    Li, Xiaoyu; Peng, Kang; Dou, Yewei; Chen, Jiasheng; Zhang, Yue; An, Gai


    Wormhole-like mesoporous tin oxide was synthesized via a facile evaporation-induced self-assembly (EISA) method, and the gas-sensing properties were evaluated for different target gases. The effect of calcination temperature on gas-sensing properties of mesoporous tin oxide was investigated. The results demonstrate that the mesoporous tin oxide sensor calcined at 400 °C exhibits remarkable selectivity to ethanol vapors comparison with other target gases and has a good performance in the operating temperature and response/recovery time. This might be attributed to their high specific surface area and porous structure, which can provide more active sites and generate more chemisorbed oxygen spices to promote the diffusion and adsorption of gas molecules on the surface of the gas-sensing material. A possible formation mechanism of the mesoporous tin oxide and the enhanced gas-sensing mechanism are proposed. The mesoporous tin oxide shows prospective detecting application in the gas sensor fields.

  12. Versatility of Evaporation-Induced Self-Assembly (EISA Method for Preparation of Mesoporous TiO2 for Energy and Environmental Applications

    Directory of Open Access Journals (Sweden)

    Luther Mahoney


    Full Text Available Evaporation-Induced Self-Assembly (EISA method for the preparation of mesoporous titanium dioxide materials is reviewed. The versatility of EISA method for the rapid and facile synthesis of TiO2 thin films and powders is highlighted. Non-ionic surfactants such as Pluronic P123, F127 and cationic surfactants such as cetyltrimethylammonium bromide have been extensively employed for the preparation of mesoporous TiO2. In particular, EISA method allows for fabrication of highly uniform, robust, crack-free films with controllable thickness. Eleven characterization techniques for elucidating the structure of the EISA prepared mesoporous TiO2 are discussed in this paper. These many characterization methods provide a holistic picture of the structure of mesoporous TiO2. Mesoporous titanium dioxide materials have been employed in several applications that include Dye Sensitized Solar Cells (DSSCs, photocatalytic degradation of organics and splitting of water, and batteries.

  13. Facile Synthesis of Wormhole-Like Mesoporous Tin Oxide via Evaporation-Induced Self-Assembly and the Enhanced Gas-Sensing Properties. (United States)

    Li, Xiaoyu; Peng, Kang; Dou, Yewei; Chen, Jiasheng; Zhang, Yue; An, Gai


    Wormhole-like mesoporous tin oxide was synthesized via a facile evaporation-induced self-assembly (EISA) method, and the gas-sensing properties were evaluated for different target gases. The effect of calcination temperature on gas-sensing properties of mesoporous tin oxide was investigated. The results demonstrate that the mesoporous tin oxide sensor calcined at 400 °C exhibits remarkable selectivity to ethanol vapors comparison with other target gases and has a good performance in the operating temperature and response/recovery time. This might be attributed to their high specific surface area and porous structure, which can provide more active sites and generate more chemisorbed oxygen spices to promote the diffusion and adsorption of gas molecules on the surface of the gas-sensing material. A possible formation mechanism of the mesoporous tin oxide and the enhanced gas-sensing mechanism are proposed. The mesoporous tin oxide shows prospective detecting application in the gas sensor fields.

  14. One-step fabrication of thermally stable TiO2/SiO2 nanocomposite microspheres by evaporation-induced self-assembly. (United States)

    Bahadur, J; Sen, D; Mazumder, S; Sastry, P U; Paul, B; Bhatt, H; Singh, S G


    The evaporation-induced self-assembly of mixed colloids has been employed to synthesize microspheres of TiO(2)/SiO(2) nanocomposites. Small-angle neutron/X-ray scattering and scanning electron microscopy experiments reveal the hierarchical morphology of the microspheres. Although the internal structure of the microspheres, consisting of solely silica nanoparticles, gets significantly modified with time because of the reduction in the high specific surface area by internal coalescence, the same for the composite microspheres remains stable over an aging time of 1 year. Such temporal stability of the composite microspheres is attributed to the inhibition of coalescence of the silica nanoparticles in the presence of titania nanoparticles. X-ray diffraction and thermogravimetric results show the improved thermal stability of the composite grains against the anatase-to-rutile phase transition. Such thermal stability is attributed to the suppression of the growth of titania nanoparticles in the presence of silica nanoparticles. The UV-vis results indicate the confinement effect of the TiO(2) nanoparticles in the silica matrix. A plausible mechanism has been elucidated for the formation of microspheres with different morphology during self-assembly.

  15. Reflection of circularly polarized light and the effect of particle distribution on circular dichroism in evaporation induced self-assembled cellulose nanocrystal thin films (United States)

    Hewson, D.; Vukusic, P.; Eichhorn, S. J.


    Evaporation induced self-assembled (EISA) thin films of cellulose nanocrystals (CNCs) have shown great potential for displaying structural colour across the visible spectrum. They are believed primarily to reflect left handed circularly polarised (LCP) light due to their natural tendency to form structures comprising left handed chirality. Accordingly the fabrication of homogenously coloured CNC thin films is challenging. Deposition of solid material towards the edge of a dried droplet, via the coffee-stain effect, is one such difficulty in achieving homogenous colour across CNC films. These effects are most easily observed in films prepared from droplets where observable reflection of visible light is localised around the edge of the dry film. We report here, the observation of both left and right hand circularly polarised (LCP/RCP) light in reflection from distinct separate regions of CNC EISA thin films and we elucidate how these reflections are dependent on the distribution of CNC material within the EISA thin film. Optical models of reflection are presented which are based on structures revealed using high resolution transmission electron microscopy (TEM) images of film cross sections. We have also employed spectroscopic characterisation techniques to evaluate the distribution of solid CNC material within a selection of CNC EISA thin films and we have correlated this distribution with polarised light spectra collected from each film. We conclude that film regions from which RCP light was reflected were associated with lower CNC concentrations and thicker film regions.

  16. Reflection of circularly polarized light and the effect of particle distribution on circular dichroism in evaporation induced self-assembled cellulose nanocrystal thin films

    Directory of Open Access Journals (Sweden)

    D. Hewson


    Full Text Available Evaporation induced self-assembled (EISA thin films of cellulose nanocrystals (CNCs have shown great potential for displaying structural colour across the visible spectrum. They are believed primarily to reflect left handed circularly polarised (LCP light due to their natural tendency to form structures comprising left handed chirality. Accordingly the fabrication of homogenously coloured CNC thin films is challenging. Deposition of solid material towards the edge of a dried droplet, via the coffee-stain effect, is one such difficulty in achieving homogenous colour across CNC films. These effects are most easily observed in films prepared from droplets where observable reflection of visible light is localised around the edge of the dry film. We report here, the observation of both left and right hand circularly polarised (LCP/RCP light in reflection from distinct separate regions of CNC EISA thin films and we elucidate how these reflections are dependent on the distribution of CNC material within the EISA thin film. Optical models of reflection are presented which are based on structures revealed using high resolution transmission electron microscopy (TEM images of film cross sections. We have also employed spectroscopic characterisation techniques to evaluate the distribution of solid CNC material within a selection of CNC EISA thin films and we have correlated this distribution with polarised light spectra collected from each film. We conclude that film regions from which RCP light was reflected were associated with lower CNC concentrations and thicker film regions.

  17. Synthesis of CaO-SiO2-P2O5 mesoporous bioactive glasses with high P2O5 content by evaporation induced self assembly process. (United States)

    Zhao, Shan; Li, Yanbao; Li, Dongxu


    Mesoporous bioactive glasses (MBGs) of the CaO-SiO(2)-P(2)O(5) system containing relatively high P(2)O(5) contents (10-30 mol%) were prepared from a sol-gel. An evaporation-induced self-assembly (EISA) technique was used with poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (EO(20)-PO(70)-EO(20), P123) acting as a template. The structural, morphological and textural properties of MBGs were investigated by small-angle X-ray diffraction (SAXRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and a N(2) sorption/desorption technique. SAXRD and TEM results display the reduced long-range ordering of mesopores with increasing P(2)O(5) content. N(2) sorption/desorption analysis shows that all three samples exhibit a type IV isotherm with type H1 hysteresis loops, characteristic of independent cylindrical slim pore channels and this material has a Barret-Joyner-Halenda (BJH) model pore size of ~4 nm and BET specific surface area ~430 m(2)/g. NMR results indicate a more condensed framework for samples with 30 mol% P(2)O(5) than samples with 10 mol% P(2)O(5). For in vitro bioactivity tests where samples were soaked in simulated body fluid (SBF), samples with 30 mol% P(2)O(5) showed higher crystallinity than those with lower P(2)O(5) contents Silicon concentration increased in SBF solution during the soaking period, which indicates MBGs can be degradable in SBF solution.

  18. Stabilization of Self-Assembled Alumina Mesophases

    NARCIS (Netherlands)

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


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

  19. Self-Assembly of Block and Graft Copolymers in Organic Solvents: An Overview of Recent Advances

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    Leonard Ionut Atanase


    Full Text Available This review is an attempt to update the recent advances in the self-assembly of amphiphilic block and graft copolymers. Their micellization behavior is highlighted for linear AB, ABC triblock terpolymers, and graft structures in non-aqueous selective polar and non-polar solvents, including solvent mixtures and ionic liquids. The micellar characteristics, such as particle size, aggregation number, and morphology, are examined as a function of the copolymers’ architecture and molecular characteristics.

  20. Enhancing Self-Assembly in Cellulose Nanocrystal Suspensions Using High-Permittivity Solvents. (United States)

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


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

  1. Effect of the RE (RE = Eu, Er) doping on the structural and textural properties of mesoporous TiO{sub 2} thin films obtained by evaporation induced self-assembly method

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    Borlaf, Mario, E-mail: [Instituto de Cerámica y Vidrio, CSIC, C/Kelsen, 5, Cantoblanco, E-28049 Madrid (Spain); Caes, Sebastien; Dewalque, Jennifer [LCIS-GREENMAT, Institute of Chemistry, University of Liege, B6 Sart Tilman, 4000 Liege (Belgium); Colomer, María Teresa; Moreno, Rodrigo [Instituto de Cerámica y Vidrio, CSIC, C/Kelsen, 5, Cantoblanco, E-28049 Madrid (Spain); Cloots, Rudi; Boschini, Frederic [LCIS-GREENMAT, Institute of Chemistry, University of Liege, B6 Sart Tilman, 4000 Liege (Belgium); APTIS, Institute of Physics, University of Liege, B5 Sart Tilman, 4000 Liege (Belgium)


    Polymeric sol–gel route has been used for the preparation of TiO{sub 2} and RE{sub 2}O{sub 3–}TiO{sub 2} (RE = Eu, Er) mesoporous thin films by evaporation induced self-assembly method using Si (100) as a substrate. The influence of the relative humidity (RH) on the preparation of the film has been studied being necessary to work under 40% RH in order to obtain homogeneous and transparent thin films. The films were annealed at different temperatures until 900 °C/1 h and the anatase crystallization and its crystal size evolution were followed by low angle X-ray diffraction. Neither the anatase–rutile transition nor the formation of other compounds was observed in the studied temperature range. Ellipsoporosimetry studies demonstrated that the thickness of the thin films did not change after calcination at 500 °C, the porosity was constant until 700 °C, the pore size increased and the specific surface area decreased with temperature. Moreover, the effect of the doping with Er{sup 3+} and Eu{sup 3+} was studied and a clear inhibition of the crystal growth and the sintering process was detected (by transmission electron and atomic force microscopy) when the doped films are compared with the undoped ones. Finally, Eu{sup 3+} and Er{sup 3+} f–f transitions were detected by PL measurements. - Highlights: • Eu and Er–TiO{sub 2} mesoporous films were prepared by evaporation induced self-assembly. • Influence of humidity on porosity and photoluminescent properties has been tested. • Influence of calcination on structural and textural properties has been also studied. • f–f transitions indicate that the thin films are active photoluminescent materials.

  2. Synthesis of organic-inorganic hybrid compounds and their self-assembled behavior in different solvents. (United States)

    Zhuang, Xuewen; Wang, Wenguang; Hao, Jingcheng


    Self-assembly behavior of polyoxometalates (POMs) is influenced by the functional group linked with polyoxometalates structure. We modified the POMs with organic molecule terpyridine to endow POMs the ability to assemble into nanostructure and control the properties of POMs. An amphiphilic organic-inorganic hybrid compound was prepared through combining the 4'-para-phenylcarboxyl-2,2':6',2''-terpyridine (PPCT) with POM to form the (TBA) 3 POM-PPCT. After cationic exchange, tetrabutylammonium cation (TBA + ) can be turned into H + to produce H 3 POM-PPCT. H 3 POM-PPCT showed excellent self-assembly behavior in different solvents. By adjusting the proportion of solvents, different fibers and leaf-like aggregates were obtained, which were determined by SEM and TEM observations. According to the experimental observations, mechanism of the formation of nanostructures was established. The redox properties of POMs can be maintained after the modification with PPCT, which were demonstrated by cyclic voltammetry (CV) measurements. The successful synthesis of these POMs may provide us an opportunity to find more functionalized ramifications of POMs, with self-assembled structures controlled in different solvent, but the interesting properties of these novel POMs can also provide motivation and guidance for the further development of novel functionalized POMs. Copyright © 2018 Elsevier Inc. All rights reserved.

  3. Solvent Controlled Structural Transition of KI4K Self-Assemblies: from Nanotubes to Nanofibrils. (United States)

    Zhao, Yurong; Deng, Li; Wang, Jiqian; Xu, Hai; Lu, Jian R


    The structural modulation of peptide and protein assemblies under well-controlled conditions is of both fundamental and practical significance. In spite of extensive studies, it remains hugely challenging to tune the self-assembled nanostructures in a controllable manner because the self-assembly processes are dictated by various noncovalent interactions and their interplay. We report here how to manipulate the self-assembly of a designed, symmetric amphiphilic peptide (KI4K) via the solvent-controlled structural transition. Structural transition processes were carefully followed by the combination of transmission electronic microscopy (TEM), atomic force microscopy (AFM), circular dichroism (CD), Fourier transform infrared spectroscopy (FTIR), and small angle neutron scattering (SANS). The results show that the introduction of acetonitrile into water significantly affected the hydrophobic interactions among hydrophobic side chains while imposing little impact on the β-sheet hydrogen bonding between peptide backbones. A structural transition occurred from nanotubes to helical/twisted ribbons and then to thin fibrils with the addition of acetonitrile due to the reduced hydrophobic interactions and the consequent weakening of the lateral stacking between KI4K β-sheets. The increased intermolecular electrostatic repulsions among lysine side chain amino groups had little effect on the lateral stacking of KI4K β-sheets due to the molecular symmetry. Complementary molecular dynamic (MD) simulations also indicated the solvation of acetonitrile molecules into the hydrophobic domains weakening the coherence between the neighboring sheets.

  4. Formation and Mechanism of Superhydrophobic/Hydrophobic Surfaces Made from Amphiphiles through Droplet-Mediated Evaporation-Induced Self-Assembly. (United States)

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


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

  5. Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

    KAUST Repository

    Zhao, Kui


    The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport and optoelectronic properties. Yet, to date the vast majority of studies have focused on the fast solution process itself, with studies of slower intrinsic molecular self-assembly in formulations lagging behind. Here we have investigated molecular self-assembly during spontaneous organization and uncovered how changes in formulation influence the microstructure, morphology and transport properties of conjugated polymer thin films. Our results suggest that the polymer-solvent interaction is the key factor for the molecular self-assembly and changes in macroscopic charge transport, which is in contrast with most solution processes, such as spin-coating and blade coating, where solvent drying kinetics dominates the aggregation and crystallization processes. Energetically favourable interactions between the polymer and its solvent are shown to cause chain expansion, resulting in a large hydrodynamic volume and few chain entanglements in solution. This provides molecular freedom for self-assembly and is shown to greatly enhance the local and long range order of the polymer, intra-chain backbone planarity and crystallite size. These improvements, in turn, are shown to endow the conjugated polymer with high carrier transport, as demonstrated by organic thin film transistors.

  6. Solvent evaporation induced aggregating assembly approach to three-dimensional ordered mesoporous silica with ultralarge accessible mesopores. (United States)

    Wei, Jing; Wang, Hai; Deng, Yonghui; Sun, Zhenkun; Shi, Lin; Tu, Bo; Luqman, Mohammad; Zhao, Dongyuan


    A solvent evaporation induced aggregating assembly (EIAA) method has been demonstrated for synthesis of highly ordered mesoporous silicas (OMS) in the acidic tetrahydrofuran (THF)/H(2)O mixture by using poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA) as the template and tetraethylorthosilicate (TEOS) as the silica precursor. During the continuous evaporation of THF (a good solvent for PEO-b-PMMA) from the reaction solution, the template molecules, together with silicate oligomers, were driven to form composite micelles in the homogeneous solution and further assemble into large particles with ordered mesostructure. The obtained ordered mesoporous silicas possess a unique crystal-like morphology with a face centered cubic (fcc) mesostructure, large pore size up to 37.0 nm, large window size (8.7 nm), high BET surface area (508 m(2)/g), and large pore volume (1.46 cm(3)/g). Because of the large accessible mesopores, uniform gold nanoparticles (ca. 4.0 nm) can be introduced into mesopores of the OMS materials using the in situ reduction method. The obtained Au/OMS materials were successfully applied to fast catalytic reduction of 4-nitrophenol in the presence of NaHB(4) as the reductant. The supported catalysts can be reused for catalytic reactions without significant decrease in catalysis performance even after 10 cycles. © 2011 American Chemical Society

  7. Solvent evaporation induced graphene powder with high volumetric capacitance and outstanding rate capability for supercapacitors (United States)

    Zhang, Xiaozhe; Raj, Devaraj Vasanth; Zhou, Xufeng; Liu, Zhaoping


    Graphene-based electrode materials for supercapacitors usually suffer from poor volumetric performance due to the low density. The enhancement of volumetric capacitance by densification of graphene materials, however, is usually accompanied by deterioration of rate capability, as the huge contraction of pore size hinders rapid diffusion of electrolytes. Thus, it is important to develop suitable pore size in graphene materials, which can sustain fast ion diffusion and avoid excessive voids to acquire high density simultaneously for supercapacitor applications. Accordingly, we propose a simple solvent evaporation method to control the pore size of graphene powders by adjusting the surface tension of solvents. Ethanol is used instead of water to reduce the shrinkage degree of graphene powder during solvent evaporation process, due to its lower surface tension comparing with water. Followed by the assistance of mechanical compression, graphene powder having high compaction density of 1.30 g cm-3 and a large proportion of mesopores in the pore size range of 2-30 nm is obtained, which delivers high volumetric capacitance of 162 F cm-3 and exhibits outstanding rate performance of 76% capacity retention at a high current density of 100 A g-1 simultaneously.

  8. Solvent effect on the formation of self-assembled monolayer on DLC surface between n-hexane and Vertrel XF

    Energy Technology Data Exchange (ETDEWEB)

    Tan Manlin [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen University Town, Shenzhen 518055 (China)], E-mail:; Zhang Huayu; Wang Yulei [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen University Town, Shenzhen 518055 (China); Ma Hongtao [SAE Technologies Development (Dongguan) Co. Ltd., Dongguan 523087 (China); Zhu Jiaqi [Center for Composite Materials, Harbin Institute of Technology, Harbin 150018 (China); Han Jiecai [Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen University Town, Shenzhen 518055 (China); Center for Composite Materials, Harbin Institute of Technology, Harbin 150018 (China)


    Self-assembled monolayers of 1H,1H,2H,2H-perfluorodecyltrichloro-silane (FDTS) have been deposited on the diamond-like carbon (DLC) film-coated magnetic heads with two different solvents, n-hexane and Vertrel XF. In order to investigate the solvent effect on the monolayer formation, a series of FDTS monolayers were prepared by varying the solution concentrations which were respectively characterized by time-of-flight mass spectroscopy, contact angle measurements and atomic force microscopy. Results showed that high density of aggregations were present for the FDTS monolayers using the n-hexane solvent, while the monolayer formed on the DLC surface using the Vertrel XF solvent exhibited excellent quality and reproducibility and no aggregations were observed.

  9. Self-assembly of poly(vinylidene fluoride–polystyrene block copolymers in solution: Effects of the length of polystyrene block and solvent compositions

    Directory of Open Access Journals (Sweden)

    Yao Wu


    Full Text Available We report the first preliminary and extensive study on the solution self-assembly behaviors of poly(vinylidene fluoride–b-polystyrene (PVDF–PS block copolymers. The two PVDF–PS polymers we examined have the same length of PVDF block with number averaged repeating unit of 180, but distinctly different lengths of PS block with number averaged repeating unit of 125 and 1202. The self-assembly experiments were carried out in a series of mixture solutions containing a good solvent N,N-dimethylformamide and a selective solvent with different ratios. Our results showed that the self-assembly process was greatly affected by the two factors we examined, i.e. the length of the PS block and the solvent composition. We hope that our study could stimulate more research on the self-assembly of PVDF-containing polymers in solution.

  10. Evaporation-induced assembly of biomimetic polypeptides

    International Nuclear Information System (INIS)

    Keyes, Joseph; Junkin, Michael; Cappello, Joseph; Wu Xiaoyi; Wong, Pak Kin


    We report an evaporation assisted plasma lithography (EAPL) process for guided self-assembly of a biomimetic silk-elastinlike protein (SELP). We demonstrate the formation of SELP structures from millimeter to submicrometer range on plasma-treatment surface templates during an evaporation-induced self-assembly process. The self-assembly processes at different humidities and droplet volumes were investigated. The process occurs efficiently in a window of optimized operating conditions found to be at 70% relative humidity and 8 μl volume of SELP solution. The EAPL approach provides a useful technique for the realization of functional devices and systems using these biomimetic materials

  11. Self-assembly of star micelle into vesicle in solvents of variable quality: the star micelle retains its core-shell nanostructure in the vesicle. (United States)

    Liu, Nijuan; He, Qun; Bu, Weifeng


    Intra- and intermolecular interactions of star polymers in dilute solutions are of fundamental importance for both theoretical interest and hierarchical self-assembly into functional nanostructures. Here, star micelles with a polystyrene corona and a small ionic core bearing platinum(II) complexes have been regarded as a model of star polymers to mimic their intra- and interstar interactions and self-assembled behaviors in solvents of weakening quality. In the chloroform/methanol mixture solvents, the star micelles can self-assemble to form vesicles, in which the star micelles shrink significantly and are homogeneously distributed on the vesicle surface. Unlike the morphological evolution of conventional amphiphiles from micellar to vesicular, during which the amphiphilic molecules are commonly reorganized, the star micelles still retain their core-shell nanostructures in the vesicles and the coronal chains of the star micelle between the ionic cores are fully interpenetrated.

  12. Strongly Iridescent Hybrid Photonic Sensors Based on Self-Assembled Nanoparticles for Hazardous Solvent Detection

    Directory of Open Access Journals (Sweden)

    Ayaka Sato


    Full Text Available Facile detection and the identification of hazardous organic solvents are essential for ensuring global safety and avoiding harm to the environment caused by industrial wastes. Here, we present a simple method for the fabrication of silver-coated monodisperse polystyrene nanoparticle photonic structures that are embedded into a polydimethylsiloxane (PDMS matrix. These hybrid materials exhibit a strong green iridescence with a reflectance peak at 550 nm that originates from the close-packed arrangement of the nanoparticles. This reflectance peak measured under Wulff-Bragg conditions displays a 20 to 50 nm red shift when the photonic sensors are exposed to five commonly employed and highly hazardous organic solvents. These red-shifts correlate well with PDMS swelling ratios using the various solvents, which suggests that the observable color variations result from an increase in the photonic crystal lattice parameter with a similar mechanism to the color modulation of the chameleon skin. Dynamic reflectance measurements enable the possibility of clearly identifying each of the tested solvents. Furthermore, as small amounts of hazardous solvents such as tetrahydrofuran can be detected even when mixed with water, the nanostructured solvent sensors we introduce here could have a major impact on global safety measures as innovative photonic technology for easily visualizing and identifying the presence of contaminants in water.

  13. Two-component self-assembly with solvent leading to "wet" and microcrystalline organogel fibers. (United States)

    Löfman, Miika; Lahtinen, Manu; Rissanen, Kari; Sievänen, Elina


    The microcrystalline fibers of N-(2-aminoethyl)-3α-hydroxy-5β-cholan-24-amide 1 provided a useful model system for studying the complex relationship between morphology, experimental parameters, solvent, and the phenomenon of organogelation. The presence of solvents in the solid forms of 1 along with crystallization behavior suggested solvate formation and polymorphic behavior. Forty solid state- and xerogel samples of 1 formed in organic solvents and in three categories of experimental conditions were analyzed with single crystal X-ray diffraction (XRD), powder X-ray diffraction (PXRD), Raman microscopy, and attenuated total reflection Fourier-transform infrared spectroscopy (ATR FTIR). Two polymorphs and four isostructural aromatic solvates of 1 were found among some unknown forms in the samples. Single crystal X-ray structures of one polymorph and bromobenzene solvate were obtained, the latter from a xerogel. Multiple crystal forms could be present in a sample, and their contributions to gelation were estimated taking the experimental conditions into account. Gelator 1 could act as a variable component gelator, either alone or in combination with an aromatic solvent. The research brings new insight into the structures of microcrystalline organogel fibers, linking solvate/inclusion crystal formation with microcrystalline fibers of an organogelator for the first time. Copyright © 2014 Elsevier Inc. All rights reserved.

  14. Self-assembly of phospholipid-PEG coating on nanoparticles through dual solvent exchange


    Tong, Sheng; Hou, Sijian; Ren, Binbin; Zheng, Zhilan; Bao, Gang


    We coated nanoparticles including iron oxide nanoparticles and quantum dots with phospholipid-PEG using the newly developed dual solvent exchange method and demonstrated that, compared with the conventional film hydration method, the coating efficiency and quality of coated nanoparticles can be significantly improved. A better control of surface coating density and the amount of reactive groups on nanoparticle surface is achieved, allowing conjugation of different moieties with desirable surf...

  15. Solvent-driven symmetry of self-assembled nanocrystal superlattices-A computational study

    KAUST Repository

    Kaushik, Ananth P.


    The preference of experimentally realistic sized 4-nm facetted nanocrystals (NCs), emulating Pb chalcogenide quantum dots, to spontaneously choose a crystal habit for NC superlattices (Face Centered Cubic (FCC) vs. Body Centered Cubic (BCC)) is investigated using molecular simulation approaches. Molecular dynamics simulations, using united atom force fields, are conducted to simulate systems comprised of cube-octahedral-shaped NCs covered by alkyl ligands, in the absence and presence of experimentally used solvents, toluene and hexane. System sizes in the 400,000-500,000-atom scale followed for nanoseconds are required for this computationally intensive study. The key questions addressed here concern the thermodynamic stability of the superlattice and its preference of symmetry, as we vary the ligand length of the chains, from 9 to 24 CH2 groups, and the choice of solvent. We find that hexane and toluene are "good" solvents for the NCs, which penetrate the ligand corona all the way to the NC surfaces. We determine the free energy difference between FCC and BCC NC superlattice symmetries to determine the system\\'s preference for either geometry, as the ratio of the length of the ligand to the diameter of the NC is varied. We explain these preferences in terms of different mechanisms in play, whose relative strength determines the overall choice of geometry. © 2012 Wiley Periodicals, Inc.

  16. Effect of Entrapped Solvent on the Evolution of Lateral Order in Self-Assembled P(S-r-MMA)/PS-b-PMMA Systems with Different Thicknesses. (United States)

    Giammaria, Tommaso Jacopo; Ferrarese Lupi, Federico; Seguini, Gabriele; Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina; Laus, Michele; Perego, Michele


    Block copolymers (BCPs) are emerging as a cost-effective nanofabrication tool to complement conventional optical lithography because they self-assemble in highly ordered polymeric templates with well-defined sub-20-nm periodic features. In this context, cylinder-forming polystyrene-block-poly(methyl methacrylate) BCPs are revealed as an interesting material of choice because the orientation of the nanostructures with respect to the underlying substrate can be effectively controlled by a poly(styrene-random-methyl methacrylate) random copolymer (RCP) brush layer grafted to the substrate prior to BCP deposition. In this work, we investigate the self-assembly process and lateral order evolution in RCP + BCP systems consisting of cylinder-forming PS-b-PMMA (67 kg mol -1 , PS fraction of ∼70%) films with thicknesses of 30, 70, 100, and 130 nm deposited on RCP brush layers having thicknesses ranging from 2 to 20 nm. The self-assembly process is promoted by a rapid thermal processing machine operating at 250 °C for 300 s. The level of lateral order is determined by measuring the correlation length (ξ) in the self-assembled BCP films. Moreover, the amount of solvent (Φ) retained in the RCP + BCP systems is measured as a function of the thicknesses of the RCP and BCP layers, respectively. In the 30-nm-thick BCP films, an increase in Φ as a function of the thickness of the RCP brush layer significantly affects the self-assembly kinetics and the final extent of the lateral order in the BCP films. Conversely, no significant variations of ξ are observed in the 70-, 100-, and 130-nm-thick BCP films with increasing Φ.

  17. Photovoltaic self-assembly.

    Energy Technology Data Exchange (ETDEWEB)

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


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

  18. A solvent evaporation route towards fabrication of hierarchically porous ZSM-11 with highly accessible mesopores

    DEFF Research Database (Denmark)

    Song, Wen; Liu, Zhiting; Liu, Liping


    A route to generate hierarchically porous zeolite ZSM-11 has been paved via solvent evaporation induced self-assembly assisted by hexadecyltrimethoxysilane to produce a preformed dry gel, followed by its subsequent transformation into zeolite via steam-assisted-crystallization. The crystallization...

  19. Tuning the self-assembly of oligothiophenes on chemical vapor deposition graphene: effect of functional group, solvent, and substrate. (United States)

    Sun, Xiuling; Mu, Youbing; Zhang, Jia; Wang, Xiaona; Hu, Pingan; Wan, Xiaobo; Guo, Zongxia; Lei, Shengbin


    Tuning and characterizing the interfacial structure of organic semiconductors on graphene is essential for graphene-based devices. Regulation of the supramolecular assembling structure of oligothiophenes on graphene by changing functional groups attached to the backbone of oligothiophenes is described and the assembling behavior is compared with that on the basal plane of highly oriented pyrolytic graphite. It reveals that terminal functional groups attached to the conjugated backbone of oligothiophene can entirely change the assembling structures. Significant solvent and substrate effects have also been confirmed by comparing the assembling structures of oligothiophenes deposited from tetrahydrofuran, 1,2,4-trichlorobenzene, and octanoic acid onto graphene and graphite. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Challenges in the Structure Determination of Self-Assembled Metallacages: What Do Cage Cavities Contain, Internal Vapor Bubbles or Solvent and/or Counterions? (United States)

    Givelet, Cecile C; Dron, Paul I; Wen, Jin; Magnera, Thomas F; Zamadar, Matibur; Čépe, Klára; Fujiwara, Hiroki; Shi, Yue; Tuchband, Michael R; Clark, Noel; Zbořil, Radek; Michl, Josef


    Proving the structures of charged metallacages obtained by metal ion coordination-driven solution self-assembly is challenging, and the common use of routine NMR spectroscopy and mass spectrometry is unreliable. Carefully determined diffusion coefficients from diffusion-ordered proton magnetic resonance (DOSY NMR) for six cages of widely differing sizes lead us to propose a structural reassignment of two molecular cages from a previously favored trimer to a pentamer or hexamer, and another from a trimer to a much higher oligomer, possibly an intriguing tetradecamer. In the former case, strong support for the reassignment to a larger cage is provided by an observation of a slow reversible transformation of the initially formed cage into a smaller but spectrally very similar one upon dilution. In the latter case, freeze-fracture transmission electron micrographs demonstrate that at least some of the solutions are colloidal, and high-resolution electron transmission and atomic force microscopy images are compatible with a tetradecamer but not a trimer. Comparison of solute partial molar volumes deduced from measurement of solution density with volumes anticipated from molecular models argues strongly against the presence of large voids (solvent vapor bubbles) in cages dissolved in nitromethane. The presence of bubbles was previously proposed in an attempt to account for the bilinear nature of the Eyring plot of the rate constant for pyridine ligand edge exchange reaction in one of the cages and for the unusual activation parameters in the high-temperature regime. An alternative interpretation is proposed now.

  1. Ultraporous superhydrophobic gas-permeable nano-layers by scalable solvent-free one-step self-assembly (United States)

    Liu, Guanyu; Wong, William S. Y.; Nasiri, Noushin; Tricoli, Antonio


    Superhydrophobic materials with excellent humidity tolerance, high porosity and light transmittance are being investigated for numerous applications including moisture-sensitive catalysts and perovskite solar cells. Here, we report the one-step solvent-free synthesis of ultraporous superhydrophobic nano-layers by the on-the-fly functionalization of nanoparticle aerosols. Short exposure of surfaces to hot Mn3O4, ZnO and TiO2 aerosols results in ultraporous nanoparticle networks with repulsive dewetting state approaching ideal Cassie-Baxter superhydrophobicity. In addition to showcasing sliding angles of ca. 0° and very low contact angle hysteresis of 3° +/- 2°, these optimal nano-layers have up to 98% porosity and pore size of several micrometres, a key feature to enable efficient penetration of gases to the substrate surface. The stability of this ultraporous superhydrophobic morphology is demonstrated by rapidly applying Moses effect-functionality to substrates that parts water up to 5 mm high. This scalable synthesis method offers a flexible and rapid approach for the production of numerous moisture-resistant devices including gas sensors, catalysts and perovskite solar cells.Superhydrophobic materials with excellent humidity tolerance, high porosity and light transmittance are being investigated for numerous applications including moisture-sensitive catalysts and perovskite solar cells. Here, we report the one-step solvent-free synthesis of ultraporous superhydrophobic nano-layers by the on-the-fly functionalization of nanoparticle aerosols. Short exposure of surfaces to hot Mn3O4, ZnO and TiO2 aerosols results in ultraporous nanoparticle networks with repulsive dewetting state approaching ideal Cassie-Baxter superhydrophobicity. In addition to showcasing sliding angles of ca. 0° and very low contact angle hysteresis of 3° +/- 2°, these optimal nano-layers have up to 98% porosity and pore size of several micrometres, a key feature to enable efficient

  2. Self-assembly and hierarchical patterning of aligned organic nanowire arrays by solvent evaporation on substrates with patterned wettability. (United States)

    Bao, Rong-Rong; Zhang, Cheng-Yi; Zhang, Xiu-Juan; Ou, Xue-Mei; Lee, Chun-Sing; Jie, Jian-Sheng; Zhang, Xiao-Hong


    The controlled growth and alignment of one-dimensional organic nanostructures at well-defined locations considerably hinders the integration of nanostructures for electronic and optoelectronic applications. Here, we demonstrate a simple process to achieve the growth, alignment, and hierarchical patterning of organic nanowires on substrates with controlled patterns of surface wettability. The first-level pattern is confined by the substrate patterns of wettability. Organic nanostructures are preferentially grown on solvent wettable regions. The second-level pattern is the patterning of aligned organic nanowires deposited by controlling the shape and movement of the solution contact lines during evaporation on the wettable regions. This process is controlled by the cover-hat-controlled method or vertical evaportation method. Therefore, various new patterns of organic nanostructures can be obtained by combing these two levels of patterns. This simple method proves to be a general approach that can be applied to other organic nanostructure systems. Using the as-prepared patterned nanowire arrays, an optoelectronic device (photodetector) is easily fabricated. Hence, the proposed simple, large-scale, low-cost method of preparing patterns of highly ordered organic nanostructures has high potential applications in various electronic and optoelectronic devices.

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


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

  4. Self-assembled nanostructures

    CERN Document Server

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


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

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

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


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

  6. Macroscopic magnetic Self assembly

    NARCIS (Netherlands)

    Löthman, Per Arvid


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

  7. Condensation-Enhanced Self-Assembly as a Route to High Surface Area alpha-Aluminas

    NARCIS (Netherlands)

    Perez, Lidia Lopez; Zarubina, Valeriya; Heeres, Hero Jan; Melian-Cabrera, Ignacio


    High surface area nanosized alpha-alumina has been obtained by thermally treating a sol-gel-derived mesophase at 1200 degrees C; the mesophase was synthesized by a sol-gel route involving evaporation induced self-assembly (EISA) of a hydrolyzed gel from Al-tri-sec-butoxide in s-BuOH in the presence

  8. Self-assembly of self-assembled molecular triangles

    Indian Academy of Sciences (India)

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

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

    Lombardo, Michael T.

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

  10. Peptide amphiphile self-assembly (United States)

    Iscen, Aysenur; Schatz, George C.


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

  11. Self-assembly of self-assembled molecular triangles

    Indian Academy of Sciences (India)

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

  12. Evaporation induced wrinkling of graphene oxide at the nanoparticle interface. (United States)

    Wang, Feng; Liu, Juewen


    With the thickness of only a single atomic layer, graphene displays many interesting surface properties. A general observation is that wrinkles are formed on graphene oxide (GO) when it is dried in the presence of adsorbed inorganic nanoparticles. In this case, evaporation induced wrinkling is not an elastic deformation but is permanent. Understanding the nanoscale force of wrinkle formation is important for device fabrication and sensing. Herein, we employ surface functionalized gold nanoparticles (AuNPs) as a model system. All tested AuNPs induced wrinkling, including those capped by DNA, polymers and proteins. The size of AuNPs is less important compared to the properties of solvent. Wrinkle formation is attributed to drying related capillary force acting on the GO surface, and a quantitative equation is derived. After drying, the adsorption affinity between GO and AuNPs is increased due to the increased contact area.

  13. Evaporation induced wrinkling of graphene oxide at the nanoparticle interface (United States)

    Wang, Feng; Liu, Juewen


    With the thickness of only a single atomic layer, graphene displays many interesting surface properties. A general observation is that wrinkles are formed on graphene oxide (GO) when it is dried in the presence of adsorbed inorganic nanoparticles. In this case, evaporation induced wrinkling is not an elastic deformation but is permanent. Understanding the nanoscale force of wrinkle formation is important for device fabrication and sensing. Herein, we employ surface functionalized gold nanoparticles (AuNPs) as a model system. All tested AuNPs induced wrinkling, including those capped by DNA, polymers and proteins. The size of AuNPs is less important compared to the properties of solvent. Wrinkle formation is attributed to drying related capillary force acting on the GO surface, and a quantitative equation is derived. After drying, the adsorption affinity between GO and AuNPs is increased due to the increased contact area.With the thickness of only a single atomic layer, graphene displays many interesting surface properties. A general observation is that wrinkles are formed on graphene oxide (GO) when it is dried in the presence of adsorbed inorganic nanoparticles. In this case, evaporation induced wrinkling is not an elastic deformation but is permanent. Understanding the nanoscale force of wrinkle formation is important for device fabrication and sensing. Herein, we employ surface functionalized gold nanoparticles (AuNPs) as a model system. All tested AuNPs induced wrinkling, including those capped by DNA, polymers and proteins. The size of AuNPs is less important compared to the properties of solvent. Wrinkle formation is attributed to drying related capillary force acting on the GO surface, and a quantitative equation is derived. After drying, the adsorption affinity between GO and AuNPs is increased due to the increased contact area. Electronic supplementary information (ESI) available: Methods. See DOI: 10.1039/c4nr05832a

  14. Self-assembly of cyclodextrins

    DEFF Research Database (Denmark)

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


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

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

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


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

  16. Membranes Prepared by Self-assembly and Chelation Assisted Phase Inversion

    KAUST Repository

    Xie, Yihui


    We combine self-assembly in solution, complexation with metallic salts and phase separation induced by solvent-non-solvent exchange to prepare nanostructured membranes for separation in the nanofiltration range. The method was applied to synthesized poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) copolymers dissolved in a selective solvent mixture and immersed in aqueous Cu2+ or Ag+ solutions.

