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Sample records for assembled polymer nanowires

  1. Electronic polymers and DNA self-assembled in nanowire transistors.

    PubMed

    Hamedi, Mahiar; Elfwing, Anders; Gabrielsson, Roger; Inganäs, Olle

    2013-02-11

    Aqueous self-assembly of DNA and molecular electronic materials can lead to the creation of innumerable copies of identical devices, and inherently programmed complex nanocircuits. Here self-assembly of a water soluble and highly conducting polymer PEDOT-S with DNA in aqueous conditions is shown. Orientation and assembly of the conducting DNA/PEDOT-S complex into electrochemical DNA nanowire transistors is demonstrated.

  2. Assembly of Ultrathin Gold Nanowires: From Polymer Analogue to Colloidal Block.

    PubMed

    Chen, Yuan; Wang, Yawen; Peng, Jian; Xu, Qingchi; Weng, Jian; Xu, Jun

    2017-03-28

    Ultrathin nanowires (NWs) are considered to be ideal building blocks for the assembly of complex nanostructures toward future nanodevices. The polymer/particle duality of ultrathin NWs plays an important role in the study of solution phase self-assembly behavior of ultrathin NWs; yet it has not been fully exploited. Herein, we demonstrate the effects of the polymer/particle duality of ultrathin NWs on the morphologies of assembled complex nanostructures. The length of ultrathin AuNWs directly correlates with the flexibility of NWs and affects the polymer-like assembly of NWs, while the concentration of surfactants determines interfacial tension and ligand-solvent interactions and affects both polymer-like and colloidal assembly of NWs. By fine-tuning these two factors, ultrathin AuNWs can swing between "soft" and "hard" building blocks, and highly uniform nanorings, nanograins, nanobundles, and superlattice-like nanospheres are obtained. The different assembly behavior of long and short NWs can be considered as two components to construct anisotropic complex nanostructures, in analogy with the fabrication of polymer-inorganic nanoparticle hybrid nanostructures. We synthesized anisotropic structures of Au nanodiamond rings and nanonecklaces by the coassembly of polymer-like long NWs with particle-like short NWs or Au nanoparticles. This strategy could potentially be extended to the organization of anisotropic complex nanostructures with other ultrathin NW systems in the future.

  3. Polymer-Mediated Self-Assembly of TiO2@Cu2O Core-Shell Nanowire Array for Highly Efficient Photoelectrochemical Water Oxidation.

    PubMed

    Yuan, Weiyong; Yuan, Jia; Xie, Jiale; Li, Chang Ming

    2016-03-09

    Phototoelectrochemical (PEC) water splitting represents a highly promising strategy to convert solar energy to chemical energy in the form of hydrogen, but its performance is severely limited by the water oxidation reaction. We conformally grew an ultrathin and continuous coating of Cu2O on TiO2 nanowire array (NWA) to form a truly core-shell TiO2@Cu2O NWA via a new facile, economical, and scalable polymer-mediated self-assembly approach, in which the polymer serves as a stabilizer, reductant, and linker simultaneously. This heteronanostructure was subsequently directly used as a photoanode for PEC water splitting, showing a photocurrent density of 4.66 mA cm(-2) at 1.23 V vs RHE in 0.5 M Na2SO4 solution and a maximum photoconversion efficiency of 0.71%, both of which are the highest reported for TiO2-based photoanodes measured under the same conditions (neutral conditions and without any sacrificial agent). The superior PEC performance of the TiO2@Cu2O NWA toward water oxidation is primarily due to much enhanced visible light collection and charge separation for high charge carrier density as well as greatly facilitated charge transfer and transport. This work not only offers a novel TiO2@Cu2O core-shell NWA photoanode for highly efficient PEC water oxidation and investigate its enhancement mechanism but also provides scientific insights into the mechanism of the polymer-mediated self-assembly, which can be further extended to fabricate various other core-shell nanoarchitectures for broad applications.

  4. Optical routing and sensing with nanowire assemblies.

    PubMed

    Sirbuly, Donald J; Law, Matt; Pauzauskie, Peter; Yan, Haoquan; Maslov, Alex V; Knutsen, Kelly; Ning, Cun-Zheng; Saykally, Richard J; Yang, Peidong

    2005-05-31

    The manipulation of photons in structures smaller than the wavelength of light is central to the development of nanoscale integrated photonic systems for computing, communications, and sensing. We assemble small groups of freestanding, chemically synthesized nanoribbons and nanowires into model structures that illustrate how light is exchanged between subwavelength cavities made of three different semiconductors. The coupling strength of the optical linkages formed when nanowires are brought into contact depends both on their volume of interaction and angle of intersection. With simple coupling schemes, lasing nanowires can launch coherent pulses of light through ribbon waveguides that are up to a millimeter in length. Also, interwire coupling losses are low enough to allow light to propagate across several right-angle bends in a grid of crossed ribbons. The fraction of the guided wave traveling outside the wire/ribbon cavities is used to link nanowires through space and to separate colors within multiribbon networks. In addition, we find that nanoribbons function efficiently as waveguides in liquid media and provide a unique means for probing molecules in solution or in proximity to the waveguide surface. Our results lay the spadework for photonic devices based on assemblies of active and passive nanowire elements and presage the use of nanowire waveguides in microfluidics and biology.

  5. The Self- and Directed Assembly of Nanowires

    NASA Astrophysics Data System (ADS)

    Smith, Benjamin David

    This thesis explores the self- and directed assembly of nanowires. Specifically, we examine the driving forces behind nanowire self-assembly and the macro-structures that are formed. Particle-dense, oriented nanowire structures show promise in the fields of photonics, energy, sensing, catalysis, and electronics. Arrays of spherical particles have already found uses in electronic inks, sensing arrays, and many other commercial applications; but, it is a challenge to create specific arrays of morphologically and/or compositionally anisotropic particles. The following chapters illuminate the interactions that drive the assembly of anisotropic particles in high density solutions in the absence of applied fields or solution drying. Special emphasis is placed on the structures that are formed. The properties of micro- and nanoparticles and their assembly are introduced in Chapter 1. In particular, the properties of shape and material anisotropic particles are highlighted, while challenges in producing desired arrays are discussed. In this thesis, metallic nanowires of increasing complexity were used to examine the self-assembly behavior of both shape and material anisotropic particles. Nanowires were synthesized through templated electrodeposition. In this process, porous alumina membranes served as a template in which metal salts were reduced to form particles. Upon template dissolution, billions of nominally identical particles were released. We specifically focused on segmented, metallic nanowires 2-13 mum in length and 180 to 350 nm in diameter. Since these particles have strong van der Waals (VDWs) attractions, an electrostatically repulsive coating was necessary to prevent aggregation; we used small molecule, DNA, or amorphous silica coatings. Nanowires and their coatings were characterized by electron microscopy. In order to study self-assembly behavior, particle-dense aqueous suspensions were placed within an assembly chamber defined by a silicone spacer. The

  6. Assembling silver nanowires using optoelectronic tweezers

    NASA Astrophysics Data System (ADS)

    Zhang, Shuailong; Cooper, Jonathan M.; Neale, Steve L.

    2016-03-01

    Light patterned dielectrophoresis or optoelectronic tweezers (OET) has been proved to be an effective micromanipulation technology for cell separation, cell sorting and control of cell interactions. Apart from being useful for cell biology experiments, the capability of moving small objects accurately also makes OET an attractive technology for other micromanipulation applications. In particular, OET has the potential to be used for efficiently and accurately assembling small optoelectronic/electronic components into circuits. This approach could produce a step change in the size of the smallest components that are routinely assembled; down from the current smallest standard component size of 400×200 μm (0402 metric) to components a few microns across and even nanostructured components. In this work, we have demonstrated the use of OET to manipulate conductive silver nanowires into different patterns. The silver nanowires (typical diameter: 60 nm; typical length: 10 μm) were suspended in a 15 mS/m solution of KCL in water and manipulated by positive dielectrophoresis force generated by OET. A proof-of-concept demonstration was also made to prove the feasibility of using OET to manipulate silver nanowires to form a 150-μm-long conductive path between two isolated electrodes. It can be seen that the resistance between two electrodes was effectively brought down to around 700 Ω after the silver nanowires were assembled and the solution evaporated. Future work in this area will focus on increasing the conductivity of these tracks, encapsulating the assembled silver nanowires to prevent silver oxidation and provide mechanical protection, which can be achieved via 3D printing and inkjet printing technology.

  7. Fabrication of patterned polymer nanowire arrays.

    PubMed

    Fang, Hao; Yuan, Dajun; Guo, Rui; Zhang, Su; Han, Ray P S; Das, Suman; Wang, Zhong Lin

    2011-02-22

    A method for the large-scale fabrication of patterned organic nanowire (NW) arrays is demonstrated by the use of laser interference patterning (LIP) in conjunction with inductively coupled plasma (ICP) etching. The NW arrays can be fabricated after a short ICP etching of periodic patterns produced through LIP. Arrays of NWs have been fabricated in UV-absorbent polymers, such as PET (polyethylene terephthalate) and Dura film (76% polyethylene and 24% polycarbonate), through laser interference photon ablation and in UV transparent polymers such as PVA (polyvinyl acetate) and PP (polypropylene) through laser interference lithography of a thin layer of photoresist coated atop the polymer surface. The dependence of the structure and morphology of NWs as a function of initial pattern created by LIP and the laser energy dose in LIP is discussed. The absence of residual photoresist atop the NWs in UV-transparent polymers is confirmed through Raman spectroscopy.

  8. Assembly and magnetic properties of nickel nanoparticles on silicon nanowires

    SciTech Connect

    Picraux, Samuel T; Manandhar, Pradeep; Nazaretski, E; Thompson, J

    2009-01-01

    The directed assembly of magnetic Ni nanoparticles at the tips of silicon nanowires is reported. Using electrodeposition Ni shells of thickness from 10 to 100 nm were selectively deposited on Au catalytic seeds at the ends of nanowires. Magnetic characterization confirms a low coercivity ({approx}115 Oe) ferromagnetic behavior at 300 K. This approach to multifunctional magnetic-semiconducting nanostructure assembly could be extended to electrodeposition of other materials on the nanowire ends, opening up novel ways of device integration. Such magnetically functionalized nanowires offer a new approach to developing novel highly localized magnetic probes for high resolution magnetic resonance force microscopy.

  9. Chirality-Discriminated Conductivity of Metal-Amino Acid Biocoordination Polymer Nanowires.

    PubMed

    Zheng, Jianzhong; Wu, Yijin; Deng, Ke; He, Meng; He, Liangcan; Cao, Jing; Zhang, Xugang; Liu, Yaling; Li, Shunxing; Tang, Zhiyong

    2016-09-27

    Biocoordination polymer (BCP) nanowires are successfully constructed through self-assembly of chiral cysteine amino acids and Cd cations in solution. The varied chirality of cysteine is explored to demonstrate the difference of BCP nanowires in both morphology and structure. More interestingly and surprisingly, the electrical property measurement reveals that, although all Cd(II)/cysteine BCP nanowires behave as semiconductors, the conductivity of the Cd(II)/dl-cysteine nanowires is 4 times higher than that of the Cd(II)/l-cysteine or Cd(II)/d-cysteine ones. The origin of such chirality-discriminated characteristics registered in BCP nanowires is further elucidated by theoretical calculation. These findings demonstrate that the morphology, structure, and property of BCP nanostructures could be tuned by the chirality of the bridging ligands, which will shed light on the comprehension of chirality transcription as well as construction of chirality-regulated functional materials.

  10. Sensing properties of assembled Bi2S3 nanowire arrays

    NASA Astrophysics Data System (ADS)

    Kunakova, G.; Meija, R.; Bite, I.; Prikulis, J.; Kosmaca, J.; Varghese, J.; Holmes, J. D.; Erts, Donats

    2015-09-01

    Bismuth sulfide (Bi2S3) nanowires were grown in porous aluminium oxide template and a selective chemical etching was applied to transfer the nanowires to a solution. Well aligned nanowire arrays were assembled on pre-patterned silicon substrates employing dielectrophoresis. Electron beam lithography was used to connect aligned individual nanowires to the common macroelectrode. In order to evaluate the conductometric sensing performance of the Bi2S3 nanowires, current-voltage characteristics were measured at different relative humidity (RH) levels (5-80%) / argon medium. The response of the Bi2S3 nanowires depending of RH is found to be considerably different from those reported for other types of nanowire RH sensor devices.

  11. Increasing the efficiency of polymer solar cells by silicon nanowires.

    PubMed

    Eisenhawer, B; Sensfuss, S; Sivakov, V; Pietsch, M; Andrä, G; Falk, F

    2011-08-05

    Silicon nanowires have been introduced into P3HT:[60]PCBM solar cells, resulting in hybrid organic/inorganic solar cells. A cell efficiency of 4.2% has been achieved, which is a relative improvement of 10% compared to a reference cell produced without nanowires. This increase in cell performance is possibly due to an enhancement of the electron transport properties imposed by the silicon nanowires. In this paper, we present a novel approach for introducing the nanowires by mixing them into the polymer blend and subsequently coating the polymer/nanowire blend onto a substrate. This new onset may represent a viable pathway to producing nanowire-enhanced polymer solar cells in a reel to reel process.

  12. Laterally assembled nanowires for ultrathin broadband solar absorbers.

    PubMed

    Song, Kyung-Deok; Kempa, Thomas J; Park, Hong-Gyu; Kim, Sun-Kyung

    2014-05-05

    We studied optical resonances in laterally oriented Si nanowire arrays by conducting finite-difference time-domain simulations. Localized Fabry-Perot and whispering-gallery modes are supported within the cross section of each nanowire in the array and result in broadband light absorption. Comparison of a nanowire array with a single nanowire shows that the current density (J(SC)) is preserved for a range of nanowire morphologies. The J(SC) of a nanowire array depends on the spacing of its constituent nanowires, which indicates that both diffraction and optical antenna effects contribute to light absorption. Furthermore, a vertically stacked nanowire array exhibits significantly enhanced light absorption because of the emergence of coupled cavity-waveguide modes and the mitigation of a screening effect. With the assumption of unity internal quantum efficiency, the J(SC) of an 800-nm-thick cross-stacked nanowire array is 14.0 mA/cm², which yields a ~60% enhancement compared with an equivalent bulk film absorber. These numerical results underpin a rational design strategy for ultrathin solar absorbers based on assembled nanowire cavities.

  13. Aluminum Nanowire Arrays via Directed Assembly.

    PubMed

    Nesbitt, Nathan T; Merlo, Juan M; Rose, Aaron H; Calm, Yitzi M; Kempa, Krzysztof; Burns, Michael J; Naughton, Michael J

    2015-11-11

    Freestanding and vertically-oriented metal nanowire arrays have potential utility in a number of applications, but presently lack a route to fabrication. Template-based techniques, such as electrodeposition into lithographically defined nanopore arrays, have produced well-ordered nanowire arrays with a maximum pitch of about 2 μm; such nanowires, however, tend to cluster due to local attractive forces. Here, we modify this template fabrication method to produce well-ordered, vertically-oriented, freestanding Al nanowire arrays, etched from an underlying Al substrate, with highly tunable pitch. In addition, optical measurements demonstrated that the nanowires support the propagation of surface plasmon polaritons.

  14. Fabrication of Si3N4 nanowire membranes: free standing disordered nanopapers and aligned nanowire assemblies

    NASA Astrophysics Data System (ADS)

    Liu, Haitao; Fang, Minghao; Huang, Zhaohui; Huang, Juntong; Liu, Yan-gai; Wu, Xiaowen

    2016-08-01

    Herein, ultralong silicon nitride nanowires were synthesized via a chemical vapor deposition method by using the low-cost quartz and silicon powder as raw materials. Simple processes were used for the fabrication of disordered and ordered nanowire membranes of pure silicon nitride nanowires. The nanowires in the disordered nanopapers are intertwined with each other to form a paper-like structure which exhibit excellent flame retardancy and mechanical properties. Fourier-transform infrared spectroscopy and thermal gravity analysis were employed to characterize the refractory performance of the disordered nanopapers. Highly ordered nanowire membranes were also assembled through a three-phase assembly approach which make the Si3N4 nanowires have potential use in textured ceramics and semiconductor field. Moreover, the surface nanowires can also be modified to be hydrophobic; this characteristic make the as-prepared nanowires have the potential to be assembled by the more effective Langmuir-Blodgett method and also make the disordered nanopapers possess a super-hydrophobic surface.

  15. Enhanced Photoresponse of Conductive Polymer Nanowires Embedded with Au Nanoparticles.

    PubMed

    Zhang, Junchang; Zhong, Liubiao; Sun, Yinghui; Li, Anran; Huang, Jing; Meng, Fanben; Chandran, Bevita K; Li, Shuzhou; Jiang, Lin; Chen, Xiaodong

    2016-04-20

    A conductive polymer nanowire embedded with a 1D Au nanoparticle chain with defined size, shape, and interparticle distance is fabricated which demonstrates enhanced photoresponse behavior. The precise and controllable positioning of 1D Au nanoparticle chain in the conductive polymer nanowire plays a critical role in modulating the photoresponse behavior by excitation light wavelength or power due to the coupled-plasmon effect of 1D Au nanoparticle chain.

  16. Electrically Conductive Metal Nanowire Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Luo, Xiaoxiong

    This thesis investigates electrically conductive polymer nanocomposites formulated with metal nanowires for electrostatic discharge and electromagnetic interference shielding. Copper nanowires (CuNWs) of an average length of 1.98 mum and diameter of 25 +/- 4 nm were synthesized. The oxidation reaction of the CuNWs in air can be divided into two stages at weight of 111.2% on TGA curves. The isoconversional activation energies determined by Starink method were used to fit the different master plots. Johnson-Mehl-Avrami (JMA) equation gave the best fit. The surface atoms of the CuNWs are the sites for the random nucleation and the crystallite strain in the CuNWs is the driving force for the growth of nuclei mechanism during the oxidation process. To improve the anti-oxidation properties of the CuNWs, silver was coated onto the surface of the CuNWs in Ag-amine solution. The prepared silver coated CuNWs (AgCuNWs) with silver content of 66.52 wt. %, diameter of 28--33 nm exhibited improved anti-oxidation behavior. The electrical resistivity of the AgCuNW/low density polyethylene (LDPE) nanocomposites is lower than that of the CuNW/LDPE nanocomposites with the same volume percentage of fillers. The nanocomposites formulated with CuNWs and polyethylenes (PEs) were compared to study the different interaction between the CuNWs and the different types of PE matrices. The electrical conductivity of the different PE matrices filled with the same concentrations of CuNWs correlated well with the level of the CuNW dispersion. The intermolecular force and entanglement resulting from the different macromolecular structures such as molecular weight and branching played an important role in the dispersion, electrical properties and rheological behaviour of the CuNW/PE nanocomposites. Ferromagnetic polycrystalline nickel nanowires (NiNWs) were synthesized with uniform diameter of ca. 38 nm and an average length of 2.68 mum. The NiNW linear low density polyethylene (LLDPE

  17. Self-Assembled PbSe Nanowire:Perovskite Hybrids.

    PubMed

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

    2015-12-02

    Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

  18. Self assembled silicon nanowire Schottky junction assisted by collagen

    NASA Astrophysics Data System (ADS)

    Stievenard, Didier; Sahli, Billel; Coffinier, Yannick; Boukherroub, Rabah; Melnyk, Oleg

    2008-03-01

    We present results on self assembled silicon nanowire Schottky junction assisted by collagen fibrous. The collagen is the principle protein of connective human tissues. It presents the double interest to be a low cost biological material with the possibility to be combed as the DNA molecule. First, the collagen was combed on OTS modified surface with gold electrodes. Second, silicon nanowires were grown on silicon substrate by CVD of silane gas (SiH4) at high temperature (500 C) using a vapor-liquid-solid (VLS) process and gold particles as catalysts. In order to increase electrostatic interaction between the collagen and the nanowires, these latters were chemically modified by mercaptopropylmethoxysilane (MPTS), then chemically oxidized. Therefore, the nanowires were transferred from their substrate into water and a drop of it deposited on the surface. Nanowires are only bound to collagen and in particular, in electrode gaps. The formation of spontaneous Schotkty junction is demonstrated by current-voltage characteristics.

  19. Location deterministic biosensing from quantum-dot-nanowire assemblies

    SciTech Connect

    Liu, Chao; Kim, Kwanoh; Fan, D. L.

    2014-08-25

    Semiconductor quantum dots (QDs) with high fluorescent brightness, stability, and tunable sizes, have received considerable interest for imaging, sensing, and delivery of biomolecules. In this research, we demonstrate location deterministic biochemical detection from arrays of QD-nanowire hybrid assemblies. QDs with diameters less than 10 nm are manipulated and precisely positioned on the tips of the assembled Gold (Au) nanowires. The manipulation mechanisms are quantitatively understood as the synergetic effects of dielectrophoretic (DEP) and alternating current electroosmosis (ACEO) due to AC electric fields. The QD-nanowire hybrid sensors operate uniquely by concentrating bioanalytes to QDs on the tips of nanowires before detection, offering much enhanced efficiency and sensitivity, in addition to the position-predictable rationality. This research could result in advances in QD-based biomedical detection and inspires an innovative approach for fabricating various QD-based nanodevices.

  20. Nanomanufacturing Strategy for Aligned Assembly of Nanowire Arrays

    NASA Astrophysics Data System (ADS)

    Shin, Kyeong-Sik; Chui, Chi On

    2012-05-01

    The work reported here concerns a proposed nanomanufacturing strategy to assemble aligned quasi-one-dimensional nanostructure arrays with intrinsic and concurrent control over the resultant number, pitch, and linewidth. For the first time, a standard lithography and crystallographic etching approach have been combined to synthesize periodic, sublithographic, and line edge roughness (LER)-free surface arrays for selective conjugation of nanowires. Key experimental modules have been developed, including the formation of LER-free substrate arrays, formation of periodically dissimilar surfaces, selective conjugation of nanowires, and stamping transfer of nanowire arrays. In particular, successful assembly of Si nanowires onto periodic Si/SiO x surfaces and subsequent transfer of the resultant aligned Si nanowire arrays onto a different substrate surface have been repeatedly demonstrated. The dependences and probability of nanowire aligned assembly have also been examined. The proposed strategy is based on a wafer-scale and very large-scale integration (VLSI)-compatible philosophy, and alignment to pre-existing features on the target substrate is also inherently allowed as a side benefit. Besides, LER-free features could be created, which arguably enables extreme linewidth scaling with suppressed variations.

  1. Fabrication of polymer nanowires via maskless O2 plasma etching.

    PubMed

    Du, Ke; Wathuthanthri, Ishan; Liu, Yuyang; Kang, Yong Tae; Choi, Chang-Hwan

    2014-04-25

    In this paper, we introduce a simple fabrication technique which can pattern high-aspect-ratio polymer nanowire structures of photoresist films by using a maskless one-step oxygen plasma etching process. When carbon-based photoresist materials on silicon substrates are etched by oxygen plasma in a metallic etching chamber, nanoparticles such as antimony, aluminum, fluorine, silicon or their compound materials are self-generated and densely occupy the photoresist polymer surface. Such self-masking effects result in the formation of high-aspect-ratio vertical nanowire arrays of the polymer in the reactive ion etching mode without the necessity of any artificial etch mask. Nanowires fabricated by this technique have a diameter of less than 50 nm and an aspect ratio greater than 20. When such nanowires are fabricated on lithographically pre-patterned photoresist films, hierarchical and hybrid nanostructures of polymer are also conveniently attained. This simple and high-throughput fabrication technique for polymer nanostructures should pave the way to a wide range of applications such as in sensors, energy storage, optical devices and microfluidics systems.

  2. Conducting polymer nanowire arrays for high performance supercapacitors.

    PubMed

    Wang, Kai; Wu, Haiping; Meng, Yuena; Wei, Zhixiang

    2014-01-15

    This Review provides a brief summary of the most recent research developments in the fabrication and application of one-dimensional ordered conducting polymers nanostructure (especially nanowire arrays) and their composites as electrodes for supercapacitors. By controlling the nucleation and growth process of polymerization, aligned conducting polymer nanowire arrays and their composites with nano-carbon materials can be prepared by employing in situ chemical polymerization or electrochemical polymerization without a template. This kind of nanostructure (such as polypyrrole and polyaniline nanowire arrays) possesses high capacitance, superior rate capability ascribed to large electrochemical surface, and an optimal ion diffusion path in the ordered nanowire structure, which is proved to be an ideal electrode material for high performance supercapacitors. Furthermore, flexible, micro-scale, threadlike, and multifunctional supercapacitors are introduced based on conducting polyaniline nanowire arrays and their composites. These prototypes of supercapacitors utilize the high flexibility, good processability, and large capacitance of conducting polymers, which efficiently extend the usage of supercapacitors in various situations, and even for a complicated integration system of different electronic devices.

  3. Bottlebrush Polymers: Synthesis, Rheology, and Self-Assembly

    NASA Astrophysics Data System (ADS)

    Dalsin, Samuel J.

    Bottlebrush polymers are comb-like molecules with a high density of side chains grafted along a central backbone. Due to their unique conformational properties, bottlebrush polymers have become attractive candidates for developing new photonic bandgap materials, nanotubes and nanowires, or drug delivery vehicles, to name a few. This dissertation primarily investigates the rheological properties and self-assembly behavior of bottlebrush polymer molecules made using a variety of different polymerization routes. A considerable portion of the work is directed towards the linear rheology of model, polyolefin-based bottlebrush polymers with independently varied branch and backbone lengths. These studies demonstrate how the tight spacing between branch points effectively precludes backbone entanglement in the polymer melts, but it does not inhibit the formation of entanglements among the branched side chains. Furthermore, the relaxation profiles reveal transient scaling behavior in which the dynamics transition from Zimm-like to Rouse-like at increasing relaxation times. These results highlight the distinct conformational character of bottlebrushes at different length scales. The latter parts of this work report on the self-assembly behavior of bottlebrush diblock polymers composed of atactic polypropylene and polystyrene side chains. The diblock samples are analyzed using small-angle X-ray scattering and atomic force microscopy. Nearly all of the samples display strong segregation between the two blocks, owing to the large molar mass of typical bottlebrush polymers. Consequently, only one experimental sample displays an accessible order-disorder transition temperature. The strong segregation is also shown to affect the ability of large bottlebrush diblocks to readily achieve well-ordered nanostructures by self-assembly. Finally, results of the most symmetric (by volume fraction) diblock samples are compared with predictions of a newly developed self-consistent field

  4. Thermodynamics of the adsorption of flexible polymers on nanowires

    SciTech Connect

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-09

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. In conclusion, the classification of the transitions is performed by microcanonical inflection-point analysis.

  5. Thermodynamics of the adsorption of flexible polymers on nanowires

    DOE PAGES

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-09

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached tomore » or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. In conclusion, the classification of the transitions is performed by microcanonical inflection-point analysis.« less

  6. Thermodynamics of the adsorption of flexible polymers on nanowires

    SciTech Connect

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-14

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. The classification of the transitions is performed by microcanonical inflection-point analysis.

  7. Thermodynamics of the adsorption of flexible polymers on nanowires

    NASA Astrophysics Data System (ADS)

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-01

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. The classification of the transitions is performed by microcanonical inflection-point analysis.

  8. Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers.

    PubMed

    Liu, Wei; Liu, Nian; Sun, Jie; Hsu, Po-Chun; Li, Yuzhang; Lee, Hyun-Wook; Cui, Yi

    2015-04-08

    Solid-state electrolytes provide substantial improvements to safety and electrochemical stability in lithium-ion batteries when compared with conventional liquid electrolytes, which makes them a promising alternative technology for next-generation high-energy batteries. Currently, the low mobility of lithium ions in solid electrolytes limits their practical application. The ongoing research over the past few decades on dispersing of ceramic nanoparticles into polymer matrix has been proved effective to enhance ionic conductivity although it is challenging to form the efficiency networks of ionic conduction with nanoparticles. In this work, we first report that ceramic nanowire fillers can facilitate formation of such ionic conduction networks in polymer-based solid electrolyte to enhance its ionic conductivity by three orders of magnitude. Polyacrylonitrile-LiClO4 incorporated with 15 wt % Li0.33La0.557TiO3 nanowire composite electrolyte exhibits an unprecedented ionic conductivity of 2.4 × 10(-4) S cm(-1) at room temperature, which is attributed to the fast ion transport on the surfaces of ceramic nanowires acting as conductive network in the polymer matrix. In addition, the ceramic-nanowire filled composite polymer electrolyte shows an enlarged electrochemical stability window in comparison to the one without fillers. The discovery in the present work paves the way for the design of solid ion electrolytes with superior performance.

  9. Computational design of co-assembling protein-DNA nanowires

    NASA Astrophysics Data System (ADS)

    Mou, Yun; Yu, Jiun-Yann; Wannier, Timothy M.; Guo, Chin-Lin; Mayo, Stephen L.

    2015-09-01

    Biomolecular self-assemblies are of great interest to nanotechnologists because of their functional versatility and their biocompatibility. Over the past decade, sophisticated single-component nanostructures composed exclusively of nucleic acids, peptides and proteins have been reported, and these nanostructures have been used in a wide range of applications, from drug delivery to molecular computing. Despite these successes, the development of hybrid co-assemblies of nucleic acids and proteins has remained elusive. Here we use computational protein design to create a protein-DNA co-assembling nanomaterial whose assembly is driven via non-covalent interactions. To achieve this, a homodimerization interface is engineered onto the Drosophila Engrailed homeodomain (ENH), allowing the dimerized protein complex to bind to two double-stranded DNA (dsDNA) molecules. By varying the arrangement of protein-binding sites on the dsDNA, an irregular bulk nanoparticle or a nanowire with single-molecule width can be spontaneously formed by mixing the protein and dsDNA building blocks. We characterize the protein-DNA nanowire using fluorescence microscopy, atomic force microscopy and X-ray crystallography, confirming that the nanowire is formed via the proposed mechanism. This work lays the foundation for the development of new classes of protein-DNA hybrid materials. Further applications can be explored by incorporating DNA origami, DNA aptamers and/or peptide epitopes into the protein-DNA framework presented here.

  10. Assembly of Ultrathin Gold Nanowires into Honeycomb Macroporous Pattern Films with High Transparency and Conductivity.

    PubMed

    He, Ying; Chen, Yuan; Xu, Qingchi; Xu, Jun; Weng, Jian

    2017-03-01

    Because of its promising properties, honeycomb macroporous pattern (HMP) film has attracted increasing attention. It has been realized in many artificial nanomaterials, but the formation of these HMPs was attributed to templates or polymer/supermolecule/surfactant assistant assembly. Pure metal HMP film has been difficult to produce using a convenient colloidal template-free method. In this report, a unique template-free approach for preparation of Au HMP film with high transparency and conductivity is presented. Ultrathin Au nanowires, considered a linear polymer analogue, are directly assembled into HMP film on various substrates using a traditional static breath figure method. Subsequent chemical cross-linking and oxygen plasma treatment greatly enhance the stability and conductivity of the HMP film. The resulting HMP film exhibits great potential as an ideal candidate for transparent flexible conductive nanodevices.

  11. Self-assembled diphenylalanine nanowires for cellular studies and sensor applications.

    PubMed

    Sasso, Luigi; Vedarethinam, Indumathi; Emnéus, Jenny; Svendsen, Winnie E; Castillo-León, Jaime

    2012-04-01

    In this paper we present a series of experiments showing that vertical self-assembled diphenylalanine peptide nanowires (PNWs) are a suitable candidate material for cellular biosensing. We grew HeLa and PC12 cells onto PNW modified gold surfaces and observed no hindrance of cell growth caused by the peptide nanostructures; furthermore we studied the properties of PNWs by investigating their influence on the electrochemical behavior of gold electrodes. The PNWs were functionalized with polypyrrole (PPy) by chemical polymerization, therefore creating conducting peptide/polymer nanowire structures vertically attached to a metal electrode. The electroactivity of such structures was characterized by cyclic voltammetry. The PNW/PPy modified electrodes were finally used as amperometric dopamine sensors, yielding a detection limit of 3,1 microM.

  12. Designing and building nanowires: directed nanocrystal self-assembly into radically branched and zigzag PbS nanowires

    NASA Astrophysics Data System (ADS)

    Xu, Fan; Ma, Xin; Gerlein, L. Felipe; Cloutier, Sylvain G.

    2011-07-01

    Lead sulfide nanowires with controllable optoelectronic properties would be promising building blocks for various applications. Here, we report the hot colloidal synthesis of radically branched and zigzag nanowires through self-attachment of star-shaped and octahedral nanocrystals in the presence of multiple surfactants. We obtained high-quality single-crystal nanowires with uniform diameter along the entire length, and the size of the nanowire can be tuned by tailoring the reaction parameters. This slow oriented attachment provides a better understanding of the intricacies of this complex nanocrystal assembly process. Meanwhile, these self-assembled nanowire structures have appealing lateral conformations with narrow side arms or highly faceted edges, where strong quantum confinement can occur. Consequently, the single-crystal nanowire structures exhibit strong photoluminescence in the near-infrared region with a large blue-shift compared to the bulk material.

  13. Stepwise Self-Assembly of P3HT/CdSe Hybrid Nanowires with Enhanced Photoconductivity.

    PubMed

    Xu, Jingjing; Hu, Jianchen; Liu, Xinfeng; Qiu, Xiaohui; Wei, Zhixiang

    2009-08-18

    A facile approach to prepare poly(3-hexylthiophene) (P3HT)/cadmium selenide quantum dot (CdSe QD) hybrid coaxial nanowires by a stepwise self-assembly process is reported. P3HT nanowires of ≈20 nm diameter are first prepared by self-assembly in a poor solvent such as cyclohexanone, and then as-prepared CdSe QDs are deposited compactly onto the P3HT nanowires by non-covalent interactions between P3HT and CdSe. When illuminated with white light, the hybrid nanowires show enhanced photoconductivity compared with the pristine P3HT nanowires and the blended nanocomposites.

  14. Size dependent nanomechanics of coil spring shaped polymer nanowires

    PubMed Central

    Ushiba, Shota; Masui, Kyoko; Taguchi, Natsuo; Hamano, Tomoki; Kawata, Satoshi; Shoji, Satoru

    2015-01-01

    Direct laser writing (DLW) via two-photon polymerization (TPP) has been established as a powerful technique for fabrication and integration of nanoscale components, as it enables the production of three dimensional (3D) micro/nano objects. This technique has indeed led to numerous applications, including micro- and nanoelectromechanical systems (MEMS/NEMS), metamaterials, mechanical metamaterials, and photonic crystals. However, as the feature sizes decrease, an urgent demand has emerged to uncover the mechanics of nanosized polymer materials. Here, we fabricate coil spring shaped polymer nanowires using DLW via two-photon polymerization. We find that even the nanocoil springs follow a linear-response against applied forces, following Hooke’s law, as revealed by compression tests using an atomic force microscope. Further, the elasticity of the polymer material is found to become significantly greater as the wire radius is decreased from 550 to 350 nm. Polarized Raman spectroscopy measurements show that polymer chains are aligned in nanowires along the axis, which may be responsible for the size dependence. Our findings provide insight into the nanomechanics of polymer materials fabricated by DLW, which leads to further applications based on nanosized polymer materials. PMID:26612544

  15. Energy harvesting performance of piezoelectric ceramic and polymer nanowires.

    PubMed

    Crossley, Sam; Kar-Narayan, Sohini

    2015-08-28

    Energy harvesting from ubiquitous ambient vibrations is attractive for autonomous small-power applications and thus considerable research is focused on piezoelectric materials as they permit direct inter-conversion of mechanical and electrical energy. Nanogenerators (NGs) based on piezoelectric nanowires are particularly attractive due to their sensitivity to small-scale vibrations and may possess superior mechanical-to-electrical conversion efficiency when compared to bulk or thin-film devices of the same material. However, candidate piezoelectric nanowires have hitherto been predominantly analyzed in terms of NG output (i.e. output voltage, output current and output power density). Surprisingly, the corresponding dynamical properties of the NG, including details of how the nanowires are mechanically driven and its impact on performance, have been largely neglected. Here we investigate all realizable NG driving contexts separately involving inertial displacement, applied stress T and applied strain S, highlighting the effect of driving mechanism and frequency on NG performance in each case. We argue that, in the majority of cases, the intrinsic high resonance frequencies of piezoelectric nanowires (∼tens of MHz) present no barrier to high levels of NG performance even at frequencies far below resonance (<1 kHz) typically characteristic of ambient vibrations. In this context, we introduce vibrational energy harvesting (VEH) coefficients ηS and ηT, based on intrinsic materials properties, for comparing piezoelectric NG performance under strain-driven and stress-driven conditions respectively. These figures of merit permit, for the first time, a general comparison of piezoelectric nanowires for NG applications that takes into account the nature of the mechanical excitation. We thus investigate the energy harvesting performance of prototypical piezoelectric ceramic and polymer nanowires. We find that even though ceramic and polymer nanowires have been found, in

  16. Stirring-assisted assembly of nanowires at liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Li, Wen-Ze; Wei, Wei; Chen, Jun-Yi; He, Ji-Xiang; Xue, Sheng-Nan; Zhang, Jing; Liu, Xia; Li, Xiang; Fu, Yu; Jiao, Yong-Hua; Zhang, Kai; Liu, Fuchun; Han, En-Hou

    2013-03-01

    The assembly of Ag nanowires on quartz substrates from suspensions of water and ethylene glycol under stirring has been investigated. The introduction of stirring makes a remarkable difference to the assembly morphology. Firstly, the surface coverage of Ag nanowires is increased by a factor of 4 (in water) and 8 (in ethylene glycol) with stirring. Secondly, the Ag nanowires assembled in the stirred ethylene glycol dispersion were highly aligned. The influence of the surface of substrates, solvents and profile of the nanowires on the alignment has been explored, which indicates that stirring is an efficient way to generate nanowire arrays. This study has revealed the great potential of the stirring-assisted assembly technique in producing structurally controlled nanoarchitectures, opening up new opportunities for manufacturing ordered nanomaterials.

  17. Bridging length scales to measure polymer assembly.

    PubMed

    Kaye, Bryan; Yoo, Tae Yeon; Foster, Peter J; Yu, Che-Hang; Needleman, Daniel J

    2017-03-29

    Time-resolvable quantitative measurements of polymer concentration are very useful to elucidate protein polymerization pathways. There are numerous techniques to measure polymer concentrations in purified protein solutions, but few are applicable in vivo Here we develop a methodology combining microscopy and spectroscopy to overcome the limitations of both approaches for measuring polymer concentration in cells and cell extracts. This technique is based on quantifying the relationship between microscopy and spectroscopy measurements at many locations. We apply this methodology to measure microtubule assembly in tissue culture cells and Xenopus egg extracts using two-photon microscopy with FLIM measurements of FRET. We find that the relationship between FRET and two-photon intensity quantitatively agrees with predictions. Furthermore, FRET and intensity measurements change as expected with changes in acquisition time, labeling ratios, and polymer concentration. Taken together, these results demonstrate that this approach can quantitatively measure microtubule assembly in complex environments. This methodology should be broadly useful for studying microtubule nucleation and assembly pathways of other polymers.

  18. Synthesis and supramolecular assembly of biomimetic polymers

    NASA Astrophysics Data System (ADS)

    Marciel, Amanda Brittany

    A grand challenge in materials chemistry is the synthesis of macromolecules and polymers with precise shapes and architectures. Polymer microstructure and architecture strongly affect the resulting functionality of advanced materials, yet understanding the static and dynamic properties of these complex macromolecules in bulk has been difficult due to their inherit polydispersity. Single molecule studies have provided a wealth of information on linear flexible and semi-flexible polymers in dilute solutions. However, few investigations have focused on industrially relevant complex topologies (e.g., star, comb, hyperbranched polymers) in industrially relevant solution conditions (e.g., semi-dilute, concentrated). Therefore, from this perspective there is a strong need to synthesize precision complex architectures for bulk studies as well as complex architectures compatible with current single molecule techniques to study static and dynamic polymer properties. In this way, we developed a hybrid synthetic strategy to produce branched polymer architectures based on chemically modified DNA. Overall, this approach enables control of backbone length and flexibility, as well as branch grafting density and chemical identity. We utilized a two-step scheme based on enzymatic incorporation of non-natural nucleotides containing bioorthogonal dibenzocyclooctyne (DBCO) functional groups along the main polymer backbone, followed by copper-free "click" chemistry to graft synthetic polymer branches or oligonucleotide branches to the DNA backbone, thereby allowing for the synthesis of a variety of polymer architectures, including three-arm stars, H-polymers, graft block copolymers, and comb polymers for materials assembly and single molecule studies. Bulk materials properties are also affected by industrial processing conditions that alter polymer morphology. Therefore, in an alternative strategy we developed a microfluidic-based approach to assemble highly aligned synthetic

  19. Nanostructured assemblies from amphiphilic ABC multiblock polymers

    NASA Astrophysics Data System (ADS)

    Hillmyer, Marc A.

    2012-02-01

    Amphiphilic AB diblock copolymers containing a water compatible segment can self-assemble in aqueous media to give supramolecular structures that include simple spherical micelles and macromolecular vesicles termed polymersomes. Amphiphilic ABA triblocks with hydrophobic end blocks can adopt analogous structures but can also form gels at high polymer concentrations. The structural and chemical diversity demonstrated in block copolymer micelles and gels makes them attractive for applications ranging from drug delivery to personal care products to nanoreactors. The inclusion of a third block in amphiphilic ABC triblock systems can lead to a much wider array of self-assembled structures that depend not only on composition but also on block sequence, architecture and incompatibility considerations. I will present our recent efforts on tuning micelle and gel structure and behavior using controlled architecture ABC triblocks. The combination of diverse polymer segments into a single macromolecule is a powerful method for development of self-assembled structures with both new form and new function.

  20. Zinc Oxide Nanowire Interphase for Enhanced Lightweight Polymer Fiber Composites

    NASA Technical Reports Server (NTRS)

    Sodano, Henry A.; Brett, Robert

    2011-01-01

    The objective of this work was to increase the interfacial strength between aramid fiber and epoxy matrix. This was achieved by functionalizing the aramid fiber followed by growth of a layer of ZnO nanowires on the fiber surface such that when embedded into the polymer, the load transfer and bonding area could be substantially enhanced. The functionalization procedure developed here created functional carboxylic acid surface groups that chemically interact with the ZnO and thus greatly enhance the strength of the interface between the fiber and the ZnO.

  1. Thermoelectric properties of large-scale Zn3P2 nanowire assemblies.

    PubMed

    Brockway, Lance; Vasiraju, Venkata; Asayesh-Ardakani, Hasti; Shahbazian-Yassar, Reza; Vaddiraju, Sreeram

    2014-04-11

    Gram quantities of both unfunctionalized and 1,4-benzenedithiol (BDT) functionalized zinc phosphide (Zn3P2) nanowire powders, synthesized using direct reaction of zinc and phosphorus, were hot-pressed into highly dense pellets (≥98% of the theoretical density) for the determination of their thermoelectric performance. It was deduced that mechanical flexibility of the nanowires is essential for consolidating them in randomly oriented fashion into dense pellets, without making any major changes to their morphologies. Electrical and thermal transport measurements indicated that the enhanced thermoelectric performance expected of individual Zn3P2 nanowires is still retained within large-scale nanowire assemblies. A maximum reduction of 28% in the thermal conductivity of Zn3P2 resulted from nanostructuring. Use of nanowire morphology also led to enhanced electrical conductivity in Zn3P2. Interface engineering of the nanowires in the pellets, accomplished by hot-pressing BDT functionalized nanowires, resulted in an increase on both the Seebeck coefficient and the electrical conductivity of the nanowire pellets. It is believed that filtering of low energy carriers resulting from the variation of the chemical compositions at the nanowire interfaces is responsible for this phenomenon. Overall, this study indicated that mechanical properties of the nanowires along with the chemical compositions of their surfaces play a hitherto unknown, but vital, role in realizing highly efficient bulk thermoelectric modules based on nanowires.

  2. Thermoelectric properties of large-scale Zn3 P2 nanowire assemblies

    NASA Astrophysics Data System (ADS)

    Brockway, Lance; Vasiraju, Venkata; Asayesh-Ardakani, Hasti; Shahbazian-Yassar, Reza; Vaddiraju, Sreeram

    2014-04-01

    Gram quantities of both unfunctionalized and 1,4-benzenedithiol (BDT) functionalized zinc phosphide (Zn3P2) nanowire powders, synthesized using direct reaction of zinc and phosphorus, were hot-pressed into highly dense pellets (≥98% of the theoretical density) for the determination of their thermoelectric performance. It was deduced that mechanical flexibility of the nanowires is essential for consolidating them in randomly oriented fashion into dense pellets, without making any major changes to their morphologies. Electrical and thermal transport measurements indicated that the enhanced thermoelectric performance expected of individual Zn3P2 nanowires is still retained within large-scale nanowire assemblies. A maximum reduction of 28% in the thermal conductivity of Zn3P2 resulted from nanostructuring. Use of nanowire morphology also led to enhanced electrical conductivity in Zn3P2. Interface engineering of the nanowires in the pellets, accomplished by hot-pressing BDT functionalized nanowires, resulted in an increase on both the Seebeck coefficient and the electrical conductivity of the nanowire pellets. It is believed that filtering of low energy carriers resulting from the variation of the chemical compositions at the nanowire interfaces is responsible for this phenomenon. Overall, this study indicated that mechanical properties of the nanowires along with the chemical compositions of their surfaces play a hitherto unknown, but vital, role in realizing highly efficient bulk thermoelectric modules based on nanowires.

  3. Supramolecular assembly in telechelic polymer blends

    NASA Astrophysics Data System (ADS)

    Elliott, R.; Fredrickson, Glenn H.

    2009-10-01

    Equilibrium, supramolecular assembly in melt blends of two species of telechelic polymers with reversible bonding sites at both ends is theoretically investigated. The bonding between polymers, whether between like or dislike chains, is controlled by affinities of chain bonding set by specified bond energies. Low affinities, or low overall bond strength, results in a monodisperse population of unlinked chains while larger affinities cause longer chains to assemble, forming a polydisperse blend. We investigate sequentially blends with only homobonding (like chain), only heterobonding (dislike chain), and finally a mixed homo- and heterobonding melt. In the first case, the effects of longer chain assembly and polydispersity in a homogeneous melt and its bulk demixing transition are explored. In contrast with the homobonding case, large heterobonding affinities cause alternating blocks to assemble into multiblock copolymers, which can lead to mesophases. The weak bonding region between bulk phase separation and mesophase stability is investigated and a novel Lifshitz point is found indicating a region prone to emulsify. Mixed homo- and heterobonding systems are also examined. Polymeric segments of both species are modeled as flexible Gaussian threads and nonspecific interactions between dissimilar blocks are contactlike Flory-Huggins repulsions. The melts are assumed to be incompressible and all calculations are carried out within mean-field theory. A new integral equation formalism is developed for enumerating all linear species in these complex supramolecular systems, and the random phase approximation and numerical self-consistent field theory are invoked in this context to map out a variety of phase diagrams.

  4. Cationic Antimicrobial Polymers and Their Assemblies

    PubMed Central

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

    2013-01-01

    Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

  5. Self-assembly of semiconductor organogelator nanowires for photoinduced charge separation.

    PubMed

    Wicklein, André; Ghosh, Suhrit; Sommer, Michael; Würthner, Frank; Thelakkat, Mukundan

    2009-05-26

    We investigated an innovative concept of general validity based on an organogel/polymer system to generate donor-acceptor nanostructures suitable for charge generation and charge transport. An electron conducting (acceptor) perylene bisimide organogelator forms nanowires in suitable solvents during gelation process. This phenomenon was utilized for its self-assembly in an amorphous hole conducting (donor) polymer matrix to realize an interpenetrating donor-acceptor interface with inherent morphological stability. The self-assembly and interface generation were carried out either stepwise or in a single-step. Morphology of the donor-acceptor network in thin films obtained via both routes were studied by a combination of scanning electron microscopy and atomic force microscopy. Additionally, photoinduced charge separation and charge transport in these systems were tested in organic solar cells. Fabrication steps of multilayer organogel/polymer photovoltaic devices were optimized with respect to morphology and surface roughness by introducing additional smoothening layers and charge injection/blocking layers. An inverted cell geometry was used here in which electrons are collected at the bottom electrode and holes at the top electrode. The simultaneous preparation of the interface exhibits almost 3-fold improvement in device characteristics compared to the successive method. The device characteristics under AM1.5 spectral conditions and 100 mW/cm(2) for the simultaneous preparation route are short circuit current J(sc) = 0.28 mA cm(-2), open circuit voltage V(OC) = 390 mV, fill factor FF = 38%, and a power conversion efficiency eta = 0.041%.

  6. Nanoparticles in Polymers: Assembly, Rheology and Properties

    NASA Astrophysics Data System (ADS)

    Rao, Yuanqiao

    Inorganic nanoparticles have the potential of providing functionalities that are difficult to realize using organic materials; and nanocomposites is an effective mean to impart processibility and construct bulk materials with breakthrough properties. The dispersion and assembly of nanoparticles are critical to both processibility and properties of the resulting product. In this talk, we will discuss several methods to control the hierarchical structure of nanoparticles in polymers and resulting rheological, mechanical and optical properties. In one example, polymer-particle interaction and secondary microstructure were designed to provide a low viscosity composition comprising exfoliated high aspect ratio clay nanoparticles; in another example, the microstructure control through templates was shown to enable unique thermal mechanical and optical properties. Jeff Munro, Stephanie Potisek, Phillip Hustad; all of the Dow Chemical Company are co-authors.

  7. Generalized Redox-Responsive Assembly of Carbon-Sheathed Metallic and Semiconducting Nanowire Heterostructures.

    PubMed

    Choi, Sinho; Kim, Jieun; Hwang, Dae Yeon; Park, Hyungmin; Ryu, Jaegeon; Kwak, Sang Kyu; Park, Soojin

    2016-02-10

    One-dimensional metallic/semiconducting materials have demonstrated as building blocks for various potential applications. Here, we report on a unique synthesis technique for redox-responsive assembled carbon-sheathed metal/semiconducting nanowire heterostructures that does not require a metal catalyst. In our approach, germanium nanowires are grown by the reduction of germanium oxide particles and subsequent self-catalytic growth during the thermal decomposition of natural gas, and simultaneously, carbon sheath layers are uniformly coated on the nanowire surface. This process is a simple, reproducible, size-controllable, and cost-effective process whereby most metal oxides can be transformed into metallic/semiconducting nanowires. Furthermore, the germanium nanowires exhibit stable chemical/thermal stability and outstanding electrochemical performance including a capacity retention of ∼96% after 1200 cycles at the 0.5-1C rate as lithium-ion battery anode.

  8. Self-assembled nanowire array capacitors: capacitance and interface state profile

    NASA Astrophysics Data System (ADS)

    Li, Qiliang; Xiong, Hao D.; Liang, Xuelei; Zhu, Xiaoxiao; Gu, Diefeng; Ioannou, Dimitris E.; Baumgart, Helmut; Richter, Curt A.

    2014-04-01

    Direct characterization of the capacitance and interface states is very important for understanding the electronic properties of a nanowire transistor. However, the capacitance of a single nanowire is too small to precisely measure. In this work we have fabricated metal-oxide-semiconductor capacitors based on a large array of self-assembled Si nanowires. The capacitance and conductance of the nanowire array capacitors are directly measured and the interface state profile is determined by using the conductance method. We demonstrate that the nanowire array capacitor is an effective platform for studying the electronic properties of nanoscale interfaces. This approach provides a useful and efficient metrology for the study of the physics and device properties of nanoscale metal-oxide-semiconductor structures.

  9. Self-assembled nanowire array capacitors: capacitance and interface state profile.

    PubMed

    Li, Qiliang; Xiong, Hao D; Liang, Xuelei; Zhu, Xiaoxiao; Gu, Diefeng; Ioannou, Dimitris E; Baumgart, Helmut; Richter, Curt A

    2014-04-04

    Direct characterization of the capacitance and interface states is very important for understanding the electronic properties of a nanowire transistor. However, the capacitance of a single nanowire is too small to precisely measure. In this work we have fabricated metal-oxide-semiconductor capacitors based on a large array of self-assembled Si nanowires. The capacitance and conductance of the nanowire array capacitors are directly measured and the interface state profile is determined by using the conductance method. We demonstrate that the nanowire array capacitor is an effective platform for studying the electronic properties of nanoscale interfaces. This approach provides a useful and efficient metrology for the study of the physics and device properties of nanoscale metal-oxide-semiconductor structures.