  17. Distinct self-assembly of dithiol monolayers on Au(1 1 1) in water and hexane (United States)

    Sharif, Aisyah M.; Laffir, Fathima R.; Buckley, D. Noel; Silien, Christophe


    The self-assembly of 1,4-benzenedimethanethiol on Au(1 1 1), at low concentration in water and in hexane which are respectively polar and non-polar solvent, has been studied by scanning tunneling microscopy (STM). The data reveal that, on clean Au(1 1 1), a complete and ordered self-assembled monolayer (SAM) of lying-down dithiols can form within a few seconds in water. While in hexane the adsorption is initially impeded by the rapid growth of an ordered hexane film that is gradually replaced by disordered domains of dithiol until completion of a saturated monolayer. Complemented by X-ray photoelectron spectroscopy measurements, the STM images resolve the progression of the self-assembly in both these polar and non-polar solvent, and highlight how the self-assembly depends on the trio solvent, dithiol, and substrate.

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

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


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

  19. Large area porous gold films deposited by evaporation-induced colloidal crystal growth. (United States)

    Zhang, Renyun; Hummelgård, Magnus; Olin, Håkan


    Films that are nanostructured in two- or three-dimensions, such as porous ones, are made by several methods including templated growth and self-assembly. Here, we report on a new method that is based on evaporation-induced growth of nanoparticle gold films on a water surface. The film growth was done in a similar way to the well-known evaporation-induced colloidal crystal growth method, but in contrast, we did not directly deposit the film on a solid substrate. The films were instead created on top of a water surface. After the growth process, the films were deposited directly on substrates by a simple pick-up procedure. The deposited porous gold films were uniform with a thickness of 100 nm and had a sheet resistance of 100 Omega/sq. There are several advantages with our method, including simplicity of the protocol, large film area, flexibility in the choice of substrate to be coated, and the ability for multilayer coatings. The latter points to opportunities for fabrication of multilayer 3D porous structure, which may have wide applications in sensors and electrochemical determinations.

  20. Self-assembled nanostructured metamaterials (United States)

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


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

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

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


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

  2. Synthesis and Self-Assembly of Gold Nanoparticles by Chemically Modified Polyol Methods under Experimental Control

    Directory of Open Access Journals (Sweden)

    Nguyen Viet Long


    Full Text Available In our present research, bottom-up self-assembly of gold (Au nanoparticles on a flat copper (Cu substrate is performed by a facile method. The very interesting evidence of self-assembly of Au nanoparticles on the top of the thin assembled layer was observed by scanning electron microscopy (SEM. We had discovered one of the most general and simple methods for the self-assembly of metal nanoparticles. The general physical and chemical mechanisms of the evaporation process of the solvents can be used for self-assembly of the as-prepared nanoparticles. The important roles of molecules of the used solvents are very critical to self-assembly of the as-prepared Au nanoparticles in the case without using any polymers for those processes. It is clear that self-assembly of such one nanosystem of the uniform Au nanoparticles is fully examined. Finally, an exciting surface plasmon resonance (SPR phenomenon of the pure Au nanoparticles in the solvent was fully discovered in their exciting changes of the narrow and large SPR bands according to synthesis time. The SPR was considered as the collective oscillation of valence electrons of the surfaces of the pure Au nanoparticles in the solvent by incident ultraviolet-visible light. Then, the frequency of light photons matches the frequency of the oscillation of surface electrons of the Au nanoparticles that are excited.

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

    Rasale, Dnyaneshwar B; Das, Apurba K


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

  4. Chemical Reactions Directed Peptide Self-Assembly

    Directory of Open Access Journals (Sweden)

    Dnyaneshwar B. Rasale


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

  5. Formation of Mesostructured Nanoparticles through Self-Assembly and Aerosol Process

    Energy Technology Data Exchange (ETDEWEB)

    Brinker, C. Jeffrey; Fan, Hongyou; Lu, Yunfeng; Rieker, Thomas; Stump, Arron; Ward, Timothy L.


    Silica nanoparticles exhibiting hexagonal, cubic, and vesicular mesostructures have been prepared using aerosol assisted, self-assembled process. This process begins with homogennous aerosol droplets containing silica source, water, ethanol, and surfactant, in which surfactant concentration is far below the critical micelle concentration (cmc). Solvent evaporation enriches silica and surfactant inducing interfacial self-assembly confined to a spherical aerosol droplet and results in formation of completely solid, ordered spherical particles with stable hexagonal, cubic, or vesicular mesostructures.

  6. Molecular self-assembly advances and applications

    CERN Document Server

    Dequan, Alex Li


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

  7. Self-Assembly of Infinite Structures

    Directory of Open Access Journals (Sweden)

    Scott M. Summers


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

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

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


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

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

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

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

  10. Distinct self-assembly of dithiol monolayers on Au(1 1 1) in water and hexane

    Energy Technology Data Exchange (ETDEWEB)

    Sharif, Aisyah M. [Department of Physics and Energy, University of Limerick (Ireland); Materials and Surface Science Institute, University of Limerick (Ireland); Laffir, Fathima R. [Materials and Surface Science Institute, University of Limerick (Ireland); Buckley, D. Noel [Department of Physics and Energy, University of Limerick (Ireland); Materials and Surface Science Institute, University of Limerick (Ireland); Silien, Christophe, E-mail: [Department of Physics and Energy, University of Limerick (Ireland); Materials and Surface Science Institute, University of Limerick (Ireland)


    Highlights: • The self-assembly of 1,4-benzenedimethanethiol in water and in hexane is studied. • The initial phase of assembly is revealed for each solvent using STM and XPS. • Water stabilizes an ordered lying-down phase. • Hexane coadsorbs with benzenedimethanethiol and promotes standing-up absorption. - Abstract: The self-assembly of 1,4-benzenedimethanethiol on Au(1 1 1), at low concentration in water and in hexane which are respectively polar and non-polar solvent, has been studied by scanning tunneling microscopy (STM). The data reveal that, on clean Au(1 1 1), a complete and ordered self-assembled monolayer (SAM) of lying-down dithiols can form within a few seconds in water. While in hexane the adsorption is initially impeded by the rapid growth of an ordered hexane film that is gradually replaced by disordered domains of dithiol until completion of a saturated monolayer. Complemented by X-ray photoelectron spectroscopy measurements, the STM images resolve the progression of the self-assembly in both these polar and non-polar solvent, and highlight how the self-assembly depends on the trio solvent, dithiol, and substrate.

  11. Application of self-consistent field theory to self-assembled bilayer membranes

    International Nuclear Information System (INIS)

    Zhang Ping-Wen; Shi An-Chang


    Bilayer membranes self-assembled from amphiphilic molecules such as lipids, surfactants, and block copolymers are ubiquitous in biological and physiochemical systems. The shape and structure of bilayer membranes depend crucially on their mechanical properties such as surface tension, bending moduli, and line tension. Understanding how the molecular properties of the amphiphiles determine the structure and mechanics of the self-assembled bilayers requires a molecularly detailed theoretical framework. The self-consistent field theory provides such a theoretical framework, which is capable of accurately predicting the mechanical parameters of self-assembled bilayer membranes. In this mini review we summarize the formulation of the self-consistent field theory, as exemplified by a model system composed of flexible amphiphilic chains dissolved in hydrophilic polymeric solvents, and its application to the study of self-assembled bilayer membranes. (topical review)

  12. Self-assembly and headgroup effect in nanostructured organogels via cationic amphiphile-graphene oxide composites.

    Directory of Open Access Journals (Sweden)

    Tifeng Jiao

    Full Text Available Self-assembly of hierarchical graphene oxide (GO-based nanomaterials with novel functions has received a great deal of attentions. In this study, nanostructured organogels based on cationic amphiphile-GO composites were prepared. The gelation behaviors of amphiphile-GO composites in organic solvents can be regulated by changing the headgroups of amphiphiles. Ammonium substituted headgroup in molecular structures in present self-assembled composites is more favorable for the gelation in comparison to pyridinium headgroup. A possible mechanism for headgroup effects on self-assembly and as-prepared nanostructures is proposed. It is believed that the present amphiphile-GO self-assembled system will provide an alternative platform for the design of new GO nanomaterials and soft matters.

  13. Polymorphism of lipid self-assembly systems

    International Nuclear Information System (INIS)

    Takahashi, Hiroshi


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

  14. Directed Self-Assembly of Nanodispersions

    Energy Technology Data Exchange (ETDEWEB)

    Furst, Eric M [University of Delaware


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

  15. Nanoscale Structure of Self-Assembling Hybrid Materials of Inorganic and Electronically Active Organic Phases

    Energy Technology Data Exchange (ETDEWEB)

    Sofos, M.; Goswami, D.A. Stone D.K.; Okasinski, J.S.; Jin, H.; Bedzyk, M.J.; Stupp, S.I. (NWU)


    Hybrid materials with nanoscale structure that incorporates inorganic and organic phases with electronic properties offer potential in an extensive functional space that includes photovoltaics, light emission, and sensing. This work describes the nanoscale structure of model hybrid materials with phases of silica and electronically active bola-amphiphile assemblies containing either oligo(p-phenylene vinylene) or oligo(thiophene) segments. The hybrid materials studied here were synthesized by evaporation-induced self-assembly and characterized by X-ray scattering techniques. Grazing-incidence X-ray scattering studies of these materials revealed the formation of two-dimensional hexagonally packed cylindrical micelles of the organic molecules with diameters between 3.1 and 3.6 nm and cylindrical axes parallel to the surface. During the self-assembly process at low pH, the cylindrical aggregates of conjugated molecules become surrounded by silica giving rise to a hybrid structure with long-range order. Specular X-ray reflectivity confirmed the long-range periodicity of the hybrid films within a specific range of molar ratios of tetraethyl orthosilicate to cationic amphiphile. We did not observe any long-range ordering in fully organic analogues unless quaternary ammonium groups were replaced by tertiary amines. These observations suggest that charge screening in these biscationic conjugated molecules by the mineral phase is a key factor in the evolution of long range order in the self-assembling hybrids.

  16. Micellar Self-Assembly of Block Copolymers for Fabrication of Nanostructured Membranes

    KAUST Repository

    Marques, Debora S.


    This research work examines the process of block copolymer membrane fabrication by self-assembly combined by non-solvent induced phase separation. Self-assembly takes place from the preparation of the primordial solution until the moment of immersion in a non-solvent bath. These mechanisms are driven thermodynamically but are limited by kinetic factors. It is shown in this work how the ordering of the assembly of micelles is improved by the solution parameters such as solvent quality and concentration of block copolymer. Order transitions are detected, yielding changes in the morphology. The evaporation of the solvents after casting is demonstrated to be essential to reach optimum membrane structure. The non-solvent bath stops the phase separation at an optimum evaporation time.

  17. Self-assembled nanoparticle deposits formed at the contact line of evaporating micrometer-size droplets (United States)

    Govor, Leonid V.; Reiter, Günter; Parisi, Jürgen; Bauer, Gottfried H.


    We report on the formation of self-assembled rings of Co Pt3 nanoparticles (ring diameter ranging from 0.6 to 1.5 μm , particle diameter 6 nm ) formed in an evaporating thin film. The latter was achieved on the surface of water by spreading a binary mixture composed of two solutions: nitrocellulose dissolved in amyl acetate and Co Pt3 particles stabilized by hexadecylamine dissolved in hexane. The self-assembly process of the nanometer-sized particles into micrometer-sized rings results from phase separation in a thin film of the mixed solutions, leading to a bilayer, and the subsequent decomposition during solvent evaporation of the top hexadecylamine-rich layer into droplets. Finally, the evaporation of the remaining solvent from these droplets gives rise to a retraction of their contact line. The Co Pt3 particles located at the contact line follow its motion and self-assemble along this line.

  18. Micellar Self-Assembly of Recombinant Resilin-/Elastin-Like Block Copolypeptides. (United States)

    Weitzhandler, Isaac; Dzuricky, Michael; Hoffmann, Ingo; Garcia Quiroz, Felipe; Gradzielski, Michael; Chilkoti, Ashutosh


    Reported here is the synthesis of perfectly sequence defined, monodisperse diblock copolypeptides of hydrophilic elastin-like and hydrophobic resilin-like polypeptide blocks and characterization of their self-assembly as a function of structural parameters by light scattering, cryo-TEM, and small-angle neutron scattering. A subset of these diblock copolypeptides exhibit lower critical solution temperature and upper critical solution temperature phase behavior and self-assemble into spherical or cylindrical micelles. Their morphologies are dictated by their chain length, degree of hydrophilicity, and hydrophilic weight fraction of the ELP block. We find that (1) independent of the length of the corona-forming ELP block there is a minimum threshold in the length of the RLP block below which self-assembly does not occur, but that once that threshold is crossed, (2) the RLP block length is a unique molecular parameter to independently tune self-assembly and (3) increasing the hydrophobicity of the corona-forming ELP drives a transition from spherical to cylindrical morphology. Unlike the self-assembly of purely ELP-based block copolymers, the self-assembly of RLP-ELPs can be understood by simple principles of polymer physics relating hydrophilic weight fraction and polymer-polymer and polymer-solvent interactions to micellar morphology, which is important as it provides a route for the de novo design of desired nanoscale morphologies from first principles.

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

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


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

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

    Wang, Chao; Wang, Zhiqiang; Zhang, Xi


    The process of self-assembly spontaneously creates well-defined structures from various chemical building blocks. Self-assembly can include different levels of complexity: it can be as simple as the dimerization of two small building blocks driven by hydrogen bonding or as complicated as a cell membrane, a remarkable supramolecular architecture created by a bilayer of phospholipids embedded with functional proteins. The study of self-assembly in simple systems provides a fundamental understanding of the driving forces and cooperativity behind these processes. Once the rules are understood, these guidelines can facilitate the research of highly complex self-assembly processes. Among the various components for self-assembly, an amphiphilic molecule, which contains both hydrophilic and hydrophobic parts, forms one of the most powerful building blocks. When amphiphiles are dispersed in water, the hydrophilic component of the amphiphile preferentially interacts with the aqueous phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent. Therefore, the amphiphiles aggregate to form different molecular assemblies based on the repelling and coordinating forces between the hydrophilic and hydrophobic parts of the component molecules and the surrounding medium. In contrast to conventional amphiphiles, supra-amphiphiles are constructed on the basis of noncovalent interactions or dynamic covalent bonds. In supra-amphiphiles, the functional groups can be attached to the amphiphiles by noncovalent synthesis, greatly speeding their construction. The building blocks for supra-amphiphiles can be either small organic molecules or polymers. Advances in the development of supra-amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. When polymers are used to construct supra-amphiphiles, the resulting

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

    Raymond, David W.


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

  2. Bola-amphiphile self-assembly

    DEFF Research Database (Denmark)

    Svaneborg, Carsten


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

  3. Self-assembled nanogaps for molecular electronics

    International Nuclear Information System (INIS)

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


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

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


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

  5. Self-assembly of patchy colloidal dumbbells

    NARCIS (Netherlands)

    Avvisati, Guido; Vissers, Teun; Dijkstra, Marjolein


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

  6. Self-assembled nanogaps for molecular electronics

    DEFF Research Database (Denmark)

    Tang, Qingxin; Tong, Yanhong; Jain, Titoo


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

  7. Self-assembled nanolaminate coatings (SV)

    Energy Technology Data Exchange (ETDEWEB)

    Fan, H.


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

  8. Effect of linear alcohol molecular size on the self-assembly of fullerene whiskers

    International Nuclear Information System (INIS)

    Amer, Maher S.; Todd, T. Kyle; Busbee, John D.


    Highlights: → The longer the alcohol molecule, the shorter the length of the assembled whisker. → Interaction between alcohol and fullerene solvent is the key factor. → The stronger the alcohol/solvent interaction, the longer the whisker. - Abstract: The recent development of self-assembled fullerene whiskers and wires has created an enormous potential and resolved a serious challenge for utilizing such unique class of carbon material in advanced nano-scale, molecular-based electronic, optical, and thermal devices. In this paper we investigate, the self-assembly of C 60 molecules into one-dimensional whiskers using a series of linear alcohols H(CH 2 ) n OH, with n changing from 1 (methanol) to 3 (isopropyl alcohol), to elucidate the effect of alcohol molecular size on the size distribution of the self-assemble fullerene whiskers. Our results show that the length of the produced fullerene whiskers is affected by the molecular size of the alcohol used in the process. The crucial role played by solvent/alcohol interaction in the assembly process is discussed. In addition, Raman spectroscopy measurements support the notion that the self-assembled whiskers are primarily held by depletion forces and no evidence of fullerene polymerization was observed.

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

    Ge, Zhishen; Liu, Shiyong


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

  10. Self assembly of highly-ordered nanoparticle monolayers.

    Energy Technology Data Exchange (ETDEWEB)

    Bigioni, T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.; Univ. of Chicago


    When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  12. Selective self-assembly of adenine-silver nanoparticles forms rings resembling the size of cells (United States)

    Choi, Sungmoon; Park, Soonyoung; Yang, Seon-Ah; Jeong, Yujin; Yu, Junhua


    Self-assembly has played critical roles in the construction of functional nanomaterials. However, the structure of the macroscale multicomponent materials built by the self-assembly of nanoscale building blocks is hard to predict due to multiple intermolecular interactions of great complexity. Evaporation of solvents is usually an important approach to induce kinetically stable assemblies of building blocks with a large-scale specific arrangement. During such a deweting process, we tried to monitor the possible interactions between silver nanoparticles and nucleobases at a larger scale by epifluorescence microscopy, thanks to the doping of silver nanoparticles with luminescent silver nanodots. ssDNA oligomer-stabilized silver nanoparticles and adenine self-assemble to form ring-like compartments similar to the size of modern cells. However, the silver ions only dismantle the self-assembly of adenine. The rings are thermodynamically stable as the drying process only enrich the nanoparticles-nucleobase mixture to a concentration that activates the self-assembly. The permeable membrane-like edge of the ring is composed of adenine filaments glued together by silver nanoparticles. Interestingly, chemicals are partially confined and accumulated inside the ring, suggesting that this might be used as a microreactor to speed up chemical reactions during a dewetting process. PMID:26643504

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

    NARCIS (Netherlands)

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


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

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

    Liang, Hongjun

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

  15. Controllable Self-Assembly of Amphiphilic Zwitterionic PBI Towards Tunable Surface Wettability of the Nanostructures. (United States)

    Ye, Yong; Lü, Baozhong; Cheng, Wenyu; Wu, Zhen; Wei, Jie; Yin, Meizhen


    Amphiphilic molecules have received wide attention as they possess both hydrophobic and hydrophilic properties, and can form diverse nanostructures in selective solvents. Herein, we report an asymmetric amphiphilic zwitterionic perylene bisimide (AZP) with an octyl chain and a zwitterionic group on the opposite imide positions of perylene tetracarboxylic dianhydride. The controllable nanostructures of AZP with tunable hydrophilic/hydrophobic surface have been investigated through solvent-dependent amphiphilic self-assembly as confirmed by SEM, TEM, and contact angle measurements. The planar perylene core of AZP contributes to strong π-π stacking, while the amphiphilic balance of asymmetric AZP adjusts the self-assembly property. Additionally, due to intermolecular π-π stacking and solvent-solute interactions, AZP could self-assemble into hydrophilic microtubes in a polar solvent (acetone) and hydrophobic nanofibers in an apolar solvent (hexane). This facile method provides a new pathway for controlling the surface properties based on an asymmetric amphiphilic zwitterionic perylene bisimide. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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


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

  17. Ternary self-assemblies in water

    DEFF Research Database (Denmark)

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


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

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

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


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

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

    Indian Academy of Sciences (India)


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

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

    Shieh, Aileen

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

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

    Humenik, Martin; Lang, Gregor; Scheibel, Thomas


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

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

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


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

  3. Simulation of macromolecule self-assembly in solution: A multiscale approach

    Energy Technology Data Exchange (ETDEWEB)

    Lavino, Alessio D., E-mail:; Barresi, Antonello A., E-mail:; Marchisio, Daniele L., E-mail: [Dipartimento di Scienza Applicata e Tecnologia, Istituto di Ingegneria Chimica, Politecnico di Torino, Duca degli Abruzzi 24, 10129 Torino (Italy); Pasquale, Nicodemo di, E-mail: [School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UnitedKingdom (United Kingdom); Carbone, Paola, E-mail: [School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL, UnitedKingdom (United Kingdom)


    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.

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

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


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

  5. Morphological deformation during evaporation induced assembly of mixed colloidal suspension (United States)

    Sen, D.; Melo, J. S.; Bahadur, J.; Mazumder, S.; Bhattacharya, S.; D'Souza, S. F.


    Sphere to deformed doughnut type transformation of colloidal droplets during evaporation induced assembly of colloidal silica and E. coli was observed. Distortion modulations get amplified with increase in volume fraction of anisotropic soft colloidal component. Reduction in elastic constants of formed shell, at the boundary of a drying droplet, and the anisotropic nature of bacterial component facilitate the deformation process. The charge modification of E. coli surface by Poly cationic Polytheleneimine ceases the morphological transformation and results spherical assembled grains. Hierarchical structures of these assembled colloidal grains have been probed using electron microscopy and small- angle neutron scattering techniques.

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

    Ziener, Ulrich


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

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

    Kegel, Willem


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

  8. Self-assembled silicon oxide nanojunctions

    International Nuclear Information System (INIS)

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


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

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

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


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

  10. Molecular simulations of self-assembly processes in metal-organic frameworks: Model dependence (United States)

    Biswal, Debasmita; Kusalik, Peter G.


    Molecular simulation is a powerful tool for investigating microscopic behavior in various chemical systems, where the use of suitable models is critical to successfully reproduce the structural and dynamic properties of the real systems of interest. In this context, molecular dynamics simulation studies of self-assembly processes in metal-organic frameworks (MOFs), a well-known class of porous materials with interesting chemical and physical properties, are relatively challenging, where a reasonably accurate representation of metal-ligand interactions is anticipated to play an important role. In the current study, we both investigate the performance of some existing models and introduce and test new models to help explore the self-assembly in an archetypal Zn-carboxylate MOF system. To this end, the behavior of six different Zn-ion models, three solvent models, and two ligand models was examined and validated against key experimental structural parameters. To explore longer time scale ordering events during MOF self-assembly via explicit solvent simulations, it is necessary to identify a suitable combination of simplified model components representing metal ions, organic ligands, and solvent molecules. It was observed that an extended cationic dummy atom (ECDA) Zn-ion model combined with an all-atom carboxylate ligand model and a simple dipolar solvent model can reproduce characteristic experimental structures for the archetypal MOF system. The successful use of these models in extensive sets of molecular simulations, which provide key insights into the self-assembly mechanism of this archetypal MOF system occurring during the early stages of this process, has been very recently reported.

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

    Shah, Vivek B; Biswas, Pratim


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

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

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


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

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

    Avvisati, Guido; Vissers, Teun; Dijkstra, Marjolein


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

  14. Self-assembled nanocages based on the coiled coil bundle motif (United States)

    Sinha, Nairiti; Villegas, Jose; Saven, Jeffery; Kiick, Kristi; Pochan, Darrin

    Computational design of coiled coil peptide bundles that undergo solution phase self-assembly presents a diverse toolbox for engineering new materials with tunable and pre-determined nanostructures that can have various end applications such as in drug delivery, biomineralization and electronics. Self-assembled cages are especially advantageous as the cage geometry provides three distinct functional sites: the interior, the exterior and the solvent-cage interface. In this poster, syntheses and characterization of a peptide cage based on computationally designed homotetrameric coiled coil bundles as building blocks is discussed. Techniques such as Transmission Electron Microscopy (TEM), Small-Angle Neutron Scattering (SANS) and Analytical Ultracentrifugation (AUC) are employed to characterize the size, shape and molecular weight of the self-assembled peptide cages under different pH and temperature conditions. Various self-assembly pathways such as dialysis and thermal quenching are shown to have a significant impact on the final structure of these peptides in solution. Comparison of results with the target cage design can be used to iteratively improve the peptide design and provide greater understanding of its interactions and folding.

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


    Bensaude Vincent, Bernadette


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

  16. Synthesis of nanocrystals and nanocrystal self-assembly (United States)

    Chen, Zhuoying

    Chapter 1. A general introduction is presented on nanomaterials and nanoscience. Nanoparticles are discussed with respect to their structure and properties. Ferroelectric materials and nanoparticles in particular are highlighted, especially in the case of the barium titanate, and their potential applications are discussed. Different nanocrystal synthetic techniques are discussed. Nanoparticle superlattices, the novel "meta-materials" built from self-assembly at the nanoscale, are introduced. The formation of nanoparticle superlattices and the importance and interest of synthesizing these nanostructures is discussed. Chapter 2. Advanced applications for high k dielectric and ferroelectric materials in the electronics industry continues to demand an understanding of the underlying physics in decreasing dimensions into the nanoscale. The first part of this chapter presents the synthesis, processing, and electrical characterization of nanostructured thin films (thickness ˜100 nm) of barium titanate BaTiO3 built from uniform nanoparticles (alcohols were used to study the effect of size and morphological control over the nanocrystals. Techniques including X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and high-resolution electron microscopy are used to examine crystallinity and morphology. Chapter 3. By investigating the self-assembly of cadmium selenide-gold (CdSe-Au) nanoparticle mixtures by transmission electron microscopy after solvent evaporation, the effect of solvents in the formation process of CdSe-Au binary nanoparticle superlattices (BNSLs) was studied. 1-dodecanethiol was found to be critical in generating conditions necessary for superlattice formation, prior to the other factors that likely determine structure, highlighting the dual role of this organic polar molecule as both ligand and high boiling point/crystallization solvent. The influence of thiol was investigated under various concentrations (and also

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

    Bouchard, Ann M.; Osbourn, Gordon C.


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

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

    Shetye, Sheetal B.

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

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

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


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

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

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


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

  1. Shape Restoration by Active Self-Assembly

    Directory of Open Access Journals (Sweden)

    D. Arbuckle


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

  2. Fluxible nanoclusters of Fe3O4 nanocrystal-embedded polyaniline by macromolecule-induced self-assembly. (United States)

    Huang, Jing; Li, Qi; Li, Denian; Wang, Yue; Dong, Lijie; Xie, Haian; Wang, Jun; Xiong, Chuanxi


    We have prepared Fe3O4 nanocrystal-embedded polyaniline hybrids with well-defined cluster-like morphology through macromolecule-induced self-assembly. These magnetic and electrically conductive composite nanoclusters show flowability at room temperature in the absence of any solvent, which offers great potential in applications such as microwave absorbents and electromagnetic shielding coatings. This macromolecule-induced self-assembly strategy can be readily applied on the fabrication of other ion oxide/conjugated polymer composites to achieve robust multifunctional materials.

  3. Self-Assembly of Magnetic Colloids in Soft Confinement

    NARCIS (Netherlands)

    Liu, P.


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

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

    NARCIS (Netherlands)

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


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

  5. Electrostatic Self-Assembly of Polysaccharides into Nanofibers

    DEFF Research Database (Denmark)

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


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

  6. Self-assembled nanofiber coatings for controlling cell responses

    NARCIS (Netherlands)

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

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

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

    Indian Academy of Sciences (India)

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

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

    Indian Academy of Sciences (India)

    Usha P Kar


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

  9. Self-Assembly of Faceted Colloidal Particles

    NARCIS (Netherlands)

    Gantapara, A.P.


    A colloidal dispersion consists of insoluble microscopic particles that are suspended in a solvent. Typically, a colloid is a particle for which at least one of its dimension is within the size range of a nanometer to a micron. Due to collisions with much smaller solvent molecules, colloids perform

  10. Molecular Self-Assembly Strategy for Generating Catalytic Hybrid Polypeptides. (United States)

    Maeda, Yoshiaki; Fang, Justin; Ikezoe, Yasuhiro; Pike, Douglas H; Nanda, Vikas; Matsui, Hiroshi


    Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β-sheets and amyloid fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. The enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality.

  11. Morphology evolution of PS-b-PDMS block copolymer and its hierarchical directed self-assembly on block copolymer templates

    DEFF Research Database (Denmark)

    Rasappa, Sozaraj; Schulte, Lars; Borah, Dipu


    Cylinder-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS, 27.2k-b-11.7k, SD39) block copolymer having a total molecular weight of 39 kg mol−1 was exploited to achieve in-plane morphologies of lines, dots and antidots. Brush-free self-assembly of the SD39 on silicon substrates was invest...... substrates provides a simplified method for surface nanopatterning, templated growth of nanomaterials and nanofabrication....... the pattern into the underlying substrate. Directed self-assembly and hierarchical directed self-assembly on block copolymer templates for confinement of dots was successfully demonstrated. The strategy for achieving multiple morphologies using one BCP by mere choice of the annealing solvents on unmodified...

  12. Water droplets as template for next-generation self-assembled poly-(etheretherketone) with cardo membranes. (United States)

    Gugliuzza, Annarosa; Aceto, Marianna Carmela; Macedonio, Francesca; Drioli, Enrico


    Next generation PEEK-WC membranes have been fabricated by using an innovative self-assembly technique. Patterned architectures have been achieved via a solvent-reduced and water-assisted process, resulting in honeycomb packed geometry. The membranes exhibit monodisperse pores with size and shape comparable to those left by templating water droplets. Influencing factors for the formation of self-assembled poly-(etheretherketone) with Cardo [PEEK-WC] membranes have been evaluated, identifying the critical parameters for nucleation, growth, and propagation of the droplet-mobile arrays through the overall films. Structure-transport relationships have been discussed according to the results achieved from the implementation of membrane distillation processes, yielding indication about the suitability of self-assembled PEEK-WC films to work as interfaces in contactor operations.

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

    Roy, Debmalya; Shastri, Babita; Mukhopadhyay, K


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

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

    Ansari, Haris Masood

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

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

    Grabow, Wade W; Jaeger, Luc


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

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

    NARCIS (Netherlands)

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


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

  17. Topographic characterization of the self-assembled nanostructures of chitosan on mica surface by atomic force microscopy

    International Nuclear Information System (INIS)

    Wang, Li; Wu, Jiafeng; Guo, Yan; Gong, Coucong; Song, Yonghai


    Graphical abstract: - Highlights: • Nanocomposites of chitosan film were prepared by simple self-assembly from solvent media. • Chitosan molecules assembled on mica surface of nanoparticles, fibril and membrane with varied chitosan concentration. • Chitosan molecules assembled with different nanostructure under varied pH. • The optimum drying temperature for forming chitosan membrane is about 65 °C. - Abstract: In this work, the self-assembled nanostructures of chitosan on mica surface formed from various solvents were investigated by using atomic force microscopy. The effects of various factors on the self-assembled nanostructures of chitosan on mica surface, including solvents, the concentration of chitosan, the pH of solution and the drying temperature, were explored in detail. Our experimental data resulted in the conclusion that chitosan molecules could self-assemble on mica surface to form various nanostructures such as nanoparticles, fibril and film. Nanoparticles were always formed on mica surface from CCl 4 , C 6 H 6 , CH 2 Cl 2 solution, fibril preferred to form on mica surface from CH 3 CH 2 OH and CH 3 OH solution and the optimal solvent to form film was found to be CH 3 CN. Low concentration, pH and temperature were helpful for the formation of nanoparticles, medium concentration, pH and temperature resulted in fibril and high concentration, pH and temperature were often beneficial to forming chitosan films. The study of self-assembled nanostructures of chitosan on mica surface would provide new insight into the development of chitosan-based load-bearing materials.

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

    Olvera de La Cruz, Monica


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

  19. Self-Assembled Monolayers for Dental Implants

    Directory of Open Access Journals (Sweden)

    Sidónio C. Freitas


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

  20. Self-assembling holographic biosensors and biocomputers.

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

    Greiner, A.; Wendorff, J. H.

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

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

    Aytun, Taner

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

  4. Hierarchical superhydrophobic/hydrophilic substrates based on nanospheres self-assembly onto micro-pillars (United States)

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


    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°.

  5. Circuits and programmable self-assembling DNA structures


    Carbone, Alessandra; Seeman, Nadrian C.


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

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

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


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

  7. Magnetic manipulation of self-assembled colloidal asters.

    Energy Technology Data Exchange (ETDEWEB)

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


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

  8. In situ monitoring of structural changes during colloidal self-assembly. (United States)

    Koh, Yaw Koon; Wong, Chee Cheong


    Reflectance spectroscopy is utilized to monitor structural changes during the self-assembly of a monodisperse colloidal system at the meniscus of a sessile drop on an inert substrate. Treating the ordered colloidal structure as a photonic crystal is equivalent to monitoring the changes in the photonic band gap (PBG) as the colloidal system self-assembles heterogeneously into a crystal through solvent evaporation in ambient conditions. Using a modified Bragg's law model of the photonic crystal, we can trace the structural evolution of the self-assembling colloidal system. After a certain induction period, a face-centered cubic (FCC) structure emerges, albeit with a lattice parameter larger than that of a true close-packed structure. This FCC structure is maintained while the lattice parameter shrinks continuously with further increase in the colloidal concentration due to drying. When the structure reaches a lattice parameter 1.09 times the size of that of a true close-packed structure, it undergoes an abrupt decrease in lattice spacing, apparently similar to those reported for lattice-distortive martensitic transformations. This abrupt final lattice shrinkage agrees well with the estimated Debye screening length of the electric double layer of charged colloids and could be the fundamental reason behind the cracking commonly seen in colloidal crystals.

  9. Towards Ordered Silicon Nanostructures through Self-Assembling Mechanisms and Processes

    Directory of Open Access Journals (Sweden)

    R. A. Puglisi


    Full Text Available The design and development of innovative architectures for memory storage and energy conversion devices are at the forefront of current research efforts driving us towards a sustainable future. However, issues related to the cost, efficiency, and reliability of current technologies are still severely limiting their overtake of the standard designs. The use of ordered nanostructured silicon is expected to overcome these limitations and push the advancement of the alternative technologies. Specifically, self-assembling of block copolymers has been recognized as a promising and cost-effective approach to organize silicon nanostructures. This work reviews some of the most important findings on block copolymer self-assembling and complements those with the results of new experimental studies. First of all, a quantitative analysis is presented on the ordering and fluctuations expected in the synthesis of silicon nanostructures by using standard synthesis methods like chemical vapour deposition. Then the effects of the several parameters guiding the ordering mechanisms in the block copolymer systems, such as film thickness, molecular weight, annealing conditions, solvent, and substrate topography are discussed. Finally, as a proof of concept, an in-house developed example application to solar cells is presented, based on silicon nanostructures resulting from self-assembling of block copolymers.

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

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


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

  11. Self-assembly of diphenylalanine backbone homologues and their combination with functionalized carbon nanotubes. (United States)

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


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

  12. Self-assembly morphology effects on the crystallization of semicrystalline block copolymer thin film (United States)

    Wei, Yuhan; Pan, Caiyuan; Li, Binyao; Han, Yanchun


    Self-assembly morphology effects on the crystalline behavior of asymmetric semicrystalline block copolymer polystyrene-block-poly(L-lactic acid) thin film were investigated. Firstly, a series of distinctive self-assembly aggregates, from spherical to ellipsoid and rhombic lamellar micelles (two different kinds of rhombic micelles, defined as rhomb 1 and rhomb 2) was prepared by means of promoting the solvent selectivity. Then, the effects of these self-assembly aggregates on crystallization at the early stage of film evolution were investigated by in situ hot stage atomic force microscopy. Heterogeneous nucleation initiated from the spherical micelles and dendrites with flat on crystals appeared with increasing temperature. At high temperature, protruding structures were observed due to the thickening of the flat-on crystals and finally more thermodynamically stable crystallization formed. Annealing the rhombic lamellar micelles resulted in different phenomena. Turtle-shell-like crystalline structure initiated from the periphery of the rhombic micelle 1 and spread over the whole film surface in the presence of mostly noncrystalline domain interior. Erosion and small hole appeared at the surface of the rhombic lamellar micelle 2; no crystallization like that in rhomb 1 occurred. It indicated that the chain-folding degree was different in these two micelles, which resulted in different annealing behaviors.

  13. Effective interactions between nanoparticles: Creating temperature-independent solvation environments for self-assembly (United States)

    Yadav, Hari O. S.; Shrivastav, Gourav; Agarwal, Manish; Chakravarty, Charusita


    correlation of mass dipoles on the two nanoparticles. One expects therefore that during self-assembly using solvent evaporation, temperature can be used as a structure-directing factor as long as good solvent conditions are maintained. It also suggests that disordered configurations may emerge as solvent quality decreases due to increasing role of short-range attractions and ligand fluctuation-driven anisotropy. The possibilities of using structural estimators of various thermodynamic quantities to analyse the interplay of ligand fluctuations and solvent quality in self-assembly as well as to design solvation environments are discussed.

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

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

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

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

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

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

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

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

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

    Cusumano, Stephen

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

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

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


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

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

    Sinko, Robert; Keten, Sinan


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

  1. Surface Modification of Self-Assembled Graphene Oxide for Cell Culture Studies (United States)

    Swain, John E., III

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

  2. High stability of self-assembled peptide nanowires against thermal, chemical, and proteolytic attacks. (United States)

    Ryu, Jungki; Park, Chan Beum


    Understanding the self-assembly of peptides into ordered nanostructures is recently getting much attention since it can provide an alternative route for fabricating novel bio-inspired materials. In order to realize the potential of the peptide-based nanofabrication technology, however, more information is needed regarding the integrity or stability of peptide nanostructures under the process conditions encountered in their applications. In this study, we investigated the stability of self-assembled peptide nanowires (PNWs) and nanotubes (PNTs) against thermal, chemical, proteolytic attacks, and their conformational changes upon heat treatment. PNWs and PNTs were grown by the self-assembly of diphenylalanine (Phe-Phe), a peptide building block, on solid substrates at different chemical atmospheres and temperatures. The incubation of diphenylalanine under aniline vapor at 150 degrees C led to the formation of PNWs, while its incubation with water vapor at 25 degrees C produced PNTs. We analyzed the stability of peptide nanostructures using multiple tools, such as electron microscopy, thermal analysis tools, circular dichroism, and Fourier-transform infrared spectroscopy. Our results show that PNWs are highly stable up to 200 degrees C and remain unchanged when incubated in aqueous solutions (from pH 1 to 14) or in various chemical solvents (from polar to non-polar). In contrast, PNTs started to disintegrate even at 100 degrees C and underwent a conformational change at an elevated temperature. When we further studied their resistance to a proteolytic environment, we discovered that PNWs kept their initial structure while PNTs fully disintegrated. We found that the high stability of PNWs originates from their predominant beta-sheet conformation and the conformational change of diphenylalanine nanostructures. Our study suggests that self-assembled PNWs are suitable for future nano-scale applications requiring harsh processing conditions. 2009 Wiley Periodicals, Inc.

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

    DEFF Research Database (Denmark)

    Canning, John; Lindoy, Lachlan; Huyang, George


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

  4. A Multiple-Scale Analysis of Evaporation Induced Marangoni Convection

    KAUST Repository

    Hennessy, Matthew G.


    This paper considers the stability of thin liquid layers of binary mixtures of a volatile (solvent) species and a nonvolatile (polymer) species. Evaporation leads to a depletion of the solvent near the liquid surface. If surface tension increases for lower solvent concentrations, sufficiently strong compositional gradients can lead to Bénard-Marangoni-type convection that is similar to the kind which is observed in films that are heated from below. The onset of the instability is investigated by a linear stability analysis. Due to evaporation, the base state is time dependent, thus leading to a nonautonomous linearized system which impedes the use of normal modes. However, the time scale for the solvent loss due to evaporation is typically long compared to the diffusive time scale, so a systematic multiple scales expansion can be sought for a finite-dimensional approximation of the linearized problem. This is determined to leading and to next order. The corrections indicate that the validity of the expansion does not depend on the magnitude of the individual eigenvalues of the linear operator, but it requires these eigenvalues to be well separated. The approximations are applied to analyze experiments by Bassou and Rharbi with polystyrene/toluene mixtures [Langmuir, 25 (2009), pp. 624-632]. © 2013 Society for Industrial and Applied Mathematics.