  10. Redox-exchange induced heterogeneous RuO2-conductive polymer nanowires.

    PubMed

    Gui, Zhe; Duay, Jonathon; Hu, Junkai; Lee, Sang Bok

    2014-06-28

    A redox exchange mechanism between potassium perruthenate (KRuO4) and the functional groups of selected polymers is used here to induce RuO2 into and onto conductive polymer nanowires by simply soaking the polymer nanowire arrays in KRuO4 solution. Conductive polymer nanowire arrays of polypyrrole (PPY) and poly(3,4-ethylenedioxythiophene) (PEDOT) were studied in this work. SEM and TEM results show that the RuO2 material was distributed differently in the PPY and PEDOT nanowire matrices. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy were used to confirm the dispersion and formation of RuO2 materials in these polymer nanowires. Cyclic voltammetry and galvanostatic charge-discharge experiments were used to characterize their electrochemical performance. RuO2-polymer samples prepared with a 6 min soaking time in 10 mM KRuO4 solution show a high specific capacitance of 371 F g(-1) and 500 F g(-1) for PEDOT-based and PPY-based composite nanowires, respectively. This is attributed to the high exposure area of the conductive RuO2 and the good conductivity of the polymer matrix. This work demonstrates a simple method to synthesize heterogeneous polymer based-materials through the redox reaction between conductive polymers and high oxidation state transition metal oxide ions. Different heterogeneous nanocomposites were obtained depending on the polymer properties, and high energy storage performance of the metal oxides can be achieved within these heterogeneous nanostructures.

  11. Lithium-Assisted Self-Assembly of Aluminum Carbide Nanowires and Nanoribbons

    SciTech Connect

    Zhang, Hai-Feng; Dohnalkova, Alice ); Wang, Chongmin ); Young, James S. ); Buck, Edgar C. ); Wang, Lai-Sheng

    2001-12-01

    We report on the synthesis and self-assembly of Al4C3 nanowires and nanoribbons using lithium as a catalyst. Large quantities of Al4C3 nanowires (diameters from 5 to 70 nm) and nanoribbons (5-70 nm thick and 20-5600 nm wide) tens of micrometers long were synthesized serendipitously in a solid-state reaction involving Al/C/Li at less than 780 degrees Celsius. High-resolution electron microscopy revealed that the nanowires all grew along the c-axis of hexagonal Al4C3, whereas the nanoribbons all grew within the basal plane. The facile synthesis of the Al4C3 nanowires and nanoribbons suggest similar nanostructures of other carbide and nitride materials may be made using the lithium-assisted self-assembly process.

  12. Polymer-like conformation and growth kinetics of Bi2S3 nanowires.

    PubMed

    Cademartiri, Ludovico; Guerin, Gerald; Bishop, Kyle J M; Winnik, Mitchell A; Ozin, Geoffrey A

    2012-06-06

    One-dimensional inorganic crystals (i.e., crystalline nanowires) are one of the most intensely investigated classes of materials of the past two decades. Despite this intense effort, an important question has yet to be answered: do nanowires display some of the unique characteristics of polymers as their diameter is progressively decreased? This work addresses this question with three remarkable findings on the growth and form of ultrathin Bi(2)S(3) nanowires. (i) Their crystallization in solution is quantitatively describable as a form of living step-growth polymerization: an apparently exclusive combination of addition of "monomer" to the ends of the nanowires and coupling of fully formed nanowires "end-to-end", with negligible termination and initiation. (ii) The rate constants of these two main processes are comparable to those of analogous processes found in polymerization. (iii) The conformation of these nanowires is quantitatively described as a worm-like conformation analytically analogous to that of semiflexible polymers and characterized by a persistence length of 17.5 nm (shorter than that of double-stranded DNA) and contour lengths of hundreds of micrometers (longer than those of most synthetic polymers). These findings do not prove a chemical analogy between crystals and polymers (it is unclear if the monomer is a molecular entity tout court) but demonstrate a physical analogy between crystallization and polymerization. Specifically, they (i) show that the crystallization of ensembles of nanoscale inorganic crystals can be conceptually analogous to polymerization and can be described quantitatively with the same experimental and mathematical tools, (ii) demonstrate that one-dimensional nanocrystals can display topological characteristics of polymers (e.g., worm-like conformation in solution), (iii) establish a unique experimental model system for the investigation of polymer-like topological properties in inorganic crystals, and (iv) provide new

  13. Highly flexible silver nanowire electrodes for shape-memory polymer light-emitting diodes.

    PubMed

    Yu, Zhibin; Zhang, Qingwu; Li, Lu; Chen, Qi; Niu, Xiaofan; Liu, Jun; Pei, Qibing

    2011-02-01

    Shape-memory polymer light-emitting diodes (PLEDs) using a new silver nanowire/polymer electrode are reported. The electrode can be stretched by up to 16% with only a small increase in sheet resistance. Large deformation shape change and recovery of the PLEDs to various bistable curvatures result in minimal loss of electroluminescence performance.

  14. Heterojunction photovoltaics using GaAs nanowires and conjugated polymers.

    PubMed

    Ren, Shenqiang; Zhao, Ni; Crawford, Samuel C; Tambe, Michael; Bulović, Vladimir; Gradecak, Silvija

    2011-02-09

    We demonstrate an organic/inorganic solar cell architecture based on a blend of poly(3-hexylthiophene) (P3HT) and narrow bandgap GaAs nanowires. The measured increase of device photocurrent with increased nanowire loading is correlated with structural ordering within the active layer that enhances charge transport. Coating the GaAs nanowires with TiO(x) shells passivates nanowire surface states and further improves the photovoltaic performance. We find that the P3HT/nanowire cells yield power conversion efficiencies of 2.36% under white LED illumination for devices containing 50 wt % of TiO(x)-coated GaAs nanowires. Our results constitute important progress for the use of nanowires in large area solution processed hybrid photovoltaic cells and provide insight into the role of structural ordering in the device performance.

  15. Nanowires and Nanostructures That Grow Like Polymer Molecules

    SciTech Connect

    Shaw, Santosh; Cademartiri, Ludovico

    2013-09-20

    Unique properties (e.g., rubber elasticity, viscoelasticity, folding, reptation) determine the utility of polymer molecules and derive from their morphology (i.e., one-dimensional connectivity and large aspect ratios) and flexibility. Crystals do not display similar properties because they have smaller aspect ratios, they are rigid, and they are often too large and heavy to be colloidally stable. We argue, with the support of recent experimental studies, that these limitations are not fundamental and that they might be overcome by growth processes that mimic polymerization. Furthermore, we (i) discuss the similarities between crystallization and polymerization, (ii) critically review the existing experimental evidence of polymer-like growth kinetic and behavior in crystals and nanostructures, and (iii) propose heuristic guidelines for the synthesis of “polymer-like” crystals and assemblies. Understanding these anisotropic materials at the boundary between molecules and solids will determine whether we can confer the unique properties of polymer molecules to crystals, expanding them with topology, dynamics, and information and not just tuning them with size.

  16. Zinc oxide nanowire interphase for enhanced interfacial strength in lightweight polymer fiber composites.

    PubMed

    Ehlert, Gregory J; Sodano, Henry A

    2009-08-01

    A novel functionalization method for aramid fibers is developed to enhance the bonding of a ZnO nanowire interphase grown on the fiber surface for interfacial strength enhancement. The nanowire interphase functionally grades the typically discrete interface and reduces the stress concentration between the fiber and matrix. The functionalization process is developed to improve the bonding between the ZnO nanowires and the aramid fiber and is validated through Fourier transform IR and X-ray photoelectron spectroscopy studies. Mechanical testing shows significant improvement in the interfacial shear strength with no decrease in the base fiber strength. This is the only technique found in the literature for the growth of a nanowire interphase on polymer fibers for structural enhancement without degrading the in-plane properties of the bulk composite. Furthermore, it is firmly shown that the functionalization process is a necessary condition for enhanced interfacial strength, demonstrating that ZnO nanowires strongly interact with carboxylic acid functional groups.

  17. Polymer and biopolymer mediated self-assembly of gold nanoparticles.

    PubMed

    Ofir, Yuval; Samanta, Bappaditya; Rotello, Vincent M

    2008-09-01

    Gold nanoparticle-polymer composites are versatile and diverse functional materials, with applications in optical, electronic and sensing devices. This tutorial review focuses on the use of polymers to control the assembly of gold nanoparticles. Examples of synthetic polymers and biopolymers are provided, as well as applications of the composite materials in sensing and memory devices.

  18. Ultraviolet photodetection of flexible ZnO nanowire sheets in polydimethylsiloxane polymer

    PubMed Central

    Motta, Nunzio; Lee, Soonil

    2012-01-01

    Summary ZnO nanowires are normally exposed to an oxygen atmosphere to achieve high performance in UV photodetection. In this work we present results on a UV photodetector fabricated using a flexible ZnO nanowire sheet embedded in polydimethylsiloxane (PDMS), a gas-permeable polymer, showing reproducible UV photoresponse and enhanced photoconduction. PDMS coating results in a reduced response speed compared to that of a ZnO nanowire film in air. The rising speed is slightly reduced, while the decay time is prolonged by about a factor of four. We conclude that oxygen molecules diffusing in PDMS are responsible for the UV photoresponse. PMID:23016139

  19. Metal-conductive polymer hybrid nanostructures: preparation and electrical properties of palladium-polyimidazole nanowires.

    PubMed

    Al-Hinai, Mariam; Hassanien, Reda; Watson, Scott M D; Wright, Nicholas G; Houlton, Andrew; Horrocks, Benjamin R

    2016-03-04

    A simple, convenient method for the formation of hybrid metal/conductive polymer nanostructures is described. Polyimidazole (PIm) has been templated on λ-DNA via oxidative polymerisation of imidazole using FeCl3 to produce conductive PIm/DNA nanowires. The PIm/DNA nanowires were decorated with Pd (Pd/PIm/DNA) by electroless reduction of PdCl4(-2) with NaBH4 in the presence of PIm/DNA; the choice of imidazole was motivated by the potential Pd(II) binding site at the pyridinic N atom. The formation of PIm/DNA and the presence of metallic Pd on Pd/PIm/DNA nanowires were verified by FTIR, UV-vis and XPS spectroscopy techniques. AFM studies show that the nanowires have diameters in the range 5-45 nm with a slightly greater mean diameter (17.1 ± 0.75 nm) for the Pd-decorated nanowires than the PIm/DNA nanowires (14.5 ± 0.89 nm). After incubation for 24 h in the polymerisation solution, the PIm/DNA nanowires show a smooth, uniform morphology, which is retained after decoration with Pd. Using a combination of scanned conductance microscopy, conductive AFM and two-terminal measurements we show that both types of nanowire are conductive and that it is possible to discriminate different possible mechanisms of transport. The conductivity of the Pd/PIm/DNA nanowires, (0.1-1.4 S cm(-1)), is comparable to the PIm/DNA nanowires (0.37 ± 0.029 S cm(-1)). In addition, the conductance of Pd/PIm/DNA nanowires exhibits Arrhenius behaviour (E(a )= 0.43 ± 0.02 eV) as a function of temperature in contrast to simple Pd/DNA nanowires. These results indicate that although the Pd crystallites on Pd/PIm/DNA nanowires decorate the PIm polymer, the major current pathway is through the polymer rather than the Pd.

  20. Metal-conductive polymer hybrid nanostructures: preparation and electrical properties of palladium-polyimidazole nanowires

    NASA Astrophysics Data System (ADS)

    Al-Hinai, Mariam; Hassanien, Reda; Watson, Scott M. D.; Wright, Nicholas G.; Houlton, Andrew; Horrocks, Benjamin R.

    2016-03-01

    A simple, convenient method for the formation of hybrid metal/conductive polymer nanostructures is described. Polyimidazole (PIm) has been templated on λ-DNA via oxidative polymerisation of imidazole using FeCl3 to produce conductive PIm/DNA nanowires. The PIm/DNA nanowires were decorated with Pd (Pd/PIm/DNA) by electroless reduction of {{{{PdCl}}}4}2- with NaBH4 in the presence of PIm/DNA; the choice of imidazole was motivated by the potential Pd(II) binding site at the pyridinic N atom. The formation of PIm/DNA and the presence of metallic Pd on Pd/PIm/DNA nanowires were verified by FTIR, UV-vis and XPS spectroscopy techniques. AFM studies show that the nanowires have diameters in the range 5-45 nm with a slightly greater mean diameter (17.1 ± 0.75 nm) for the Pd-decorated nanowires than the PIm/DNA nanowires (14.5 ± 0.89 nm). After incubation for 24 h in the polymerisation solution, the PIm/DNA nanowires show a smooth, uniform morphology, which is retained after decoration with Pd. Using a combination of scanned conductance microscopy, conductive AFM and two-terminal measurements we show that both types of nanowire are conductive and that it is possible to discriminate different possible mechanisms of transport. The conductivity of the Pd/PIm/DNA nanowires, (0.1-1.4 S cm-1), is comparable to the PIm/DNA nanowires (0.37 ± 0.029 S cm-1). In addition, the conductance of Pd/PIm/DNA nanowires exhibits Arrhenius behaviour (E a = 0.43 ± 0.02 eV) as a function of temperature in contrast to simple Pd/DNA nanowires. These results indicate that although the Pd crystallites on Pd/PIm/DNA nanowires decorate the PIm polymer, the major current pathway is through the polymer rather than the Pd.

  1. Room Temperature Sensing Achieved by GaAs Nanowires and oCVD Polymer Coating.

    PubMed

    Wang, Xiaoxue; Ermez, Sema; Goktas, Hilal; Gradečak, Silvija; Gleason, Karen

    2017-04-13

    Novel structures comprised of GaAs nanowire arrays conformally coated with conducting polymers (poly(3,4-ethylenedioxythiophene) (PEDOT) or poly(3,4-ethylenedioxythiophene-co-3-thiophene acetic acid) display both sensitivity and selectivity to a variety of volatile organic chemicals. A key feature is room temperature operation, so that neither a heater nor the power it would consume, is required. It is a distinct difference from traditional metal oxide sensors, which typically require elevated operational temperature. The GaAs nanowires are prepared directly via self-seeded metal-organic chemical deposition, and conducting polymers are deposited on GaAs nanowires using oxidative chemical vapor deposition (oCVD). The range of thickness for the oCVD layer is between 100 and 200 nm, which is controlled by changing the deposition time. X-ray diffraction analysis indicates an edge-on alignment of the crystalline structure of the PEDOT coating layer on GaAs nanowires. In addition, the positive correlation between the improvement of sensitivity and the increasing nanowire density is demonstrated. Furthermore, the effect of different oCVD coating materials is studied. The sensing mechanism is also discussed with studies considering both nanowire density and polymer types. Overall, the novel structure exhibits good sensitivity and selectivity in gas sensing, and provides a promising platform for future sensor design.

  2. Assembly of Poly(3-hexylthiophene)/CdSe Hybrid Nanowires by Cocrystallization

    SciTech Connect

    Bokel, Felica A.; Sudeep, P. K.; Pentzer, Emily; Emrick, Todd; Hayward, Ryan C.

    2011-04-12

    We present a new method to preorganize electron donor and acceptor materials into hybrid nanowire structures, enabled by crystallization of regioregular poly(3-hexylthiophene) (rrP3HT) in solution in the presence of CdSe nanorods functionalized with the same polymer. These well-organized nanocomposite fibers are potentially attractive building blocks for optoelectronic devices and active layers in photovoltaics.

  3. Polymer chain alignment and transistor properties of nanochannel-templated poly(3-hexylthiophene) nanowires

    NASA Astrophysics Data System (ADS)

    Oh, Seungjun; Hayakawa, Ryoma; Pan, Chengjun; Sugiyasu, Kazunori; Wakayama, Yutaka

    2016-08-01

    Nanowires of semiconducting poly(3-hexylthiophene) (P3HT) were produced by a nanochannel-template technique. Polymer chain alignment in P3HT nanowires was investigated as a function of nanochannel widths (W) and polymer chain lengths (L). We found that the ratio between chain length and channel width (L/W) was a key parameter as regards promoting polymer chain alignment. Clear dichroism was observed in polarized ultraviolet-visible (UV-Vis) absorption spectra only at a ratio of approximately L/W = 2, indicating that the L/W ratio must be optimized to achieve uniaxial chain alignment in the nanochannel direction. We speculate that an appropriate L/W ratio is effective in confining the geometries and conformations of polymer chains. This discussion was supported by theoretical simulations based on molecular dynamics. That is, the geometry of the polymer chains, including the distance and tilting angles of the chains in relation to the nanochannel surface, was dominant in determining the longitudinal alignment along the nanochannels. Thus prepared highly aligned polymer nanowire is advantageous for electrical carrier transport and has great potential for improving the device performance of field-effect transistors. In fact, a one-order improvement in carrier mobility was observed in a P3HT nanowire transistor.

  4. Electric conductivity-tunable transparent flexible nanowire-filled polymer composites: orientation control of nanowires in a magnetic field.

    PubMed

    Nagai, Takayuki; Aoki, Nobuyuki; Ochiai, Yuichi; Hoshino, Katsuyoshi

    2011-07-01

    Cobalt compound nanowires were dispersed in a transparent nonconductive polymer film by merely stirring, and the film's transparency and electrical conductivity were examined. This composite film is a unique system in which the average length of the nanowires exceeds the film's thickness. Even in such a system, a percolation threshold existed for the electric conductivity in the direction of the film thickness, and the value was 0.18 vol%. The electric conductivity value changed from ∼1 × 10(-12) S/cm to ∼1 × 10(-3) S/cm when the volume fraction exceeded the threshold. The electric conductivity apparently followed the percolation model until the volume fraction of the nanowires was about 0.45 vol %. The visible light transmission and electric conductivity of the composite film of about 1 vol % nanowires were 92% and 5 × 10(-3) S/cm, respectively. Moreover, the electric conductivity in the direction parallel to the film surface did not depend on the amount of the dispersed nanowires, and its value was about 1 × 10(-14) S/cm. Even in a weak magnetic field of about 100 mT, the nanowires were aligned in a vertical and parallel direction to the film surface, and the electric conductivity of each aligned composite film was 2.0 × 10(-2) S/cm and 2.1 × 10(-12) S/cm. The relation between the average wire length and the electric conductivity was examined, and the effect of the magnetic alignment on that relation was also examined.

  5. Grooved nanowires from self-assembling hairpin molecules for solar cells.

    PubMed

    Tevis, Ian D; Tsai, Wei-Wen; Palmer, Liam C; Aytun, Taner; Stupp, Samuel I

    2012-03-27

    One of the challenges facing bulk heterojunction organic solar cells is obtaining organized films during the phase separation of intimately mixed donor and acceptor components. We report here on the use of hairpin-shaped sexithiophene molecules to generate by self-assembly grooved nanowires as the donor component in bulk heterojunction solar cells. Photovoltaic devices were fabricated via spin-casting to produce by solvent evaporation a percolating network of self-assembled nanowires and fullerene acceptors. Thermal annealing was found to increase power conversion efficiencies by promoting domain growth while still maintaining this percolating network of nanostructures. The benefits of self-assembly and grooved nanowires were examined by building devices from a soluble sexithiophene derivative that does not form one-dimensional structures. In these systems, excessive phase separation caused by thermal annealing leads to the formation of defects and lower device efficiencies. We propose that the unique hairpin shape of the self-assembling molecules allows the nanowires as they form to interact well with the fullerenes in receptor-ligand type configurations at the heterojunction of the two domains, thus enhancing device efficiencies by 23%.

  6. Nanostructured photovoltaic materials using block polymer assemblies

    NASA Astrophysics Data System (ADS)

    Mastroianni, Sarah Elizabeth

    Despite its potential as an abundant, sustainable alternative to non-renewable energy sources, solar energy currently is underutilized. Photovoltaics, which convert energy from sunlight into electricity, commonly are made from inorganic semiconductor materials that require expensive manufacturing and processing techniques. Alternatively, organic materials can be used to produce flexible and lightweight organic photovoltaic (OPV) devices, which can be prepared using solution-based processing techniques. However, OPV devices are limited by low efficiencies and short lifetimes compared to their inorganic counterparts. In OPV systems, charge carriers are generated in the active layer via the separation of excitons (electron-hole pairs) at interfaces between donor and acceptor materials. Because excitons have a limited diffusion length (˜10 nm), they may recombine before reaching a donor-acceptor interface if domain sizes are large. This exciton recombination can limit device efficiency; thus, the design parameters for improved active layer morphologies include large interfacial areas, small size scales, and continuous conducting pathways. Currently, most OPV devices are prepared by blending donor and acceptor materials in bulk heterojunction (BHJ) devices, often resulting in non-ideal, process-dependent morphologies. Alternatively, the self-assembly of block polymers (BP)s offers a reproducible means to generate nanostructured active layers. The work presented in this dissertation examines the synthetic approaches to preparing BPs containing different electroactive materials: non-conjugated, amorphous poly(vinyl-m-triphenylamine) [PVmTPA] and conjugated poly(3-alkythiophene) [P3AT] p-type materials as well as fullerene-based n-type materials. The synthesis and self-assembly of a model poly(methyl methacrylate)- b-PVmTPA system is presented. This work was extended to synthesize PVmTPA BPs with complementary poly(methyl methacrylate- co-hydroxyethyl methacrylate) [P

  7. Development of Hierarchical Polymer@Pd Nanowire-Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink.

    PubMed

    Mir, Sajjad Husain; Ochiai, Bungo

    2016-06-01

    A facile one-pot approach for preparing hierarchical nanowire-networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal-complexation-induced phase separation with functionalized graft copolymers and subsequent self-assembly of PdNPs. The nanospheres hierarchically assembled into the nanowire-network upon drying. The Pd nanowire-network served as an active catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling reactions. As low as 500 μmol % Pd was sufficient for quantitative reactions, and the origin of the high activity is ascribed to the highly active sites originating from high-index facets, kinks, and coalesced structures. The catalyst can be recycled via simple filtration and washing, maintaining its high activity owing to the micrometer-sized hierarchical structure of the nanomaterial. The polymer@Pd nanosphere also served as a printable conductive ink for a translucent grid pattern with excellent horizontal conductivity (7.5×10(5) S m(-1)).

  8. Ultra long SiC nanowires with fluctuating diameters synthesized in a polymer pyrolysis CVD route

    NASA Astrophysics Data System (ADS)

    Li, Gong-Yi; Li, Xiao-Dong; Wang, Hao; Liu, Lin

    2009-12-01

    Large areas of millimeters long β-SiC nanowires with fluctuating diameters were synthesized in a polymer pyrolysis CVD (PPCVD) route. Polycarbosilane was used as the raw material. The morphology and structure of the nanowires were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results showed that the nanowires had non-periodically fluctuating diameters in the range of 100-250 nm along the axial direction, and were composed of well crystalline β-SiC along the <111> direction. The vapor-solid (VS) mechanism was employed to interpret the nanowires growth procedure, and the diameter fluctuation was resulted from the varying concentration of the local silane fragments.

  9. Dynamic self-assembly of coordination polymers in aqueous solution.

    PubMed

    Li, Wen; Kim, Yongju; Li, Jingfang; Lee, Myongsoo

    2014-08-07

    The construction of supramolecular polymers has been intensively pursued because the nanostructures formed through weak non-covalent interactions can be triggered by external stimuli leading to smart materials and sensors. Self-assemblies of coordination polymers consisting of metal ions and organic ligands in aqueous solution also provide particular contributions in this area. The main motivation for developing those coordination polymers originates from the value-added combination between metal ions and ligands. This review highlights the recent progress of the dynamic self-assembly of coordination polymers that result from the sophisticated molecular design, towards fabricating stimuli-responsive systems and bio-related materials. Dynamic structural changes and switchable physical properties triggered by various stimuli are summarized. Finally, the outlook for aqueous nanostructures originated from the dynamic self-assembly of coordination polymers is also presented.

  10. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    SciTech Connect

    Garzon, Fernando H.; Wilson, Mahlon S.; Banham, Dustin; Ye, Siyu; More, Karren Leslie

    2015-12-03

    Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of well dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.

  11. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    DOE PAGES

    Garzon, Fernando H.; Wilson, Mahlon S.; Banham, Dustin; ...

    2015-12-03

    Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of wellmore » dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.« less

  12. Self-assembled quantum dots in a nanowire system for quantum photonics.

    PubMed

    Heiss, M; Fontana, Y; Gustafsson, A; Wüst, G; Magen, C; O'Regan, D D; Luo, J W; Ketterer, B; Conesa-Boj, S; Kuhlmann, A V; Houel, J; Russo-Averchi, E; Morante, J R; Cantoni, M; Marzari, N; Arbiol, J; Zunger, A; Warburton, R J; Fontcuberta i Morral, A

    2013-05-01

    Quantum dots embedded within nanowires represent one of the most promising technologies for applications in quantum photonics. Whereas the top-down fabrication of such structures remains a technological challenge, their bottom-up fabrication through self-assembly is a potentially more powerful strategy. However, present approaches often yield quantum dots with large optical linewidths, making reproducibility of their physical properties difficult. We present a versatile quantum-dot-in-nanowire system that reproducibly self-assembles in core-shell GaAs/AlGaAs nanowires. The quantum dots form at the apex of a GaAs/AlGaAs interface, are highly stable, and can be positioned with nanometre precision relative to the nanowire centre. Unusually, their emission is blue-shifted relative to the lowest energy continuum states of the GaAs core. Large-scale electronic structure calculations show that the origin of the optical transitions lies in quantum confinement due to Al-rich barriers. By emitting in the red and self-assembling on silicon substrates, these quantum dots could therefore become building blocks for solid-state lighting devices and third-generation solar cells.

  13. Compliant silver nanowire-polymer composite electrodes for bistable large strain actuation.

    PubMed

    Yun, Sungryul; Niu, Xiaofan; Yu, Zhibin; Hu, Weili; Brochu, Paul; Pei, Qibing

    2012-03-08

    A new compliant electrode-based on silver nanowire-polymer composite has been developed. The composite electrode has low sheet resistance (as low as 10 Ω/sq), remains conductive (10(2) -10(3) Ω/sq) at strains as high as 140%, and can support Joule heating. The combination of the composite and a bistable electroactive polymer produces electrically-induced, large-strain actuation and relaxation, reversibly without the need of mechanical programming.

  14. Molecular Recognition Directed Self-Assembly of Supramolecular Polymers

    DTIC Science & Technology

    1994-06-30

    SUPRAMOLECULAR POLYMERS by V. Percec, J. Heck, G. Johansson, D. Tomazos, M. Kawasumi and G. Ungar Published in the J. Macromol. SOi: Part A: Pure...W.asetaqIom OC JOS0l 4 TITE AN SUBITLES. FUNDING NUMBERS Molecular Recognition Directed Self-Assembly of Suprainolecular Polymers N00014-89--J-1828 6. AUTHOR(S...comparison between various supramolecular (generated via H-bonding, iions) and molecular " polymer backbones" will be made. The present limitations

  15. Self-Assembly of Silver Nanowire Ring Structures Driven by the Compressive Force of a Liquid Droplet.

    PubMed

    Seong, Baekhoon; Park, Hyun Sung; Chae, Ilkyeong; Lee, Hyungdong; Wang, Xiaofeng; Jang, Hyung-Seok; Jung, Jaehyuck; Lee, Changgu; Lin, Liwei; Byun, Doyoung

    2017-04-11

    In a nanowire dispersed in liquid droplets, the interplay between the surface tension of the liquid and the elasticity of the nanowire determines the final morphology of the bent or buckled nanowire. Here, we investigate the fabrication of a silver nanowire ring generated as the nanowire encapsulated inside of fine droplets. We used a hybrid aerodynamic and electrostatic atomization method to ensure the generation of droplets with scalable size in the necessary regime for ring formation. We analytically calculate the compressive force of the droplet driven by surface tension as the key mechanism for the self-assembly of ring structures. Thus, for potential large-scale manufacturing, the droplet size provides a convenient parameter to control the realization of ring structures from nanowires.

  16. Helically assembled π-conjugated polymers with circularly polarized luminescence

    PubMed Central

    Watanabe, Kazuyoshi; Akagi, Kazuo

    2014-01-01

    We review the recent progress in the field of helically assembled π-conjugated polymers, focusing on aromatic conjugated polymers with interchain helical π-stacking that exhibit circularly polarized luminescence (CPL). In Part 1, we discuss optically active polymers with white-colored CPL and the amplification of the circular polarization through liquid crystallinity. In Part 2, we focus on the stimuli-responsive CPL that results from changes in the conformation and aggregation state of π-conjugated molecules and polymers. In Part 3, we discuss the self-assembly of achiral cationic π-conjugated polymers into circularly polarized luminescent supramolecular nanostructures with the aid of other chiral molecules. PMID:27877698

  17. Dynamic Ad-Dimer Twisting Assisted Nanowire Self-Assembly on Si(001)

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Tao; Wang, E. G.; Wang, D. S.; Mizuseki, H.; Kawazoe, Y.; Naitoh, M.; Nishigaki, S.

    2005-06-01

    Based on ab initio total energy calculation, we show that a dynamic ad-dimer twisting assisted (DATA) process plays a crucial role in facilitating a novel structural reconstruction involving surface and subsurface atoms on Si(001). It leads to self-assembly of long nanowires of group-V elements (Bi, Sb) in the trenches of surface dimer vacancy lines (DVLs) with a characteristic double-dimer configuration. The key to this is the lowering of the kinetic barrier by the DATA process in conjunction with a favorable interaction between ad-dimers and step edges in DVLs. The present results provide an excellent account for experimental observations and reveal the atomistic origin and the dynamic transformation path for nanowire self-assembly on Si(001).

  18. Self-assembled quantum dot structures in a hexagonal nanowire for quantum photonics.

    PubMed

    Yu, Ying; Dou, Xiu-Ming; Wei, Bin; Zha, Guo-Wei; Shang, Xiang-Jun; Wang, Li; Su, Dan; Xu, Jian-Xing; Wang, Hai-Yan; Ni, Hai-Qiao; Sun, Bao-Quan; Ji, Yuan; Han, Xiao-Dong; Niu, Zhi-Chuan

    2014-05-01

    Two types of quantum nanostructures based on self-assembled GaAs quantumdots embedded into GaAs/AlGaAs hexagonal nanowire systems are reported, opening a new avenue to the fabrication of highly efficient single-photon sources, as well as the design of novel quantum optics experiments and robust quantum optoelectronic devices operating at higher temperature, which are required for practical quantum photonics applications.

  19. Nonlinear optical studies of aqueous interfaces, polymers, and nanowires

    NASA Astrophysics Data System (ADS)

    Onorato, Robert Michael

    -transfer-to-solvent band and a Langmuir adsorption model are used to determine the affinity of bromide for both the air/water and dodecanol/water interfaces in the molar concentration regime. The Gibbs free energy of adsorption for the former is determined to be -1.4 kJ/mol with a lower 90% confidence limit of -4.1 kJ/mol. For the dodecanol/water interface the data are best fit with a Gibbs free energy of +8 kJ/mol with an estimated a lower limit of -4 kJ/mol. Adsorption of ions to the air/water interface in the millimolar regime is a particularly interesting phenomenon. In Chapter 4, the affinity of sodium chloride and sodium bromide to the air/water interface is probed by UV-SHG. Both salts exhibit a strong adsorption, with free energies greater than -20 kJ/mol. Interestingly, sodium chloride exhibits a stronger affinity for the interface than does sodium iodide, which was previously studied by Poul Peterson. This is counter to both experimental and theoretical results for higher concentrations. It has been predicted that ion adsorption is dictated by strong and opposing electrostatic and entropic forces. The change in order of ion interfacial affinity can be explained by relatively small changes in these forces at different concentrations and ionic strengths. In Chapters 5 and 6, other work using nonlinear optical techniques is described. Coherent anti-Stokes Raman scattering microscopy is a promising tool for chemically selective imaging based on molecular vibrations. While CARS is currently used as a biological imaging tool, many variations are still being developed, perhaps the most important being multiplex CARS microscopy. Multiplex CARS has the advantage of comparing images based on different molecular vibrations without changing the excitation wavelengths. In Chapter 5, I demonstrate both high spectral and spatial resolution multiplex CARS imaging of polymer films using a simple scheme for chirped CARS with a spectral bandwidth of 300 cm-1. In Chapter 6, the nonlinear optical

  20. Self-assembled DNA nanostructures and DNA-templated silver nanowires

    NASA Astrophysics Data System (ADS)

    Park, Sung Ha

    DNA-based nanotechnology has been attractive as a novel assembly method for fabricating nanostructures for the last two decades. Artificially designed, self-assembled DNA nanostructures have been reported with various geometrical structures and functionalities: one- and two-dimensional periodically patterned structures, three-dimensional polyhedra, nanomechanical devices, molecular computers, and organization of other functionalized molecules. This thesis describes self-assembled DNA nanostructures and DNA-templated metallic nanowires. One- and two-dimensional periodically patterned superstructures, such as filaments, lattices, nanoribbons, nanotracks, and nanogrids, utilizing newly conceived two distinct DNA motifs---three helix bundles, and the cross-tiles as well as synthetic double-stranded DNA molecules---will be discussed with unique design schemes and characteristics. DNA complexes have been visualized by high-resolution tapping mode atomic force microscopy under buffer. Their dimensions are shown to be in excellent agreement with designed structures. We have also presented fabrication of size-controllable, fully addressable, and precisely programmable DNA-based nanomatrices, consisting of two different cross-tiles using a novel stepwise assembly technique. Especially in design and construction of functionalized electronic nanodevices, properly fabricated DNA lattices can serve as a precisely controllable and programmable scaffold for organizing functionalized nanomaterials. DNA-templated metallic nanowires are an example demonstration of DNA molecules' scaffold capability and have been considered an interesting research subject for the last decade. Until recently, mostly native lambda-DNA molecules have been used as template for fabricating various metallic nanowires, such as silver, gold, palladium, platinum, and copper. In this thesis, we also present fabrication of metallic silver nanowires templated on artificially designed one-dimensional DNA

  1. Simple assembly of long nanowires through substrate stretching

    NASA Astrophysics Data System (ADS)

    Dong, Jianjin; Mohieddin Abukhdeir, Nasser; Goldthorpe, Irene A.

    2015-12-01

    Although nanowire (NW) alignment has been previously investigated, minimizing limitations such as process complexity and NW breakage, as well as quantifying the quality of alignment, have not been sufficiently addressed. A simple, low cost, large-area, and versatile alignment method is reported that is applicable for NWs either grown on a substrate or synthesized in solution. Metal and semiconductor NWs with average lengths of up to 16 μm are aligned through the stretching of polyvinyl alcohol (PVA) films, which compared to other stretching methods results in superior alignment because of the large stretching ratio of PVA. Poly[oxy(methyl-1,2-ethanediyl)] is employed as lubricant to prevent NW breakage. To quantify NW alignment, a simple and effective image processing method is presented. The alignment process results in an order parameter (S) of NW alignment as high as 0.97.

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

    NASA Astrophysics Data System (ADS)

    Braun, Erez

    2000-03-01

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

  3. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly.

    PubMed

    Yan, Hao; Hohman, J Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E P; Carlson, Robert M K; Tkachenko, Boryslav A; Fokin, Andrey A; Schreiner, Peter R; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P; Shen, Zhi-Xun; Melosh, Nicholas A

    2017-03-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of 'solid' inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  4. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    NASA Astrophysics Data System (ADS)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2016-12-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  5. Patterning of conducting polymers using charged self-assembled monolayers.

    PubMed

    Jung, Mi-Hee; Lee, Hyoyoung

    2008-09-02

    We introduce a new approach to pattern conducting polymers by combining oppositely charged conducting polymers on charged self-assembled monolayers (SAMs). The polymer resist pattern behaves as a physical barrier, preventing the formation of SAMs. The patterning processes were carried out using commercially available conducting polymers: a negatively charged PEDOT/PSS (poly(3,4-ethylene-dioxythiophene)/poly(4-stylenesulphonic acid)) and a positively charged polypyrrole (PPy). A bifunctional NH 2 (positively charged) or COOH (negatively charged) terminated alkane thiol or silane was directly self-assembled on a substrate (Au or SiO 2). A suspension of the conducting polymers (PEDOT/PSS and PPy) was then spin-coated on the top surface of the SAMs and allowed to adsorb on the oppositely charged SAMs via an electrostatic driving force. After lift-off of the polymer resist, i.e., poly(methyl methacrylate, PMMA), using acetone, the conducting polymers remained on the charged SAMs surface. Optical microscopy, Auger electron spectroscopy, and atomic force microscopy reveal that the prepared nanolines have low line edge roughness and high line width resolution. Thus, conducting polymer patterns with high resolution could be produced by simply employing charged bifunctional SAMs. It is anticipated that this versatile new method can be applied to device fabrication processes of various nano- and microelectronics.

  6. Development of multifunctional fiber reinforced polymer composites through ZnO nanowire arrays

    NASA Astrophysics Data System (ADS)

    Malakooti, Mohammad H.; Patterson, Brendan A.; Hwang, Hyun-Sik; Sodano, Henry A.

    2016-04-01

    Piezoelectric nanowires, in particular zinc oxide (ZnO) nanowires, have been vastly used in the fabrication of electromechanical devices to convert wasted mechanical energy into useful electrical energy. Over recent years, the growth of vertically aligned ZnO nanowires on various structural fibers has led to the development of fiber-based nanostructured energy harvesting devices. However, the development of more realistic energy harvesters that are capable of continuous power generation requires a sufficient mechanical strength to withstand typical structural loading conditions. Yet, a durable, multifunctional material system has not been developed thoroughly enough to generate electrical power without deteriorating the mechanical performance. Here, a hybrid composite energy harvester is fabricated in a hierarchical design that provides both efficient power generating capabilities while enhancing the structural properties of the fiber reinforced polymer composite. Through a simple and low-cost process, a modified aramid fabric with vertically aligned ZnO nanowires grown on the fiber surface is embedded between woven carbon fabrics, which serve as the structural reinforcement as well as the top and the bottom electrodes of the nanowire arrays. The performance of the developed multifunctional composite is characterized through direct vibration excitation and tensile strength examination.

  7. Non-resonant Mie scattering: Emergent optical properties of core-shell polymer nanowires

    PubMed Central

    Khudiyev, Tural; Huseyinoglu, Ersin; Bayindir, Mehmet

    2014-01-01

    We provide the in-depth characterization of light-polymer nanowire interactions in the context of an effective Mie scattering regime associated with low refractive index materials. Properties of this regime sharply contrast with these of resonant Mie scattering, and involve the formation of strictly forward-scattered and coupling-free optical fields in the vicinity of core-shell polymer nanowires. Scattering from these optical fields is shown to be non-resonant in nature and independent from incident polarization. In order to demonstrate the potential utility of this scattering regime in one-dimensional (1D) polymeric nanostructures, we fabricate polycarbonate (PC) - polyvinylidene difluoride (PVDF) core-shell nanowires using a novel iterative thermal drawing process that yields uniform and indefinitely long core-shell nanostructures. These nanowires are successfully engineered for novel nanophotonics applications, including size-dependent structural coloration, efficient light capture on thin-film solar cells, optical nano-sensors with ultrahigh sensitivity and a mask-free photolithography method suitable for the straightforward production of 1D nanopatterns. PMID:24714206

  8. Highly conductive self-assembled nanoribbons of coordination polymers.

    PubMed

    Welte, Lorena; Calzolari, Arrigo; Di Felice, Rosa; Zamora, Felix; Gómez-Herrero, Julio

    2010-02-01

    Organic molecules can self-assemble into well-ordered structures, but the conductance of these structures is limited, which is a disadvantage for applications in molecular electronics. Conductivity can be improved by using coordination polymers-in which metal centres are incorporated into a molecular backbone-and such structures have been used as molecular wires by self-assembling them into ordered films on metal surfaces. Here, we report electrically conductive nanoribbons of the coordination polymer [Pt(2)I(S(2)CCH(3))(4)](n) self-assembled on an insulating substrate by direct sublimation of polymer crystals. Conductance atomic force microscopy is used to probe the electrical characteristics of a few polymer chains ( approximately 10) within the nanoribbons. The observed currents exceed those previously sustained in organic and metal-organic molecules assembled on surfaces by several orders of magnitude and over much longer distances. These results, and the results of theoretical calculations based on density functional theory, confirm coordination polymers as candidate materials for applications in molecular electronics.

  9. Inorganic Nanowires-Assembled Layered Paper as the Valve for Controlling Water Transportation.

    PubMed

    Chen, Fei-Fei; Zhu, Ying-Jie; Xiong, Zhi-Chao; Sun, Tuan-Wei; Shen, Yue-Qin; Yang, Ri-Long

    2017-03-29

    Layered materials with open interlayer channels enable various applications such as tissue engineering, ionic and molecular sieving, and electrochemical devices. However, most reports focus on the two-dimensional nanosheets-assembled layered materials, whose interlayer spacing is limited at the nanometer scale. Herein, we demonstrate that one-dimensional inorganic nanowires are the ideal building blocks for the construction of layered materials with open interlayer channels as well, which has not aroused much attention before. It is found that the relatively long inorganic nanowires are capable of assembling into free-standing layered paper with open interlayer channels during the filtration process. The spacings of interlayer channels between adjacent layers are up to tens of micrometers, which are much larger than those of the two-dimensional nanosheets-assembled layered materials. But the closed interlayer channels are observed when the relatively short inorganic nanowires are used as building blocks. The mechanism based on the relationship between the structural variation and the nanowires used is proposed, including the surface charge amplified effect, surface charge superimposed effect, and pillarlike supporting effect. According to the proposed mechanism, we have successfully fabricated a series of layered paper sheets whose architectures (including interlayer channels of cross section and pores on the surface) show gradient changes. The as-prepared layered paper sheets are employed as the valves for controlling water transportation. Tunable water transportation is achieved by the synergistic effect between in-plane interlayer channels (horizontal transportation) from the open to the closed states, and through-layer pores (vertical transportation) without surface modification or intercalation of any guest species.

  10. Assembly and performance of silicone polymer waveguides

    NASA Astrophysics Data System (ADS)

    Lostutter, Calob K.; Hodge, Malcolm H.; Marrapode, Thomas R.; Swatowski, Brandon W.; Weidner, W. Ken

    2016-03-01

    We report on the functionality and key performance properties of 50 μm x 50 μm flexible graded index silicone polymer waveguides. The materials show low optical propagation losses of < 0.04 dB/cm @ 850 nm over 1 m lengths as well as stability to 2000 hours 85°C/85% relative humidity and 5 cycles of 260°C solder wave reflow testing. Methods to fabricate large area panels are demonstrated for scaled manufacturing of polymer based optical printed wiring boards. The polymer waveguides are terminated with a passive direct fiber attach method. Fully MPO connectorized waveguide panels are realized and their optical performance properties assessed.

  11. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    PubMed Central

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-01-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V−1s−1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  12. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-04-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V‑1s‑1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements.

  13. Design directed self-assembly of donor-acceptor polymers.

    PubMed

    Marszalek, Tomasz; Li, Mengmeng; Pisula, Wojciech

    2016-09-21

    Donor-acceptor polymers with an alternating array of donor and acceptor moieties have gained particular attention during recent years as active components of organic electronics. By implementation of suitable subunits within the conjugated backbone, these polymers can be made either electron-deficient or -rich. Additionally, their band gap and light absorption can be precisely tuned for improved light-harvesting in solar cells. On the other hand, the polymer design can also be modified to encode the desired supramolecular self-assembly in the solid-state that is essential for an unhindered transport of charge carriers. This review focuses on three major factors playing a role in the assembly of donor-acceptor polymers on surfaces which are (1) nature, geometry and substitution position of solubilizing alkyl side chains, (2) shape of the conjugated polymer defined by the backbone curvature, and (3) molecular weight which determines the conjugation length of the polymer. These factors adjust the fine balance between attractive and repulsive forces and ensure a close polymer packing important for an efficient charge hopping between neighboring chains. On the microscopic scale, an appropriate domain formation with a low density of structural defects in the solution deposited thin film is crucial for the charge transport. The charge carrier transport through such thin films is characterized by field-effect transistors as basic electronic elements.

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

    PubMed

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

    2014-11-10

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

  15. Novel polymer nanowire crystals of diketopyrrolopyrrole-based copolymer with excellent charge transport properties.

    PubMed

    Kim, Ji Ho; Lee, Dae Hee; Yang, Da Seul; Heo, Dong Uk; Kim, Kyung Hwan; Shin, Jicheol; Kim, Hyun-Ji; Baek, Kyung-Youl; Lee, Kwangyeol; Baik, Hionsuck; Cho, Min Ju; Choi, Dong Hoon

    2013-08-14

    The first demonstration of polymer nanowire (PNW) crystals based on a diketopyrrolopyrrole-based copolymer (i.e., PDTTDPP), and their application to field-effect transistors (FETs) is reported. Remarkably, transmission electron microscopy and selected area electron diffraction analyses of the PNW reveal its single-crystalline (SC) nature. FETs fabricated of a SC PNW exhibit a maximal charge carrier mobility of ≈7.00 cm(2) V(-1) s(-1) , which is almost one order of magnitude higher than that of the thin-film transistors made of the same polymer (PDTTDPP).

  16. Optimization of VO2 nanowire polymer composite thermochromic films by optical simulation

    NASA Astrophysics Data System (ADS)

    Naoi, Yuki; Amano, Jun

    2016-12-01

    Thermochromic films with high efficiency, transparency, and flexibility are highly desirable for energy-efficient smart window films. Vanadium oxide (VO2)-nanoparticle-embedded flexible polymer composite films are the most promising thermochromic films because of the sharp phase transition of insulating to metallic phases of VO2 at 68 °C with visible transparency and a large change in transmittance at near-infrared wavelengths before and after the metal-insulator phase transition. This paper describes the simulation of high-efficiency thermochromic polymer composite films embedded with VO2 nanoparticles of various sizes to investigate the optimum VO2 nanowire size and length.

  17. Fabrication of controllable and stable In2O3 nanowire transistors using an octadecylphosphonic acid self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Lim, Taekyung; Han, Junebeom; Seo, Keumyoung; Joo, Min-Kyu; Kim, Jae-Sung; Kim, Wung-Yeon; Kim, Gyu-Tae; Ju, Sanghyun

    2015-04-01

    The controllability and stability of nanowire transistor characteristics are essential for the development of low-noise and fast-switching nano-electronic devices. In this study, the positive shift of threshold voltage and the improvement of interface quality on In2O3 nanowire transistors were simultaneously achieved by using octadecylphosphonic acid (OD-PA) self-assembly. Following the chemical bond of OD-PA molecules on the surface of In2O3 nanowires, the threshold voltage was positively shifted to 2.95 V, and the noise amplitude decreased to approximately 87.5%. The results suggest that an OD-PA self-assembled monolayer can be used to manipulate and stabilize the transistor characteristics of nanowire-based memory and display devices that require high-sensitivity, low-noise, and fast-response.

  18. Ferritin-Polymer Conjugates: Grafting Chemistry and Self-Assembly

    DTIC Science & Technology

    2009-10-26

    polymer core-shell structures by co-assembly. 9 A numbers of BNPs including cowpea mosaic virus, turnip yellow mosaic virus, and bacteriophage P22...Figure 11. Synthetic route for fluorescent crosslinkers. Turnip yellow mosaic virus (TYMV), a plant virus with unique structural and chemical

  19. New Metal-organic Polymers Through Subcomponent Self-Assembly

    DTIC Science & Technology

    2012-07-27

    material using subcomponent self-assembly. We developed the synthesis of double helical polymeric species according to the general procedure...to use - diketones as subcomponents for polymers. She then shifted her efforts to other projects, funded by the European Research Council. Because

  20. Fabricating photoswitches and field-effect transistors from self-assembled tetra(2-isopropyl-5-methyphenoxy) copper phthalocyanines nanowires.

    PubMed

    Cheng, Chuanwei; Gao, Junshan; Xu, Guoyue; Zhang, Haiqian; Li, Yingying; Luo, Yan

    2009-05-01

    Tetra(2-isopropyl-5-methyphenoxy) copper phthalocyanine (CuPc) nanowires synthesized by a facile, low temperature self-assembled route, were incorporated into nano-devices: photoswitch and organic field-effect transistor. The devices were capable of switching on/off reversibly and fast by turning the 808 nm infrared light on/off. And the carrier mobility micro of CuPc nanowires incorporated in the devices was -0.02 cm2/V x s. The prelimenary results in this study show the potential application of metal phthalocyanine nanowires in low-cost fabrication of nano photo-electric devices.

  1. Surface directed assembly of conjugated polymers for optoelectronics

    NASA Astrophysics Data System (ADS)

    Liang, Ziqi

    Conjugated polymers combining the optical and electronic properties of semiconductors with advantages of organic materials are being explored as active components in various types of thin-film electronic and optoelectronic devices. The realization of conjugated polymer based electronics and optoelectronics critically depends on developing novel approaches for assembling this new class of materials into a controlled fashion. We have developed new non-photolithographic methods for the spatial deposition of conjugated polymers. As a proof-of-concept of these methods, the well-known luminescent polymer, poly(p-phenylene vinylene) (PPV), has been used as a model structure in our work. One strategy is based on the modification of solid substrates with microcontact-printed self-assembled monolayers (SAMs) that serve as templates for the deposition of PPVs from solution. Conjugated polymer patterns have also been generated by directly stamping of PPVs onto the reactive SAMs-coated substrates. In both methods, PPVs were covalently immobilized onto the supporting surface through the formation of amide bonds, thus rendering great stability of the resulting patterns. Well-defined PPV micropatterns have been fully characterized by UV-vis spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM) and fluorescence optical microscopy. The interaction between PPVs and the underlying surface was analyzed by grazing-angle reflectance Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Many applications based on conjugated polymers require the controlled assembly of the polymers as multilayer structures, in which molecules with different functionality can be incorporated into individual layers with precisely controlled thickness. We have developed a series of layer-by-layer (LbL) assembly approaches to multilayer conjugated polymer thin films. Hydrogen-bonding interaction and covalent coupling reaction have been utilized

  2. Enzyme-responsive polymer assemblies constructed through covalent synthesis and supramolecular strategy.

    PubMed

    Ding, Yan; Kang, Yuetong; Zhang, Xi

    2015-01-21

    Enzyme-responsive polymer assemblies have proved to be promising candidates for biomaterials, biomedicine and biosensing. Traditionally, these assemblies are prepared by the self-assembly of polymer building blocks which are covalently conjugated with enzyme-responsive moieties. Moreover, a supramolecular strategy has recently been developed for the preparation of enzyme-responsive polymer assemblies where the enzyme-responsive moieties are non-covalently complexed with the polymer building blocks. In addition, kinetic studies have been conducted on the enzyme-responsive behaviour of the polymer assemblies, which paves the way for tuning the response rate of the assemblies in a controlled manner.

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

    PubMed

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

    2015-01-01

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

  4. Polymer electrolyte membrane assembly for fuel cells

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2000-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  5. Polymer electrolyte membrane assembly for fuel cells

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2002-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  6. Bioreceptor-conducting polymer multilayer assemblies for biosensing

    NASA Astrophysics Data System (ADS)

    Samuelson, Lynne A.; Alva, Shridhara; Kumar, Jayant; Kaplan, David L.; Tripathy, Sukant K.

    1998-04-01

    This research focuses on the organized integration of biological receptors and polymers into thin film architectures for biosensing applications. Layer-by-layer electrostatic adsorption was used for the first time to form alternating protein-conducting polymer multilayers. The light-harvesting, phycobiliproteins and the enzyme, alkaline phosphatase were the bioreceptors investigated and sulfonated polystyrene, poly(diallyl dimethyl ammonium chloride) and a new enzymatically polymerized, water soluble, polyaniline were the polymer counterions used for deposition. Spectroscopic characterization was used to determine both multilayer formation and biosensing function of the final bioreceptor-polymer assemblies. These techniques have proven to be simple, chemically mild, and versatile and are expected to find application in the fabrication of ultrathin films for biosensors, opto- electronic devices and biomedical applications.

  7. Particle-Directed Assembly of Semiflexible Polymer Chains

    NASA Astrophysics Data System (ADS)

    McGovern, Michael; Dorfman, Kevin; Morse, David

    We use molecular dynamics simulations to investigate several models of semiflexible polymers that exhibit an attractive interaction with spherical particles. The organization of semiflexible polymer chains through attractive interactions with spherical particles occurs in several important processes in nature, such as the winding of DNA around histones and counter-ion condensation of charged polymers. The process is also of technological interest in the packaging of DNA for delivery to cells. In this presentation, we will present data on both the phase behavior and the kinetics of self-assembly as a function of the stiffness of the polymers, the attractive potential between the monomers and the particles, and the relative size of the monomers and particles. Our simulations suggest a transition between globular and rod-like aggregates that changes from a gradual to a sudden transition depending on particle size, and that rod formation is a slow, nucleation dependent process.

  8. DNA nanotubes self-assembled from triple-crossover tiles as templates for conductive nanowires

    PubMed Central

    Liu, Dage; Park, Sung Ha; Reif, John H.; LaBean, Thomas H.