  5. Self-Assembly Kinetics of Colloidal Particles inside Monodispersed Micro-Droplet and Fabrication of Anisotropic Photonic Crystal Micro-Particles

    Directory of Open Access Journals (Sweden)

    Ming-Yu Zhang


    Full Text Available A new microfluidic approach to preparing anisotropic colloidal photonic crystal microparticles is developed and the self-assembly kinetics of colloidal nanoparticles is discussed. Based on the “coffee ring” effect in the self-assembly process of colloidal silica particle in strong solvent extraction environment, we successfully prepared anisotropic photonic crystal microparticles with different shapes and improved optical properties. The shapes and optical properties of photonic crystal microparticles can be controlled by adjusting the droplet size and extraction rate. We studied the self-assembly mechanism of colloidal silica particles in strong solvent extraction environment, which has potential applications in a variety of fields including optical communication technology, environmental response, photo-catalysis and chromic material.

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

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


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

  7. Understanding the structure and performance of self-assembled triblock terpolymer membranes

    KAUST Repository

    Pendergast, MaryTheresa M.


    Nanoporous membranes represent a possible route towards more precise particle and macromolecular separations, which are of interest across many industries. Here, we explored membranes with vertically-aligned nanopores formed from a poly(isoprene-. b-styrene-. b-4 vinyl pyridine) (ISV) triblock terpolymer via a hybrid self-assembly/nonsolvent induced phase separation process (S-NIPS). ISV concentration, solvent composition, and evaporation time in the S-NIPS process were varied to tailor ordering of the selective layer and produce enhanced water permeability. Here, water permeability was doubled over previous versions of ISV membranes. This was achieved by increasing volatile solvent concentration, thereby decreasing the evaporation period required for self-assembly. Fine-tuning was required, however, since overly-rapid evaporation did not yield the desired pore structure. Transport models, used to relate the in-. situ structure to the performance of these materials, revealed narrowing of pores and blocking by the dense region below. It was shown that these vertically aligned nanoporous membranes compare favorably with commercial ultrafiltration membranes formed by NIPS and track-etching processes, which suggests that there is practical value in further developing and optimizing these materials for specific industrial separations. © 2013 Elsevier B.V.

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

    Arefi, Hadi H.; Yamamoto, Takeshi


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

  9. Diphenylalanine peptide nanotubes self-assembled on functionalized metal surfaces for potential application in drug-eluting stent. (United States)

    Zohrabi, Tayebeh; Habibi, Neda; Zarrabi, Ali; Fanaei, Maryam; Lee, Lai Yeng


    This study focuses on the potential of diphenylalanine self-assembled peptide nanotubes (FF Nts) for delivery of flufenamic acid (FA) from metal implants. Self-assembly of FF Nts was studied in solution and on surfaces of glass, silicone and gold substrates. FA was loaded inside the shell of FF Nts and subsequently FF/FA Nts were attached to gold surfaces. The substrate were characterized by Field Emission Scanning Electron Microscopy (FESEM), fluorescence microscopy, confocal microscopy, and UV-vis spectroscopy. Release of FA from FF Nts were investigated by immersing coated metal substrates in phosphate-buffered saline for 12 days. Self-assembly of FF in water and solvent resulted in formation of nanotubes, which efficiently loaded 98% of FA with concentration of 20 µg/mL. FESEM images confirmed successful attachment of FF/FA Nts to functionalized gold substrates. In vitro release studies indicated using FF Nts has prolonged the release rate of FA for several days. Biocompatibility studied confirmed more than 50% of the cells were alive in concentration of 250-1000 µg/mL of FF Nts thus suggesting the potential of peptide based self-assemble nanostructures as an alternate system for polymer coating in drugs eluting stents. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2280-2290, 2016. © 2016 Wiley Periodicals, Inc.

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

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


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

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

    Evans, Constantine G; Winfree, Erik


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

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

    Halverson, Jonathan D.; Tkachenko, Alexei V.


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

  13. Theoretical aspects of self-assembly of proteins: A Kirkwood-Buff-theory approach (United States)

    Ben-Naim, Arieh


    A new approach to the problem of self-assembly of proteins induced by temperature, pressure, or changes in solute concentration is presented. The problem is formulated in terms of Le Chatelier principle, and a solution is sought in terms of the Kirkwood-Buff theory of solutions. In this article we focus on the pressure and solute effects on the association-dissociation equilibrium. We examine the role of both hydrophobic and hydrophilic effects. We argue that the latter are more important than the former. The solute effect, on the other hand, depends on the preferential solvation of the monomer and the aggregate with respect to solvent and co-solvent molecules. An experimental approach based on model compounds to study these effects is suggested.

  14. Hierarchically porous bio-inspired films prepared by combining "breath figure" templating and selectively degradable block copolymer directed self-assembly. (United States)

    Bertrand, Arthur; Bousquet, Antoine; Lartigau-Dagron, Christine; Billon, Laurent


    Polymer films with hierarchical micro- and nano-porosities were prepared by combining the fast solvent evaporation "Breath Figure" (BF) method, exhibiting a highly regular honeycomb micro-porous texture, with the additional nanoscale self-assembly of polylactide-block-polystyrene (PLA-b-PS) diblock copolymers, PLA being used thereafter as a sacrificial component for nano-porosity.

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

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


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

  16. Synthesis and Self-Assembly of Triangulenium Salts

    DEFF Research Database (Denmark)

    Shi, Dong

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

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

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


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

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

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


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

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

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


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

  20. Self-Assembly in Biosilicification and Biotemplated Silica Materials

    Directory of Open Access Journals (Sweden)

    Francisco M. Fernandes


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

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

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


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

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

    International Nuclear Information System (INIS)

    Loo, Yihua; Hauser, Charlotte A E


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Synthesis, characterization, and self-assembly of bicarbamates and tri-carbamates (United States)

    Singh, Rajiv Kumar

    Recent decades have witnessed the discovery of a wide variety of nanomaterials. These nanomaterials vary from zero-dimensional nanodots to three-dimensional nanoflowers. However the properties of these nanomaterials have not been fully explored. A majority of the nonmaterials discovered so far are inorganic. There is little information about nanomaterials which are entirely based on organic compounds. Therefore this thesis focuses on the synthesis of two-dimensional nanosheets based on organic frameworks. In this study, a number of two-armed and three-armed carboxamides and carbamates have been synthesized, characterized and self-assembly process was studied. The self-assembly of these amides and carbamates were studied in a large number of single solvents as well as combination of solvents. Two-armed amides and carbamates having aromatic cores are found to have poor solubility in all but DMF and DMSO. The two-armed amides and carbamates having linker alkyl chain are found to have good solubility and crystal formation in a few solvents, but the quality of the crystal is not good enough for the XRD analysis. The polar solvents along with a trace amount of water are found to be more effective in getting perfect crystals of three-armed carbamates for X-ray crystallography. Carbamates with side-arms of three carbons and a cyclohexyl ring form perfect quality crystals in EtOAc, MeCN, and THF:H2O. In the process of growing single crystal several crystallization techniques were used. Slow evaporation process is found to be more efficient in getting good quality crystal. The crystal structures of carbamates have been determined as a part of the project. The morphology of the nanosheets was also studied by the transmission electron microscope (TEM). The TEM image of the carbamates reveals that its morphology is two-dimensional sheet. Additionally, data from powdered XRD have also revealed the formation of same or similar crystalline isoform from a variety of conditions.

  5. Preparation and Characterization of Binary Organogels via Some Azobenzene Amino Derivatives and Different Fatty Acids: Self-Assembly and Nanostructures

    Directory of Open Access Journals (Sweden)

    Haiying Guo


    Full Text Available In present work the gelation behaviors of binary organogels composed of azobenzene amino derivatives and fatty acids with different alkyl chains in various organic solvents were designed and investigated. Their gelation behaviors in 20 solvents were tested as new binary organic gelators. It showed that the length of alkyl substituent chains and azobenzene segment have played a crucial role in the gelation behavior of all gelator mixtures in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Morphological studies revealed that the gelator molecules self-assemble into different aggregates from lamella, wrinkle, to belt with change of solvents. Spectral studies indicated that there existed different H-bond formation and hydrophobic force, depending on different substituent chains in molecular skeletons. The present work may also give new perspectives for designing new binary organogelators and soft materials.

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

    Directory of Open Access Journals (Sweden)

    Øystein Stakkestad


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

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


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

  10. Glyco-Nanoparticles Made from Self-Assembly of Maltoheptaose-block-Poly(methyl methacrylate): Micelle, Reverse Micelle, and Encapsulation. (United States)

    Zepon, Karine M; Otsuka, Issei; Bouilhac, Cécile; Muniz, Edvani C; Soldi, Valdir; Borsali, Redouane


    The synthesis and the solution-state self-assembly of the "hybrid" diblock copolymers, maltoheptaose-block-poly(methyl methacrylate) (MH-b-PMMA), into large compound micelles (LCMs) and reverve micelle-type nanoparticles, are reported in this paper. The copolymers were self-assembled in water and acetone by direct dissolution method, and the morphologies of the nanoparticles were investigated by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), transmission electron microscopy (TEM), atomic force microscopy (AFM), proton nuclear magnetic resonance ((1)H NMR), and fluorescence spectroscopy as a function of the volume fraction of the copolymer hydrophobic block, copolymer concentration, stirring speed, and solvent polarity. The DLS measurements and TEM images showed that the hydrodynamic radius (Rh) of the LCMs obtained in water increases with the copolymer concentration. Apart from that, increasing the stirring speed leads to polydispersed aggregations of the LCMs. On the other hand, in acetone, the copolymers self-assembled into reverse micelle-type nanoparticles having Rh values of about 6 nm and micellar aggregates, as revealed the results obtained from DLS, AFM, and (1)H NMR analyses. The variation in micellar structure, that is, conformational inversion from LCMs to reverse micelle-type structures in response to polarity of the solvent, was investigated by apparent water contact angle (WCA) and (1)H NMR analyses. This conformational inversion of the nanoparticles was further confirmed by encapsulation and release of hydrophobic guest molecule, Nile red, characterized by fluorescence spectroscopy.

  11. Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles (United States)

    Chen, Yihuang; Wang, Zewei; He, Yanjie; Yoon, Young Jun; Jung, Jaehan; Zhang, Guangzhao; Lin, Zhiqun


    The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.

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

    International Nuclear Information System (INIS)

    Striolo, Alberto


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

  13. Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation (United States)

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


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

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

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


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

  15. Self-assembled monolayers of metallosalophenes on gold

    NARCIS (Netherlands)

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


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

  16. Self-assembly of hydrofluorinated Janus graphene monolayer

    DEFF Research Database (Denmark)

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei


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

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

    DEFF Research Database (Denmark)

    Reeler, Nini Elisabeth Abildgaard

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

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


    Yang Yongkun; Burkhard Peter


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

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

    NARCIS (Netherlands)

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


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

  20. Suprmolecular chirality of self-assembled systems in solution

    NARCIS (Netherlands)

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


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

  1. Hierarchical self-assembly of complex polyhedral microcontainers

    International Nuclear Information System (INIS)

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


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

  2. Multiphonon capture processes in self-assembled quantum dots

    DEFF Research Database (Denmark)

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


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

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

    Sengupta, Sanchita; Würthner, Frank


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

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

    Indian Academy of Sciences (India)

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

  5. Self-Assembled Microwires of Terephthalic Acid and Melamine

    Directory of Open Access Journals (Sweden)

    Hong Wang


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

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

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


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

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

    NARCIS (Netherlands)

    Yildirim, O.


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

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

    Indian Academy of Sciences (India)

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

  9. Self-assembling electroactive hydrogels for flexible display technology

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    NARCIS (Netherlands)

    Vutukuri, H.R.


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

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

    Indian Academy of Sciences (India)

    Usha P Kar


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

  12. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)


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

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

    Indian Academy of Sciences (India)

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

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

    NARCIS (Netherlands)

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


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

  15. Self-assembling bilayers of palladiumthiolates in organic media

    Indian Academy of Sciences (India)


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

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

    NARCIS (Netherlands)

    Robson Marsden, Hana


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

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

    African Journals Online (AJOL)

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

  18. Self-assembling electroactive hydrogels for flexible display technology

    International Nuclear Information System (INIS)

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


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

  19. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)

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

  20. Molecular modeling of directed self-assembly of block copolymers: Fundamental studies of processing conditions and evolutionary pattern design (United States)

    Khaira, Gurdaman Singh

    from the information in inverse space is a challenging task. Using the optimization techniques and molecular simulations discussed in the first chapter, a methodology to reconstruct BCP morphology from X-ray scattering data is described. It is shown that only a handful of simulation parameters that come directly from experiment are able to describe the morphologies observed from real X-ray scattering experiments. The last chapter focuses on the use of solvents to assist the self-assembly of BCPs. Additional functionality to capture the process of solvent annealing is also discussed. The bulk behavior of solvated mixtures of BCPs with solvents of various affinities is described, and the results are consistent with the experimentally observed behavior of BCPs in the presence of solvents.

  1. Template-Free Supracolloidal Self-Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids. (United States)

    Nonappa; Lahtinen, Tanja; Haataja, Johannes S; Tero, Tiia-Riikka; Häkkinen, Hannu; Ikkala, Olli


    We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au 102 -pMBA 44 ) under aqueous conditions into hexagonally packed monolayer-thick two-dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template-free manner by the spontaneous patchiness of the pMBA ligands around the Au 102 -pMBA 44 nanoclusters preferably towards equatorial plane, thus promoting inter-nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findings encourage to explore atomically precise nanoclusters towards highly controlled colloidal self-assemblies. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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


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

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

    Perumal, Shiamalee

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

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

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


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

  5. Self-assembling peptide hydrogels immobilized on silicon surfaces

    International Nuclear Information System (INIS)

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


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

  6. Regulation of substituent groups on morphologies and self-assembly of organogels based on some azobenzene imide derivatives (United States)

    Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Zhou, Jingxin; Gao, Faming


    In this paper, new azobenzene imide derivatives with different substituent groups were designed and synthesized. Their gelation behaviors in 21 solvents were tested as novel low-molecular-mass organic gelators. It was shown that the alkyl substituent chains and headgroups of azobenzene residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle, lamella, and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between amide groups and conformations of methyl chains. The present work may give some insight to the design and character of new organogelators and soft materials with special molecular structures.

  7. Nanostructures and Self-Assembly of Organogels via Benzimidazole/Benzothiazole Imide Derivatives with Different Alkyl Substituent Chains

    Directory of Open Access Journals (Sweden)

    Xihai Shen


    Full Text Available New benzimidazole/benzothiazole imide derivatives with different alkyl substituent chains were designed and synthesized. Their gelation behaviors in 22 solvents were tested as novel low-molecular-mass organic gelators. The test showed that the alkyl substituent chains and headgroups of benzimidazole/benzothiazole residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. SEM and AFM observations revealed that the gelator molecules self-assemble into different aggregates from wrinkle, lamella and belt to dot with change of solvents. Spectral studies indicated that there existed different H-bond formation between imide groups and hydrophobic force of alkyl substituent chains in molecular skeletons. The present work may give some insights into design and character of new organogelators and soft materials with special molecular structures.

  8. High-Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-Assembled Monolayers

    KAUST Repository

    Kim, Gi-Hwan


    © 2015 American Chemical Society. The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls.

  9. Controlled synthesis of pompon-like self-assemblies of Pd nanoparticles under microwave irradiation

    International Nuclear Information System (INIS)

    Tong Xia; Zhao Yanxi; Huang Tao; Liu Hanfan; Liew, Kong Yong


    Pd nanoparticles with uniform, self-assembled pompon-like nanostructure were synthesized by thermal decomposition of palladium acetate under microwave irradiation with methyl isobutyl ketone (MIBK) as a solvent in the presence of a little amount of ethylene glycol (EG) and KOH without using any special stabilizers. The as-synthesized Pd nano-pompons were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray powder diffraction. The results show that the as-prepared Pd nano-pompons with the average diameters in the range of 28-81 nm were self-assemblies organized by hundreds of smaller primary nanoparticles with an average dimension of about 2.4 nm. The sizes of Pd nano-pompons can be well controlled by adjusting the concentration of palladium acetate. A little amount of EG and KOH also plays an important role in controlling the size, uniformity and dispersion of Pd nano-pompons. The Pd nano-pompons can be easily supported on γ-Al 2 O 3 and their catalytic activity was examined preliminarily.

  10. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

    KAUST Repository

    Zhao, Kui


    We demonstrate that local and long range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the dielectric surface with solution-state disentanglement and pre-aggregation of P3HT in a theta solvent, leading to a very significant enhancement of the field effect carrier mobility. The pre-aggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of pre-aggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of pre-aggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to un-aggregated polymer chains. Additional investigations reveal the combined pre-aggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known pre-aggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  11. Nanospheres Prepared by Self-Assembly of Random Copolymers in Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Eri Yoshida


    Full Text Available The synthesis of spherical particles was attained by the direct self-assembly of poly[2-(perfluorooctylethyl acrylate-random-acrylic acid], P(POA-r-AA, and by the indirect self-assembly poly[POA-random-2-(dimethylaminoethyl acrylate], P(POA-r-DAA, with dicarboxylic acids in supercritical carbon dioxide (scCO2. The copolymers formed spherical particles with hundreds of nanometer diameters in a heterogeneous state at pressures lower than the cloud point pressure. The formation of spherical particles was also dependent on the temperature. The formation of spherical particles could be optimized through varying the solvent quality by the manipulation of the CO2 pressure and temperature for the different copolymer compositions. The dynamic light scattering and 1H NMR studies demonstrated that the nanospheres had the micellar structures consisting of the CO2-philic POA shells and the CO2-phobic AA or DAA cores including the main chain cores. The nanospheres produced the superhydrophobic surfaces based on the water-proof shells of the POA units.

  12. RAFT Synthesis and Self-Assembly of Free-Base Porphyrin Cored Star Polymers

    Directory of Open Access Journals (Sweden)

    Lin Wu


    Full Text Available Reversible addition fragmentation chain transfer (RAFT synthesis and self-assembly of free-base porphyrin cored star polymers are reported. The polymerization, in the presence of a free-base porphyrin cored chain transfer agent (CTA-FBP, produced porphyrin star polymers with controlled molecular weights and narrow polydispersities for a number of monomers including N, N-dimethylacrylamide (DMA and styrene (St. Well-defined amphiphilic star block copolymers, P-(PS-PDMA4 and P-(PDMA-PS4 (P: porphyrin, were also prepared and used for self-assembly studies. In methanol, a selective solvent for PDMA, spherical micelles were observed for both block copolymers as characterized by TEM. UV-vis studies suggested star-like micelles were formed from P-(PS-PDMA4, while P-(PDMA-PS4 aggregated into flower-like micelles. Spectrophotometric titrations indicated that the optical response of these two micelles to external ions was a function of micellar structures. These structure-related properties will be used for micelle studies and functional material development in the future.

  13. Self-Assembly of Carotenoids During Solution Casting of Solar Devices (United States)

    Alwis, Dusantha; Ratnaweera, Dilru; Etampawala, Thusitha; Dadmun, Mark; Chandrika, Udumalagala; Jayaweera, Pradeep


    Self assembly of carotenoids is a common phenomenon in nature and seems to be closely related to the functions of these natural dyes in solar devices. The large absorption coefficients in the visible region of carotenoids make them a well suited natural resource for dye-sensitized solar cells (DSSC). The performance of carotenoid based solar devices mainly depends on the photo-electrochemical properties of the active material (carotenoids) and their self-assembled morphology within solar devises. These associations of molecules will affect the light absorption, emission and energy harvesting abilities of these solar devices. Two types of highly conjugated natural carotenoids having mono and dicarboxy terminal groups, namely bixin and norbixin, were extracted from annatto seeds. In the current study, small angle neutron scattering experiments were carried out to examine the modes of assemblies of bixin and norbixin during solution processing of DSSCs. Spherical shape aggregates with rough interfaces were observed in acetone medium, which is a good solvent for hydrocarbon chain. The shape of the aggregates slightly deviates from spherical to slightly elongated shape at high volume fractions of carotenoids. Bixin and norbixin show different association behaviors as a function of their concentration.

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

    International Nuclear Information System (INIS)

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


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

  15. Synthesis, optical properties, and helical self-assembly of a bivaline-containing tetraphenylethene (United States)

    Li, Hongkun; Zheng, Xiaoyan; Su, Huimin; Lam, Jacky W. Y.; Sing Wong, Kam; Xue, Shan; Huang, Xuejiao; Huang, Xuhui; Li, Bing Shi; Tang, Ben Zhong


    A chiral tetraphenylethene derivative with two valine-containing attachments (TPE-DVAL), was synthesized by Cu(I)-catalyzed azide-alkyne “click” reaction. The optical properties and self-assembling behaviours of TPE-DVAL were investigated. The molecule is non-emissive and circular dichroism (CD)-silent in solution, but shows strong fluorescence and Cotton effects in the aggregation state, demonstrating aggregation-induced emission (AIE) and CD (AICD) characteristics. TPE-DVAL exhibits good circularly polarized luminescence (CPL) when depositing on the surface of quartz to allow the evaporation of its 1,2-dichloroethane solution. SEM and TEM images of the molecule show that the molecule readily self-assembles into right-handed helical nanofibers upon the evaporation of its solvent of DCE. The molecular alignments and interactions in assembling process are further explored through XRD analysis and computational simulation. The driving forces for the formation of the helical fibers were from the cooperative effects of intermolecular hydrogen bonding, π-π interactions and steric effect.

  16. Periodic grating-like patterns induced by self assembly of gelator fibres in nematic gels. (United States)

    Ramarao, Pratibha; Topnani, Neha Bhagwani; N, Prutha


    Periodic orientation patterns occurring in nematic gels revealed by optical and scanning electron microscopy are found to be formed by spontaneous self assembly of fibrous aggregates of a low-molecular weight organogelator in an aligned thermotropic liquid crystal (LC). The self organization into the periodic structure is also reflected in a calorimetric study which shows the occurrence of three thermoreversible states viz. isotropic liquid, nematic and nematic gel. The segregation and self assembly of the fibrous aggregates leading to the pattern formation is attributed to the highly polar LC and the hydrogen bonding between gelator molecules as shown by x-ray diffraction and vibrational spectroscopy. This study aims to investigate in detail the effect of the chemical nature and alignment of an anisotropic solvent on the morphology of the gelator fibres and the resulting gelation process. The periodic organization of the LC rich and fibre rich regions can also provide a technique of obtaining templates for positioning nanoparticle arrays in an LC matrix which can lead to novel devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

    KAUST Repository

    Musteata, Valentina-Elena


    Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

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

    Pochan, Darrin; Deming, Tim; Schneider, Joel


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

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

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


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

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

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


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

  1. Nanostructured Colloidal Particles by Confined Self-Assembly of Block Copolymers in Evaporative Droplets

    Directory of Open Access Journals (Sweden)

    Minsoo P. Kim


    Full Text Available Block copolymers (BCPs can create various morphology by self-assembly in bulk or film. Recently, using BCPs in confined geometries such as thin film (one-dimension, cylindrical template (two-dimension, or emulsion droplet (three-dimension, nanostructured BCP particles have been prepared, in which unique nanostructures of the BCP are formed via solvent annealing process and can be controlled depending on molecular weight ratio and interaction parameter of the BCPs, and droplet size. Moreover, by tuning interfacial property of the BCP particles, anisotropic particles with unique nanostructures have been prepared. Furthermore, for practical application such as drug delivery system, sensor, self-healing, metamaterial, and optoelectronic device, functional nanoparticles can be incorporated inside BCP particles. In this article, we summarize recent progress on the production of structured BCP particles and composite particles with metallic nanoparticles.

  2. Synthesis of In2S3 nanoplates and their self-assembly into superlattices. (United States)

    Zhong, Haizheng; Ye, Mingfu; Zhou, Yi; Yang, Chunhe; Li, Yongfang


    Ultrathin nanoplates of beta-phase semiconductor In2S3 with the diameter of 50 - 80 nm and a thickness of 1.85 nm were synthesized via a simple hot injection solution method with Hexadecylamine (HDA) as ligand, and the nanoplates self-assembled into superlattices by face to face stacking during evaporation of the solvent. The nanoplates and the assembled superlattices were characterized by XRD, TEM, HRTEM, XPS etc. The TEM and XRD results display that the nanocrystals are highly crystalline, hexagonal shape, and uniform in thickness. A strong quantum confinement effect of the 2D nanoplates was observed from the UV-Vis and PL spectra for the first time in the In2S3 nanoplates. A possible mechanism of the synthesis and assembly was proposed.

  3. Synthesis, Self-Assembly and Photoresponsive Liquid Crystals Based on Azobenzene Derivatives. (United States)

    Wang, Hongyan; Han, Yi; Yuan, Wei; Wu, Mengjiao; Chen, Yulan


    A new class of rod-coil-rod molecules with an azobenzene core were synthesized. They were found to form robust organogels in several kinds of organic solvents. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), FT-IR spectroscopy, UV-vis absorption spectroscopy, 1H NMR, and X-ray diffraction (XRD) revealed that in these organogels, the molecules self-assembled into nanofiber network with an H-type aggregation mode under the joint effect of Pi-Pi stacking, intermolecular hydrogen bonding, and van der Waals forces. Interestingly, the incorporation of the azobenzene mesogene into the rigid core led to photo-isomerizable liquid crystal materials, which exhibited fast responsiveness to light and temperature, along with the trans-cis transition stimulated by UV light and heating. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Chemically Transformable Configurations of Mercaptohexadecanoic Acid Self-Assembled Monolayers Adsorbed on Au(111)

    International Nuclear Information System (INIS)

    van Buuren, T; Bostedt, C; Nelson, A J; Terminello, L J; Vance, A L; Fadley, C S; Willey, T M


    Carboxyl terminated Self-Assembled Monolayers (SAMs) are commonly used in a variety of applications, with the assumption that the molecules form well ordered monolayers. In this work, NEXAFS verifies well ordered monolayers can be formed using acetic acid in the solvent. Disordered monolayers with unbound molecules present in the result using only ethanol. A stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. This reorientation of the endgroup is reversible with tilted over, hydrogen bound carboxyl groups while carboxylate-ion endgroups are upright. C1s photoemission shows that SAMs formed and rinsed with acetic acid in ethanol, the endgroups are protonated, while without, a large fraction of the molecules on the surface are carboxylate terminated

  5. Design colloidal particle morphology and self-assembly for coating applications. (United States)

    Jiang, Shan; Van Dyk, Antony; Maurice, Alvin; Bohling, James; Fasano, David; Brownell, Stan


    The progressive replacement of organic solvent-based coatings by waterborne latex polymer coatings has substantially renovated the coating industry, and generated huge environmental and health benefits. Today, on top of the continuing demand for higher performance and lower costs, the coating industry faces tighter regulation and higher sustainability standards. In addition, the new waterborne coatings have created unique opportunities and challenges in terms of fundamental understanding and research development. To address these challenges, polymer latex binders with diverse particle morphologies have been developed to improve coating performance. Furthermore, colloidal self-assembly has been utilized to help manufacturers make better paint with less cost. In this report, we review the recent progress in both fundamental study and industrial application in the context of developing new generation architectural coating materials. We introduce the basic concepts in coating materials and showcase several key technologies that have been implemented to improve coating performance. These technologies also represent the most important considerations in architectural coating design.

  6. Metal complexation and monolayer self-assembly of the bio-organic semiconductor Alizarin

    Energy Technology Data Exchange (ETDEWEB)

    Uppal, Neeti [Dept. Earth and Environmental Sciences, Ludwig-Maximilians-Universitaet Muenchen (LMU) and Center for NanoSciences (CeNS), Muenchen (Germany); Institut fuer Physik, Universitaet Augsburg (Germany); Gast, Norbert [Dept. Earth and Environmental Sciences, Ludwig-Maximilians-Universitaet Muenchen (LMU) and Center for NanoSciences (CeNS), Muenchen (Germany); Zentrum Neue Technologien, Deutsches Museum, Muenchen (Germany); Bueno, Martin [Fakultaet Feinwerk- und Mikrotechnik, Physikalische Technik, Hochschule Muenchen (Germany); Heckl, Wolfgang M. [Dept. of Physics, Technische Universitaet Muenchen (TUM), Garching (Germany); Zentrum Neue Technologien, Deutsches Museum, Muenchen (Germany); Trixler, Frank [Dept. Earth and Environmental Sciences, Ludwig-Maximilians-Universitaet Muenchen (LMU) and Center for NanoSciences (CeNS), Muenchen (Germany); Dept. of Physics, Technische Universitaet Muenchen (TUM), Garching (Germany); Zentrum Neue Technologien, Deutsches Museum, Muenchen (Germany)


    Organic Solid/Solid Wetting Deposition (OSWD) (Trixler et al.: Chem.Eur.J. 13 (2007), 7785) enables to deposit insoluble molecules such as organic pigments and semiconductors on substrate surfaces under ambient conditions. We explore the potential of OSWD to grow and manipulate monolayers of biomolecules and their chelates on graphite and use Alizarin as a model system - a natural organic compound which occurs mainly as an anthraquinone glycoside in plants. Our investigations via Scanning Tunneling Microscopy (STM), Tunneling Spectroscopy (TS) and Molecular Modelling reveal that OSWD works also with bio-organic molecules and chelate complexes and show that the advantages of OSWD (self-assembly under ambient conditions in a non-solvent environment, nanomanipulation via molecular extraction) can all be tapped.

  7. Stable emulsions formed by self-assembly of interfacial networks of dipeptide derivatives. (United States)

    Bai, Shuo; Pappas, Charalampos; Debnath, Sisir; Frederix, Pim W J M; Leckie, Joy; Fleming, Scott; Ulijn, Rein V


    We demonstrate the use of dipeptide amphiphiles that, by hand shaking of a biphasic solvent system for a few seconds, form emulsions that remain stable for months through the formation of nanofibrous networks at the organic/aqueous interface. Unlike absorption of traditional surfactants, the interfacial networks form by self-assembly through π-stacking interactions and hydrogen bonding. Altering the dipeptide sequence has a dramatic effect on the properties of the emulsions formed, illustrating the possibility of tuning emulsion properties by chemical design. The systems provide superior long-term stability toward temperature and salts compared to with sodium dodecyl sulfate (SDS) and can be enzymatically disassembled causing on-demand demulsification under mild conditions. The interfacial networks facilitate highly tunable and stable encapsulation and compartmentalization with potential applications in cosmetics, therapeutics, and food industry.

  8. Vesicles from Amphiphilic Dumbbells and Janus Dendrimers: Bioinspired Self-Assembled Structures for Biomedical Applications

    Directory of Open Access Journals (Sweden)

    Soraya Taabache


    Full Text Available The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size.

  9. Self-assembled gelatin-ι-carrageenan encapsulation structures for intestinal-targeted release applications. (United States)

    Gómez-Mascaraque, Laura G; Llavata-Cabrero, Beatriz; Martínez-Sanz, Marta; Fabra, María José; López-Rubio, Amparo


    In this work, natural biopolymeric encapsulation structures were developed through the self-assembly of gelatin and ι-carrageenan in aqueous solutions. The interactions of this binary system and of a ternary system containing a polyphenol-rich extract were deeply explored for the development of intestinal delivery systems. The processing of the structures (extrusion vs. freeze-drying) greatly influenced release properties, explained by the specific interactions between gelatin and polyphenols, thus allowing for tuning the processing conditions depending on the desired target application. Release was further controlled by incorporating a divalent salt, giving raise to extract-loaded ι-carrageenan/gelatin capsules with adequate release profiles for intestinal targeted delivery. These results demonstrate the potential of exploiting biopolymer interactions for designing bioactive delivery systems using environmentally friendly processes which do not involve the use of toxic or harsh solvents or cross-linkers. Copyright © 2018 Elsevier Inc. All rights reserved.

  10. Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes. (United States)

    Ghosh, Soumya; Hammes-Schiffer, Sharon


    Electrochemical electron transfer reactions play an important role in energy conversion processes with many technological applications. Electrodes modified by self-assembled monolayers (SAMs) exhibit reduced double layer effects and are used in molecular electronics. An important quantity for calculating the electron transfer rate constant is the reorganization energy, which is associated with changes in the solute geometry and the environment. In this Letter, an approach for calculating the electrochemical reorganization energy for a redox molecule attached to or near a SAM modified electrode is presented. This integral equations formalism polarizable continuum model (IEF-PCM) approach accounts for the detailed electronic structure of the molecule, as well as the contributions from the electrode, SAM, and electronic and inertial solvent responses. The calculated total reorganization energies are in good agreement with experimental data for a series of metal complexes in aqueous solution. This approach will be useful for calculating electron transfer rate constants for molecular electrocatalysts.

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

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


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

  12. Molecular Gels Materials with Self-Assembled Fibrillar Networks

    CERN Document Server

    Weiss, Richard G


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

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

    Barry, Rachael; Gitai, Zemer


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

  14. Quantitative self-assembly prediction yields targeted nanomedicines (United States)

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


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

  15. Synthesis and Self-Assembly of Triangulenium Salts

    DEFF Research Database (Denmark)

    Shi, Dong

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

  16. Environmental and Sensing Applications of Molecular Self-Assembly

    Energy Technology Data Exchange (ETDEWEB)

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


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

  17. Thermomechanical Response of Self-Assembled Nanoparticle Membranes

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Chandrashekhar V. Kulkarni


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

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


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

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

    Indian Academy of Sciences (India)


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

  2. Coherence and dephasing in self-assembled quantum dots

    DEFF Research Database (Denmark)

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


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

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

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


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

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


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


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

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

    Czech Academy of Sciences Publication Activity Database

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


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

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

    Singh, Pankaj Kumar

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

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

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


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

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

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


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

  9. Electrostatic Force Microscopy of Self Assembled Peptide Structures

    DEFF Research Database (Denmark)

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


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

  10. Protein nanorings organized by poly(styrene-block-ethylene oxide) self-assembled thin films (United States)

    Malmström, Jenny; Wason, Akshita; Roache, Fergus; Yewdall, N. Amy; Radjainia, Mazdak; Wei, Shanghai; Higgins, Michael J.; Williams, David E.; Gerrard, Juliet A.; Travas-Sejdic, Jadranka


    This study explores the use of block copolymer self-assembly to organize Lsmα, a protein which forms stable doughnut-shaped heptameric structures. Here, we have explored the idea that 2-D crystalline arrays of protein filaments can be prepared by stacking doughnut shaped Lsmα protein into the poly(ethylene oxide) blocks of a hexagonal microphase-separated polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer. We were able to demonstrate the coordinated assembly of such a complex hierarchical nanostructure. The key to success was the choice of solvent systems and protein functionalization that achieved sufficient compatibility whilst still promoting assembly. Unambiguous characterisation of these structures is difficult; however AFM and TEM measurements confirmed that the protein was sequestered into the PEO blocks. The use of a protein that assembles into stackable doughnuts offers the possibility of assembling nanoscale optical, magnetic and electronic structures.This study explores the use of block copolymer self-assembly to organize Lsmα, a protein which forms stable doughnut-shaped heptameric structures. Here, we have explored the idea that 2-D crystalline arrays of protein filaments can be prepared by stacking doughnut shaped Lsmα protein into the poly(ethylene oxide) blocks of a hexagonal microphase-separated polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer. We were able to demonstrate the coordinated assembly of such a complex hierarchical nanostructure. The key to success was the choice of solvent systems and protein functionalization that achieved sufficient compatibility whilst still promoting assembly. Unambiguous characterisation of these structures is difficult; however AFM and TEM measurements confirmed that the protein was sequestered into the PEO blocks. The use of a protein that assembles into stackable doughnuts offers the possibility of assembling nanoscale optical, magnetic and electronic structures. Electronic supplementary

  11. Self-assembly and omniphobic property of fluorinated unit end-functionalized poly(methyl methacrylate) (United States)

    Junyan, Liang; Pingdi, Xu; Jingxian, Bao; Ling, He; Nan, Zhu


    The self-assembly behavior of fluorinated unit end-functionalized poly(methyl methacrylate) (PDFHM-ef-PMMA) in solution and its influence on the surface microstructure, elemental composition and omniphobic property of cast film was investigated in this work. Specifically, three mixed solutions of tetrahydrofuran (THF)/methanol (MeOH), THF/H2O and THF/H2O/MeOH in various compositions were employed separately as the selective solvents. In THF/MeOH solution, the aggregate morphologies of PDFHM-ef-PMMA changed gradually from core-shell spheres to worm, and then to elliptical vesicles as MeOH content increased. In THF/H2O solution, spherical and bowl-shaped aggregates with significantly larger sizes than those in THF/MeOH solution were favored despite lower H2O content. The further addition of MeOH to THF/H2O mixture could reduce the size of aggregate but hardly change original aggregate morphology. During the film formation process, those self-assembled aggregates in THF/MeOH solution fused with one another to form a smooth surface. When such surface was fully covered by fluorinated segments, the outstanding hexadecane and water slide-off properties and ink-resistant property required for antifouling application were demonstrated. Instead, the aggregates formed in THF/H2O/MeOH mixture were subjected to secondary aggregation of PDFHM-ef-PMMA chains during solvent evaporation, leading to the formation of a particulate film with poor adhesion towards glass plate and hexadecane-repellent property.

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

    KAUST Repository

    Moreno Chaparro, Nicolas


    Isoporous membranes manufactured from diblock copolymer are successfully produced at laboratory scale under controlled conditions. Because of the complex phenomena involved, membrane preparation requires trial and error methodologies to find the optimal conditions, leading to a considerable demand of resources. Experimental insights demonstrate that the self-assembly of the block copolymers in solution has an effect on the final membrane structure. Nevertheless, the complete understanding of these multi-scale phenomena is elusive. Herein we use the coarse-grained method Dissipative Particle Dynamics to study the self-assembly of block copolymers that are used for the preparation of the membranes. To simulate representative time and length scales, we introduce a framework for model reduction of polymer chain representations for dissipative particle dynamics, which preserves the properties governing the phase equilibria. We reduce the number of degrees of freedom by accounting for the correlation between beads in fine-grained models via power laws and the consistent scaling of the simulation parameters. The coarse-graining models are consistent with the experimental evidence, showing a morphological transition of the aggregates as the polymer concentration and solvent affinity change. We show that hexagonal packing of the micelles can occur in solution within different windows of polymer concentration depending on the solvent affinity. However, the shape and size dispersion of the micelles determine the characteristic arrangement. We describe the order of crew-cut micelles using a rigid-sphere approximation and propose different phase parameters that characterize the emergence of monodisperse-spherical micelles in solution. Additionally, we investigate the effect of blending asymmetric diblock copolymers (AB/AC) over the properties of the membranes. We observe that the co-assembly mechanism localizes the AC molecules at the interface of A and B domains, and induces

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

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


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

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

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


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

  15. Self-assembly of inorganic nanoparticles: Ab ovo (United States)

    Kotov, Nicholas A.