    2004-01-01

    DNA-based nanotechnology is currently being developed as a general assembly method for nanopatterned materials that may find use in electronics, sensors, medicine, and many other fields. Here we present results on the construction and characterization of DNA nanotubes, a self-assembling superstructure composed of DNA tiles. Triple-crossover tiles modified with thiol-containing double-stranded DNA stems projected out of the tile plane were used as the basic building blocks. Triple-crossover nanotubes display a constant diameter of ≈25 nm and have been observed with lengths up to 20 μm. We present high-resolution images of the constructs, experimental evidence of their tube-like nature as well as data on metallization of the nanotubes to form nanowires, and electrical conductivity measurements through the nanowires. DNA nanotubes represent a potential breakthrough in the self-assembly of nanometer-scale circuits for electronics layout because they can be targeted to connect at specific locations on larger-scale structures and can subsequently be metallized to form nanometer-scale wires. The dimensions of these nanotubes are also perfectly suited for applications involving interconnection of molecular-scale devices with macroscale components fabricated by conventional photolithographic methods. PMID:14709674

  9. Parylene C-on-photoresist (POP): a low temperature spacer scheme for polymer/metal nanowire fabrication

    NASA Astrophysics Data System (ADS)

    Li, Yuanhui; Xie, Quan; Wang, Wei; Zheng, Mingxin; Zhang, Hao; Lei, Yinhua; Zhang, Haixia Alice; Wu, Wengang; Li, Zhihong

    2011-06-01

    This work introduced a novel spacer scheme for polymer/metal nanowire preparation by combining Parylene C and photoresist (Parylene C on photoresist, POP, process), both of which possess a low temperature fabrication essence. Adhesion between the Parylene C and the substrate with photoresist onside was improved by introducing a modified silanization pretreatment. Parylene C filled in an undercut generated by regular lithography on a dual-layered photoresist was left as nanometer-sized residues after an isotropic oxygen plasma etching. Parylene C nanowires with the minimal width down to 200 nm were successfully obtained by this POP-based spacer technique, and were then utilized as the etching mask for ion milling of the metal films beneath to realize corresponding chromium/gold nanowires. The present POP scheme will expand the application of the spacer technique in polymer/metal nanowire fabrication for integrated micro/nanoelectromechanical systems.

  10. Silicon nanowire charge-trap memory incorporating self-assembled iron oxide quantum dots.

    PubMed

    Huang, Ruo-Gu; Heath, James R

    2012-11-19

    Charge-trap non-volatile memory devices based upon the precise integration of quantum dot storage elements with silicon nanowire field-effect transistors are described. Template-assisted assembly yields an ordered array of FeO QDs within the trenches that separate highly aligned SiNWs, and injected charges are reversibly stored via Fowler-Nordheim tunneling into the QDs. Stored charges shift the transistor threshold voltages, providing the basis for a memory device. Quantum dot size is found to strongly influence memory performance metrics.

  11. The controllable assembly of nanorods, nanowires and microwires of a perylenediimide molecule with photoswitching property

    NASA Astrophysics Data System (ADS)

    Ma, Ying; An, Boxing; Wang, Meng; Shi, Fangxiao; Wang, Qing; Gu, Yaxin; Niu, Wanyang; Fan, Zhaorong; Shang, Yanli; Wang, Dan; Zhao, Cong

    2015-07-01

    By using an electron donor-acceptor molecule that consists of a perylenediimide (PDI) core bonded with two ferrocene (Fc) units, well-defined nanorods, nanowires and microwires of PDI-Fc were formed through simply adjusting the initial concentration of PDI-Fc in dichloromethane or CH2Cl2. Moreover, the two-ended devices based on individual microwire were fabricated. Highly reproducible and sensitive photo response characteristics were demonstrated in the microwire through controlling the white light on and off with different light intensities. The assembly strategy via complementary donors and acceptors is of significance for constructing photoconductive systems and developing novel functional devices.

  12. Aligned and Electrospun Piezoelectric Polymer Fiber Assembly and Scaffold

    NASA Technical Reports Server (NTRS)

    Scott-Carnell, Lisa A. (Inventor); Siochi, Emilie J. (Inventor); Holloway, Nancy M. (Inventor); Leong, Kam W. (Inventor); Kulangara, Karina (Inventor)

    2015-01-01

    A scaffold assembly and related methods of manufacturing and/or using the scaffold for stem cell culture and tissue engineering applications are disclosed which at least partially mimic a native biological environment by providing biochemical, topographical, mechanical and electrical cues by using an electroactive material. The assembly includes at least one layer of substantially aligned, electrospun polymer fiber having an operative connection for individual voltage application. A method of cell tissue engineering and/or stem cell differentiation uses the assembly seeded with a sample of cells suspended in cell culture media, incubates and applies voltage to one or more layers, and thus produces cells and/or a tissue construct. In another aspect, the invention provides a method of manufacturing the assembly including the steps of providing a first pre-electroded substrate surface; electrospinning a first substantially aligned polymer fiber layer onto the first surface; providing a second pre-electroded substrate surface; electrospinning a second substantially aligned polymer fiber layer onto the second surface; and, retaining together the layered surfaces with a clamp and/or an adhesive compound.

  13. Functional 2D nanoparticle/polymer array: Interfacial assembly, transfer, characterization, and coupling to photonic crystal cavities

    NASA Astrophysics Data System (ADS)

    Xiong, Shisheng

    We developed a universal, facile and robust method to prepare free-standing, ordered and patternable nanoparticle/polymer monolayer arrays by evaporation-induced self-assembly at a fluid interface. The ultra-thin monolayer nanoparticle/polymer arrays are sufficiently robust that they can be transferred to arbitrary substrates, even with complex topographies. More importantly, the Poly (methyl methacrylate) (PMMA) in the system serves as a photoresist enabling two modes of electron beam (e-beam) nanoparticle patterning. These ultra-thin films of monolayer nanoparticle arrays are of fundamental interest as 2D artificial solids for electronic, magnetic and optical properties and are also of technological interest for a diverse range of applications in micro- and macro-scale devices including photovoltaics, sensors, catalysis, and magnetic storage. By co-assembly with block co-polymers, the nanoparticles were selectively positioned in one specific phase, representing a high throughput route for creating nanoparticle patterns. The self-assembly process was investigated by combined in-situ grazing incidence small angle x-ray scattering (GISAXS) and numerical simulation. By e-beam irradiation of free-standing 2D NP/polymer arrays, anisotropic nanowire arrays have been fabricated. Additionally, preliminary investigation on assembly of binary nanoparticle arrays has also been introduced, serving as promising future directions of interfacial assembly. Controlling the rate of spontaneous emission and thus promoting the photon generation efficiency is a key step toward fabrication of Quantum dot based single-photon sources, and harnessing of light energy from emitters with a broad emitting spectrum. Coupling of photo emitters to photonic cavities without perturbing the optical performance of cavities remains as a challenge in study of Purcell effect based on quantum electrodynamics. Taking advantage of interfacial assembly and transfer, we have achieved controlled deposition

  14. Self-Assembly of Emulsion Droplets into Polymer Chains

    NASA Astrophysics Data System (ADS)

    Bargteil, Dylan; McMullen, Angus; Brujic, Jasna

    We experimentally investigate `beads-on-a-string' models of polymers using the spontaneous assembly of emulsion droplets into linear chains. Droplets functionalized with surface-mobile DNA allow for programmable 'monomers' through which we can influence the three-dimensional structure of the assembled 'polymer'. Such model polymers can be used to study conformational changes of polypeptides and the principles governing protein folding. In our system, we find that droplets bind via complementary DNA strands that are recruited into adhesion patches. Recruitment is driven by the DNA hybridization energy, and is limited by the energy cost of surface deformation and the entropy loss of the mobile linkers, yielding adhesion patches of a characteristic size with a given number of linkers. By tuning the initial surface coverage of linkers, we control valency between the droplets to create linear or branched polymer chains. We additionally control the flexibility of the model polymers by varying the salt concentration and study their dynamics between extended and collapsed states. This system opens the possibility of programming stable three-dimensional structures, such as those found within folded proteins.

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

    PubMed Central

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

    2012-01-01

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

  16. Supramolecular assembly of C3 peptidic molecules into helical polymers.

    PubMed

    Dai, Yutang; Zhao, Xin; Su, Xinyan; Li, Guangyu; Zhang, Afang

    2014-08-01

    Self-assembly of C3 discotic molecules bearing dipeptide pendants into helical supramolecular polymers is investigated. The dipeptides are constituted from glycine and alanine with altered sequence, aiming at modulating the steric hindrance and examining the steric effects on the assembly. This steric hindrance effect is further illustrated with a dipeptide formed from glycine and valine, which carries a much larger isopropyl side unit. Their supramolecular polymerization is examined in various organic solvents and at different temperatures. The assembly morphology is directly visualized with atomic force microscopy. It is found that small changes in the dipeptide motifs in combination with solvent structure and the solution concentrations lead to different expression of the supramolecular assembly.

  17. Silicon nanowire growth and transistor fabrication by self-assembling "grow-in-place" approach

    NASA Astrophysics Data System (ADS)

    Shan, Yinghui

    Nanowires have attracted much attention recently owing to their ability to serve as critical building blocks for emerging nanotechnologies. Silicon nanowires (SiNWs) are particularly promising because of the central role of silicon in semiconductor industry. SiNWs would allow device fabrication with high density and their high surface to volume ratio offers high sensitivity. In addition, the possible quantum confinement in SiNWs may further enhance device performances and open windows for exploiting fundamental properties. Intense researches have been carried out in SiNW growth and device fabrication. However, there are still challenges in SiNW growth controls, such as size, number, shape, position, orientation, and inter-wire spacings. To make devices from these SiNWs, post-growth processing steps are needed, such as SiNW collecting, picking, positioning, aligning, and assembling. Due to the extremely small size of SiNWs, there are also challenges in SiNW device fabrication. To solve these challenges in both SiNW growth control and device fabrication, we introduced a novel self-assembling "grow-in-place" approach. Our approach combined vapor-liquid-solid (VLS) nanowire growth mechanism and pre-fabricated nanochannel template. The VLS growth mechanism offers the ability of controlling nanowire size and shape by nanochannel templates. The pre-fabricated nanochannel template guides nanowire growth and offers good SiNW growth control. SiNWs and silicon nanoribbons (SiNRs) with different sizes have been successfully grown in our nanochannel templates. Characterizations on their size, shape, composition, and crystallinity of the SiNW/Rs have confirmed that our "grow-in-place" approach offers good controls on crystalline SiNW/Rs size, shape, number, orientation, position, and inter-wire spacing. So our approach solved the challenges in SiNW growth control. Our grow-in-place approach also solved the challenges in SiNW device fabrication. We introduced two versions of

  18. Field-directed assembly of nanowires: identifying directors, disruptors and indices to maximize the device yield

    NASA Astrophysics Data System (ADS)

    Sam, Mahshid; Moghimian, Nima; Bhiladvala, Rustom B.

    2015-12-01

    Individually-addressable nano-electro-mechanical (NEMS) devices have been used to demonstrate sensitive mass detection to the single-proton level, as well as neutral-particle mass spectrometry. The cost of individually securing or patterning such devices is proportional to their number or the chip area covered. This limits statistical support for new research, as well as paths to the commercial availability of extraordinarily sensitive instruments. Field-directed assembly of synthesized nanowires addresses this problem and shows potential for low-cost, large-area coverage with NEMS devices. For positive dielectrophoresis (pDEP) as the main assembly director, the space of field, geometric and material parameters is large, with combinations that can serve either as directors or disruptors for directed assembly. We seek parameter values to obtain the best yield, by introducing a rational framework to reduce trial-and-error. We show that sorting the disruptors by severity and eliminating those weakly coupled to the director, allows reduction of the parameter space. The remaining disruptors are then represented compactly by dimensionless parameters. In the example protocol chosen, a single dimensionless parameter, the yield index, allows minimization of disruptors by the choice of frequency. Following this, the voltage may be selected to maximize the yield. Using this framework, we obtained 94% pre-clamped and 88% post-clamped yield over 57000 nanowire sites. Organizing the parameter space using a director-disruptor framework, with economy introduced by non-dimensional parameters, provides a path to controllably decrease the effort and cost of manufacturing nanoscale devices. This should help in the commercialization of individually addressable nanodevices.Individually-addressable nano-electro-mechanical (NEMS) devices have been used to demonstrate sensitive mass detection to the single-proton level, as well as neutral-particle mass spectrometry. The cost of

  19. Simulation-assisted self-assembly of multicomponent polymers into hierarchical assemblies with varied morphologies.

    PubMed

    Cai, Chunhua; Li, Yongliang; Lin, Jiaping; Wang, Liquan; Lin, Shaoliang; Wang, Xiao-Song; Jiang, Tao

    2013-07-22

    As you like it: The synthesis of supramolecular hierarchical nanostructures with designed morphologies has been realized through computer-simulation-guided multicomponent assembly of polypeptide-based block copolymers and homopolymers. By adjusting the attraction between hydrophobic polypeptide rods, as well as other parameters such as the molar ratio of copolymers and the rigidity of polymers, a variety of morphologies were obtained.

  20. Heterogeneous Configuration of a Ag Nanowire/Polymer Composite Structure for Selectively Stretchable Transparent Electrodes.

    PubMed

    Kim, Youngmin; Jun, Sungwoo; Ju, Byeong-Kwon; Kim, Jong-Woong

    2017-03-01

    One of the most important aspects that we need to consider in the design of intrinsically stretchable electrodes is that most electronic devices that can be formed on them are not stretchable themselves. This discrepancy can induce severe stress singularities at the interfaces between stiff devices and stretchable electrodes, leading to catastrophic device delamination when the substrate is stretched. Here, we suggest a novel solution to this challenge which involves introducing a photolithography-based rigid-island approach to fabricate the heterogeneous configuration of a silver nanowire (AgNW)/polymer composite structure. For this, we designed two new transparent polymers: a photopatternable polymer that is rigid yet flexible, and a stretchable polymer, both of which have identical acrylate functional groups. Patterning of the rigid polymer and subsequent overcoating of the soft polymer formed rigid island disks embedded in the soft polymer, resulting in a selectively stretchable transparent film. Strong covalent bonds instead of weak physical interactions between the polymers strengthened the cohesive force at the interface of the rigid/soft polymers. Inverted-layer processing with a percolated AgNW network was used to form a heterogeneous AgNW/polymer composite structure that can be used as a selectively stretchable transparent electrode. An optimized structural configuration prevented the resistance of the rigid electrode from varying up to a lateral strain of 70%. A repeated stretch/release test with 60% strain for 5000 cycles did not cause any severe damage to the structure, revealing that the fabricated structure was mechanically stable and reliable.

  1. Solvothermal synthesis, stirring-assisted assembly and photoelectric performance of Te nanowires.

    PubMed

    Zhong, Bin Nian; Fei, Guang Tao; Fu, Wen Biao; Gong, Xin Xin; Gao, Xu Dong; Zhang, Li De

    2016-12-07

    Tellurium nanowires (NWs) are attractive one-dimensional materials for many applications, yet most synthesis processes require hazardous chemical reducing agents and extreme operating conditions. Here we described a solvothermal synthesis of Te NWs using a non-toxic reducing agent, ascorbic acid. Then the Te NWs were assembled into a well-aligned film through a stirring-assisted oil-water-air interface assembly method and a Te NWs photodetector was fabricated which is sensitive to infrared radiation. The photodetector based on the well-aligned Te NWs film had a series of more excellent photoelectric properties than that based on those being randomly oriented. For example, the photoresponsivity of the former is 10(3) times larger, and the response time is 1.15 × 10(3) times shorter, than those of the latter.

  2. Templated Self-Assembly of Ultrathin Gold Nanowires by Nanoimprinting for Transparent Flexible Electronics.

    PubMed

    Maurer, Johannes H M; González-García, Lola; Reiser, Beate; Kanelidis, Ioannis; Kraus, Tobias

    2016-05-11

    We fabricated flexible, transparent, and conductive metal grids as transparent conductive materials (TCM) with adjustable properties by direct nanoimprinting of self-assembling colloidal metal nanowires. Ultrathin gold nanowires (diameter below 2 nm) with high mechanical flexibility were confined in a stamp and readily adapted to its features. During drying, the wires self-assembled into dense bundles that percolated throughout the stamp. The high aspect ratio and the bundling yielded continuous, hierarchical superstructures that connected the entire mesh even at low gold contents. A soft sintering step removed the ligand barriers but retained the imprinted structure. The material exhibited high conductivities (sheet resistances down to 29 Ω/sq) and transparencies that could be tuned by changing wire concentration and stamp geometry. We obtained TCMs that are suitable for applications such as touch screens. Mechanical bending tests showed a much higher bending resistance than commercial ITO: conductivity dropped by only 5.6% after 450 bending cycles at a bending radius of 5 mm.

  3. Microscale Electrospinning of Polymer Nanowires for Sensing Applications

    DTIC Science & Technology

    2005-09-01

    Yes PVA - Poly(vinyl alcohol) PEO - Poly(ethylene oxide) PECH - Poly( epichlorohydrin ) PIB - Poly(isobutylene) PNVP - Poly(n-vinyl pyrrolidone) Figure 3...0.14 Current (Anus) Figure 6: I-V curve for the device of figure 5 Poly( epichlorohydrin ) - PECH is an attractive polymer for chemical sensing due to...four-component array was measured and was distinct for each vapor. Poly( epichlorohydrin ) (PECH), Mw of 700,000 , poly(ethylene Oxide) (PEO) Mw of

  4. Assembling and properties of the polymer-particle nanostructured materials

    NASA Astrophysics Data System (ADS)

    Sheparovych, Roman

    Complementary properties of the soft and hard matter explain its common encounter in many natural and manmade applications. A combination of flexible organic macromolecules and hard mineral clusters results in new materials far advantageous than its constituents alone. In this work we study assembling of colloidal nanocrystals and polymers into complex nanostructures. Magnetism, surface wettability and adhesion comprise properties of interest for the obtained nanocomposites. Applying a magnetic field induces a reversible 1D ordering of the magnetically susceptible particles. This property was employed in the fabrication of the permanent chains of magnetite nanocrystals (d=15nm). In the assembling process the aligned particles were bound together using polyelectrolyte macromolecules. The basics of the binding process involved an electrostatic interaction between the positively charged polyelectrolyte and the negative surface of the particles (aqueous environment). Adsorption of the polymer molecules onto several adjacent particles in the aligned 1D aggregate results in the formation of the permanent particulate chains. Positive charges of the adsorbed polyelectrolyte molecules stabilize the dispersion of the obtained nanostructures in water. Magnetization measurements revealed that superparamagnetic nanoparticles, being assembled into 1D ordered structures, attain magnetic coercivity. This effect originates from the magnetostatic interaction between the neighboring magnetite nanocrystals. The preferable dipole alignment of the assembled nanoparticles is directed along the chain axis. Another system studied in this project includes polymer-particle responsive surface coatings. Tethered polymer chains and particles bearing different functionalities change surface properties upon restructuring of the composite layer. When the environment favors polymer swelling (good solvent), the polymer chains segregate to the surface and cover the particles. In the opposite case

  5. Structure of assemblies of metal nanowires in mesoporous alumina membranes studied by EXAFS, XANES, X-ray diffraction and SAXS.

    PubMed

    Benfield, Robert E; Grandjean, Didier; Dore, John C; Esfahanian, Hamid; Wu, Zhonghua; Kröll, Michael; Geerkens, Marcus; Schmid, Günter

    2004-01-01

    Mesoporous alumina membranes ("anodic aluminium oxide", or "AAO") are made by anodic oxidation of aluminium metal. These membranes contain hexagonal arrays of parallel non-intersecting cylindrical pores perpendicular to the membrane surface. By varying the anodisation voltage, the pore diameters are controllable within the range 5-250 nm. We have used AAO membranes as templates for the electrochemical deposition of metals within the pores to produce nanowires. These represent assemblies of one-dimensional quantum wires with prospective applications in electronic, optoelectronic and magnetic devices. Detailed characterisation of the structures of these nanowire assemblies on a variety of length scales is essential to understand their physical properties and evaluate their possible applications. We have used EXAFS, XANES, WAXS, high energy X-ray diffraction and SAXS to study their structure and bonding. In this paper we report the results of our studies of four different nanowire systems supported in AAO membranes. These are the ferromagnetic metals iron and cobalt, the superconducting metal tin, and the semiconductor gallium nitride. Iron nanowires in pores of diameter over the range 12 nm-72 nm are structurally very similar to bcc bulk iron. They have a strong preferred orientation within the alumina pores. Their XANES shows significant differences from that of bulk iron, showing that the electronic structure of the iron nanowires depends systematically on their diameter. Cobalt nanowires are composed of a mixture of hcp and fcc phases, but the ratio of the two phases does not depend in a simple way on the pore diameter or preparation conditions. In bulk cobalt, the fcc beta-phase is normally stable only at high temperatures. Strong preferred orientation of the c-axis in the pores was found. Tin nanowires in alumina membranes with pores diameters between 12 nm and 72 nm have a tetragonal beta-structure at ambient temperature and also at 80 K. Magnetic

  6. Multi-functional particle assemblies in polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Jiao, Yang

    Self-assembly into ordered and equilibrium configurations underlie the microphase separation of block copolymers, protein folding and anisotropic aggregation of functionalized nanoparticles. In this project, we explored the assembly of polymer-grafted magnetic nanoparticles in solution and bulk states to combine various properties, such as ionic conductivity, mechanical reinforcement and responsiveness to external flows, within the same sample. The multi-functionality of iron oxide nanoparticles in polymer media is achieved using bottom-up approaches. Starting from the particle core synthesis, many layers of functionalities are added on magnetite (Fe3O4) nanoparticles by i) grafting polystyrene chains at different densities, lengths and elasticity; by ii) functionalizing particles with ionomers; and by iii) attaching charged diblock copolymers onto particles. In these three complex systems, particle nanostructures are investigated to explain the role of interactions between particle-particle, polymer-particle and polymer-polymer. We found that polystyrene-grafted Fe3O4 nanoparticles can form strings, spherical clusters and dispersed structures in polymer matrices by tuning the polymer graft density and grafted chain length. This structural transition has been explained through chain interactions and short-range dipolar interactions. We showed that chain conformation (radius of gyration) interestingly is not influenced within different dispersion states. Small-angle x-ray and neutron scattering results reveal that matrix chains do not govern the formation of strings, but have a significant impact on the size and internal structure of aggregated particles. Our findings showed that spherical aggregates of nanoparticles with low polymer graft densities are similar to interpenetrating networks in which free matrix chains bridge the fractals of particles and control the cluster density. Further, the mechanical properties of these different composite structures under

  7. Preparation of conductive gold nanowires in confined environment of gold-filled polymer nanotubes.

    PubMed

    Mitschang, Fabian; Langner, Markus; Vieker, Henning; Beyer, André; Greiner, Andreas

    2015-02-01

    Continuous conductive gold nanofibers are prepared via the "tubes by fiber templates" process. First, poly(l-lactide) (PLLA)-stabilized gold nanoparticles (AuNP) with over 60 wt% gold are synthesized and characterized, including gel permeation chromatography coupled with a diode array detector. Subsequent electrospinning of these AuNP with template PLLA results in composite nanofibers featuring a high gold content of 57 wt%. Highly homogeneous gold nanowires are obtained after chemical vapor deposition of 345 nm of poly(p-xylylene) (PPX) onto the composite fibers followed by pyrolysis of the polymers at 1050 °C. The corresponding heat-induced transition from continuous gold-loaded polymer tubes to smooth gold nanofibers is studied by transmission electron microscopy and helium ion microscopy using both secondary electrons and Rutherford backscattered ions.

  8. Preparing high-density polymer brushes by mechanically assisted polymer assembly (MAPA)

    NASA Astrophysics Data System (ADS)

    Wu, Tao; Efimenko, Kirill; Genzer, Jan

    2001-03-01

    We introduce a novel method of modifying the surface properties of materials. This technique, called MAPA (="mechanically assisted polymer assembly"), is based on: 1) chemically attaching polymerization initiators to the surface of an elastomeric network that has been previously stretched by a certain length, Δx, and 2) growing end-anchored macromolecules using surface initiated ("grafting from") atom transfer living radical polymerization. After the polymerization, the strain is removed from the substrate, which returns to its original size causing the grafted macromolecules to stretch away from the substrate and form a dense polymer brush. We demonstrate the feasibility of the MAPA method by preparing high-density polymer brushes of poly(acryl amide), PAAm. We show that, as expected, the grafting density of the PAAm brushes can be increased by increasing Δx. We demonstrate that polymer brushes with extremely high grafting densities can be successfully prepared by MAPA.

  9. Protein Biosensors Based on Polymer Nanowires, Carbon Nanotubes and Zinc Oxide Nanorods

    PubMed Central

    M., Anish Kumar; Jung, Soyoun; Ji, Taeksoo

    2011-01-01

    The development of biosensors using electrochemical methods is a promising application in the field of biotechnology. High sensitivity sensors for the bio-detection of proteins have been developed using several kinds of nanomaterials. The performance of the sensors depends on the type of nanostructures with which the biomaterials interact. One dimensional (1-D) structures such as nanowires, nanotubes and nanorods are proven to have high potential for bio-applications. In this paper we review these three different kinds of nanostructures that have attracted much attention at recent times with their great performance as biosensors. Materials such as polymers, carbon and zinc oxide have been widely used for the fabrication of nanostructures because of their enhanced performance in terms of sensitivity, biocompatibility, and ease of preparation. Thus we consider polymer nanowires, carbon nanotubes and zinc oxide nanorods for discussion in this paper. We consider three stages in the development of biosensors: (a) fabrication of biomaterials into nanostructures, (b) alignment of the nanostructures and (c) immobilization of proteins. Two different methods by which the biosensors can be developed at each stage for all the three nanostructures are examined. Finally, we conclude by mentioning some of the major challenges faced by many researchers who seek to fabricate biosensors for real time applications. PMID:22163892

  10. Protein biosensors based on polymer nanowires, carbon nanotubes and zinc oxide nanorods.

    PubMed

    Anish Kumar, M; Jung, Soyoun; Ji, Taeksoo

    2011-01-01

    The development of biosensors using electrochemical methods is a promising application in the field of biotechnology. High sensitivity sensors for the bio-detection of proteins have been developed using several kinds of nanomaterials. The performance of the sensors depends on the type of nanostructures with which the biomaterials interact. One dimensional (1-D) structures such as nanowires, nanotubes and nanorods are proven to have high potential for bio-applications. In this paper we review these three different kinds of nanostructures that have attracted much attention at recent times with their great performance as biosensors. Materials such as polymers, carbon and zinc oxide have been widely used for the fabrication of nanostructures because of their enhanced performance in terms of sensitivity, biocompatibility, and ease of preparation. Thus we consider polymer nanowires, carbon nanotubes and zinc oxide nanorods for discussion in this paper. We consider three stages in the development of biosensors: (a) fabrication of biomaterials into nanostructures, (b) alignment of the nanostructures and (c) immobilization of proteins. Two different methods by which the biosensors can be developed at each stage for all the three nanostructures are examined. Finally, we conclude by mentioning some of the major challenges faced by many researchers who seek to fabricate biosensors for real time applications.

  11. Simulation Methods for Self-Assembled Polymers and Rings

    NASA Astrophysics Data System (ADS)

    Kindt, James T.

    2003-11-01

    New off-lattice grand canonical Monte Carlo simulation methods have been developed and used to model the equilibrium structure and phase diagrams of equilibrium polymers and rings. A scheme called Polydisperse Insertion, Removal, and Resizing (PDIRR) is used to accelerate the equilibration of the size distribution of self-assembled aggregates. This method allows the insertion or removal of aggregates (e.g., chains) containing an arbitrary number of monomers in a single Monte Carlo move, or the re-sizing of an existing aggregate. For the equilibrium polymer model under semi-dilute conditions, a several-fold increase in equilibration rate compared with single-monomer moves is observed, facilitating the study of the isotropic-nematic transition of semiflexible, self-assembled chains. Combined with the pivot-coupled GCMC method for ring simulation, the PDIRR approach also allows the phenomenological simulation of a polydisperse equilibrium phase of rings, 2-dimensional fluid domains, or flat self-assembled disks in three dimensions.

  12. Polymer adsorption-driven self-assembly of nanostructures.

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

    Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context.

  13. Self-assembled nanowire arrays as three-dimensional nanopores for filtration of DNA molecules.

    PubMed

    Rahong, Sakon; Yasui, Takao; Yanagida, Takeshi; Nagashima, Kazuki; Kanai, Masaki; Meng, Gang; He, Yong; Zhuge, Fuwei; Kaji, Noritada; Kawai, Tomoji; Baba, Yoshinobu

    2015-01-01

    Molecular filtration and purification play important roles for biomolecule analysis. However, it is still necessary to improve efficiency and reduce the filtration time. Here, we show self-assembled nanowire arrays as three-dimensional (3D) nanopores embedded in a microfluidic channel for ultrafast DNA filtration. The 3D nanopore structure was formed by a vapor-liquid-solid (VLS) nanowire growth technique, which allowed us to control pore size of the filtration material by varying the number of growth cycles. λ DNA molecules (48.5 kbp) were filtrated from a mixture of T4 DNA (166 kbp) at the entrance of the 3D nanopore structure within 1 s under an applied electric field. Moreover, we observed single DNA molecule migration of T4 and λ DNA molecules to clarify the filtration mechanism. The 3D nanopore structure has simplicity of fabrication, flexibility of pore size control and reusability for biomolecule filtration. Consequently it is an excellent material for biomolecular filtration.

  14. The controllable assembly of nanorods, nanowires and microwires of a perylenediimide molecule with photoswitching property

    SciTech Connect

    Ma, Ying; An, Boxing; Wang, Meng; Shi, Fangxiao; Wang, Qing; Gu, Yaxin; Niu, Wanyang; Fan, Zhaorong; Shang, Yanli; Wang, Dan; Zhao, Cong

    2015-07-15

    By using an electron donor–acceptor molecule that consists of a perylenediimide (PDI) core bonded with two ferrocene (Fc) units, well-defined nanorods, nanowires and microwires of PDI-Fc were formed through simply adjusting the initial concentration of PDI-Fc in dichloromethane or CH{sub 2}Cl{sub 2}. Moreover, the two-ended devices based on individual microwire were fabricated. Highly reproducible and sensitive photo response characteristics were demonstrated in the microwire through controlling the white light on and off with different light intensities. The assembly strategy via complementary donors and acceptors is of significance for constructing photoconductive systems and developing novel functional devices. - Graphical abstract: The two-ended devices based on individual microwire were fabricated. Highly reproducible and sensitive photo response characteristics were observed by controlling the white light on and off with different light intensities. - Highlights: • An electron donor–acceptor molecule (PDI-Fc) was synthesized. • Well-defined nanorods, nanowires and microwires of PDI-Fc were formed. • The two-ended devices based on individual microwire were fabricated. • Highly reproducible and sensitive photo response characteristics were observed.

  15. Ionic self-assembled wormlike nanowires and their cyclodextrin inclusion-tuned transition.

    PubMed

    Li, Qiuhong; Chen, Xiao; Wang, Xudong; Zhao, Yurong; Ma, Fumin

    2010-08-19

    Wormlike nanowires have been successfully prepared via the ionic self-assembly (ISA) route from the cationic (ferrocenylmethyl)trimethylammonium iodide (FcMI) and the anionic sodium bis(2-ethyl-1-hexyl)sulfosuccinate (AOT). The formed FcM-AOT complexes have been proved to possess a composition of equal molar ratio and show good redox activity also due to the introduction of organic metal ferrocene. These complexes exhibit an ordered hexagonal columnar structure with the lattice spacing D of 2.49 nm. More interestingly, the wormlike nanowires interweave themselves together to form a net-like structure, and some of them are large enough to exhibit a high-order crystal structure. In addition, such an ISA organized aggregate can be changed into vesicles by including the Fc blocks into beta-cyclodextrins to form another supramolecular complex. The supramolecular structure and morphology of the vesicles were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS), respectively. Both the complex fabrication and transition mechanisms are discussed and found to be controlled by the inclusion equilibrium and the cooperative binding of noncovalent interactions, including the electrostatic interactions, pi-pi stacking, and amphiphilic hydrophobic association.

  16. Micelle-Induced Self-Assembling Protein Nanowires: Versatile Supramolecular Scaffolds for Designing the Light-Harvesting System.

    PubMed

    Sun, Hongcheng; Zhang, Xiyu; Miao, Lu; Zhao, Linlu; Luo, Quan; Xu, Jiayun; Liu, Junqiu

    2016-01-26

    Organic nanoparticle induced self-assembly of proteins with periodic nanostructures is a promising and burgeoning strategy to develop functional biomimetic nanomaterials. Cricoid proteins afford monodispersed and well-defined hollow centers, and can be used to multivalently interact with geometrically symmetric nanoparticles to form one-dimensional protein nanoarrays. Herein, we report that core-cross-linked micelles can direct cricoid stable protein one (SP1) to self-assembling nanowires through multiple electrostatic interactions. One micelle can act as an organic nanoparticle to interact with two central concaves of SP1 in an opposite orientation to form a sandwich structure, further controlling the assembly direction to supramolecular protein nanowires. The reported versatile supramolecular scaffolds can be optionally manipulated to develop multifunctional integrated or synergistic biomimetic nanomaterials. Artificial light-harvesting nanowires are further developed to mimic the energy transfer process of photosynthetic bacteria for their structural similarity, by means of labeling donor and acceptor chromophores to SP1 rings and spherical micelles, respectively. The absorbing energy can be transferred within the adjacent donors around the ring and shuttling the collected energy to the nearby acceptor chromophore. The artificial light-harvesting nanowires are designed by mimicking the structural characteristic of natural LH-2 complex, which are meaningful in exploring the photosynthesis process in vitro.

  17. Self-assembled polymer MEMS sensors and actuators

    NASA Astrophysics Data System (ADS)

    Hill, Andrea J.; Claus, Richard O.; Lalli, Jennifer H.; Homer, Michelle

    2006-03-01

    This paper describes the use of Metal Rubber TM, which is an electrically-conductive, low modulus, highly-flexible, and optically transparent free-standing or conformal coating nanocomposite material that is fabricated via Electrostatic Self-Assembly (ESA), as a polymer MEMS sensor for actuator materials. ESA is an environmentally-friendly layer-by-layer fabrication technique in which Metal Rubber TM can be tailor designed at the molecular level to function as a sensor and/or electrode for active polymer devices. With its controllable and tailorable properties (such as mechanical modulus [from less than 0.1 MPa to greater than 500 MPa], electrical conductivity, sensitivity to flex and strain (tension and compression), thickness, transmission, glass transition, and more), Metal Rubber TM exhibits massive improvements over traditional stiff electrodes and sensors (with bulky/heavy wire components) that physically constrain the actuator device motion and thus limit productivity. Metal RubberTM shows exceptional potential for use as flexible sensors, electrodes, and interconnect components for many active polymer applications. One example of such is NanoSonic's Metal Rubber TM-Polymer MEMS (MR TM-PMEMS) nanocluster-based corrosion sensor for aircraft coatings that was developed for an Air Force SBIR program. MR TM-PMEMS was tailored via ESA for use as an in-situ sensor of chemical modifications and the breakdown of surface coatings via micro-strain measurements.

  18. Self-assembled hydrogels utilizing polymer-nanoparticle interactions

    NASA Astrophysics Data System (ADS)

    Appel, Eric A.; Tibbitt, Mark W.; Webber, Matthew J.; Mattix, Bradley A.; Veiseh, Omid; Langer, Robert

    2015-02-01

    Mouldable hydrogels that flow on applied stress and rapidly self-heal are increasingly utilized as they afford minimally invasive delivery and conformal application. Here we report a new paradigm for the fabrication of self-assembled hydrogels with shear-thinning and self-healing properties employing rationally engineered polymer-nanoparticle (NP) interactions. Biopolymer derivatives are linked together by selective adsorption to NPs. The transient and reversible interactions between biopolymers and NPs enable flow under applied shear stress, followed by rapid self-healing when the stress is relaxed. We develop a physical description of polymer-NP gel formation that is utilized to design biocompatible gels for drug delivery. Owing to the hierarchical structure of the gel, both hydrophilic and hydrophobic drugs can be entrapped and delivered with differential release profiles, both in vitro and in vivo. The work introduces a facile and generalizable class of mouldable hydrogels amenable to a range of biomedical and industrial applications.

  19. Optimal design of laterally assembled hexagonal silicon nanowires for broadband absorption enhancement in ultrathin solar cells

    NASA Astrophysics Data System (ADS)

    Shahraki, Mojtaba; Salehi, Mohammad Reza; Abiri, Ebrahim

    2015-11-01

    Design approaches to carry out broadband absorption in laterally assembled hexagonal silicon nanowire (NW) solar cells are investigated. Two different methods are proposed to improve the current density of silicon NW solar cells. It is observed that the key to the broadband absorption is disorder and irregularity. The first approach to reach the broadband absorption is using multiple NWs with different geometries. Nevertheless, the maximum enhancement is obtained by introducing irregular NWs. They can support more cavity modes, while scattering by NWs leads to broadening of the absorption spectra. An array of optimized irregular NWs also has preferable features compared to other broadband structures. Using irregular NW arrays, it is possible to improve the absorption enhancement of solar cells without introducing more absorbing material.

  20. Self-Assembly and Horizontal Orientation Growth of VO2 Nanowires

    PubMed Central

    Cheng, Chun; Guo, Hua; Amini, Abbas; Liu, Kai; Fu, Deyi; Zou, Jian; Song, Haisheng

    2014-01-01

    Single-crystalline vanadium dioxide (VO2) nanostructures have attracted an intense research interest recently because of their unique single-domain metal-insulator phase transition property. Synthesis of these nanostructures in the past was limited in density, alignment, or single-crystallinity. The assembly of VO2 nanowires (NWs) is desirable for a “bottom-up” approach to the engineering of intricate structures using nanoscale building blocks. Here, we report the successful synthesis of horizontally aligned VO2 NWs with a dense growth mode in the [1-100]quartz direction of a polished x-cut quartz surface using a simple vapor transport method. Our strategy of controlled growth of VO2 NWs promisingly paves the way for designing novel metal-insulator transition devices based on VO2 NWs. PMID:24965899

  1. Facile synthesis of nucleic acid-polymer amphiphiles and their self-assembly.

    PubMed

    Jia, Fei; Lu, Xueguang; Tan, Xuyu; Zhang, Ke

    2015-05-07

    A solid-phase synthesis for nucleic acid-polymer amphiphiles is developed. Using this strategy, several DNA-b-polymer amphiphiles are synthesized, and their self-assembly in aqueous solution is investigated. This general method can in principle be extended to nearly all polymers synthesized by atom transfer radical polymerization to produce a variety of nucleic acid-polymer conjugates.

  2. Layer-by-layer assembly of nanowires for three-dimensional, multifunctional electronics.

    PubMed

    Javey, Ali; Nam, SungWoo; Friedman, Robin S; Yan, Hao; Lieber, Charles M

    2007-03-01

    We report a general approach for three-dimensional (3D) multifunctional electronics based on the layer-by-layer assembly of nanowire (NW) building blocks. Using germanium/silicon (Ge/Si) core/shell NWs as a representative example, ten vertically stacked layers of multi-NW field-effect transistors (FETs) were fabricated. Transport measurements demonstrate that the Ge/Si NW FETs have reproducible high-performance device characteristics within a given device layer, that the FET characteristics are not affected by sequential stacking, and importantly, that uniform performance is achieved in sequential layers 1 through 10 of the 3D structure. Five-layer single-NW FET structures were also prepared by printing Ge/Si NWs from lower density growth substrates, and transport measurements showed similar high-performance characteristics for the FETs in layers 1 and 5. In addition, 3D multifunctional circuitry was demonstrated on plastic substrates with sequential layers of inverter logical gates and floating gate memory elements. Notably, electrical characterization studies show stable writing and erasing of the NW floating gate memory elements and demonstrate signal inversion with larger than unity gain for frequencies up to at least 50 MHz. The ability to assemble reproducibly sequential layers of distinct types of NW-based devices coupled with the breadth of NW building blocks should enable the assembly of increasing complex multilayer and multifunctional 3D electronics in the future.

  3. Self-assembly of hyperbranched polymers and its biomedical applications.

    PubMed

    Zhou, Yongfeng; Huang, Wei; Liu, Jinyao; Zhu, Xinyuan; Yan, Deyue

    2010-11-02

    Hyperbranched polymers (HBPs) are highly branched macromolecules with a three-dimensional dendritic architecture. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. In this paper, the recent developments in HBP self-assembly and their biomedical applications have been comprehensively reviewed. Many delicate supramolecular structures from zero-dimension (0D) to three-dimension (3D), such as micelles, fibers, tubes, vesicles, membranes, large compound vesicles and physical gels, have been prepared through the solution or interfacial self-assembly of amphiphilic HBPs. In addition, these supramolecular structures have shown promising applications in the biomedical areas including drug delivery, protein purification/detection/delivery, gene transfection, antibacterial/antifouling materials and cytomimetic chemistry. Such developments promote the interdiscipline researches among surpramolecular chemistry, biomedical chemistry, nano-technology and functional materials.

  4. Role of self-assembled monolayer passivation in electrical transport properties and flicker noise of nanowire transistors.

    PubMed

    Kim, Seongmin; Carpenter, Patrick D; Jean, Rand K; Chen, Haitian; Zhou, Chongwu; Ju, Sanghyun; Janes, David B

    2012-08-28

    Semiconductor nanowires have achieved great attention for integration in next-generation electronics. However, for nanowires with diameters comparable to the Debye length, which would generally be required for one-dimensional operation, surface states degrade the device performance and increase the low-frequency noise. In this study, single In(2)O(3) nanowire transistors were fabricated and characterized before and after surface passivation with a self-assembled monolayer of 1-octadecanethiol (ODT). Electrical characterization of the transistors shows that device performance can be enhanced upon ODT passivation, exhibiting steep subthreshold slope (~64 mV/dec), near zero threshold voltage (~0.6 V), high mobility (~624 cm(2)/V·s), and high on-currents (~40 μA). X-ray photoelectron spectroscopy studies of the ODT-passivated nanowires indicate that the molecules are bound to In(2)O(3) nanowires through the thiol linkages. Device simulations using a rectangular geometry to represent the nanowire indicate that the improvement in subthreshold slope and positive shift in threshold voltage can be explained in terms of reduced interface trap density and changes in fixed charge density. Flicker (low-frequency, 1/f) noise measurements show that the noise amplitude is reduced following passivation. The interface trap density before and after ODT passivation is profiled throughout the band gap energy using the subthreshold current-voltage characteristics and is compared to the values extracted from the low-frequency noise measurements. The results indicate that self-assembled monolayer passivation is a promising optimization technology for the realization of low-power, low-noise, and fast-switching applications such as logic, memory, and display circuitry.

  5. Magnetic Properties of Feni Nanowire Arrays Assembled on Porous AAO Template by AC Electrodeposition

    NASA Astrophysics Data System (ADS)

    Wang, Pangpang; Gao, Lumei; Wang, Liqun; Zhang, Dongyan; Yang, Sen; Song, Xiaoping; Qiu, Zhiyong; Murakami, Ri-Ichi

    FeNi nanowire arrays were fabricated into the pores of porous alumina template by a simple alternating current electrodeposition method in this work. FeNi nanowires with different diameters were obtained depending on the pore size arrangement of alumina templates. FeNi nanowire arrays exhibited obviously magnetic anisotropy, and the easy axis was along the nanowires. When the applied magnetic field was parallel to the nanowires, the coercivity (Hc) and the maximum remnant ratio (Mr/Ms) are considerable higher than those while the magnetic field perpendicular to the nanowires. FeNi nanowires prepared in this work are expected to be utilized as the perpendicular magnetic recording media. The magnetic domain structure and the magnetizing mechanism of FeNi nanowires were also been discussed.

  6. Phosphorylcholine substituted polyolefins: New syntheses, solution assemblies, and polymer vesicles

    NASA Astrophysics Data System (ADS)

    Kratz, Katrina A.

    This thesis describes the synthesis and applications of a new series of amphiphilic homopolymers and copolymers consisting of hydrophobic polyolefin backbone and hydrophilic phosphorylcholine (PC) pendant groups. These polymers are synthesized by ring opening metathesis polymerization (ROMP) of a novel PC- cyclooctene monomer, and copolymerization of various functionalized cyclooctene comonomers. Incorporation of different comonomers into the PC-polyolefin backbone affords copolymers with different functionalities, including crosslinkers, fluorophores, and other reactive groups, that tune the range of applications of these polymers, and their hydrophobic/hydrophilic balance. The amphiphilic nature of PC-polyolefins was exploited in oil-water interfacial assembly, providing robust polymer capsules to encapsulate and deliver nanoparticles to damaged regions of a substrate in a project termed `repair-and-go.' In repair-and-go, a flexible microcapsule filled with a solution of nanoparticles probes an imperfection-riddled substrate as it rolls over the surface. The thin capsule wall allows the nanoparticles to escape the capsules and enter into the cracks, driven in part by favorable interactions between the nanoparticle ligands and the cracked surface (i.e., hydrophobic-hydrophobic interactions). The capsules then continue their transport along the surface, filling more cracks and depositing particles into them. The amphiphilic nature of PC-polyolefins was also exploited in aqueous assembly, forming novel polymer vesicles in water. PC-polyolefin vesicles ranged in size from 50 nm to 30 µm. The mechanical properties of PC-polyolefin vesicles were measured by micropipette aspiration techniques, and found to be more robust than conventional liposomes or polymersomes prepared from block copolymers. PC-polyolefin vesicles have potential use in drug delivery; it was found that the cancer drug doxorubicin could be encapsulated efficiently in PC-polyolefin vesicles. In

  7. Bud-like silica nanowires with self-assembled long segmented stems: a novel nanostructure and its growth mechanism.

    PubMed

    Li, Qiang; Chen, Yiqing; Zhang, Xinhua; Liu, Lizhu; Guo, Taibo; Wei, Meiqin; Su, Yong; Jia, Chong

    2010-08-01

    A large quantity of bud-like silica nanowires with self-assembled long segmented stems were synthesized through thermal evaporation via using a piece of Si wafer and the mixture of Ga2O3 and carbon powder as source materials. The segmented stems were assembled from the bottom part of the bud-like silica nanowires with diameter of approximately 0.5 microm and length up to more than 20 microm. The bud-like silica nanowires could have one, two or three segmented stems. Some bud-like silica nanostrutures have a bowl-shaped cavity at their tips, others have a tail growing from their tips. The aligned silica nanowires were found extending from the thin silica shell coating the Ga ball, instead of nucleating and growing from the surface of the Ga ball directly. These interesting results could help us understand the diversity and versatility of the silica nanostructures which can be fabricated, and the knowledge of their growth mechanisms.

  8. Self-assembly of silicon nanowires studied by advanced transmission electron microscopy

    PubMed Central

    Agati, Marta; Amiard, Guillaume; Borgne, Vincent Le; Castrucci, Paola; Dolbec, Richard; De Crescenzi, Maurizio; El Khakani, My Alì

    2017-01-01

    Scanning transmission electron microscopy (STEM) was successfully applied to the analysis of silicon nanowires (SiNWs) that were self-assembled during an inductively coupled plasma (ICP) process. The ICP-synthesized SiNWs were found to present a Si–SiO2 core–shell structure and length varying from ≈100 nm to 2–3 μm. The shorter SiNWs (maximum length ≈300 nm) were generally found to possess a nanoparticle at their tip. STEM energy dispersive X-ray (EDX) spectroscopy combined with electron tomography performed on these nanostructures revealed that they contain iron, clearly demonstrating that the short ICP-synthesized SiNWs grew via an iron-catalyzed vapor–liquid–solid (VLS) mechanism within the plasma reactor. Both the STEM tomography and STEM-EDX analysis contributed to gain further insight into the self-assembly process. In the long-term, this approach might be used to optimize the synthesis of VLS-grown SiNWs via ICP as a competitive technique to the well-established bottom-up approaches used for the production of thin SiNWs. PMID:28326234

  9. Hybrid Thin Films Based Upon Polyoxometalates-Polymer Assembly

    NASA Astrophysics Data System (ADS)

    Qi, Na; Jing, Benxin; Zhu, Yingxi

    2014-03-01

    Block copolymers (BCPs) and polyoxometalates (POMs) have been used individually as building blocks for design and synthesis of novel functional materials. POM nanoclusters, the assemblies of transition metal oxides with well-defined atomic coordination structure, have been recently explored as novel nanomaterials... for catalysis, semiconductors, and even anti-cancer treatment due to their unique chemical, optical and electrical characteristics. We have explored the blending of inorganic POM nanocluster with BCPs into hierarchaically structured inorganic-organic hybrid nanocomposites. Using polystyrene-b-poly(ethylene oxide) (PS-b-PEO) thin films as the template, we have observed that the spatial organization of BCP thin films is modified by molybdenum based POM nanocluster to form 2D in-plane hexagonal ordered or 3D ordered network of POM-BCP assemblies, depending on the concentration ratio of POM to PS-b-PEO. The dielectric properties of such hybrid thin films can be enhanced by embedded POMs but show a strong dependence on the supramolecular structures of POM-polymer complexes. The assembly of nanoclusters in BCP-templated thin films could pave a new path to design new hybrid nanocomposites with uniquely combined functionality and material properties.

  10. High aspect ratio conjugated polymer nanowires for high performance field-effect transistors and phototransistors.

    PubMed

    Um, Hyun Ah; Lee, Dae Hee; Heo, Dong Uk; Yang, Da Seul; Shin, Jicheol; Baik, Hionsuck; Cho, Min Ju; Choi, Dong Hoon

    2015-05-26

    We synthesized a highly crystalline DPP-based polymer, DPPBTSPE, which contained 1,2-bis(5-(thiophen-2-yl)selenophen-2-yl)ethene as a planar and rigid electron donating group. High- and low-molecular weight (MW) DPPBTSPE fractions were collected by Soxhlet extraction and were employed to investigate their unique charge transport properties in macroscopic films and single crystalline polymer nanowire (SC-PNW), respectively. The low-MW polymer could provide well-isolated and high aspect ratio SC-PNWs, in which the direction of π-π stacking was perpendicular to the wire growing axis. The field effect transistors made of SC-PNWs exhibited remarkably high carrier mobility of 24 cm(2) V(-1) s(-1). In addition, phototransistors (PTs) made of SC-PNW showed very high performance in terms of photoresponsivity (R) and photoswitching ratio (P). The average R of the SC PNW-based PTs were in the range of 160-170 A W(-1) and the maximum R was measured at 1920 A W(-1), which is almost three orders higher than that of thin film-based PT device.

  11. Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

    PubMed

    Cheng, Chih-Chia; Chuang, Wei-Tsung; Lee, Duu-Jong; Xin, Zhong; Chiu, Chih-Wei

    2017-03-01

    A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization.

  12. Solution-processed parallel tandem polymer solar cells using silver nanowires as intermediate electrode.

    PubMed

    Guo, Fei; Kubis, Peter; Li, Ning; Przybilla, Thomas; Matt, Gebhard; Stubhan, Tobias; Ameri, Tayebeh; Butz, Benjamin; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J

    2014-12-23

    Tandem architecture is the most relevant concept to overcome the efficiency limit of single-junction photovoltaic solar cells. Series-connected tandem polymer solar cells (PSCs) have advanced rapidly during the past decade. In contrast, the development of parallel-connected tandem cells is lagging far behind due to the big challenge in establishing an efficient interlayer with high transparency and high in-plane conductivity. Here, we report all-solution fabrication of parallel tandem PSCs using silver nanowires as intermediate charge collecting electrode. Through a rational interface design, a robust interlayer is established, enabling the efficient extraction and transport of electrons from subcells. The resulting parallel tandem cells exhibit high fill factors of ∼60% and enhanced current densities which are identical to the sum of the current densities of the subcells. These results suggest that solution-processed parallel tandem configuration provides an alternative avenue toward high performance photovoltaic devices.

  13. Si6H12/Polymer Inks for Electrospinning a-Si Nanowire Lithium Ion Battery Anodes

    SciTech Connect

    Schulz, Douglas L.; Hoey, Justin; Smith, Jeremiah; Elangovan, Arumugasamy; Wu, Xiangfa; Akhatov, Iskander; Payne, Scott; Moore, Jayma; Boudjouk, Philip; Pederson, Larry; Xiao, Jie; Zhang, Jiguang

    2010-08-04

    Amorphous silicon nanowires 'a-SiNWs' have been prepared by electrospinning a liquid silane-based precursor. Cyclohexasilane 'Si6H12' was admixed with poly-methyl methacrylate (PMMA) in toluene giving an ink that was electrospun into the Si6H12/PPMA wires with diameters of 50-2000 nm. Raman spectroscopy revealed that thermal treatment at 350 C transforms this deposit into a-SiNWs. These materials were coated with a thin carbon layer and then tested as half-cells where a reasonable plateau in electrochemical cycling was observed after an initial capacity fade. Additionally, porous a-SiNWs were realized when the thermally decomposable binder polypropylene carbonate/polycyclohexene carbonate was used as the polymer carrier.

  14. Patterning of self-assembled monolayers by phase-shifting mask and its applications in large-scale assembly of nanowires

    NASA Astrophysics Data System (ADS)

    Gao, Fan; Zhang, Dakuan; Wang, Jianyu; Sheng, Yun; Yan, Shancheng; Wang, Xinran; Chen, Kunji; Shen, Jiancang; Pan, Lijia; Zhou, Minmin; Shi, Yi

    2015-01-01

    A nonselective micropatterning method of self-assembled monolayers (SAMs) based on laser and phase-shifting mask (PSM) is demonstrated. Laser beam is spatially modulated by a PSM, and periodic SAM patterns are generated sequentially through thermal desorption. Patterned wettability is achieved with alternating hydrophilic/hydrophobic stripes on octadecyltrichlorosilane monolayers. The substrate is then used to assemble CdS semiconductor nanowires (NWs) from a solution, obtaining well-aligned NWs in one step. Our results show valuably the application potential of this technique in engineering SAMs for integration of functional devices.

  15. Patterning of self-assembled monolayers by phase-shifting mask and its applications in large-scale assembly of nanowires

    SciTech Connect

    Gao, Fan; Zhang, Dakuan; Wang, Jianyu; Sheng, Yun; Wang, Xinran; Chen, Kunji; Zhou, Minmin; Yan, Shancheng; Shen, Jiancang; Pan, Lijia; Shi, Yi

    2015-01-26

    A nonselective micropatterning method of self-assembled monolayers (SAMs) based on laser and phase-shifting mask (PSM) is demonstrated. Laser beam is spatially modulated by a PSM, and periodic SAM patterns are generated sequentially through thermal desorption. Patterned wettability is achieved with alternating hydrophilic/hydrophobic stripes on octadecyltrichlorosilane monolayers. The substrate is then used to assemble CdS semiconductor nanowires (NWs) from a solution, obtaining well-aligned NWs in one step. Our results show valuably the application potential of this technique in engineering SAMs for integration of functional devices.

  16. Integrated chemical and biological systems in nanowire structures towards nano-scale sensors

    NASA Astrophysics Data System (ADS)

    Hernandez, Rose M.

    Nanowires composed of metal and conducting polymers with integrated proteins and chemical systems have been investigated as building blocks for next-generation nano-scale sensors and assemblies. These nanowires were fabricated by combining chemical and electrochemical methods of synthesis of gold and conducting polymers in nanopores of anodized alumina membranes. Polymer nanowires were synthesized from buffer solutions as a mean to promote a biocompatible environment for the incorporation of proteins. A variety of proteins were incorporated into the polymer matrix by entrapment during polymerization that imparted the polymer material with biological functionality. Another class of composite nanowires containing electro-active conducting polymer junctions was developed for applications in chemical sensor arrays. The methodologies described in this thesis provide an inexpensive and straightforward approach to the synthesis of anisotropic nanoparticles incorporating a variety of biological and inorganic species that can be integrated to current microelectronic technologies for the development of nano-scale sensor arrays.

  17. Bioinspired design and assembly of platelet reinforced polymer films.

    PubMed

    Bonderer, Lorenz J; Studart, André R; Gauckler, Ludwig J

    2008-02-22

    Although strong and stiff human-made composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the order and sophisticated hierarchy of hybrid materials built up by living organisms in nature. Clay-based nanocomposites with layered structure can reach notable stiffness and strength, but these properties are usually not accompanied by the ductility and flaw tolerance found in the structures generated by natural hybrid materials. By using principles found in natural composites, we showed that layered hybrid films combining high tensile strength and ductile behavior can be obtained through the bottom-up colloidal assembly of strong submicrometer-thick ceramic platelets within a ductile polymer matrix.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  19. Self-Assembled Hydrogels Utilising Polymer-Nanoparticle Interactions

    PubMed Central

    Appel, Eric A.; Tibbitt, Mark W.; Webber, Matthew J.; Mattix, Bradley A.; Veiseh, Omid

    2015-01-01

    Mouldable hydrogels that flow upon applied stress and rapidly self-heal are increasingly utilised as they afford minimally invasive delivery and conformal application. Here we report a new paradigm for the fabrication of self-assembled hydrogels with shear-thinning and self-healing properties employing rationally engineered polymer-nanoparticle interactions. Biopolymer derivatives are linked together by selective adsorption to nanoparticles. The transient and reversible interactions between biopolymers and nanoparticles enable flow under applied shear stress, followed by rapid self-healing when the stress is relaxed. We develop a physical description of polymer-nanoparticle gel formation that is utilised to design biocompatible gels for minimally-invasive drug delivery. Owing to the hierarchical structure of the gel, both hydrophilic and hydrophobic drugs can be entrapped and delivered with differential release profiles, both in vitro and in vivo. The work introduces a facile and generalizable class of mouldable hydrogels amenable to a range of biomedical and industrial applications. PMID:25695516

  20. Self-assembled conjugated polymer spheres as fluorescent microresonators

    PubMed Central

    Tabata, Kenichi; Braam, Daniel; Kushida, Soh; Tong, Liang; Kuwabara, Junpei; Kanbara, Takaki; Beckel, Andreas; Lorke, Axel; Yamamoto, Yohei

    2014-01-01

    Confinement of light inside an active medium cavity can amplify emission. Whispering gallery mode (WGM) is one of mechanisms that amplifies light effectively by confining it inside high-refractive-index microstructures, where light propagates along the circumference of a sphere via total internal reflection. Here we show that isolated single microspheres of 2–10 μm diameter, formed from self-assembly of π-conjugated alternating copolymers, display WGM photoemission induced by laser pumping. The wavelengths of the emission peaks depend sensitively on the sphere size, position of the excitation spot and refractive index of each polymer. The Q-factor increases with increasing sphere diameter and displays a linear correlation with the reciprocal radius, indicating that the small curvature increases the efficacy of the total internal reflection. WGM photoemission from π-conjugated polymer microspheres is unprecedented and may be of high technological impact since the microspheres fulfill the role of fluorophores, high-refractive-index media and resonators simultaneously, in addition to their simple fabrication process. PMID:25082187

  1. Crystallization-driven assembly of conjugated-polymer-based nanostructures

    SciTech Connect

    Hayward, Ryan C.

    2016-10-15

    The goal of this project has been to improve our ability to simultaneously control the organization, and therefore the opto-electronic properties, of conjugated-polymer based materials across three different length-scales: 1) the molecular scale, in the sense of controlling growth and functionalization of highly crystalline semiconducting organic materials capable of efficient charge transport, 2) the nanoscale, in terms of positioning n- and p-type materials with domain sizes comparable to exciton diffusion lengths (~ 10 nm) to facilitate charge separation, and 3) the colloidal scale, such that well-defined crystalline nanoscale building blocks can be hierarchically organized into device layers. As described in more detail below, the project was successful in generating powerful new approaches to, and improved fundamental understanding of, processing and self-assembly of organic and hybrid semiconducting materials across all three length-scales. Although the goals of the project were formulated with primarily photovoltaic architectures in mind, the outcomes of the project have significant implications for a variety of conjugated-polymer-based devices including field-effect-transistors for sensors and logic devices, as well as potentially thermoelectrics and battery electrode materials. The project has resulted in 10 peer-reviewed publications to date [1-10], with several additional manuscripts currently in preparation.

  2. Recognition-Mediated Assembly of Quantum Dot Polymer Conjugates with Controlled Morphology

    PubMed Central

    Nandwana, Vikas; Subramani, Chandramouleeswaran; Eymur, Serkan; Yeh, Yi-Cheun; Tonga, Gulen Yesilbag; Tonga, Murat; Jeong, Youngdo; Yang, Boqian; Barnes, Michael D.; Cooke, Graeme; Rotello, Vincent M.

    2011-01-01

    We have demonstrated a polymer mediated “bricks and mortar” method for the self-assembly of quantum dots (QDs). This strategy allows QDs to self-assemble into structured aggregates using complementary three-point hydrogen bonding. The resulting nanocomposites have distinct morphologies and inter-particle distances based on the ratio between QDs and polymer. Time resolved photoluminescence measurements showed that the optical properties of the QDs were retained after self-assembly. PMID:22016664

  3. Design of polymer motifs for nucleic acid recognition and assembly stabilization

    NASA Astrophysics Data System (ADS)

    Zhou, Zhun

    This dissertation describes the synthesis and assembly of bio-functional polymers and the applications of these polymers to drug encapsulation, delivery, and multivalent biomimetic macromolecular recognition between synthetic polymer and nucleic acids. The main content is divided into three parts: (1) polyacidic domains as strongly stabilizing design elements for aqueous phase polyacrylate diblock assembly; (2) small molecule/polymer recognition triggered macromolecular assembly and drug encapsulation; (3) trizaine derivatized polymer as a novel class of "bifacial polymer nucleic acid" (bPoNA) and applications of bPoNA to nanoparticle loading of DNA/RNA, silencing delivery as well as control of aptamer function. Through the studies in part (1) and part (2), it was demonstrated that well-designed polymer motifs are not only able to enhance assemblies driven by non-specific hydrophobic effect, but are also able to direct assemblies based on specific recognitions. In part (3) of this dissertation, this concept was further extended by the design of polyacrylate polymers that are capable of discrete and robust hybridization with nucleic acids. This surprising finding demonstrated both fundamental and practical applications. Overall, these studies provided insights into the rational design elements for improving the bio-functions of synthetic polymers, and significantly expanded the scope of biological applications in which polymers synthesized via controlled radical polymerization may play a role.

  4. Copper(II)-Mediated Self-Assembly of Hairpin Peptides and Templated Synthesis of CuS Nanowires.

    PubMed

    Wang, Chengdong; Sun, Yawei; Wang, Jiqian; Xu, Hai; Lu, Jian R

    2015-09-01

    The self-assembly of peptides and proteins under well-controlled conditions underlies important nanostructuring processes that could be harnessed in practical applications. Herein, the synthesis of a new hairpin peptide containing four histidine residues is reported and the self-assembly process mediated by metal ions is explored. The work involves the combined use of circular dichroism, NMR spectroscopy, UV/Vis spectroscopy, AFM, and TEM to follow the structural and morphological details of the metal-coordination-mediated folding and self-assembly of the peptide. The results indicate that by forming a tetragonal coordination geometry with four histidine residues, copper(II) ions selectively trigger the peptide to fold and then self-assemble into nanofibrils. Furthermore, the copper(II)-bound nanofibrils template the synthesis of CuS nanowires, which display a near-infrared laser-induced thermal effect.

  5. Selective crystallization of conjugated polymers into nanowires from graphene coated surfaces

    NASA Astrophysics Data System (ADS)

    Acevedo-Cartagena, Daniel; Zhu, Jiaxin; Trabanino, Elvira; Pentzer, Emily; Emrick, Todd; Briseño, Alejandro; Nonnenmann, Stephen; Hayward, Ryan

    Solution-based crystallization of conjugated polymers offers a scalable and attractive route to develop hierarchical structures for organic electronic devices, especially solar cells. The introduction of well-defined nucleation sites into metastable supersaturated solutions provides a way to regulate the crystallization behavior, and therefore the morphology of the material. We focus on metastable solutions of poly(3-hexylthiophene) (P3HT) dissolved in mixtures of m-xylene, a marginal solvent, and chlorobenzene, a good solvent. Appropriate levels of supersaturation are identified to suppress homogenous nucleation of crystals at room temperature, while allowing for crystallization on heterogeneous nucleation sites. We show that in these metastable solutions, P3HT selectively crystallizes on graphene-coated surfaces. Through in situ atomic force microscopy, we confirm that nanowires grow vertically in a face-on orientation from highly oriented pyrolytic graphite and graphene. Moreover, this method can be successfully extended to other conjugated polymers with superior electronic properties, such as poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene]. Therefore, this method is a promising route to improve the performance of organic electronics.

  6. Polymer-free Vertical Transfer of Silicon Nanowires and their Application to Energy Storage.

    PubMed

    Kim, Han-Jung; Lee, Jihye; Lee, Sang Eon; Kim, Wanjung; Kim, Hwan Jin; Choi, Dae-Geun; Park, Jong Hyeok

    2013-11-01

    Silicon nanowires (SiNWs) for use as lithium-ion battery (LIB) anode materials have been studied for their one-dimensional (1D) properties and ability to accommodate large volume changes and avoid rapid capacity fading during cycling. Although the vertical transfer of SiNWs from their original substrate onto a conducting electrode is very important, to date, there has been no report of a direct integration method without polymer binders. Here, we propose for the first time a vertical transfer method for SiNWs grown on a Si substrate directly to the current-collecting electrode without using a polymer adhesive for the use as a binder-free LIB anode. The vertical SiNWs produced using a low-cost wafer-scale metal-assisted chemical etching (MaCE) process have been successfully transferred directly to a copper electrode coated with a thin Ag layer by using a simple hot pressing method. When evaluated as an LIB anode without using conventional polymeric binder and a conducting additive, the transferred vertically aligned SiNWs showed a high specific capacity (≈2150 mAh g(-1) ) and excellent rate performance. It is believed that the anode-manufacturing process is simple and fast, thus enabling a large-scale production that is of low-cost, broadly applicable, and provides new avenues for the rational engineering of Si-based electrode materials with enhanced power density and conductivity.

  7. Salt-induced self-assembly of bacteria on nanowire arrays.

    PubMed

    Sakimoto, Kelsey K; Liu, Chong; Lim, Jongwoo; Yang, Peidong

    2014-09-10

    Studying bacteria-nanostructure interactions is crucial to gaining controllable interfacing of biotic and abiotic components in advanced biotechnologies. For bioelectrochemical systems, tunable cell-electrode architectures offer a path toward improving performance and discovering emergent properties. As such, Sporomusa ovata cells cultured on vertical silicon nanowire arrays formed filamentous cells and aligned parallel to the nanowires when grown in increasing ionic concentrations. Here, we propose a model describing the kinetic and the thermodynamic driving forces of bacteria-nanowire interactions.

  8. Self-assembly of Nanopatterns on Shape Memory Polymer Substrates

    NASA Astrophysics Data System (ADS)

    Chen, Zhongbi

    Periodic surface nanostructures provide unique acoustic, electronic, optical and mechanical properties, with potential applications to metamaterials, sensors, catalysis, medicine, etc. However, assembling nanometer scale constituents into engineering scale components or devices poses tremendous challenges such as cost reduction and scalability. In this work, we will introduce a novel directed self-assembly method that has the potential to address these challenges by forming unidirectional micro- and nano-wrinkles on engineering scale polymer substrates. The approach utilizes a smart material, shape memory polymer (SMP), as the substrate in a bi-layer thin-film/substrate system. With a specially-designed programming scheme, the SMP substrate can retract in one direction while expand in the perpendicular direction in a heating process. Consequently, the thin film corrugates and the wrinkling patterns are aligned. A parametric study that investigates how the system parameters influence the surface topology will be presented. Besides wrinkles, surface defects that occurred concurrently were also observed. We will present a progressive damage scheme and a microdomain-based model to understand and possibly help preventing the formation of defects. In addition, this work will also address our efforts in shrinking the wrinkle feature size from several microns to the tens of nanometer range. Two methods, through which the minimum wrinkle wavelength was reduced from one micron to 300 nm and further down to 35 nm will be elaborated. Such aligned wrinkles whose wavelength spanning two orders of magnitude from as small as 35 nm to as large as 5 mum will open up avenues for numerous exciting applications. The application of using the self-assembled wrinkled surface as the back-reflector in solar cells to improve the power conversion efficiency will be discussed as a case study. The long-term stability of the wrinkle topology, which is essential to efficiency boost will be

  9. Self-assembly of novel nanowires by thermolysis of fullerene and transition metal thin films

    NASA Astrophysics Data System (ADS)

    Hofmann, S.; Robertson, J.; Ducati, C.; Dunin-Borkowski, R. E.

    2004-05-01

    A wide range of nanomaterials has been grown by thermal treatment of patterned condensed-phase precursors. We present a systematic study of the thermolysis of fullerene, amorphous carbon and transition metal thin films, trying to bridge previously reported results in the high temperature regime (>900 °C) and reporting novel structures for low temperature (<550 °C) processing. The synthesis of crystals of single-walled carbon nanotubes from high temperature annealing of patterned, multilayered fullerene and nickel precursor films, could not be reproduced. A thicker fullerene layer in the presence of nickel was, however, transformed into a web-like carbon network. Low temperature processing of similar precursor patterns on sulfur-containing molybdenum grids resulted in the self-assembly of nickel sulfide nanowires and filled MoS2 nanotubes. Cobalt was found to form cobalt sulfide structures. The strongly oxidizing behaviour of iron resulted in an abundance of needle-like molybdenum oxide crystals. None of the structural formations could be seen for amorphous carbon as a substitutional thin film precursor. Based on the ease of changing precursor materials, this simple, scaleable method addresses many nanomaterials, giving new insight into growth mechanisms as well as offering synthesis control for future applications.

  10. Controlled growth mechanism of poly (3-hexylthiophene) nanowires

    NASA Astrophysics Data System (ADS)

    Kiymaz, D.; Yagmurcukardes, M.; Tomak, A.; Sahin, H.; Senger, R. T.; Peeters, F. M.; Zareie, H. M.; Zafer, C.

    2016-11-01

    Synthesis of 1D-polymer nanowires by a self-assembly method using marginal solvents is an attractive technique. While the formation mechanism is poorly understood, this method is essential in order to control the growth of nanowires. Here we visualized the time-dependent assembly of poly (3-hexyl-thiophene-2,5-diyl) (P3HT) nanowires by atomic force microscopy and scanning tunneling microscopy. The assembly of P3HT nanowires was carried out at room temperature by mixing cyclohexanone (CHN), as a poor solvent, with polymer solution in 1,2-dichlorobenzene (DCB). Both π-π stacking and planarization, obtained at the mix volume ratio of P3HT (in DCB):CHN (10:7), were considered during the investigation. We find that the length of nanowires was determined by the ordering of polymers in the polymer repetition direction. Additionally, our density functional theory calculations revealed that the presence of DCB and CHN molecules that stabilize the structural distortions due to tail group of polymers was essential for the core-wire formation.

  11. Blood-clotting-inspired reversible polymer-colloid composite assembly in flow

    NASA Astrophysics Data System (ADS)

    Chen, Hsieh; Fallah, Mohammad A.; Huck, Volker; Angerer, Jennifer I.; Reininger, Armin J.; Schneider, Stefan W.; Schneider, Matthias F.; Alexander-Katz, Alfredo

    2013-01-01

    Blood clotting is a process by which a haemostatic plug is assembled at the site of injury. The formation of such a plug, which is essentially a (bio)polymer-colloid composite, is believed to be driven by shear flow in its initial phase, and contrary to our intuition, its assembly is enhanced under stronger flowing conditions. Here, inspired by blood clotting, we show that polymer-colloid composite assembly in shear flow is a universal process that can be tailored to obtain different types of aggregates including loose and dense aggregates, as well as hydrodynamically induced ‘log’-type aggregates. The process is highly controllable and reversible, depending mostly on the shear rate and the strength of the polymer-colloidbinding potential. Our results have important implications for the assembly of polymer-colloid composites, an important challenge of immense technological relevance. Furthermore, flow-driven reversible composite formation represents a new paradigm in non-equilibrium self-assembly.

  12. Temperature-induced reversible self-assembly of diphenylalanine peptide and the structural transition from organogel to crystalline nanowires.

    PubMed

    Huang, Renliang; Wang, Yuefei; Qi, Wei; Su, Rongxin; He, Zhimin

    2014-01-01

    Controlling the self-assembly of diphenylalanine peptide (FF) into various nanoarchitectures has received great amounts of attention in recent years. Here, we report the temperature-induced reversible self-assembly of diphenylalanine peptide to microtubes, nanowires, or organogel in different solvents. We also find that the organogel in isopropanol transforms into crystalline flakes or nanowires when the temperature increases. The reversible self-assembly in polar solvents may be mainly controlled by electronic and aromatic interactions between the FF molecules themselves, which is associated with the dissociation equilibrium and significantly influenced by temperature. We found that the organogel in the isopropanol solvent made a unique transition to crystalline structures, a process that is driven by temperature and may be kinetically controlled. During the heating-cooling process, FF preferentially self-assembles to metastable nanofibers and organogel. They further transform to thermodynamically stable crystal structures via molecular rearrangement after introducing an external energy, such as the increasing temperature used in this study. The strategy demonstrated in this study provides an efficient way to controllably fabricate smart, temperature-responsive peptide nanomaterials and enriches the understanding of the growth mechanism of diphenylalanine peptide nanostructures.

  13. Temperature-induced reversible self-assembly of diphenylalanine peptide and the structural transition from organogel to crystalline nanowires

    PubMed Central

    2014-01-01

    Controlling the self-assembly of diphenylalanine peptide (FF) into various nanoarchitectures has received great amounts of attention in recent years. Here, we report the temperature-induced reversible self-assembly of diphenylalanine peptide to microtubes, nanowires, or organogel in different solvents. We also find that the organogel in isopropanol transforms into crystalline flakes or nanowires when the temperature increases. The reversible self-assembly in polar solvents may be mainly controlled by electronic and aromatic interactions between the FF molecules themselves, which is associated with the dissociation equilibrium and significantly influenced by temperature. We found that the organogel in the isopropanol solvent made a unique transition to crystalline structures, a process that is driven by temperature and may be kinetically controlled. During the heating-cooling process, FF preferentially self-assembles to metastable nanofibers and organogel. They further transform to thermodynamically stable crystal structures via molecular rearrangement after introducing an external energy, such as the increasing temperature used in this study. The strategy demonstrated in this study provides an efficient way to controllably fabricate smart, temperature-responsive peptide nanomaterials and enriches the understanding of the growth mechanism of diphenylalanine peptide nanostructures. PMID:25520600

  14. Measuring photoluminescence spectra of self-assembly array nanowire of colloidal CdSe quantum dots using scanning near-field optics microscopy

    NASA Astrophysics Data System (ADS)

    Bai, Zhongchen; Hao, Licai; Zhang, Zhengping; Qin, Shuijie

    2016-05-01

    A novel periodic array CdSe nanowire is prepared on a substrate of the porous titanium dioxide by using a self-assembly method of the colloidal CdSe quantum dots (QDs). The experimental results show that the colloidal CdSe QDs have renewedly assembled on its space scale and direction in process of losing background solvent and form the periodic array nanowire. The main peak wavelength of Photoluminescence (PL) spectra, which is measured by using a 100-nm aperture laser beam spot on a scanning near-field optics microscopy, has shifted 60 nm with compared to the colloidal CdSe QDs. Furthermore, we have measured smaller ordered nanometer structure in thin QDs area as well, a 343-nm periodic nanowire in thick QDs area and the colloidal QDs in edge of well-ordered nanowire.

  15. Self-assembly of conjugated oligomers and polymers at the interface: structure and properties.

    PubMed

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-08-07

    In this review, we give a brief account on the recent scanning tunneling microscopy investigation of interfacial structures and properties of π-conjugated semiconducting oligomers and polymers, either at the solid-air (including solid-vacuum) or at the solid-liquid interface. The structural aspects of the self-assembly of both oligomers and polymers are highlighted. Conjugated oligomers can form well ordered supramolecular assemblies either at the air-solid or liquid-solid interface, thanks to the relatively high mobility and structural uniformity in comparison with polymers. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior significantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface. For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of long range ordered supramolecular assembly. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Besides the ability in studying the assembling structures at the interfaces, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by statistic of the contour length of the adsorbed polymer chains. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. These investigations open a new avenue to fine tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in the investigation of the assembling structures and properties of

  16. Surface confined assemblies and polymers for sensing and molecular logic

    NASA Astrophysics Data System (ADS)

    de Ruiter, Graham; Altman, Marc; Motiei, Leila; Lahav, Michal; van der Boom, Milko E.

    2013-05-01

    Since the development of molecule-based sensors and the introduction of molecules mimicking the behavior of the AND gate in solution by de Silva in 1993, molecular (Boolean) Logic and Computing (MBLC) has become increasingly popular. The molecular approach toward Boolean logic resulted in intriguing proofs of concepts in solution including logic gates, half-adders, multiplexers, and flip-flop logic circuits. Molecular assemblies can perform diverse logic tasks by reconfiguring their inputs. Our recent research activities focus on MBLC with electrochromic polymers and immobilized polypyridyl complexes on solid support. We have designed a series of coordination-based thin films that are formed linearly by stepwise wet-chemical deposition or by self-propagating molecular assembly. The electrochromic properties of these films can be used for (i) detecting various analytes in solution and in the air, (ii) MBLC, (iii) electron-transfer studies, and (iv) interlayers for efficient inverted bulk-heterojunction solar cells. Our concept toward MBLC with functionalized surfaces is applicable to electrochemical and chemical inputs coupled with optical readout. Using this approach, we demonstrated various logic architectures with redox-active functionalized surfaces. Electrochemically operated sequential logic systems (e.g., flip-flops), multi-valued logic, and multi-state memory have been designed, which can improve computational power without increasing spatial requirements. Applying multi-valued digits in data storage and information processing could exponentially increase memory capacity. Our approach is applicable to highly diverse electrochromic thin films that operate at practical voltages (< 1.5 V).

  17. Self-assembly of cadmium metasilicate nanowires as a broadband optical limiter

    NASA Astrophysics Data System (ADS)

    Zheng, Chan; Dai, Chongchong; Huang, Li; Li, Wei; Chen, Wenzhe

    2016-04-01

    Cadmium metasilicate nanowires (CdSiO3 NWs) have been synthesized through a facile, eco-friendly, low-cost water-ethanol mixed-solution hydrothermal route. The transmission electron microscopy measurements of as-prepared samples indicate that the CdSiO3 NWs with diameters in the range of 10-60 nm and lengths of more than 1 μm were constructed by self-assembly of 5-10-nm CdSiO3 nanoparticles with good crystallinity. The monoclinic phase formation of the sample is studied in detail by X-ray diffraction, Fourier-transform infrared spectroscopy, and thermo gravimetric analysis. The results indicate that a pure monoclinic phase of CdSiO3 can be obtained by a hydrothermal route without further calcinations and SiO4 tetrahedra were the main constituents of the CdSiO3 NWs. The nanosecond optical limiting (OL) effects were characterized by using an open-aperture (OA) Z-scan technique with 4-ns laser pulses at both 532 and 1064 nm. Theses CdSiO3 NWs displayed an excellent OL performance at 532 and 1064 nm, which was better than carbon nanotubes, a benchmark optical limiter. Input-fluence dependent scattering measurements suggested than nonlinear scattering played an important role in the observed optical limiting behavior in CdSiO3 NWs at 532 and 1064 nm. More significantly, the NLO performance in CdSiO3 NWs incorporated solid silica gel glass has been improved in comparison to those dispersed in water. The unique structure and excellent OL property render these CdSiO3 NWs competitors in the realms of optical limiting applications.

  18. Self-assembly based nanometer-scale patterning for nanowire growth

    NASA Astrophysics Data System (ADS)

    Chandramohan, Abhishek; Sibirev, Nikolai; Dubrovskii, Vladimir G.; Mendis, Budhika; Petty, Mike C.; Gallant, Andrew J.; Zeze, Dagou A.

    2015-08-01

    Periodic nanostructure arrays have been ubiquitously exploited lately due to their properties and prospective applications in production of templates for self-induced and gold (Au)-catalysed nanowires (NWs), because this approach is relatively cheap, time-efficient and do not require electron beam lithography. The technique consists creating nanoholes in SiO2 to expose the silicon Si (111) beneath where self-induced NWs can nucleate, while nanodots deposited onto the Si (111) surface serve as catalyst seeds. For Au-catalysed NWs, a monolayer of self-assembled polystyrene nanospheres (PNS 300nm) was created on a 2 inch Si wafer by spin coating and later etched for a short time before a very thin Au-catalyst layer was deposited. In turn, for self-induced, PNS monolayer was created onto a SiO2-Si substrate. A longer etch was required to reduce PNS diameter significantly to leave relatively larger spacing where chromium is blanket deposited. PNS were lifted off by sonicating the samples in toluene produce the periodic arrays of nanodots and nanoholes, respectively. The underlying SiO2 was etched further through the nanoholes to uncover the Si below. 200 nm holes and 30-70 nm dots were demonstrated through the bespoke methods. The patterned substrates served as master templates, subsequently copied using polydimethylsiloxane (PDMS) to produce a flexible stamp for nanoimprint lithography. A bilayer resist lift off process was developed to print the replicated nanodots or nanoholes on large-area substrates onto which III-V NWs can be grown.

  19. Performance improvement in flexible polymer solar cells based on modified silver nanowire electrode

    NASA Astrophysics Data System (ADS)

    Wang, Danbei; Zhou, Weixin; Liu, Huan; Ma, Yanwen; Zhang, Hongmei

    2016-08-01

    In this work, an efficient flexible polymer solar cell was achieved by controlling the UV-ozone treatment time of silver nanowires (Ag NWs) used in the electrode and combined with other modification materials. Through optimizing the time of UV-ozone treatment, it is shown that Ag NWs electrode treated by UV-ozone for 10 s improves the power conversion efficiency (PCE) of the device based on the blend of poly(3-hexylthiophene)(P3HT): [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) from 0.76% to 1.34%. After treatment by UV-ozone, Ag NWs electrodes exhibit several promising characteristics, including high optical transparency, low sheet resistance and superior surface work function. As a consequence, the performance of devices utilizing 10 s UV-ozone-treated Ag NWs with PEDOT:PSS or MoO3 as composite anode showed higher PCEs of 2.77% (2.73%) compared with that for Ag NW electrodes without UV-ozone treatment. In addition, a PCE of 5.97% in flexible polymer solar cells based on poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b0]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl](PBDTTT-EFT):[6, 6]-phenyl C71-butyric acid methyl ester (PC71BM) as a photoactive layer was obtained.

  20. Trigger sequence can influence final morphology in the self-assembly of asymmetric telechelic polymers.

    PubMed

    Kumar, Aatish; Lowe, Christopher P; Cohen Stuart, Martien A; Bolhuis, Peter G

    2016-02-21

    We report on a numerical study of polymer network formation of asymmetric biomimetic telechelic polymers with two reactive ends based on a self-assembling collagen, elastin or silk-like polypeptide sequence. The two reactive ends of the polymer can be activated independently using physicochemical triggers such as temperature and pH. We show, using a simple coarse grained model that the order in which this triggering occurs influences the final morphology. For both of collagen-silk and elastin-silk topologies we find that for relatively short connector chains the morphology of the assembly is greatly influenced by the order of the trigger, whereas for longer chains the equilibrium situation is more easily achieved. Moreover, self-assembly is greatly enhanced at moderate collagen interaction strength, due to facilitated binding and unbinding of the peptides. This finding indicates that both the trigger sequence and strength can be used to steer self-assembly in these biomimetic polymer systems.

  1. Biocompatible or biodegradable hyperbranched polymers: from self-assembly to cytomimetic applications.

    PubMed

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

    2012-09-21

    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. Nanohelices from planar polymer self-assembled in carbon nanotubes.

    PubMed

    Fu, Hongjin; Xu, Shuqiong; Li, Yunfang

    2016-07-21

    The polymer possessing with planar structure can be activated and guided to encapsulate the inner space of SWNT and form a helix through van der Waals interaction and the π-π stacking effect between the polymer and the inner surface of SWNT. The SWNT size, the nanostructure and flexibility of polymer chain are all determine the final structures. The basic interaction between the polymer and the nanotubes is investigated, and the condition and mechanism of the helix-forming are explained particularly. Hybrid polymers improve the ability of the helix formation. This study provides scientific basis for fabricating helical polymers encapsulated in SWNTs and eventually on their applications in various areas.

  3. Nanohelices from planar polymer self-assembled in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Fu, Hongjin; Xu, Shuqiong; Li, Yunfang

    2016-07-01

    The polymer possessing with planar structure can be activated and guided to encapsulate the inner space of SWNT and form a helix through van der Waals interaction and the π-π stacking effect between the polymer and the inner surface of SWNT. The SWNT size, the nanostructure and flexibility of polymer chain are all determine the final structures. The basic interaction between the polymer and the nanotubes is investigated, and the condition and mechanism of the helix-forming are explained particularly. Hybrid polymers improve the ability of the helix formation. This study provides scientific basis for fabricating helical polymers encapsulated in SWNTs and eventually on their applications in various areas.

  4. Failure criterion of silver nanowire electrodes on a polymer substrate for highly flexible devices

    PubMed Central

    Kim, Donggyun; Kim, Sung-Hoon; Kim, Jong Hak; Lee, Jae-Chul; Ahn, Jae-Pyoung; Kim, Sang Woo

    2017-01-01

    Nanomechanical characteristics of standalone silver nanowires (Ag NWs) are a key issue for providing a failure criterion of advanced flexible electrodes that are trending towards smaller radius of curvatures (ROCs). Through in-situ tensile and buckling tests of pentagonal Ag NWs, we demonstrated that the intrinsic fracture strain provides a significant criterion to predict the mechanical and electrical failure of Ag NW electrodes under various strain modes, because the decrease in fracture strain limits figure of merit of flexible devices. The Ag NW electrodes on a polymer substrate exhibited a strain-dependent electrical failure owing to the unique deformation characteristics with a size-dependent brittle-to-ductile transition of the five-fold twinned Ag NWs. All the Ag NWs greater than approximately 40 nm in diameter exhibited brittle fracture with a size-independent stress-strain response under tensile and buckling modes, which leads to the electrical failure of flexible electrodes at the almost same threshold ROC. Meanwhile, the higher ductility of Ag NWs less than 40 nm in diameter resulted in much smaller threshold ROCs of the electrodes due to the highly extended fracture strains, which can afford a high degree of freedom for highly flexible devices. PMID:28378763

  5. A Flexible and Thin Graphene/Silver Nanowires/Polymer Hybrid Transparent Electrode for Optoelectronic Devices.

    PubMed

    Dong, Hua; Wu, Zhaoxin; Jiang, Yaqiu; Liu, Weihua; Li, Xin; Jiao, Bo; Abbas, Waseem; Hou, Xun

    2016-11-16

    A typical thin and fully flexible hybrid electrode was developed by integrating the encapsulation of silver nanowires (AgNWs) network between a monolayer graphene and polymer film as a sandwich structure. Compared with the reported flexible electrodes based on PET or PEN substrate, this unique electrode exhibits the superior optoelectronic characteristics (sheet resistance of 8.06 Ω/□ at 88.3% light transmittance). Meanwhile, the specific up-to-bottom fabrication process could achieve the superflat surface (RMS = 2.58 nm), superthin thickness (∼8 μm thickness), high mechanical robustness, and lightweight. In addition, the strong corrosion resistance and stability for the hybrid electrode were proved. With these advantages, we employ this electrode to fabricate the simple flexible organic light-emitting device (OLED) and perovskite solar cell device (PSC), which exhibit the considerable performance (best PCE of OLED = 2.11 cd/A(2); best PCE of PSC = 10.419%). All the characteristics of the unique hybrid electrode demonstrate its potential as a high-performance transparent electrode candidate for flexible optoelectronics.

  6. Failure criterion of silver nanowire electrodes on a polymer substrate for highly flexible devices.

    PubMed

    Kim, Donggyun; Kim, Sung-Hoon; Kim, Jong Hak; Lee, Jae-Chul; Ahn, Jae-Pyoung; Kim, Sang Woo

    2017-04-05

    Nanomechanical characteristics of standalone silver nanowires (Ag NWs) are a key issue for providing a failure criterion of advanced flexible electrodes that are trending towards smaller radius of curvatures (ROCs). Through in-situ tensile and buckling tests of pentagonal Ag NWs, we demonstrated that the intrinsic fracture strain provides a significant criterion to predict the mechanical and electrical failure of Ag NW electrodes under various strain modes, because the decrease in fracture strain limits figure of merit of flexible devices. The Ag NW electrodes on a polymer substrate exhibited a strain-dependent electrical failure owing to the unique deformation characteristics with a size-dependent brittle-to-ductile transition of the five-fold twinned Ag NWs. All the Ag NWs greater than approximately 40 nm in diameter exhibited brittle fracture with a size-independent stress-strain response under tensile and buckling modes, which leads to the electrical failure of flexible electrodes at the almost same threshold ROC. Meanwhile, the higher ductility of Ag NWs less than 40 nm in diameter resulted in much smaller threshold ROCs of the electrodes due to the highly extended fracture strains, which can afford a high degree of freedom for highly flexible devices.

  7. Donor-acceptor alternating copolymer nanowires for highly efficient organic solar cells.

    PubMed

    Lee, Jaewon; Jo, Sae Byeok; Kim, Min; Kim, Heung Gyu; Shin, Jisoo; Kim, Haena; Cho, Kilwon

    2014-10-22

    A donor-acceptor conjugated copolymer enables the formation of nanowire systems that can be successfully introduced into bulk-heterojunction organic solar cells. A simple binary solvent mixture that makes polarity control possible allows kinetic control over the self-assembly of the crystalline polymer into a nanowire structure during the film-forming process. The enhanced photoconductivity of the nanowire-embedded photoactive layer efficiently facilitates photon harvesting in the solar cells. The resultant maximum power conversion efficiency is 8.2% in a conventional single-cell structure, revealing a 60% higher performance than in devices without nanowires.

  8. Self-assembled LiFePO4 nanowires with high rate capability for Li-ion batteries.

    PubMed

    Peng, Lele; Zhao, Yu; Ding, Yu; Yu, Guihua

    2014-08-28

    Controlling the dimensions in the nanometer scale of olivine-type LiFePO4 has been regarded as one of the most effective strategies to improve its electrochemical performance for Li-ion batteries. In this communication, we demonstrate a novel LiFePO4 nanoarchitecture, which is composed of self-assembled single-crystalline nanowires and exhibits good rate capability with a reversible capacity of ∼110 mA h g(-1) at a current rate of 30 C, and a stable capacity retention of ∼86% after 1000 cycles at a current rate of 10 C.

  9. Surface Induced nanofiber growth by self-assembly of a silk-elastin-like protein polymer.

    PubMed

    Hwang, Wonseok; Kim, Bo-Hyun; Dandu, Ramesh; Cappello, Joseph; Ghandehari, Hamidreza; Seog, Joonil

    2009-11-03

    Many synthetic and natural peptides are known to self-assemble to form various nanostructures. During the self-assembling process, environmental conditions such as salt concentration, pH, temperature, and surface characteristics play a critical role by influencing intermolecular interactions, and hence the process of self-assembly. Here we studied the self-assembly of a genetically engineered protein polymer composed of silk-like and elastin-like repeats on a mica surface. Silk-elastin-like protein polymers (SELPs) consist of tandem repeats of Gly-Ala-Gly-Ala-Gly-Ser from Bombyx mori (silkworm) and Gly-Val-Gly-Val-Pro from mammalian elastin. At a very low polymer concentration of 1 mug/mL, SELPs self-assembled into nanofibrous structures on a mica surface. Examination using atomic force microscopy (AFM) and dynamic light scattering techniques showed that SELPs self-assembled into nanofibers in the presence of the mica surface but not in the bulk state. Ionic strength had a significant influence on nanofiber growth, indicating the importance of electrostatic interactions between the polymer and the mica surface. At low ionic strength, the kinetics of nanofiber growth showed that the mica surface effectively removed a lag phase by providing nucleating sites, facilitating nanofiber self-assembly of SELPs. Furthermore, self-assembly on additional substrates such as silicon and a hydrophobic pyrolytic carbon surface revealed that the charged hydrophilic surface provides the optimal surface to facilitate self-assembly of SELPs.

  10. Hybrid solar cells with conducting polymers and vertically aligned silicon nanowire arrays: The effect of silicon conductivity

    NASA Astrophysics Data System (ADS)

    Woo, Sungho; Hoon Jeong, Jae; Kun Lyu, Hong; Jeong, Seonju; Hyoung Sim, Jun; Hyun Kim, Wook; Soo Han, Yoon; Kim, Youngkyoo

    2012-08-01

    Organic/inorganic hybrid solar cells, based on vertically aligned n-type silicon nanowires (n-Si NWs) and p-type conducting polymers (PEDOT:PSS), were investigated as a function of Si conductivity. The n-Si NWs were easily prepared from the n-Si wafer by employing a silver nanodot-mediated micro-electrochemical redox reaction. This investigation shows that the photocurrent-to-voltage characteristics of the n-Si NW/PEDOT:PSS cells clearly exhibit a stable rectifying diode behavior. The increase in current density and fill factor using high conductive silicon is attributed to an improved charge transport towards the electrodes achieved by lowering the device's series resistance. Our results also show that the surface area of the nanowire that can form heterojunction domains significantly influences the device performance.

  11. Epitaxial self-assembly of binary molecular components into branched nanowire heterostructures for photonic applications.

    PubMed

    Kong, Qinghua; Liao, Qing; Xu, Zhenzhen; Wang, Xuedong; Yao, Jiannian; Fu, Hongbing

    2014-02-12

    We report a sequential epitaxial growth to prepare organic branched nanowire heterostructures (BNwHs) consisting of a microribbon trunk of 1,4-dimethoxy-2,5-di[4'-(cyano)styryl]benzene (COPV) with multiple nanowire branches of 2,4,5-triphenylimidazole (TPI) in a one-pot solution synthesis. The synthesis involves a seeded-growth process, where COPV microribbons are grown first as a trunk followed by a seeded-growth of TPI nanowire branches at the pregrown trunk surfaces. Selected area electron diffraction characterizations reveal that multiple hydrogen-bonding interactions between TPI and COPV components play an essential role in the epitaxial growth as a result of the structural matching between COPV and TPI crystals. A multichannel optical router was successfully realized on the basis of the passive waveguides of COPV green photoluminescence (PL) along TPI nanowire branches in a single organic BNwH.

  12. Self-assembly of supramolecularly engineered polymers and their biomedical applications.

    PubMed

    Wang, Dali; Tong, Gangsheng; Dong, Ruijiao; Zhou, Yongfeng; Shen, Jian; Zhu, Xinyuan

    2014-10-18

    Noncovalent interactions provide a flexible method of engineering various chemical entities with tailored properties. Specific noncovalent interactions between functionalized small molecules, macromolecules or both of them bearing complementary binding sites can be used to engineer supramolecular complexes that display unique structure and properties of polymers, which can be defined as supramolecularly engineered polymers. Due to their dynamic tunable structures and interesting physical/chemical properties, supramolecularly engineered polymers have recently received more and more attention from both academia and industry. In this feature article, we summarize the recent progress in the self-assembly of supramolecularly engineered polymers as well as their biomedical applications. In view of different molecular building units, the supramolecularly engineered polymers can be classified into the following three major types: supramolecularly engineered polymers built by small molecules, supramolecularly engineered polymers built by small molecules and macromolecules, and supramolecularly engineered polymers built by macromolecules, which possess distinct morphologies, definite architectures and specific functions. Owing to the reversible nature of the noncovalent interactions, the supramolecularly engineered polymers have exhibited unique features or advantages in molecular self-assembly, for example, facile preparation and functionalization, controllable morphologies and structures, dynamic self-assembly processes, adjustable performance, and so on. Furthermore, the self-assembled supramolecular structures hold great potential as promising candidates in various biomedical fields, including bioimaging, drug delivery, gene transfection, protein delivery, regenerative medicine and tissue engineering. Such developments in the self-assembly of supramolecularly engineered polymers and their biomedical applications greatly promote the interdiscipline research among

  13. Layer-by-layer assembly synthesis of ZnO/SnO{sub 2} composite nanowire arrays as high-performance anode for lithium-ion batteries

    SciTech Connect

    Wang, Jiazheng; Du, Ning; Zhang, Hui; Yu, Jingxue; Yang, Deren

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer SnO{sub 2} nanoparticles was deposited on ZnO nanoarrays through layer-by-layer assembly. Black-Right-Pointing-Pointer The composite nanowire arrays show improved performance as anode for Li-ion battery. Black-Right-Pointing-Pointer Improved performance was attributed to the combining advantages of each ingredient. -- Abstract: A layer-by-layer approach has been developed to synthesize ZnO/SnO{sub 2} composite nanowire arrays on copper substrate. ZnO nanowire arrays have been first prepared on copper substrate through seed-assisted method, and then, the surface of ZnO nanowires have been modified by the polyelectrolyte. After oxidation-reduction reaction, SnO{sub 2} layer has been deposited onto the surface of ZnO nanowires. The as-synthesized ZnO/SnO{sub 2} composite nanowire arrays have been applied as anode for lithium-ion batteries, which show high reversible capacity and good cycling stability compared to pure ZnO nanowire arrays and SnO{sub 2} nanoparticles. It is believed that the improved performance may be attributed to the high capacity of SnO{sub 2} and the good cycling stability of the array structure on current collector.

  14. Engineered Polymer-Transferrin Conjugates as Self-Assembling Targeted Drug Delivery Systems.

    PubMed

    Makwana, Hiteshri; Mastrotto, Francesca; Magnusson, Johannes Pall; Sleep, Darrell; Hay, Joanna; Nicholls, Karl J; Allen, Stephanie; Alexander, Cameron

    2017-03-28

    Polymer-protein conjugates can be engineered to self-assemble into discrete and well-defined drug delivery systems which combine the advantages of receptor targeting and controlled drug release. We designed specific conjugates of the iron-binding and transport protein, transferrin (Tf), to combine the advantages of this serum-stable protein as a targeting agent for cancer cells with self-assembling polymers to act as carriers of cytotoxic drugs. Tf variants were expressed with cysteine residues at sites spanning different regions of the protein surface and the polymer conjugates grown from these variants were compared with polymer conjugates grown from non-selectively derivatised sites on native Tf. The resulting synthetic biopolymer hybrids were evaluated for self-assembly properties, size and topology, ability to carry an anti-cancer drug (paclitaxel) and cytotoxicity with and without a drug payload in a representative human colon cancer cell line. The results demonstrated that the engineered Tf variant polymer conjugates formed better-defined self-assembled nanoparticles than the non-selectively derivatised conjugates and showed greater efficacy in paclitaxel delivery. A polymer conjugate grown from a specific Tf variant, S415C was found to be taken up rapidly into cancer cells expressing the Tf-receptor, and, while tolerated well by cells in the absence of drugs, was as cytotoxic as free paclitaxel when loaded with the drug. Importantly, the S415C conjugate polymer was not the most active variant in Tf-receptor binding, suggesting that the nanoscale self-assembly of the polymer-protein hybrid is also a key factor in delivery efficacy. The data overall suggest new design rules for polymer-biopolymer hybrids and therapeutic delivery systems which include engineering specific residues for conjugation which mediate nanoscale assembly as well as control of ligand-receptor interactions to target specific cell types.

  15. Synergy of Two Assembly Languages in DNA Nanostructures: Self-Assembly of Sequence-Defined Polymers on DNA Cages.

    PubMed

    Chidchob, Pongphak; Edwardson, Thomas G W; Serpell, Christopher J; Sleiman, Hanadi F

    2016-04-06

    DNA base-pairing is the central interaction in DNA assembly. However, this simple four-letter (A-T and G-C) language makes it difficult to create complex structures without using a large number of DNA strands of different sequences. Inspired by protein folding, we introduce hydrophobic interactions to expand the assembly language of DNA nanotechnology. To achieve this, DNA cages of different geometries are combined with sequence-defined polymers containing long alkyl and oligoethylene glycol repeat units. Anisotropic decoration of hydrophobic polymers on one face of the cage leads to hydrophobically driven formation of quantized aggregates of DNA cages, where polymer length determines the cage aggregation number. Hydrophobic chains decorated on both faces of the cage can undergo an intrascaffold "handshake" to generate DNA-micelle cages, which have increased structural stability and assembly cooperativity, and can encapsulate small molecules. The polymer sequence order can control the interaction between hydrophobic blocks, leading to unprecedented "doughnut-shaped" DNA cage-ring structures. We thus demonstrate that new structural and functional modes in DNA nanostructures can emerge from the synergy of two interactions, providing an attractive approach to develop protein-inspired assembly modules in DNA nanotechnology.

  16. Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

    PubMed Central

    Wang, Jie; Qiu, Zhiqiang; Wang, Yiming; Li, Li; Pham, Duc-Truc; Prud’homme, Robert K

    2016-01-01

    Summary The employment of cyclodextrin host–guest complexation to construct supramolecular assemblies with an emphasis on polymer networks is reviewed. The main driving force for this supramolecular assembly is host–guest complexation between cyclodextrin hosts and guest groups either of which may be discrete molecular species or substituents on a polymer backbone. The effects of such complexation on properties at the molecular and macroscopic levels are discussed. It is shown that cyclodextrin complexation may be used to design functional polymer materials with tailorable properties, especially for photo-, pH-, thermo- and redox-responsiveness and self-healing. PMID:26877808

  17. Organic-Inorganic Shish-Kebabs: Nanocrystal Kebabs Periodically Assembled on Stretched Flexible Polymer Shish

    NASA Astrophysics Data System (ADS)

    Lin, Zhiqun; Xu, Hui; Xu, Yuci; Pang, Xinchang; He, Yanjie; Jung, Jaehan; Xia, Haiping

    2015-03-01

    We report an unconventional yet general strategy to craft an exciting variety of 1D necklace-like nanostructures comprising uniform functional nanodisks periodically assembled along a stretched flexible polymer chain by capitalizing on judiciously designed amphiphilic worm-like diblock copolymer as nanoreactors. These nanostructures can be regarded as organic-inorganic shish-kebabs, in which nanodisk kebabs periodically situated on a stretched polymer shish. Simulations based on self-consistent field theory reveal that the formation of organic-inorganic shish-kebabs is guided by the self-assembled elongated star-like diblock copolymer constituents constrained on the highly stretched polymer chain.

  18. Fe-nitrilotriacetic acid coordination polymer nanowires: an effective sensing platform for fluorescence-enhanced nucleic acid detection

    NASA Astrophysics Data System (ADS)

    Zhou, Yunchun; Liu, Qian; Sun, Xuping; Kong, Rongmei

    2017-02-01

    The determination of specific nucleic acid sequences is key in identifying disease-causing pathogens and genetic diseases. In this paper we report the utilization of Fe-nitrilotriacetic acid coordination polymer nanowires as an effective nanoquencher for fluorescence-enhanced nucleic acid detection. The detection is fast and the whole process can be completed within 15 min. This nanosensor shows a low detection limit of 0.2 nM with selectivity down to single-base mismatch. This work provides us with an attractive sensing platform for applications.

  19. Nanohelices from planar polymer self-assembled in carbon nanotubes

    PubMed Central

    Fu, Hongjin; Xu, Shuqiong; Li, Yunfang

    2016-01-01

    The polymer possessing with planar structure can be activated and guided to encapsulate the inner space of SWNT and form a helix through van der Waals interaction and the π-π stacking effect between the polymer and the inner surface of SWNT. The SWNT size, the nanostructure and flexibility of polymer chain are all determine the final structures. The basic interaction between the polymer and the nanotubes is investigated, and the condition and mechanism of the helix-forming are explained particularly. Hybrid polymers improve the ability of the helix formation. This study provides scientific basis for fabricating helical polymers encapsulated in SWNTs and eventually on their applications in various areas. PMID:27440493

  20. Hybridization of inorganic nanoparticles and polymers to create regular and reversible self-assembly architectures.

    PubMed

    Zhang, Hao; Liu, Yi; Yao, Dong; Yang, Bai

    2012-09-21

    Inorganic nanoparticles (NPs) with diversified functionalities are promising candidates in future optoelectronic and biomedical applications, which greatly depend on the capability to arrange NPs into higher-order architectures in a controllable way. This issue is considered to be solved by means of self-assembly. NPs can participate in self-assembly in different manners, such as smart self-organization with blended molecules, as the carriers of host molecules for assembly and disassembly with guest molecules, as netpoints to endow the architectures specific functionalities, and so forth. To enhance the structural stability of the as-prepared assembly architectures, polymers have been utilized to create NP-polymer composites. Meanwhile, such a strategy also demonstrates the possibility of integrating the functionalities of NPs and/or polymers by forming regular architectures. The emerging interest in the current optoelectronic and biological areas strongly demands intelligent nanocomposites, which are produced by combination of the excellent functionalities of NPs and the responsiveness of polymers. On the basis of the recent progress in fabricating NP-polymer composites, this critical review summarizes the development of new methods for fabricating regular self-assembly architectures, highlights the reversible assembly and disassembly behavior, and indicates the potential applications.

  1. Hyperbranched polymer vesicles: from self-assembly, characterization, mechanisms, and properties to applications.

    PubMed

    Jiang, Wenfeng; Zhou, Yongfeng; Yan, Deyue

    2015-06-21

    Vesicles, including lipid vesicles, surfactant vesicles, as well as polymer vesicles, have been extensively investigated over the past fifty years. Among them, polymer vesicles have attracted more and more attention because of their low permeability, superior stability and toughness, in addition to the numerous possibilities for tailoring physical, chemical and biological properties. Polymer vesicles are generally fabricated through the self-assembly of amphiphilic polymers with a linear architecture. Recently, as representative polymers with a highly branched three-dimensional architecture, hyperbranched polymers have also exhibited great potential for preparing vesicles. The resultant hyperbranched polymer vesicles, defined as branched-polymersomes (BPs), have shown unique properties, such as giant and easily tuned vesicle sizes, facile functionalization, a special formation mechanism, and appealing solution behaviours. In this tutorial review, ten years of advances in BPs have been summarized since their first discovery in the year 2004, including the syntheses of vesicle-forming hyperbranched polymers, self-assembly methods, self-assembly mechanisms, as well as the special properties. In addition, the cytomimetic, biomedical and other initiatory applications of BPs are also included.