    There are numerous remarkable studies related to the self-organization of polymers, coordination compounds, microscale particles, biomolecules, macroscale particles, surfactants, and reactive molecules on surfaces. The focus of this paper is on the self-organization of nanoscale inorganic particles or simply nanoparticles (NPs). Although there are fascinating and profound discoveries made with other self-assembling structures, the ones involving NPs deserve particular attention because they (a) are omnipresent in Nature; (b) have relevance to numerous disciplines (physics, chemistry, biology, astronomy, Earth sciences, and others); (c) embrace most of the features, geometries, and intricacies observed for the self-organization of other chemical species; (d) offer new tools for studies of self-organization phenomena; and (e) have a large economic impact, extending from energy and construction industries, to optoelectronics, biomedical technologies, and food safety. Despite the overall success of the field it is necessary to step back from its multiple ongoing research venues and consider two questions: What is self-assembly of nanoparticles? and Why do we need to study it? The reason to bring them up is to achieve greater scientific depth in the understanding of these omnipresent phenomena and, perhaps, deepen their multifaceted impact. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

  16. Self-assembly of lipopolysaccharide layers on allantoin crystals. (United States)

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


    Self-assembly of lipopolysaccharides (LPS) on solid surfaces is important for the study of bacterial membranes, but has not been possible due to technical difficulties and the lack of suitable solid supports. Recently we found that crystals of the natural compound allantoin selectively bind pure LPS with sub-nanomolar affinity. The physicochemical origins of this selectivity and the adsorption mode of LPS on allantoin crystals remain, however, unknown. In this study we present evidence that LPS adsorption on allantoin crystals is initiated through hydrogen-bond attachment of hydrophilic LPS regions. Hydrophobic interactions between alkyl chains of adjacently adsorbed LPS molecules subsequently promote self-assembly of LPS layers. The essential role of hydrogen-bond interactions is corroborated by our finding that allantoin crystals bind to practically any hydrophilic surface chemistry. Binding contributions of hydrophobic interactions between LPS alkyl chains are evidenced by the endothermic nature of the adsorption process and explain why the binding affinity for LPS is several orders of magnitude higher than for proteins (lysozyme, BSA and IgG) and polysaccharides. Self-assembly of LPS layers via hydrogen-bond attachment on allantoin crystals emerges as a novel binding mechanism and could be considered as a practical method for preparing biomimetic membranes on a solid support. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Probabilistic inverse design for self-assembling materials (United States)

    Jadrich, R. B.; Lindquist, B. A.; Truskett, T. M.


    One emerging approach for the fabrication of complex architectures on the nanoscale is to utilize particles customized to intrinsically self-assemble into a desired structure. Inverse methods of statistical mechanics have proven particularly effective for the discovery of interparticle interactions suitable for this aim. Here we evaluate the generality and robustness of a recently introduced inverse design strategy [B. A. Lindquist et al., J. Chem. Phys. 145, 111101 (2016)] by applying this simulation-based machine learning method to optimize for interparticle interactions that self-assemble particles into a variety of complex microstructures as follows: cluster fluids, porous mesophases, and crystalline lattices. Using the method, we discover isotropic pair interactions that lead to the self-assembly of each of the desired morphologies, including several types of potentials that were not previously understood to be capable of stabilizing such systems. One such pair potential led to the assembly of the highly asymmetric truncated trihexagonal lattice and another produced a fluid containing spherical voids, or pores, of designed size via purely repulsive interactions. Through these examples, we demonstrate several advantages inherent to this particular design approach including the use of a parametrized functional form for the optimized interparticle interactions, the ability to constrain the range of said parameters, and compatibility of the inverse design strategy with a variety of simulation protocols (e.g., positional restraints).

  18. Molecular Motions in Functional Self-Assembled Nanostructures

    Directory of Open Access Journals (Sweden)

    Jean-Marc Saiter


    Full Text Available The construction of “smart” materials able to perform specific functions at the molecular scale through the application of various stimuli is highly attractive but still challenging. The most recent applications indicate that the outstanding flexibility of self-assembled architectures can be employed as a powerful tool for the development of innovative molecular devices, functional surfaces and smart nanomaterials. Structural flexibility of these materials is known to be conferred by weak intermolecular forces involved in self-assembly strategies. However, some fundamental mechanisms responsible for conformational lability remain unexplored. Furthermore, the role played by stronger bonds, such as coordination, ionic and covalent bonding, is sometimes neglected while they can be employed readily to produce mechanically robust but also chemically reversible structures. In this review, recent applications of structural flexibility and molecular motions in self-assembled nanostructures are discussed. Special focus is given to advanced materials exhibiting significant performance changes after an external stimulus is applied, such as light exposure, pH variation, heat treatment or electromagnetic field. The crucial role played by strong intra- and weak intermolecular interactions on structural lability and responsiveness is highlighted.

  19. Chitosan Based Self-Assembled Nanoparticles in Drug Delivery

    Directory of Open Access Journals (Sweden)

    Javier Pérez Quiñones


    Full Text Available Chitosan is a cationic polysaccharide that is usually obtained by alkaline deacetylation of chitin poly(N-acetylglucosamine. It is biocompatible, biodegradable, mucoadhesive, and non-toxic. These excellent biological properties make chitosan a good candidate for a platform in developing drug delivery systems having improved biodistribution, increased specificity and sensitivity, and reduced pharmacological toxicity. In particular, chitosan nanoparticles are found to be appropriate for non-invasive routes of drug administration: oral, nasal, pulmonary and ocular routes. These applications are facilitated by the absorption-enhancing effect of chitosan. Many procedures for obtaining chitosan nanoparticles have been proposed. Particularly, the introduction of hydrophobic moieties into chitosan molecules by grafting to generate a hydrophobic-hydrophilic balance promoting self-assembly is a current and appealing approach. The grafting agent can be a hydrophobic moiety forming micelles that can entrap lipophilic drugs or it can be the drug itself. Another suitable way to generate self-assembled chitosan nanoparticles is through the formation of polyelectrolyte complexes with polyanions. This paper reviews the main approaches for preparing chitosan nanoparticles by self-assembly through both procedures, and illustrates the state of the art of their application in drug delivery.

  20. Molecular pathways for defect annihilation in directed self-assembly (United States)

    Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo; Khaira, Gurdaman; Segal-Peretz, Tamar; Rincon-Delgadillo, Paulina A.; Li, Weihua; Müller, Marcus; Nealey, Paul F.; de Pablo, Juan J.


    Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm2. In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales—a handful of nanometers—and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail. PMID:26515095

  1. Tile-based self-assembly of a triple-helical polysaccharide into cell wall-like mesoporous nanocapsules. (United States)

    Wu, Chaoxi; Wang, Xiaoying; Wang, Jianjing; Zhang, Zhen; Wang, Zhiping; Wang, Yifei; Tang, Shunqing


    Tile-based self-assembly is a robust system in the construction of three-dimensional DNA nanostructures but it has been rarely applied to other helical biopolymers. β-Glucan is an immunoactive natural polymer which exists in a triple helical conformation. Herein, we report that β-glucan, after modification using two types of short chain acyl groups, can self-assemble into tiles with inactivated sticky ends at the interface of two solvents. These tiles consist of a single layer of helices laterally aligned, and the sticky ends can be activated when a few acyl groups at the ends are removed; these tiles can further pack into mesoporous nanocapsules, in a similar process as the sticky DNA tiles pack into complex polyhedral nano-objects. These nanocapsules were found to have targeted effects to antigen presenting cells in a RAW264.7 cell model. Our study suggests that tile-based self-assembly can be a general strategy for helical biopolymers, and on fully exploiting this strategy, various new functional nanostructures will become accessible in the future.

  2. Self-assembled silk sericin/poloxamer nanoparticles as nanocarriers of hydrophobic and hydrophilic drugs for targeted delivery

    Energy Technology Data Exchange (ETDEWEB)

    Mandal, Biman B; Kundu, S C, E-mail: kundu@hijli.iitkgp.ernet.i [Department of Biotechnology, Indian Institute of Technology, Kharagpur 721302 (India)


    In recent times self-assembled micellar nanoparticles have been successfully employed in tissue engineering for targeted drug delivery applications. In this review, silk sericin protein from non-mulberry Antheraea mylitta tropical tasar silk cocoons was blended with pluronic F-127 and F-87 in the presence of solvents to achieve self-assembled micellar nanostructures capable of carrying both hydrophilic (FITC-inulin) and hydrophobic (anticancer drug paclitaxel) drugs. The fabricated nanoparticles were subsequently characterized for their size distribution, drug loading capability, cellular uptake and cytotoxicity. Nanoparticle sizes ranged between 100 and 110 nm in diameter as confirmed by dynamic light scattering. Rapid uptake of these particles into cells was observed in in vitro cellular uptake studies using breast cancer MCF-7 cells. In vitro cytotoxicity assay using paclitaxel-loaded nanoparticles against breast cancer cells showed promising results comparable to free paclitaxel drugs. Drug-encapsulated nanoparticle-induced apoptosis in MCF-7 cells was confirmed by FACS and confocal microscopic studies using Annexin V staining. Up-regulation of pro-apoptotic protein Bax, down-regulation of anti-apoptotic protein Bcl-2 and cleavage of regulatory protein PARP through Western blot analysis suggested further drug-induced apoptosis in cells. This study projects silk sericin protein as an alternative natural biomaterial for fabrication of self-assembled nanoparticles in the presence of poloxamer for successful delivery of both hydrophobic and hydrophilic drugs to target sites.

  3. Modeling the self-assembly of lipids and nanotubes in solution: forming vesicles and bicelles with transmembrane nanotube channels. (United States)

    Dutt, Meenakshi; Kuksenok, Olga; Nayhouse, Michael J; Little, Steven R; Balazs, Anna C


    Via dissipative particle dynamics (DPD), we simulate the self-assembly of end-functionalized, amphiphilic nanotubes and lipids in a hydrophilic solvent. Each nanotube encompasses a hydrophobic stalk and two hydrophilic ends, which are functionalized with end-tethered chains. With a relatively low number of the nanotubes in solution, the components self-assemble into stable lipid-nanotube vesicles. As the number of nanotubes is increased, the system exhibits a vesicle-to-bicelle transition, resulting in stable hybrid bicelle. Moreover, our results reveal that the nanotubes cluster into distinct tripod-like structures within the vesicles and aggregate into a ring-like assembly within the bicelles. For both the vesicles and bicelles, the nanotubes assume trans-membrane orientations, with the tethered hairs extending into the surrounding solution or the encapsulated fluid. Thus, the hairs provide a means of regulating the transport of species through the self-assembled structures. Our findings provide guidelines for creating nanotube clusters with distinctive morphologies that might be difficult to achieve through more conventional means. The results also yield design rules for creating synthetic cell-like objects or microreactors that can exhibit biomimetic functionality.

  4. Self-assembled silk sericin/poloxamer nanoparticles as nanocarriers of hydrophobic and hydrophilic drugs for targeted delivery

    International Nuclear Information System (INIS)

    Mandal, Biman B; Kundu, S C


    In recent times self-assembled micellar nanoparticles have been successfully employed in tissue engineering for targeted drug delivery applications. In this review, silk sericin protein from non-mulberry Antheraea mylitta tropical tasar silk cocoons was blended with pluronic F-127 and F-87 in the presence of solvents to achieve self-assembled micellar nanostructures capable of carrying both hydrophilic (FITC-inulin) and hydrophobic (anticancer drug paclitaxel) drugs. The fabricated nanoparticles were subsequently characterized for their size distribution, drug loading capability, cellular uptake and cytotoxicity. Nanoparticle sizes ranged between 100 and 110 nm in diameter as confirmed by dynamic light scattering. Rapid uptake of these particles into cells was observed in in vitro cellular uptake studies using breast cancer MCF-7 cells. In vitro cytotoxicity assay using paclitaxel-loaded nanoparticles against breast cancer cells showed promising results comparable to free paclitaxel drugs. Drug-encapsulated nanoparticle-induced apoptosis in MCF-7 cells was confirmed by FACS and confocal microscopic studies using Annexin V staining. Up-regulation of pro-apoptotic protein Bax, down-regulation of anti-apoptotic protein Bcl-2 and cleavage of regulatory protein PARP through Western blot analysis suggested further drug-induced apoptosis in cells. This study projects silk sericin protein as an alternative natural biomaterial for fabrication of self-assembled nanoparticles in the presence of poloxamer for successful delivery of both hydrophobic and hydrophilic drugs to target sites.

  5. Self-assembled silk sericin/poloxamer nanoparticles as nanocarriers of hydrophobic and hydrophilic drugs for targeted delivery (United States)

    Mandal, Biman B.; Kundu, S. C.


    In recent times self-assembled micellar nanoparticles have been successfully employed in tissue engineering for targeted drug delivery applications. In this review, silk sericin protein from non-mulberry Antheraea mylitta tropical tasar silk cocoons was blended with pluronic F-127 and F-87 in the presence of solvents to achieve self-assembled micellar nanostructures capable of carrying both hydrophilic (FITC-inulin) and hydrophobic (anticancer drug paclitaxel) drugs. The fabricated nanoparticles were subsequently characterized for their size distribution, drug loading capability, cellular uptake and cytotoxicity. Nanoparticle sizes ranged between 100 and 110 nm in diameter as confirmed by dynamic light scattering. Rapid uptake of these particles into cells was observed in in vitro cellular uptake studies using breast cancer MCF-7 cells. In vitro cytotoxicity assay using paclitaxel-loaded nanoparticles against breast cancer cells showed promising results comparable to free paclitaxel drugs. Drug-encapsulated nanoparticle-induced apoptosis in MCF-7 cells was confirmed by FACS and confocal microscopic studies using Annexin V staining. Up-regulation of pro-apoptotic protein Bax, down-regulation of anti-apoptotic protein Bcl-2 and cleavage of regulatory protein PARP through Western blot analysis suggested further drug-induced apoptosis in cells. This study projects silk sericin protein as an alternative natural biomaterial for fabrication of self-assembled nanoparticles in the presence of poloxamer for successful delivery of both hydrophobic and hydrophilic drugs to target sites.

  6. High-throughput development of amphiphile self-assembly materials: fast-tracking synthesis, characterization, formulation, application, and understanding. (United States)

    Mulet, Xavier; Conn, Charlotte E; Fong, Celesta; Kennedy, Danielle F; Moghaddam, Minoo J; Drummond, Calum J


    application. High-throughput data analysis is crucial at all stages to keep pace with data collection. In this Account, we describe high-throughput advances in the field of amphiphile self-assembly, focusing on nanostructured lyotropic liquid crystalline materials, which form when amphiphiles are added to a polar solvent. We outline recent progress in the automated preparation of amphiphile molecules and their nanostructured self-assembly systems both in the bulk phase and in dispersed colloidal particulate systems. Once prepared, we can structurally characterize these systems by establishing phase behavior in a high-throughput manner with both laboratory (infrared and light polarization microscopy) and synchrotron facilities (small-angle X-ray scattering). Additionally, we provide three case studies to demonstrate how chemists can use high-throughput approaches to evaluate the functional performance of amphiphile self-assembly materials. The high-throughput methodology for the set-up and characterization of large matrix in meso membrane protein crystallization trials can illustrate an application of bulk phase self-assembling amphiphiles. For dispersed colloidal systems, two nanomedicine examples highlight advances in high-throughput preparation, characterization, and evaluation: drug delivery and magnetic resonance imaging agents.

  7. Self-Assembly of Plasmonic Nanoclusters for Optical Metauids (United States)

    Schade, Nicholas Benjamin

    I discuss experimental progress towards developing a material with an isotropic, negative index of refraction at optical frequencies. The simplest way to make such a material is to create a metafluid, or a disordered collection of subwavelength, isotropic electromagnetic resonators. Small clusters of metal particles, such as tetrahedra, serve as these constituents. What is needed are methods for manufacturing these structures with high precision and in sufficient yield that their resonances are identical. Jonathan Fan et al. [Science, 328 (5982), 1135-1138, 2010] demonstrated that colloidal self-assembly is a means of preparing electromagnetic resonators from metal nanoparticles. However, the resonances are sensitive to the separation gaps between particles. Standard synthesis routes for metal nanoparticles yield crystals or nanoshells that are inadequate for metafluids due to polydispersity, faceting, and thermal instabilities. To ensure that the separation gaps and resonances are uniform, more monodisperse spherical particles are needed. An additional challenge is the self-assembly of tetrahedral clusters in high yield from these particles. In self-assembly approaches that others have examined previously, the yield of any particular type of cluster is low. In this dissertation I present solutions to several of these problems, developed in collaboration with my research group and others. We demonstrate that slow chemical etching can transform octahedral gold crystals into ultrasmooth, monodisperse nanospheres. The particles can serve as seeds for the growth of larger octahedra which can in turn be etched. The size of the gold nanospheres can therefore be adjusted as desired. We further show that in colloidal mixtures of two sphere species that strongly bind to one another, the sphere size ratio determines the size distribution of self-assembled clusters. At a critical size ratio, tetrahedral clusters assemble in high yield. We explain the experimentally observed

  8. Combustion and self-assembly of nanoenergetic materials (United States)

    Malchi, Jonathan Yaniv

    The recent worldwide interest in nanotechnology spans a wide variety of scientific fields such as electronics, biology, materials science and medicine. Because of their extremely small dimensions, nanoparticles demonstrate properties different from matter at larger scales. Understanding these unusual properties and utilizing them for macroscale devices is an overall goal for nanotechnology. Moreover, manipulating these small particles into organized structures is crucial for taking full advantage of what nanotechnology has to offer, however it has proven to be a difficult task. Recent work utilizing electrostatic forces shows great potential for the self-assembly of nanoparticles into organized two-dimensional and three-dimensional structures. Overall, this work examines how nanotechnology and self-assembly can benefit the field of energetic materials. Because of aluminum's high energy density and low cost, it has been used in the field of energetic materials for several decades. In order to achieve sufficient energy release rates, aluminum is typically manufactured as a powder having spherical particles with diameters on the micron scale. It is well-known that decreasing the original particle diameter of a fuel particle will increase the burning time and, thus, energy release rate. Therefore, aluminum particles have recently been made to have diameters on the nanoscale, and shown to be advantageous for several applications. The combustion of nanoaluminum (nAl) in various systems is the primary focus of this study. A progression of experiments is used to analyze the combustion of nAl: (1) a fully heterogeneous flame spread system, (2) a semi-homogeneous sonicated thermite system and (3) a quasi-homogeneous self-assembled thermite system. The flame spread experiment physically separates the nAl from the gaseous oxidizer allowing for a well-understood convective, diffusive, reactive system to be analyzed. Because of the simplicity of the experimental setup, variables

  9. A Novel Poly(vinylidene fluoride)-Based 4-Miktoarm Star Terpolymer: Synthesis and Self-Assembly

    KAUST Repository

    Patil, Yogesh Raghunath


    A well-defined amphiphilic miktoarm polymer incorporating poly(vinylidene fluoride) (PVDF), polystyrene (PS), and poly(ethylene glycol) (PEG) blocks was synthesized via a combination of atom-transfer radical polymerization (ATRP), iodine transfer radical polymerization (ITP), and copper-catalyzed azide-alkyne cycloaddition (CuAAC). Morphology and self-assembly of this star polymer were examined in organic solvents and in water. The aggregates formed in water were found to possess unusual frustrated topology due to immiscibility of PS and PVDF. The polymer was evaluated for transport of small hydrophobic molecules in water.

  10. Improved insulin loading in poly (lactic-co-glycolic) acid (PLGA) nanoparticles upon self-assembly with lipids

    DEFF Research Database (Denmark)

    Garcia Diaz, Maria; Foged, Camilla; Nielsen, Hanne Mørck


    . The nanoparticles were characterized in terms of size, zeta potential, insulin encapsulation efficiency and loading capacity. Upon pre-assembly with lipids, there was an increased distribution of insulin into the organic phase of the emulsion, eventually resulting in significantly enhanced encapsulation...... of insulin into poly(lactic-co-glycolic) acid (PLGA) nanoparticles by pre-assembly with amphiphilic lipids. Insulin was complexed with soybean phosphatidylcholine or sodium caprate by self-assembly and subsequently loaded into PLGA nanoparticles by using the double emulsion-solvent evaporation technique...

  11. Morphology, directed self-assembly and pattern transfer from a high molecular weight polystyrene-block-poly(dimethylsiloxane) block copolymer film (United States)

    Cheng, Li-Chen; Bai, Wubin; Fernandez Martin, Eduardo; Tu, Kun-Hua; Ntetsikas, Konstantinos; Liontos, George; Avgeropoulos, Apostolos; Ross, C. A.


    The self-assembly of block copolymers with large feature sizes is inherently challenging as the large kinetic barrier arising from chain entanglement of high molecular weight (MW) polymers limits the extent over which long-range ordered microdomains can be achieved. Here, we illustrate the evolution of thin film morphology from a diblock copolymer of polystyrene-block-poly(dimethylsiloxane) exhibiting total number average MW of 123 kg mol-1, and demonstrate the formation of layers of well-ordered cylindrical microdomains under appropriate conditions of binary solvent mix ratio, commensurate film thickness, and solvent vapor annealing time. Directed self-assembly of the block copolymer within lithographically patterned trenches occurs with alignment of cylinders parallel to the sidewalls. Fabrication of ordered cobalt nanowire arrays by pattern transfer was also implemented, and their magnetic properties and domain wall behavior were characterized.

  12. Self-assembly of amorphous biophotonic nanostructures by phase separation

    Energy Technology Data Exchange (ETDEWEB)

    Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar; Mochrie, Simon G.J.; Cao, Hui; Prum, Richard O.; (Yale)


    Some of the most vivid colors in the animal kingdom are created not by pigments, but by wavelength-selective scattering of light from nanostructures. Here we investigate quasi-ordered nanostructures of avian feather barbs which produce vivid non-iridescent colors. These {beta}-keratin and air nanostructures are found in two basic morphologies: tortuous channels and amorphous packings of spheres. Each class of nanostructure is isotropic and has a pronounced characteristic length scale of variation in composition. These local structural correlations lead to strong backscattering over a narrow range of optical frequencies and little variation with angle of incidence. Such optical properties play important roles in social and sexual communication. To be effective, birds need to precisely control the development of these nanoscale structures, yet little is known about how they grow. We hypothesize that multiple lineages of birds have convergently evolved to exploit phase separation and kinetic arrest to self-assemble spongy color-producing nanostructures in feather barbs. Observed avian nanostructures are strikingly similar to those self-assembled during the phase separation of fluid mixtures; the channel and sphere morphologies are characteristic of phase separation by spinodal decomposition and nucleation and growth, respectively. These unstable structures are locked-in by the kinetic arrest of the {beta}-keratin matrix, likely through the entanglement or cross-linking of supermolecular {beta}-keratin fibers. Using the power of self-assembly, birds can robustly realize a diverse range of nanoscopic morphologies with relatively small physical and chemical changes during feather development.

  13. Electrochemically controlled self-assembly of block copolymer nanostructures (United States)

    Eitouni, Hany Basam

    Organometallic block copolymers, wherein one block is composed of alternating ferrocene and dialkylsilane units in the main chain, undergo self-assembly to form microphase-separated ordered structures similarly to typical organic block copolymers. The 1,1'-dimethylsilylferrocenophane monomer was synthesized and polymerized anionically with other monomers to make a variety of different organometallic block copolymers. The phase behavior and thermodynamic interactions of anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) and poly(isoprene-block-ferrocenyldimethylsilane) (IF) copolymers were examined using depolarized light scattering, small angle x-ray and neutron scattering (SAXS and SANS), and transmission electron microscopy. The temperature-dependence of the Flory-Huggins parameter, chi, and the statistical segment lengths of SF and IF copolymers were determined by SAXS and SANS using the random phase approximation. The thermodynamic interactions in poly(ferrocenyldimethylsilane) diblock copolymers were systematically adjusted by oxidizing the ferrocene moieties with silver salts and examined using SAXS and depolarized light scattering. The polymers retained microphase separated ordered structures upon oxidation and showed systematic changes in the location of the order-disorder transition as a function of extent of oxidation. By controlling the redox properties of the ferrocene moiety in the backbone of the polymer, we present a method for controlling the self-assembled microstructure and hence bulk material properties. Using electrochemical techniques, a novel means of controlling the order-disorder transition of block copolymers was discovered. By applying very small electrical potentials to disordered solutions of organometallic block copolymers, oriented ordered grains were formed near one electrode, the result of electrochemical reactions. After reversing the electrical bias on the system, the ordered grains disappeared and new

  14. Understanding the self-assembly of TCNQ on Cu(111)

    DEFF Research Database (Denmark)

    Stradi, Daniele; Borca, Bogdana; Barja, Sara


    The structure of self-assembled monolayers of 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) adsorbed on Cu(111) has been studied using a combination of scanning tunnelling microscopy (STM) experiments and density functional theory (DFT) calculations. We show that the polymorphism of the self...... perpendicular to the other. Conversely, when the substrate is held at room temperature during deposition and slightly annealed afterwards, a more complex structure with five molecules per unit cell is formed. DFT calculations complement the experimental results by revealing that the building blocks of the two...

  15. Photobleaching-activated micropatterning on self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Scrimgeour, Jan; Kodali, Vamsi K; Kovari, Daniel T; Curtis, Jennifer E, E-mail: jennifer.curtis@physics.gatech.ed [School of Physics and Petit Institute for Bioengineering and Biosciences (IBB), Georgia Institute of Technology, 837 State St, Atlanta, GA 30332 (United States)


    Functional chemical micropatterns were fabricated by exploiting the photobleaching of dye-coupled species near methacrylate self-assembled monolayers. Using this approach we have demonstrated that multiple chemistries can be coupled to the monolayer using a standard fluorescence microscope. The surface bound functional groups remain active and patterns with feature sizes down to 3 {mu}m can be readily achieved with excellent signal-to-noise ratio. Control over the ligand binding density was demonstrated to illustrate the convenient route provided by this platform for fabricating complex spatial gradients in ligand density.

  16. Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

    CERN Document Server

    Garti, Nissim


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

  17. A 3D Optical Metamaterial Made by Self-Assembly

    KAUST Repository

    Vignolini, Silvia


    Optical metamaterials have unusual optical characteristics that arise from their periodic nanostructure. Their manufacture requires the assembly of 3D architectures with structure control on the 10-nm length scale. Such a 3D optical metamaterial, based on the replication of a self-assembled block copolymer into gold, is demonstrated. The resulting gold replica has a feature size that is two orders of magnitude smaller than the wavelength of visible light. Its optical signature reveals an archetypal Pendry wire metamaterial with linear and circular dichroism. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao


    The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

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

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


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

  20. Formation and Characterization of Silicon Self-assembled Nanodots

    International Nuclear Information System (INIS)

    Idrees, Fatima Aldaw; Sakrani, Samsudi; Othaman, Zulkafli


    Silicon self-assembled quantum dots have been successfully prepared on corning glass (7059) substrate. The samples were fabricated using the common technique RF magnetron sputtering system depend on plasma excitation at varying growth parameters and high temperature of more than 500 deg. C. The measurements of average dots size estimated to be 36 nm is confirmed by using AFM. The PL peak located at 570 nm, informed band gap energy = 2.10 eV larger than bulk material band gap, that confirmed the miniaturized of the dots. To measure the Silicon atomic% deposit on corning glass (7059) substrate EDX has been used.

  1. Rapid self-assembly of block copolymers to photonic crystals (United States)

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.


    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  2. Equation of State for Phospholipid Self-Assembly

    DEFF Research Database (Denmark)

    Marsh, Derek


    of transfer converge at ∼-18°C. An equation of state for the free energy of self-assembly formulated from this thermodynamic data depends on the heat capacity of transfer as the sole parameter needed to specify a particular lipid. For lipids lacking calorimetric data, measurement of the critical micelle...... concentration at a single temperature suffices to define an effective heat capacity according to the model. Agreement with the experimental temperature dependence of the critical micelle concentration is then good. The predictive powers should extend also to amphiphile partitioning and the kinetics of lipid...

  3. Long lived coherence in self-assembled quantum dots

    DEFF Research Database (Denmark)

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


    We report measurements of ultralong coherence in self-assembled quantum dots. Transient four-wave mixing experiments at 5 K show an average dephasing time of 372 ps, corresponding to a homogeneous linewidth of 3.5 mu eV, which is significantly smaller than the linewidth observed in single-dot...... luminescence. Time-resolved luminescence measurements show a lifetime of the dot ground state of 800 ps, demonstrating the presence of pure dephasing at finite temperature. The homogeneous width is lifetime limited only at temperatures approaching 0 K....

  4. Self-assembling peptides form nanodiscs that stabilize membrane proteins

    DEFF Research Database (Denmark)

    Midtgaard, Søren Roi; Pedersen, Martin Cramer; Kirkensgaard, Jacob Judas Kain


    New methods to handle membrane bound proteins, e.g. G-protein coupled receptors (GPCRs), are highly desirable. Recently, apoliprotein A1 (ApoA1) based lipoprotein particles have emerged as a new platform for studying membrane proteins, and it has been shown that they can self-assemble in combinat......New methods to handle membrane bound proteins, e.g. G-protein coupled receptors (GPCRs), are highly desirable. Recently, apoliprotein A1 (ApoA1) based lipoprotein particles have emerged as a new platform for studying membrane proteins, and it has been shown that they can self...

  5. Biomimetic self-assembly of a functional asymmetrical electronic device. (United States)

    Boncheva, Mila; Gracias, David H; Jacobs, Heiko O; Whitesides, George M


    This paper introduces a biomimetic strategy for the fabrication of asymmetrical, three-dimensional electronic devices modeled on the folding of a chain of polypeptide structural motifs into a globular protein. Millimeter-size polyhedra-patterned with logic devices, wires, and solder dots-were connected in a linear string by using flexible wire. On self-assembly, the string folded spontaneously into two domains: one functioned as a ring oscillator, and the other one as a shift register. This example demonstrates that biomimetic principles of design and self-organization can be applied to generate multifunctional electronic systems of complex, three-dimensional architecture.

  6. Directed self-assembly graphoepitaxy template generation with immersion lithography (United States)

    Ma, Yuansheng; Lei, Junjiang; Andres Torres, J.; Hong, Le; Word, James; Fenger, Germain; Tritchkov, Alexander; Lippincott, George; Gupta, Rachit; Lafferty, Neal; He, Yuan; Bekaert, Joost; Vanderberghe, Geert


    We present an optimization methodology for the template designs of subresolution contacts using directed self-assembly (DSA) with graphoepitaxy and immersion lithography. We demonstrate the flow using a 60-nm-pitch contact design in doublet with Monte Carlo simulations for DSA. We introduce the notion of template error enhancement factor (TEEF) to gauge the sensitivity of DSA printing infidelity to template printing infidelity and evaluate optimized template designs with TEEF metrics. Our data show that source mask optimization and inverse lithography technology are critical to achieve sub-80 nm non-L0 pitches for DSA patterns using 193i.

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

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


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

  8. Long coherence times in self-assembled semiconductor quantum dots

    DEFF Research Database (Denmark)

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


    We report measurements of ultra-long coherence in self-assembled quantum dots. Transient four-wave mixing experiments at 5 K show an average dephasing time of 372 ps, corresponding to a homogeneous linewidth of 3.5 mueV, which is significantly smaller than the linewidth observed in single-dot...... luminescence. Time-resolved luminescence measurements show a lifetime of the dot ground state of 800 ps demonstrating the presence of pure dephasing at finite temperature. The homogeneous width is lifetime limited only at temperatures approaching 0 K....

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

    Directory of Open Access Journals (Sweden)

    Eugen Stulz


    Full Text Available We describe the synthesis of terpyridine modified DNA strands which selectively form DNA nanotubes through orthogonal hydrogen bonding and metal complexation interactions. The short DNA strands are designed to self-assemble into long duplexes through a sticky-end approach. Addition of weakly binding metals such as Zn(II and Ni(II induces the formation of tubular arrays consisting of DNA bundles which are 50-200 nm wide and 2-50 nm high. TEM shows additional long distance ordering of the terpy-DNA complexes into fibers.

  10. Biomimetic engineering: towards a self-assembled nanotechnology

    International Nuclear Information System (INIS)

    Braach-Maksvytis, V.


    Full text: The Nanoscience and Systems program was set up within CSIRO Telecommunications and Industrial Physics three years ago with an emphasis on biomimetic engineering, with the aim of developing new cross-disciplinary research in traditional physics areas. By combining expertise in experimental and theoretical physics with biology and chemistry, new approaches towards understanding and using nanoscale systems and devices are being explored. Research in the program ranges from using self-assembled lipid membranes for surface passivation of GaAs transistors to the electrical properties of nanoparticle films and devices. An overview of the research will be given, highlighting the diversity of nanotechnology applications

  11. Self-assembled thiol monolayers with carboxylic acid functionality: Measuring pH-dependent phase transitions with the quartz crystal microbalance

    International Nuclear Information System (INIS)

    Wang, J.; Frostman, L.M.; Ward, M.D.


    The resonant frequency of the quartz crystal microbalance (QCM) coated with self-assembled thiol monolayers with carboxylic acid functionality is measured while the pH of the aqueous solvent is changed in this paper. Increased tensile stress with increasing pH activity partially contributed to the QCM response, but the major contribution was due to changes in the viscoelastic properties of the hydrodynamic layer in contact with the QCM. 28 refs., 3 figs

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

    Li, Hongxia; Zheng, Guojun; Zhu, Shaozhou


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

  13. Unknown Aspects of Self-Assembly of PbS Microscale Superstructures (United States)

    Querejeta-Fernández, Ana; Hernández-Garrido, Juan C.; Yang, Hengxi; Zhou, Yunlong; Varela, Aurea; Parras, Marina; Calvino-Gámez, José J.; González-Calbet, Jose M.; Green, Peter F.; Kotov, Nicholas A.


    A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints this field requires advancements in three principle directions: a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and micro-levels of organization; b) understanding of disassembly/deconstruction processes; and c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: 1) nucleation of early PbS NPs with an average diameter of 31 nm; 2) assembly into 100–500 nm octahedral mesocrystals; 3) assembly into 1000–2500 nm hyperbranched stars; 4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; 5) deconstruction into rods and cubooctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern–determining forces that include vander Waals and electrostatic (charge-charge, dipole-dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy harvesting devices which require organization of PbS components at multiple scales. PMID:22515512

  14. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail:


    Highlights: • One-pot synthesis of α-helical-terminated self-assembled monolayers on Au(111). • Synthesis of high density, structured, and covalently bound α-helices on Au(111). • Characterization by surface-averaged and single molecule techniques. • Peptide-terminated surfaces for fabrication of biomaterials and sensors. - Abstract: The Huisgen cycloaddition reaction (“click” chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  15. Self-assembled peptides for coating of active sulfur nanoparticles in lithium–sulfur battery

    Energy Technology Data Exchange (ETDEWEB)

    Jewel, Yead; Yoo, Kisoo; Liu, Jin; Dutta, Prashanta, E-mail: [Washington State University, School of Mechanical and Materials Engineering (United States)


    Development of lithium–sulfur (Li–S) battery is hindered by poor cyclability due to the loss of sulfur, although Li–S battery can provide high energy density. Coating of sulfur nanoparticles can help maintain active sulfur in the cathode of Li–S battery, and hence increase the cyclability. Among myriad of coating materials, synthetic peptides are very attractive because of their spontaneous self-assembly as well as electrical conductive characteristics. In this study, we explored the use of various synthetic peptides as a coating material for sulfur nanoparticles. Atomistic simulations were carried out to identify optimal peptide structure and density for coating sulfur nanoparticles. Three different peptide models, poly-proline, poly(leucine–lysine) and poly-histidine, are selected for this study based on their peptide–peptide and peptide-sulfur interactions. Simulation results show that both poly-proline and poly(leucine–lysine) can form self-assembled coating on sulfur nanoparticles (2–20 nm) in pyrrolidinone, a commonly used solvent for cathode slurry. We also studied the structural integrity of these synthetic peptides in organic [dioxolane (DOL) and dimethoxyethane (DME)] electrolyte used in Li–S battery. Both peptides show stable structures in organic electrolyte (DOL/DME) used in Li–S battery. Furthermore, the dissolution of sulfur molecules in organic electrolyte is investigated in the absence and presence of these peptide coatings. It was found that only poly(leucine–lysine)-based peptide can most effectively suppress the sulfur loss in electrolyte, suggesting its potential applications in Li–S battery as a coating material.Graphical abstract.

  16. Modulation of intra- and inter-sheet interactions in short peptide self-assembly by acetonitrile in aqueous solution

    International Nuclear Information System (INIS)

    Deng Li; Zhao Yurong; Zhou Peng; Xu Hai; Wang Yanting


    Besides our previous experimental discovery (Zhao Y R, et al . 2015 Langmuir , 31, 12975) that acetonitrile (ACN) can tune the morphological features of nanostructures self-assembled by short peptides KIIIIK (KI4K) in aqueous solution, further experiments reported in this work demonstrate that ACN can also tune the mass of the self-assembled nanostructures. To understand the microscopic mechanism how ACN molecules interfere peptide self-assembly process, we conducted a series of molecular dynamics simulations on a monomer, a cross- β sheet structure, and a proto-fibril of KI4K in pure water, pure ACN, and ACN-water mixtures, respectively. The simulation results indicate that ACN enhances the intra-sheet interaction dominated by the hydrogen bonding (H-bonding) interactions between peptide backbones, but weakens the inter-sheet interaction dominated by the interactions between hydrophobic side chains. Through analyzing the correlations between different groups of solvent and peptides and the solvent behaviors around the proto-fibril, we have found that both the polar and nonpolar groups of ACN play significant roles in causing the opposite effects on intermolecular interactions among peptides. The weaker correlation of the polar group of ACN than water molecule with the peptide backbone enhances H-bonding interactions between peptides in the proto-fibril. The stronger correlation of the nonpolar group of ACN than water molecule with the peptide side chain leads to the accumulation of ACN molecules around the proto-fibril with their hydrophilic groups exposed to water, which in turn allows more water molecules close to the proto-fibril surface and weakens the inter-sheet interactions. The two opposite effects caused by ACN form a microscopic mechanism clearly explaining our experimental observations. (paper)

  17. Halogen bonding versus hydrogen bonding induced 2D self-assembled nanostructures at the liquid-solid interface revealed by STM. (United States)

    Wu, Yican; Li, Jinxing; Yuan, Yinlun; Dong, Meiqiu; Zha, Bao; Miao, Xinrui; Hu, Yi; Deng, Wenli


    We design a bifunctional molecule (5-bromo-2-hexadecyloxy-benzoic acid, 5-BHBA) with a bromine atom and a carboxyl group and its two-dimensional self-assembly is experimentally and theoretically investigated by using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The supramolecular self-organization of 5-BHBA in two different solvents (1-octanoic acid and n-hexadecane) at the liquid-solid interface at different solution concentrations is obviously different due to the cooperative and competitive intermolecular halogen and hydrogen bonds. Three kinds of nanoarchitectures composed of dimers, trimers and tetramers are formed at the 1-octanoic acid/graphite interface based on -COOHHOOC-, triangular C[double bond, length as m-dash]OBrH-C, -BrO(H), BrBr, and OH interactions. Furthermore, by using n-hexadecane as the solvent, two kinds of self-assembled linear patterns can be observed due to the coadsorption, in which the dimers are formed by intermolecular -COOHHOOC- hydrogen bonds. The molecule-solvent and solvent-solvent van der Waals force and intermolecular hydrogen bonds dominate the formation of coadsorbed patterns. We propose that the cooperative and competitive halogen and hydrogen bonds are related to the polarity of the solvent and the type of molecule-solvent interaction. The intermolecular binding energy of different dimers and their stability are supported by theoretical calculations. The result provides a new and innovative insight to induce the 2D self-assembled nanostructures by halogen and hydrogen bonds at the liquid-solid interface.