  2. Host-Guest Binding-Site-Tunable Self-Assembly of Stimuli-Responsive Supramolecular Polymers.

    PubMed

    Yao, Hao; Qi, Miao; Liu, Yuyang; Tian, Wei

    2016-06-13

    Despite the remarkable progress made in controllable self-assembly of stimuli-responsive supramolecular polymers (SSPs), a basic issue that has not been consideration to date is the essential binding site. The noncovalent binding sites, which connect the building blocks and endow supramolecular polymers with their ability to respond to stimuli, are expected to strongly affect the self-assembly of SSPs. Herein, the design and synthesis of a dual-stimuli thermo- and photoresponsive Y-shaped supramolecular polymer (SSP2) with two adjacent β-cyclodextrin/azobenzene (β-CD/Azo) binding sites, and another SSP (SSP1) with similar building blocks, but only one β-CD/Azo binding site as a control, are described. Upon gradually increasing the polymer solution temperature or irradiating with UV light, SSP2 self-assemblies with a higher binding-site distribution density; exhibits a flower-like morphology, smaller size, and more stable dynamic aggregation process; and greater controllability for drug-release behavior than those observed with SSP1 self-assemblies. The host-guest binding-site-tunable self-assembly was attributed to the positive cooperativity generated among adjacent binding sites on the surfaces of SSP2 self-assemblies. This work is beneficial for precisely controlling the structural parameters and controlled release function of SSP self-assemblies.

  3. Self-assembled ZnS nanowire arrays: synthesis, in situ Cu doping and field emission

    NASA Astrophysics Data System (ADS)

    Liu, Baodan; Bando, Yoshio; Jiang, Xin; Li, Chun; Fang, Xiaosheng; Zeng, Haibo; Terao, Takeshi; Tang, Chengchun; Mitome, Masanori; Golberg, Dmitri

    2010-09-01

    Well-aligned single-crystalline ZnS nanowire arrays have been grown on highly conductive Cu substrates through controlling the morphology evolution of self-patterned ZnS nanoparticles. The ZnS nanowires have sharp tips with an average size of ~ 30 nm and a length of ~ 3 µm. Field emission measurements demonstrated that the aligned ZnS nanowires grown on Cu substrates are excellent field emitters having a turn-on field as low as 2.92 V µm - 1 and a field-enhancement factor as high as 3400. The use of highly conductive metal substrate may promote the commercial applications of ZnS-based emitters in flat panel displays and other optoelectronic devices.

  4. Surface-confined assemblies and polymers for molecular logic.

    PubMed

    de Ruiter, Graham; van der Boom, Milko E

    2011-08-16

    Stimuli responsive materials are capable of mimicking the operation characteristics of logic gates such as AND, OR, NOR, and even flip-flops. Since the development of molecular sensors and the introduction of the first AND gate in solution by de Silva in 1993, Molecular (Boolean) Logic and Computing (MBLC) has become increasingly popular. In this Account, we present recent research activities that focus on MBLC with electrochromic polymers and metal polypyridyl complexes on a solid support. Metal polypyridyl complexes act as useful sensors to a variety of analytes in solution (i.e., H(2)O, Fe(2+/3+), Cr(6+), NO(+)) and in the gas phase (NO(x) in air). This information transfer, whether the analyte is present, is based on the reversible redox chemistry of the metal complexes, which are stable up to 200 °C in air. The concurrent changes in the optical properties are nondestructive and fast. In such a setup, the input is directly related to the output and, therefore, can be represented by one-input logic gates. These input-output relationships are extendable for mimicking the diverse functions of essential molecular logic gates and circuits within a set of Boolean algebraic operations. Such a molecular approach towards Boolean logic has yielded a series of proof-of-concept devices: logic gates, multiplexers, half-adders, and flip-flop logic circuits. MBLC is a versatile and, potentially, a parallel approach to silicon circuits: assemblies of these molecular gates can perform a wide variety of logic tasks through reconfiguration of their inputs. Although these developments do not require a semiconductor blueprint, similar guidelines such as signal propagation, gate-to-gate communication, propagation delay, and combinatorial and sequential logic will play a critical role in allowing this field to mature. For instance, gate-to-gate communication by chemical wiring of the gates with metal ions as electron carriers results in the integration of stand-alone systems: the

  5. Formation and properties of surface-anchored polymer assemblies with tunable physico-chemical characteristics

    NASA Astrophysics Data System (ADS)

    Wu, Tao

    We describe two new methodologies leading to the formation of novel surface-anchored polymer assemblies on solid substrates. While the main goal is to understand the fundamentals pertaining to the preparation and properties of the surface-bound polymer assemblies (including neutral and chargeable polymers), several examples also are mentioned throughout the Thesis that point out to practical applications of such structures. The first method is based on generating assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates. These structures are prepared by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from these substrate-bound initiator centers ("grafting from"). We apply this technique to prepare grafting density gradients of poly(acryl amide) (PAAm) and poly(acrylic acid) (PAA) on silica-covered substrates. We show that using the grafting density gradient geometry, the characteristics of surface-anchored polymers in both the low grafting density ("mushroom") regime as well as the high grafting density ("brush") regime can be accessed conveniently on a single sample. We use a battery of experimental methods, including Fourier transform infrared spectroscopy (FTIR), Near-edge absorption fine structure spectroscopy (NEXAFS), contact angle, ellipsometry, to study the characteristics of the surface-bound polymer layers. We also probe the scaling laws of neutral polymer as a function of grafting density, and for weak polyelectrolyte, in addition to the grafting density, we study the affect of solution ionic strength and pH values. In the second novel method, which we coined as "mechanically assisted polymer assembly" (MAPA), we form surface anchored polymers by "grafting from" polymerization initiators deposited on elastic surfaces that have been previously extended uniaxially by a certain length increment, Deltax. Upon releasing the strain in the

  6. Solution-state polymer assemblies influence BCS class II drug dissolution and supersaturation maintenance.

    PubMed

    Dalsin, Molly C; Tale, Swapnil; Reineke, Theresa M

    2014-02-10

    Spray dried dispersions (SDDs), solid dispersions of polymer excipients and active pharmaceuticals, are important to the field of oral drug delivery for improving active stability, bioavailability, and efficacy. Herein, we examine the influence of solution-state polymer assemblies on amorphous spray-dried dispersion (SDD) performance with two BCS II model drugs, phenytoin and probucol. These drugs were spray dried with 4 model polymer excipients consisting of poly(ethylene-alt-propylene) (PEP), N,N,-dimethylacrylamide (DMA), or 2-methacrylamido glucopyranose (MAG): amphiphilic diblock ter- and copolymers, PEP-P(DMA-grad-MAG) and PEP-PDMA, and their respective hydrophilic analogues, P(DMA-grad-MAG) and PDMA. Selective and nonselective solvents for the hydrophilic block of the diblock ter- and copolymers were used to induce or repress solution-state assemblies prior to spray drying. Prespray dried solution-state assemblies of these four polymers were probed with dynamic light scattering (DLS) and showed differences in solution assembly size and structure (free polymer versus aggregates versus micelles). Solid-state structures of spray dried dispersions (SDDs) showed a single glass transition event implying a homogeneous mixture of drug/polymer. Crystallization temperatures and enthalpies indicated that the drugs interact mostly with the DMA-containing portions of the polymers. Scanning electron microscopy was used to determine SDD particle size and morphology for the various polymer-drug pairings. In vitro dissolution tests showed excellent performance for one system, spray-dried PEP-PDMA micelles with probucol. Dissolution structures were investigated through DLS to determine drug-polymer aggregates that lead to enhanced SDD performance. Forced aggregation of the polymer into regular micelle structures was found to be a critical factor to increase the dissolution rate and supersaturation maintenance of SDDs, and may be an attractive platform to exploit in excipient

  7. Water-repellent ZnO nanowires films obtained by octadecylsilane self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Badre, C.; Pauporté, T.; Turmine, M.; Dubot, P.; Lincot, D.

    2008-05-01

    Zinc oxide (ZnO) films with well-controlled morphologies have been prepared by electrochemical deposition. A seed layer of nanocrystallites of ZnO was prepared from which ZnO nanowires were grown from a low concentration of ZnCl 2. The nanowires are rough and dense and their superhydrophilicity is enhanced. A treatment with an alkylsilane (octadecylsilane) yields superhydrophobic surfaces with very high advancing and receding contact angles 173°/172° and a very low roll-off angle. Our superhydrophobic films are stable for more than 6 months.

  8. Self-assembled ZnO agave-like nanowires and anomalous superhydrophobicity

    NASA Astrophysics Data System (ADS)

    Yang, Y. H.; Li, Z. Y.; Wang, B.; Wang, C. X.; Chen, D. H.; Yang, G. W.

    2005-09-01

    Thin films of ZnO agave-like nanowires were prepared on amorphous carbon thin layers on silicon substrates using thermal chemical vapour transport and condensation without any metal catalysts. The unusual superhydrophobicity of the fabricated surface was measured; the water contact angle reaches 151.1°. On the basis of experimental and theoretical analyses, it appears likely that the biomimetic microcomposite and nanocomposite surfaces of the prepared thin films of ZnO agave-like nanowires are responsible for the excellent superhydrophobicity.

  9. Microwave-Assisted Rapid Synthesis of Self-Assembled T-Nb2 O5 Nanowires for High-Energy Hybrid Supercapacitors.

    PubMed

    Yang, Huiling; Xu, Henghui; Wang, Libin; Zhang, Lei; Huang, Yunhui; Hu, Xianluo

    2017-03-23

    Recently ion-intercalation hybrid supercapacitors, with high energy density at high power density, have been widely investigated to meet ever-increasing practical demands. Here, a unique hybrid supercapacitor has been designed and fabricated using self-assembled orthorhombic-phase niobium oxide@carbon (T-Nb2 O5 @C) nanowires as an anode and commercially available activated carbon as a cathode. The 3D-interconnected T-Nb2 O5 @C nanowires have been synthesized through a highly efficient microwave-solvothermal method, combined with subsequent thermal treatment. The experimental parameters (e.g., time and temperature) can be easily programmed, and the synthesis time can be significantly shortened, thus enabling the buildup of abundant recipes for the engineering of scaled-up production. The Li-ion intercalation pseudocapacitance electrode, made from the as-formed self-assembled T-Nb2 O5 @C nanowires, shows excellent charge storage and transfer capability. When assembled into a hybrid supercapacitor with a cathode of activated carbon, a high energy density of 60.6 Wh kg(-1) and a high power density of 8.5 kW kg(-1) with outstanding stability are achieved. In virtue of easy optimization and programmability of the synthetic strategy, and the remarkable electrochemical performance, the self-assembled T-Nb2 O5 @C nanowires offer a promising anode for asymmetric hybrid supercapacitors.

  10. Cycling performance and thermal stability of lithium polymer cells assembled with ionic liquid-containing gel polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Yun, Ye Sun; Kim, Jin Hee; Lee, Sang-Young; Shim, Eun-Gi; Kim, Dong-Won

    Gel polymer electrolytes containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and a small amount of additive (vinylene carbonate, fluoroethylene carbonate, and ethylene carbonate) are prepared, and their electrochemical properties are investigated. The cathodic limit of the gel polymer electrolytes can be extended to 0 V vs. Li by the formation of a protective solid electrolyte interphase on the electrode surface. Using these gel polymer electrolytes, lithium metal polymer cells composed of a lithium anode and a LiNi 1/3Co 1/3Mn 1/3O 2 cathode are assembled, and their cycling performances are evaluated at room temperature. The cells show good cycling performance, comparable to that of a cell assembled with gel polymer electrolyte containing standard liquid electrolyte (1.0 M LiPF 6 in ethylene carbonate/diethylene carbonate). Flammability tests and differential scanning calorimetry studies show that the presence of the ionic liquid in the gel polymer electrolyte considerably improves the safety and thermal stability of the cells.

  11. Towards controlled polymer brushes via a self-assembly-assisted-grafting-to approach

    PubMed Central

    Zhou, Tian; Qi, Hao; Han, Lin; Barbash, Dmitri; Li, Christopher Y.

    2016-01-01

    Precise synthesis of polymer brushes to modify the surface of nanoparticles and nanodevices for targeted applications has been one of the major focuses in the community for decades. Here we report a self-assembly-assisted-grafting-to approach to synthesize polymer brushes on flat substrates. In this method, polymers are pre-assembled into two-dimensional polymer single crystals (PSCs) with functional groups on the surface. Chemically coupling the PSCs onto solid substrates leads to the formation of polymer brushes. Exquisite control of the chain folding in PSCs allows us to obtain polymer brushes with well-defined grafting density, tethering points and brush conformation. Extremely high grafting density (2.12 chains per nm2) has been achieved in the synthesized single-tethered polymer brushes. Moreover, polymer loop brushes have been successfully obtained using oddly folded PSCs from telechelic chains. Our approach combines some of the important advantages of conventional ‘grafting-to' and ‘grafting-from' methods, and is promising for tailored synthesis of polymer brushes. PMID:27009369

  12. Silver Nanowire/MnO2 Nanowire Hybrid Polymer Nanocomposites: Materials with High Dielectric Permittivity and Low Dielectric Loss.

    PubMed

    Zeraati, Ali Shayesteh; Arjmand, Mohammad; Sundararaj, Uttandaraman

    2017-04-13

    This study reports the fabrication of hybrid nanocomposites based on silver nanowire/manganese dioxide nanowire/poly(methyl methacrylate) (AgNW/MnO2NW/PMMA), using a solution casting technique, with outstanding dielectric permittivity and low dielectric loss. AgNW was synthesized using the hard-template technique, and MnO2NW was synthesized employing a hydrothermal method. The prepared AgNW:MnO2NW (2.0:1.0 vol %) hybrid nanocomposite showed a high dielectric permittivity (64 at 8.2 GHz) and low dielectric loss (0.31 at 8.2 GHz), which are among the best reported values in the literature in the X-band frequency range (8.2-12.4 GHz). The superior dielectric properties of the hybrid nanocomposites were attributed to (i) dimensionality match between the nanofillers, which increased their synergy, (ii) better dispersion state of AgNW in the presence of MnO2NW, (iii) positioning of ferroelectric MnO2NW in between AgNWs, which increased the dielectric permittivity of nanodielectrics, thereby increasing dielectric permittivity of the hybrid nanocomposites, (iv) barrier role of MnO2NW, i.e., cutting off the contact spots of AgNWs and leading to lower dielectric loss, and (v) AgNW aligned structure, which increased the effective surface area of AgNWs, as nanoelectrodes. Comparison of the dielectric properties of the developed hybrid nanocomposites with the literature highlights their great potential for flexible capacitors.

  13. Meso-scale Modeling of Self-assembly of Polymer-Grafted Nanoparticles

    NASA Astrophysics Data System (ADS)

    Mancini, Derrick; Deshmukh, Sanket; Sankaranarayanan, Subramanian

    2015-03-01

    We develop meso-scale models to explore the self-assembly behavior of polymer-grafted nanoparticles. Specifically, we study nanoparticles with grafts of the thermo-sensitive polymer poly(N-isopropylacrylamide) (PNIPAM), which undergoes a coil-to-globule transition across the LCST at around 305 K. The atomic-scale mechanism of the coil-to-globule transition of polymers grafted nanoparticles and their interactions (agglomeration, assembly behavior) with other particles that are in its vicinity is poorly understood, yet knowledge about these interactions would enable designing novel self-assembled materials with well-defined structural and dynamical properties. Additionally, the effects of chemical nature, geometry, and morphology of the nanoparticle surface on the conformational transition of thermo-sensitive polymers is also unknown. We report on 1) development of all-atom models of polymer-grafted nanoparticles to conduct MD simulations at atomic-levels and 2) perform mesoscopic scaling of the conformational dynamics resulting from the atomistic simulations with the aid of coarse-grained or meso-scale models of PNIPAM and its composites. Coarse-grained simulations allow modeling of larger assemblies of polymer-grafted nanoparticles over longer time scales. This research used resources of the Center for Nanoscale Materials and the Argonne Leadership Computing Facility at Argonne National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC02-06CH11357.

  14. Understanding Molecular Interactions within Chemically Selective Layered Polymer Assemblies

    SciTech Connect

    Gary J. Blanchard

    2009-06-30

    This work focuses on two broad issues. These are (1) the molecular origin of the chemical selectivity achieved with ultrathin polymer multilayers, and (2) how the viscoelastic properties of the polymer layers are affected by exposure to solvent and analytes. These issues are inter-related, and to understand them we need to design experiments that probe both the energetic and kinetic aspects of interfacial adsorption processes. This project focuses on controling the chemical structure, thickness, morphology and sequential ordering of polymer layers bound to interfaces using maleimide-vinyl ether and closely related alternating copolymerization chemistry and efficient covalent cross-linking reactions that allow for layer-by-layer polymer deposition. This chemistry has been developed during the funding cycle of this Grant. We have measure the equilibrium constants for interactions between specific layers within the polymer interfaces and size-controlled, surface-functionalized gold nanoparticles. The ability to control both size and functionality of gold nanoparticle model analytes allows us to evaluate the average “pore size” that characterizes our polymer films. We have measured the “bulk” viscosity and shear modulus of the ultrathin polymer films as a function of solvent overlayer identity using quartz crystal microbalance complex impedance measurements. We have measured microscopic viscosity at specific locations within the layered polymer interfaces with time-resolved fluorescence lifetime and depolarization techniques. We combine polymer, cross-linking and nanoparticle synthetic expertise with a host of characterization techniques, including QCM gravimetry and complex impedance analysis, steady state and time-resolved spectroscopies.

  15. Thermally Induced Charge Reversal of Layer-by-Layer Assembled Single-Component Polymer Films.

    PubMed

    Richardson, Joseph J; Tardy, Blaise L; Ejima, Hirotaka; Guo, Junling; Cui, Jiwei; Liang, Kang; Choi, Gwan H; Yoo, Pil J; De Geest, Bruno G; Caruso, Frank

    2016-03-23

    Temperature can be harnessed to engineer unique properties for materials useful in various contexts and has been shown to affect the layer-by-layer (LbL) assembly of polymer thin films and cause physical changes in preassembled polymer thin films. Herein we demonstrate that exposure to relatively low temperatures (≤ 100 °C) can induce physicochemical changes in cationic polymer thin films. The surface charge of polymer films containing primary and secondary amines reverses after heating (from positive to negative), and different characterization techniques are used to show that the change in surface charge is related to oxidation of the polymer that specifically occurs in the thin film state. This charge reversal allows for single-polymer LbL assembly to be performed with poly(allylamine) hydrochloride (PAH) through alternating heat/deposition steps. Furthermore, the negative charge induced by heating reduces the fouling and cell-association of PAH-coated planar and particulate substrates, respectively. This study highlights a unique property of thin films which is relevant to LbL assembly and biofouling and is of interest for the future development of thin polymer films for biomedical systems.

  16. A strategy for tuning achiral main-chain polymers into helical assemblies and chiral memory systems.

    PubMed

    Yang, Dong; Zhao, Yin; Lv, Kai; Wang, Xiufeng; Zhang, Wei; Zhang, Li; Liu, Minghua

    2016-01-28

    A general strategy to tune the achiral main chain polymers into helical nanoassemblies was proposed based on the co-gelation approach. As an example, two achiral main chain polymers, PCz8 and PSi8, were selected, and their co-assembly with an amphiphilic l- or d-glutamide gelator was investigated. Although the polymers could not form gels individually, they could form co-gels with the gelator and the resultant gels exhibited macroscopic supramolecular chirality, which could be confirmed by CD spectra and SEM observations. Moreover, the supramolecular chirality can be memorized even after the gelator molecules were removed. Remarkably, either the gelator-containing or gelator-free chiral polymer assemblies showed circularly polarized luminescence (CPL), which is usually inherent to intrinsic chiral polymers. It was suggested that during the co-gelation, the chirality of the gelator was transferred to and memorized by the achiral polymers. The approach seems to be general and we provided the first example to tune the achiral polymers into helical assemblies through the co-gelation.

  17. Patterned polymer nanowire arrays as an effective protein immobilizer for biosensing and HIV detection

    NASA Astrophysics Data System (ADS)

    Shen, Yue; Liu, Yingyi; Zhu, Guang; Fang, Hao; Huang, Yunhui; Jiang, Xingyu; Wang, Zhong L.

    2012-12-01

    We report an array of polymeric nanowires for effectively immobilizing biomolecules on biochips owing to the large surface area. The nanowires were fabricated in predesigned patterns using an inductively coupled plasma (ICP) etching process. Microfluidic biochips integrated using the substrates with arrays of nanowires and polydimethylsiloxane channels have been demonstrated to be effective for detecting antigens, and a detection limit of antigens at 0.2 μg mL-1 has been achieved, which is improved by a factor of 50 compared to that based on flat substrates without the nanowires. In addition, the high sensitivity for clinical detection of human immunodeficiency virus (HIV) antibody has also been demonstrated, showing a 20 times enhancement in fluorescent signal intensity between the samples with positive and negative HIV.

  18. Performance of polymer nano composite membrane electrode assembly using Alginate as a dopant in polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Mulijani, S.

    2016-11-01

    Polymer membrane and composite polymer for membrane electrode assembly (MEAs) are synthesized and studied for usage in direct methanol fuel cell (DMFC). In this study, we prepared 3 type of MEAs, polystyrene (PS), sulfonated polystyrene (SPS) and composite polymer SPS-alginat membrane via catalyst hot pressed method. The performance and properties of prepared MEAs were evaluated and analyzed by impedance spectrometry and scanning electron microscopy (SEM). The result showed that, water up take of MEA composite polymer SPS-alginate was obtained higher than that in SPS and PS. The proton conductivity of MEA-SPS-alginate was also higher than that PS and PSS. SEM characterization revealed that the intimate contact between the carbon catalyst layers (CL) and the membranes, and the uniformly porous structure correlate positively with the MEAs prepared by hot pressed method, exhibiting high performances for DMFC.

  19. Performance of polymer nano composite membrane electrode assembly using Alginate as a dopant in polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Mulijani, S.

    2017-01-01

    Polymer membrane and composite polymer for membrane electrode assembly (MEAs) are synthesized and studied for usage in direct methanol fuel cell (DMFC). In this study, we prepared 3 type of MEAs, polystyrene (PS), sulfonated polystyrene (SPS) and composite polymer SPS-alginat membrane via catalyst hot pressed method. The performance and properties of prepared MEAs were evaluated and analyzed by impedance spectrometry and scanning electron microscopy (SEM). The result showed that, water up take of MEA composite polymer SPS-alginate was obtained higher than that in SPS and PS. The proton conductivity of MEA-SPS-alginate was also higher than that PS and PSS. SEM characterization revealed that the intimate contact between the carbon catalyst layers (CL) and the membranes, and the uniformly porous structure correlate positively with the MEAs prepared by hot pressed method, exhibiting high performances for DMFC.

  20. Double-sided brush-shaped TiO2 nanostructure assemblies with highly ordered nanowires for dye-sensitized solar cells.

    PubMed

    Zha, Chenyang; Shen, Liming; Zhang, Xiaoyan; Wang, Yifeng; Korgel, Brian A; Gupta, Arunava; Bao, Ningzhong

    2014-01-08

    We describe a seeded hydrothermal process for the growth of unique double-sided brush-shaped (DSBS) TiO2 nanostructure assemblies consisting of highly ordered rutile nanowires vertically aligned around an annealed TiO2 nanoparticle layer. The annealed TiO2 nanoparticle layer seeds the nanowire growth and also supports the DSBS structure. The morphology of the DSBS TiO2 nanostructure depends on the hydrothermal reaction time. The diameter of the nanowires is about 6.6 nm, and with increasing reaction time from 1 to 8 h the nanowire length increases from 0.6 to 6.2 μm, whereas the thickness of the nanoparticle layer decreases from 4.3 to 2.8 μm. These free-standing nanowire arrays provide large internal surface area, which is essential for minimizing carrier recombination in high performance photovoltaic devices. Furthermore, the nanowire architecture can help increase the rate of charge transport as compared to particulate films because of lower concentration of grain boundaries. The power conversion efficiency of backside (DSBS TiO2/FTO photoanode) illuminated dye-sensitized solar cells fabricated using the DSBS TiO2 nanostructure assembly is found to be depended on the nanowire length. A cell fabricated using 15.2 μm thick nanostructures sensitized by N719 has a short-circuit current density of 12.18 mA cm(-2), 0.78 V open circuit potential, and a 0.59 filling factor, yielding a maximum power conversion efficiency of 5.61% under AM 1.5 illumination.

  1. Self-assembled organic nanowires for high power density lithium ion batteries.

    PubMed

    Luo, Chao; Huang, Ruiming; Kevorkyants, Ruslan; Pavanello, Michele; He, Huixin; Wang, Chunsheng

    2014-03-12

    The electroactive organic materials are promising alternatives to inorganic electrode materials for the new generation of green Li-ion batteries due to their sustainability, environmental benignity, and low cost. Croconic acid disodium salt (CADS) was used as Li-ion battery electrode, and CADS organic wires with different diameters were fabricated through a facile synthetic route using antisolvent crystallization method to overcome the challenges of low electronic conductivity of CADS and lithiation induced strain. The CADS nanowire exhibits much better electrochemical performance than its crystal bulk material and microwire counterpart. CADS nanowire with a diameter of 150 nm delivers a reversible capability of 177 mAh g(-1) at a current density of 0.2 C and retains capacity of 170 mAh g(-1) after 110 charge/discharge cycles. The nanowire structure also remarkably enhances the kinetics of croconic acid disodium salt. The CADS nanowire retains 50% of the 0.1 C capacity even when the current density increases to 6 C. In contrast, the crystal bulk and microwire material completely lose their capacities when the current density merely increases to 2 C. Such a high rate performance of CADS nanowire is attributed to its short ion diffusion pathway and large surface area, which enable fast ion and electron transport in the electrode. The theoretical calculation suggests that lithiation of CADS experiences an ion exchange process. The sodium ions in CADS will be gradually replaced by lithium ions during the lithiation and delithiation of CADS electrode, which is confirmed by inductively coupled plasma test.

  2. Monitoring Protein Capsid Assembly with a Conjugated Polymer Strain Sensor.

    PubMed

    Cingil, Hande E; Storm, Ingeborg M; Yorulmaz, Yelda; te Brake, Diane W; de Vries, Renko; Cohen Stuart, Martien A; Sprakel, Joris

    2015-08-12

    Semiconducting polymers owe their optoelectronic properties to the delocalized electronic structure along their conjugated backbone. Their spectral features are therefore uniquely sensitive to the conformation of the polymer, where mechanical stretching of the chain leads to distinct vibronic shifts. Here we demonstrate how the optomechanical response of conjugated polyelectrolytes can be used to detect their encapsulation in a protein capsid. Coating of the sensor polymers by recombinant coat proteins induces their stretching due to steric hindrance between the proteins. The resulting mechanical planarizations lead to pronounced shifts in the vibronic spectra, from which the process of capsid formation can be directly quantified. These results show how the coupling between vibronic states and mechanical stresses inherent to conjugated polymers can be used to noninvasively measure strains at the nanoscale.

  3. Stabilization of 2D assemblies of silver nanoparticles by spin-coating polymers

    NASA Astrophysics Data System (ADS)

    Hu, Longyu; Pfirman, Aubrie; Chumanov, George

    2015-12-01

    Silver nanoparticles self-assembled on poly(4-vinylpyridine) modified surfaces were spin-coated with poly(methyl methacrylate), poly(butyl methacrylate) and polystyrene from anisole and toluene solutions. The polymers filled the space between the particles thereby providing stabilization of the assemblies against particle aggregation when dried or chemically modified. The polymers did not coat the top surface of the nanoparticles offering the chemical accessibility to the metal surface. This was confirmed by converting the stabilized nanoparticles into silver sulfide and gold clusters. Etching the nanoparticles resulted in crater-like polymeric structures with the cavities extending down to the underlying substrate. Electrochemical reduction of silver inside the craters was performed. The approach can be extended to other nanoparticle assemblies and polymers.

  4. Cooperative self-assembly of porphyrins with polymers possessing bioactive functions.

    PubMed

    Zhao, Lizhi; Qu, Rui; Li, Ang; Ma, Rujiang; Shi, Linqi

    2016-11-15

    Natural porphyrin derivatives possess many interesting functions in biological systems. They are integrated into proteins that are essential for biological activities. Many efforts have been dedicated to mimic the microenvironment and augment the function of porphyrin/protein scaffolds. To achieve such goals, self-assembly has become one of the popular methods to construct porphyrin/protein-mimicking materials owing to its various choices of building blocks and a simple preparation process over chemical modification. Desirable characteristics of building blocks for protein mimicking include high molecular weight, predictable conformations in solution, and appropriate functional residuals. With these aims in mind, polymers are ideal candidates due to their multiple-level hierarchies derived from their chemical and spatial structures. In this review, design strategies for the cooperative self-assembly of porphyrins with polymers and the main efforts towards the implementation of porphyrin/polymer assembly for biomimetic composites with bioactive functions will be addressed.

  5. Bioreducible nanocapsules prepared from the self-assembly of branched polymer in nanodroplet.

    PubMed

    Wang, Long-Hai; Ding, Sheng-Gang; Yan, Jun-Jie; You, Ye-Zi

    2014-02-01

    Though great attention has been paid in constructing well-defined nano-structures via the self-assembly of amphiphilic macromolecules, the self-assembly of non-amphiphilic macromolecules in nanodroplet has drawn less attention up to now. Recently, we prepared a temperature-responsive PEG-based branched polymer with disulfide bonds in its backbone via reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-(2-methoxyethoxy) ethyl methacrylate, oligo(ethylene glycol) methacrylate, and N,N'-cystamine bisacrylamide. Subsequently, we loaded the branched polymer into nanodroplets, and have found that the self-assembly behaviors of this branched poly-mer in the nanodroplet are different from those in common solution. Bioreducible nanocapsules with tunable size can easily formed in nanodroplet even at high concentration.

  6. Study of (Cyclic Peptide)-Polymer Conjugate Assemblies by Small-Angle Neutron Scattering.

    PubMed

    Koh, Ming Liang; FitzGerald, Paul A; Warr, Gregory G; Jolliffe, Katrina A; Perrier, Sébastien

    2016-12-19

    We present a fundamental study into the self-assembly of (cyclic peptide)-polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small-angle neutron scattering (SANS). This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self-assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore, we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.

  7. All-in-one assembly based on 3D-intertangled and cross-jointed architectures of Si/Cu 1D-nanowires for lithium ion batteries

    PubMed Central

    Hwang, Chihyun; Kim, Tae-Hee; Cho, Yoon-Gyo; Kim, Jieun; Song, Hyun-Kon

    2015-01-01

    All-in-one assemblies of separator, electrode and current collector (SECA) for lithium ion batteries are presented by using 1D nanowires of Si and Cu (nwSi and nwCu). Even without binders, integrity of SECA is secured via structural joints based on ductility of Cu as well as entanglement of nwSi and nwCu. By controlling the ratio of the nanowires, the number of contact points and voids accommodating volume expansion of Si active material are tunable. Zero volume expansion and high energy density are simultaneously achievable by the architecture. PMID:25720334

  8. Mussel-inspired Fluoro-Polydopamine Functionalization of Titanium Dioxide Nanowires for Polymer Nanocomposites with Significantly Enhanced Energy Storage Capability

    NASA Astrophysics Data System (ADS)

    Wang, Guanyao; Huang, Xingyi; Jiang, Pingkai

    2017-02-01

    High-dielectric-constant polymer nanocomposites are demonstrated to show great promise as energy storage materials. However, the large electrical mismatch and incompatibility between nanofillers and polymer matrix usually give rise to significantly reduced breakdown strength and weak energy storage capability. Therefore, rational selection and elaborate functionalization of nanofillers to optimize the performance of polymer nanocomposites are vital. Herein, inspired by adhesive proteins in mussels, a facile modification by fluoro-polydopamine is employed to reinforce the compatibility of TiO2 nanowires in the fluoropolymer matrix. The loading of 2.5 vol % f-DOPA@TiO2 NWs leads to an ultrahigh discharged energy density of 11.48 J cm‑3 at 530 MV m‑1, more than three times of commercial biaxial-oriented polypropylene (BOPP, 3.56 J cm‑3 at 600 MV m‑1). A gratifying high energy density of 9.12 J cm‑3 has also been obtained with nanofiller loading as high as 15 vol % at 360 MV m‑1, which is nearly double to that of pure P(VDF-HFP) (4.76 J cm‑3 at 360 MV m‑1). This splendid energy storage capability seems to rival or exceed most of previously reported nano-TiO2 based nanocomposites. The methods presented here provide deep insights into the design of polymer nanocomposites for energy storage applications.

  9. Mussel-inspired Fluoro-Polydopamine Functionalization of Titanium Dioxide Nanowires for Polymer Nanocomposites with Significantly Enhanced Energy Storage Capability.

    PubMed

    Wang, Guanyao; Huang, Xingyi; Jiang, Pingkai

    2017-02-22

    High-dielectric-constant polymer nanocomposites are demonstrated to show great promise as energy storage materials. However, the large electrical mismatch and incompatibility between nanofillers and polymer matrix usually give rise to significantly reduced breakdown strength and weak energy storage capability. Therefore, rational selection and elaborate functionalization of nanofillers to optimize the performance of polymer nanocomposites are vital. Herein, inspired by adhesive proteins in mussels, a facile modification by fluoro-polydopamine is employed to reinforce the compatibility of TiO2 nanowires in the fluoropolymer matrix. The loading of 2.5 vol % f-DOPA@TiO2 NWs leads to an ultrahigh discharged energy density of 11.48 J cm(-3) at 530 MV m(-1), more than three times of commercial biaxial-oriented polypropylene (BOPP, 3.56 J cm(-3) at 600 MV m(-1)). A gratifying high energy density of 9.12 J cm(-3) has also been obtained with nanofiller loading as high as 15 vol % at 360 MV m(-1), which is nearly double to that of pure P(VDF-HFP) (4.76 J cm(-3) at 360 MV m(-1)). This splendid energy storage capability seems to rival or exceed most of previously reported nano-TiO2 based nanocomposites. The methods presented here provide deep insights into the design of polymer nanocomposites for energy storage applications.

  10. Mussel-inspired Fluoro-Polydopamine Functionalization of Titanium Dioxide Nanowires for Polymer Nanocomposites with Significantly Enhanced Energy Storage Capability

    PubMed Central

    Wang, Guanyao; Huang, Xingyi; Jiang, Pingkai

    2017-01-01

    High-dielectric-constant polymer nanocomposites are demonstrated to show great promise as energy storage materials. However, the large electrical mismatch and incompatibility between nanofillers and polymer matrix usually give rise to significantly reduced breakdown strength and weak energy storage capability. Therefore, rational selection and elaborate functionalization of nanofillers to optimize the performance of polymer nanocomposites are vital. Herein, inspired by adhesive proteins in mussels, a facile modification by fluoro-polydopamine is employed to reinforce the compatibility of TiO2 nanowires in the fluoropolymer matrix. The loading of 2.5 vol % f-DOPA@TiO2 NWs leads to an ultrahigh discharged energy density of 11.48 J cm−3 at 530 MV m−1, more than three times of commercial biaxial-oriented polypropylene (BOPP, 3.56 J cm−3 at 600 MV m−1). A gratifying high energy density of 9.12 J cm−3 has also been obtained with nanofiller loading as high as 15 vol % at 360 MV m−1, which is nearly double to that of pure P(VDF-HFP) (4.76 J cm−3 at 360 MV m−1). This splendid energy storage capability seems to rival or exceed most of previously reported nano-TiO2 based nanocomposites. The methods presented here provide deep insights into the design of polymer nanocomposites for energy storage applications. PMID:28225047

  11. Magnetic properties and Verwey transition of quasi-one-dimensional magnetite nanowire arrays assembled in alumina templates

    NASA Astrophysics Data System (ADS)

    Zhang, Li-Ying; Xue, De-Sheng; Xu, Xue-Fei; Gui, An-Biao

    2005-06-01

    Magnetite (Fe 3O 4) has been successfully assembled into anodic alumina templates by an electrochemical method followed by a heat-treating process. Here, we report on the magnetic properties of these so formed nanowires and the Verwey transition measured by vibrating sample magnetometer and SQUID. A Mössbauer spectrum was collected to verify the magnetic orientation of the wires, and a tilt of the moment of 45° with respect to the wire axis was found. These wires show perpendicular magnetic anisotropy mainly due to the average easy axis of the grains pointing along the wire axis. The temperature dependence of the coercity, remanence, and the magnetization undergo a major change at 50 K, induced by the Verwey transition, which occurs at a temperature much lower than for bulk materials (120 K). The behavior of the magnetization in the vicinity of 50 K as well as its field-dependent properties was interpreted using the magneto-electronic model.

  12. Layer-by-layer assembly of clay-filled polymer nanocomposite thin films

    NASA Astrophysics Data System (ADS)

    Jang, Woo-Sik

    2008-10-01

    A variety of functional thin films can be produced using the layer-by-layer assembly technique. In this work, assemblies of anionic clay and cationic polymer were studied with regard to film growth and gas barrier properties. A simple, yet flexible robotic dipping system, for the preparation of these thin films, was built. The robot alternately dips a substrate into aqueous mixtures with rinsing and drying in between. Thin films of sodium montmorillonite clay and cationic polymer were grown and studied on poly(ethylene terephthalate) film or a silicon wafer. After 30 clay polymer bilayers were deposited, the resulting transparent film had an oxygen transmission rate (OTR) below 0.005 cm3/m2/day/atm. This low OTR, which is unprecedented for a clay-filled polymer composite, is believed to be due to a "brick wall" nanostructure comprised of completely exfoliated clay bricks in polymeric "mortar". The growth of polymer and clay assemblies is then shown to be controlled by altering the pH of polyethylenimine (PEI). Growth, oxygen permeability, and mechanical behavior of clay-PEI assemblies were studied as a function of pH in an effort to tailor the behavior of these thin films. Thicker deposition at high pH resulted in reduced oxygen permeability and lower modulus, which highlights the tailorability of this system.

  13. Drug conjugation to cyclic peptide-polymer self-assembling nanotubes.

    PubMed

    Blunden, Bianca M; Chapman, Robert; Danial, Maarten; Lu, Hongxu; Jolliffe, Katrina A; Perrier, Sébastien; Stenzel, Martina H

    2014-09-26

    We show for the first time how polymeric nanotubes (NTs) based on self-assembled conjugates of polymers and cyclic peptides can be used as an efficient drug carrier. RAPTA-C, a ruthenium-based anticancer drug, was conjugated to a statistical co-polymer based on poly(2-hydroxyethyl acrylate) (pHEA) and poly(2-chloroethyl methacrylate) (pCEMA), which formed the shell of the NTs. Self-assembly into nanotubes (length 200-500 nm) led to structures exhibiting high activity against cancer cells.

  14. The magnetic assembly of polymer colloids in a ferrofluid and its display applications.

    PubMed

    Liu, Jing; Mao, Yiwu; Ge, Jianping

    2012-03-07

    Nonmagnetic polymer colloids have been assembled into colloidal photonic crystals in a ferrofluid by applying an external magnetic field based on the dipole-dipole interactions of "magnetic holes". The photonic crystal disassembles immediately when the magnetic field is removed. The mechanism of assembly can be explained by two simultaneous processes: phase separation and colloidal assembly. In this work, increasing the size of the building blocks still produces colorful photonic crystals due to their 2nd order diffraction. With a larger building block, the magnetic response between the polymer colloids is greatly enhanced so that an instant and reversible assembly/disassembly can be realized in a much weaker magnetic field and lower ferrofluid concentration. Based on these investigations, a magnetically controlled photonic display unit has been fabricated, which works in a weak magnetic field, has stable reflection signals and possesses fast and reversible on/off switching of reflections.

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

    SciTech Connect

    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

    2016-07-19

    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 micellarto- 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. In conclusion, 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.

  16. Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

    DOE PAGES

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; ...

    2016-07-19

    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 incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- 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. In conclusion, 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.« less

  17. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    DOE PAGES

    Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; ...

    2015-04-24

    In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks).more » The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.« less

  18. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    SciTech Connect

    Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; Henderson, Ian M.; Bouxsein, Nathan F.

    2015-04-24

    In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.

  19. Self-assembled growth of GaN nanowires on amorphous Al x O y : from nucleation to the formation of dense nanowire ensembles.

    PubMed

    Sobanska, M; Fernández-Garrido, S; Zytkiewicz, Z R; Tchutchulashvili, G; Gieraltowska, S; Brandt, O; Geelhaar, L

    2016-08-12

    We present a comprehensive description of the self-assembled nucleation and growth of GaN nanowires (NWs) by plasma-assisted molecular beam epitaxy on amorphous Al x O y buffers (a-Al x O y ) prepared by atomic layer deposition. The results are compared with those obtained on nitridated Si(111). Using line-of-sight quadrupole mass spectrometry, we analyze in situ the incorporation of Ga starting from the incubation and nucleation stages till the formation of the final nanowire ensemble and observe qualitatively the same time dependence for the two types of substrates. However, on a-Al x O y the incubation time is shorter and the nucleation faster than on nitridated Si. Moreover, on a-Al x O y we observe a novel effect of decrease in incorporated Ga flux for long growth durations which we explain by coalescence of NWs leading to reduction of the GaN surface area where Ga may reside. Dedicated samples are used to analyze the evolution of surface morphology. In particular, no GaN nuclei are detected when growth is interrupted during the incubation stage. Moreover, for a-Al x O y , the same shape transition from spherical cap-shaped GaN crystallites to the NW-like geometry is found as it is known for nitridated Si. However, while the critical radius for this transition is only slightly larger for a-Al x O y than for nitridated Si, the critical height is more than six times larger for a-Al x O y . Finally, we observe that in fully developed NW ensembles, the substrate no longer influences growth kinetics and the same N-limited axial growth rate is measured on both substrates. We conclude that the same nucleation and growth processes take place on a-Al x O y as on nitridated Si and that these processes are of a general nature. Quantitatively, nucleation proceeds somewhat differently, which indicates the influence of the substrate, but once shadowing limits growth processes to the upper part of the NW ensemble, they are not affected anymore by the type of substrate.

  20. One-step synthesis and patterning of aligned polymer nanowires on a substrate

    DOEpatents

    Wang, Zhong L [Marietta, GA; Wang, Xudong [Atlanta, GA; Morber, Jenny R [Atlanta, GA; Liu, Jin [Danbury, CT

    2011-11-08

    In a method of making a polymer structure on a substrate a layer of a first polymer, having a horizontal top surface, is applied to a surface of the substrate. An area of the top surface of the polymer is manipulated to create an uneven feature that is plasma etched to remove a first portion from the layer of the first polymer thereby leaving the polymer structure extending therefrom. A light emitting structure includes a conductive substrate from which an elongated nanostructure of a first polymer extends. A second polymer coating is disposed about the nanostructure and includes a second polymer, which includes a material such that a band gap exists between the second polymer coating and the elongated nanostructure. A conductive material coats the second polymer coating. The light emitting structure emits light when a voltage is applied between the conductive substrate and the conductive coating.

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

    PubMed Central

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

    2015-01-01

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

  2. Healable capacitive touch screen sensors based on transparent composite electrodes comprising silver nanowires and a furan/maleimide diels-alder cycloaddition polymer.

    PubMed

    Li, Junpeng; Liang, Jiajie; Li, Lu; Ren, Fengbo; Hu, Wei; Li, Juan; Qi, Shuhua; Pei, Qibing

    2014-12-23

    A healable transparent capacitive touch screen sensor has been fabricated based on a healable silver nanowire-polymer composite electrode. The composite electrode features a layer of silver nanowire percolation network embedded into the surface layer of a polymer substrate comprising an ultrathin soldering polymer layer to confine the nanowires to the surface of a healable Diels-Alder cycloaddition copolymer and to attain low contact resistance between the nanowires. The composite electrode has a figure-of-merit sheet resistance of 18 Ω/sq with 80% transmittance at 550 nm. A surface crack cut on the conductive surface with 18 Ω is healed by heating at 100 °C, and the sheet resistance recovers to 21 Ω in 6 min. A healable touch screen sensor with an array of 8×8 capacitive sensing points is prepared by stacking two composite films patterned with 8 rows and 8 columns of coupling electrodes at 90° angle. After deliberate damage, the coupling electrodes recover touch sensing function upon heating at 80 °C for 30 s. A capacitive touch screen based on Arduino is demonstrated capable of performing quick recovery from malfunction caused by a razor blade cutting. After four cycles of cutting and healing, the sensor array remains functional.

  3. TiO₂ nanowire dispersions in viscous polymer matrix: electrophoretic alignment and optical properties.

    PubMed

    Šutka, Andris; Saal, Kristjan; Kisand, Vambola; Lõhmus, Rünno; Joost, Urmas; Timusk, Martin

    2014-10-17

    The changes in optical properties during TiO₂ nanowire orientation in polydimethylsiloxane (PDMS) matrix under the influence of an electric field are strongly influenced by nanowire (NW) diameter. It was demonstrated for the first time that either positive or negative change in transmittance can be induced by NW alignment parallel to the electric field depending on the NW diameter. These effects can be explained by the interplay between scattering and reflectance. Experimental findings reported could be important for smart window applications for the regulation of visible or even infrared transparency, thus reducing the energy consumption by air conditioning systems in buildings and automobiles in the future.

  4. Construction of supramolecular hyperbranched polymers via the "tweezering directed self-assembly" strategy.

    PubMed

    Tian, Yu-Kui; Yang, Zhi-Shuai; Lv, Xiao-Qin; Yao, Ri-Sheng; Wang, Feng

    2014-08-28

    A bis-alkynylplatinum(II) terpyridine tweezer-alkynylgold(III) diphenylpyridine guest is shown to maintain the specific complexation in the presence of a B21C7-secondary ammonium salt recognition motif, which facilitates the formation of supramolecular hyperbranched polymers via the "tweezering directed self-assembly" strategy.

  5. Assembly of colloidal molecules, polymers, and crystals in acoustic and magnetic fields.

    PubMed

    Yang, Ye; Pham, An T; Cruz, Daniela; Reyes, Christopher; Wiley, Benjamin J; Lopez, Gabriel P; Yellen, Benjamin B

    2015-08-26

    A dynamically adjustable colloidal assembly technique is presented, which combines magnetic and acoustic fields to produce a wide range of colloidal structures, ranging from discrete colloidal molecules, to polymer networks and crystals. The structures can be stabilized and dried, making them suitable for the fabrication of advanced materials.

  6. Efficient self-assembly in water of long noncovalent polymers by nucleobase analogues.

    PubMed

    Cafferty, Brian J; Gállego, Isaac; Chen, Michael C; Farley, Katherine I; Eritja, Ramon; Hud, Nicholas V

    2013-02-20

    Molecular self-assembly is widely appreciated to result from a delicate balance between several noncovalent interactions and solvation effects. However, current design approaches for achieving self-assembly in water with small, synthetic molecules do not consider all aspects of the hydrophobic effect, in particular the requirement of surface areas greater than 1 nm(2) for an appreciable free energy of hydration. With the concept of a minimum hydrophobic surface area in mind, we designed a system that achieves highly cooperative self-assembly in water. Two weakly interacting low-molecular-weight monomers (cyanuric acid and a modified triaminopyrimidine) are shown to form extremely long supramolecular polymer assemblies that retain water solubility. The complete absence of intermediate assemblies means that the observed equilibrium is between free monomers and supramolecular assemblies. These observations are in excellent agreement with literature values for the free energy of nucleic acid base interactions as well as the calculated free energy penalty for the exposure of hydrophobic structures in water. The results of our study have implications for the design of new self-assembling structures and hydrogel-forming molecules and may provide insights into the origin of the first RNA-like polymers.

  7. Polymer self-assembling of light converting microlenses arrays

    NASA Astrophysics Data System (ADS)

    Coppola, S.; Mandracchia, B.; Nasti, G.; Vespini, V.; Pareo, P.; Carbone, L.; Manca, M.; Gigli, G.; Ferraro, P.

    2014-05-01

    In the case of light emitting semiconducting polymers, different techniques have been used for the fabrication of electroluminescent devices. Experiments and characterizations have been carried out at different operating voltages and for voltage dependent emission color also combining the processability of organic materials with efficient luminescence displayed by inorganic nanocrystals (NCs). In fact, the experimental perspective to disperse emitting colloidal NCs into polymers has allowed to further engineer hybrid organic-inorganic materials introducing innovative functionalities as for instance photoluminescence conversion capabilities. This has proved of great interest for novel applications such as the fabrication of photonic crystals and, notably, of innovative solar cells showing enhanced efficiency. Here we report on the fabrication of novel active micro-optical elements made by a mixture of rod-shaped inorganic NCs dispersed into poly-dimethylsiloxane.

  8. Covalently Connected Polymer-Protein Nanostructures Fabricated by a Reactive Self-Assembly Approach.

    PubMed

    Ju, Yuanyuan; Xing, Cheng; Wu, Dongxia; Wu, Yunfang; Wang, Lianyong; Zhao, Hanying

    2017-03-08

    The synthesis of polymer-protein nanostructures opens up a new avenue for the development of new biomaterials. In this research, covalently connected polymer-protein nanostructures were fabricated through a reactive self-assembly approach. Poly(tert-butyl methacrylate-co-pyridyl disulfide methacrylamide) (PtBMA-co-PPDSMA) was synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. Covalently connected nanostructures (CCNs) with hydrophobic polymer cores and hydrophilic protein coronae were prepared by adding solutions of PtBMA-co-PPDSMA/DMF to aqueous solutions of bovine serum albumin (BSA). The thiol-disulfide exchange reaction between pyridyl disulfide groups on the polymer chains and thiol groups on the protein molecules plays a key role in the fabrication of CCNs. The self-assembly process was investigated by dynamic light scattering (DLS) and stopped-flow techniques. DLS results indicated that the sizes of the CCNs were determined by the initial polymer concentration, the BSA concentration, and the average number of thiol groups on BSA molecules. TEM and sodium dodecyl sulfate polyacrylamide gel electrophoresis were used to analyze the nanostructures. Far-UV circular dichroism results demonstrated that the original folded conformations of BSA molecules were basically maintained in the reactive self-assembly process. Compared with native BSA, the secondary structure and conformation change of coronal BSA induced by urea or thermal treatment were remarkably suppressed. The cytotoxicity assays demonstrated that the CCNs were essentially nontoxic to Hela and COS-7 cells.

  9. Enhancement of Interface Characteristics of Neural Probe Based on Graphene, ZnO Nanowires, and Conducting Polymer PEDOT.

    PubMed

    Ryu, Mingyu; Yang, Jae Hoon; Ahn, Yumi; Sim, Minkyung; Lee, Kyung Hwa; Kim, Kyungsoo; Lee, Taeju; Yoo, Seung-Jun; Kim, So Yeun; Moon, Cheil; Je, Minkyu; Choi, Ji-Woong; Lee, Youngu; Jang, Jae Eun

    2017-03-29

    In the growing field of brain-machine interface (BMI), the interface between electrodes and neural tissues plays an important role in the recording and stimulation of neural signals. To minimize tissue damage while retaining high sensitivity, a flexible and a smaller electrode with low impedance is required. However, it is a major challenge to reduce electrode size while retaining the conductive characteristics of the electrode. In addition, the mechanical mismatch between stiff electrodes and soft tissues creates damaging reactive tissue responses. Here, we demonstrate a neural probe structure based on graphene, ZnO nanowires, and conducting polymer that provides flexibility and low impedance performance. A hybrid Au and graphene structure was utilized to achieve both flexibility and good conductivity. Using ZnO nanowires to increase the effective surface area drastically decreased the impedance value and enhanced the signal-to-noise ratio (SNR). A poly[3,4-ethylenedioxythiophene] (PEDOT) coating on the neural probe improved the electrical characteristics of the electrode while providing better biocompatibility. In vivo neural signal recordings showed that our neural probe can detect clearer signals.

  10. Separation of Armchair SWNTs by Using Polymer Conformation Guided Assembly

    DTIC Science & Technology

    2013-08-22

    30 Publications 36 Reference List 38     2 Introduction Single-walled carbon nanotubes (SWNTs) are among the most...with 12, the polymer 15 of linear geometry also forms the donor-acceptor complex resulting in enhanced interactions with graphene or carbon nanotubes .32...Band engineering of oxygen doped single-walled carbon nanotubes , NANOSCALE 2011, 6 2465-2468.  R. Gunasingh; C. Kah; K. Quarles; et al

  11. Shape origin of self-assembled Ge nanowires grown on Si(113)

    NASA Astrophysics Data System (ADS)

    Bottomley, D. J.; Omi, H.; Ogino, T.

    2000-03-01

    In experiment, it has been observed that the deposition of 5 to 8 ML of Ge on Si(113) at temperatures between 400 and 500 deg C leads to the formation of Ge nanowires about 20 nm wide and 150 nm long, on average, with facetted sides [1]. Here we investigate the origin of this shape using anisotropic linear elasticity theory. We have calculated the stress and strain tensors for Ge on Si(113) assuming a flat film and no intermixing. The stress along the elongated nanowire [33 -2] axis is -6.27 GPa; that along the perpendicular [1 -1 0] axis is -5.75 GPa. There is no shear stress and no stress along [113]. The strain in the surface plane is -3.81%; the strain along [113] is +2.26%. There is a shear strain, which changes the angle between the film’s [113] and [33 -2] axes to 90.95 deg. The results of the calculation enable us to discuss the origin of the nanowire shape. The most obvious hypothesis is that the shape anisotropy arises from stress anisotropy in the film, which promotes anisotropic elastic relaxation. But our results show that the stress is 9% greater along the elongated axis than along the perpendicular axis. Therefore we can state that the shape does not arise from the stress anisotropy. Other possibilities are considered: we consider the most probable cause of the shape anisotropy to be the existence of lower surface free energy facets in the <33 -2> zone than in the <1 -1 0> zone for the (113) surface. [1] H. Omi and T. Ogino, Phys. Rev. B 59, 7521 (1999).