  18. Silver nanoprisms self-assembly on differently functionalized silica surface

    International Nuclear Information System (INIS)

    Pilipavicius, J; Chodosovskaja, A; Beganskiene, A; Kareiva, A


    In this work colloidal silica/silver nanoprisms (NPRs) composite coatings were made. Firstly colloidal silica sols were synthesized by sol-gel method and produced coatings on glass by dip-coating technique. Next coatings were silanized by (3-Aminopropyl)triethoxysilane (APTES), N-[3-(Trimethoxysilyl)propyl]ethylenediamine (AEAPTMS), (3- Mercaptopropyl)trimethoxysilane (MPTMS). Silver NPRs where synthesized via seed-mediated method and high yield of 94±15 nm average edge length silver NPRs were obtained with surface plasmon resonance peak at 921 nm. Silica-Silver NPRs composite coatings obtained by selfassembly on silica coated-functionalized surface. In order to find the most appropriate silanization way for Silver NPRs self-assembly, the composite coatings were characterized by scanning electron microscopy (SEM), dynamic light scattering (DLS), water contact angle (CA) and surface free energy (SFE) methods. Results have showed that surface functionalization is necessary to achieve self-assembled Ag NPRs layer. MPTMS silanized coatings resulted sparse distribution of Ag NPRs. Most homogeneous, even distribution composite coatings obtained on APTES functionalized silica coatings, while AEAPTMS induced strong aggregation of Silver NPRs

  19. Physical principles of filamentous protein self-assembly kinetics

    International Nuclear Information System (INIS)

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


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

  20. Probabilistic Performance Guarantees for Distributed Self-Assembly

    KAUST Repository

    Fox, Michael J.


    In distributed self-assembly, a multitude of agents seek to form copies of a particular structure, modeled here as a labeled graph. In the model, agents encounter each other in spontaneous pairwise interactions and decide whether or not to form or sever edges based on their two labels and a fixed set of local interaction rules described by a graph grammar. The objective is to converge on a graph with a maximum number of copies of a given target graph. Our main result is the introduction of a simple algorithm that achieves an asymptotically maximum yield in a probabilistic sense. Notably, agents do not need to update their labels except when forming or severing edges. This contrasts with certain existing approaches that exploit information propagating rules, effectively addressing the decision problem at the level of subgraphs as opposed to individual vertices. We are able to obey more stringent locality requirements while also providing smaller rule sets. The results can be improved upon if certain requirements on the labels are relaxed. We discuss limits of performance in self-assembly in terms of rule set characteristics and achievable maximum yield.

  1. Silver nanoprisms self-assembly on differently functionalized silica surface (United States)

    Pilipavicius, J.; Chodosovskaja, A.; Beganskiene, A.; Kareiva, A.


    In this work colloidal silica/silver nanoprisms (NPRs) composite coatings were made. Firstly colloidal silica sols were synthesized by sol-gel method and produced coatings on glass by dip-coating technique. Next coatings were silanized by (3-Aminopropyl)triethoxysilane (APTES), N-[3-(Trimethoxysilyl)propyl]ethylenediamine (AEAPTMS), (3- Mercaptopropyl)trimethoxysilane (MPTMS). Silver NPRs where synthesized via seed-mediated method and high yield of 94±15 nm average edge length silver NPRs were obtained with surface plasmon resonance peak at 921 nm. Silica-Silver NPRs composite coatings obtained by selfassembly on silica coated-functionalized surface. In order to find the most appropriate silanization way for Silver NPRs self-assembly, the composite coatings were characterized by scanning electron microscopy (SEM), dynamic light scattering (DLS), water contact angle (CA) and surface free energy (SFE) methods. Results have showed that surface functionalization is necessary to achieve self-assembled Ag NPRs layer. MPTMS silanized coatings resulted sparse distribution of Ag NPRs. Most homogeneous, even distribution composite coatings obtained on APTES functionalized silica coatings, while AEAPTMS induced strong aggregation of Silver NPRs.

  2. Self-Assembling Multifunctional Peptide Dimers for Gene Delivery Systems

    Directory of Open Access Journals (Sweden)

    Kitae Ryu


    Full Text Available Self-assembling multifunctional peptide was designed for gene delivery systems. The multifunctional peptide (MP consists of cellular penetrating peptide moiety (R8, matrix metalloproteinase-2 (MMP-2 specific sequence (GPLGV, pH-responsive moiety (H5, and hydrophobic moiety (palmitic acid (CR8GPLGVH5-Pal. MP was oxidized to form multifunctional peptide dimer (MPD by DMSO oxidation of thiols in terminal cysteine residues. MPD could condense pDNA successfully at a weight ratio of 5. MPD itself could self-assemble into submicron micelle particles via hydrophobic interaction, of which critical micelle concentration is about 0.01 mM. MPD showed concentration-dependent but low cytotoxicity in comparison with PEI25k. MPD polyplexes showed low transfection efficiency in HEK293 cells expressing low level of MMP-2 but high transfection efficiency in A549 and C2C12 cells expressing high level of MMP-2, meaning the enhanced transfection efficiency probably due to MMP-induced structural change of polyplexes. Bafilomycin A1-treated transfection results suggest that the transfection of MPD is mediated via endosomal escape by endosome buffering ability. These results show the potential of MPD for MMP-2 targeted gene delivery systems due to its multifunctionality.

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

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


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

  4. Designing self-assembling 3D structures of microcapsules (United States)

    Li, Like; Shum, Henry; Shklyaev, Oleg; Yashin, Victor; Balazs, Anna

    Self-assembly of complex, three-dimensional structures is commonly achieved by biological cells but difficult to realize in synthetic systems with micron-scale or larger components. Some previous modeling studies have considered only the planar self-assembly of microcapsules on a substrate. In this work, nanoparticles released from the capsules bind to the substrate and to the shells of nearby capsules. The non-uniform nanoparticle deposition on a capsule's surface leads to adhesion gradients, which drive the capsules to effectively ``climb'' on top of one another and self-organize in the vertical direction. We determine conditions that favor this structural organization. In particular, we study how the vertical structuring depends on the background fluid flow, the topography of the microcapsules and the underlying surface, the capsule-capsule interaction and that between the capsules and the substrate. The findings can provide design rules for the autonomous creation of novel nanocomposites, where the layers are formed from nanoparticle-containing and nanoparticle-decorated microcapsules.

  5. Hidden geometries in networks arising from cooperative self-assembly. (United States)

    Šuvakov, Milovan; Andjelković, Miroslav; Tadić, Bosiljka


    Multilevel self-assembly involving small structured groups of nano-particles provides new routes to development of functional materials with a sophisticated architecture. Apart from the inter-particle forces, the geometrical shapes and compatibility of the building blocks are decisive factors. Therefore, a comprehensive understanding of these processes is essential for the design of assemblies of desired properties. Here, we introduce a computational model for cooperative self-assembly with the simultaneous attachment of structured groups of particles, which can be described by simplexes (connected pairs, triangles, tetrahedrons and higher order cliques) to a growing network. The model incorporates geometric rules that provide suitable nesting spaces for the new group and the chemical affinity of the system to accept excess particles. For varying chemical affinity, we grow different classes of assemblies by binding the cliques of distributed sizes. Furthermore, we characterize the emergent structures by metrics of graph theory and algebraic topology of graphs, and 4-point test for the intrinsic hyperbolicity of the networks. Our results show that higher Q-connectedness of the appearing simplicial complexes can arise due to only geometric factors and that it can be efficiently modulated by changing the chemical potential and the polydispersity of the binding simplexes.

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

    International Nuclear Information System (INIS)

    Suo, Z.; Lu, W.


    Experimental evidence has accumulated in the recent decade that nanoscale patterns can self-assemble on solid surfaces. A two-component monolayer grown on a solid surface may separate into distinct phases. Sometimes the phases select sizes about 10 nm, and order into an array of stripes or disks. This paper reviews a model that accounts for these behaviors. Attention is focused on thermodynamic forces that drive the self-assembly. A double-welled, composition-dependent free energy drives phase separation. The phase boundary energy drives phase coarsening. The concentration-dependent surface stress drives phase refining. It is the competition between the coarsening and the refining that leads to size selection and spatial ordering. These thermodynamic forces are embodied in a nonlinear diffusion equation. Numerical simulations reveal rich dynamics of the pattern formation process. It is relatively fast for the phases to separate and select a uniform size, but exceedingly slow to order over a long distance, unless the symmetry is suitably broken

  7. Self-assembled rosette nanotubes encapsulate and slowly release dexamethasone

    Directory of Open Access Journals (Sweden)

    Chen Y


    Full Text Available Yupeng Chen1,2, Shang Song2, Zhimin Yan3, Hicham Fenniri3, Thomas J Webster2,41Department of Chemistry, Brown University, Providence, RI, USA; 2School of Engineering, Brown University, Providence, RI, USA; 3National Institute for Nanotechnology and Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada; 4Department of Orthopedics, Brown University, Providence, RI, USAAbstract: Rosette nanotubes (RNTs are novel, self-assembled, biomimetic, synthetic drug delivery materials suitable for numerous medical applications. Because of their amphiphilic character and hollow architecture, RNTs can be used to encapsulate and deliver hydrophobic drugs otherwise difficult to deliver in biological systems. Another advantage of using RNTs for drug delivery is their biocompatibility, low cytotoxicity, and their ability to engender a favorable, biologically-inspired environment for cell adhesion and growth. In this study, a method to incorporate dexamethasone (DEX, an inflammatory and a bone growth promoting steroid into RNTs was developed. The drug-loaded RNTs were characterized using diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR and UV-Vis spectroscopy. Results showed for the first time that DEX can be easily and quickly encapsulated into RNTs and released to promote osteoblast (bone-forming cell functions over long periods of time. As a result, RNTs are presented as a novel material for the targeted delivery of hydrophobic drugs otherwise difficult to deliver.Keywords: nanotubes, drug delivery, self-assembly, physiological conditions

  8. Self-assembly of colloids with magnetic caps

    Energy Technology Data Exchange (ETDEWEB)

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


    In our earlier work (Steinbach et al., 2016 ) we investigated a homogeneous system of magnetically capped colloidal particles that self-assembled via two structural patterns of different symmetry. The particles could form a compact, equilateral triangle with a three-fold rotational symmetry and zero dipole moment and a staggered chain with mirror symmetry with a net magnetisation perpendicular to the chain. The system exhibited a bistability already in clusters of three particles. Based on observations of a real magnetic particles system, analytical calculations and molecular dynamics simulations, it has been shown that the bistability is a result of an anisotropic magnetisation distribution with rotational symmetry inside the particles. The present study is a logical extension of the above research and forms a preparatory stage for the study of a self-assembly of such magnetic particles under the influence of an external magnetic field. Since the magnetic field is only an additive contribution to the total ground state energy, we can study the interparticle interaction energies of candidate ground state structures based on the field-free terms. - Highlights: • Analytical calculations of the energies of ground state candidates for colloids with magnetic caps. • Computer simulations confirmed the theoretical model. • The structural transition between ground states was found.

  9. Self-assembly of dodecaphenyl POSS thin films (United States)

    Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor


    The self-assembly abilities of Dodecaphenyl Polyhedral Oligomeric Silsesquioxane thin films on Si(1 0 0) surfaces were studied. Due to their thermal properties - relatively low sublimation temperature and preservation of molecular structure - cage type silsesquioxanes are ideal material for the preparation of a thin films by Physical Vapor Deposition. The Ultra-High Vacuum environment and the deposition precision of the PVD method enable the study of early stages of thin film growth and its molecular organization. X-ray Reflectivity and Atomic Force Microscopy measurements allow to pursuit size-effects in the structure of thin films with thickness ranges from less than a single molecular layer up to several tens of layers. Thermal treatment of the thin films triggered phase change: from a poorly ordered polycrystalline film into a well-ordered multilayer structure. Self-assembly of the layers is the effect of the π-stacking of phenyl rings, which force molecules to arrange in a superlattice, forming stacks of alternating organic-inorganic layers.

  10. Synthesis and self-assembly of complex hollow materials

    KAUST Repository

    Zeng, Hua Chun


    Hollow materials with interiors or voids and pores are a class of lightweight nanostructured matters that promise many future technological applications, and they have received significant research attention in recent years. On the basis of well-known physicochemical phenomena and principles, for example, several solution-based protocols have been developed for the general preparation of these complex materials under mild reaction conditions. This article is thus a short introductory review on the synthetic aspects of this field of development. The synthetic methodologies can be broadly divided into three major categories: (i) template-assisted synthesis, (ii) self-assembly with primary building blocks, and (iii) induced matter relocations. In most cases, both synthesis and self-assembly are involved in the above processes. Further combinations of these methodologies appear to be very important, as they will allow one to prepare functional materials at a higher level of complexity and precision. The synthetic strategies are introduced through some simple case studies with schematic illustrations. Salient features of the methods developed have been summarized, and some urgent issues of this field have also been indicated. © 2011 The Royal Society of Chemistry.

  11. Self-assembled single-phase perovskite nanocomposite thin films. (United States)

    Kim, Hyun-Suk; Bi, Lei; Paik, Hanjong; Yang, Dae-Jin; Park, Yun Chang; Dionne, Gerald F; Ross, Caroline A


    Thin films of perovskite-structured oxides with general formula ABO(3) have great potential in electronic devices because of their unique properties, which include the high dielectric constant of titanates, (1) high-T(C) superconductivity in cuprates, (2) and colossal magnetoresistance in manganites. (3) These properties are intimately dependent on, and can therefore be tailored by, the microstructure, orientation, and strain state of the film. Here, we demonstrate the growth of cubic Sr(Ti,Fe)O(3) (STF) films with an unusual self-assembled nanocomposite microstructure consisting of (100) and (110)-oriented crystals, both of which grow epitaxially with respect to the Si substrate and which are therefore homoepitaxial with each other. These structures differ from previously reported self-assembled oxide nanocomposites, which consist either of two different materials (4-7) or of single-phase distorted-cubic materials that exhibit two or more variants. (8-12) Moreover, an epitaxial nanocomposite SrTiO(3) overlayer can be grown on the STF, extending the range of compositions over which this microstructure can be formed. This offers the potential for the implementation of self-organized optical/ferromagnetic or ferromagnetic/ferroelectric hybrid nanostructures integrated on technologically important Si substrates with applications in magnetooptical or spintronic devices.

  12. Managing lifelike behavior in a dynamic self-assembled system (United States)

    Ropp, Chad; Bachelard, Nicolas; Wang, Yuan; Zhang, Xiang

    Self-organization can arise outside of thermodynamic equilibrium in a process of dynamic self-assembly. This is observed in nature, for example in flocking birds, but can also be created artificially with non-living entities. Such dynamic systems often display lifelike properties, including the ability to self-heal and adapt to environmental changes, which arise due to the collective and often complex interactions between the many individual elements. Such interactions are inherently difficult to predict and control, and limit the development of artificial systems. Here, we report a fundamentally new method to manage dynamic self-assembly through the direct external control of collective phenomena. Our system consists of a waveguide filled with mobile scattering particles. These particles spontaneously self-organize when driven by a coherent field, self-heal when mechanically perturbed, and adapt to changes in the drive wavelength. This behavior is governed by particle interactions that are completely mediated by coherent wave scattering. Compared to hydrodynamic interactions which lead to compact ordered structures, our system displays sinusoidal degeneracy and many different steady-state geometries that can be adjusted using the external field.

  13. Free surface BCP self-assembly process characterization with CDSEM (United States)

    Levi, Shimon; Weinberg, Yakov; Adan, Ofer; Klinov, Michael; Argoud, Maxime; Claveau, Guillaume; Tiron, Raluca


    A simple and common practice to evaluate Block copolymers (BCP) self-assembly performances, is on a free surface wafer. With no guiding pattern the BCP designed to form line space pattern for example, spontaneously rearranges to form a random fingerprint type of a pattern. The nature of the rearrangement is dictated by the physical properties of the BCP moieties, wafer surface treatment and the self-assembly process parameters. Traditional CDSEM metrology algorithms are designed to measure pattern with predefined structure, like linespace or oval via holes. Measurement of pattern with expected geometry can reduce measurement uncertainty. Fingerprint type of structure explored in this dissertation, poses a challenge for CD-SEM measurement uncertainty and offers an opportunity to explore 2D metrology capabilities. To measure this fingerprints we developed a new metrology approach that combines image segmentation and edge detection to measure 2D pattern with arbitrary rearrangement. The segmentation approach enabled to quantify the quality of the BCP material and process, detecting 2D attributes such as: CD and CDU at one axis, and number of intersections, length and number of PS fragments, etched PMMA spaces and donut shapes numbers on the second axis. In this paper we propose a 2D metrology to measure arbitrary BCP pattern on a free surface wafer. We demonstrate experimental results demonstrating precision data, and characterization of PS-b-PMMA BCP, intrinsic period L0 = 38nm (Arkema), processed at different bake time and temperatures.

  14. Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles (United States)

    Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai


    Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.

  15. Hierarchical Self-Assembly of Light Guided Spinning Microgears (United States)

    Aubret, Antoine; Youssef, Mena; Sacanna, Stefano; Palacci, Jeremie; Sacanna Group, NYU Team


    In this work, we demonstrate the self-assembly of microgears obtained from the guided construction of tailored self-propelled particles used as primary building blocks. The experiment relies on our control of phoretic phenomena: the migration of particles in a solute gradient. We activate a photocatalytic material, the hematite, and trigger the decomposition of hydrogen peroxide to set concentration gradient. We use this effect to engineer phototactic swimmers, attracted to the region of high illumination. We guide the swimmers to form robust and highly persistent microgears. They interact with each other through hydrodynamics and diffusiophoretically through the chemical clouds of fuel consumption. Multiple rotors are studied and we specifically address the dynamics of two rotors. We show that the microgears move collectively or synchronize thanks to the interaction of their chemical clouds. Increasing the number of microrotors (N = 2 - 7), we form an active crystal which can rotate, re-organize, change shape, and exhibit phase synchronization between its individual components. Such crystal made of non-equilibrium rotating gears at the microscale is unique. Our study paves the way for better understanding and control of emergent phenomena in collection of active spinning particles. It is a promising avenue for the creation of cutting-edge materials using emergent behavior from hierarchical self-assembly to unveil untapped functionalities. This work is supported by NSF CAREER DMR 1554724.

  16. Block copolymer systems: from single chain to self-assembled nanostructures. (United States)

    Giacomelli, Cristiano; Schmidt, Vanessa; Aissou, Karim; Borsali, Redouane


    Recent advances in the field of macromolecular engineering applied to the fabrication of nanostructured materials using block copolymer chains as elementary building blocks are described in this feature article. By highlighting some of our work in the area and accounting for the contribution of other groups, we discuss the relationship between the physical-chemical properties of copolymer chains and the characteristics of nano-objects originating from their self-assembly in solution and in bulk, with emphasis on convenient strategies that allow for the control of composition, functionality, and topology at different levels of sophistication. In the case of micellar nanoparticles in solution, in particular, we present approaches leading to morphology selection via macromolecular architectural design, the functionalization of external solvent-philic shells with biomolecules (polysaccharides and proteins), and the maximization of micelle loading capacity by the suitable choice of solvent-phobic polymer segments. The fabrication of nanomaterials mediated by thin block copolymer films is also discussed. In this case, we emphasize the development of novel polymer chain manipulation strategies that ultimately allow for the preparation of precisely positioned nanodomains with a reduced number of defects via block-selective chemical reactivity. The challenges facing the soft matter community, the urgent demand to convert huge public and private investments into consumer products, and future possible directions in the field are also considered herein.

  17. Self-assembled micro-organogels for 3D printing silicone structures (United States)

    O’Bryan, Christopher S.; Bhattacharjee, Tapomoy; Hart, Samuel; Kabb, Christopher P.; Schulze, Kyle D.; Chilakala, Indrasena; Sumerlin, Brent S.; Sawyer, W. Gregory; Angelini, Thomas E.


    The widespread prevalence of commercial products made from microgels illustrates the immense practical value of harnessing the jamming transition; there are countless ways to use soft, solid materials that fluidize and become solid again with small variations in applied stress. The traditional routes of microgel synthesis produce materials that predominantly swell in aqueous solvents or, less often, in aggressive organic solvents, constraining ways that these exceptionally useful materials can be used. For example, aqueous microgels have been used as the foundation of three-dimensional (3D) bioprinting applications, yet the incompatibility of available microgels with nonpolar liquids, such as oils, limits their use in 3D printing with oil-based materials, such as silicone. We present a method to make micro-organogels swollen in mineral oil, using block copolymer self-assembly. The rheological properties of this micro-organogel material can be tuned, leveraging the jamming transition to facilitate its use in 3D printing of silicone structures. We find that the minimum printed feature size can be controlled by the yield stress of the micro-organogel medium, enabling the fabrication of numerous complex silicone structures, including branched perfusable networks and functional fluid pumps. PMID:28508071

  18. Biodegradable self-assembled PEG-PCL-PEG micelles for hydrophobic honokiol delivery: I. Preparation and characterization

    International Nuclear Information System (INIS)

    Gong Changyang; Wei Xiawei; Wang Xiuhong; Wang Yujun; Guo Gang; Mao Yongqiu; Luo Feng; Qian Zhiyong


    This study aims to develop self-assembled poly(ethylene glycol)-poly(ε-caprolactone)-poly(ethylene glycol) (PEG-PCL-PEG, PECE) micelles to encapsulate hydrophobic honokiol (HK) in order to overcome its poor water solubility and to meet the requirement of intravenous administration. Honokiol loaded micelles (HK-micelles) were prepared by self-assembly of PECE copolymer in aqueous solution, triggered by its amphiphilic characteristic assisted by ultrasonication without any organic solvents, surfactants and vigorous stirring. The particle size of the prepared HK-micelles measured by Malvern laser particle size analyzer were 58 nm, which is small enough to be a candidate for an intravenous drug delivery system. Furthermore, the HK-micelles could be lyophilized into powder without any adjuvant, and the re-dissolved HK-micelles are stable and homogeneous with particle size about 61 nm. Furthermore, the in vitro release profile showed a significant difference between the rapid release of free HK and the much slower and sustained release of HK-micelles. Moreover, the cytotoxicity results of blank micelles and HK-micelles showed that the PECE micelle was a safe carrier and the encapsulated HK retained its potent antitumor effect. In short, the HK-micelles were successfully prepared by an improved method and might be promising carriers for intravenous delivery of HK in cancer chemotherapy, being effective, stable, safe (organic solvent and surfactant free), and easy to produce and scale up.

  19. Biodegradable self-assembled PEG-PCL-PEG micelles for hydrophobic honokiol delivery: I. Preparation and characterization (United States)

    Gong, ChangYang; Wei, XiaWei; Wang, XiuHong; Wang, YuJun; Guo, Gang; Mao, YongQiu; Luo, Feng; Qian, ZhiYong


    This study aims to develop self-assembled poly(ethylene glycol)-poly(ɛ-caprolactone)-poly(ethylene glycol) (PEG-PCL-PEG, PECE) micelles to encapsulate hydrophobic honokiol (HK) in order to overcome its poor water solubility and to meet the requirement of intravenous administration. Honokiol loaded micelles (HK-micelles) were prepared by self-assembly of PECE copolymer in aqueous solution, triggered by its amphiphilic characteristic assisted by ultrasonication without any organic solvents, surfactants and vigorous stirring. The particle size of the prepared HK-micelles measured by Malvern laser particle size analyzer were 58 nm, which is small enough to be a candidate for an intravenous drug delivery system. Furthermore, the HK-micelles could be lyophilized into powder without any adjuvant, and the re-dissolved HK-micelles are stable and homogeneous with particle size about 61 nm. Furthermore, the in vitro release profile showed a significant difference between the rapid release of free HK and the much slower and sustained release of HK-micelles. Moreover, the cytotoxicity results of blank micelles and HK-micelles showed that the PECE micelle was a safe carrier and the encapsulated HK retained its potent antitumor effect. In short, the HK-micelles were successfully prepared by an improved method and might be promising carriers for intravenous delivery of HK in cancer chemotherapy, being effective, stable, safe (organic solvent and surfactant free), and easy to produce and scale up.

  20. The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations (United States)

    Dabić, Dario; Brkljačić, Lidija; Tandarić, Tana; Žinić, Mladen; Vianello, Robert; Frkanec, Leo; Kobetić, Renata


    Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc)2, depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na+ cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na+ cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. [Figure not available: see fulltext.

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

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


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

  2. Morphological Evolution of Block Copolymer Particles: Effect of Solvent Evaporation Rate on Particle Shape and Morphology. (United States)

    Shin, Jae Man; Kim, YongJoo; Yun, Hongseok; Yi, Gi-Ra; Kim, Bumjoon J


    Shape and morphology of polymeric particles are of great importance in controlling their optical properties or self-assembly into unusual superstructures. Confinement of block copolymers (BCPs) in evaporative emulsions affords particles with diverse structures, including prolate ellipsoids, onion-like spheres, oblate ellipsoids, and others. Herein, we report that the evaporation rate of solvent from emulsions encapsulating symmetric polystyrene-b-polybutadiene (PS-b-PB) determines the shape and internal nanostructure of micron-sized BCP particles. A distinct morphological transition from the ellipsoids with striped lamellae to the onion-like spheres was observed with decreasing evaporation rate. Experiments and dissipative particle dynamics (DPD) simulations showed that the evaporation rate affected the organization of BCPs at the particle surface, which determined the final shape and internal nanostructure of the particles. Differences in the solvent diffusion rates in PS and PB at rapid evaporation rates induced alignment of both domains perpendicular to the particle surface, resulting in ellipsoids with axial lamellar stripes. Slower evaporation rates provided sufficient time for BCP organization into onion-like structures with PB as the outermost layer, owing to the preferential interaction of PB with the surroundings. BCP molecular weight was found to influence the critical evaporation rate corresponding to the morphological transition from ellipsoid to onion-like particles, as well as the ellipsoid aspect ratio. DPD simulations produced morphologies similar to those obtained from experiments and thus elucidated the mechanism and driving forces responsible for the evaporation-induced assembly of BCPs into particles with well-defined shapes and morphologies.

  3. Chemical and entropic control on the molecular self-assembly process


    Packwood, Daniel M.; Han, Patrick; Hitosugi, Taro


    Molecular self-assembly refers to the spontaneous assembly of molecules into larger structures. In order to exploit molecular self-assembly for the bottom-up synthesis of nanomaterials, the effects of chemical control (strength of the directionality in the intermolecular interaction) and entropic control (temperature) on the self-assembly process should be clarified. Here we present a theoretical methodology that unambiguously distinguishes the effects of chemical and entropic control on the ...

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

    Directory of Open Access Journals (Sweden)

    Rose Franck


    Full Text Available AbstractMicrotubules are filamentous proteins that act as a substrate for the translocation of motor proteins. As such, they may be envisioned as a scaffold for the self-assembly of functional materials and devices. Physisorption, self-assembly and combing are here investigated as a potential prelude to microtubule-templated self-assembly. Dense films of self-assembled microtubules were successfully produced, as well as patterns of both dendritic and non-dendritic bundles of microtubules. They are presented in the present paper and the mechanism of their formation is discussed.

  5. Protective Coatings for Space System Components Fabricated Using Ionic Self Assembled Monolayer Processes

    National Research Council Canada - National Science Library

    Miler, Mike


    Self-assembled multilayer thin film fabrication methods offer unique opportunities to incorporate multiple functionalities into coatings for space system materials and structures as well as consumer products...

  6. Applications of molecular self-assembly in tissue engineering (United States)

    Harrington, Daniel Anton

    This thesis studied the application of three self-assembling molecular systems, as potential biomaterials for tissue engineering applications. Cholesteryl-(L-lactic acid)n molecules form thermotropic liquid crystals, which could be coated onto the inner and outer pores of biodegradable PLLA scaffolds, while retaining the lamellar order of the neat material. Primary bovine chondrocytes were cultured on these structures, demonstrating improved attachment and extended retention of phenotype on the C-LA-coated scaffolds. No difference in fibronectin adsorption to C-LA and PLLA surfaces was observed, suggesting a strong role for cholesterol in influencing cell phenotype. A family of peptide-amphiphiles, bearing the "RGD" adhesion sequence from fibronectin, was also assessed in the contexts of cartilage and bladder repair. These molecules self-assemble into one-dimensional fibers, with diameters of 6--8 nm, and lengths of 500 nm or greater. Chondrocytes were seeded and cultured on covalently-crosslinked PA gels and embedded within calcium-triggered PA gels. Cells became dormant over time, but remained viable, suggesting an inappropriate display of the adhesion sequence to cells. A family of "branched" PA molecules with lysine dendron headgroups was designed, in an effort to increase the spatial separation between molecules in the assembled state, and to theoretically improve epitope accessibility. These molecules coated reliably onto PGA fiber scaffolds, and dramatically increased the attachment of human bladder smooth muscle cells, possibly through better epitope display or electrostatic attraction. They also formed strong gels with several negatively-charged biologically-relevant macromolecules. In a third system, amphiphilic segmented dendrimers based on phenylene vinylene and L-lysine entered cells through an endocytic pathway with no discernible toxic effect on cell proliferation or morphology. These amphiphiles formed complex aggregates in aqueous solution, likely

  7. Principles Governing the Self Assembly of Polypeptide Nanoparticles (United States)

    Wahome, Newton

    Self assembling systems on the nanometer scale afford the advantage of being able to control submicron level events. In this study, we focus on the self-assembling polypeptide nanoparticles (SAPN). The SAPN scaffold is made up of oligomerizing domains that align along the principle rotational axes of icosahedral symmetry. By aligning them along these axes, a particle with spherical geometry can be achieved. This particle can be utilized as a vaccine, as a drug delivery vehicle, or as a biomedical imaging device. This research will try to answer why the SAPN self-assembles into distinct molecular weight ranges while mostly maintaining a spherical morphology. The first means will be theoretical and computational, where we will utilize a mathematical formalism to find out how the packing of SAPN's monomeric units can occur within symmetric space. Then molecular dynamics will be run within this symmetric space to test the per amino acid residue susceptibility of SAPN towards becoming polymorphic in nature. Means for examining the aggregation propensity of SAPN will be also be tested. Specifically, the relationship of different sequences of SAPN with pH will be elucidated. Co-assembly of SAPN to reduce the surface density of an aggregation prone epitope will be tested. Also, aggregation reduction consisting of the exchange of an anionic denaturant with a positively charged suppressor in order to mitigate a priori peptide association and misfolding, will also be attempted. SAPN has been shown to be an immunogenic platform for the presentation of pathogen derived antigens. We will attempt to show the efficacy of presenting an antigen from HIV-1 which is structurally restrained to best match the native conformation on the virus. Immunological studies will be performed to test the effect of this approach, as well testing the antigenicity of the nanoparticle in the absence of adjuvant. Finally, the antigen presenting nanoparticles will undergo formulation testing, to measure

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

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


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

  9. Mechanical properties of polyelectrolyte multilayer self-assembled films

    International Nuclear Information System (INIS)

    Dai Xinhua; Zhang Yongjun; Guan Ying; Yang Shuguang; Xu Jian


    The mechanical properties of electrostatic self-assembled multilayer films from polyacrylic acid (PAA) and C 60 -ethylenediamine adduct (C 60 -EDA) or poly(allylamine hydrochloride) (PAH) were evaluated by atomic force microscopy (AFM) wear experiments. Because of the higher molecular weight of PAH, the wear resistance of the (PAH/PAA) 10 film is higher than that of the (PAH/PAA) 2 (C 60 -EDA/PAA) 8 film; that is, the former is mechanically more stable than the latter. The mechanical stability of both films can be improved significantly by heat treatment, which changes the nature of the linkage from ionic to covalent. The AFM measurement also reveals that the (PAH/PAA) 2 (C 60 -EDA/PAA) 8 film is softer than the (PAH/PAA) 10 film. The friction properties of the heated films were measured. These films can be developed as potential lubrication coatings for microelectromechanical systems

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

    Lenz, Martin; Witten, Thomas A


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

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

    Lenz, Martin; Witten, Thomas A.


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

  12. Phase Diagrams of Electrostatically Self-Assembled Amphiplexes

    Energy Technology Data Exchange (ETDEWEB)

    V Stanic; M Mancuso; W Wong; E DiMasi; H Strey


    We present the phase diagrams of electrostatically self-assembled amphiplexes (ESA) comprised of poly(acrylic acid) (PAA), cetyltrimethylammonium chloride (CTACl), dodecane, pentanol, and water at three different NaCl salt concentrations: 100, 300, and 500 mM. This is the first report of phase diagrams for these quinary complexes. Adding a cosurfactant, we were able to swell the unit cell size of all long-range ordered phases (lamellar, hexagonal, Pm3n, Ia3d) by almost a factor of 2. The added advantage of tuning the unit cell size makes such complexes (especially the bicontinuous phases) attractive for applications in bioseparation, drug delivery, and possibly in oil recovery.

  13. Lithographically-directed self-assembly of nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Liddle, J. Alexander; Cui, Yi; Alivisatos, Paul


    The combination of lithography and self-assembly provides apowerful means of organizing solution-synthesized nanostructures for awide variety of applications. We have developed a fluidic assembly methodthat relies on the local pinning of a moving liquid contact line bylithographically produced topographic features to concentratenanoparticles at those features. The final stages of the assembly processare controlled first by long-range immersion capillary forces and then bythe short-range electrostatic and Van der Waal's interactions. We havesuccessfully assembled nanoparticles from 50 nm to 2 nm in size usingthis technique and have also demonstrated the controlled positioning ofmore complex nanotetrapod structures. We have used this process toassemble Au nanoparticles into pre-patterned electrode structures andhave performed preliminary electrical characterization of the devices soformed. The fluidic assembly method is capable of very high yield, interms of positioning nanostructures at each lithographically-definedlocation, and of excellent specificity, with essentially no particledeposition between features.

  14. Self-assembled tunable photonic hyper-crystals. (United States)

    Smolyaninova, Vera N; Yost, Bradley; Lahneman, David; Narimanov, Evgenii E; Smolyaninov, Igor I


    We demonstrate a novel artificial optical material, the "photonic hyper-crystal", which combines the most interesting features of hyperbolic metamaterials and photonic crystals. Similar to hyperbolic metamaterials, photonic hyper-crystals exhibit broadband divergence in their photonic density of states due to the lack of usual diffraction limit on the photon wave vector. On the other hand, similar to photonic crystals, hyperbolic dispersion law of extraordinary photons is modulated by forbidden gaps near the boundaries of photonic Brillouin zones. Three dimensional self-assembly of photonic hyper-crystals has been achieved by application of external magnetic field to a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing.

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

    Directory of Open Access Journals (Sweden)

    Giovanni Filippo Palmieri


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

  16. Bioengineering towards self-assembly of particulate vaccines. (United States)

    Rehm, Bernd H A


    There is an unmet demand for safe and efficient vaccines for prevention of various infectious diseases. Subunit vaccines comprise selected pathogen specific antigens are a safe alternative to whole organism vaccines. However they often lack immunogenicity. Natural and synthetic self-assembling polymers and proteins will be reviewed in view their use to encapsulate and/or display antigens to serve as immunogenic antigen carriers for induction of protective immunity. Recent advances made in in vivo assembly of antigen-displaying polyester inclusions will be a focus. Particulate vaccines are inherently immunogenic due to enhanced uptake by antigen presenting cells which process antigens mediating adaptive immune responses. Bioengineering approaches enable the design of tailor-made particulate vaccines to fine tune immune responses towards protective immunity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. A self assembled monolayer based microfluidic sensor for urea detection (United States)

    Srivastava, Saurabh; Solanki, Pratima R.; Kaushik, Ajeet; Ali, Md. Azahar; Srivastava, Anchal; Malhotra, B. D.


    Urease (Urs) and glutamate dehydrogenase (GLDH) have been covalently co-immobilized onto a self-assembled monolayer (SAM) comprising of 10-carboxy-1-decanthiol (CDT) via EDC-NHS chemistry deposited onto one of the two patterned gold (Au) electrodes for estimation of urea using poly(dimethylsiloxane) based microfluidic channels (2 cm × 200 μm × 200 μm). The CDT/Au and Urs-GLDH/CDT/Au electrodes have been characterized using Fourier transform infrared (FTIR) spectroscopy, contact angle (CA), atomic force microscopy (AFM) and electrochemical cyclic voltammetry (CV) techniques. The electrochemical response measurement of a Urs-GLDH/CDT/Au bioelectrode obtained as a function of urea concentration using CV yield linearity as 10 to 100 mg dl-1, detection limit as 9 mg dl-1 and high sensitivity as 7.5 μA mM-1 cm-2.

  18. Communication: Programmable self-assembly of thin-shell mesostructures (United States)

    Halverson, Jonathan D.; Tkachenko, Alexei V.


    We study numerically the possibility of programmable self-assembly of various thin-shell architectures. They include clusters isomorphic to fullerenes C20 and C60, finite and infinite sheets, tube-shaped and toroidal mesostructures. Our approach is based on the recently introduced directionally functionalized nanoparticle platform, for which we employ a hybrid technique of Brownian dynamics with stochastic bond formation. By combining a number of strategies, we were able to achieve a near-perfect yield of the desired structures with a reduced "alphabet" of building blocks. Among those strategies are the following: the use of bending rigidity of the interparticle bond as a control parameter, programming the morphology with a seed architecture, use of chirality-preserving symmetries for reduction of the particle alphabet, and the hierarchic approach.

  19. Controlled doping by self-assembled dendrimer-like macromolecules (United States)

    Wu, Haigang; Guan, Bin; Sun, Yingri; Zhu, Yiping; Dan, Yaping


    Doping via self-assembled macromolecules might offer a solution for developing single atom electronics by precisely placing individual dopants at arbitrary location to meet the requirement for circuit design. Here we synthesize dendrimer-like polyglycerol macromolecules with each carrying one phosphorus atom in the core. The macromolecules are immobilized by the coupling reagent onto silicon surfaces that are pre-modified with a monolayer of undecylenic acid. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) are employed to characterize the synthesized macromolecules and the modified silicon surfaces, respectively. After rapid thermal annealing, the phosphorus atoms carried by the macromolecules diffuse into the silicon substrate, forming dopants at a concentration of 1017 cm-3. Low-temperature Hall effect measurements reveal that the ionization process is rather complicated. Unlike the widely reported simple ionization of phosphorus dopants, nitrogen and carbon are also involved in the electronic activities in the monolayer doped silicon.

  20. Infrared spectroscopy of self-assembled monolayer films on silicon (United States)

    Rowell, N. L.; Tay, Lilin; Boukherroub, R.; Lockwood, D. J.


    Infrared vibrational spectroscopy in an attenuated total reflection (ATR) geometry has been employed to investigate the presence of organic thin layers on Si-wafer surfaces. The phenomena have been simulated to show there can be a field enhancement with the presented single-reflection ATR (SR-ATR) approach which is substantially larger than for conventional ATR or specular reflection. In SR-ATR, a discontinuity of the field normal to the film contributes a field enhancement in the lower index thin film causing a two order of magnitude increase in sensitivity. SR-ATR was employed to characterize a single monolayer of undecylenic acid self-assembled on Si(1 1 1) and to investigate a two monolayer system obtained by adding a monolayer of bovine serum albumin protein.

  1. Electrochromic properties of self-assembled nanoparticle multilayer films

    International Nuclear Information System (INIS)

    Xue Bo; Li Hong; Zhang Lanlan; Peng Jun


    Hexagonal tungsten bronze (HTB) nanocrystal and TiO 2 nanoparticles were assembled into thin films by layer-by-layer self-assembly method. HTB nanocrystals were synthesized by hydrothermal route at 155 o C. UV-Vis spectra showed that the HTB/TiO 2 films exhibit a linear increase in film thickness with assembly exposure steps. The electrochromic property of the film was carefully investigated. Cyclic voltammetry indicated that the redox peak was around -0.5 V. The electrochromic contrast, coloration efficiency, switching speed, stability and optical memory were carefully investigated. The films vary from white to blue and finally dark brown. The electrochromic contrast is 63.9% at 633 nm. The coloration efficiency of the films is relatively high. The response time is less than 3 s.

  2. Dynamic simulations of many-body electrostatic self-assembly (United States)

    Lindgren, Eric B.; Stamm, Benjamin; Maday, Yvon; Besley, Elena; Stace, A. J.


    Two experimental studies relating to electrostatic self-assembly have been the subject of dynamic computer simulations, where the consequences of changing the charge and the dielectric constant of the materials concerned have been explored. One series of calculations relates to experiments on the assembly of polymer particles that have been subjected to tribocharging and the simulations successfully reproduce many of the observed patterns of behaviour. A second study explores events observed following collisions between single particles and small clusters composed of charged particles derived from a metal oxide composite. As before, observations recorded during the course of the experiments are reproduced by the calculations. One study in particular reveals how particle polarizability can influence the assembly process. This article is part of the theme issue `Modern theoretical chemistry'.

  3. Bioactive self-assembled peptide nanofibers for corneal stroma regeneration. (United States)

    Uzunalli, G; Soran, Z; Erkal, T S; Dagdas, Y S; Dinc, E; Hondur, A M; Bilgihan, K; Aydin, B; Guler, M O; Tekinay, A B


    Defects in the corneal stroma caused by trauma or diseases such as macular corneal dystrophy and keratoconus can be detrimental for vision. Development of therapeutic methods to enhance corneal regeneration is essential for treatment of these defects. This paper describes a bioactive peptide nanofiber scaffold system for corneal tissue regeneration. These nanofibers are formed by self-assembling peptide amphiphile molecules containing laminin and fibronectin inspired sequences. Human corneal keratocyte cells cultured on laminin-mimetic peptide nanofibers retained their characteristic morphology, and their proliferation was enhanced compared with cells cultured on fibronectin-mimetic nanofibers. When these nanofibers were used for damaged rabbit corneas, laminin-mimetic peptide nanofibers increased keratocyte migration and supported stroma regeneration. These results suggest that laminin-mimetic peptide nanofibers provide a promising injectable, synthetic scaffold system for cornea stroma regeneration. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  4. Graphene growth by conversion of aromatic self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Turchanin, Andrey [Institute of Physical Chemistry, Friedrich Schiller University Jena (Germany); Jena Center for Soft Matter (JCSM), Jena (Germany); Center for Energy and Environmental Chemistry Jena (CEEC), Jena (Germany); Abbe Center of Photonics (ACP), Jena (Germany)


    Despite present diversity of graphene production methods there is still a high demand for improvement of the existing production schemes or development of new. Here a method is reviewed to produce graphene employing aromatic self-assembled monolayers (SAMs) as molecular precursors. This method is based on electron irradiation induced crosslinking of aromatic SAMs resulting in their conversion into carbon nanomembranes (CNMs) with high thermal stability and subsequent pyrolysis of CNMs into graphene in vacuum or in the inert atmosphere. Depending on the production conditions, such as chemical structure of molecular precursors, irradiation and annealing parameters, various properties of the produced graphene sheets including shape, crystallinity, thickness, optical properties and electric transport can be adjusted. The assembly of CNM/graphene van der Waals heterostructures opens a flexible route to non-destructive chemical functionalization of graphene for a variety of applications in electronic and photonic devices. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Vijay, E-mail: [Centre for Nanoscience and Engineering, Indian Institute of Science-Bangalore (India); Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); Puri, Paridhi; Nain, Shivani [Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); Bhat, K. N. [Centre for Nanoscience and Engineering, Indian Institute of Science-Bangalore (India); Sharma, N. N. [Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); School of Automobile, Mechanical & Mechatronics, Manipal University-Jaipur (India)


    Treatment of surfaces to change the interaction of fluids with them is a critical step in constructing useful microfluidics devices, especially those used in biological applications. Selective modification of inorganic materials such as Si, SiO{sub 2} and Si{sub 3}N{sub 4} is of great interest in research and technology. We evaluated the chemical formation of OTS self-assembled monolayers on silicon substrates with different dielectric materials. Our investigations were focused on surface modification of formerly used common dielectric materials SiO{sub 2}, Si{sub 3}N{sub 4} and a-poly. The improvement of wetting behaviour and quality of monolayer films were characterized using Atomic force microscope, Scanning electron microscope, Contact angle goniometer, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) monolayer deposited oxide surface.

  6. Fabrication of bioinspired nanostructured materials via colloidal self-assembly (United States)

    Huang, Wei-Han

    Through millions of years of evolution, nature creates unique structures and materials that exhibit remarkable performance on mechanicals, opticals, and physical properties. For instance, nacre (mother of pearl), bone and tooth show excellent combination of strong minerals and elastic proteins as reinforced materials. Structured butterfly's wing and moth's eye can selectively reflect light or absorb light without dyes. Lotus leaf and cicada's wing are superhydrophobic to prevent water accumulation. The principles of particular biological capabilities, attributed to the highly sophisticated structures with complex hierarchical designs, have been extensively studied. Recently, a large variety of novel materials have been enabled by natural-inspired designs and nanotechnologies. These advanced materials will have huge impact on practical applications. We have utilized bottom-up approaches to fabricate nacre-like nanocomposites with "brick and mortar" structures. First, we used self-assembly processes, including convective self-assembly, dip-coating, and electrophoretic deposition to form well oriented layer structure of synthesized gibbsite (aluminum hydroxide) nanoplatelets. Low viscous monomer was permeated into layered nanoplatelets and followed by photo-curing. Gibbsite-polymer composite displays 2 times higher tensile strength and 3 times higher modulus when compared with pure polymer. More improvement occurred when surface-modified gibbsite platelets were cross-linked with the polymer matrix. We observed ˜4 times higher strength and nearly 1 order of magnitude higher modulus than pure polymer. To further improve the mechanical strength and toughness of inorganicorganic nanocomposites, we exploited ultrastrong graphene oxide (GO), a single atom thick hexagonal carbon sheet with pendant oxidation groups. GO nanocomposite is made by co-filtrating GO/polyvinyl alcohol suspension on 0.2 im pore-sized membrane. It shows ˜2 times higher strength and ˜15 times higher

  7. Magnetic ToF GISANS on self-assembled nanoparticles (United States)

    Glavic, Artur; Josten, Elisabeth; Petracic, Oleg; Lauter, Valeria


    Nanoparticle superlattices can be considered as novel type of materials with controllable electronic, optical and magnetic properties. Their building blocks are nanoparticles (or ``nanocrystals'') from a metallic, metal-oxide, or semiconducting material or hybrid between different materials. Using self-assembling techniques it is possible to create a large amount of highly ordered 3D structures, which we have investigated for their structural and magnetic properties. The lateral ordering is quantified using electron microscopy and grazing incidence small angle X-ray scattering (GISAXS). The macroscopic magnetic behavior and correlations are investigated by superconducting quantum interference device (SQUID) magnetometry. Utilizing the time of flight (ToF) magnetism reflectometer at SNS the magnetic correlations have been studied with polarized GISANS and PNR. This research at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.

  8. Self-Assembled PbSe Nanowire:Perovskite Hybrids

    KAUST Repository

    Yang, Zhenyu


    © 2015 American Chemical Society. Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

  9. Nanophotonic Fabrication Self-Assembly and Deposition Techniques

    CERN Document Server

    Yatsui, Takashi


    Nanophotonics, a novel optical technology, utilizes the local interaction between nanometric particles via optical near fields. The optical near fields are the elementary surface excitations on nanometric particles, i.e. dressed photons that carry material energy. Of the variety of qualitative innovations in optical technology realized by nanophotonics, this books focuses on fabrication. To fabricate nano-scale photonic devices with nanometer-scale controllability in size and position, we developed a self-assembly method for size- and position-controlled ultra-long nanodot chains using a novel effect of near-field optical desorption. A novel deposition and etching scheme under nonresonant conditions is also demonstrated and its origin is reviewed.

  10. Self-Assembled InAs Nanowires as Optical Reflectors. (United States)

    Floris, Francesco; Fornasari, Lucia; Marini, Andrea; Bellani, Vittorio; Banfi, Francesco; Roddaro, Stefano; Ercolani, Daniele; Rocci, Mirko; Beltram, Fabio; Cecchini, Marco; Sorba, Lucia; Rossella, Francesco


    Subwavelength nanostructured surfaces are realized with self-assembled vertically-aligned InAs nanowires, and their functionalities as optical reflectors are investigated. In our system, polarization-resolved specular reflectance displays strong modulations as a function of incident photon energy and angle. An effective-medium model allows one to rationalize the experimental findings in the long wavelength regime, whereas numerical simulations fully reproduce the experimental outcomes in the entire frequency range. The impact of the refractive index of the medium surrounding the nanostructure assembly on the reflectance was estimated. In view of the present results, sensing schemes compatible with microfluidic technologies and routes to innovative nanowire-based optical elements are discussed.

  11. Functional Molecular Junctions Derived from Double Self-Assembled Monolayers. (United States)

    Seo, Sohyeon; Hwang, Eunhee; Cho, Yunhee; Lee, Junghyun; Lee, Hyoyoung


    Information processing using molecular junctions is becoming more important as devices are miniaturized to the nanoscale. Herein, we report functional molecular junctions derived from double self-assembled monolayers (SAMs) intercalated between soft graphene electrodes. Newly assembled molecular junctions are fabricated by placing a molecular SAM/(top) electrode on another molecular SAM/(bottom) electrode by using a contact-assembly technique. Double SAMs can provide tunneling conjugation across the van der Waals gap between the terminals of each monolayer and exhibit new electrical functions. Robust contact-assembled molecular junctions can act as platforms for the development of equivalent contact molecular junctions between top and bottom electrodes, which can be applied independently to different kinds of molecules to enhance either the structural complexity or the assembly properties of molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers. (United States)

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping


    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10(-15) cm(2) s(-1), 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value.

  13. Tuning electronic transport in a self-assembled nanocomposite. (United States)

    Chang, Wei Sea; Liu, Heng-Jui; Tra, Vu Thanh; Chen, Jhih-Wei; Wei, Tzu-Chiao; Tzeng, W Y; Zhu, Yuanmin; Kuo, Ho-Hung; Hsieh, Ying-Hui; Lin, Jheng-Cyuan; Zhan, Qian; Luo, Chih Wei; Lin, Jiunn-Yuan; He, Jr-Hau; Wu, Chung Lin; Chu, Ying-Hao


    Self-assembled nanocomposites with a high interface-to-volume ratio offer an opportunity to overcome limitations in current technology, where intriguing transport behaviors can be tailored by the choice of proper interactions of constituents. Here we integrated metallic perovskite oxide SrRuO3-wurzite semiconductor ZnO nanocomposites to investigate the room-temperature metal-insulator transition and its effect on photoresponse. We demonstrate that the band structure at the interface can be tuned by controlling the interface-to-volume ratio of the nanocomposites. Photoinduced carrier injection driven by visible light was detected across the nanocomposites. This work shows the charge interaction of the vertically integrated multiheterostructures by incorporating a controllable interface-to-volume ratio, which is essential for optimization of the design and functionality of electronic devices.

  14. Modeling self-assembly and phase behavior in complex mixtures. (United States)

    Balazs, Anna C


    Using a variety of computational techniques, I investigate how the self-assembly of complex mixtures can be guided by surfaces or external stimuli to form spatially regular or temporally periodic patterns. Focusing on mixtures in confined geometries, I examine how thermodynamic and hydrodynamic effects can be exploited to create regular arrays of nanowires or monodisperse, particle-filled droplets. I also show that an applied light source and chemical reaction can be harnessed to create hierarchically ordered patterns in ternary, phase-separating mixtures. Finally, I consider the combined effects of confining walls and a chemical reaction to demonstrate that a swollen polymer gel can be driven to form dynamically periodic structures. In addition to illustrating the effectiveness of external factors in directing the self-organization of multicomponent mixtures, the selected examples illustrate how coarse-grained models can be used to capture both the equilibrium phase behavior and the dynamics of these complex systems.

  15. Engineering self-assembled bioreactors from protein microcompartments

    Energy Technology Data Exchange (ETDEWEB)

    Savage, David [Univ. of California, Berkeley, CA (United States)


    The goals of this research are to understand how organisms such as bacteria segregate certain metabolic processes inside of specific structures, or “microcompartments,” in the cell and apply this knowledge to develop novel engineered microcompartments for use in nanotechnology and metabolic engineering. For example, in some bacteria, self-assembling protein microcompartments called carboxysomes encapsulate the enzymes involved in carbon fixation, enabling the cell to utilize carbon dioxide more effectively than if the enzymes were free in the cell. The proposed research will determine how structures such as carboxysomes assemble and function in bacteria and develop a means for creating novel, synthetic microcompartments for optimizing production of specific energy-rich compounds.

  16. Modelling the self-assembly of virus capsids (United States)

    Johnston, Iain G.; Louis, Ard A.; Doye, Jonathan P. K.


    We use computer simulations to study a model, first proposed by Wales (2005 Phil. Trans. R. Soc. A 363 357), for the reversible and monodisperse self-assembly of simple icosahedral virus capsid structures. The success and efficiency of assembly as a function of thermodynamic and geometric factors can be qualitatively related to the potential energy landscape structure of the assembling system. Even though the model is strongly coarse-grained, it exhibits a number of features also observed in experiments, such as sigmoidal assembly dynamics, hysteresis in capsid formation and numerous kinetic traps. We also investigate the effect of macromolecular crowding on the assembly dynamics. Crowding agents generally reduce capsid yields at optimal conditions for non-crowded assembly, but may increase yields for parameter regimes away from the optimum. Finally, we generalize the model to a larger triangulation number T = 3, and observe assembly dynamics more complex than that seen for the original T = 1 model.

  17. Crystalline particles from self-assembled divinyl oligomers

    International Nuclear Information System (INIS)

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


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

  18. Sulfonation of alkyl phenyl ether self-assembled monolayers. (United States)

    Katash, Irit; Luo, Xianglin; Sukenik, Chaim N


    The sulfonation of phenyl ether decorated self-assembled monolayers (SAMs) was studied with an eye toward creating surfaces with a particularly high negative charge density based on a close-packed array of phenyl rings with more than one sulfonic acid group per molecule. The product distribution and kinetics of this process were studied by ultraviolet, infrared, and photoelectron spectroscopies and by monitoring changes in the thickness and wetting properties of the SAM. The sulfonation chemistry could be effected without undermining monolayer integrity and the isomer distribution of ortho- and para-monosulfonated material, along with the percentages of mono- and disulfonated molecules could be established throughout the process. As doubly sulfonated molecules appeared, the reaction slowed drastically. Ultimately, sulfonation stops completely with approximately 60% of the molecules disulfonated and 20% each of the two monosulfonated isomers. This striking constraint on monolayer reactivity and the relationship between the surface chemistry and variations in SAM structure are discussed.

  19. Guided self-assembly of nanostructured titanium oxide

    International Nuclear Information System (INIS)

    Wang Baoxiang; Rozynek, Zbigniew; Fossum, Jon Otto; Knudsen, Kenneth D; Yu Yingda


    A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiO x nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiO x nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiO x nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiO x nanorods with rough surfaces are formed by the self-assembly of TiO x nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiO x nanorods shows stronger ER properties than that of the other nanostructured TiO x particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect. (paper)

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

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


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

  1. Self-assembling hybrid diamond-biological quantum devices (United States)

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


    The realization of scalable arrangements of nitrogen vacancy (NV) centers in diamond remains a key challenge on the way towards efficient quantum information processing, quantum simulation and quantum sensing applications. Although technologies based on implanting NV-centers in bulk diamond crystals or hybrid device approaches have been developed, they are limited by the achievable spatial resolution and by the intricate technological complexities involved in achieving scalability. We propose and demonstrate a novel approach for creating an arrangement of NV-centers, based on the self-assembling capabilities of biological systems and their beneficial nanometer spatial resolution. Here, a self-assembled protein structure serves as a structural scaffold for surface functionalized nanodiamonds, in this way allowing for the controlled creation of NV-structures on the nanoscale and providing a new avenue towards bridging the bio-nano interface. One-, two- as well as three-dimensional structures are within the scope of biological structural assembling techniques. We realized experimentally the formation of regular structures by interconnecting nanodiamonds using biological protein scaffolds. Based on the achievable NV-center distances of 11 nm, we evaluate the expected dipolar coupling interaction with neighboring NV-centers as well as the expected decoherence time. Moreover, by exploiting these couplings, we provide a detailed theoretical analysis on the viability of multiqubit quantum operations, suggest the possibility of individual addressing based on the random distribution of the NV intrinsic symmetry axes and address the challenges posed by decoherence and imperfect couplings. We then demonstrate in the last part that our scheme allows for the high-fidelity creation of entanglement, cluster states and quantum simulation applications.

  2. Mixed carboranethiol self-assembled monolayers on gold surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, Adem [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Sohrabnia, Nima [Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey); Yilmaz, Ayşen [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey); Danışman, M. Fatih, E-mail: [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)


    Highlights: • M1 binds to the gold surface preferentially when co-deposited with M9 or O1. • Contact angles show similar trends regardless of the gold substrate roughness. • Contact angles were lower, with higher hysteresis, on template stripped gold. • Mixed carboranethiol SAMs have similar morphological properties regardless of mixing ratio. - Abstract: Carboranethiol self-assembled monolayers on metal surfaces have been shown to be very convenient systems for surface engineering. Here we have studied pure and mixed self-assembled monolayers (SAMs) of three different carboranethiol (CT) isomers on gold surfaces. The isomers were chosen with dipole moments pointing parallel to (m-1-carboranethiol, M1), out of (m-9-carboranethiol, M9) and into (o-1-carboranethiol, O1) the surface plane, in order to investigate the effect of dipole moment orientation on the film properties. In addition, influence of the substrate surface morphology on the film properties was also studied by using flame annealed (FA) and template stripped (TS) gold surfaces. Contact angle measurements indicate that in M1/M9 and M1/O1 mixed SAMs, M1 is the dominant species on the surface even for low M1 ratio in the growth solution. Whereas for O1/M9 mixed SAMs no clear evidence could be observed indicating dominance of one of the species over the other one. Though contact angle values were lower and hysteresis values were higher for SAMs grown on TS gold surfaces, the trends in the behavior of the contact angles with changing mixing ratio were identical for SAMs grown on both substrates. Atomic force microscopy images of the SAMs on TS gold surfaces indicate that the films have similar morphological properties regardless of mixing ratio.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    Imagine free-standing flexible membranes with highly-aligned arrays of carbon nanotubes (CNTs) running through their thickness. Perhaps with both ends of the CNTs open for highly controlled nanofiltration? Or CNTs at heights uniformly above a polymer membrane for a flexible array of nanoelectrodes or field-emitters? How about CNT films with incredible amounts of accessible surface area for analyte adsorption? These self-assembled crystalline nanotubes consist of multiple layers of graphene sheets rolled into concentric cylinders. Tube diameters (3-300 nm), inner-bore diameters (2-15 nm), and lengths (nanometers - microns) are controlled to tailor physical, mechanical, and chemical properties. We proposed to explore growth and characterize nanotube arrays to help determine their exciting functionality for Sandia applications. Thermal chemical vapor deposition growth in a furnace nucleates from a metal catalyst. Ordered arrays grow using templates from self-assembled hexagonal arrays of nanopores in anodized-aluminum oxide. Polymeric-binders can mechanically hold the CNTs in place for polishing, lift-off, and membrane formation. The stiffness, electrical and thermal conductivities of CNTs make them ideally suited for a wide-variety of possible applications. Large-area, highly-accessible gas-adsorbing carbon surfaces, superb cold-cathode field-emission, and unique nanoscale geometries can lead to advanced microsensors using analyte adsorption, arrays of functionalized nanoelectrodes for enhanced electrochemical detection of biological/explosive compounds, or mass-ionizers for gas-phase detection. Materials studies involving membrane formation may lead to exciting breakthroughs in nanofiltration/nanochromatography for the separation of chemical and biological agents. With controlled nanofilter sizes, ultrafiltration will be viable to separate and preconcentrate viruses and many strains of bacteria for 'down-stream' analysis.

  4. Origami inspired self-assembly of patterned and reconfigurable particles. (United States)

    Pandey, Shivendra; Gultepe, Evin; Gracias, David H


    There are numerous techniques such as photolithography, electron-beam lithography and soft-lithography that can be used to precisely pattern two dimensional (2D) structures. These technologies are mature, offer high precision and many of them can be implemented in a high-throughput manner. We leverage the advantages of planar lithography and combine them with self-folding methods(1-20) wherein physical forces derived from surface tension or residual stress, are used to curve or fold planar structures into three dimensional (3D) structures. In doing so, we make it possible to mass produce precisely patterned static and reconfigurable particles that are challenging to synthesize. In this paper, we detail visualized experimental protocols to create patterned particles, notably, (a) permanently bonded, hollow, polyhedra that self-assemble and self-seal due to the minimization of surface energy of liquefied hinges(21-23) and (b) grippers that self-fold due to residual stress powered hinges(24,25). The specific protocol described can be used to create particles with overall sizes ranging from the micrometer to the centimeter length scales. Further, arbitrary patterns can be defined on the surfaces of the particles of importance in colloidal science, electronics, optics and medicine. More generally, the concept of self-assembling mechanically rigid particles with self-sealing hinges is applicable, with some process modifications, to the creation of particles at even smaller, 100 nm length scales(22, 26) and with a range of materials including metals(21), semiconductors(9) and polymers(27). With respect to residual stress powered actuation of reconfigurable grasping devices, our specific protocol utilizes chromium hinges of relevance to devices with sizes ranging from 100 μm to 2.5 mm. However, more generally, the concept of such tether-free residual stress powered actuation can be used with alternate high-stress materials such as heteroepitaxially deposited semiconductor

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


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

  6. Ordering and dynamics of oligo(phenylene ethynylene) self-assembled monolayers on Au(111)

    NARCIS (Netherlands)

    Wu, Hairong; Sotthewes, Kai; Schön, Peter Manfred; Vancso, Gyula J.; Zandvliet, Henricus J.W.


    Self-assembled monolayers of 4-[4′-(phenylethynyl)-phenylethynyl]-benzenethiolate (PPB-S) molecules on flame annealed Au(111) have been investigated by ultra-high vacuum scanning tunneling microscopy. We have found a hitherto unknown self-assembled monolayer phase. This phase consists of a

  7. Comparative self-assembly studies and self-sorting of two ...

    Indian Academy of Sciences (India)

    The propensity for self-assembly of NDI-1 was greater due to symmetrical placement of two amide groups on either arms of this chromophore which allowed -stacking in tandem with hydrogen-bonding, while NDI-2 formed thermally more stable self-assembled fibres possibly due to location of two amide groups in close ...

  8. From self-organization to self-assembly: a new materialism? (United States)

    Vincent, Bernadette Bensaude


    While self-organization has been an integral part of academic discussions about the distinctive features of living organisms, at least since Immanuel Kant's Critique of Judgement, the term 'self-assembly' has only been used for a few decades as it became a hot research topic with the emergence of nanotechnology. Could it be considered as an attempt at reducing vital organization to a sort of assembly line of molecules? Considering the context of research on self-assembly I argue that the shift of attention from self-organization to self-assembly does not really challenge the boundary between chemistry and biology. Self-assembly was first and foremost investigated in an engineering context as a strategy for manufacturing without human intervention and did not raise new perspectives on the emergence of vital organization itself. However self-assembly implies metaphysical assumptions that this paper tries to disentangle. It first describes the emergence of self-assembly as a research field in the context of materials science and nanotechnology. The second section outlines the metaphysical implications and will emphasize a sharp contrast between the ontology underlying two practices of self-assembly developed under the umbrella of synthetic biology. And unexpectedly, we shall see that chemists are less on the reductionist side than most synthetic biologists. Finally, the third section ventures some reflections on the kind of design involved in self-assembly practices.

  9. Three-dimensional visualization and characterization of polymeric self-assemblies by Transmission Electron Microtomography

    NARCIS (Netherlands)

    H. Jinnai (Hiroshi); T. Higuchi (Takeshi); X. Zhuge (Jason); A. Kumamoto (Akihito); K.J. Batenburg (Joost); Y. Ikuhara (Yuichi)


    textabstractSelf-assembling structures and their dynamical processes in polymeric systems have been investigated using three-dimensional transmission electron microscopy (3D-TEM). Block copolymers (BCPs) self-assemble into nanoscale periodic structures called microphase-separated structures, a deep

  10. Macroscopic equivalence for microscopic motion in a turbulence driven three-dimensional self-assembly reactor

    NARCIS (Netherlands)

    Hageman, T. A. G.; Löthman, P. A.; Dirnberger, M.; Elwenspoek, M.; Manz, A; Abelmann, L.

    We built and characterised a macroscopic self-assembly reactor that agitates magnetic, centimeter-sized particles with a turbulent water flow. By scaling up the self-assembly processes to the centimeter-scale, the characteristic time constant scale also drastically increases. This makes the system a

  11. Challenges and advances in the field of self-assembled membranes

    NARCIS (Netherlands)

    van Rijn, Patrick; Tutus, Murat; Kathrein, Christine; Zhu, Leilei; Wessling, Matthias; Schwaneberg, Ulrich; Boeker, Alexander


    Self-assembled membranes are of vital importance in biological systems e. g. cellular and organelle membranes, however, more focus is being put on synthetic self-assembled membranes not only as an alternative for lipid membranes but also as an alternative for lithographic methods. More

  12. A self-assembled monolayer-assisted surface microfabrication and release technique

    NARCIS (Netherlands)

    Kim, B.J.; Liebau, M.; Huskens, Jurriaan; Reinhoudt, David; Brugger, J.P.


    This paper describes a method of thin film and MEMS processing which uses self-assembled monolayers as ultra-thin organic surface coating to enable a simple removal of microfabricated devices off the surface without wet chemical etching. A 1.5-nm thick self-assembled monolayer of

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

    Indian Academy of Sciences (India)

    such compounds should be possible to segregate eas- ily by solvent molecules or guest molecules to provide different packing patterns which may lead to different arrangements. If the dimeric motifs are not dislodged by guest or solvent molecules, then also there are pos- sibilities to reorganize the dimeric motifs to closely.

  14. INTRODUCTION: New trends in simulating colloids and self-assembling systems New trends in simulating colloids and self-assembling systems (United States)

    Foffi, Giuseppe; Kahl, Gerhard


    University Of Oxford and Athanassios Panagiotopoulos—University Of Princeton) focused on the remarkable ability of colloidal systems to self-organize in well-defined composite objects. New simulation techniques and theoretical approaches were presented and discussed that offer a deeper understanding of self-assembly phenomena in colloidal physics and, eventually to uncover design rules for self-assembly. Particular emphasis was put on an emerging new class of colloidal particles, so-called patchy colloids. The second workshop, entitled 'New Trends in Simulating Colloids: From Models to Applications', (organized by Giuseppe Foffi—Ecole Polytechnique Fédérale De Lausanne, Gerhard Kahl—Vienna Technical University and Richard Vink—Georg-August-Universität Göttingen) focused on new methodological devices in theoretical and simulation approaches that provided a more profound insight in colloidal physics in general. A large variety of theoretical tools, ranging from different simulation techniques over classical density functional theory to efficient optimization techniques were presented. For details about the tools presented in both workshops we refer the reader to the contributions of this special issue. The 'round table' discussion meetings were highly useful in providing an overview of yet unsolved problems and to point out directions for future work. From the phenomenological point of view, among those are the question on the relevance of hydrodynamic interactions, the problem whether to treat solvents in an explicit or implicit way, or the relevance of multibody interactions, to name but a few. With respect to the methods it was agreed that future developments on dynamic Monte Carlo simulations or on rare events and multiscale techniques are urgently required. The presence of the experimentalists was also of great help in focusing attention on the systems that are going to represent the scientific challenges in the next years. It was interesting that while new

  15. Multifunctional hardmask neutral layer for directed self-assembly (DSA) patterning (United States)

    Guerrero, Douglas J.; Hockey, Mary Ann; Wang, Yubao; Calderas, Eric


    Micro-phase separation for directed self-assembly (DSA) can be executed successfully only when the substrate surface on which the block co-polymer (BCP) is coated has properties that are ideal for attraction to each polymer type. The neutral underlayer (NUL) is an essential and critical component in DSA feasibility. Properties conducive for BCP patterning are primarily dependent on "brush" or "crosslinked" random co-polymer underlayers. Most DSA flows also require a lithography step (reflection control) and pattern transfer schemes at the end of the patterning process. A novel multifunctional hardmask neutral layer (HM NL) was developed to provide reflection control, surface energy matching, and pattern transfer capabilities in a grapho-epitaxy DSA process flow. It was found that the ideal surface energy for the HM NL is in the range of 38-45 dyn/cm. The robustness of the HM NL against exposure to process solvents and developers was identified. Process characteristics of the BCP (thickness, bake time and temperature) on the HM NL were defined. Using the HM NL instead of three distinct layers - bottom anti-reflective coating (BARC) and neutral and hardmask layers - in DSA line-space pitch tripling and contact hole shrinking processes was demonstrated. Finally, the capability of the HM NL to transfer a pattern into a 100-nm spin-on carbon (SOC) layer was shown.

  16. Vertical Conducting Nanodomains Self-Assembled from Poly(3-hexylthiophene)-Based Diblock Copolymer Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Y Lee; S Kim; H Yang; M Jang; S Hwang; H Lee; K Baek


    We have synthesized {pi}-conjugated poly(3-hexyl thiophene)-block-poly(methyl methacrylate) (P3HT-b-PMMA) with a P3HT molecular weight of 11 kDa and a PMMA volume fraction of 0.53, which potentially has several organic electronic applications. Its phase-separation behavior was investigated for various thicknesses cast from organic solvents. When cast onto 300 nm thick SiO{sub 2} dielectrics from toluene, in which the P3HT segments have limited solubility, the P3HT-b-PMMA films consist of nanofibrillar self-assemblies of laterally {pi}-stacked P3HT chains. In contrast, the P3HT segments were found to be highly mobile in chlorobenzene, generating a typical phase-separation morphology consisting of vertically conducting P3HT nanodomains on these dielectrics. As the thickness of the cast films increased, however, the topmost surface becomes covered with {pi}-conjugated nanofibrils that are laterally oriented with respect to the surface. Due to the anisotropic domain orientations of P3HT, top-gate organic field-effect transistors (OFETs) containing the P3HT-b-PMMA films exhibited enhanced electrical performance compared to bottom-gate OFETs.

  17. Synthesis and self-assembling of responsive polysaccharide-based copolymers in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Nivia do N.; Balaban, Rosangela de C. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Halila, Sami; Borsali, Redouane, E-mail:, E-mail: [Centre de Recherche sur les Macromolecules Vegetales (CERMAV), Grenoble (France)


    This work reports the synthesis and the thermoresponsive self-assembly behavior of carboxymethylcellulose-g-JeffamineM2070 and carboxymethylcellulose-g-JeffamineM600 copolymers in aqueous media. They were prepared through the grafting of two different types of amino-terminated poly(ethylene oxide-co-propylene oxide) chains onto the carboxylate groups of carboxymethylcellulose, by using water-soluble carbodiimide derivative and N-hydroxysuccinimide as coupling reagents. The grafting efficiency was confirmed by infrared and the degree of substitution by {sup 1}H NMR integrations. The salt effect on cloud point temperature was evaluated into different solvents (Milli-Q water, 0.5M NaCl, synthetic sea water (SSW) and 0.5M K{sub 2}CO{sub 3}) by UV-Vis and dynamic light scattering (DLS) measurements. Both copolymers showed lower cloud point temperature in 0.5M K2CO3 than in 0.5M NaCl and in SSW, which was attributed to the higher ionic strength for K{sub 2}CO{sub 3} combined to the ability of CO{sub 3}{sup 2-} to decrease polymer-water interactions. Copolymers chains displayed higher hydrodynamic radii than CMC precursor at 25 and 60 °C in saline solutions, and self-associations changed as a function of the environment and copolymer composition. (author)

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

    Directory of Open Access Journals (Sweden)

    Francesco Di Stasio


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

  19. One-dimensional self-assembly of phenylacetylene macrocycles: effect of peripheral substituents. (United States)

    Li, Jie; Zhou, Wei; Yang, Jiping; Lang, Xiufeng; Huang, Pengcheng


    Tetra- and tri-substituted m-phenylacetylene macrocycles with diethylene glycol monoethyl ether (DEG) phenylether peripheral side chains (PAM 1 and PAM 1') were synthesized, and both of them could self-assemble into well-defined one-dimensional (1D) structures through two kinds of fabrication processing. The recrystallization approach led to similar microbelts for PAMs 1 and 1' with hundreds of microns in length, 2-4 μm in width, and 200-300 nm in thickness. But AFM, XRD, and spectrum characterizations indicated that the microbelts of PAM 1' had smaller intercolumnar distances and more favorable π-π stacking. Two different nanostructures were obtained through the other processing of solvent evaporation: nanobelts for PAM 1 and twisted nanorods for PAM 1'. The different molecular arrangement and nanostructures could be ascribed to the different molecular structures, especially the different positioning of the peripheral substituents. This research provides a potential control over the morphology and the structure of the 1D assembly by adjusting the molecular structure as well as the sample processing. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. Electrostatic self-assembly in polyelectrolyte-neutral block copolymers and oppositely charged surfactant solutions

    International Nuclear Information System (INIS)

    Berret, J.-F.Jean-Francois; Oberdisse, Julian


    We report on small-angle neutron scattering (SANS) of colloidal complexes resulting from the electrostatic self-assembly of polyelectrolyte-neutral copolymers and oppositely charged surfactants. The polymers are double hydrophilic block copolymers of low molecular weight (between 5000 and 50 000 g/mol). One block is a polyelectrolyte chain, which can be either positively or negatively charged, whereas the second block is neutral and in good solvent conditions. In aqueous solutions, surfactants with an opposite charge to that of the polyelectrolyte interact strongly with these copolymers. The two species associate into stable 100 nm-colloidal complexes which exhibit a core-shell microstructure. For different polymer/surfactant couples, we have shown that the core is constituted from densely packed surfactant micelles connected by the polyelectrolyte chains. The outer part of the complex is a corona formed by the neutral soluble chains. Using a model of aggregation based on a Monte-Carlo algorithm, we have simulated the internal structure of the aggregates. The model assumes spherical cages containing one to several hundreds of micelles in a closely packed state. The agreement between the model and the data is remarkable

  1. Improving anticancer activity and reducing systemic toxicity of doxorubicin by self-assembled polymeric micelles

    International Nuclear Information System (INIS)

    Gou Maling; Shi Huashan; Guo Gang; Men Ke; Zhang Juan; Li Zhiyong; Luo Feng; Qian Zhiyong; Wei Yuquan; Zheng Lan; Zhao Xia


    In an attempt to improve anticancer activity and reduce systemic toxicity of doxorubicin (Dox), we encapsulated Dox in monomethoxy poly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) micelles by a novel self-assembly procedure without using surfactants, organic solvents or vigorous stirring. These Dox encapsulated MPEG-PCL (Dox/MPEG-PCL) micelles with drug loading of 4.2% were monodisperse and ∼ 20 nm in diameter. The Dox can be released from the Dox/MPEG-PCL micelles; the Dox-release at pH 5.5 was faster than that at pH 7.0. Encapsulation of Dox in MPEG-PCL micelles enhanced the cellular uptake and cytotoxicity of Dox on the C-26 colon carcinoma cell in vitro, and slowed the extravasation of Dox in the transgenic zebrafish model. Compared to free Dox, Dox/MPEG-PCL micelles were more effective in inhibiting tumor growth in the subcutaneous C-26 colon carcinoma and Lewis lung carcinoma models, and prolonging survival of mice bearing these tumors. Dox/MPEG-PCL micelles also induced lower systemic toxicity than free Dox. In conclusion, incorporation of Dox in MPEG-PCL micelles enhanced the anticancer activity and decreased the systemic toxicity of Dox; these Dox/MPEG-PCL micelles are an interesting formulation of Dox and may have potential clinical applications in cancer therapy.

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

    Bisoyi, Hari Krishna; Kumar, Sandeep


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

  3. Synthesis and self-assembling of responsive polysaccharide-based copolymers in aqueous media

    International Nuclear Information System (INIS)

    Marques, Nivia do N.; Balaban, Rosangela de C.; Halila, Sami; Borsali, Redouane


    This work reports the synthesis and the thermoresponsive self-assembly behavior of carboxymethylcellulose-g-JeffamineM2070 and carboxymethylcellulose-g-JeffamineM600 copolymers in aqueous media. They were prepared through the grafting of two different types of amino-terminated poly(ethylene oxide-co-propylene oxide) chains onto the carboxylate groups of carboxymethylcellulose, by using water-soluble carbodiimide derivative and N-hydroxysuccinimide as coupling reagents. The grafting efficiency was confirmed by infrared and the degree of substitution by 1 H NMR integrations. The salt effect on cloud point temperature was evaluated into different solvents (Milli-Q water, 0.5M NaCl, synthetic sea water (SSW) and 0.5M K 2 CO 3 ) by UV-Vis and dynamic light scattering (DLS) measurements. Both copolymers showed lower cloud point temperature in 0.5M K2CO3 than in 0.5M NaCl and in SSW, which was attributed to the higher ionic strength for K 2 CO 3 combined to the ability of CO 3 2- to decrease polymer-water interactions. Copolymers chains displayed higher hydrodynamic radii than CMC precursor at 25 and 60 °C in saline solutions, and self-associations changed as a function of the environment and copolymer composition. (author)

  4. The structural coloration of textile materials using self-assembled silica nanoparticles (United States)

    Gao, Weihong; Rigout, Muriel; Owens, Huw


    The work presented investigates how to produce structural colours on textile materials by applying a surface coating of silica nanoparticles (SNPs). Uniform SNPs with particle diameters in a controlled micron size range (207-350 nm) were synthesized using a Stöber-based solvent varying (SV) method which has been reported previously. Photonic crystals (PCs) were formed on the surface of a piece of textile fabric through a process of natural sedimentation self-assembly of the colloidal suspension containing uniform SNPs. Due to the uniformity and a particular diameter range of the prepared SNPs, structural colours were observed from the fabric surface due to the Bragg diffraction of white light with the ordered structure of the silica PCs. By varying the mean particle diameter, a wide range of spectral colours from red to blue were obtained. The comparison of structural colours on fabrics and on glasses suggests that a smooth substrate is critical when producing materials with high colour intensity and spatial uniformity. This work suggested a promising approach to colour textile materials without the need for traditional dyes and/or pigments. [Figure not available: see fulltext.

  5. Simulations of the confinement of ubiquitin in self-assembled reverse micelles (United States)

    Tian, Jianhui; García, Angel E.


    We describe the effects of confinement on the structure, hydration, and the internal dynamics of ubiquitin encapsulated in reverse micelles (RM). We performed molecular dynamics simulations of the encapsulation of ubiquitin into self-assembled protein/surfactant reverse micelles to study the positioning and interactions of the protein with the RM and found that ubiquitin binds to the RM interface at low salt concentrations. The same hydrophobic patch that is recognized by ubiquitin binding domains in vivo is found to make direct contact with the surfactant head groups, hydrophobic tails, and the iso-octane solvent. The fast backbone N-H relaxation dynamics show that the fluctuations of the protein encapsulated in the RM are reduced when compared to the protein in bulk. This reduction in fluctuations can be explained by the direct interactions of ubiquitin with the surfactant and by the reduced hydration environment within the RM. At high concentrations of excess salt, the protein does not bind strongly to the RM interface and the fast backbone dynamics are similar to that of the protein in bulk. Our simulations demonstrate that the confinement of protein can result in altered protein dynamics due to the interactions between the protein and the surfactant.