  12. Tuning the Assembly of Spherical Nanoparticles in Semicrystalline Polymers

    NASA Astrophysics Data System (ADS)

    Zhao, Dan; Jestin, Jacques; Zhao, Longxi; Kumar, Sanat K.; Mohammadkhani, Mohammad; Benicewicz, Brian C.

    We propose a simple, novel strategy to controlling nanoparticle (NPs) dispersion states in a semi-crystalline polymer matrix exploiting the kinetics of polymer crystallization. The system consists of poly(methyl methacrylate) grafted spherical silica NPs and poly(ethylene oxide) matrices, which are thermodynamically miscible in the melt. We first show that no remarkable change was observed in the spatial dispersion of NPs upon fast crystallization. However, for slow crystallization, both TEM and X-ray/neutron scattering reveal that the system starts to be organized in a ``layer-by-layer'' architecture, where the NPs are aligned in the amorphous phases intercalated by the crystalline lamellar phases. More importantly, we have found that the resulting ``sheet-like'' NP morphology gives rise to a 2-fold increase in the storage modulus but without compromising the fracture toughness of the neat polymer. These results open pathways for creating in-situ biomimetic hierarchical structures with improved mechanical properties through a simple, single-step crystallization processing, which could lead to new applications for this largest class of commercially relevant polymeric materials.

  13. Supramolecular star polymers. Increased molecular weight with decreased polydispersity through self-assembly.

    PubMed

    Todd, Eric M; Zimmerman, Steven C

    2007-11-28

    A ditopic structure containing two heterocyclic DeAP units and programmed to self-assemble is used as an initiation unit for the synthesis of polylactide and polystyrene. The resultant polymers self-assemble into higher molecular weight structures with a lower molecular weight distribution. The largest discrete nanoscale polymeric assembly is proposed to be a hexameric star with a molecular weight of ca. 92.7 kDa. All polymeric assemblies generally exhibit PDI values of 1.3 to 1.5, which are lower than the PDI value of the corresponding polymeric arms. A hexameric assembly is stabilized by 30 hydrogen bonds, including six AADD.DDAA contacts. The hexameric star is formed under conditions that are at least partially controlled by kinetics.

  14. Quantum phase slips in superconducting Nb nanowire networks deposited on self-assembled Si templates

    NASA Astrophysics Data System (ADS)

    Cirillo, C.; Trezza, M.; Chiarella, F.; Vecchione, A.; Bondarenko, V. P.; Prischepa, S. L.; Attanasio, C.

    2012-10-01

    Robust porous silicon substrates were employed for generating interconnected networks of superconducting ultrathin Nb nanowires. Scanning electron microscopy analysis was performed to investigate the morphology of the samples, which constitute of polycrystalline single wires with grain size of about 10 nm. The samples exhibit nonzero resistance over a broad temperature range below the critical temperature, fingerprint of phase slippage processes. The transport data are satisfactory reproduced by models describing both thermal and quantum fluctuations of the superconducting order parameter in thin homogeneous superconducting wires.

  15. Fully solution-processed semitransparent organic solar cells with a silver nanowire cathode and a conducting polymer anode.

    PubMed

    Yim, Jong Hyuk; Joe, Sung-yoon; Pang, Christina; Lee, Kyung Moon; Jeong, Huiseong; Park, Ji-Yong; Ahn, Yeong Hwan; de Mello, John C; Lee, Soonil

    2014-03-25

    We report the fabrication of efficient indium-tin-oxide-free organic solar cells based on poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM). All layers of the devices from the lowermost silver nanowire cathode to the uppermost conducting polymer anode are deposited from solution and processed at plastic-compatible temperatures<200 °C. Owing to the absence of an opaque metal electrode, the devices are semitransparent with potential applications in power-generating windows and tandem-cells. The measured power conversion efficiencies (PCEs) of 2.3 and 2.0% under cathode- and anode-side illumination, respectively, match previously reported PCE values for equivalent semitransparent organic solar cells using indium tin oxide.

  16. Ultrathin Nanotube/Nanowire Electrodes by Spin-Spray Layer-by-Layer Assembly: A Concept for Transparent Energy Storage.

    PubMed

    Gittleson, Forrest S; Hwang, Daniel; Ryu, Won-Hee; Hashmi, Sara M; Hwang, Jonathan; Goh, Tenghooi; Taylor, André D

    2015-10-27

    Fully integrated transparent devices require versatile architectures for energy storage, yet typical battery electrodes are thick (20-100 μm) and composed of optically absorbent materials. Reducing the length scale of active materials, assembling them with a controllable method and minimizing electrode thickness should bring transparent batteries closer to reality. In this work, the rapid and controllable spin-spray layer-by-layer (SSLbL) method is used to generate high quality networks of 1D nanomaterials: single-walled carbon nanotubes (SWNT) and vanadium pentoxide (V2O5) nanowires for anode and cathode electrodes, respectively. These ultrathin films, deposited with ∼2 nm/bilayer precision are transparent when deposited on a transparent substrate (>87% transmittance) and electrochemically active in Li-ion cells. SSLbL-assembled ultrathin SWNT anodes and V2O5 cathodes exhibit reversible lithiation capacities of 23 and 7 μAh/cm(2), respectively at a current density of 5 μA/cm(2). When these electrodes are combined in a full cell, they retain ∼5 μAh/cm(2) capacity over 100 cycles, equivalent to the prelithiation capacity of the limiting V2O5 cathode. The SSLbL technique employed here to generate functional thin films is uniquely suited to the generation of transparent electrodes and offers a compelling path to realize the potential of fully integrated transparent devices.

  17. Fabrication of microstructured polymer films using breath-figure-templated assembly

    NASA Astrophysics Data System (ADS)

    Srinivasarao, Mohan; Sharma, Vivek; Crne, Matija

    2010-03-01

    Breath figures formed on evaporating polymer solutions exposed to the blast of humid air involve growth and self-assembly of water drops that are non-coalescent. The ordered arrays of nearly monodisperse drops, eventually evaporate away, leaving a microstructured, porous polymer film. We elucidate the mechanism of this breath-figure-templated assembly, by accounting for various transport and thermodynamic processes that control the dynamics of drop nucleation, growth, noncoalescence and self-assembly. The theoretical framework developed in this study allows one to rationalize and predict the structure and size of pores. We provide an exemplary study where we use coat these films with inorganic oxides and mimic the structural color of Papilio palinurus butterfly.

  18. Alignment of human cardiomyocytes on laser patterned biphasic core/shell nanowire assemblies

    NASA Astrophysics Data System (ADS)

    Kiefer, Karin; Lee, Juseok; Haidar, Ayman; Martinez Miró, Marina; Akkan, Cagri Kaan; Veith, Michael; Cenk Aktas, Oral; Abdul-Khaliq, Hashim

    2014-12-01

    The management of end stage heart failure patients is only possible by heart transplantation or by the implantation of artificial hearts as a bridge for later transplantation. However, these therapeutic strategies are limited by a lack of donor hearts and by the associated complications, such as coagulation and infection, due to the used artificial mechanical circulatory assist devices. Therefore, new strategies for myocardial regenerative approaches are under extensive research to produce contractile myocardial tissue in the future to replace non-contractile myocardial ischemic and scarred tissue. Different approaches, such as cell transplantation, have been studied intensively. Although successful approaches have been observed, there are still limitations to the application. It is envisaged that myocardial tissue engineering can be used to help replace infarcted non-contractile tissue. The developed tissue should later mimic the aligned fibrillar structure of the extracellular matrix and provide important guidance cues for the survival, function and the needed orientation of cardiomyocytes. Nanostructured surfaces have been tested to provide a guided direction that cells can follow. In the present study, the cellular adhesion/alignment of human cardiomyocytes and the biocompatibility have been investigated after cultivation on different laser-patterned nanowires compared with unmodified nanowires. As a result, the nanostructured surfaces possessed good biocompatibility before and after laser modification. The laser-induced scalability of the pattern enabled the growth and orientation of the adhered myocardial tissue. Such approaches may be used to modify the surface of potential scaffolds to develop myocardial contractile tissue in the future.

  19. Dissipative particle dynamics simulations of polymer-protected nanoparticle self-assembly.

    PubMed

    Spaeth, Justin R; Kevrekidis, Ioannis G; Panagiotopoulos, Athanassios Z

    2011-11-14

    Dissipative particle dynamics simulations were used to study the effects of mixing time, solute solubility, solute and diblock copolymer concentrations, and copolymer block length on the rapid coprecipitation of polymer-protected nanoparticles. The simulations were aimed at modeling Flash NanoPrecipitation, a process in which hydrophobic solutes and amphiphilic block copolymers are dissolved in a water-miscible organic solvent and then rapidly mixed with water to produce composite nanoparticles. A previously developed model by Spaeth et al. [J. Chem. Phys. 134, 164902 (2011)] was used. The model was parameterized to reproduce equilibrium and transport properties of the solvent, hydrophobic solute, and diblock copolymer. Anti-solvent mixing was modeled using time-dependent solvent-solute and solvent-copolymer interactions. We find that particle size increases with mixing time, due to the difference in solute and polymer solubilities. Increasing the solubility of the solute leads to larger nanoparticles for unfavorable solute-polymer interactions and to smaller nanoparticles for favorable solute-polymer interactions. A decrease in overall solute and polymer concentration produces smaller nanoparticles, because the difference in the diffusion coefficients of a single polymer and of larger clusters becomes more important to their relative rates of collisions under more dilute conditions. An increase in the solute-polymer ratio produces larger nanoparticles, since a collection of large particles has less surface area than a collection of small particles with the same total volume. An increase in the hydrophilic block length of the polymer leads to smaller nanoparticles, due to an enhanced ability of each polymer to shield the nanoparticle core. For unfavorable solute-polymer interactions, the nanoparticle size increases with hydrophobic block length. However, for favorable solute-polymer interactions, nanoparticle size exhibits a local minimum with respect to the

  20. Synthesis, characterisation and electrical properties of supramolecular DNA-templated polymer nanowires of 2,5-(bis-2-thienyl)-pyrrole.

    PubMed

    Watson, Scott M D; Hedley, Joseph H; Galindo, Miguel A; Al-Said, Said A F; Wright, Nick G; Connolly, Bernard A; Horrocks, Benjamin R; Houlton, Andrew

    2012-09-17

    Supramolecular polymer nanowires have been prepared by using DNA-templating of 2,5-(bis-2-thienyl)-pyrrole (TPT) by oxidation with FeCl(3) in a mixed aqueous/organic solvent system. Despite the reduced capacity for strong hydrogen bonding in polyTPT compared to other systems, such as polypyrrole, the templating proceeds well. FTIR spectroscopic studies confirm that the resulting material is not a simple mixture and that the two types of polymer interact. This is indicated by shifts in bands associated with both the phosphodiester backbone and the nucleobases. XPS studies further confirm the presence of DNA and TPT, as well as dopant Cl(-) ions. Molecular dynamics simulations on a [{dA(24):dT(24)}/{TPT}(4)] model support these findings and indicate a non-coplanar conformation for oligoTPT over much of the trajectory. AFM studies show that the resulting nanowires typically lie in the 7-8 nm diameter range and exhibit a smooth, continuous, morphology. Studies on the electrical properties of the prepared nanowires by using a combination of scanned conductance microscopy, conductive AFM and variable temperature two-terminal I-V measurements show, that in contrast to similar DNA/polymer systems, the conductivity is markedly reduced compared to bulk material. The temperature dependence of the conductivity shows a simple Arrhenius behaviour consistent with the hopping models developed for redox polymers.

  1. Tuning the sphere-to-rod transition in the self-assembly of thermoresponsive polymer hybrids.

    PubMed

    Lee, Jangwook; Park, Honghyun; Jeong, Eun Ju; Kwark, Young-Je; Lee, Kuen Yong

    2015-12-01

    Nano-scale drug delivery systems have undergone extensive development, and control of size and structure is critical for regulation of their biological responses and therapeutic efficacy. Amphiphilic polymers that form self-assembled structures in aqueous media have been investigated and used for the diagnosis and therapy of various diseases, including cancer. Here, we report the design and fabrication of thermoresponsive polymeric micelles from alginate conjugated with poly(N-isopropylacrylamide) (PNIPAAm). Alginate-PNIPAAm hybrids formed self-aggregated structures in response to temperature changes near body temperature. A structural transition from micellar spheres to rods of alginate-PNIPAAm hybrids was observed depending on the molecular weight of PNIPAAm and the polymer concentration. Additionally, hydrogels with nanofibrous structures were formed by simply increasing the polymer concentration. This approach to controlling the structure of polymer micelles from nanoparticles to fibrous hydrogels may be useful in applications in drug delivery and tissue engineering.

  2. Energetics and Geometry of FtsZ Polymers: Nucleated Self-Assembly of Single Protofilaments☆

    PubMed Central

    Huecas, Sonia; Llorca, Oscar; Boskovic, Jasminka; Martín-Benito, Jaime; Valpuesta, José María; Andreu, José Manuel

    2008-01-01

    Essential cell division protein FtsZ is an assembling GTPase which directs the cytokinetic ring formation in dividing bacterial cells. FtsZ shares the structural fold of eukaryotic tubulin and assembles forming tubulin-like protofilaments, but does not form microtubules. Two puzzling problems in FtsZ assembly are the nature of protofilament association and a possible mechanism for nucleated self-assembly of single-stranded protofilaments above a critical FtsZ concentration. We assembled two-dimensional arrays of FtsZ on carbon supports, studied linear polymers of FtsZ with cryo-electron microscopy of vitrified unsupported solutions, and formulated possible polymerization models. Nucleated self-assembly of FtsZ from Escherichia coli with GTP and magnesium produces flexible filaments 4–6 nm-wide, only compatible with a single protofilament. This agrees with previous scanning transmission electron microscopy results and is supported by recent cryo-electron tomography studies of two bacterial cells. Observations of double-stranded FtsZ filaments in negative stain may come from protofilament accretion on the carbon support. Preferential protofilament cyclization does not apply to FtsZ assembly. The apparently cooperative polymerization of a single protofilament with identical intermonomer contacts is explained by the switching of one inactive monomer into the active structure preceding association of the next, creating a dimer nucleus. FtsZ behaves as a cooperative linear assembly machine. PMID:18024502

  3. Energetics and geometry of FtsZ polymers: nucleated self-assembly of single protofilaments.

    PubMed

    Huecas, Sonia; Llorca, Oscar; Boskovic, Jasminka; Martín-Benito, Jaime; Valpuesta, José María; Andreu, José Manuel

    2008-03-01

    Essential cell division protein FtsZ is an assembling GTPase which directs the cytokinetic ring formation in dividing bacterial cells. FtsZ shares the structural fold of eukaryotic tubulin and assembles forming tubulin-like protofilaments, but does not form microtubules. Two puzzling problems in FtsZ assembly are the nature of protofilament association and a possible mechanism for nucleated self-assembly of single-stranded protofilaments above a critical FtsZ concentration. We assembled two-dimensional arrays of FtsZ on carbon supports, studied linear polymers of FtsZ with cryo-electron microscopy of vitrified unsupported solutions, and formulated possible polymerization models. Nucleated self-assembly of FtsZ from Escherichia coli with GTP and magnesium produces flexible filaments 4-6 nm-wide, only compatible with a single protofilament. This agrees with previous scanning transmission electron microscopy results and is supported by recent cryo-electron tomography studies of two bacterial cells. Observations of double-stranded FtsZ filaments in negative stain may come from protofilament accretion on the carbon support. Preferential protofilament cyclization does not apply to FtsZ assembly. The apparently cooperative polymerization of a single protofilament with identical intermonomer contacts is explained by the switching of one inactive monomer into the active structure preceding association of the next, creating a dimer nucleus. FtsZ behaves as a cooperative linear assembly machine.

  4. π-Conjugated polymer anisotropic organogel nanofibrous assemblies for thermoresponsive photonic switches.

    PubMed

    Narasimha, Karnati; Jayakannan, Manickam

    2014-11-12

    The present work demonstrates one of the first examples of π-conjugated photonic switches (or photonic wave plates) based on the tailor-made π-conjugated polymer anisotropic organogel. New semicrystalline segmented π-conjugated polymers are designed with rigid aromatic oligophenylenevinylene π-core and flexible alkyl chain along the polymer backbone. These polymers are found to be self-assembled as semicrystalline or amorphous with respect to the number of carbon atoms in the alkyl units. These semicrystalline polymers produce organogels having nanofibrous morphology of 20 nm thickness with length up to 5 μm. The polymer organogel is aligned in a narrow glass capillary, and this anisotropic gel device is further demonstrated as photonic switches. The glass capillary device behaves as typical λ/4 photonic wave plates upon the illumination of the plane polarized light. The λ/4 photonic switching ability is found to be maximum at θ = 45° angle under the cross polarizers. The orthogonal arrangements of the gel capillaries produce dark and bright spots as on-and-off optical switches. Thermoreversibility of the polymer organogel (also its xerogel) was exploited to construct thermoresponsive photonic switches for the temperature window starting from 25 to 160 °C. The organic photonic switch concept can be adapted to large number of other π-conjugated materials for optical communication and storage.

  5. Directed Self-assembly of Nanoparticles at the Polymer Surface by Highly Compressible Supercritical Carbon Dioxide

    SciTech Connect

    M Asada; P Gin; M Endoh; S Satija; T Taniguchi; T Koga

    2011-12-31

    We report a versatile route for self-assembly of polymer-soluble nanoparticles at the polymer surface using highly compressible supercritical carbon dioxide (scCO{sub 2}). Polystyrene and poly(methyl methacrylate)-based nanocomposite thin films with functionalized polyhedral oligomeric silsesquioxane and phenyl C{sub 61} butyric acid methyl ester nanoparticles were prepared on Si substrates and exposed to scCO{sub 2} at different pressures under the isothermal condition of 36 C. The resultant structures could be then preserved by the vitrification process of the glassy polymers via quick pressure quench to atmospheric pressure and subsequently characterized by using various surface sensitive experimental techniques in air. We found that the surface segregation of these nanoparticles is induced in the close vicinity of P = 8.2 MPa where the excess absorption of the fluid into the polymers maximizes. However, when the film thickness becomes less than about 4R{sub g} thick (where R{sub g} is the radius of polymer gyration), the uniform dispersion of the nanoparticles is favorable instead even at the same CO{sub 2} conditions. We clarify that the phase transition is correlated with the emergence of a concentration gradient of the fluid at the polymer/CO{sub 2} interface and is a general phenomenon for different polymer-nanoparticle interactions.

  6. High-power density piezoelectric energy harvesting using radially strained ultrathin trigonal tellurium nanowire assembly.

    PubMed

    Lee, Tae Il; Lee, Sangmin; Lee, Eungkyu; Sohn, Sungwoo; Lee, Yean; Lee, Sujeong; Moon, Geondae; Kim, Dohyang; Kim, Youn Sang; Myoung, Jae Min; Wang, Zhong Lin

    2013-06-04

    A high-yield solution-processed ultrathin (<10 nm) trigonal tellurium (t-Te) nanowire (NW) is introduced as a new class of piezoelectric nanomaterial with a six-fold higher piezoelectric constant compared to conventional ZnO NWs for a high-volume power-density nanogenerator (NG). While determining the energy-harvesting principle in a NG consisting of t-Te NW, it is theoretically and experimentally found that t-Te NW is piezoelectrically activated only by creating strain in its radial direction, along which it has an asymmetric crystal structure. Based upon this mechanism, a NG with a monolayer consisting of well-aligned t-Te NWs and a power density of 9 mW/cm(3) is fabricated.

  7. Morphology and growth mechanism study of self-assembled silicon nanowires synthesized by thermal evaporation

    NASA Astrophysics Data System (ADS)

    Zhang, Z.; Fan, X. H.; Xu, L.; Lee, C. S.; Lee, S. T.

    2001-03-01

    Silicon nanowires (SiNWs) grown from `sunflower-seed'- and `mushroom'-shaped particles have been observed by electron microscopies. The SiNWs were synthesized by thermal evaporation of SiO powders without any metal catalysts. The SiNWs grown on the sunflower-seed-shaped particles had sub-branches of SiNWs terminated by Si bulbs. The SiNWs on the mushroom-shaped particles were densely and uniformly distributed on the surface of the mushroom cone. The growth history suggests that these SiNWs were formed by nucleation which originated from the surface of amorphous SiO particle matrixes via phase separation and precipitation followed by growth through oxide-assisted vapor-soild reaction.

  8. Self-assembly of polymers in confined geometrics.

    SciTech Connect

    Curro, John G.; Ye, Yuan; McCoy, John Dwane

    2003-10-01

    Athermal, tethered chains are modeled with Density Functional (DFT) theory for both the explicit solvent and continuum solvent cases. The structure of DFT is shown to reduce to Self-Consistent-Field (SCF) theory in the incompressible limit where there is symmetry between solvent and monomer, and to Single-Chain-Mean-Field (SCMF) theory in the continuum solvent limit. We show that by careful selection of the reference and ideal systems in DFT theory, self-consistent numerical solutions can be obtained, thereby avoiding the single chain Monte Carlo simulation in SCMF theory. On long length scales, excellent agreement is seen between the simplified DFT theory and Molecular Dynamics simulations of both continuum solvents and explicit-molecule solvents. In order to describe the structure of the polymer and solvent near the surface it is necessary to include compressibility effects and the nonlocality of the field.

  9. Efficient Organic/Inorganic Hybrid Solar Cell Integrating Polymer Nanowires and Inorganic Nanotetrapods.

    PubMed

    Xu, Weizhe; Tan, Furui; Liu, Xiansheng; Zhang, Weifeng; Qu, Shengchun; Wang, Zhijie; Wang, Zhanguo

    2017-12-01

    Constructing a highly efficient bulk-heterojunction is of critical importance to the hybrid organic/inorganic solar cells. Here in this work, we introduce a novel hybrid architecture containing P3HT nanowire and CdSe nanotetrapod as bicontinuous charge channels for holes and electrons, respectively. Compared to the traditionally applied P3HT molecules, the well crystallized P3HT nanowires qualify an enhanced light absorption at the long wavelength as well as strengthened charge carrier transport in the hybrid active layer. Accordingly, based on efficient dissociation of photogenerated excitons, the interpercolation of these two nano-building blocks allows a photovoltaic conversion efficiency of 1.7% in the hybrid solar cell, up to 42% enhancement compared to the reference solar cell with traditional P3HT molecules as electron donor. Our work provides a promising hybrid structure for efficient organic/inorganic bulk-heterojunction solar cells.

  10. Efficient Organic/Inorganic Hybrid Solar Cell Integrating Polymer Nanowires and Inorganic Nanotetrapods

    NASA Astrophysics Data System (ADS)

    Xu, Weizhe; Tan, Furui; Liu, Xiansheng; Zhang, Weifeng; Qu, Shengchun; Wang, Zhijie; Wang, Zhanguo

    2017-01-01

    Constructing a highly efficient bulk-heterojunction is of critical importance to the hybrid organic/inorganic solar cells. Here in this work, we introduce a novel hybrid architecture containing P3HT nanowire and CdSe nanotetrapod as bicontinuous charge channels for holes and electrons, respectively. Compared to the traditionally applied P3HT molecules, the well crystallized P3HT nanowires qualify an enhanced light absorption at the long wavelength as well as strengthened charge carrier transport in the hybrid active layer. Accordingly, based on efficient dissociation of photogenerated excitons, the interpercolation of these two nano-building blocks allows a photovoltaic conversion efficiency of 1.7% in the hybrid solar cell, up to 42% enhancement compared to the reference solar cell with traditional P3HT molecules as electron donor. Our work provides a promising hybrid structure for efficient organic/inorganic bulk-heterojunction solar cells.

  11. Polymer-mediated nanorod self-assembly predicted by dissipative particle dynamics simulations.

    PubMed

    Khani, Shaghayegh; Jamali, Safa; Boromand, Arman; Hore, Michael J A; Maia, Joao

    2015-09-14

    Self-assembly of nanoparticles in polymer matrices is an interesting and growing subject in the field of nanoscience and technology. We report herein on modelling studies of the self-assembly and phase behavior of nanorods in a homopolymer matrix, with the specific goal of evaluating the role of deterministic entropic and enthalpic factors that control the aggregation/dispersion in such systems. Grafting polymer brushes from the nanorods is one approach to control/impact their self-assembly capabilities within a polymer matrix. From an energetic point of view, miscible interactions between the brush and the matrix are required for achieving a better dispersibility; however, grafting density and brush length are the two important parameters in dictating the morphology. Unlike in previous computational studies, the present Dissipative Particle Dynamics (DPD) simulation framework is able to both predict dispersion or aggregation of nanorods and determine the self-assembled structure, allowing for the determination of a phase diagram, which takes all of these factors into account. Three types of morphologies are predicted: dispersion, aggregation and partial aggregation. Moreover, favorable enthalpic interactions between the brush and the matrix are found to be essential for expanding the window for achieving a well-dispersed morphology. A three-dimensional phase diagram is mapped on which all the afore-mentioned parameters are taken into account. Additionally, in the case of immiscibility between brushes and the matrix, simulations predict the formation of some new and tunable structures.

  12. A general route to nanocrystal kebabs periodically assembled on stretched flexible polymer shish.

    PubMed

    Xu, Hui; Xu, Yuci; Pang, Xinchang; He, Yanjie; Jung, Jaehan; Xia, Haiping; Lin, Zhiqun

    2015-03-01

    Assembling nanoparticles into one-dimensional (1D) nanostructures with precisely controlled size and shape renders the exploration of new properties and construction of 1D miniaturized devices possible. The physical properties of such nanostructures depend heavily on the size, chemical composition, and surface chemistry of nanoparticle constituents, as well as the close proximity of adjacent nanoparticles within the 1D nanostructure. Chemical synthesis provides an intriguing alternative means of creating 1D nanostructures composed of self-assembled nanoparticles in terms of material diversity, size controllability, shape regularity, and low-cost production. However, this is an area where progress has been slower. We report an unconventional yet general strategy to craft an exciting variety of 1D nanonecklace-like nanostructures comprising uniform functional nanodiscs periodically assembled along a stretched flexible polymer chain by capitalizing on judiciously designed amphiphilic worm-like diblock copolymers as nanoreactors. These nanostructures can be regarded as organic-inorganic shish-kebabs, in which nanodisc kebabs are periodically situated on a stretched polymer shish. Simulations based on self-consistent field theory reveal that the formation of organic-inorganic shish-kebabs is guided by the self-assembled elongated star-like diblock copolymer constituents constrained on the highly stretched polymer chain.

  13. A general route to nanocrystal kebabs periodically assembled on stretched flexible polymer shish

    PubMed Central

    Xu, Hui; Xu, Yuci; Pang, Xinchang; He, Yanjie; Jung, Jaehan; Xia, Haiping; Lin, Zhiqun

    2015-01-01

    Assembling nanoparticles into one-dimensional (1D) nanostructures with precisely controlled size and shape renders the exploration of new properties and construction of 1D miniaturized devices possible. The physical properties of such nanostructures depend heavily on the size, chemical composition, and surface chemistry of nanoparticle constituents, as well as the close proximity of adjacent nanoparticles within the 1D nanostructure. Chemical synthesis provides an intriguing alternative means of creating 1D nanostructures composed of self-assembled nanoparticles in terms of material diversity, size controllability, shape regularity, and low-cost production. However, this is an area where progress has been slower. We report an unconventional yet general strategy to craft an exciting variety of 1D nanonecklace-like nanostructures comprising uniform functional nanodiscs periodically assembled along a stretched flexible polymer chain by capitalizing on judiciously designed amphiphilic worm-like diblock copolymers as nanoreactors. These nanostructures can be regarded as organic-inorganic shish-kebabs, in which nanodisc kebabs are periodically situated on a stretched polymer shish. Simulations based on self-consistent field theory reveal that the formation of organic-inorganic shish-kebabs is guided by the self-assembled elongated star-like diblock copolymer constituents constrained on the highly stretched polymer chain. PMID:26601151

  14. Dendronized Polymers: Synthesis, Characterization, Assembly at Interfaces, and Manipulation.

    PubMed

    Schlüter; Rabe

    2000-03-01

    Dendrimers are presently one of the most intensely studied classes of compounds because of their unusual structure. They can be described as a jungle of entangled branches traversed by winding trails which lead to sweet fruits and bright blossoms. On these trails one can reach the thicket's interior as well as find a way out. Expressed less lyrically, this thicket stands for regularly branched, densely packed structures, and the trails represent voids and channels not filled by bent back branches but by solvent. The fruit and blossoms are photochemically, electrochemically, or synthetically addressable units, catalytically active sites, etc., and the back and forth on the trails stands for transport processes. In a mathematical sense dendrimers are enveloped by an interface, which defines what is either in or out. This interface is shaped like a sphere if the trails are filled to bursting. Otherwise dendrimers are more flattened like amoeba, especially if in contact with a surface. The high density of the functional groups, the expansion of these compounds to a range of several nanometers, the existence of usable "surface" and transport possibilities in and with them have made dendrimers interesting candidates for many applications. This review describes how dendrimer construction and polymer synthesis were combined and used to move from fully or flattened spherical shapes to cylindrical ones. The shape-inducing influence of dendritic substituents can be driven to create nanoobjects with a cylindrical shape, which not only considerably widens the range of applications for the dendrimer class but also opens up new perspectives for supramolecular and polymer chemistry. Because of the sheer size of the described objects and complexity of shape-related properties, research in this area must necessarily be interdisciplinary. This article tries to mirror this by giving special attention not only to synthesis but also the characterization and behavior of these compounds

  15. Self-assembly of three-dimensional supramolecular polymers through cooperative tetrathiafulvalene radical cation dimerization.

    PubMed

    Tian, Jia; Ding, Yu-Di; Zhou, Tian-You; Zhang, Kang-Da; Zhao, Xin; Wang, Hui; Zhang, Dan-Wei; Liu, Yi; Li, Zhan-Ting

    2014-01-07

    The self-assembly of a new type of three-dimensional (3D) supramolecular polymers from tetrahedral monomers in both organic and aqueous media is described. We have designed and synthesized two tetraphenylmethane derivatives T1 and T2, both of which bear four tetrathiafulvalene (TTF) units. When the TTF units were oxidized to the radical cation TTF(.+) , their pre-organized tetrahedral arrangement remarkably enhanced their intermolecular dimerization, leading to the formation of new 3D spherical supramolecular polymers. The structure of the supramolecular polymers has been inferred on the basis of UV/Vis absorption, electron paramagnetic resonance, cyclic voltammetry, and dynamic light scattering (DLS) analysis, as well as by comparing these properties with those of the self-assembled structures of mono-, di-, and tritopic control compounds. DLS experiments revealed that the spherical supramolecular polymers had hydrodynamic diameters of 68 nm for T1 (75 μM) in acetonitrile and 105 nm for T2 (75 μM) in water/acetonitrile (1:1). The 3D spherical structures of the supramolecular polymers formed in different solvents were also supported by SEM and AFM experiments.

  16. Novel thermoresponsive assemblies of co-grafted natural and synthetic polymers for water purification.

    PubMed

    Paneysar, Joginder Singh; Barton, Stephen; Chandra, Sudeshna; Ambre, Premlata; Coutinho, Evans

    2017-03-01

    Water contamination and its purification are a global problem. The current approach to purify water is reduction of impurities to acceptable levels. One of the ways to achieve this is by use of water-soluble polymers that extract organic and metallic contaminants, from water. This paper presents a blend of composite polymers that eliminates both the contaminants simultaneously by the principle of adsorption at lower critical solution temperature. These composite polymers have been synthesized by grafting poly(N,N-diethylacrylamide), poly(N-isopropylacrylamide) and poly(N-vinylcaprolactam) on-to the natural polymer chitosan or its derivatives, giving smart graft polymeric assemblies (GPAs). One of the graft polymers, GPA-2, exhibits excellent adsorption properties able to remove metal ions like cadmium, cobalt, copper, lead, iron and also organic impurities like chlorophenol and phthalic anhydride. Studies reveal that 6 mg/ml GPA-2 is able to effect a 100% removal of organic impurities - chlorophenol (50 ppm) and phthalic anhydride (70 ppm) - from water, while complete removal of the heavy metal ions (Cu(+2), Co(+2) and Cd(+2)) together at 30 ppm concentration has been achieved with 7.5 mg/ml GPA-2. The reduction in level of impurities along with recyclability and reproducibility in the elimination spectrum makes these assemblies promising materials in water treatment.

  17. Preparation of protein nano-objects by assembly of polymer-grafted proteins.

    PubMed

    Fukui, Yuuka; Sakai, Daiki; Fujimoto, Keiji

    2016-12-01

    We carried out surface-grafting from proteins and their assembling into objects with unique nanostructured materials (nano-objects). To immobilize polymer-initiating sites, amino groups of bovine serum albumin (BSA) were allowed to react with iniferter groups (BSA-i). Then, graft polymerization of N-isopropyl acrylamide (NIPAM) was performed by light-initiated living radical polymerization from immobilized iniferter moieties of BSA-i. The polymer-grafted BSA (BSA-g-PNIPAM) was assembled into nano-objects through the precipitation of PNIPAM graft chains and their sizes and morphologies were tuned by the chain length, the density and the chemical structure of graft polymers in addition to the environmental conditions such as temperature and pH. It was possible to retain the structures of nano-objects by thermal denaturation via heat treatment. Fluorescent substances were encapsulated in particulate nano-objects (nanoparticles) assembled from PNIPAM-g-BSA and their release could be regulated by tuning pH and temperature. Next, further graft polymerization from PNIPAM-grafted BSA was carried out by living radical polymerization of a cationic monomer, N,N-dimethylamino propyl acrylamide methyl chloride quaternary (DMAPAAQ). The grafted polymer was composed of a block copolymer of PNIPAM and a cationic polymer (PDMAPAAQ) and the gel-like nano-object was generated by increasing temperature. In contrast to PNIPAM-g-BSA, it became insoluble even when the temperature decreased, probably due to the electrostatic association between anionic regions of BSA and cationic regions of graft polymers. Coating of BSA-g-P(NIPAM-b-DMAPAAQ) enabled to form a uniform thin layer over a human hair. A free-standing membrane could be obtained by peeling from a water repellent substrate to create a porous membrane.

  18. In Situ Assembly of Ultrathin PtRh Nanowires to Graphene Nanosheets as Highly Efficient Electrocatalysts for the Oxidation of Ethanol.

    PubMed

    Shen, Yi; Gong, Bin; Xiao, Kaijun; Wang, Lei

    2017-02-01

    One-dimensional (1D) anisotropic platinum-based nanowires are promising electrocatalysts in polymer electrolyte membrane fuel cells owing to the inherent structural merits. Herein, we report an in situ growth of ultrathin PtRh nanowires (diameters of 2-3 nm) on graphene nanosheets via the oriented attachment pathway. Mechanistic studies reveal that graphene nanosheets play a critical role in the nucleation and growth of PtRh nanowires. The resulting hybrid of PtRh nanowire decorated graphene nanosheets shows outstanding activity and durability toward ethanol electro-oxidation. It exhibits a specific current density of 2.8 mA cm(-2) and a mass-normalized current density of 1 A mg(-1) metal, which are 5.4 and 3.1 times those of the state-of-the-art Pt/C catalyst, respectively. After 2000 cyclic tests, it maintains 86% of the initial electrochemically active surface area, which is larger than that of 63% obtained from the Pt/C catalyst. The superior performance is attributed to the combination of the advantageous 1D morphological motif with the synergistic effects of PtRh alloys and graphene nanosheet support.

  19. Thermal stability of electrodeposited platinum nanowires and morphological transformations at elevated temperatures.

    PubMed

    Rauber, M; Muench, F; Toimil-Molares, M E; Ensinger, W

    2012-11-30

    Pt nanowires were prepared by template electrodeposition using ion track etched polymer membranes and analysed with respect to their thermal stability. Driven by Rayleigh instability, the polycrystalline Pt nanostructures experienced structural transformations and finally fragmented into linear chains of nanospheres at temperatures much below the melting point of bulk Pt. Morphological changes were systematically studied by electron microscopy and compared with previously reported results on other metal nanowires and theoretical predictions. In addition, nanowires could readily be interconnected to two-dimensional assemblies by taking advantage of the rapid diffusion processes. This study will help to predict the durability of integrated nanowires and contributes to the understanding of thermal-induced transformations for polycrystalline nanowires.

  20. Self Assembled Spin Coated and Bulk Films of a Novel Polydiacetylene as Second Order NLO Polymers

    DTIC Science & Technology

    1994-05-31

    T Code: 4132016 W.H. Kim, B. Bihari, R. Moody, N. B. Kodali , J.KumarS.K. Dr. JoAnn Milliken Tripathy. 7. PHI-OUHMING OFH-NIZATION NAMIE(S) AND...Self Assembled Spin Coated and Bulk Films of a Novel Polydiacetylene as Second Order NLO Polymers by W.H. Kim, B. Bihari, R. Moody, N. B. Kodali ...POLYMERS W. H. Kim, B. Bihari+, R. Moody+, N. B. Kodali , J. Kumar+, and S. K. Tripathy, University of Massachusetts-Lowell, Center for Advanced Materials

  1. Controlling self-assembly and ordering of block polymer nanostructures in thin films

    NASA Astrophysics Data System (ADS)

    Luo, Ming

    Block polymers have garnered significant attention in the past few decades due to their ability to self-assemble into a boundless array of structures such as spheres, cylinders, gyroid, and lamellae. The sizes of the periodical structures typically are 5 - 100 nm, making them ideal for emerging nanotechnologies, such as nanolithography, nanotemplating, nanoporous membranes, and photonics devices. Many of these applications require thin film geometries, in which the block polymers form well-ordered nanostructures and precisely controlled domain orientations. Understanding the factors that affect thin film phase behavior and being able to control the nanostructures, domain orientation, and domain ordering in thin film is essential to realizing the full potential of these unique materials. In this dissertation, I describe significant efforts to manipulate the block polymer thin film structures, direct the nanostructure ordering, and understand the connection between the macromolecular molecular structures and the block polymer properties. First, substrate surface modification with chlorosilane was employed to manipulate the nanostructure of poly(styrene- b-isoprene-b-styrene) (SIS) thin films. A morphological transformation from parallel cylinders to hexagonally perforated lamellae (HPL) was identified, in a high-throughput fashion, using gradient methods. The gradient methods are highly adaptable for the possible universal manipulation of thin film nanostructures. Second, rastering solvent vapor annealing - soft shear method was developed and demonstrated as a simple, yet highly effective method to achieve macroscopic alignment of SIS cylinders. This method substantially improves on previous approaches by using simple instrumentation to unlock an array of alignment patterns with a variety of self-assembling polymers and provides feasibility and flexibility for practical industrial production. Next, the interfacial mixing characteristics of tapered block polymer were

  2. Surfactant self-assembly in oppositely charged polymer networks. Theory.

    PubMed

    Hansson, Per

    2009-10-01

    The interaction of ionic surfactants with polyion networks of opposite charge in an aqueous environment is analyzed theoretically by applying a recent theory of surfactant ion-polyion complex salts (J. Colloid. Int. Sci. 2009, 332, 183). The theory takes into account attractive and repulsive polyion-mediated interactions between the micelles, the deformation of the polymer network, the mixing of micelles, polyion chains, and simple ions with water, and the hydrophobic free energy at the micelle surface. The theory is used to calculate binding isotherms, swelling isotherms, surfactant aggregation numbers, compositions of complexes,and phase structure under various conditions. Factors controlling the gel volume transition and conditions for core/shell phase coexistence are investigated in detail, as well as the influence of salt. In particular, the interplay between electrostatic and elastic interactions is highlighted. Results from theory are compared with experimental data reported in the literature. The agreement is found to be semiquantitative or qualitative. The theory explains both the discrete volume transition observed in systems where the surfactant is in excess over the polyion and the core/shell phase coexistence in systems where the polyion is in excess.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  4. High-performance ambipolar self-assembled Au/Ag nanowire based vertical quantum dot field effect transistor

    NASA Astrophysics Data System (ADS)

    Song, Xiaoxian; Zhang, Yating; Zhang, Haiting; Yu, Yu; Cao, Mingxuan; Che, Yongli; Wang, Jianlong; Dai, Haitao; Yang, Junbo; Ding, Xin; Yao, Jianquan

    2016-10-01

    Most lateral PbSe quantum dot field effect transistors (QD FETs) show a low on current/off current (I on/I off) ratio in charge transport measurements. A new strategy to provide generally better performance is to design PbSe QD FETs with vertical architecture, in which the structure parameters can be tuned flexibly. Here, we fabricated a novel room-temperature operated vertical quantum dot field effect transistor with a channel of 580 nm, where self-assembled Au/Ag nanowires served as source transparent electrodes and PbSe quantum dots as active channels. Through investigating the electrical characterization, the ambipolar device exhibited excellent characteristics with a high I on/I off current ratio of about 1 × 105 and a low sub-threshold slope (0.26 V/decade) in the p-type regime. The all-solution processing vertical architecture provides a convenient way for low cost, large-area integration of the device.

  5. From single atoms to self-assembled quantum single-atomic nanowires: noble metal atoms on black phosphorene monolayers.

    PubMed

    Zhao, X J; Shan, Wen-Wen; He, Hao; Xue, Xinlian; Guo, Z X; Li, S F

    2017-03-15

    Transition metal (TM) nanostructures, such as one dimensional (1D) nanowires with/without substrates, usually possess drastically different properties from their bulk counterparts, due to their distinct stacking and electronic confinement. Correspondingly, it is of great importance to establish the dominant driving force in forming 1D single-metal-atom-wires (SMAWs). Here, with first-principles calculations, taking the black phosphorene (BP) monolayer as a prototype 2D substrate, we investigate the energetic and kinetic properties of all the 5d-TM atoms on the 2D substrate to reveal the mechanism of formation of SMAWs. In contrast to other 5d- and 4d-TMs, noble metal elements Pd and Pt are found to prefer to grow along the trough in an atom-by-atom manner, self-assembling into SMAWs with a significant magic growth behavior. This is due to distinct binding energies and diffusion barriers along the trough, i.e., zig-zag direction, as compared to other directions of the BP. The present findings are valuable in the fabrication and modulation of 1D nanostructures which can be anticipated to possess desirable functionalities for potential applications such as in nanocatalysis, nanosensors, and related areas.

  6. High-performance ambipolar self-assembled Au/Ag nanowire based vertical quantum dot field effect transistor.

    PubMed

    Song, Xiaoxian; Zhang, Yating; Zhang, Haiting; Yu, Yu; Cao, Mingxuan; Che, Yongli; Wang, Jianlong; Dai, Haitao; Yang, Junbo; Ding, Xin; Yao, Jianquan

    2016-10-07

    Most lateral PbSe quantum dot field effect transistors (QD FETs) show a low on current/off current (I on/I off) ratio in charge transport measurements. A new strategy to provide generally better performance is to design PbSe QD FETs with vertical architecture, in which the structure parameters can be tuned flexibly. Here, we fabricated a novel room-temperature operated vertical quantum dot field effect transistor with a channel of 580 nm, where self-assembled Au/Ag nanowires served as source transparent electrodes and PbSe quantum dots as active channels. Through investigating the electrical characterization, the ambipolar device exhibited excellent characteristics with a high I on/I off current ratio of about 1 × 10(5) and a low sub-threshold slope (0.26 V/decade) in the p-type regime. The all-solution processing vertical architecture provides a convenient way for low cost, large-area integration of the device.

  7. Polymer Directed Self-Assembly of pH-Responsive Antioxidant Nanoparticles

    PubMed Central

    Tang, Christina; Amin, Devang; Messersmith, Phillip B.; Anthony, John E.; Prud’homme, Robert K.

    2015-01-01

    We have developed pH-responsive, multifunctional nanoparticles based on encapsulation of an antioxidant, tannic acid (TA), using Flash NanoPrecipitation, a polymer directed self-assembly method. Formation of insoluble coordination complexes of tannic acid and iron during mixing drives nanoparticle assembly. Tuning the core material to polymer ratio, the size of the nanoparticles can be readily tuned between 50 and 265 nm. The resulting nanoparticle is pH-responsive, i.e. stable at pH 7.4 and soluble under acidic conditions due to the nature of the coordination complex. Further, the coordination complex can be coprecipitated with other hydrophobic materials such as therapeutics or imaging agents. For example, coprecipitation with a hydrophobic fluorescent dye creates fluorescent nanoparticles. In vitro, the nanoparticles have low cytotoxicity show antioxidant activity. Therefore, these particles may facilitate intracellular delivery of antioxidants. PMID:25760226

  8. Polymer directed self-assembly of pH-responsive antioxidant nanoparticles.

    PubMed

    Tang, Christina; Amin, Devang; Messersmith, Phillip B; Anthony, John E; Prud'homme, Robert K

    2015-03-31

    We have developed pH-responsive, multifunctional nanoparticles based on encapsulation of an antioxidant, tannic acid (TA), using flash nanoprecipitation, a polymer directed self-assembly method. Formation of insoluble coordination complexes of tannic acid and iron during mixing drives nanoparticle assembly. Tuning the core material to polymer ratio, the size of the nanoparticles can be readily tuned between 50 and 265 nm. The resulting nanoparticle is pH-responsive, i.e., stable at pH 7.4 and soluble under acidic conditions due to the nature of the coordination complex. Further, the coordination complex can be coprecipitated with other hydrophobic materials such as therapeutics or imaging agents. For example, coprecipitation with a hydrophobic fluorescent dye creates fluorescent nanoparticles. In vitro, the nanoparticles have low cytotoxicity and show antioxidant activity. Therefore, these particles may facilitate intracellular delivery of antioxidants.

  9. Markov model-based polymer assembly from force field-parameterized building blocks

    NASA Astrophysics Data System (ADS)

    Durmaz, Vedat

    2015-03-01

    A conventional by hand construction and parameterization of a polymer model for the purpose of molecular simulations can quickly become very work-intensive and time-consuming. Using the example of polyglycerol, I present a polymer decompostion strategy yielding a set of five monomeric residues that are convenient for an instantaneous assembly and subsequent force field simulation of a polyglycerol polymer model. Force field parameters have been developed in accordance with the classical Amber force field. Partial charges of each unit were fitted to the electrostatic potential using quantum-chemical methods and slightly modified in order to guarantee a neutral total polymer charge. In contrast to similarly constructed models of amino acid and nucleotide sequences, the glycerol building blocks may yield an arbitrary degree of bifurcations depending on the underlying probabilistic model. The iterative development of the overall structure as well as the relation of linear to branching units is controlled by a simple Markov model which is presented with few algorithmic details. The resulting polymer is highly suitable for classical explicit water molecular dynamics simulations on the atomistic level after a structural relaxation step. Moreover, the decomposition strategy presented here can easily be adopted to many other (co)polymers.

  10. Controlling the assembly of nanoparticle mixtures with two orthogonal polymer complexation reactions.

    PubMed

    Zhang, Dan; Pelton, Robert

    2012-02-14

    Self-assembly from mixed dispersions of three sizes of monodisperse polystyrene nanoparticles, large (L), medium (M), and small (S), was controlled by coating each particle type with either a monofunctional or bifunctional polymer capable of participating in specific complexation reactions. The complexation reactions were (1) complexation between phenolic polymers and polyethylene glycol (PEG) containing polymers and (2) condensation of phenylboronic acid containing polymers with polyols. These complexation reactions function independently and can be "turned off" independently; phenylboronic acid complexation was reversed by lowering the pH, whereas the interactions of phenolic copolymers with PEG copolymers could be reversed by adding excess PEG homopolymer. The specificity and reversibility of the interactions was demonstrated by the formation of simple binary aggregates from mixtures. The bifunctional copolymers were poly(vinyl phenol-co-diallyldimethyl ammonium chloride), Ph-DADMAC, and poly(3-acrylamide phenylboronic acid-co-PEG methacrylate), PBA-PEG. The monofunctional polymer was polyvinylalcohol, PVA. Ph-DADMAC forms complexes with PBA-PEG (H-bonding) and with anionic surfaces or polymers (electrostatic/polyelectrolyte complexation). PBA-PEG complexes with Ph-DADMAC (H-bonding) and with PVA (boronate ester formation). PVA does not interact with Ph-DADMAC; therefore, PVA coated particles do not deposit onto Ph-DADMAC coated particles.

  11. Assembly of polythiophenes on responsive polymer microgels for the highly selective detection of ammonia gas

    SciTech Connect

    Chang, Aiping; Peng, Yahui; Li, Zezhou; Yu, Xiang; Hong, Kunlun; Zhou, Shuiqin; Wu, Weitai

    2016-04-05

    For this study, a class of smart composite materials based on the assembly of conjugated polymers on responsive polymer microgels has been prepared. We have chosen poly(3-((2-(2-methoxyethoxy)ethoxy)methyl)-thiophene) as the model conjugated polymer and an ammonia-responsive microgel of phenoxazinium-functionalized poly(N-isopropylacrylamide-co-propargyl acrylate) as the model template. Under this design, the composite materials can combine the electrical conductivity of the conjugated polymers and the ammonia recognisability of the ammonia-responsive polymer microgels; the cooperation of these properties allows the reversible control of electrical conductivity by ammonia gas. Those composite materials can not only adapt to ammonia gas, but also convert changes in the concentration of ammonia into conductance, allowing the electrical detection of ammonia gas with high selectivity. This makes the composite materials different from the conductive polymer platforms reported previously, which may also respond to non-ammonia gases and the response induced by non-ammonia gases is close to that induced by ammonia gas. Using these composite materials as sensing materials for the electrical detection of ammonia gas, the detection limit can reach as low as 1.1 ppb. Finally, these features enable their use for the electrical detection of ammonia in breath.

  12. Assembly of polythiophenes on responsive polymer microgels for the highly selective detection of ammonia gas

    DOE PAGES

    Chang, Aiping; Peng, Yahui; Li, Zezhou; ...

    2016-04-05

    For this study, a class of smart composite materials based on the assembly of conjugated polymers on responsive polymer microgels has been prepared. We have chosen poly(3-((2-(2-methoxyethoxy)ethoxy)methyl)-thiophene) as the model conjugated polymer and an ammonia-responsive microgel of phenoxazinium-functionalized poly(N-isopropylacrylamide-co-propargyl acrylate) as the model template. Under this design, the composite materials can combine the electrical conductivity of the conjugated polymers and the ammonia recognisability of the ammonia-responsive polymer microgels; the cooperation of these properties allows the reversible control of electrical conductivity by ammonia gas. Those composite materials can not only adapt to ammonia gas, but also convert changes in the concentrationmore » of ammonia into conductance, allowing the electrical detection of ammonia gas with high selectivity. This makes the composite materials different from the conductive polymer platforms reported previously, which may also respond to non-ammonia gases and the response induced by non-ammonia gases is close to that induced by ammonia gas. Using these composite materials as sensing materials for the electrical detection of ammonia gas, the detection limit can reach as low as 1.1 ppb. Finally, these features enable their use for the electrical detection of ammonia in breath.« less

  13. Directed self-assembly of block copolymers for high breakdown strength polymer film capacitors

    SciTech Connect

    Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim; Yager, Kevin G.; Yuan, Guangcui; Satija, Sushil K.; Durstock, Michael F.; Raghavan, Dharmaraj; Karim, Alamgir

    2016-03-04

    Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (EBD) and dielectric permittivity (εr) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher EBD over that of component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ~50% enhancement in EBD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in EBD is attributed to the “barrier effect”, where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in EBD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. Lastly, this approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.

  14. Polymer Grafted Nanoparticle Assemblies: From Optical to Mechanical Performance through Clusters, Monolayers and Monoliths

    NASA Astrophysics Data System (ADS)

    Vaia, Richard

    Solution or melt-based fabrication of large area, matrix-free, ordered assemblies of polymer grafted nanoparticles (PGN) will enable additive manufacturing of novel membrane, electronic, and photonic elements. Due to the single component nature of these hybrids, aggregation and phase separation common in blended polymer nanocomposites are avoided. Architecturally, PGNs combine characteristics of colloids, brushes and high molecular weight polymers. Thus the processing-structure-property relationship of the entangled PGN assembly is unique from analogous condensed nano-structures, such as ligand stabilized nanoparticles, hard-sphere colloids, star macromolecules and linear chain - nanoparticle blends. Here in, we will discuss the intermediate character of PGNs with respect to deformability, physical aging, and rapid fabrication of stable, large-area, ordered PGN monolayers. For example, processing via flow coating follows that of classic colloids; however local structure and order within the PGN assembly is determined by the canopy architecture and substrate interactions. From this insight, large-area (cm2), highly-ordered, monolayer polystyrene-Au nanoparticle films that are resistant to de-wetting can be fabricated on substrates with high interface energy (80 mN/m) within seconds using flow-coating and a volatile solvent (THF). Overall these findings imply intriguing parallels between PGN assemblies and other mesoscale ordered polymeric systems including hard-soft block copolymers and semi-crystalline polymers. With the appropriate corona architecture, PGNs afford opportunities to design high inorganic fraction hybrids that retain processibility and enable the creation of films and fibers for next generation optoelectronic applications. Aknowledgement: Justin Che, Christopher A. Grabowski, Yang Jiao, Ming-Siao Hsiao, Kyoungweon Park, Lawrence Drummy.