  6. Molecular self-assembly for biological investigations and nanoscale lithography (United States)

    Cheunkar, Sarawut

    Small, diffusible molecules when recognized by their binding partners, such as proteins and antibodies, trigger enzymatic activity, cell communication, and immune response. Progress in analytical methods enabling detection, characterization, and visualization of biological dynamics at the molecular level will advance our exploration of complex biological systems. In this dissertation, analytical platforms were fabricated to capture membrane-associated receptors, which are essential proteins in cell signaling pathways. The neurotransmitter serotonin and its biological precursor were immobilized on gold substrates coated with self-assembled monolayers (SAMs) of oligo(ethylene glycol)alkanethiols and their reactive derivatives. The SAM-coated substrates present the biologically selective affinity of immobilized molecules to target native membrane-associated receptors. These substrates were also tested for biospecificity using antibodies. In addition, small-molecule-functionalized platforms, expressing neurotransmitter pharmacophores, were employed to examine kinetic interactions between G-protein-coupled receptors and their associated neurotransmitters. The binding interactions were monitored using a quartz crystal microbalance equipped with liquid-flow injection. The interaction kinetics of G-protein-coupled serotonin 1A receptor and 5-hydroxytyptophan-functionalized surfaces were studied in a real-time, label-free environment. Key binding parameters, such as equilibrium dissociation constants, binding rate constants, and dissociative half-life, were extracted. These parameters are critical for understanding and comparing biomolecular interactions in modern biomedical research. By integrating self-assembly, surface functionalization, and nanofabrication, small-molecule microarrays were created for high-throughput screening. A hybrid soft-lithography, called microcontact insertion printing, was used to pattern small molecules at the dilute scales necessary for highly

  7. Directed self-assembly of mesoscopic components for led applications (United States)

    Tkachenko, Anton

    Light-emitting diodes (LEDs) constitute a rapidly evolving and fast growing technology that promises to replace incandescent bulbs and compact fluorescent lights in many illumination applications. Large-area LED luminaires have a capability to transform lighting by providing a venue for development of smart lighting systems with additional benefits, such as visible light communications, sensing, health and productivity improvement through color temperature control, capability of creating "virtual sky" ceiling, and many others. The objective of this work is to explore directed self-assembly (DSA) approaches suitable for cost-effective assembly of large amount of LEDs and other mesoscopic (i.e. millimeter and sub-millimeter) electronic components and thus to enable manufacturing of smart lighting luminaires. Existing alternative approaches for assembly of semiconductor dies are examined including transfer printing, laser-assisted die transfer, and various directed self-assembly approaches using shape-recognition, magnetic and capillary forces, etc. After comparing their advantages and limitations, we developed two approaches to magnetic force-assisted DSA of LEDs on a large-area substrate in liquid and air medium. The first approach involves pick-up of buoyant and magnetic dies from the liquid surface onto the flexible substrate in a roll-to-roll process. The possibility of high-speed assembly of LED dies is demonstrated, but with a low yield due to the influence of the capillary force of the carrier liquid and the difficulty in ensuring reliable supply of dies to the assembly interface. To overcome the aforementioned challenges this process was modified to assemble the dies by sinking them onto the receiving substrate with a stencil mask on top, demonstrating LED assembly with a very low error rate but at a lower speed. A solder-assisted self-alignment is used to further improve placement precision and to ensure the proper orientation of the dies. The second

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

    Directory of Open Access Journals (Sweden)

    Mina Salimimarand


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

  9. Self-assembly of conducting polymer nanowires at air-water interface and its application for gas sensors

    International Nuclear Information System (INIS)

    Xu Jianhua; Jiang Yadong; Yang Yajie; Yu Junsheng


    Conducting polymer poly (3, 4-ethylenedioxythiophene) (PEDOT) nanowires were prepared by wetting Al 2 O 3 membrane (AAO) template method, which could be well dispersed in organic solvent with ultrasonic treatment. In order to obtain highly ordered structure of nanowires, the self-assembly film of nanowires at air/water interface was investigated by Langmuir-Blodgett (LB) technique. The results showed that PEDOT nanowire-surfactant complex at air/water interface had well self-assembly capability, and the stable float layer was formed with collapse pressure more than 50 mN/m. This well arranged nanowire film was transferred onto interdigitated electrode successfully as novel gas sensing layer through a vertical dipping method. The as-prepared PEDOT nanowire gas sensor was applied to the precise detection of NH 3 and HCl gas, especially for low gas concentration (lower than 5 ppm), and showed higher gas sensitivity than conventional nanowire gas sensor. The chemical sensors based on ordered PEDOT nanowires presented good reversibility and reproducibility in response. Notably, our work presents an appropriate methodology for fabricating ordered conducting polymer nanomaterial for gas sensor and other applications

  10. Anandamide and analogous endocannabinoids: a lipid self-assembly study

    Energy Technology Data Exchange (ETDEWEB)

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Mulet, Xavier; Drummond, Calum J.


    Anandamide, the endogenous agonist of the cannabinoid receptors, has been widely studied for its interesting biological and medicinal properties and is recognized as a highly significant lipid signaling molecule within the nervous system. Few studies have, however, examined the effect of the physical conformation of anandamide on its function. The study presented herein has focused on characterizing the self-assembly behaviour of anandamide and four other endocannabinoid analogues of anandamide, viz., 2-arachidonyl glycerol, arachidonyl dopamine, 2-arachidonyl glycerol ether (noladin ether), and o-arachidonyl ethanolamide (virodhamine). Molecular modeling of the five endocannabinoid lipids indicates that the highly unsaturated arachidonyl chain has a preference for a U or J shaped conformation. Thermal phase studies of the neat amphiphiles showed that a glass transition was observed for all of the endocannabinoids at {approx} -110 C with the exception of anandamide, with a second glass transition occurring for 2-arachidonyl glycerol, 2-arachidonyl glycerol ether, and virodhamine (-86 C, -95 C, -46 C respectively). Both anandamide and arachidonyl dopamine displayed a crystal-isotropic melting point (-4.8 and -20.4 C respectively), while a liquid crystal-isotropic melting transition was seen for 2-arachidonyl glycerol (-40.7 C) and 2-arachidonyl glycerol ether (-71.2 C). No additional transitions were observed for virodhamine. Small angle X-ray scattering and cross polarized optical microscopy studies as a function of temperature indicated that in the presence of excess water, both 2-arachidonyl glycerol and anandamide form co-existing Q{sub II}{sup G} (gyroid) and Q{sub II}{sup D} (diamond) bicontinuous cubic phases from 0 C to 20 C, which are kinetically stable over a period of weeks but may not represent true thermodynamic equilibrium. Similarly, 2-arachidonyl glycerol ether acquired an inverse hexagonal (HII) phase in excess water from 0 C to 40 C, while

  11. Solvent induced supramolecular anisotropy in molecular gels

    Energy Technology Data Exchange (ETDEWEB)

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


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

  12. Solvent induced supramolecular anisotropy in molecular gels

    International Nuclear Information System (INIS)

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


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

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

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


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

  14. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui


    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  15. Self-assembled albumin nanoparticles for combination therapy in prostate cancer

    Directory of Open Access Journals (Sweden)

    Lian H


    Full Text Available Huibo Lian,1 Jinhui Wu,2 Yiqiao Hu,2 Hongqian Guo1 1Department of Urology, Drum Tower Hospital, Medical School of Nanjing University, 2State Key Laboratory of Pharmaceutical Biotechnology, Medical School of Nanjing University, Nanjing, Jiangsu, People’s Republic of China Abstract: Resistance to regular treatment strategies is a big challenge in the treatment of castration-resistant prostate cancer. Combination of photothermal and photodynamic therapy (PTT/PDT with chemotherapy offers unique advantages over monotherapy alone. However, free drugs, such as photosensitizers and chemotherapeutic agents, lack tumor-targeted accumulation and can be easily eliminated from the body. Moreover, most of the PTT drugs are hydrophobic and their organic solvents have in vivo toxicity, thereby limiting their potential in clinical translation. Herein, simple multifunctional nanoparticles (NPs using IR780 (a near-infrared dye and docetaxel (DTX-loaded nanoplatform based on human serum albumin (HSA (HSA@IR780@DTX was developed for targeted imaging and for PTT/PDT with chemotherapy for the treatment of castration-resistant prostate cancer treatment. In this platform, HSA is a biocompatible nanocarrier that binds to both DTX and IR780. DTX and IR780, as hydrophobic drug, can induce the self-assembly of HSA proteins. Transmission electron microscopic imaging showed that NPs formed by self-assembly are spherical with a smooth surface with a hydrodynamic diameter of 146.5±10.8 nm. The cytotoxicity of HSA@IR780@DTX NPs with or without laser irradiation in prostate cancer cells (22RV1 was determined via CCK-8 assay. The antitumor effect of HSA@IR780@DTX plus laser irradiation was better than either HSA@IR780@DTX without laser exposure or single PTT heating induced by HSA@IR780 NPs under near-infrared laser, suggesting a significant combined effect in comparison to monotherapy. Near-infrared fluorescence imaging showed that HSA@IR780@DTX NPs could preferentially

  16. White-Emissive Self-Assembled Organic Microcrystals. (United States)

    Li, Zhi Zhou; Liang, Feng; Zhuo, Ming Peng; Shi, Ying Li; Wang, Xue Dong; Liao, Liang Sheng


    Organic semiconductor micro-/nanocrystals with regular shapes have been demonstrated for many applications, such as organic field-effect transistors, organic waveguide devices, organic solid-state lasers, and therefore are inherently ideal building blocks for the key circuits in the next generation of miniaturized optoelectronics. In the study, blue-emissive organic molecules of 1,4-bis(2-methylstyryl)benzene (o-MSB) can assemble into rectangular microcrystals at a large scale via the room-temperature solution-exchange method. Because of the Förster resonance energy transfer, the energy of the absorbed photons by the host matrix organic molecules of o-MSB can directly transfer to the dopant organic molecules of tetracene or 1,2:8,9-dibenzopentacene (DBP), which then emit visible photons in different colors from blue to green, and to yellow. More impressively, by modulating the doping molar ratios of DBP to o-MSB, bright white-emissive organic microcrystals with well-preserved rectangular morphology can be successfully achieved with a low doping ratio of 1.5%. These self-assembled organic semiconductor microcrystals with multicolor emissions can be the white-light sources for the integrated optical circuits at micro-/nanoscale. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Fatigue crack propagation in self-assembling nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Tatiana N. Pashirova


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

  20. Self assembly and magnetism of living biological molecules

    Directory of Open Access Journals (Sweden)

    Sutiman Bambang Sumitro


    Full Text Available Biological molecules are essentially nano size structure. All of them are complex structure with specifi c function dedicated to perform normal ordered organizational system. The forces for their work are non-covalent interactions; include spontaneous folding of proteins, DNA, RNA and other bio-macromolecules, ligand-receptors interactions, assembly-disassembly of macromolecule, and transportation or movement of many other nano size sub cellular components. The non-covalent interactions are weak bonds system that is low energetic chemical and physical forces. The energetic forces are mainly atomic forces such as electromagnetic force emergence from electron spinning and transitions at every atom of the complex macromolecular structure. The energy will work along with different level of energy, and atomic positioning within macromolecules. This paper review and discuss the role of magnetism on molecular working process as part of thermodynamically open systems to develop order, which is constantly receiving, transforming and dissipating energy, can and do continually exhibit self assembly and organization, along with the self repairing, and perpetuation.

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

    Shanmugaraju, Sankarasekaran; Mukherjee, Partha Sarathi


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

  2. Self-assembly mechanism for limit-periodic structure (United States)

    Marcoux, Catherine; Socolar, Joshua


    Limit-periodic (LP) structures, which are the union of an infinite set of periodic lattices with ever increasing lattice constants, present a challenge for self-assembly protocols. We consider the possibility of forming a LP phase in a slow quench of a collection of colloidal particles designed to mimic the Taylor-Socolar monotile system. A toy model with discrete tile orientations and mismatch energies yields the LP state through an infinite sequence of phase transitions. Here we present the results of Monte Carlo simulations of slow quenches of identical hard disks with embedded magnetic dipoles, allowing for continuous rotations of the close-packed disks. Surprisingly, an extremely slow quench still results in the spontaneous emergence of the LP state even when the system has a periodic ground state. The series of phase transitions preempts the formation of the periodic phase, leading to low energy states separated from the ground state by insurmountable free energy barriers. Supported by the NSF Research Triangle MRSEC (DMR-1121107).

  3. Copper pattern on self-assembled monolayer through microcontact printing. (United States)

    Liu, Zheng-Chun; Yang, Fei-Peng; Xu, Xiao-Wen; Guo, Can; Liu, Jian-Xin


    Cu pattern on 3-mercaptopropyltrimethoxysilane self-assembled monolayers (MPTS-SAMs) modified glass substrate was achieved by a combination of hydrophobic treatment through microcontact printing, activation and electroless plating. The MPTS-SAMs modified glass substrate was selectively deactivated by microcontact printing 1-hexadecanethiol ethanol solution. X-ray photoelectron spectroscopy (XPS) and water contact angle measurements confirmed that a selectively deactivated pattern was obtained, which was attributed to the formation of disulfide linkages between MPTS and 1-hexadecanethiol. The substrate was selectively activated by dipping into Ag colloids solution and then applied for electroless Cu plating. XPS spectra suggested an ideal catalytic pattern on the substrate due to the deposition of Ag particles on the MPTS and the formation of S-Ag bonds. SEM showed that the microstructure of Cu pattern on MPTS-SAMs was in good agreement with the corresponding silicon master with a resolution of 10 microm. The average electrical resistivity was about 1.8 x 10(-6) omegacm, measured by four-point probe technique. The results suggested that microcontact printing deactivating reagents on SAMs is a potential technique for Cu patterns preparation.

  4. Proton electroinsertion in self-assembled materials for neutralization pseudocapacitors. (United States)

    Facci, Tiago; Gomes, Wellington J A S; Bravin, Bruno; Araújo, Diógenes M; Huguenin, Fritz


    We propose novel pseudocapacitors that can store energy related to the partial entropy change associated with proton concentration variations following neutralization reactions. In this situation, it is possible to obtain electrochemical energy after the complete charge/discharge cycle conducted in electrolytic solutions with different proton concentrations. To this end, we prepared modified electrodes from phosphomolybdic acid (PMA), poly(3,4-ethylenedioxythiophene/poly(styrenesulfonate) (PEDOT-PSS), and polyallylamine (PAH) by the layer-by-layer (LbL) method and investigated their electrochemical behavior, aiming to use them in these neutralization pseudocapacitors. We analyzed the potentiodynamic profile of the current density at several scan rates, to evaluate the reversibility of the proton electroinsertion process, which is crucial to maximum energy storage efficiency. On the basis of the proposed reaction mechanism and by using frequency-domain measurements and models, we determined rate constants at different potentials. Our results demonstrated that the conducting polymer affects the self-assembled matrixes, ensuring that energy storage is high (22.5 kJ mol(-1)). The process involved neutralization of a hydrochloric acid solution from pH = 1 to pH = 6, which corresponds to 40% of the neutralization enthalpy.

  5. Self-assembled patterns from evaporating layered fluids

    International Nuclear Information System (INIS)

    Govor, L V; Parisi, J; Bauer, G H; Reiter, G


    We studied the formation of tree-like patterns of polymer aggregates and rings of nanoparticles during evaporation from a fluid film. We utilize phase separation between two immiscible fluids to generate a double-layer film which dries up in a sequential manner. Both fluid layers may contain a solute, polymer aggregates or nanoparticles. During evaporation of the top layer, instabilities may occur and direct a self-assembly process of the solute which may be further affected by an instability of the bottom layer at a later stage. We present two cases where, after evaporation of the top fluid layer, the solute was adsorbed on the surface of the bottom fluid layer. In comparison to dewetting of a single fluid layer on a solid substrate, the advantage of our double-layer approach lies in the deposition of the solute on the surface of the bottom fluid layer. The relatively high mobility of the solute on such a fluid surface favors the formation of ordered patterns, driven by an instability of the bottom layer.

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

    KAUST Repository

    Al-Rehili, Safa’a


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

  7. Formation and size distribution of self-assembled vesicles. (United States)

    Huang, Changjin; Quinn, David; Sadovsky, Yoel; Suresh, Subra; Hsia, K Jimmy


    When detergents and phospholipid membranes are dispersed in aqueous solutions, they tend to self-assemble into vesicles of various shapes and sizes by virtue of their hydrophobic and hydrophilic segments. A clearer understanding of such vesiculation processes holds promise for better elucidation of human physiology and disease, and paves the way to improved diagnostics, drug development, and drug delivery. Here we present a detailed analysis of the energetics and thermodynamics of vesiculation by recourse to nonlinear elasticity, taking into account large deformation that may arise during the vesiculation process. The effects of membrane size, spontaneous curvature, and membrane stiffness on vesiculation and vesicle size distribution were investigated, and the critical size for vesicle formation was determined and found to compare favorably with available experimental evidence. Our analysis also showed that the critical membrane size for spontaneous vesiculation was correlated with membrane thickness, and further illustrated how the combined effects of membrane thickness and physical properties influenced the size, shape, and distribution of vesicles. These findings shed light on the formation of physiological extracellular vesicles, such as exosomes. The findings also suggest pathways for manipulating the size, shape, distribution, and physical properties of synthetic vesicles, with potential applications in vesicle physiology, the pathobiology of cancer and other diseases, diagnostics using in vivo liquid biopsy, and drug delivery methods.

  8. Self-Assembly of Protein Nanostructures to Enhance Biosensor Sensitivity (United States)

    Olsen, Bradley; Dong, Xuehui; Obermeyer, Allie

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


    Energy Technology Data Exchange (ETDEWEB)

    Monson, Peter [University of Massachusetts; Auerbach, Scott [University of Massachusetts


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

  10. Coding for hydrogel organization through signal guided self-assembly. (United States)

    Yan, Kun; Ding, Fuyuan; Bentley, William E; Deng, Hongbing; Du, Yumin; Payne, Gregory F; Shi, Xiao-Wen


    Complex structured soft matter may have important applications in the field of tissue engineering and biomedicine. However, the discovery of facile methods to exquisitely manipulate the structure of soft matter remains a challenge. In this report, a multilayer hydrogel is fabricated from the stimuli-responsive aminopolysaccharide chitosan by using spatially localized and temporally controlled sequences of electrical signals. By programming the imposed cathodic input signals, chitosan hydrogels with varying layer number and thickness can be fabricated. The inputs of electrical signals induce the formation of hydrogel layers while short interruptions create interfaces between each layer. The thickness of each layer is controlled by the charge transfer (Q = ∫idt) during the individual deposition step and the number of multilayers is controlled by the number of interruptions. Scanning electron micrographs (SEMs) reveal organized fibrous structures within each layer that are demarcated by compact orthogonal interlayer structures. This work demonstrates for the first time that an imposed sequence of electrical inputs can trigger the self-assembly of multilayered hydrogels and thus suggests the broader potential for creating an electrical "code" to generate complex structures in soft matter.

  11. Magnetic Actuation of Self-assembled Bacteria Inspired Nanoswimmers (United States)

    Ali, Jamel; Cheang, U. Kei; Martindale, James D.; Jabbarzadeh, Mehdi; Fu, Henry C.; Kim, Min Jun


    Currently, there is growing interest in developing nanoscale swimmers for biological and biomedical tasks. Of particular interest is the development of soft stimuli-responsive nanorobots to probe cellular and sub-cellular environments. While there have been a few reports of nanoscale robotic swimmers, which have shown potential to be used for these tasks, they often lack multifuctionality. In particular, no man-made soft nanoscale material has been able to match the ability of natural bacterial flagella to undergo rapid and reversible morphological changes in response to multiple forms of environmental stimuli. Towards this end, we report self-assembled stimuli-responsive nanoscale robotic swimmers composed of single or multiple bacterial flagella and attached to magnetic nanoparticles. We visualize the movement of flagella using high resolution fluorescence microscopy while controlling these swimmers via a magnetic control system. Differences in in propulsion before and after the change in flagellar form are observed. Furthermore, we demonstrate the ability to induce flagellar bundling in multiflagellated nanoswimmers. This work was funded by the National Science Foundation (DMR 1712061 and CMMI 1737682 to M.J.K. and DMR 1650970 and CBET 1651031 to H.C.F.), and the Korea Evaluation Institute of Industrial Technology (MOTIE) (NO. 10052980) award to M.J.K.

  12. Bioinspired synthesis and self-assembly of hybrid organic–inorganic nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Honghu [Iowa State Univ., Ames, IA (United States)


    Nature is replete with complex organic–inorganic hierarchical materials of diverse yet specific functions. These materials are intricately designed under physiological conditions through biomineralization and biological self-assembly processes. Tremendous efforts have been devoted to investigating mechanisms of such biomineralization and biological self-assembly processes as well as gaining inspiration to develop biomimetic methods for synthesis and self-assembly of functional nanomaterials. In this work, we focus on the bioinspired synthesis and self-assembly of functional inorganic nanomaterials templated by specialized macromolecules including proteins, DNA and polymers. The in vitro biomineralization process of the magnetite biomineralizing protein Mms6 has been investigated using small-angle X-ray scattering. Templated by Mms6, complex magnetic nanomaterials can be synthesized on surfaces and in the bulk. DNA and synthetic polymers have been exploited to construct macroscopic two- and three-dimensional (2D and 3D) superlattices of gold nanocrystals. Employing X-ray scattering and spectroscopy techniques, the self-assembled structures and the self-assembly mechanisms have been studied, and theoretical models have been developed. Our results show that specialized macromolecules including proteins, DNA and polymers act as effective templates for synthesis and self-assembly of nanomaterials. These bottom-up approaches provide promising routes to fabricate hybrid organic–inorganic nanomaterials with rationally designed hierarchical structures, targeting specific functions.

  13. Quantitative computational models of molecular self-assembly in systems biology (United States)

    Thomas, Marcus; Schwartz, Russell


    Molecular self-assembly is the dominant form of chemical reaction in living systems, yet efforts at systems biology modeling are only beginning to appreciate the need for and challenges to accurate quantitative modeling of self-assembly. Self-assembly reactions are essential to nearly every important process in cell and molecular biology and handling them is thus a necessary step in building comprehensive models of complex cellular systems. They present exceptional challenges, however, to standard methods for simulating complex systems. While the general systems biology world is just beginning to deal with these challenges, there is an extensive literature dealing with them for more specialized self-assembly modeling. This review will examine the challenges of self-assembly modeling, nascent efforts to deal with these challenges in the systems modeling community, and some of the solutions offered in prior work on self-assembly specifically. The review concludes with some consideration of the likely role of self-assembly in the future of complex biological system models more generally.

  14. Quantitative computational models of molecular self-assembly in systems biology. (United States)

    Thomas, Marcus; Schwartz, Russell


    Molecular self-assembly is the dominant form of chemical reaction in living systems, yet efforts at systems biology modeling are only beginning to appreciate the need for and challenges to accurate quantitative modeling of self-assembly. Self-assembly reactions are essential to nearly every important process in cell and molecular biology and handling them is thus a necessary step in building comprehensive models of complex cellular systems. They present exceptional challenges, however, to standard methods for simulating complex systems. While the general systems biology world is just beginning to deal with these challenges, there is an extensive literature dealing with them for more specialized self-assembly modeling. This review will examine the challenges of self-assembly modeling, nascent efforts to deal with these challenges in the systems modeling community, and some of the solutions offered in prior work on self-assembly specifically. The review concludes with some consideration of the likely role of self-assembly in the future of complex biological system models more generally.

  15. Isoporous PS-b-PEO ultrafiltration membranes via self-assembly and water-induced phase separation

    KAUST Repository

    Karunakaran, Madhavan


    A simple and efficient approach towards the fabrication of a skinned membrane with highly ordered pores in the nanometer range is presented here. We successfully combined the self-assembly of PS-b-PEO block copolymer and water induced phase separation for the preparation of isoporous PS-b-PEO block copolymer membranes. We produced for the first time asymmetric isoporous PS-b-PEO membranes with a 100nm thin isoporous separating layer using water at room temperature as coagulant. This was possible by careful selection of the block lengths and the solvent system. FESEM, AFM and TEM measurements were employed to characterize the nanopores of membranes. The pure water fluxes were measured and the flux of membrane was exceptionally high (around 800Lm-2h-1bar-1). Protein rejection measurements were carried out for this membrane and the membrane had a retention of about 67% of BSA and 99% of γ-globulin. © 2013 Elsevier B.V.

  16. Directed Self-Assembly of Asymmetric Block Copolymers in Thin Films Driven by Uniaxially Aligned Topographic Patterns. (United States)

    Lee, Dong-Eun; Ryu, Jaegeon; Hong, Dongki; Park, Soojin; Lee, Dong Hyun; Russell, Thomas P


    We present a simple, versatile approach to generate highly ordered nanostructures of block copolymers (BCPs) using rubbed surfaces. A block of poly(tetrafluoroethylene) (PTFE) was dragged across a flat substrate surface above the melting point of PTFE transferring a highly aligned PTFE topographic pattern to the substrate. Si wafer, glass, and polyimide films were used as substrates. Thin films of cylinder-forming asymmetric polystyrene-block-poly(2-vinylpyridine) copolymers (S2VPs) were solvent annealed on the surfaces having the transferred surface pattern to induce their directed self-assembly. Cylinders of P2VP oriented normal to the surface are markedly aligned along the rubbing direction and used as templates to generate extremely uniform arrays of various metallic nanoparticles of gold, silver, and platinum over a large area.

  17. Docking System Design and Self-Assembly Control of Distributed Swarm Flying Robots

    Directory of Open Access Journals (Sweden)

    Hongxing Wei


    Full Text Available This paper presents a novel docking system design and the distributed self-assembly control strategy for a Distributed Swarm Flying Robot (DSFR. The DSFR is a swarm robot comprising many identical robot modules that are able to move on the ground, dock with each other and fly coordinately once self-assembled into a robotic structure. A generalized adjacency matrix method is proposed to describe the configurations of robotic structures. Based on the docking system and the adjacency matrix, experiments are performed to demonstrate and verify the self-assembly control strategy.

  18. Polymersomes with asymmetric membranes and self-assembled superstructures using pentablock quintopolymers resolved by electron tomography

    KAUST Repository

    Haataja, J. S.


    Polystyrene-block-poly(1,4-isoprene)-block-poly(dimethyl siloxane)-block-poly(tert-butyl methacrylate)-block-poly(2-vinyl pyridine), PS-b-PI-b-PDMS-b-PtBMA-b-P2VP, self-assembles in acetone into polymersomes with asymmetric (directional) PI-b-PDMS membranes. The polymersomes, in turn, self-assemble into superstructures. Analogically to supravesicular structures at a smaller length scale, we refer to them as suprapolymersome structures. Electron tomograms are shown to be invaluable in the structural assessment of such complex self-assemblies.

  19. Monitoring the hydration of DNA self-assembled monolayers using an extensional nanomechanical resonator

    DEFF Research Database (Denmark)

    Cagliani, Alberto; Kosaka, Priscila; Tamayo, Javier


    We have fabricated an ultrasensitive nanomechanical resonator based on the extensional vibration mode to weigh the adsorbed water on self-assembled monolayers of DNA as a function of the relative humidity. The water adsorption isotherms provide the number of adsorbed water molecules per nucleotide...... for monolayers of single stranded (ss) DNA and after hybridization with the complementary DNA strand. Our results differ from previous data obtained with bulk samples, showing the genuine behavior of these self-assembled monolayers. The hybridization cannot be inferred from the water adsorption isotherms due...... on the interaction between water and self-assembled monolayers of nucleic acids....

  20. DNA–melamine hybrid molecules: from self-assembly to nanostructures

    Directory of Open Access Journals (Sweden)

    Rina Kumari


    Full Text Available Single-stranded DNA–melamine hybrid molecular building blocks were synthesized using a phosphoramidation cross-coupling reaction with a zero linker approach. The self-assembly of the DNA–organic hybrid molecules was achieved by DNA hybridization. Following self-assembly, two distinct types of nanostructures in the form of linear chains and network arrays were observed. The morphology of the self-assembled nanostructures was found to depend on the number of DNA strands that were attached to a single melamine molecule.

  1. Tuning the size of a redox-active tetrathiafulvalene-based self-assembled ring

    Directory of Open Access Journals (Sweden)

    Sébastien Bivaud


    Full Text Available The synthesis of a new Pd coordination-driven self-assembled ring M6L3 constructed from a concave tetrapyridyl π-extended tetrathiafulvalene ligand (exTTF is described. The same ligand is also able to self-assemble in a M4L2 mode as previously described. Herein, we demonstrate that the bulkiness of the ancillary groups in the Pd complex allows for modulating the size and the shape of the resulting discrete self-assembly, which therefore incorporate two (M4L2 or three (M6L3 electroactive exTTF sidewalls.

  2. Self-assembly and reactive molding techniques for controlling the interface and dispersion of the particulate phase in nanocomposites (United States)

    Pranger, Lawrence A.

    This research explored the processing and properties of PNCs using a polyfurfural alcohol (PFA) matrix. The precursor for PFA, furfuryl alcohol (FA) is sourced from feedstocks rich in hemicellulose, such as corn cobs, oat hulls and wood. To exploit FA as a polymerizable solvent, cellulose whiskers (CW) and montmorillonite clay (MMT) were used as the nanoparticle phase. Results from PNC processing show that CW and MMT can be dispersed in the PFA matrix by means of insitu polymerization, without the use of surfactants or dilution in solvents. Both CW and MMT nanoparticles catalyze the polymerization of furfuryl alcohol (FA). Moreover, the insitu intercalative polymerization of FA in the interlayer galleries of MMT leads to the complete exfoliation of the MMT in the PFA matrix. CW and MMT both function as effective matrix modifiers, increasing the thermal stability of PFA nanocomposites compared to pure PFA polymer. The increased thermal stability is seen as significant increases in the onset of degradation and in residual weight at high temperature. This research also explored the surface functionalization of Cu, Ni and Pt substrates by self-assembly of a range of difunctional linker molecules. Characterization by XPS and PM-IRRAS indicate that diisocyanides and dicarboxylic acids both form chemically "sticky" surfaces after self-assembly on Cu and Ni. Sticky surfaces may provide a means of increasing nanoparticle dispersion in metal nanocluster filled PNCs, by increasing their interaction with the matrix polymer. Another potential application for sticky surfaces on Cu is in the ongoing miniaturization of circuit boards. The functionalization of Cu bond pad substrates with linker molecules may provide an alternate means of bonding components to their bond pads, with higher placement accuracy compared to solder bumps.

  3. Self-assembled electrical materials from contorted aromatics (United States)

    Xiao, Shengxiong

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

  4. Self-assembling protein nanoparticles in the design of vaccines

    Directory of Open Access Journals (Sweden)

    Jacinto López-Sagaseta


    Full Text Available For over 100 years, vaccines have been one of the most effective medical interventions for reducing infectious disease, and are estimated to save millions of lives globally each year. Nevertheless, many diseases are not yet preventable by vaccination. This large unmet medical need demands further research and the development of novel vaccines with high efficacy and safety. Compared to the 19th and early 20th century vaccines that were made of killed, inactivated, or live-attenuated pathogens, modern vaccines containing isolated, highly purified antigenic protein subunits are safer but tend to induce lower levels of protective immunity. One strategy to overcome the latter is to design antigen nanoparticles: assemblies of polypeptides that present multiple copies of subunit antigens in well-ordered arrays with defined orientations that can potentially mimic the repetitiveness, geometry, size, and shape of the natural host-pathogen surface interactions. Such nanoparticles offer a collective strength of multiple binding sites (avidity and can provide improved antigen stability and immunogenicity. Several exciting advances have emerged lately, including preclinical evidence that this strategy may be applicable for the development of innovative new vaccines, for example, protecting against influenza, human immunodeficiency virus, and respiratory syncytial virus. Here, we provide a concise review of a critical selection of data that demonstrate the potential of this field. In addition, we highlight how the use of self-assembling protein nanoparticles can be effectively combined with the emerging discipline of structural vaccinology for maximum impact in the rational design of vaccine antigens.

  5. Spin Properties of Transition-Metallorganic Self-Assembled Molecules

    International Nuclear Information System (INIS)

    Yu, Zhi Gang


    This report summarizes SRI's accomplishments on the project, 'Spin Properties of Transition-Metallorganic Self-Assembled Molecules' funded by the Office of Basic Energy Sciences, US Department of Energy. We have successfully carried out all tasks identified in our proposal and gained significant knowledge and understanding of spin-polarized electronic structure, spin relaxation, and spin-dependent transport in transition-metallorganic molecules and enhohedral fullerenes. These molecules contain integrated spin and charge components and will enable us to achieve sophisticated functions in spintronics and quantum computing at molecular level with simple circuitry and easy fabrication. We have developed microscopic theories that describe the underlying mechanisms of spin-dependent porcesses and constructed quantitative modeling tools that compute several important spin properties. These results represent the basic principles governing the spin-dependent behaviors in nanostructures containing such molecules. Based on these results we have shown that novel device functions, such as electrically controlled g-factor and noninvasive electrical detection of spin dynamics, can be achieved in these nanostructures. Some of our results have been published in peer-reviewed journals and presented at professional conferences. In addition, we have established a close collaboration with experimentalists at Oxford University, UK (Dr. J. Morton and Prof. G. Briggs), Princeton University (Dr. A. Tyryshkin and Prof. S. Lyon), University of Delaware (Prof. E. Nowak), and University of California (Profs. R. Kawakami and J. Shi), who have been studying related systems and supplying us with new experimental data. We have provided our understanding and physical insights to the experimentalists and helped analyze their experimental measurements. The collaboration with experimentalists has also broadened our research scope and helped us focus on the most relevant issues concerning these

  6. Spin Properties of Transition-Metallorganic Self-Assembled Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Zhi Gang Yu


    This report summarizes SRI's accomplishments on the project, 'Spin Properties of Transition-Metallorganic Self-Assembled Molecules' funded by the Office of Basic Energy Sciences, US Department of Energy. We have successfully carried out all tasks identified in our proposal and gained significant knowledge and understanding of spin-polarized electronic structure, spin relaxation, and spin-dependent transport in transition-metallorganic molecules and enhohedral fullerenes. These molecules contain integrated spin and charge components and will enable us to achieve sophisticated functions in spintronics and quantum computing at molecular level with simple circuitry and easy fabrication. We have developed microscopic theories that describe the underlying mechanisms of spin-dependent porcesses and constructed quantitative modeling tools that compute several important spin properties. These results represent the basic principles governing the spin-dependent behaviors in nanostructures containing such molecules. Based on these results we have shown that novel device functions, such as electrically controlled g-factor and noninvasive electrical detection of spin dynamics, can be achieved in these nanostructures. Some of our results have been published in peer-reviewed journals and presented at professional conferences. In addition, we have established a close collaboration with experimentalists at Oxford University, UK (Dr. J. Morton and Prof. G. Briggs), Princeton University (Dr. A. Tyryshkin and Prof. S. Lyon), University of Delaware (Prof. E. Nowak), and University of California (Profs. R. Kawakami and J. Shi), who have been studying related systems and supplying us with new experimental data. We have provided our understanding and physical insights to the experimentalists and helped analyze their experimental measurements. The collaboration with experimentalists has also broadened our research scope and helped us focus on the most relevant issues

  7. Surface Mediated Self-Assembly of Amyloid Peptides (United States)

    Fakhraai, Zahra


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

  8. Engineering Fluorogen Activating Proteins into Self-Assembling Materials (United States)

    Saunders, Matthew J.; Liu, Wen; Szent-Gyorgyi, Christopher; Wen, Yi; Drennen, Zachary; Waggoner, Alan S.; Meng, Wilson S.


    We present herein characteristics of a conjugate in which dL5, a fluorogen-activating protein (FAP) and AEAEAKAK, an amphiphilic peptide are combined to form a solid-phase fluorescence-detection platform. The FAP dL5 is a covalently linked dimer of two identical light chain variable fragments which activates the fluorescence of the fluorogen malachite green (MG). The amphiphilic peptide of sequence AEAEAKAK is a building block of stimuli-responsive materials that undergoes sol-gel phase transition at high ionic strengths. We hypothesize that the novel bi-functional protein containing both the FAP and the amphiphile, termed dL5_EAK, co-assembles with the self-assembling peptide [AEAEAKAK]2 (EAK16-II) to form an insoluble membrane composite whereby the fluorescence enhancement function of the FAP domain remains intact. Denaturing polyacrylamide electrophoresis indicated that greater than 78% of dL5_EAK incorporates into the EAK16-II membrane. Conversely, less than 32% of dL5 without the EAK sequence associates with the insoluble fraction of EAK16-II in buffers. Membranes containing dL5_EAK and EAK16-II exhibited at least 4-fold higher fluorescence intensity compared to mixtures containing dL5 and EAK16-II. Scanning electron microscopy revealed the presence of particulates, presumably FAPs, scattering on the membrane fibrils. The evidence suggests a system of materials that can be developed into in situ-forming local sensors by immobilizing dL5 into coacervate, on which MG can be detected. It is envisioned that dL5 membranes can be established in diseased locales to monitor infiltration and migration of inflammatory cells marked with antibodies conjugated to MG. PMID:23573960

  9. Evaporation, diffusion and self-assembly at drying interfaces. (United States)

    Roger, K; Sparr, E; Wennerström, H


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

  10. Surface Decoration on Polymeric Gate Dielectrics for Flexible Organic Field-Effect Transistors via Hydroxylation and Subsequent Monolayer Self-Assembly. (United States)

    Yan, Yan; Huang, Long-Biao; Zhou, Ye; Han, Su-Ting; Zhou, Li; Sun, Qijun; Zhuang, Jiaqing; Peng, Haiyan; Yan, He; Roy, V A L


    A simple photochemical reaction based on confined photocatalytic oxidation (CPO) treatment and hydrolysis was employed to efficiently convert C-H bonds into C-OH groups on polymeric material surfaces, followed by investigation of monolayer self-assembly decoration on polymeric dielectrics via chemical bonding for the organic field-effect transistors (OFETs) applications. This method is a low temperature process and has negligible etching effect on polymeric dielectric layers. Various types of self-assembled monolayers have been tested and successfully attached onto the hydroxylated polymeric dielectric surfaces through chemical bonding, ensuring the stability of decorated functional films during the subsequent device fabrication consisting of solution processing of the polymer active layer. With the surface decoration of functional groups, both n-type and p-type polymers exhibit enhanced carrier mobilities in the unipolar OFETs. In addition, enhanced and balanced mobilities are obtained in the ambipolar OFETs with the blend of polymer semiconductors. The anchored self-assembled monolayers on the dielectric surfaces dramatically preclude the solvent effect, thus enabling an improvement of carrier mobility up to 2 orders of magnitude. Our study opens a way of targeted modifications of polymeric surfaces and related applications in organic electronics.

  11. Nano-dot formation using self-assembled 3-mercaptopropionic acid thin films prepared by facile atmospheric-vapor-adsorption method on Au(1 1 1) (United States)

    Nakamura, Tohru; Kimura, Ryota; Sakai, Hideki; Abe, Masahiko; Kondoh, Hiroshi; Ohta, Toshiaki; Matsumoto, Mutsuyoshi


    Nanometer scale structures of self-assembled films consisting of 3-mercaptopropionic acid (MPA) were formed by using electric stimuli between scanning tunneling microscope (STM) Au tips and gold surfaces. The obtained structures were compared with those using bare gold surfaces and hexanethiol films on Au(1 1 1) under the same conditions. X-ray photoelectron spectroscopy measurements revealed that self-assembled ultrathin films of the corresponding thiol molecules were fabricated on Au(1 1 1) by a facile atmospheric-vapor-adsorption (AVA) method without solvent. Comparison of nano-structure formation suggested that the self-assembled thin films of 3-mercatopropionic acid molecules gave nano-dots below the height of voltage pulses where gold atom emission from Au tips and surface evaporation of Au(1 1 1) take place. It was found that 3-mercaptopropionic acid films easily produced much better nano-dots on Au(1 1 1) than hexanethiol films probably due to the formation of hydrogen bonding networks and/or the reactions of 3-mercaptopropionic acid when electric pulses were applied to the films.

  12. Block copolymer self-assembly fundamentals and applications in formulation of nano-structured fluids (United States)

    Sarkar, Biswajit

    Dispersions of nanoparticles in polymer matrices form hybrid materials that can exhibit superior structural and functional properties and find applications in e.g. thermo-plastics, electronics, polymer electrolytes, catalysis, paint formulations, and drug delivery. Control over the particle location and orientation in the polymeric matrices are essential in order to realize the enhanced mechanical, electrical, and optical properties of the nanohybrids. Block copolymers, composed of two or more different monomers, are promising for controlling particle location and orientation because of their ability to organize into ordered nanostructures. Fundamental questions pertaining to nanoparticle-polymer interfacial interactions remain open and formulate the objectives of our investigation. Particle-polymer enthalpic and entropic interactions control the nanoparticle dispersion in polymer matrices. Synthetic chemical methods for modifying the particle surface in order to control polymer-particle interactions are involved and large scale production is not possible. In the current approach, a physical method is employed to control polymer-particle interactions. The use of commercially available solvents is found to be effective in modifying particle-polymer interfacial interactions. The approach is applicable to a wide range of particle-polymer systems and can thereby enable large scale processing of polymer nanohybrids. The systems of silica nanoparticles dispersed in long-range or short-range self-assembled structures of aqueous poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers (Pluronics) is considered here. The effect of various parameters such as the presence of organic solvents, pH, and particle size on the block copolymer organization and the ensuing particle-polymer interactions are investigated. Favorable surface interactions between the deprotonated silica nanoparticle and PEO-rich domain facilitate particle

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

    DEFF Research Database (Denmark)

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


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

  14. Self-assembling peptide-based building blocks in medical applications

    Energy Technology Data Exchange (ETDEWEB)

    Acar, Handan; Srivastava, Samanvaya; Chung, Eun Ji; Schnorenberg, Mathew R.; Barrett, John C.; LaBelle, James L.; Tirrell, Matthew


    Peptides and peptide-conjugates, comprising natural and synthetic building blocks, are an increasingly popular class of biomaterials. Self-assembled nanostructures based on peptides and peptide-conjugates offer advantages such as precise selectivity and multifunctionality that can address challenges and limitations in the clinic. In this review article, we discuss recent developments in the design and self-assembly of various nanomaterials based on peptides and peptide-conjugates for medical applications, and categorize them into two themes based on the driving forces of molecular self-assembly. First, we present the self-assembled nanostructures driven by the supramolecular interactions between the peptides, with or without the presence of conjugates. The studies where nanoassembly is driven by the interactions between the conjugates of peptide-conjugates are then presented. Particular emphasis is given to in vivo studies focusing on therapeutics, diagnostics, immune modulation and regenerative medicine. Finally, challenges and future perspectives are presented.

  15. Logical NAND and NOR Operations Using Algorithmic Self-assembly of DNA Molecules (United States)

    Wang, Yanfeng; Cui, Guangzhao; Zhang, Xuncai; Zheng, Yan

    DNA self-assembly is the most advanced and versatile system that has been experimentally demonstrated for programmable construction of patterned systems on the molecular scale. It has been demonstrated that the simple binary arithmetic and logical operations can be computed by the process of self assembly of DNA tiles. Here we report a one-dimensional algorithmic self-assembly of DNA triple-crossover molecules that can be used to execute five steps of a logical NAND and NOR operations on a string of binary bits. To achieve this, abstract tiles were translated into DNA tiles based on triple-crossover motifs. Serving as input for the computation, long single stranded DNA molecules were used to nucleate growth of tiles into algorithmic crystals. Our method shows that engineered DNA self-assembly can be treated as a bottom-up design techniques, and can be capable of designing DNA computer organization and architecture.

  16. Self-assembly and flux closure studies of magnetic nanoparticle rings

    DEFF Research Database (Denmark)

    Wei, Alexander; Kasama, Takeshi; Dunin-Borkowski, Rafal E.


    Thermoremanent magnetic nanoparticles (MNPs) can self-assemble into rings through dipolar interactions, when dispersed under appropriate conditions. Analysis of individual MNP rings and clusters by off-axis electron holography reveals bistable flux closure (FC) states at ambient temperatures...

  17. Integrating DNA strand-displacement circuitry with DNA tile self-assembly (United States)

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


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

  18. Heterogeneous electron transfer kinetics and electrocatalytic behaviour of mixed self-assembled ferrocenes and SWCNT layers

    CSIR Research Space (South Africa)

    Nkosi, D


    Full Text Available The electron transfer dynamics and electrocatalytic behaviour of ferrocene-terminated self-assembled monolayers (SAMs), co-adsorbed with single-walled carbon nanotubes (SWCNTs) on a gold electrode, have been interrogated for the first time...

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

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


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

  20. Ionic Self Assembled Monolayer (ISAM) Processes for Electronic Materials and Devices

    National Research Council Canada - National Science Library

    Miller, Mike


    .... Ionic self-assembled monolayer (ISAM) techniques for the fabrication of multilayer nanoparticle/polymer structures offer low manufacturing costs, advantages of processing at ambient temperature and pressure, ability to produce devices...

  1. Self-assembled peptide-based nanostructures: Smart nanomaterials toward targeted drug delivery. (United States)

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


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

  2. Cytoskeletal motor-driven active self-assembly in in vitro systems. (United States)

    Lam, A T; VanDelinder, V; Kabir, A M R; Hess, H; Bachand, G D; Kakugo, A


    Molecular motor-driven self-assembly has been an active area of soft matter research for the past decade. Because molecular motors transform chemical energy into mechanical work, systems which employ molecular motors to drive self-assembly processes are able to overcome kinetic and thermodynamic limits on assembly time, size, complexity, and structure. Here, we review the progress in elucidating and demonstrating the rules and capabilities of motor-driven active self-assembly. We focus on the types of structures created and the degree of control realized over these structures, and discuss the next steps necessary to achieve the full potential of this assembly mode which complements robotic manipulation and passive self-assembly.

  3. Self Assembly of Ionic Liquids at the Air/Water Interface

    Czech Academy of Sciences Publication Activity Database

    Minofar, Babak


    Roč. 3, aug (2015), s. 27-40 ISSN 2245-4551 Institutional support: RVO:67179843 Keywords : Ionic liquids * air/ water interface * self assembly * ion- water interaction * ion-ion interaction Subject RIV: CE - Biochemistry

  4. Self assembly of rectangular shapes on concentration programming and probabilistic tile assembly models. (United States)

    Kundeti, Vamsi; Rajasekaran, Sanguthevar


    Efficient tile sets for self assembling rectilinear shapes is of critical importance in algorithmic self assembly. A lower bound on the tile complexity of any deterministic self assembly system for an n × n square is [Formula: see text] (inferred from the Kolmogrov complexity). Deterministic self assembly systems with an optimal tile complexity have been designed for squares and related shapes in the past. However designing [Formula: see text] unique tiles specific to a shape is still an intensive task in the laboratory. On the other hand copies of a tile can be made rapidly using PCR (polymerase chain reaction) experiments. This led to the study of self assembly on tile concentration programming models. We present two major results in this paper on the concentration programming model. First we show how to self assemble rectangles with a fixed aspect ratio ( α:β ), with high probability, using Θ( α + β ) tiles. This result is much stronger than the existing results by Kao et al. (Randomized self-assembly for approximate shapes, LNCS, vol 5125. Springer, Heidelberg, 2008) and Doty (Randomized self-assembly for exact shapes. In: proceedings of the 50th annual IEEE symposium on foundations of computer science (FOCS), IEEE, Atlanta. pp 85-94, 2009)-which can only self assembly squares and rely on tiles which perform binary arithmetic. On the other hand, our result is based on a technique called staircase sampling . This technique eliminates the need for sub-tiles which perform binary arithmetic, reduces the constant in the asymptotic bound, and eliminates the need for approximate frames (Kao et al. Randomized self-assembly for approximate shapes, LNCS, vol 5125. Springer, Heidelberg, 2008). Our second result applies staircase sampling on the equimolar concentration programming model (The tile complexity of linear assemblies. In: proceedings of the 36th international colloquium automata, languages and programming: Part I on ICALP '09, Springer-Verlag, pp 235

  5. Synthesis, characterization and self-assembly of Co complexes ...

    Indian Academy of Sciences (India)

    dual electron density as guest atoms were unsuccessful, although atoms of solvent molecule (DMF) were ob- served but could not be modelled satisfactorily during the structure refinement. Therefore data were corrected for disordered electron density by using the SQUEEZE procedure implemented in PLATON.21 A total ...

  6. Length distribution of stiff, self-assembled polymers at thermal equilibrium. (United States)

    Lee, Chiu Fan


    We investigate the length distribution of self-assembled, long and stiff polymers at thermal equilibrium. Our analysis is based on calculating the partition functions of stiff polymers of variable lengths in the elastic regime. Our conclusion is that the length distribution of this self-assembled system follows closely the exponential distribution, except at the short length limit. We then discuss the implications of our results on the experimentally observed length distributions in amyloid fibrils.

  7. Hyper-Assembly of Self-Assembled Glycoclusters Mediated by Specific Carbohydrate-Carbohydrate Interactions. (United States)

    Yan, Gengwei; Yamaguchi, Takumi; Suzuki, Tatsuya; Yanaka, Saeko; Sato, Sota; Fujita, Makoto; Kato, Koichi


    Hybridization of a self-assembled, spherical complex with oligosaccharides containing Lewis X, a functional trisaccharide displayed on various cell surfaces, yielded well-defined glycoclusters. The self-assembled glycoclusters exhibited homophilic hyper-assembly in aqueous solution in a Ca 2+ -dependent manner through specific carbohydrate-carbohydrate interactions, offering a structural scaffold for functional biomimetic systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A Complete Physical Germanium-on-Silicon Quantum Dot Self-Assembly Process


    Alkhatib, Amro; Nayfeh, Ammar


    Achieving quantum dot self-assembly at precise pre-defined locations is of vital interest. In this work, a novel physical method for producing germanium quantum dots on silicon using nanoindentation to pre-define nucleation sites is described. Self-assembly of ordered ~10?nm height germanium quantum dot arrays on silicon substrates is achieved. Due to the inherent simplicity and elegance of the proposed method, the results describe an attractive technique to manufacture semiconductor quantum ...

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

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


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

  10. A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands

    Directory of Open Access Journals (Sweden)

    Sébastien Goeb


    Full Text Available Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf(OTf2 (M = Pd or Pt; dppf = 1,1′-bis(diphenylphosphinoferrocene; OTf = trifluoromethane-sulfonate complexes. Both species are fully characterized and are constituted of 12 electro-active subunits that can be reversibly oxidized.

  11. pH-responsive self-assembly of polysaccharide through a rugged energy landscape


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


    Self-assembling polysaccharides can form complex networks with structures and properties highly dependent on the sequence of triggering cues. Controlling the emergence of such networks provides an opportunity to create soft matter with unique features; however, it requires a detailed understanding of the subtle balance between the attractive and repulsive forces that drives the stimuli-induced self-assembly. Here we employ all-atom molecular dynamics simulations on the order of 100 ns to stud...

  12. Ultrashort Cationic Naphthalene-Derived Self-Assembled Peptides as Antimicrobial Nanomaterials


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


    Self-assembling dipeptides conjugated to naphthalene show considerable promise as nanomaterial structures, biomaterials, and drug delivery devices. Biomaterial infections are responsible for high rates of patient mortality and morbidity. The presence of biofilm bacteria, which thrive on implant surfaces, are a huge burden on healthcare budgets, as they are highly resistant to current therapeutic strategies. Ultrashort cationic self-assembled peptides represent a highly innovative and cost-eff...

  13. Structural Transitions of Solvent-Free Oligomer-Grafted Nanoparticles

    KAUST Repository

    Chremos, Alexandros


    Novel structural transitions of solvent-free oligomer-grafted nanoparticles are investigated by using molecular dynamics simulations of a coarse-grained bead-spring model. Variations in core size and grafting density lead to self-assembly of the nanoparticles into a variety of distinct structures. At the boundaries between different structures, the nanoparticle systems undergo thermoreversible transitions. This structural behavior, which has not been previously reported, deviates significantly from that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions. © 2011 American Physical Society.

  14. Self-assembly of microcapsules via colloidal bond hybridization and anisotropy (United States)

    Evers, Chris H. J.; Luiken, Jurriaan A.; Bolhuis, Peter G.; Kegel, Willem K.


    Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable owing to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and the colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy and deformability have not yet been realized. Here we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogously to the simplest chemical bond—in which two isotropic orbitals hybridize into the molecular orbital of H2—these flexible groups redistribute on binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, whereas anisotropic snowman-shaped particles self-assemble into hollow monolayer microcapsules. A modest change in the building blocks thus results in much greater complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into markedly more complex structures than do similar particles that are isotropic or non-deformable.

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

    Directory of Open Access Journals (Sweden)

    Domenico Lombardo


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

  16. Self-assembled peptide nanomaterials for biomedical applications: promises and pitfalls

    Directory of Open Access Journals (Sweden)

    Sun L


    Full Text Available Linlin Sun,1,2 Chunli Zheng,3 Thomas J Webster1,2,4 1Wenzhou Institute of Biomaterials and Engineering, Wenzhou Medical University, Wenzhou, Zhejiang, People’s Republic of China; 2Department of Chemical Engineering, Northeastern University, Boston, MA, USA; 3Pharmaceutical Research Institute, China Pharmaceutical University, Nanjing, People’s Republic of China; 4Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, Saudi Arabia Abstract: Over the last several decades, a great number of advances have been made in the area of self-assembled supramolecules for regenerative medicine. Such advances have involved the design, preparation, and characterization of brand new self-assembled peptide nanomaterials for a variety of applications. Among all biomolecules considered for self-assembly applications, peptides have attracted a great deal of attention as building blocks for bottom-up fabrication, due to their versatility, ease of manufacturing, low costs, tunable structures, and versatile properties. Herein, some of the more exciting new designs of self-assembled peptides and their associated unique features are reviewed and several promising applications of how self-assembled peptides are advancing drug delivery, tissue engineering, antibacterial therapy, and biosensor device applications are highlighted. Keywords: self-assembly, peptides, biomedical applications, drug delivery, antibacterial therapy, biosensor devices

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

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


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

  18. Self assembling bioactive materials for cell adhesion in tissue repair (United States)

    Hwang, Julia J.

    This work involved the study of biodegradable and biocompatible materials that have the potential to modify tissue engineering scaffolds through self assembly, generating multiple layers that deliver bioactivity. Diblock biomaterials containing cholesteryl moieties and oligomers of lactic acid units were found to form single crystals when precipitated from hot ethanol and smectic liquid crystalline phases when cast as a film. Cell culture experiments on these films with 3T3 and 3T6 fibroblasts indicated that these ordered materials form surfaces with specific chemistries that favored cell adhesion, spreading, and proliferation suggesting the potential of mediating human tissue repair. The author believes the cholesteryl moieties found on the surface play a key role in determining cell behavior. Cholesteryl-(L-lactic acid) diblock molecules were then functionalized with moieties including vitamin Bx, cholesterol, and the anti-inflammatory drug indomethacin. An unstable activated ester between indomethacin and the diblock molecule resulted in the release of indomethacin into the culture medium which inhibited the proliferation of 3T3 fibroblasts. Finally, a series of molecules were designed to incorporate dendrons based on amino acids at the termini of the diblock structures. It was determined that lysine, a basic amino acid, covalently coupled to cholesteryl-(L-lactic acid) can promote cell adhesion and spreading while negatively charged and zwitterionic 2nd generation dendrons based on aspartic acid do not. Incorporation of the well known arginine-glycine-aspartic acid (RGD) sequence, which is found in many adhesive proteins, to the dendrons imparted integrin-mediated cell adhesion as evidenced by the formation of stress fibers. We also explored the capacity of integrin receptors to bind to ligands that are not the linear form of RGD, but have R, G, and D spatially positioned to mimic the linear RGD environments. For this purpose, the arms of the 2 nd generation

  19. Double smectic self-assembly in block copolypeptide complexes

    KAUST Repository

    Haataja, Johannes S.


    We show double smectic-like self-assemblies in the solid state involving alternating layers of different polypeptide α-helices. We employed rod-coil poly(γ-benzyl l-glutamate)-block-poly(l-lysine) (PBLG-b-PLL) as the polymeric scaffold, where the PLL amino residues were ionically complexed to di-n-butyl phosphate (diC4P), di(2-ethylhexyl) phosphate (diC2/6P), di(2-octyldodecyl) phosphate (diC8/12P), or di-n-dodecyl phosphate (diC12P), forming PBLG-b-PLL(diC4P), PBLG-b-PLL(diC2/6P), PBLG-b-PLL(diC8/12P), and PBLG-b-PLL(diC12P) complexes, respectively. The complexes contain PBLG α-helices of fixed diameter and PLL-surfactant complexes adopting either α-helices of tunable diameters or β-sheets. For PBLG-b-PLL(diC4P), that is, using a surfactant with short n-butyl tails, both blocks were α-helical, of roughly equal diameter and thus with minor packing frustrations, leading to alternating PBLG and PLL(diC4P) smectic layers of approximately perpendicular alignment of both types of α-helices. Surfactants with longer and branched alkyl tails lead to an increased diameter of the PLL-surfactant α-helices. Smectic alternating PBLG and PLL(diC2/6P) layers involve larger packing frustration, which leads to poor overall order and suggests an arrangement of tilted PBLG α-helices. In PBLG-b-PLL(diC8/12P), the PLL(diC8/12P) α-helices are even larger and the overall structure is poor. Using a surfactant with two linear n-dodecyl tails leads to well-ordered β-sheet domains of PLL(diC12P), consisting of alternating PLL and alkyl chain layers. This dominates the whole assembly, and at the block copolypeptide length scale, the PBLG α-helices do not show internal order and have poor organization. Packing frustration becomes an important aspect to design block copolypeptide assemblies, even if frustration could be relieved by conformational imperfections. The results suggest pathways to control hierarchical liquid-crystalline assemblies by competing interactions and by

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

    NARCIS (Netherlands)

    Newton, A.C.


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

  1. Structural properties of self-assembled polymeric micelles

    DEFF Research Database (Denmark)

    Mortensen, K.


    At present, the thermodynamic understanding of complex copolymer systems is undergoing important developments. Block copolymers aggregate in selective solvents into micelles of various form and size depending on molecular architecture and interaction parameters. The micelles constitute the basis...... for a variety of novel mesophases, including biocontinuous phases and networks of ordered cross-linking micelles. Research has focused on structural studies of block copolymer systems, using small-angle scattering of X-rays and neutrons....

  2. Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers. (United States)

    Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming


    The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical

  3. Multifunctional hybrid networks based on self assembling peptide sequences (United States)

    Sathaye, Sameer

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

  4. Templated self-assembly of SiGe quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Dais, Christian


    This PhD thesis reports on the fabrication and characterization of exact aligned SiGe quantum dot structures. In general, SiGe quantum dots which nucleate via the Stranski-Krastanov growth mode exhibit broad size dispersion and nucleate randomly on the surface. However, to tap the full potential of SiGe quantum dots it is necessary to control the positioning and size of the dots on a nanometer length, e.g. for electronically addressing of individual dots. This can be realized by so-called templated self-assembly, which combines top-down lithography with bottom-up selfassembly. In this process the lithographically defined pits serve as pre-defined nucleation points for the epitaxially grown quantum dots. In this thesis, extreme ultraviolet interference lithography at a wavelength of e=13.4 nm is employed for prepatterning of the Si substrates. This technique allows the precise and fast fabrication of high-resolution templates with a high degree of reproducibility. The subsequent epitaxial deposition is either performed by molecular beam epitaxy or low-pressure chemical vapour deposition. It is shown that the dot nucleation on pre-patterned substrates depends strongly on the lithography parameters, e.g. size and periodicity of the pits, as well as on the epitaxy parameters, e.g. growth temperature or material coverage. The interrelations are carefully analyzed by means of scanning force microscopy, transmission electron microscopy and X-ray diffraction measurements. Provided that correct template and overgrowth parameters are chosen, perfectly aligned and uniform SiGe quantum dot arrays of different period, size as well as symmetry are created. In particular, the quantum dot arrays with the so far smallest period (35 nm) and smallest size dispersion are fabricated in this thesis. Furthermore, the strain fields of the underlying quantum dots allow the fabrication of vertically aligned quantum dot stacks. Combining lateral and vertical dot alignment results in three

  5. Self-assembly of fibronectin mimetic peptide-amphiphile nanofibers (United States)

    Rexeisen, Emilie Lynn

    umbilical vein endothelial cells and alpha5beta1 integrins immobilized on an AFM tip preferred binding to a fibronectin mimetic peptide that contained both hydrophilic and hydrophobic residues in the linker and a medium length spacer. Most cells require a three-dimensional scaffold in order to thrive. To incorporate the fibronectin mimetic peptide into a three-dimensional structure, a single hydrocarbon tail was attached to form a peptideamphiphile. Single-tailed peptide-amphiphiles have been shown to form nanofibers in solution and gel after screening of the electrostatic charges in the headgroup. These gels show promise as scaffolds for tissue engineering. A fibronectin mimetic peptide-amphiphile containing a linker with alternating hydrophobic and hydrophilic residues was designed to form nanofibers in solution. The critical micelle concentration of the peptide-amphiphile was determined to be 38 muM, and all subsequent experiments were performed above this concentration. Circular dichroism (CD) spectroscopy indicated that the peptide headgroup of the peptide-amphiphile forms an alpha+beta secondary structure; whereas, the free peptide forms a random secondary structure. Cryogenic-transmission electron microscopy (cryo-TEM) and small angle neutron scattering showed that the peptide-amphiphile self-assembled into nanofibers. The cryo-TEM images showed single nanofibers with a diameter of 10 nm and lengths on the order of microns. Images of higher peptideamphiphile concentrations showed evidence of bundling between individual nanofibers, which could give rise to gelation behavior at higher concentrations. The peptide-amphiphile formed a gel at concentrations above 6 mM. A 10 mM sample was analyzed with oscillating plate rheometry and was found to have an elastic modulus within the range of living tissue, showing potential as a possible scaffold for tissue engineering.

  6. Sustained delivery of VEGF from designer self-assembling peptides improves cardiac function after myocardial infarction

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Hai-dong [Department of Anatomy, School of Basic Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203 (China); Cui, Guo-hong; Yang, Jia-jun [Department of Neurology, Shanghai No. 6 People' s Hospital, Shanghai Jiaotong University School of Medicine, Shanghai 200233 (China); Wang, Cun [Institutes of Biomedical Sciences, Fudan University, Shanghai 200032 (China); Zhu, Jing; Zhang, Li-sheng; Jiang, Jun [Department of Anatomy, School of Basic Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203 (China); Shao, Shui-jin, E-mail: [Department of Anatomy, School of Basic Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203 (China)


    Highlights: Black-Right-Pointing-Pointer The designer peptide LRKKLGKA could self-assemble into nanofibers. Black-Right-Pointing-Pointer Injection of LRKKLGKA peptides could promote the sustained delivery of VEGF. Black-Right-Pointing-Pointer Injection of VEGF with LRKKLGKA peptides lead to sufficient angiogenesis. Black-Right-Pointing-Pointer Injection of VEGF with LRKKLGKA peptides improves heart function. -- Abstract: Poor vascularization and insufficient oxygen supply are detrimental to the survival of residual cardiomyocytes or transplanted stem cells after myocardial infarction. To prolong and slow the release of angiogenic factors, which stimulate both angiogenesis and vasculogenesis, we constructed a novel self-assembling peptide by attaching the heparin-binding domain sequence LRKKLGKA to the self-assembling peptide RADA16. This designer self-assembling peptide self-assembled into nanofiber scaffolds under physiological conditions, as observed by atomic force microscopy. The injection of designer self-assembling peptides can efficiently provide the sustained delivery of VEGF for at least 1 month. At 4 weeks after transplantation, cardiac function was improved, and scar size and collagen deposition were markedly reduced in the group receiving VEGF with the LRKKLGKA scaffolds compared with groups receiving VEGF alone, LRKKLGKA scaffolds alone or VEGF with RADA16 scaffolds. The microvessel density in the VEGF with LRKKLGKA group was higher than that in the VEGF with RADA16 group. TUNEL and cleaved caspase-3 expression assays showed that the transplantation of VEGF with LRKKLGKA enhanced cell survival in the infarcted heart. These results present the tailor-made peptide scaffolds as a new generation of sustained-release biomimetic biomaterials and suggest that the use of angiogenic factors along with designer self-assembling peptides can lead to myocardial protection, sufficient angiogenesis, and improvement in cardiac function.

  7. Polymerization Induced Self-Assembly of Alginate Based Amphiphilic Graft Copolymers Synthesized by Single Electron Transfer Living Radical Polymerization. (United States)

    Kapishon, Vitaliy; Whitney, Ralph A; Champagne, Pascale; Cunningham, Michael F; Neufeld, Ronald J


    Alginate-based amphiphilic graft copolymers were synthesized by single electron transfer living radical polymerization (SET-LRP), forming stable micelles during polymerization induced self-assembly (PISA). First, alginate macroinitiator was prepared by partial depolymerization of native alginate, solubility modification and attachment of initiator. Depolymerized low molecular weight alginate (∼12 000 g/mol) was modified with tetrabutylammonium, enabling miscibility in anhydrous organic solvents, followed by initiator attachment via esterification yielding a macroinitiator with a degree of substitution of 0.02, or 1-2 initiator groups per alginate chain. Then, methyl methacrylate was polymerized from the alginate macroinitiator in mixtures of water and methanol, forming poly(methyl methacrylate) grafts, prior to self-assembly, of ∼75 000 g/mol and polydispersity of 1.2. PISA of the amphiphilic graft-copolymer resulted in the formation of micelles with diameters of 50-300 nm characterized by light scattering and electron microscopy. As the first reported case of LRP from alginate, this work introduces a synthetic route to a preparation of alginate-based hybrid polymers with a precise macromolecular architecture and desired functionalities. The intended application is the preparation of micelles for drug delivery; however, LRP from alginate can also be applied in the field of biomaterials to the improvement of alginate-based hydrogel systems such as nano- and microhydrogel particles, islet encapsulation materials, hydrogel implants, and topical applications. Such modified alginates can also improve the function and application of native alginates in food and agricultural applications.

  8. Efficient sampling of reversible cross-linking polymers: Self-assembly of single-chain polymeric nanoparticles (United States)

    Oyarzún, Bernardo; Mognetti, Bortolo Matteo


    We present a new simulation technique to study systems of polymers functionalized by reactive sites that bind/unbind forming reversible linkages. Functionalized polymers feature self-assembly and responsive properties that are unmatched by the systems lacking selective interactions. The scales at which the functional properties of these materials emerge are difficult to model, especially in the reversible regime where such properties result from many binding/unbinding events. This difficulty is related to large entropic barriers associated with the formation of intra-molecular loops. In this work, we present a simulation scheme that sidesteps configurational costs by dedicated Monte Carlo moves capable of binding/unbinding reactive sites in a single step. Cross-linking reactions are implemented by trial moves that reconstruct chain sections attempting, at the same time, a dimerization reaction between pairs of reactive sites. The model is parametrized by the reaction equilibrium constant of the reactive species free in solution. This quantity can be obtained by means of experiments or atomistic/quantum simulations. We use the proposed methodology to study the self-assembly of single-chain polymeric nanoparticles, starting from flexible precursors carrying regularly or randomly distributed reactive sites. We focus on understanding differences in the morphology of chain nanoparticles when linkages are reversible as compared to the well-studied case of irreversible reactions. Intriguingly, we find that the size of regularly functionalized chains, in good solvent conditions, is non-monotonous as a function of the degree of functionalization. We clarify how this result follows from excluded volume interactions and is peculiar of reversible linkages and regular functionalizations.

  9. Nanoscale silicon substrate patterns from self-assembly of cylinder forming poly(styrene)-block-poly(dimethylsiloxane) block copolymer on silane functionalized surfaces. (United States)

    Borah, Dipu; Cummins, Cian; Rasappa, Sozaraj; Watson, Scott M D; Pike, Andrew R; Horrocks, Benjamin R; Fulton, David A; Houlton, Andrew; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Morris, Michael A


    Poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) is an excellent block copolymer (BCP) system for self-assembly and inorganic template fabrication because of its high Flory-Huggins parameter (χ ∼ 0.26) at room temperature in comparison to other BCPs, and high selective etch contrast between PS and PDMS block for nanopatterning. In this work, self-assembly in PS-b-PDMS BCP is achieved by combining hydroxyl-terminated poly(dimethylsiloxane) (PDMS-OH) brush surfaces with solvent vapor annealing. As an alternative to standard brush chemistry, we report a simple method based on the use of surfaces functionalized with silane-based self-assembled monolayers (SAMs). A solution-based approach to SAM formation was adopted in this investigation. The influence of the SAM-modified surfaces upon BCP films was compared with polymer brush-based surfaces. The cylinder forming PS-b-PDMS BCP and PDMS-OH polymer brush were synthesized by sequential living anionic polymerization. It was observed that silane SAMs provided the appropriate surface chemistry which, when combined with solvent annealing, led to microphase segregation in the BCP. It was also demonstrated that orientation of the PDMS cylinders may be controlled by judicious choice of the appropriate silane. The PDMS patterns were successfully used as an on-chip etch mask to transfer the BCP pattern to underlying silicon substrate with sub-25 nm silicon nanoscale features. This alternative SAM/BCP approach to nanopattern formation shows promising results, pertinent in the field of nanotechnology, and with much potential for application, such as in the fabrication of nanoimprint lithography stamps, nanofluidic devices or in narrow and multilevel interconnected lines.

  10. Rational Design of Molecular Gelator - Solvent Systems Guided by Solubility Parameters (United States)

    Lan, Yaqi

    Self-assembled architectures, such as molecular gels, have attracted wide interest among chemists, physicists and engineers during the past decade. However, the mechanism behind self-assembly remains largely unknown and no capability exists to predict a priori whether a small molecule will gelate a specific solvent or not. The process of self-assembly, in molecular gels, is intricate and must balance parameters influencing solubility and those contrasting forces that govern epitaxial growth into axially symmetric elongated aggregates. Although the gelator-gelator interactions are of paramount importance in understanding gelation, the solvent-gelator specific (i.e., H-bonding) and nonspecific (dipole-dipole, dipole-induced and instantaneous dipole induced forces) intermolecular interactions are equally important. Solvent properties mediate the self-assembly of molecular gelators into their self-assembled fibrillar networks. Herein, solubility parameters of solvents, ranging from partition coefficients (logP), to Henry's law constants (HLC), to solvatochromic ET(30) parameters, to Kamlet-Taft parameters (beta, alpha and pi), to Hansen solubility parameters (deltap, deltad, deltah), etc., are correlated with the gelation ability of numerous classes of molecular gelators. Advanced solvent clustering techniques have led to the development of a priori tools that can identify the solvents that will be gelled and not gelled by molecular gelators. These tools will greatly aid in the development of novel gelators without solely relying on serendipitous discoveries.

  11. Functional materials derived from block copolymer self-assembly

    DEFF Research Database (Denmark)

    Li, Tao

    surface energy, including polymers, silicon and graphene, thus bypassing the laborious and delicate substrate chemical pre-modification. To push the boundary even further for minimal lithography steps, a scalable ultra-fast block copolymer lithography procedure is developed. Using selective solvent spin....... We believe this project opens up for a number of strategies aiming at the creation of high-performance functional materials on the length scale of sub-20 nanometers that cannot be manufactured in an easy fashion by conventional top-down lithography methods....

  12. Self-Assembled Fluorinated Organogelators for Surface Modification

    Directory of Open Access Journals (Sweden)

    Anilkumar Raghavanpillai


    Full Text Available A new class of alkyl- and perfluoroalkyl-containing urea and amide derivatives was synthesized from amino acid derivatives. Most of these compounds showed excellent gelation behavior in organic solvents at low concentrations. A few organogelators selected from the initial screening were used for surface modification of fibrous substrates to create hydrophobic and oleophobic composites. The hydrophobic and oleophobic behaviors of these composites were ascribed to a combination of increased surface roughness and the alkyl/fluorinated functionalities present in the gelator backbone.

  13. Templated self-assembly of square symmetry arrays from an ABC triblock terpolymer. (United States)

    Chuang, Vivian P; Gwyther, Jessica; Mickiewicz, Rafal A; Manners, Ian; Ross, Caroline A


    Self-assembly provides the ability to create well-controlled nanostructures with electronic or chemical functionality and enables the synthesis of a wide range of useful devices. Diblock copolymers self-assemble into periodic arrays of microdomains with feature sizes of typically 10-50 nm, and have been used to make a wide range of devices such as silicon capacitors and transistors, photonic crystals, and patterned magnetic media(1-3). However, the cylindrical or spherical microdomains in diblock copolymers generally form close-packed structures with hexagonal symmetry, limiting their device applications. Here we demonstrate self-assembly of square-symmetry patterns from a triblock terpolymer in which one organometallic block imparts high etch selectivity and etch resistance. Long-range order is imposed on the microdomain arrays by self-assembly on topographical substrates, and the orientation of both square lattices and in-plane cylinders is controlled by the substrate chemistry. Pattern transfer is demonstrated by making an array of square-packed 30 nm tall, 20 nm diameter silica pillars. Templated self-assembly of triblock terpolymers can generate nanostructures with geometries that are unattainable from diblock copolymers, significantly enhancing the capabilities of block copolymer lithography.

  14. Multifunctional Self-Assembled Monolayers for Organic Field-Effect Transistors (United States)

    Cernetic, Nathan

    Organic field effect transistors (OFETs) have the potential to reach commercialization for a wide variety of applications such as active matrix display circuitry, chemical and biological sensing, radio-frequency identification devices and flexible electronics. In order to be commercially competitive with already at-market amorphous silicon devices, OFETs need to approach similar performance levels. Significant progress has been made in developing high performance organic semiconductors and dielectric materials. Additionally, a common route to improve the performance metric of OFETs is via interface modification at the critical dielectric/semiconductor and electrode/semiconductor interface which often play a significant role in charge transport properties. These metal oxide interfaces are typically modified with rationally designed multifunctional self-assembled monolayers. As means toward improving the performance metrics of OFETs, rationally designed multifunctional self-assembled monolayers are used to explore the relationship between surface energy, SAM order, and SAM dipole on OFET performance. The studies presented within are (1) development of a multifunctional SAM capable of simultaneously modifying dielectric and metal surface while maintaining compatibility with solution processed techniques (2) exploration of the relationship between SAM dipole and anchor group on graphene transistors, and (3) development of self-assembled monolayer field-effect transistor in which the traditional thick organic semiconductor is replaced by a rationally designed self-assembled monolayer semiconductor. The findings presented within represent advancement in the understanding of the influence of self-assembled monolayers on OFETs as well as progress towards rationally designed monolayer transistors.

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

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


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

  16. Self-assembly: a minimalist route to the fabrication of nanomaterials. (United States)

    Lazzari, Massimo; Rodríguez-Abreu, Carlos; Rivas, José; López-Quintela, M Arturo


    Self-assembly of molecular or nonmolecular components by non-covalent interactions offers an invaluable tool for the preparation of discrete nanostructures and extended 2D and 3D materials, which are often not accessible by any other fabrication process. In this article we summarize the most recent advances in the generation of nanomaterials such as self-assembled monolayers (SAMs) and structures formed from amphiphilic molecules, colloids, peptides, and polymers by nontemplated self-assembly either at the solid state or in solution. The current status of templated self-assembly and the use of self-assembled structures as template and for patterning other materials is also covered. A special emphasis is placed on strategies presenting either original and somehow exploratory approaches, eventually combining bottom-up and top-down methods, or that concern methods for the production of materials with potential application, e.g., in photonics, as sensors, for drug delivery and electric and magnetic devices. In all the sections, we outline self-organization and applications enabled with self-separated block copolymers.

  17. Chemical and entropic control on the molecular self-assembly process. (United States)

    Packwood, Daniel M; Han, Patrick; Hitosugi, Taro


    Molecular self-assembly refers to the spontaneous assembly of molecules into larger structures. In order to exploit molecular self-assembly for the bottom-up synthesis of nanomaterials, the effects of chemical control (strength of the directionality in the intermolecular interaction) and entropic control (temperature) on the self-assembly process should be clarified. Here we present a theoretical methodology that unambiguously distinguishes the effects of chemical and entropic control on the self-assembly of molecules adsorbed to metal surfaces. While chemical control simply increases the formation probability of ordered structures, entropic control induces a variety of effects. These effects range from fine structure modulation of ordered structures, through to degrading large, amorphous structures into short, chain-shaped structures. Counterintuitively, the latter effect shows that entropic control can improve molecular ordering. By identifying appropriate levels of chemical and entropic control, our methodology can, therefore, identify strategies for optimizing the yield of desired nanostructures from the molecular self-assembly process.

  18. Beta-Sheet-Forming, Self-Assembled Peptide Nanomaterials towards Optical, Energy, and Healthcare Applications. (United States)

    Kim, Sungjin; Kim, Jae Hong; Lee, Joon Seok; Park, Chan Beum


    Peptide self-assembly is an attractive route for the synthesis of intricate organic nanostructures that possess remarkable structural variety and biocompatibility. Recent studies on peptide-based, self-assembled materials have expanded beyond the construction of high-order architectures; they are now reporting new functional materials that have application in the emerging fields such as artificial photosynthesis and rechargeable batteries. Nevertheless, there have been few reviews particularly concentrating on such versatile, emerging applications. Herein, recent advances in the synthesis of self-assembled peptide nanomaterials (e.g., cross β-sheet-based amyloid nanostructures, peptide amphiphiles) are selectively reviewed and their new applications in diverse, interdisciplinary fields are described, ranging from optics and energy storage/conversion to healthcare. The applications of peptide-based self-assembled materials in unconventional fields are also highlighted, such as photoluminescent peptide nanostructures, artificial photosynthetic peptide nanomaterials, and lithium-ion battery components. The relation of such functional materials to the rapidly progressing biomedical applications of peptide self-assembly, which include biosensors/chips and regenerative medicine, are discussed. The combination of strategies shown in these applications would further promote the discovery of novel, functional, small materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Controllable self-assembly of NaREF4 upconversion nanoparticles and their distinctive fluorescence properties (United States)

    Liu, Xiaoxia; Ni, Yaru; Zhu, Cheng; Fang, Liang; Kou, Jiahui; Lu, Chunhua; Xu, Zhongzi


    The paper presents the growth of hexagonal NaYF4:Yb3+, Tm3+ nanocrystals with tunable sizes induced by different contents of doped Yb3+ ions (10%-99.5%) using the thermal decomposition method. These nanoparticles, which have different sizes, are then self-assembled at the interface of cyclohexane and ethylene and transferred onto a normal glass slide. It is found that the size of nanoparticles directs their self-assembly. Due to the appropriate size of 40.5 nm, 15% Yb3+ ions doped nanoparticles are able to be self-assembled into an ordered inorganic monolayer membrane with a large area of about 10 × 10 μm2. More importantly, the obvious short-wave (300-500 nm) fluorescence improvement of the ordered 2D self-assembly structure is observed to be relative to disordered nanoparticles, which is because intrinsic absorption and scattering of upconversion nanoparticles leads to the self-loss of fluorescence, especially the short-wave fluorescence inside the disordered structure, and the relative emission of short-wave fluorescence is reduced. The construction of a 2D self-assembly structure can effectively avoid this and improve the radiated short-wave fluorescence, especially UV photons, and is able to direct the design of new types of solid-state optical materials in many fields.

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

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


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