  15. Simultaneous Nano- and Microscale Control of Nanofibrous Microspheres Self-Assembled from Star-Shaped Polymers.

    PubMed

    Zhang, Zhanpeng; Marson, Ryan L; Ge, Zhishen; Glotzer, Sharon C; Ma, Peter X

    2015-07-08

    Star-shaped polymers with varying arm numbers and arm lengths are synthesized, and self-assembled into microspheres, which are either smooth or fibrous on the nanoscale, and either nonhollow, hollow, or spongy on the microscale. The molecular architecture and functional groups determine the structure on both length scales. This exciting mechanistic discovery guides simultaneous control of both the nano- and microfeatures of the microspheres.

  16. Directed self-assembly of block copolymers for high breakdown strength polymer film capacitors

    DOE PAGES

    Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim; ...

    2016-03-04

    Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (EBD) and dielectric permittivity (εr) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher EBD over that of component polymers. Multilayeredmore » films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ~50% enhancement in EBD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in EBD is attributed to the “barrier effect”, where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in EBD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. Lastly, this approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.« less

  17. Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors.

    PubMed

    Samant, Saumil P; Grabowski, Christopher A; Kisslinger, Kim; Yager, Kevin G; Yuan, Guangcui; Satija, Sushil K; Durstock, Michael F; Raghavan, Dharmaraj; Karim, Alamgir

    2016-03-01

    Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (EBD) and dielectric permittivity (εr) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher EBD over that of component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ∼50% enhancement in EBD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in EBD is attributed to the "barrier effect", where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in EBD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. This approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.

  18. Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

    PubMed Central

    Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

    2013-01-01

    Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

  19. Polymer-Carbon Nanotube Composite Films at the Oil/Water Interface: Assembly and Properties

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Feng, Tao; Russell, Thomas P.

    2015-03-01

    Efficient carbon nanotube assembly at the oil/water interface was achieved by dissolving cationic polymers in the oil phase and oxidized nanotubes in the water phase, the two components spontaneously forming salt bridges to produce a composite interfacial film of nanoscopic thickness. As seen by pendant drop tensiometry, parameters such as carbon nanotube and polymer concentration, pH, polymer molecular weight, and degree of nanotube oxidation all affect assembly strongly, with measured trends to be described and explained. The frequency-dependent elastic and viscous moduli of films in dilation were characterized by interfacial pendant drop rheology. Structural (fast, minutes) and adsorption/desorption (slow, tens of minutes) relaxations were both noted, and at frequencies intermediate to the two, almost insensitive to assembly parameters, the films displayed expected behaviors for 2D critical gels, i.e., at the crossover between fluid and solid. Tan(delta) was frequency-independent over one to two decades of frequency, and the modulus of linear stress relaxation was a power law in time. Films wrinkled by larger (nonlinear) strains recovered over the structural relaxation time. Support: NSF-sponsored UMass MRSEC and the US DoE Office of Basic Energy Science through Contract DE-FG02-04ER46126.

  20. Tuning assembly size in Peptide-based supramolecular polymers by modulation of subunit association affinity.

    PubMed

    Oshaben, Kaylyn M; Horne, W Seth

    2014-04-14

    Nature uses proteins and nucleic acids to form a wide array of functional architectures, and scientists have found inspiration from these structures in the rational design of synthetic biomaterials. We have recently shown that a modular subunit consisting of two α-helical coiled coil peptides attached at their midpoints by an organic linking group can spontaneously self-assemble in aqueous solution to form a soluble supramolecular polymer. Here we explore the use of coiled-coil association affinity, readily tuned by amino acid sequence, as a means to predictably alter properties of these supramolecular assemblies. A series of dimeric coiled-coil peptide sequences with identical quaternary folded structures but systematically altered folded stability were designed and biophysically characterized. The sequences were cross-linked to generate a series of branched, self-assembling biomacromolecular subunits. A clear relationship is observed between coiled-coil association affinity and apparent hydrodynamic diameter of the supramolecular polymers formed by these subunits. Our results provide a family of soluble supramolecular polymers of tunable size and well-characterized coiled-coil sequences that add to the library of building blocks available for use in the rational design of protein-based supramolecular biomaterials.

  1. Electrospun conjugated polymer nanofibers as miniaturized light sources: control of morphology, optical properties, and assembly

    NASA Astrophysics Data System (ADS)

    Camposeo, A.; Fasano, V.; Moffa, M.; Polini, A.; Di Camillo, D.; Ruggieri, F.; Santucci, S.; Lozzi, L.; Persano, L.; Pisignano, D.

    2014-10-01

    Light-emitting nanostructures made by conjugated polymers show interesting emission and electronic properties. In this work we report on novel approaches for the fabrication and control of light-emitting nanofibers by electrospinning. The shape, size and light-emitting properties of the fibers can be specifically tailored by acting on the composition of the solution used for the electrospinning process, an approach allowing for obtaining fibers ranging from micrometer-sized ribbons to almost cylindrical fibers with diameters down to few hundreds of nanometers. Moreover, following proper process optimization these fibers can also be precisely positioned in ordered arrays by near-field electrospinning, a method that exploits the stable region of the polymer jet. The possibility of precisely shaping the conjugated polymer fibers and of assembling the fiber in ordered arrays, combined with enhanced emission properties, opens interesting perspectives for developing novel emitting flexible nanomaterials suitable for light sourcing and optical sensing.

  2. Minimal energy packings of weakly semiflexible polymers: Application to targeted self-assembly of nanostructures

    NASA Astrophysics Data System (ADS)

    Harwayne-Gidansky, Jared; Hoy, Robert S.; O'Hern, Corey S.

    2012-02-01

    Using exact enumeration, we characterize how structure, mechanical and thermodynamic stability of minimal energy packings of short ``sticky tangent sphere'' (SHS) polymer chains vary with angular interaction strength kb and equilibrium bond angle θ0. While flexible SHS polymers possess highly degenerate ground states (i. e. many differently ordered ``macrostates'' [1]), angular interactions dramatically break this degeneracy. The macrostate associated with the ground state semiflexible packing changes as kb and θ0 are varied. Further degeneracy breaking arises from angular interactions' influence on packing size, asymmetry, and vibrational entropy. The strength of these effects increases with chain length N. Our exact analysis provides design principles for self-assembly of polymers into a variety of structures that can be tuned by varying N, kb and θ0. [4pt] [1] R. S. Hoy and C. S. O'Hern, Phys. Rev. Lett. 105, 068001 (2010).

  3. Anisotropic Self-Assembly of Supramolecular Polymers and Plasmonic Nanoparticles at the Liquid-Liquid Interface.

    PubMed

    Armao Iv, Joseph J; Nyrkova, Irina; Fuks, Gad; Osypenko, Artem; Maaloum, Mounir; Moulin, Emilie; Arenal, Raul; Gavat, Odile; Semenov, Alexander; Giuseppone, Nicolas

    2017-02-15

    The study of supramolecular polymers in the bulk, in diluted solution, and at the solid-liquid interface has recently become a major topic of interest, going from fundamental aspects to applications in materials science. However, examples of supramolecular polymers at the liquid-liquid interface are mostly unexplored. Here, we describe the supramolecular polymerization of triarylamine molecules and their light-triggered organization at a chloroform-water interface. The resulting interfacial nematic layer of these 1D supramolecular polymers is further used as a template for the precise alignment of spherical gold nanoparticles coming from the water phase. These hybrid thin films are spontaneously formed in a single process, without chemical prefunctionalization of the metallic nanoparticles, and their ordering is improved by centrifugation. The resulting polymer chains and strings of nanoparticles can be co-aligned with high anisotropy over very large distances. By using a combination of experimental and theoretical investigations, we decipher the full sequence of this oriented self-assembly process. In such a highly anisotropic configuration, electron energy loss spectroscopy reveals that the self-assembled nanoparticles behave as plasmonic waveguides.

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

    PubMed

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Hu, Hanlin; Amassian, Aram

    2016-08-03

    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 substrate with solution-state disentanglement and preaggregation of P3HT in a θ solvent, leading to a very significant enhancement of the field effect carrier mobility. The preaggregation 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 preaggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of preaggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to unaggregated polymer chains in the same conditions. Additional measurements reveal the combined preaggregation 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 preaggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  5. All Nanowire Integrated Sensor Circuitry

    DTIC Science & Technology

    2008-04-01

    of single crystalline nanomaterials. Highly ordered and parallel arrays of optically active CdSe nanowires and high mobility Ge/Si nanowires are...for enabling the fabrication of the all- nanowire sensor circuitry. First, highly aligned CdSe and Ge/Si NW arrays were assembled at pre-defined...FETs (Tl and T2) amplifying the photoresponse of a CdSe nanosensor. (B) Schematic of the all- nanowire optical sensor circuit based on ordered

  6. Conjugated polymer-silicon nanowire array hybrid Schottky diode for solar cell application.

    PubMed

    Zhang, Fute; Song, Tao; Sun, Baoquan

    2012-05-17

    The hybrid Schottky diode based on silicon nanowire arrays (SiNWs) and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) has been fabricated for high performance solar cells. The length of SiNWs on a silicon substrate, which is prepared by metal-assisted chemical etching, can be tuned by adjusting the length of the etching time. In addition, the average distances between the adjacent silicon nanowires can be controlled by changing the immersing time in a saturated PCl(5) solution. The hybrid devices are made from the SiNWs with different wire lengths and various distances between adjacent wires by spin-casting PEDOT:PSS on the silicon substrates. It is found that the length and density play leading roles in the electric output characteristics. The device made from SiNWs with optimum morphology can achieve a power conversion efficiency of 7.3%, which is much improved in comparison with that of the planar one. The measurement of the transient photovoltage decay and the analysis of the current versus voltage curve indicate that the charge recombination process is a dominant factor on the device performance.

  7. Conjugated polymer-silicon nanowire array hybrid Schottky diode for solar cell application

    NASA Astrophysics Data System (ADS)

    Zhang, Fute; Song, Tao; Sun, Baoquan

    2012-05-01

    The hybrid Schottky diode based on silicon nanowire arrays (SiNWs) and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) has been fabricated for high performance solar cells. The length of SiNWs on a silicon substrate, which is prepared by metal-assisted chemical etching, can be tuned by adjusting the length of the etching time. In addition, the average distances between the adjacent silicon nanowires can be controlled by changing the immersing time in a saturated PCl5 solution. The hybrid devices are made from the SiNWs with different wire lengths and various distances between adjacent wires by spin-casting PEDOT:PSS on the silicon substrates. It is found that the length and density play leading roles in the electric output characteristics. The device made from SiNWs with optimum morphology can achieve a power conversion efficiency of 7.3%, which is much improved in comparison with that of the planar one. The measurement of the transient photovoltage decay and the analysis of the current versus voltage curve indicate that the charge recombination process is a dominant factor on the device performance.

  8. Tunable Self-Assembly of Genetically Engineered Silk-Elastin-Like Protein Polymers

    PubMed Central

    Xia, Xiao-Xia; Xu, Qiaobing; Hu, Xiao; Qin, Guokui; Kaplan, David L.

    2011-01-01

    Silk-elastin-like protein polymers (SELPs), consisting of the repeating units of silk and elastin blocks, combine a set of outstanding physical and biological properties of silk and elastin. Due to the unique properties, SELPs have been widely fabricated into various materials for the applications in drug delivery and tissue engineering. However, little is known about the fundamental self-assembly characteristics of these remarkable polymers. Here we propose a two-step self-assembly process of SELPs in aqueous solution for the first time and report the importance of the ratio of silk to elastin blocks in a SELP’s repeating unit on the assembly of the SELP. Through precise tuning of the ratio of silk to elastin, various structures including nanoparticles, hydrogels and nanofibers could be generated either reversibly or irreversibly. This assembly process might provide opportunities to generate innovative smart materials for biosensors, tissue engineering and drug delivery. Furthermore, the newly developed SELPs in this study may be potentially useful as biomaterials for controlled drug delivery and biomedical engineering. PMID:21955178

  9. Tunable self-assembly of genetically engineered silk--elastin-like protein polymers.

    PubMed

    Xia, Xiao-Xia; Xu, Qiaobing; Hu, Xiao; Qin, Guokui; Kaplan, David L

    2011-11-14

    Silk--elastin-like protein polymers (SELPs), consisting of the repeating units of silk and elastin blocks, combine a set of outstanding physical and biological properties of silk and elastin. Because of the unique properties, SELPs have been widely fabricated into various materials for the applications in drug delivery and tissue engineering. However, little is known about the fundamental self-assembly characteristics of these remarkable polymers. Here we propose a two-step self-assembly process of SELPs in aqueous solution for the first time and report the importance of the ratio of silk-to-elastin blocks in a SELP's repeating unit on the assembly of the SELP. Through precise tuning of the ratio of silk to elastin, various structures including nanoparticles, hydrogels, and nanofibers could be generated either reversibly or irreversibly. This assembly process might provide opportunities to generate innovative smart materials for biosensors, tissue engineering, and drug delivery. Furthermore, the newly developed SELPs in this study may be potentially useful as biomaterials for controlled drug delivery and biomedical engineering.

  10. Self-assembling semiconducting polymers--rods and gels from electronic materials.

    PubMed

    Clark, Andrew P-Z; Shi, Chenjun; Ng, Benny C; Wilking, James N; Ayzner, Alexander L; Stieg, Adam Z; Schwartz, Benjamin J; Mason, Thomas G; Rubin, Yves; Tolbert, Sarah H

    2013-02-26

    In an effort to favor the formation of straight polymer chains without crystalline grain boundaries, we have synthesized an amphiphilic conjugated polyelectrolyte, poly(fluorene-alt-thiophene) (PFT), which self-assembles in aqueous solutions to form cylindrical micelles. In contrast to many diblock copolymer assemblies, the semiconducting backbone runs parallel, not perpendicular, to the long axis of the cylindrical micelle. Solution-phase micelle formation is observed by X-ray and visible light scattering. The micelles can be cast as thin films, and the cylindrical morphology is preserved in the solid state. The effects of self-assembly are also observed through spectral shifts in optical absorption and photoluminescence. Solutions of higher-molecular-weight PFT micelles form gel networks at sufficiently high aqueous concentrations. Rheological characterization of the PFT gels reveals solid-like behavior and strain hardening below the yield point, properties similar to those found in entangled gels formed from surfactant-based micelles. Finally, electrical measurements on diode test structures indicate that, despite a complete lack of crystallinity in these self-assembled polymers, they effectively conduct electricity.

  11. Engineering aqueous fiber assembly into silk-elastin-like protein polymers.

    PubMed

    Zeng, Like; Jiang, Linan; Teng, Weibing; Cappello, Joseph; Zohar, Yitshak; Wu, Xiaoyi

    2014-07-01

    Self-assembled peptide/protein nanofibers are valuable 1D building blocks for creating complex structures with designed properties and functions. It is reported that the self-assembly of silk-elastin-like protein polymers into nanofibers or globular aggregates in aqueous solutions can be modulated by tuning the temperature of the protein solutions, the size of the silk blocks, and the charge of the elastin blocks. A core-sheath model is proposed for nanofiber formation, with the silk blocks in the cores and the hydrated elastin blocks in the sheaths. The folding of the silk blocks into stable cores--affected by the size of the silk blocks and the charge of the elastin blocks--plays a critical role in the assembly of silk-elastin nanofibers. Furthermore, enhanced hydrophobic interactions between the elastin blocks at elevated temperatures greatly influence the nanoscale features of silk-elastin nanofibers.

  12. Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

    PubMed

    Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming

    2017-03-03

    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

  13. Novel 3D nano-antennas of self-assembled zinc oxide on silver nanowires

    NASA Astrophysics Data System (ADS)

    Sanchez, John Eder

    The manipulation of geometrical and structural arrangement of nano-devices, especially nanoantennas (nantennnas), is highly desirable for a precise controlling and monitoring of the multidirectional radiation pattern generated from the active elements on nanoantenna (nantenna) applications. Here we report the epitaxial growing of ZnO nanorods preferentially oriented along the [0001] direction on pentagonal faces (010) of Ag nanowires (Ag/ZnO ). The Ag/ZnO nanosystem, resembling an hierarchal aerial antenna, was obtained using an innovative microwave irradiation process. There, the combination of chemical synthesis along accelerated micro wave irradiation digestion process, allows us to control precisely the morphology and distribution of the Ag/ZnO nanostructure. Because of the high order arrangement exhibited for the nanosystem as well as high rate of reproducibility in the production process, we opted to tested the nanostructures in a set of experiments ranging from the bulk properties down to in-situ nanoscale; in order to gain valuable information from the experiments and with the aim to give a real application to the nanomaterial. In this order, first, we described the far and near electric field generated for the nantenna obtained from electrical radiation patterns resulting from phase map reconstruction using off-axis electron holography. It is important to notice that knowing the properties at nanoscale level, it will give key insight of mechanism through which the metal-semiconductor (Ag-ZnO) behaves in opto-electronic applications. In fact, using electric numerical approximations methods for a finite number of ZnO nanorods on Ag nanowires it was shown that the electric radiation intensities maps match closely the experimental results obtained with electron holography. Additionally, to reinforce the understanding of how the metal-semiconductor (Ag-ZnO) nanostructures could be used as an active element on photo-signal reception/transmitter generation it was

  14. Controlled evaporative self-assembly of poly(acrylic acid) in a confined geometry for fabricating patterned polymer brushes.

    PubMed

    Men, Yonghong; Xiao, Peng; Chen, Jing; Fu, Jun; Huang, Youju; Zhang, Jiawei; Xie, Zhengchao; Wang, Wenqin; Chen, Tao

    2014-04-29

    A simple yet robust approach was exploited to fabricate large-scaled patterned polymer brushes by combining controlled evaporative self-assembly (CESA) in a confined geometry and self-initiated photografting and photopolymerization (SIPGP). Our method was carried out without any sophisticated instruments, free of lithography, overcoming current difficulties in fabricating polymer patterns by using complex instruments.

  15. Solvent-responsive self-assembly of amphiphilic invertible polymers determined with SANS.

    PubMed

    Kudina, Olena; Kohut, Ananiy; Tarnavchyk, Ihor; Hevus, Ivan; Voronov, Andriy

    2014-04-01

    Amphiphilic invertible polymers (AIPs) are a new class of macromolecules that self-assemble into micellar structures and rapidly change structure in response to changes in solvent polarity. Using small-angle neutron scattering (SANS) data, we obtained a quantitative description of the invertible micellar assemblies (IMAs). The detailed composition and size of the assemblies (including the effect of temperature) were measured in aqueous and toluene polymer solutions. The results show that the invertible macromolecules self-assemble into cylindrical core-shell micellar structures. The composition of the IMAs in aqueous and toluene solutions was used to reveal the inversion mechanism by changing the polarity of the medium. Our experiments demonstrate that AIP unimers self-assemble into IMAs in aqueous solution, predominantly through interactions between the hydrophobic moieties of macromolecules. The hydrophobic effect (or solvophobic interaction) is the major driving force for self-assembly. When the polarity of the environment is changed from polar to nonpolar, poly(ethylene glycol) (PEG) and aliphatic dicarboxylic acid fragments of AIP macromolecules tend to replace each other in the core and the shell of the IMAs. However, neither the interior nor the exterior of the IMAs consists of fragments of a single component of the macromolecule. In aqueous solution, with the temperature increasing from 15 to 35 °C, the IMAs' mixed core from aliphatic dicarboxylic acid and PEG moieties and PEG-based shell change the structure. As a result of the progressive dehydration of the macromolecules, the hydration level (water content) in the micellar core decreases at 25 °C, followed by dehydrated PEG fragments entering the interior of the IMAs when the temperature increases to 35 °C.

  16. Dissipative particle dynamics simulations of polymer-protected nanoparticle self-assembly

    NASA Astrophysics Data System (ADS)

    Spaeth, Justin R.; Kevrekidis, Ioannis G.; Panagiotopoulos, Athanassios Z.

    2011-11-01

    Dissipative particle dynamics simulations were used to study the effects of mixing time, solute solubility, solute and diblock copolymer concentrations, and copolymer block length on the rapid coprecipitation of polymer-protected nanoparticles. The simulations were aimed at modeling Flash NanoPrecipitation, a process in which hydrophobic solutes and amphiphilic block copolymers are dissolved in a water-miscible organic solvent and then rapidly mixed with water to produce composite nanoparticles. A previously developed model by Spaeth et al. [J. Chem. Phys. 134, 164902 (2011)], 10.1063/1.3580293 was used. The model was parameterized to reproduce equilibrium and transport properties of the solvent, hydrophobic solute, and diblock copolymer. Anti-solvent mixing was modeled using time-dependent solvent-solute and solvent-copolymer interactions. We find that particle size increases with mixing time, due to the difference in solute and polymer solubilities. Increasing the solubility of the solute leads to larger nanoparticles for unfavorable solute-polymer interactions and to smaller nanoparticles for favorable solute-polymer interactions. A decrease in overall solute and polymer concentration produces smaller nanoparticles, because the difference in the diffusion coefficients of a single polymer and of larger clusters becomes more important to their relative rates of collisions under more dilute conditions. An increase in the solute-polymer ratio produces larger nanoparticles, since a collection of large particles has less surface area than a collection of small particles with the same total volume. An increase in the hydrophilic block length of the polymer leads to smaller nanoparticles, due to an enhanced ability of each polymer to shield the nanoparticle core. For unfavorable solute-polymer interactions, the nanoparticle size increases with hydrophobic block length. However, for favorable solute-polymer interactions, nanoparticle size exhibits a local minimum with

  17. Brownian dynamics of subunit addition-loss kinetics and thermodynamics in linear polymer self-assembly.

    PubMed

    Castle, Brian T; Odde, David J

    2013-12-03

    The structure and free energy of multistranded linear polymer ends evolves as individual subunits are added and lost. Thus, the energetic state of the polymer end is not constant, as assembly theory has assumed. Here we utilize a Brownian dynamics approach to simulate the addition and loss of individual subunits at the polymer tip. Using the microtubule as a primary example, we examined how the structure of the polymer tip dictates the rate at which units are added to and lost from individual protofilaments. We find that freely diffusing subunits arrive less frequently to lagging protofilaments but bind more efficiently, such that there is no kinetic difference between leading and lagging protofilaments within a tapered tip. However, local structure at the nanoscale has up to an order-of-magnitude effect on the rate of addition. Thus, the kinetic on-rate constant, integrated across the microtubule tip (kon,MT), is an ensemble average of the varying individual protofilament on-rate constants (kon,PF). Our findings have implications for both catastrophe and rescue of the dynamic microtubule end, and provide a subnanoscale framework for understanding the mechanism of action of microtubule-associated proteins and microtubule-directed drugs. Although we utilize the specific example of the microtubule here, the findings are applicable to multistranded polymers generally.

  18. Hybrid hydrogels assembled from synthetic polymers and coiled-coil protein domains.

    PubMed

    Wang, C; Stewart, R J; Kopecek, J

    1999-02-04

    Stimuli-sensitive polymer hydrogels, which swell or shrink in response to changes in the environmental conditions, have been extensively investigated and used as 'smart' biomaterials and drug-delivery systems. Most of these responsive hydrogels are prepared from a limited number of synthetic polymers and their derivatives, such as copolymers of (meth)acrylic acid, acrylamide and N-isopropyl acrylamide. Water-soluble synthetic polymers have also been crosslinked with molecules of biological origin, such as oligopeptides and oligodeoxyribonucleotides, or with intact native proteins. Very often there are several factors influencing the relationship between structure and properties in these systems, making it difficult to engineer hydrogels with specified responses to particular stimuli. Here we report a hybrid hydrogel system assembled from water-soluble synthetic polymers and a well-defined protein-folding motif, the coiled coil. These hydrogels undergo temperature-induced collapse owing to the cooperative conformational transition of the coiled-coil protein domain. This system shows that well-characterized water-soluble synthetic polymers can be combined with well-defined folding motifs of proteins in hydrogels with engineered volume-change properties.

  19. From Cooperative Self-Assembly to Water-Soluble Supramolecular Polymers Using Coarse-Grained Simulations.

    PubMed

    Bochicchio, Davide; Pavan, Giovanni M

    2017-01-24

    Supramolecular polymers, formed via noncovalent self-assembly of elementary monomers, are extremely interesting for their dynamic bioinspired properties. In order to understand their behavior, it is necessary to access their dynamics while maintaining high resolution in the treatment of the monomer structure and monomer-monomer interactions, which is typically a difficult task, especially in aqueous solution. Focusing on 1,3,5-benzenetricarboxamide (BTA) water-soluble supramolecular polymers, we have developed a transferable coarse-grained model that allows studying BTA supramolecular polymerization in water, while preserving remarkable consistency with the atomistic models in the description of the key interactions between the monomers (hydrophobic, H-bonding, etc.), self-assembly cooperativity, and amplification of order into the growing fibers. This permitted us to monitor the amplification of the key interactions between the monomers (including H-bonding) in the BTA fibers during the dynamic polymerization process. Our molecular dynamics simulations provide a picture of a stepwise cooperative polymerization mechanism, where initial fast hydrophobic aggregation of the BTA monomers in water is followed by the slower reorganization of these disordered aggregates into ordered directional oligomers. Supramolecular polymer growth then proceeds on a slower time scale. We challenged our models via comparison with the experimental evidence, capturing the effect of temperature variations and subtle changes in the monomer structure on the polymerization and on the properties of the fibers seen in the real systems. This work provides a multiscale spatiotemporal characterization of BTA self-assembly in water and a useful platform to study a variety of BTA-based supramolecular polymers toward structure-property relationships.

  20. Hydrophobic self-assembly of a perylenediimide-linked DNA dumbbell into supramolecular polymers.

    PubMed

    Neelakandan, Prakash P; Pan, Zhengzheng; Hariharan, Mahesh; Zheng, Yan; Weissman, Haim; Rybtchinski, Boris; Lewis, Frederick D

    2010-11-10

    The self-assembly of DNA dumbbell conjugates possessing hydrophobic perylenediimide (PDI) linkers separated by an eight-base pair A-tract has been investigated. Cryo-TEM images obtained from dilute solutions of the dumbbell in aqueous buffer containing 100 mM NaCl show the presence of structures corresponding to linear end-to-end assemblies of 10-30 dumbbell monomers. The formation of assemblies of this size is consistent with analysis of the UV-vis and fluorescence spectra of these solutions for the content of PDI monomer and dimer chromophores. Assembly size is dependent upon the concentration of dumbbell and salt as well as the temperature. Kinetic analysis of the assembly process by means of salt-jump stopped-flow measurements shows that it occurs by a salt-triggered isodesmic mechanism in which the rate constants for association and dissociation in 100 mM NaCl are 3.2 × 10(7) M(-1)s(-1) and 1.0 s(-1), respectively, faster than the typical rate constants for DNA hybridization. TEM and AFM images of samples deposited from solutions having higher concentrations of dumbbell and NaCl display branched assemblies with linear regions >1 μm in length and diameters indicative of the formation of small bundles of dumbbell end-to-end assemblies. These observations provide the first example of the use of hydrophobic association for the assembly of small DNA duplex conjugates into supramolecular polymers and larger branched aggregates.

  1. Low-Temperature All-Solution-Processed Transparent Silver Nanowire-Polymer/AZO Nanoparticles Composite Electrodes for Efficient ITO-Free Polymer Solar Cells.

    PubMed

    Zhang, Xiaoqin; Wu, Jiang; Wang, Jiantai; Yang, Qingqing; Zhang, Baohua; Xie, Zhiyuan

    2016-12-21

    We present a kind of all-solution-processed transparent conductive film comprising of silver nanowire (AgNW), polyvinyl butyral (PVB), and Al-doped ZnO nanoparticles (AZO NPs) composite (APA) by layer-by-layer blade-coating on glass substrate at low temperature. This kind of transparent APA film exhibits high transmittance at a wide range of 400-700 nm. The sheet resistance of the APA film can be as low as 21 Ω sq(-1) with transmittance over 94% at 550 nm. The introduction of PVB significantly improves the APA composite adhesion to glass substrate. The overlaid coating of AZO NPs not only reduces the sheet resistance but also improves the ambient and thermal stability of the APA film. This highly conductive and transparent APA film on glass substrate is employed as the bottom electrode to fabricate high-efficiency polymer solar cells (PSCs). A power conversion efficiency of 8.98% is achieved for the PBDTTT-EFT:PC71BM PSCs employing the APA composite as transparent bottom electrode, close to 9.54% of the control device fabricated on the commercial indium tin oxide substrate. As it can be easily prepared with all-solution-processed blade-coating method at low temperature, this kind of AgNW-based composite film is promising to integrate with roll-to-roll manufacturing of flexible PSCs.

  2. Electronic structure of self-assembled Si nanowires on Ag(110) surfaces

    NASA Astrophysics Data System (ADS)

    Ohta, Taisuke; Rotenberg, Eli; Horn, Karsten

    2006-03-01

    Much attention has recently been paid to the physics of one- dimensional (1-D) systems, since exotic properties are predicted from basic theoretical consideration. However, it is not easy to realize such one-dimensional systems experimentally. Recently, Leandri et al.[1] have reported the growth of self-assembled 1D linear structures of silicon on Ag(110), perfectly aligned along [-110] direction and 16å wide. We have investigated the electronic structure of such self-assembled Si “nanowires” using angle resolved photoemission spectroscopy. The Si 2p core level line shows two narrow components in agreement with earlier work [1]. Silicon-induced features in the valence band region are observed, most clearly within the band gap of the Ag s-p states. The silicon-induced band exhibits a sizeable dispersion only in the direction along the linear structure, i.e. the [- 110] azimuth of the Ag(110) substrate. Details of the experimentally observed bands will be presented and related to the atomic structure within the 1D structure and its arrangement on the silver substrate. T.O. acknowledges financial support from Max Planck Society. Experiments were performed at the Advanced Light Source, Lawrence Berkeley National Laboratory operated by the U.S. DOE under Contract No. DE-AC03-76SF00098. [1] C. Leandri et al., Self-aligned silicon quantum wires on Ag (110), Surface Science 574 (2005) L9 L15

  3. Enhanced photoelectrochemical biosensing performances for graphene (2D) - Titanium dioxide nanowire (1D) heterojunction polymer conductive nanosponges.

    PubMed

    Muthuchamy, N; Lee, K-P; Gopalan, A-I

    2017-03-15

    In this work, an efficient photoelectrochemical (PEC) biosensing platform has been designed and developed based on graphene (G) through modifying it into an electroconductive polymer nanosponge (EPNS) and with the incorporation of titanium dioxide nanowires (TiO2 NW) (designated as TiO2 (G) NW@EPNS). Functioning as an efficient immobilization matrix for immobilization of the enzyme Cytochrome C (Cyt C), TiO2 (G) NW@EPNS delivers features for an efficient PEC biosensor, such as fast kinetics of direct electron transfer (DET) to the electrode and effective separation of photogenerated holes and electrons. TiO2 (G) NW@EPNS exhibited DET to the electrode with a highly heterogeneous electron transfer rate constant of 6.29±0.002s(-1). The existence of TiO2, G and EPNS in conjunction facilitates DET between the electrode surface and the protein. The fabricated PEC nitrite ion (NO2(-)) biosensor showed superior analytical performances such as wide linear range (0.5-9000µM), lowest detection limit (0.225mM) and excellent specificity for NO2(-) in the presence other interferences at a very low bias potential (-0.11V). This study opens up the feasibility of fabricating a PEC biosensor for any analyte using a matrix comprising of G and a photoactive material and EPNS, because these components synergistically contribute to effective immobilization of on enzyme, DET to the electrode and simple read-out under the light.

  4. The influence of self-assembly behavior of nanoparticles on the dielectric polymer composites

    SciTech Connect

    Lu, Xin; Li, Weiping Wang, Tingting; Jiang, Long; Luo, Laihui; Hua, Dayin; Zhu, Yuejin

    2013-11-15

    To clearify the influence of the distribution of the conductive nanoparticles on the dielectric properties of the corresponding polymer composites, the microstructure and dielectric character of the composites based on the oleic acid modified ferroferric oxide and polyvinylidene fluoride (PVDF) polymer have been studied experimentally. It is found that these composites exhibit a normal percolative phase transition over the filler content from insulator to conductor, consistent with the classical percolation theory. However, when the percentage of fillers is at a certain value which is below the percolation threshold, these nanoparticles can assemble into a special porous structure in the PVDF matrix, associated with the enhancement of dielectric constant at low frequency. In addition, the controllable dispersion of conducting nanoparticles in a polymer matrix can prevent premature agglomeration at low filling fractions and avoid the appearance of anomalously early percolation. Therefore, the self-assembly behavior of nanoparticles can be beneficial to preparation of the high dielectric constant and low loss composites for the application of electric energy storage.

  5. Advances in nanowire bioelectronics

    NASA Astrophysics Data System (ADS)

    Zhou, Wei; Dai, Xiaochuan; Lieber, Charles M.

    2017-01-01

    Semiconductor nanowires represent powerful building blocks for next generation bioelectronics given their attractive properties, including nanometer-scale footprint comparable to subcellular structures and bio-molecules, configurable in nonstandard device geometries readily interfaced with biological systems, high surface-to-volume ratios, fast signal responses, and minimum consumption of energy. In this review article, we summarize recent progress in the field of nanowire bioelectronics with a focus primarily on silicon nanowire field-effect transistor biosensors. First, the synthesis and assembly of semiconductor nanowires will be described, including the basics of nanowire FETs crucial to their configuration as biosensors. Second, we will introduce and review recent results in nanowire bioelectronics for biomedical applications ranging from label-free sensing of biomolecules, to extracellular and intracellular electrophysiological recording.

  6. Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

    NASA Astrophysics Data System (ADS)

    Zhan, Honglei; Liang, Jun F.

    2016-12-01

    Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

  7. Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid.

    PubMed

    Zhan, Honglei; Liang, Jun F

    2016-12-09

    Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

  8. Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

    PubMed Central

    Zhan, Honglei; Liang, Jun F.

    2016-01-01

    Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field. PMID:27934922

  9. Electrical Characterization of Zn and ZnO Nanowires Grown on PEDOT:PSS Conductive Polymer Thin Films by Physical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Chamberlin, Matthew; Constantin, Costel

    2011-10-01

    Physical vapor deposition (PVD) techniques offer tremendous possibilities for easy fabrication of nanostructure arrays for use in thin film electronics. In this study we examine inorganic/organic heterojunctions produced by growing conductive Zn and semiconductive ZnO nanowire arrays on organic conductive PEDOT:PSS polymer thin films using simple and cost-effective PVD methods. Understanding the electrical properties of these hybrid films are of particular interest for applications in organic electronics. However, traditional systems for measuring conductivity and resistivity of thin films by the Van Der Pauw method prove problematic when dealing with soft polymeric surfaces. We present here electrical studies of ZnO- and Zn-nanowire/PEDOT:PSS heterojunctions using a modified 2-point probe method constructed from inexpensive and easily available materials.

  10. Drying-Mediated Self-Assembly of Highly Ordered Complex Structures: From Polymers to Nanoparticles

    NASA Astrophysics Data System (ADS)

    Lin, Zhiqun

    2009-03-01

    Drying of a sessile drop containing nonvolatile solutes readily self-assembles into a number of concentric ``coffee rings'' by repetitive ``stick-slip'' motion of the three-phase contact line. However, due mainly to lack of control over the evaporation process of the drop, the challenge remains to use evaporative self-assembly to rationally ``synthesize'' ``coffee rings'' of different shapes and sizes of high regularity and fidelity. Here, we report a facile, robust, and one-step evaporation method for producing in a precisely controllable manner versatile microstructures possessing high regularity, dispensing with the need for lithographic techniques and externally applied fields. Polymer or nanocrystal solutions are confined in a simple geometry comprised of a curved surface placed upon a flat substrate. By changing the shape of the upper surface of the imposed geometry, the controlled, evaporative self-assembly of polymer or nanocrystal solutions yields a variety of complex, intriguing, and well-ordered structures over large areas. As such, this method represents a significant advance in creating regularly organized, complex structures with potential applications in microelectronics, optoelectronics, and biotechnology, among other areas.

  11. Decoupling Substrate Surface Interactions in Block Polymer Thin Film Self-Assembly

    NASA Astrophysics Data System (ADS)

    Shelton, Cameron; Epps, Thomas

    2015-03-01

    Understanding the impact of the major factors that affect block polymer (BP) thin film self-assembly is necessary to control nanostructure ordering, orientation, and defect density. In this work, we systematically studied the influence of the substrate surface energy, one of the most significant parameters directing self-assembly, on wetting behavior, through-film interactions, and substrate surface field propagation. Notably, we determined the applicability of decoupled surface energy components (dispersive and polar interactions) as opposed to total surface energy, using a suite of chlorosilane monolayers and UV-ozone degradation to create a library of total, dispersive, and polar surface energy effects. Our experimental results combined with surface chemistry literature indicated repulsive total surface energy interactions are the dominant force at the substrate-polymer interface, whereas attractive decoupled surface energy interactions become significant past the contacting layer. This work represents a thorough analysis of a vital force affecting BP self-assembly as well as a blueprint for the generalized design of substrate surfaces that achieve target BP nanostructure orientations for nanolithography, templating, and nanoporous membrane applications.

  12. Nanowire-Assembled Hierarchical ZnCo2O4 Microstructure Integrated with a Low-Power Microheater for Highly Sensitive Formaldehyde Detection.

    PubMed

    Long, Hu; Harley-Trochimczyk, Anna; Cheng, Siyi; Hu, Hao; Chi, Won Seok; Rao, Ameya; Carraro, Carlo; Shi, Tielin; Tang, Zirong; Maboudian, Roya

    2016-11-23

    Nanowire-assembled 3D hierarchical ZnCo2O4 microstructure is synthesized by a facile hydrothermal route and a subsequent annealing process. In comparison to simple nanowires, the resulting dandelion-like structure yields more open spaces between nanowires, which allow for better gas diffusion and provide more active sites for gas adsorption while maintaining good electrical conductivity. The hierarchical ZnCo2O4 microstructure is integrated on a low-power microheater platform without using binders or conductive additives. The hierarchical structure of the ZnCo2O4 sensing material provides reliable electrical connection across the sensing electrodes. The resulting sensor exhibits an ultralow detection limit of 3 ppb toward formaldehyde with fast response and recovery as well as good selectivity to CO, H2, and hydrocarbons such as n-pentane, propane, and CH4. The sensor only consumes ∼5.7 mW for continuous operation at 300 °C with good long-term stability. The excellent sensing performance of this hierarchical structure based sensor suggests the advantages of combining such structures with microfabricated heaters for practical low-power sensing applications.

  13. Germanium doping of self-assembled GaN nanowires grown by plasma-assisted molecular beam epitaxy

    SciTech Connect

    Schörmann, Jörg; Hille, Pascal; Schäfer, Markus; Müßener, Jan; Becker, Pascal; Klar, Peter J.; Hofmann, Detlev M.; Teubert, Jörg; Eickhoff, Martin; Kleine-Boymann, Matthias; Rohnke, Marcus; Mata, Maria de la; Arbiol, Jordi

    2013-09-14

    Germanium doping of GaN nanowires grown by plasma-assisted molecular beam epitaxy on Si(111) substrates is studied. Time of flight secondary ion mass spectrometry measurements reveal a constant Ge-concentration along the growth axis. A linear relationship between the applied Ge-flux and the resulting ensemble Ge-concentration with a maximum content of 3.3×10{sup 20} cm{sup −3} is extracted from energy dispersive X-ray spectroscopy measurements and confirmed by a systematic increase of the conductivity with Ge-concentration in single nanowire measurements. Photoluminescence analysis of nanowire ensembles and single nanowires reveals an exciton localization energy of 9.5 meV at the neutral Ge-donor. A Ge-related emission band at energies above 3.475 eV is found that is assigned to a Burstein-Moss shift of the excitonic emission.

  14. Germanium doping of self-assembled GaN nanowires grown by plasma-assisted molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Schörmann, Jörg; Hille, Pascal; Schäfer, Markus; Müßener, Jan; Becker, Pascal; Klar, Peter J.; Kleine-Boymann, Matthias; Rohnke, Marcus; de la Mata, Maria; Arbiol, Jordi; Hofmann, Detlev M.; Teubert, Jörg; Eickhoff, Martin

    2013-09-01

    Germanium doping of GaN nanowires grown by plasma-assisted molecular beam epitaxy on Si(111) substrates is studied. Time of flight secondary ion mass spectrometry measurements reveal a constant Ge-concentration along the growth axis. A linear relationship between the applied Ge-flux and the resulting ensemble Ge-concentration with a maximum content of 3.3×1020 cm-3 is extracted from energy dispersive X-ray spectroscopy measurements and confirmed by a systematic increase of the conductivity with Ge-concentration in single nanowire measurements. Photoluminescence analysis of nanowire ensembles and single nanowires reveals an exciton localization energy of 9.5 meV at the neutral Ge-donor. A Ge-related emission band at energies above 3.475 eV is found that is assigned to a Burstein-Moss shift of the excitonic emission.

  15. Nonvolatile Transistor Memory with Self-Assembled Semiconducting Polymer Nanodomain Floating Gates.

    PubMed

    Wang, Wei; Kim, Kang Lib; Cho, Suk Man; Lee, Ju Han; Park, Cheolmin

    2016-12-14

    Organic field effect transistor based nonvolatile memory (OFET-NVM) with semiconducting nanofloating gates offers additional benefits over OFET-NVMs with conventional metallic floating gates due to the facile controllability of charge storage based on the energetic structure of the floating gate. In particular, an all-in-one tunneling and floating-gate layer in which the semiconducting polymer nanodomains are self-assembled in the dielectric tunneling layer is promising. In this study, we utilize crystals of a p-type semiconducting polymer in which the crystalline lamellae of the polymer are spontaneously developed and embedded in the tunneling matrix as the nanofloating gate. The widths and lengths of the polymer nanodomains are approximately 20 nm and a few hundred nanometers, respectively. An OFET-NVM containing the crystalline nanofloating gates exhibits memory performance with a large memory window of 10 V, programming/erasing switching endurance for over 500 cycles, and a long retention time of 5000 s. Moreover, the device performance is improved by comixing with an n-type semiconductor; thus, the solution-processed p- and n-type double floating gates capable of storing both holes and electrons allow for the multilevel operation of our OFET-NVM. Four highly reliable levels (two bits per cell) of charge trapping and detrapping are achieved using this OFET-NVM by accurately choosing the programming/erasing voltages.

  16. Effect of Charge Patterning on the Phase Behavior of Polymer Coacervates for Charge Driven Self Assembly

    NASA Astrophysics Data System (ADS)

    Radhakrishna, Mithun; Sing, Charles E.

    Oppositely charged polymers can undergo associative liquid-liquid phase separation when mixed under suitable conditions of ionic strength, temperature and pH to form what are known as `polymeric complex coacervates'. Polymer coacervates find use in diverse array of applications like microencapsulation, drug delivery, membrane filtration and underwater adhesives. The similarity between complex coacervate environments and those in biological systems has also found relevance in areas of bio-mimicry. Our previous works have demonstrated how local charge correlations and molecular connectivity can drastically affect the phase behavior of coacervates. The precise location of charges along the chain therefore dramatically influences the local charge correlations, which consequently influences the phase behavior of coacervates. We investigate the effect of charge patterning along the polymer chain on the phase behavior of coacervates in the framework of the Restricted Primitive Model using Gibbs Ensemble Monte Carlo simulations. Our results show that charge patterning dramatically changes the phase behavior of polymer coacervates, which contrasts with the predictions of the classical Voorn-Overbeek theory. This provides the basis for designing new materials through charge driven self assembly by controlling the positioning of the charged monomers along the chain.

  17. Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

    PubMed Central

    Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto

    2017-01-01

    In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels. PMID:28100492

  18. Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

    NASA Astrophysics Data System (ADS)

    Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto; Barker, Thomas H.

    2017-01-01

    In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels.

  19. Nanowire mesh solar fuels generator

    DOEpatents

    Yang, Peidong; Chan, Candace; Sun, Jianwei; Liu, Bin

    2016-05-24

    This disclosure provides systems, methods, and apparatus related to a nanowire mesh solar fuels generator. In one aspect, a nanowire mesh solar fuels generator includes (1) a photoanode configured to perform water oxidation and (2) a photocathode configured to perform water reduction. The photocathode is in electrical contact with the photoanode. The photoanode may include a high surface area network of photoanode nanowires. The photocathode may include a high surface area network of photocathode nanowires. In some embodiments, the nanowire mesh solar fuels generator may include an ion conductive polymer infiltrating the photoanode and the photocathode in the region where the photocathode is in electrical contact with the photoanode.

  20. Optically induced mode splitting in self-assembled, high quality-factor conjugated polymer microcavities

    PubMed Central

    Braam, Daniel; Kushida, Soh; Niemöller, Robert; Prinz, Günther M.; Saito, Hitoshi; Kanbara, Takaki; Kuwabara, Junpei; Yamamoto, Yohei; Lorke, Axel

    2016-01-01

    We investigate the whispering gallery modes (WGMs) of self-assembled single microspheres. They consist of a recently developed highly fluorescent π-conjugated copolymer and exhibit excellent optical properties with Q-factors up to 104. Under continuous laser irradiation, we observe a splitting of the highly degenerate spherical WGMs into a multiplet of lines. Comparison with the calculated spectral response of a weakly distorted sphere shows that the optical excitation induces a change of the optical path length in the microcavity so that it resembles a prolate spheroid. The separation of the lines is given by the ellipticity and the azimuthal mode number. Measurements in various gaseous environments suggest that the distortion is caused by light induced oxidation of the polymer. Our findings show that photooxidation can be a beneficial mechanism for in-situ tuning of optically active polymer structures. PMID:26781838

  1. Assembly of poly(dopamine) films mixed with a nonionic polymer.

    PubMed

    Zhang, Yan; Thingholm, Bo; Goldie, Kenneth N; Ogaki, Ryosuke; Städler, Brigitte

    2012-12-21

    Poly(dopamine) (PDA) coatings have recently attracted considerable interest for a variety of applications. Here, we investigate the film deposition of dopamine mixed with a nonionic polymer (i.e., poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), and poly(N-vinyl pyrrolidone) (PVP)) onto silica substrates using X-ray photoelectron spectroscopy and quartz crystal microbalance. Furthermore, we assess the possibility of coating silica colloids to yield polymer capsules and liposomes with these mixtures. We found that mixed PDA/PEG and PDA/PVA films are deposited without the need for a covalent linker such as an amine or thiol. We also discovered the first material, namely, PVP, that can suppress PDA film assembly. These fundamental findings give further insight into PDA film properties and contribute to establish PDA as a widely applicable coating.

  2. Unconventional multiple ring structure formation from evaporation-induced self-assembly of polymers.

    PubMed

    Bi, Wuguo; Wu, Xiangyang; Yeow, Edwin K L

    2012-07-31

    The formation of multiring deposits of poly(2-vinylpyridine) (P2VP) from the evaporation of a P2VP-(2,6-lutidine + water) drop on a glass substrate does not conform to the conventional pinning-depinning mechanism. Instead, ringlike deposits are formed when the droplet undergoes several cycles of spreading and receding where, for each spreading event, a P2VP ridge is formed at the contact line when the polymer flows toward the outward advancing edge. The complex interplay between an outward solutal-Marangoni flow due to a higher concentration of the polymer at the contact line and an inward solvent-Marangoni flow arising from the differences in volatilities and surface tensions of the pure solvent components plays an important role in enhancing the droplet spreading rate. The newly discovered surface patterning mechanism has important implications in the development of novel techniques for inducing self-assembly of functional materials from evaporating drops.

  3. Aligned nanostructured polymers by magnetic-field-directed self-assembly of a polymerizable lyotropic mesophase.

    PubMed

    Tousley, Marissa E; Feng, Xunda; Elimelech, Menachem; Osuji, Chinedum O

    2014-11-26

    Magnetic-field-directed assembly of lyotropic surfactant mesophases provides a scalable approach for the fabrication of aligned nanoporous polymers by templated polymerization. We develop and characterize a lyotropic liquid crystalline system containing hexagonally packed cylindrical micelles of a polymerizable surfactant in a polymerizable solvent. The system exhibits negative magnetic anisotropy, resulting in the degenerate alignment of cylindrical micelles perpendicular to the magnetic field. Sample rotation during field alignment is used to effectively break this degeneracy and enable the production of uniformly well-aligned mesophases. High-fidelity retentions of the hexagonal structure and alignment were successfully achieved in polymer films produced upon UV exposure of the reactive system. The success of this effort provides a route for the fabrication of aligned nanoporous membranes suitable for highly selective separations, sensing, and templated nanomaterial synthesis.

  4. Galactosylated Polymer Nano-objects by Polymerization-Induced Self-Assembly, Potential Drug Nanocarriers.

    PubMed

    Semsarilar, Mona; Canton, Irene; Ladmiral, Vincent

    2016-01-01

    Glycopolymer-based nanostructures are invaluable tools to both study biological phenomena and to design future targeted drug delivery systems. Polymerization-induced self-assembly, especially RAFT aqueous dispersion polymerization is a unique method to prepare such polymer nanostructures, as it enables the preparation of very-well-defined morphologies at very high concentrations. Here we describe the implementation of PISA to the synthesis of galactosylated spheres, wormlike micelles and vesicles, and the preliminary results of cell toxicity, cell uptake, and cargo delivering capacity of galactose-decorated vesicles.

  5. Tailoring of self-assembled monolayer for polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Choi, Beomrak; Rhee, Jungsoo; Lee, Hong H.

    2001-09-01

    The choice of a self-assembled monolayer (SAM) is tailored to specifically remove water on an indium-tin oxide electrode and to reduce barrier height for long-term stability of polymer light-emitting diodes. Water, which is a major cause of long-term degradation, is shown to have entirely reversible effects on the power efficiency of the device. It is shown that the use of a SAM for the specific purposes results in a more than an order of magnitude increase in the half lifetime of the device based on poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene].

  6. Smart assembly of polymer fibers: lessons from major ampullate spider silk

    NASA Astrophysics Data System (ADS)

    Viney, Christopher

    1996-02-01

    Studies of major ampullate silk (MAS), especially the secretions and fibers produced by the spider Nephila clavipes (golden orb weaver), have yielded several results of potential value to the materials scientist/engineer. There are lessons to be learned about synthesis, processing and microstructural design of high-tensile polymer fibers. The 'smart' aspect of silk production in nature concerns the ability of the spider to rapidly process a concentrated, viscous aqueous solution of silk protein (stored in the gland) into water-insoluble fiber on demand. This process centers on the assembly of a shear-sensitive supramolecular liquid crystalline phase by aggregation of the solubilized globular protein molecules.

  7. Polymer/hemoglobin assemblies: biodegradable oxygen carriers for artificial red blood cells.

    PubMed

    Li, Taihang; Jing, Xiabin; Huang, Yubin

    2011-07-07

    In routine clinical procedures, blood transfusion is now suffering from the defects of the blood products, like cross-matching, short storage time and virus infection. Various blood substitutes have been designed by researchers through continual efforts. With recent progress in nanotechnology, new types of artificial red blood cells with cellular structure are available. This article aims to describe some artificial red blood cells which encapsulate or conjugate hemoglobin molecules through various approaches, especially the nanoscale self-assembly technique, to mitigate the adverse effects of free hemoglobin molecules. These types of artificial red blood cell systems, which make use of biodegradable polymers as matrix materials, show advantages over the traditional types.

  8. Temperature-Dependent Multidimensional Self-Assembly of Polyphenylene-Based "Rod-Coil" Graft Polymers.

    PubMed

    Huang, Yinjuan; Mai, Yiyong; Yang, Xiangwen; Beser, Uliana; Liu, Junzhi; Zhang, Fan; Yan, Deyue; Müllen, Klaus; Feng, Xinliang

    2015-09-16

    We present a novel type of "rod-coil" graft copolymer containing a polyphenylene backbone linked with poly(ethylene oxide) (PEO) side chains. Such graft copolymers manifest unprecedented temperature-dependent one-dimensional (1D) and two-dimensional (2D) self-assembly in solution. At 20 °C, which is higher than the crystallization temperature (Tc) of the PEO chains, the achiral graft copolymers self-organize into nanoribbons that twist into ∼30 μm ultralong helices with controlled pitch depending on the grafting ratio of the PEO chains. At 10 °C, which is lower than the Tc, quadrangular multilayer sheets of over 10 μm in lateral size are obtained. To our knowledge, this work presents the first example of controlled self-assembly of graft polymers into 1D helix and 2D sheet superstructures.

  9. Telechelic star polymers as self-assembling units from the molecular to the macroscopic scale.

    PubMed

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

    2012-12-07

    By means of multiscale molecular simulations, we show that telechelic-star polymers are a simple, robust, and tunable system, which hierarchically self-assembles into soft-patchy particles and mechanically stabilizes selected, open crystalline structures. The self-aggregating patchy behavior can be fully controlled by the number of arms per star and by the fraction of attractive monomeric units at the free ends of the arms. Such self-assembled soft-patchy particles while forming, upon augmenting density, gel-like percolating networks, preserve properties as particle size, number, and arrangement of patches per particle. In particular, we demonstrate that the flexibility inherent in the soft-patchy particles brings forward a novel mechanism that leads to the mechanical stability of diamond and simple cubic crystals over a wide range of densities, and for molecular sizes ranging from about 10 nm up to the micrometer scale.

  10. Layer-by-layer assembly of ferrocene-modified linear polyethylenimine redox polymer films.

    PubMed

    DeLuca, Jared L; Hickey, David P; Bamper, Daniel A; Glatzhofer, Daniel T; Johnson, Matthew B; Schmidtke, David W

    2013-07-22

    Herein, both electrostatic and covalent layer-by-layer assembly were used for the construction of multicomposite thin films using a ferrocene-modified linear poly(ethylenimine) redox polymer (Fc-C6-LPEI) as the cationic polyelectrolye, and poly(acrylic acid) (PAA), poly(glutamic acid) (PGA), or glucose oxidase (GOX) as the negative polyelectrolyte. The assembly of the multilayer films was characterized by cyclic voltammetry (CV), UV/Vis spectroscopy, and ellipsometry with the enzymatic response of the films containing GOX being characterized via constant potential amperometry. CV measurements suggested that the successful buildup of multilayer films was dependent upon the nature of the anionic polyelectrolyte used. Electrostatic assembly of films composed of Fc-C6-LPEI and either PAA or PGA produced large oxidation peak current densities of 630 and 670 μA cm(-2), respectively, during cyclic voltammetry. Increased measured absorbance by UV/Vis spectroscopy and increased measured film thicknesses (400-600 nm) by ellipsometry provided additional evidence of successful film formation. In contrast, the films incorporating GOX that were electrostatically assembled surprisingly produced significantly lower electrochemical responses (12 μA cm(-2)), low absorbance values, and reduced film thicknesses (~15 nm), and glucose electro-oxidation current densities less than 1 μA cm(-2), which all suggested unstable or minimal film formation. Subsequently, we developed a covalent layer-by-layer approach to fabricate films of Fc-C6-LPEI/GOX by covalently linking the amine groups of Fc-C6-LPEI to the aldehyde groups of periodate-oxidized glucose oxidase. Covalent assembly of the Fc-C6-LPEI/GOX films produced oxidation peak current densities during cyclic voltammetry of 40 μA cm(-2) and glucose electro-oxidation current densities of 220 μA cm(-2). These films also showed an increase in their thicknesses (~140 nm) relative to the electrostatic GOX films. For the films containing

  11. Modular design of domain assembly in porous coordination polymer crystals via reactivity-directed crystallization process.

    PubMed

    Fukushima, Tomohiro; Horike, Satoshi; Kobayashi, Hirokazu; Tsujimoto, Masahiko; Isoda, Seiji; Foo, Maw Lin; Kubota, Yoshiki; Takata, Masaki; Kitagawa, Susumu

    2012-08-15

    The mesoscale design of domain assembly is crucial for controlling the bulk properties of solids. Herein, we propose a modular design of domain assembly in porous coordination polymer crystals via exquisite control of the kinetics of the crystal formation process. Employing precursors of comparable chemical reactivity affords the preparation of homogeneous solid-solution type crystals. Employing precursors of distinct chemical reactivity affords the preparation of heterogeneous phase separated crystals. We have utilized this reactivity-directed crystallization process for the facile synthesis of mesoscale architecture which are either solid-solution or phase-separated type crystals. This approach can be also adapted to ternary phase-separated type crystals from one-pot reaction. Phase-separated type frameworks possess unique gas adsorption properties that are not observed in single-phasic compounds. The results shed light on the importance of crystal formation kinetics for control of mesoscale domains in order to create porous solids with unique cooperative functionality.

  12. Mono- and Bis-Terpyridine-Based Dimer and Metallo-Organic Polymers as Ionic Templates for Preparation of Multi-Metallic Au Nanocluster and Nanowires.

    PubMed

    Liu, Die; Cao, Hongda; Jiang, Zhilong; Wu, Tun; Sun, Xiaoyi; Wang, Pingshan; Moorefield, Charles N; Dai, Liming; Newkome, George R

    2016-03-01

    The preparation of multi-metallic Au nanocluster and nanowires has been achieved using terpyridine-based metallo-organic polymers as multi-ionic templates through a straightforward counterion exchange with aqueous NaAuCl4 followed by a mild reduction in-situ with sodium citrate. The mild reduction of the [TpyFeTpy]2+ x 2[AuCl4]- complex, derived from [TpyFeTpy]2+ x 2Cl- 1 (tpy = 2,2':6',2"-terpyridine), led to the formation of Au nanoclusters (Au NC) with diameters ranging from 7.5-88 nm. Each Au NC alone contained multiple nanoparticles, with diameters ranging from 2.5-4.5 nm. 1,4-bis-terpyridine based metallo-oraganic polymer [-TpyFeTpy-TpyFeTpy-]n(2n+) x [Cl]2n- 2 was found to generate a multi-ionic metallo-polymer with AuCl4- as the counterion, after mild reduction with sodium citrate, resulting in irregular zigzag shaped Au nanowires (Au NW). The prepared Au NW from the di-metallic complex 3 should find applications within electronic devices. Both Au NC and NW were also found to possess excellent catalytic properties.

  13. Self-assembly of DNA origami particles in suspension of non-absorbing depleting polymers

    NASA Astrophysics Data System (ADS)

    Siavashpouri, Mahsa; Zakhary, Mark; Wachauf, Christian; Dietz, Hendrik; Dogic, Zvonimir

    2015-03-01

    The connection between the macroscopic properties of a liquid crystalline material and the microscopic features of the constituent molecules is the essential theme that permeates the field of liquid crystals. Previous studies have shown that monodisperse rod-like colloids such as filamentous bacteriophage self-assemble into 1D twisted ribbons in presence of attractive interactions mediated by non-absorbing polymers. The microscopic properties of the colloidal particles play an important role in determining the physical properties of these mesoscopic assemblages. Using structural DNA nanotechnology, we present the design and structure of DNA origami six-helix bundles with tunable microscopic properties, which can be used as a new building block for the self-assembly of rod-like colloidal particles. We demonstrate that formation of higher order structures from the assembly of colloidal rods is universal. By tuning the chirality, aspect ratio and flexibility of the DNA origami particles we can control the physical properties of the entire self-assembled structures.

  14. Solution growth of spherulitic rod and platelet calcium phosphate assemblies through polymer-assisted mesoscopic transformations.

    PubMed

    Kosma, Vassiliki A; Beltsios, Konstantinos G

    2013-05-01

    Solution growth of apatite its precursors in the presence of urea commercial gelatin is found to lead, under appropriate conditions, to a rich spectrum of morphologies, among them high aspect ratio needles in uniform sturdy spherulitic assemblies resulting from a herein documented morphological 'Chrysalis Transformation'; the latter transformation involves the growth of parallel arrays of high aspect ratio needles within micron-scale tablets the formation of a radial needle arrangement upon disruption of tablet wrapping. A different level of gelatin leads to the formation of sturdy platelet-based spherulites through another morphological transformation. We also probe the role of four simple synthetic water-soluble polymers; we find that three of them (poly(vinyl alcohol), polyvinylpyrrolidone and polyacrylamide)) also affect substantially the assembly habits of apatite; the effect is similar to that of gelatin but the attained control is less perfect/complete. The case of poly(vinyl alcohol) provides, through variation of the degree of hydrolysis, insights as regards the chain architecture features that might favor morphological transformations. Morphological transformations of particle assemblies documented herein constitute novel ways of generating dense quasi-isotropic reinforcements with high aspect ratio ceramic particles; it becomes possible to tailor calcium phosphate phases at the structural level of crystal assembly.

  15. Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers

    PubMed Central

    Huang, Cheng; Moosmann, Markus; Jin, Jiehong; Heiler, Tobias; Schimmel, Thomas

    2012-01-01

    Summary A rapid and cost-effective lithographic method, polymer blend lithography (PBL), is reported to produce patterned self-assembled monolayers (SAM) on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity), the molar mass of the polystyrene (PS) and poly(methyl methacrylate) (PMMA), and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix) can be reproducibly induced. Either of the formed phases (PS or PMMA) can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This “monolayer copy” of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity) at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and (3-aminopropyl)triethoxysilane (APTES), and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures [1]. PMID:23019558

  16. Redox-switchable supramolecular graft polymer formation via ferrocene-cyclodextrin assembly.

    PubMed

    Szillat, Florian; Schmidt, Bernhard V K J; Hubert, Artur; Barner-Kowollik, Christopher; Ritter, Helmut

    2014-07-01

    The redox switchable formation of very well-defined supramolecular graft polymers in aqueous solution driven by host-guest interactions between ferrocene (Fc) and cyclodextrin (CD) is presented. The Fc-containing acrylic backbone copolymer (PDMA-stat-Fc) is prepared via reversible addition-fragmentation chain transfer (RAFT) copolymerization of N,N-dimethyl-acrylamide (DMA) and the novel monomer N-(ferrocenoylmethyl)acrylamide (NFMA). Via the RAFT process, copolymers containing variable Fc ratios (5-10 mol%) are prepared, affording polymers of molecular masses of close to 11,000 g mol(-1) and molar mass dispersities (Đ) of 1.2. The β-cyclodextrin (β-CD) containing building block is synthesized via RAFT-polymerization, too, in order to afford a polymer with well-defined molecular mass and low dispersity (Mn = 10 300 g mol(-1) , Đ = 1.1), employing a propargyl-functionalized chain transfer agent for the polymerization of N,N-diethylacrylamide (DEA). The polymerization product is subsequently terminated with β-CD via the regiospecific copper (I)-catalyzed 1,3-cycloaddition (PDEA-βCD). Host-guest interactions between Fc and CD lead to the formation of supramolecular graft-polymers, verified via nuclear Overhauser enhancement spectroscopy (NOESY). Importantly, their redox-responsive character is clearly confirmed via cyclic voltammetry (CV). The self-assembly of the statistical Fc-containing lateral polymer chain in aqueous solution leads to mono- and multi-core micelle-aggregates evidenced via TEM. Only diffused cloud-like, non-spherical nanostructures are observed after addition of PDEA-βCD (TEM).

  17. Engineering efficient thermoelectrics from large-scale assemblies of doped ZnO nanowires: nanoscale effects and resonant-level scattering.

    PubMed

    Brockway, Lance; Vasiraju, Venkata; Sunkara, Mahendra K; Vaddiraju, Sreeram

    2014-09-10

    Recent studies focusing on enhancing the thermoelectric performance of metal oxides were primarily motivated by their low cost, large availability of the component elements in the earth's crust, and their high stability. So far, these studies indicate that n-type materials, such as ZnO, have much lower thermoelectric performance than their p-type counterparts. Overcoming this limitation requires precisely tuning the thermal and electrical transport through n-type metal oxides. One way to accomplish this is through the use of optimally doped bulk assemblies of ZnO nanowires. In this study, the thermoelectric properties of n-type aluminum and gallium dually doped bulk assembles of ZnO nanowires were determined. The results indicated that a high zT of 0.6 at 1000 °C, the highest experimentally observed for any n-type oxide, is possible. The high performance is attributed to the tailoring of the ZnO phase composition, nanostructuring of the material, and Zn-III band hybridization-based resonant scattering.

  18. Polymer mediated layer-by-layer assembly of different shaped gold nanoparticles.

    PubMed

    Budy, Stephen M; Hamilton, Desmond J; Cai, Yuheng; Knowles, Michelle K; Reed, Scott M

    2017-02-01

    Gold nanoparticles (GNPs) have a wide range of properties with potential applications in electronics, optics, catalysis, and sensing. In order to demonstrate that dense, stable, and portable samples could be created for these applications, multiple layers of GNPs were assembled via drop casting on glass substrates by layer-by-layer (LBL) techniques. Two cationic polyelectrolytes, poly(diallyldimethylammonium chloride) and polyethyleneimine, one anionic polyelectrolyte, poly(sodium 4-styrene sulfonate), and one neutral polymer, polyvinylpyrrolidone, were combined with four different shapes of GNPs (spherical, rod, triangular prismatic, and octahedral) to prepare thin films. A subset of these polymer nanoparticle combinations were assembled into thin films. Synthesized GNPs were characterized via dynamic light scattering, UV-vis spectroscopy, and transmission electron microscopy and the LBL thin films were characterized using UV-vis spectroscopy and atomic force microscopy. Sensing applications of the nanoparticles in solution and thin films were tested by monitoring the localized surface plasmon resonance of the GNPs. LBL thin films were prepared ranging from 25 to 100 layers with optical densities at plasmon from 0.5 to 3.0. Sensitivity in solutions ranged from 14 to 1002nm/refractive index units (RIU) and films ranged from 18.8 to 135.1nm/RIU suggesting reduced access to the GNPs within the films.

  19. Facile Directed Assembly of Hollow Polymer Nanocapsules within Spontaneously Formed Catanionic Surfactant Vesicles

    SciTech Connect

    Kim, Mariya D.; Dergunov, Sergey; Richter, Andrew; Durbin, Jeffrey; Shmakov, Sergey; Jia, Ying; Kenbeilova, Saltanat; Orazbekuly, Yerbolat; Kengpeiil, Aigerim; Lindner, Erno; Pingali, Sai Venkatesh; Urban, Volker S; Weigand, Steven; Pinkhassik, Eugene

    2014-01-01

    Surfactant vesicles containing monomers in the interior of the bilayer were used to template hollow polymer nanocapsules. This study investigated the formation of surfactant/monomer assemblies by two loading methods, concurrent loading and diffusion loading. The assembly process and the resulting aggregates were investigated with dynamic light scattering, small angle neutron scattering, and small-angle X-ray scattering. Acrylic monomers formed vesicles with a mixture of cationic and anionic surfactants in a broad range of surfactant ratios. Regions with predominant formation of vesicles were broader for compositions containing acrylic monomers compared with blank surfactants. This observation supports the stabilization of the vesicular structure by acrylic monomers. Diffusion loading produced monomer-loaded vesicles unless vesicles were composed from surfactants at the ratios close to the boundary of a vesicular phase region on a phase diagram. Both concurrent-loaded and diffusion-loaded surfactant/monomer vesicles produced hollow polymer nanocapsules upon the polymerization of monomers in the bilayer followed by removal of surfactant scaffolds.

  20. Phospholipid—polymer amphiphile hybrid assemblies and their interaction with macrophages

    PubMed Central

    Panneerselvam, Karthiga; Lynge, Martin E.; Riber, Camilla Frich; Mena-Hernando, Sofia; Smith, Anton A. A.; Goldie, Kenneth N.; Zelikin, Alexander N.; Städler, Brigitte

    2015-01-01

    Recently, the combination of lipids and block copolymers has become an alternative to liposomes and polymersomes as nano-sized drug carriers. We synthesize novel block copolymers consisting of poly(cholesteryl acrylate) as the hydrophobic core and poly(N-isopropylacrylamide) (PNIPAAm) as the hydrophilic extensions. Their successful phospholipid-assisted assembly into vesicles is demonstrated using the evaporation-hydration method. The preserved thermo-responsive property of the lipid-polymer hybrids is shown by a temperature dependent adsorption behaviour of the vesicles to poly(l lysine) coated surfaces. As expected, the vesicle adsorption is found to be higher at elevated temperatures. The cellular uptake efficiency of hybrids is assessed using macrophages with applied shear stress. The amount of adhering macrophages is affected by the time and level of applied shear stress. Further, it is found that shorter PNIPAAm extensions lead to higher uptake of the assemblies by the macrophages with applied shear stress. No inherent cytotoxicity is observed at the tested conditions. Taken together, this first example of responsive lipid-polymer hybrids, and their positive biological evaluation makes them promising nano-sized drug carrier candidates. PMID:26339330

  1. Phospholipid-polymer amphiphile hybrid assemblies and their interaction with macrophages.

    PubMed

    Panneerselvam, Karthiga; Lynge, Martin E; Riber, Camilla Frich; Mena-Hernando, Sofia; Smith, Anton A A; Goldie, Kenneth N; Zelikin, Alexander N; Städler, Brigitte

    2015-09-01

    Recently, the combination of lipids and block copolymers has become an alternative to liposomes and polymersomes as nano-sized drug carriers. We synthesize novel block copolymers consisting of poly(cholesteryl acrylate) as the hydrophobic core and poly(N-isopropylacrylamide) (PNIPAAm) as the hydrophilic extensions. Their successful phospholipid-assisted assembly into vesicles is demonstrated using the evaporation-hydration method. The preserved thermo-responsive property of the lipid-polymer hybrids is shown by a temperature dependent adsorption behaviour of the vesicles to poly(l lysine) coated surfaces. As expected, the vesicle adsorption is found to be higher at elevated temperatures. The cellular uptake efficiency of hybrids is assessed using macrophages with applied shear stress. The amount of adhering macrophages is affected by the time and level of applied shear stress. Further, it is found that shorter PNIPAAm extensions lead to higher uptake of the assemblies by the macrophages with applied shear stress. No inherent cytotoxicity is observed at the tested conditions. Taken together, this first example of responsive lipid-polymer hybrids, and their positive biological evaluation makes them promising nano-sized drug carrier candidates.

  2. Controlled Segmentation of Metal Nanowire Array by Block Copolymer Lithography and Reversible Ion Loading.

    PubMed

    Mun, Jeong Ho; Cha, Seung Keun; Kim, Ye Chan; Yun, Taeyeong; Choi, Young Joo; Jin, Hyeong Min; Lee, Jae Eun; Jeon, Hyun Uk; Kim, So Youn; Kim, Sang Ouk

    2017-02-20

    Spatial arrangement of 1D nanomaterials may offer enormous opportunities for advanced electronics and photonics. Moreover, morphological complexity and chemical diversity in the nanoscale components may lead to unique properties that are hardly anticipated in randomly distributed homogeneous nanostructures. Here, controlled chemical segmentation of metal nanowire arrays using block copolymer lithography and subsequent reversible metal ion loading are demonstrated. To impose chemical heterogeneity in the nanowires generated by block copolymer lithography, reversible ion loading method highly specific for one particular polymer block is introduced. Reversibility of the metal ion loading enables area-selective localized replacement of metal ions in the self-assembled patterns and creates segmented metal nanowire arrays with different metallic components. Further integration of this method with shear aligning process produces high aligned segmented metal nanowire array with desired local chemical compositions.

  3. A new type of porous graphite foams and their integrated composites with oxide/polymer core/shell nanowires for supercapacitors: structural design, fabrication, and full supercapacitor demonstrations.

    PubMed

    Xia, Xinhui; Chao, Dongliang; Fan, Zhanxi; Guan, Cao; Cao, Xiehong; Zhang, Hua; Fan, Hong Jin

    2014-03-12

    We attempt to meet the general design requirements for high-performance supercapacitor electrodes by combining the strategies of lightweight substrate, porous nanostructure design, and conductivity modification. We fabricate a new type of 3D porous and thin graphite foams (GF) and use as the light and conductive substrates for the growth of metal oxide core/shell nanowire arrays to form integrated electrodes. The nanowire core is Co3O4, and the shell is a composite of conducting polymer (poly(3,4-ethylenedioxythiophene), PEDOT) and metal oxide (MnO2). To show the advantage of this integrated electrode design (viz., GF + Co3O4/PEDOT-MnO2 core/shell nanowire arrays), three other different less-integrated electrodes are also prepared for comparison. Full supercapacitor devices based on the GF + Co3O4/PEDOT-MnO2 as positive electrodes exhibit the best performance compared to other three counterparts due to an optimal design of structure and a synergistic effect.

  4. Dendronized organoplatinum(II) metallacyclic polymers constructed by hierarchical coordination-driven self-assembly and hydrogen-bonding interfaces.

    PubMed

    Yan, Xuzhou; Jiang, Bo; Cook, Timothy R; Zhang, Yanyan; Li, Jinying; Yu, Yihua; Huang, Feihe; Yang, Hai-Bo; Stang, Peter J

    2013-11-13

    We describe the efficient preparation of rhomboidal metallacycles that self-assemble upon mixing a donor decorated with 2-ureido-4-pyrimidinone (UPy) with acceptors containing pendant [G1]-[G3] dendrons. The formed rhomboids subsequently polymerize into dendronized organoplatinum(II) metallacyclic polymers through H-bonding UPy interfaces, which possess the structural features of conventional dendronized polymers as well as the dynamic reversibility of supramolecular polymers. Preservation of both properties in a single material is achieved by exploiting hierarchical self-assembly, namely the unification of coordination-driven self-assembly with H-bonding, which provides facile routes to dendronized metallacycles and subsequent high ordering. The supramolecular polymerization defined here represents a novel method to deliver architecturally complex and ordered polymeric materials with adaptive properties.

  5. Well-Defined Protein/Peptide-Polymer Conjugates by Aqueous Cu-LRP: Synthesis and Controlled Self-Assembly.

    PubMed

    Zhang, Qiang; Li, Muxiu; Zhu, Chongyu; Nurumbetov, Gabit; Li, Zaidong; Wilson, Paul; Kempe, Kristian; Haddleton, David M

    2015-07-29

    The synthesis of well-defined protein/peptide-polymer conjugates with interesting self-assembly behavior via single electron transfer living radical polymerization in water is described. A range of protein/peptides with different physical and chemical properties have been modified to macroinitiators and optimized polymerization conditions ensure successful polymerization from soluble, insoluble, and dispersed protein/peptide molecules or protein aggregates. This powerful strategy tolerates a range of functional monomers and mediates efficient homo or block copolymerization to generate hydrophilic polymers with controlled molecular weight (MW) and narrow MW distribution. The polymerizations from bovine insulin macroinitiators follow surface-initiated "grafting from" polymerization mechanism and may involve a series of self-assembly and disassembly processes. Synthesized insulin-polymer conjugates form spheres in water, and the self-assembly behavior could be controlled via thermal control, carbohydrate-protein interaction, and protein denaturation.

  6. Observation of the Chiral and Achiral Hexatic Phases of Self-assembled Micellar polymers

    PubMed Central

    Pal, Antara; Kamal, Md. Arif; Raghunathan, V. A.

    2016-01-01

    We report the discovery of a thermodynamically stable line hexatic (N + 6) phase in a three-dimensional (3D) system made up of self-assembled polymer-like micelles of amphiphilic molecules. The experimentally observed phase transition sequence nematic (N)  N + 6  two-dimensional hexagonal (2D-H) is in good agreement with the theoretical predictions. Further, the present study also brings to light the effect of chirality on the N + 6 phase. In the chiral N + 6 phase the bond-orientational order within each “polymer” bundle is found to be twisted about an axis parallel to the average polymer direction. This structure is consistent with the theoretically envisaged Moiré state, thereby providing the first experimental demonstration of the Moiré structure. In addition to confirming the predictions of fundamental theories of two-dimensional melting, these results are relevant in a variety of situations in chemistry, physics and biology, where parallel packing of polymer-like objects are encountered. PMID:27577927

  7. Development of block co-polymers as self-assembling templates for patterned media.

    SciTech Connect

    Warke, V.; Bakker, M. G.; Hong, K.; Mays, J.; Britt, P.; Li, X.; Wang, J.; X-Ray Science Division; Univ. of Alabama; ORNL

    2006-01-01

    Block copolymers that self-organize are of interest as templates for patterned media, as they potentially provide a low cost fabrication route. Poly(styrene)-Poly(methylmethacrylate) block co-polymers (PS-b-PMMA) of appropriate block length and PS to PMMA ratio self-assemble into a 2-D hexagonal phase in which the PS majority phase is continuous and surrounds cylinders of the minority, PMMA phase. For application of this phase to patterned media it is necessary that the cylinders of the minority phase be oriented perpendicular to the substrate surface. This can be achieved by a number of methods, including appropriate choice of substrate and use of a random co-polymer underlayer. Appropriate substrates include H-terminated silicon, some carbon coatings and some ITO glasses. Use of an acetic acid wash causes the minority PMMA component can be induced to be rearranged, giving rise to pores perpendicular to the substrate. Electrodeposition of a metal into the pores produces a hardmask which can be used with ion-milling to transfer the block co-polymer pattern onto a magnetic thin film.

  8. Self-assembly of flexible one-dimensional coordination polymers on metal surfaces.

    PubMed

    Heim, Daniel; Ecija, David; Seufert, Knud; Auwärter, Willi; Aurisicchio, Claudia; Fabbro, Chiara; Bonifazi, Davide; Barth, Johannes V

    2010-05-19

    We employed a de novo synthesized porphyrin module to construct one-dimensional (1D) Cu-coordinated polymers on Cu(111) and Ag(111) surfaces. The programmed geometry and functionality of the molecular module together with its conformational flexibility and substrate interaction yields sinuous metal-organic polymeric assemblies, based on an unusual two-fold Cu-pyridyl coordination motif. An analysis of scanning tunneling microscopy (STM) data reveals the occurrence of two enantiomers, resulting from the surface confinement that deconvolutes the module in 2D-chiral conformational isomers. The stereoisomers exhibit site-specific surface anchoring, from whence three discrete orientations are possible for each species. Their sequence and mutual arrangement determine direction and curvature of the metal-organic chains. The Cu-coordinated polymers are very similar on both Cu(111) and Ag(111), where their formation is induced by intrinsic and coevaporated adatoms, respectively, which indicates that the lateral bonding motif is predominantly independent of the substrate. In addition, molecular manipulation experiments show the collective motion of entire segments of the Cu-coordinated multi-porphyrin polymers.

  9. Enhancing the Thermal Conductance of Polymer and Sapphire Interface via Self-Assembled Monolayer.

    PubMed

    Zheng, Kun; Sun, Fangyuan; Zhu, Jie; Ma, Yongmei; Li, Xiaobo; Tang, Dawei; Wang, Fosong; Wang, Xiaojia

    2016-08-23

    Interfacial thermal conductance (ITC) receives enormous consideration because of its significance in determining thermal performance of hybrid materials, such as polymer based nanocomposites. In this study, the ITC between sapphire and polystyrene (PS) was systematically investigated by time domain thermoreflectance (TDTR) method. Silane based self-assembled monolayers (SAMs) with varying end groups, -NH2, -Cl, -SH and -H, were introduced into sapphire/PS interface, and their effects on ITC were investigated. The ITC was found to be enhanced up by a factor of 7 through functionalizing the sapphire surface with SAM, which ends with a chloride group (-Cl). The results show that the enhancement of the thermal transport across the SAM-functionalized interface comes from both strong covalent bonding between sapphire and silane-based SAM, and the high compatibility between the SAM and PS. Among the SAMs studied in this work, we found that the ITC almost linearly depends on solubility parameters, which could be the dominant factor influencing on the ITC compared with wettability and adhesion. The SAMs serve as an intermediate layer that bridges the sapphire and PS. Such a feature can be applied to ceramic-polymer immiscible interfaces by functionalizing the ceramic surface with molecules that are miscible with the polymer materials. This research provides guidance on the design of critical-heat transfer materials such as composites and nanofluids for thermal management.

  10. Electrochemical properties of multilayer film assembled by layer-by-layer adsorption of redox polymer

    NASA Astrophysics Data System (ADS)

    Sun, Tao; Zheng, Haitao; Liu, Shiyang; Liu, Pu; Zhou, Jingli; Suye, Shin-ichiro

    2009-07-01

    A redox polymer, poly(ethylenimine)ferrocene (PEI-Fc) was prepared by attaching electroactive ferrocene groups to the backbone of a water soluble, biocompatible polyelectrolyte, poly(ethylenimine), and multilayer film composed of polystyrenesulfonate sodium (PSS) and PEI-Fc was prepared by alternate layer-by-layer (LBL) self-assembly adsorption technique based on the electrostatic force between the opposite charges carried by these two polymers. UV-Vis spectra was used to monitor the LBL process, and the thickness and immobilization amount of each layer were characterized by quartz crystal microbalance (QCM), which showed the formation of nano-scale multilayer structure and linear mass increase dependent on the alternate adsorption cycles. The electrochemical properties of the PEI-Fc/PSS multilayer film modified gold electrode were investigated by cyclic voltammetry. It was observed clearly that the electrochemical properties of this multilayer film were strongly dependent on the layer number and the ferrocene content in PEI-Fc. The electrochemical kinetic was analyzed based on a general model for surface process, and the experimental data fitted well with that evaluated from the above model. This redox polymer showed potential for the construction of reagentless biosensor.

  11. Exploiting fluorescent polymers to probe the self-assembly of virus-like particles.

    PubMed

    Cadena-Nava, Ruben D; Hu, Yufang; Garmann, Rees F; Ng, Benny; Zelikin, Alexander N; Knobler, Charles M; Gelbart, William M

    2011-03-17

    The inside surfaces of the protein shells of many viruses are positively charged, thereby enhancing the self-assembly of capsid proteins around their (oppositely charged) RNA genome. These proteins have been shown to organize similarly around a variety of nonbiological, negatively charged, polymers, for example, poly(styrene sulfonate) (PSS), forming virus-like particles (VLPs). We have demonstrated recently that the VLPs formed from cowpea chlorotic mottle virus (CCMV) capsid protein increase in size (from T=2 to T=3 structures) upon increase in PSS molecular weight (from 400 kDa to 3.4 MDa), and that the total charge on the PSS exceeds that of the capsid protein by as much as a factor of 9. Here, we extend studies of this kind to PSS molecules that are sufficiently small that two or more can be packaged into VLPs. The use of 38 kDa PSS polymers that have been fluorescently labeled with Rhodamine B allows us to determine the number of PSS molecules per capsid. Electron micrographs of the VLPs show a bimodal distribution of particle diameters, with one peak centered around 19 nm, typical of a T=1 triangulation number, and the other around 21 nm, consistent with a pseudo T=2 structure; increasing the molar ratio of protein to PSS in the reaction mix shifts the VLP distribution from T=1 to T=2 structures. By combining fluorescence and gel electrophoresis measurements, it is determined that, on average, there are two polymers in each T=1 capsid and three in each T=2, with the PSS charge less than that of the capsid protein by as much as a factor of 2. VLPs of this kind provide a versatile model system for determining the principles underlying self-assembly of controlled numbers of cargo molecules in nanocontainers of increasing size.

  12. Star-like supramolecular polymers fabricated by a Keplerate cluster with cationic terminated polymers and their self-assembly into vesicles.

    PubMed

    Zhang, Qian; He, Lipeng; Wang, Hui; Zhang, Cheng; Liu, Weisheng; Bu, Weifeng

    2012-07-18

    The electrostatic combination of a Keplerate cluster, [Mo(132)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-) with cationic terminated poly(styrene) yields polyoxometalate-based supramolecular star polymers, which can further self-assemble into vesicular aggregates in CHCl(3)-MeOH mixed solvent.

  13. Thin and long silver nanowires self-assembled in ionic liquids as a soft template: electrical and optical properties.

    PubMed

    Chang, Min-Hwa; Cho, Hyun-Ah; Kim, Youn-Soo; Lee, Eun-Jong; Kim, Jin-Yeol

    2014-01-01

    Thin and long silver nanowires were successfully synthesized using the polyvinylpyrrolidone (PVP)-assisted polyol method in the presence of ionic liquids, tetrapropylammonium chloride and tetrapropylammonium bromide, which served as soft template salts. The first step involved the formation of Ag nanoparticles with a diameter of 40 to 50 nm through the reduction of silver nitrate. At the growing stage, the Ag nanoparticles were converted into thin and long one-dimensional wires, with uniform diameters of 30 ± 3 nm and lengths of up to 50 μm. These Ag nanowires showed an electrical conductivity of 0.3 × 10(5) S/cm, while the sheet resistance of a two-dimensional percolating Ag nanowire network exhibited a value of 20 Ω/sq with an optical transmittance of 93% and a low haze value.

  14. Fabrication of DNA nanowires by orthogonal self-assembly and DNA intercalation on a Au patterned Si/SiO2 surface.

    PubMed

    Kobayashi, Katsuaki; Tonegawa, Naoya; Fujii, Sho; Hikida, Jiro; Nozoye, Hisakazu; Tsutsui, Ken; Wada, Yasuo; Chikira, Makoto; Haga, Masa-Aki

    2008-11-18

    A novel Ru complex bearing both an acridine group and anchoring phosphonate groups was immobilized on a surface in order to capture double-stranded DNAs (dsDNAs) from solution. At low surface coverage, the atomic force microscopy (AFM) image revealed the "molecular dot" morphology with the height of the Ru complex ( approximately 2.5 nm) on a mica surface, indicating that four phosphonate anchor groups keep the Ru complex in an upright orientation on the surface. Using a dynamic molecular combing method, the DNA capture efficiency of the Ru complex on a mica surface was examined in terms of the effects of the number of molecular dots and surface hydrophobicity. The immobilized surface could capture DNAs; however, the optimal number of molecular dots on the surface as well as the optimal pull-up speed exist to obtain the extended dsDNAs on the surface. Applying this optimal condition to a Au-patterned Si/SiO 2 (Au/SiO 2) surface, the Au electrode was selectively covered with the Ru complex by orthogonal self-assembly of 4-mercaptbutylphosphonic acid (MBPA), followed by the formation of a Zr (4+)-phosphonate layer and the Ru complex. At the same time, the remaining SiO 2 surface was covered with octylphosphonic acid (OPA) by self-assembly. The selective immobilization of the Ru complex only on the Au electrode was identified by time-of-flight secondary-ion mass spectrometry (TOF-SIMS) imaging on the chemically modified Au/SiO 2 surface. The construction of DNA nanowires on the Au/SiO 2 patterned surface was accomplished by the molecular combing method of the selective immobilized Ru complex on Au electrodes. These interconnected nanowires between Au electrodes were used as a scaffold for the modification of Pd nanoparticles on the DNA. Furthermore, Cu metallization was achieved by electroless plating of Cu metal on a priming of Pd nanoparticles on the Pd-covered DNA nanowires. The resulting Cu nanowires showed a metallic behavior with relatively high resistance.

  15. Solution-processed low dimensional nanomaterials with self-assembled polymers for flexible photo-electronic devices (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Park, Cheolmin

    2015-09-01

    Self assembly driven by complicated but systematic hierarchical interactions offers a qualified alternative for fabricating functional micron or nanometer scale pattern structures that have been potentially useful for various organic and nanotechnological devices. Self assembled nanostructures generated from synthetic polymer systems such as controlled polymer blends, semi-crystalline polymers and block copolymers have gained a great attention not only because of the variety of nanostructures they can evolve but also because of the controllability of these structures by external stimuli. In this presentation, various novel photo-electronic materials and devices are introduced based on the solution-processed low dimensional nanomaterials such as networked carbon nanotubes (CNTs), reduced graphene oxides (rGOs) and 2 dimensional transition metal dichalcogenides (TMDs) with self assembled polymers including field effect transistor, electroluminescent device, non-volatile memory and photodetector. For instance, a nanocomposite of networked CNTs and a fluorescent polymer turned out an efficient field induced electroluminescent layer under alternating current (AC) as a potential candidate for next generation displays and lightings. Furthermore, scalable and simple strategies employed for fabricating rGO as well as TMD nanohybrid films allowed for high performance and mechanically flexible non-volatile resistive polymer memory devices and broad band photo-detectors, respectively.

  16. Supramolecular Engineering of Hierarchically Self-Assembled, Bioinspired, Cholesteric Nanocomposites Formed by Cellulose Nanocrystals and Polymers.

    PubMed

    Zhu, Baolei; Merindol, Remi; Benitez, Alejandro J; Wang, Baochun; Walther, Andreas

    2016-05-04

    Natural composites are hierarchically structured by combination of ordered colloidal and molecular length scales. They inspire future, biomimetic, and lightweight nanocomposites, in which extraordinary mechanical properties are in reach by understanding and mastering hierarchical structure formation as tools to engineer multiscale deformation mechanisms. Here we describe a hierarchically self-assembled, cholesteric nanocomposite with well-defined colloid-based helical structure and supramolecular hydrogen bonds engineered on the molecular level in the polymer matrix. We use reversible addition-fragmentation transfer polymerization to synthesize well-defined hydrophilic, nonionic polymers with a varying functionalization density of 4-fold hydrogen-bonding ureidopyrimidinone (UPy) motifs. We show that these copolymers can be coassembled with cellulose nanocrystals (CNC), a sustainable, stiff, rod-like reinforcement, to give ordered cholesteric phases with characteristic photonic stop bands. The dimensions of the helical pitch are controlled by the ratio of polymer/CNC, confirming a smooth integration into the colloidal structure. With respect to the effect of the supramolecular motifs, we demonstrate that those regulate the swelling when exposing the biomimetic hybrids to water, and they allow engineering the photonic response. Moreover, the amount of hydrogen bonds and the polymer fraction are decisive in defining the mechanical properties. An Ashby plot comparing previous ordered CNC-based nanocomposites with our new hierarchical ones reveals that molecular engineering allows us to span an unprecedented mechanical property range from highest inelastic deformation (strain up to ∼13%) to highest stiffness (E ∼ 15 GPa) and combinations of both. We envisage that further rational design of the molecular interactions will provide efficient tools for enhancing the multifunctional property profiles of such bioinspired nanocomposites.

  17. Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas

    2005-01-01

    In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect

  18. Conformational assembly and biological properties of collagen mimetic peptides and their thermally responsive polymer conjugates

    NASA Astrophysics Data System (ADS)

    Krishna, Ohm Divyam

    2011-12-01

    Collagens are one of the most abundant proteins found in body tissues and organs, endowing structural integrity, mechanical strength, and multiple biological functions. Destabilized collagen inside human body leads to various degenerative diseases (ex. osteoarthritis) and ageing. This has continued to motivate the design of synthetic peptides and bio-synthetic polypeptides to closely mimic the native collagens in terms of triple helix structure and stability, potential for higher order assembly, and biological properties. However, the widespread application of de novo collagens has been limited in part by the need for hydroxylated proline in the formation of stable triple helical structures. To address this continued need, a hydroxyproline-free, thermally stable collagen-mimetic peptide (CLP-Cys) was rationally designed via the incorporation of electrostatically stabilized amino acid triplets. CLP-Cys was synthesized via solid phase peptide synthesis. The formation and stability of the triple helical structure were indicated via circular dichroism (CD) experiments and confirmed via differential scanning calorimetry (DSC) results. CLP-Cys also self-assembled into nano-rods and micro-fibrils, as evidenced via a combination of dynamic light scattering and transmission electron microscopy. Given the high thermal stability and its propensity for higher-order assembly, CLP-Cys was further functionalized at both the ends with a thermally responsive polymer, poly(diethylene glycol methyl ether methacrylate), (PDEGMEMA) to synthesize a biohybrid triblock copolymer. The CD results indicated that the triple helical form is retained, the thermal unfolding is sustained and helix to coil transition is reversible in the triblock hybrid context. The LCST of PDEGMEMA homopolymer (26 °C) is increased (to 35 °C) upon conjugation to the hydrophilic collagen peptide domain. Further, a combination of static light scattering, Cryo-SEM, TEM and confocal microscopy elucidated that the

  19. Switchable supramolecular polymers from the orthogonal self-assembly of quadruple hydrogen bonding and benzo-21-crown-7-secondary ammonium salt recognition.

    PubMed

    Xiao, Tangxin; Feng, Xiaoqing; Wang, Qi; Lin, Chen; Wang, Leyong; Pan, Yi

    2013-09-28

    Novel linear supramolecular polymers were constructed by the orthogonal self-assembly of a heteroditopic monomer and a homoditopic monomer. The polymerization is driven by a combination of quadruple hydrogen bonding and benzo-21-crown-7 based host-guest complexation. The disassembly-assembly of these novel polymers could be reversibly switched by addition/removal of K(+).

  20. Superconducting nanowire quantum interference device based on Nb ultrathin films deposited on self-assembled porous Si templates

    NASA Astrophysics Data System (ADS)

    Cirillo, C.; Prischepa, S. L.; Trezza, M.; Bondarenko, V. P.; Attanasio, C.

    2014-10-01

    Magnetoresistance oscillations were observed on networks of superconducting ultrathin Nb nanowires presenting evidence of either thermal or quantum activated phase slips. The magnetic transport data, discussed in the framework of different scenarios, reveal that the system behaves coherently in the temperature range where the contribution of the fluctuations is important.

  1. Perspectives: Nanofibers and nanowires for disordered photonics

    NASA Astrophysics Data System (ADS)

    Pisignano, Dario; Persano, Luana; Camposeo, Andrea

    2017-03-01

    As building blocks of microscopically non-homogeneous materials, semiconductor nanowires and polymer nanofibers are emerging component materials for disordered photonics, with unique properties of light emission and scattering. Effects found in assemblies of nanowires and nanofibers include broadband reflection, significant localization of light, strong and collective multiple scattering, enhanced absorption of incident photons, synergistic effects with plasmonic particles, and random lasing. We highlight recent related discoveries, with a focus on material aspects. The control of spatial correlations in complex assemblies during deposition, the coupling of modes with efficient transmission channels provided by nanofiber waveguides, and the embedment of random architectures into individually coded nanowires will allow the potential of these photonic materials to be fully exploited, unconventional physics to be highlighted, and next-generation optical devices to be achieved. The prospects opened by this technology include enhanced random lasing and mode-locking, multi-directionally guided coupling to sensors and receivers, and low-cost encrypting miniatures for encoders and labels.

  2. Nanowire Photonic Systems

    DTIC Science & Technology

    2009-12-22

    synthesis of silicon and gallium-indium nitride alloy nanowire heterostructures to provide building blocks for photonic devices that can span the...the Si-nanowire etching profile follows the order in which dopants were introduced during synthesis : First boron for p-type, no dopant for i-type... synthesis of nanoscale building blocks, (ii) characterization of fundamental physical properties of the building blocks, and (iii) assembly of

  3. Assembly of two novel Lindqvist polyoxoanion-templated coordination polymers with standard honeycomb cavities

    NASA Astrophysics Data System (ADS)

    Sha, Jingquan; Huang, Lin; Peng, Jun; Pang, Haijun; Tian, Aixiang; Zhang, Pengpeng; Chen, Yuan; Zhu, Min

    2009-02-01

    Two novel polyoxometalate(POM)-templated coordination polymers: [Cu 2(phnz) 3][M 6O 19] (M = Mo for 1, W for 2; phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In the compounds, Lindqvist POMs as templates induce the [Cu 2(phnz) 3] complexes to 2D hexagonal metal-organic framework (MOF), which represents 6 3 topologies of dimensions ca. 13.515 × 13.515 × 13.515 Å. Furthermore, the 2D sheets are held together by Lindqvist POMs into 3D supramolecular networks with 1D channel, and Lindqvist POMs site in the channels. The successful syntheses and isolation of two compounds provide a novel example of the utility of POM clusters as templates for self-assembly extended framework with cavities.

  4. Sensitive immunosensor for tumor necrosis factor α based on dual signal amplification of ferrocene modified self-assembled peptide nanowire and glucose oxidase functionalized gold nanorod.

    PubMed

    Sun, Zhifang; Deng, Liu; Gan, Hao; Shen, Rujuan; Yang, Minghui; Zhang, Yi

    2013-01-15

    Sensitive electrochemical immunosensor for the detection of protein biomarker tumor necrosis factor α (TNF-α) was reported that uses ferrocene carboxylic acid (Fc) functionalized self-assembled peptide nanowire (Fc-PNW) as sensor platform and glucose oxidase (GOx) modified gold nanorod (GNR) as label. Greatly enhanced sensitivity is achieved based on a dual signal amplification strategy: first, the synthesized Fc-PNW used as the sensor platform increased the loading of primary anti-TNF-α antibody (Ab(1)) onto electrode surface due to its large surface area. At the same time, the Fc moiety on the nanowire is used as a mediator for GOx to catalyze the glucose reaction. Second, multiple GOx and secondary anti-TNF-α antibody (Ab(2)) molecules are bounded onto each GNR to increase the sensitivity of the immunosensor. After the preparation of the immunosensor based on the traditional sandwich protocol, the response of the immunosensor towards glucose was used as a signal to differentiate various concentrations of TNF-α. The resulting immunosensor has high sensitivity, wide linear range (0.005-10ng/mL) and good selectivity. This immunosensor preparation strategy is a promising platform for clinical screening of protein biomarkers.

  5. Facilitated embedding of silver nanowires into conformally-coated iCVD polymer films deposited on cloth for robust wearable electronics.

    PubMed

    Seo, Ji-Won; Joo, Munkyu; Ahn, Jaeho; Lee, Tae-Ik; Kim, Taek-Soo; Im, Sung Gap; Lee, Jung-Yong

    2017-03-09

    We propose that a silver nanowire (AgNW)-embedded conducting film can be monolithically applied onto an arbitrary cloth with strong adhesion and environmental stability. We employ a vapor-phase method, initiated chemical vapor deposition (iCVD), for conformal coating of a scaffold polymer film on the cloth. AgNWs are applied on the surface of iCVD polymer films, and the embedding of AgNWs is completed within only 20 s on heating the polymer-coated cloth to 70 °C. Crosslinking the copolymer at 120 °C renders the AgNW-embedded conducting films on the cloth not only thermally and chemically stable, but also mechanically robust. Moreover, when a hydrophobic encapsulating polymer layer is added on the AgNW-embedded film via iCVD, it substantially improves the stability of the cloth against thermal oxidation under hot and humid conditions, showing applicability of the technology to wearable electronics. With these robust conducting films, we demonstrate the fabrication of a waterproof cloth-based heater and circuit for a seven-segment display, thus, confirming the wide applicability of the technology developed in this study.

  6. Novel surface treatment materials for aligning block-co-polymer in directed self-assembly processes

    NASA Astrophysics Data System (ADS)

    Someya, Yasunobu; Wakayama, Hiroyuki; Endo, Takafumi; Sakamoto, Rikimaru

    2014-03-01

    Directed Self-Assembly (DSA) process is one of the attractive processes for creating the very fine pitch pattern. Especially, the contact hole shrink processes with block-co-polymer (BCP) or polymer blend materials were attractive processes for creating very small size hole patterns with better CD uniformity compare to general photo-lithography patterning. In general contact hole shrink process, the pattern of Spin-on Carbon Hardmask (SOC) or the photo Resist pattern created by Negative-Tone Development (NTD) process were selected for guide patterns. Since the alignment property of BCP was affected by the surface of these guide materials, it is important to control the surface condition of guide in order to obtain good shrunk contact hole patterns. In this study, we will report the surface treatment materials to control the surface condition of guide patterns such as SOC or NTD resist to achieve the better contact hole shrink performance. These materials were attached to guide pattern surface and controlled the surface energy.

  7. Reactive Self-Assembly of Polymers and Proteins to Reversibly Silence a Killer Protein.

    PubMed

    Ventura, Judy; Eron, Scott J; González-Toro, Daniella C; Raghupathi, Kishore; Wang, Feng; Hardy, Jeanne A; Thayumanavan, S

    2015-10-12

    Conjugation of biologically active proteins to polymeric materials is of great interest in the treatment of cancer and other diseases of protein deficiency. The conjugation of such biomacromolecules is challenging both due to their hydrophilicity and propensity to denature under non-native conditions. We describe a novel reactive self-assembly approach to "wrap" a protein with polymers, simultaneously protecting its delicate folded state and silencing its enzymatic activity. This approach has been demonstrated using caspase-3, an apoptosis-inducing protein, as the first case study. The protein-polymer conjugation is designed to be reversed under the native conditions for caspase-3, that is, the reducing environment found in the cytosol. The current strategy allowed release and recovery of up to 86% of caspase activity and nanogel-caspase-3 conjugates induced 70-80% apoptotic cell death shortly thereafter. This approach is widely generalizable and should be applicable to the intracellular delivery of a wide range of therapeutic proteins for treatment of complex and genetic diseases.

  8. Assembling semiconducting molecules by covalent attachment to a lamellar crystalline polymer substrate

    PubMed Central

    Machatschek, Rainhard; Ortmann, Patrick; Reiter, Renate; Mecking, Stefan

    2016-01-01

    Summary We have investigated the potential of polymers containing precisely spaced side-branches for thin film applications, particularly in the context of organic electronics. Upon crystallization, the side-branches were excluded from the crystalline core of a lamellar crystal. Thus, the surfaces of these crystals were covered by side-branches. By using carboxyl groups as side-branches, which allow for chemical reactions, we could functionalize the crystal with semiconducting molecules. Here, we compare properties of crystals differing in size: small nanocrystals and large single crystals. By assembling nanocrystals on a Langmuir trough, large areas could be covered by monolayers consisting of randomly arranged nanocrystals. Alternatively, we used a method based on local supersaturation to grow large area single crystals of the precisely side-branched polymer from solution. Attachment of the semiconducting molecules to the lamellar surface of large single crystals was possible, however, only after an appropriate annealing procedure. As a function of the duration of the grafting process, the morphology of the resulting layer of semiconducting molecules changed from patchy to compact. PMID:27335767

  9. Growth and assembly of functionalized nanomaterials: Using organic-inorganic polymer hybrid systems

    NASA Astrophysics Data System (ADS)

    Goel, Divya

    Precise positioning of metallic nanostructures on semiconductor surfaces is important for applications such as photovoltaics, metal interconnects, sensing platforms, and many others. The rising cost and complexity with lithographically defined structures demands a parallel fabrication process that enables easy scale up. Surface patterns formed by block copolymers are considered as a promising means to create functional nanoscopic structures needed for the fabrication of miniaturized devices. The integration of polymers with inorganic nano-materials could find widespread applications in scientific research because it provides a strategy to combine the use of polymers as hosts, and the optical, electronic, and catalytic properties of nanoparticles. This thesis explores a technique that employs patterns in block copolymers as a template for the directed self-assembly of the nanocrystals. One area investigated was the preparation of thermally stable nanoparticles that could be intercalated into block copolymers. Nanoparticles of various materials were synthesized in spherical and rod shapes with different aspect ratios. These particles were characterized by optical absorption measurements, scanning electron microscopy, high-resolution transmission electorn microscopy, and fluorescence spectroscopy. Methods were developed to functionalize these nanoparticles with thermally stable surface coatings using emulsion polymerization. A new method to control the size and spatial distribution of vertically aligned carbon nanofibers was developed, by intercalating nickel into a polymer film. Nanofibers were subsequently grown using plasma-enhanced chemical vapor deposition, and the properties of the nanofibers were characterized using TEM and electrochemical methods. The alignment of block copolymers normal to a dielectric thin film was demonstrated using AC electric fields. These studies demonstrated the underlying mechanism by which nanoscopic structure in thin films can be

  10. Polymer composites reinforced by locking-in a liquid-crystalline assembly of cellulose nanocrystallites.

    PubMed

    Tatsumi, Mio; Teramoto, Yoshikuni; Nishio, Yoshiyuki

    2012-05-14

    An attempt was made to synthesize novel composites comprising poly(2-hydroxyethyl methacrylate) (PHEMA) and cellulose nanocrystallites (CNC) (acid-treated cotton microfibrils) from suspensions of CNC in an aqueous 2-hydroxyethyl methacrylate (HEMA) monomer solution. The starting suspensions (∼5 wt % CNC) separated into an isotropic upper phase and an anisotropic bottom one in the course of quiescent standing. By way of polymerization of HEMA in different phase situations of the suspensions, we obtained films of three polymer composites, PHEMA-CNC(iso), PHEMA-CNC(aniso), and PHEMA-CNC(mix), coming from the isotropic phase, anisotropic phase, and embryonic nonseparating mixture, respectively. All the composites were transparent and, more or less, birefringent under a polarized optical microscope. A fingerprint texture typical of cholesteric liquid crystals of longer pitch spread widely in PHEMA-CNC(aniso) but rather locally appeared in PHEMA-CNC(iso). Any of the CNC incorporations into the PHEMA matrix improved the original thermal and mechanical properties of this amorphous polymer material. In dynamic mechanical measurements, the locking-in of the respective CNC assemblies gave rise to an increase in the glass-state modulus E' of PHEMA as well as a marked suppression of the E'-falling at temperatures higher than T(g) (≈ 110 °C) of the vinyl polymer. It was also observed for the composites that their modulus E' rerose in a range of about 150-190 °C, which was attributable to a secondary cross-linking formation between PHEMA chains mediated by the acidic CNC filler. The mechanical reinforcement effect of the CNC dispersions was ensured in a tensile test, whereby PHEMA-CNC(aniso) was found to surpass the other two composites in stiffness and strength.

  11. Exploiting Supramolecular Interactions for the Intramolecular Folding of Side-Chain Functionalized Polymers and Assembly of Anisotropic Colloids

    NASA Astrophysics Data System (ADS)

    Romulus, Joy

    The overarching goal presented in this thesis is the self-assembly of synthetic systems into higher ordered structures utilizing supramolecular chemistry. Noncovalent interactions including charge-transfer and hydrogen bonding as well as DNA hybridization are exploited to induce the assembly of polymers and colloids into well-defined architectures. This strategy provides a tunable handle on materials bulk properties that can be adjusted by simply changing variables such as temperature and solvent. A brief overview of design principles for the supramolecular assembly of side-chain functionalized polymers is presented. The polymerization technique selected was living ring-opening metathesis polymerization (ROMP), thus affording control over molecular weight and molecular weight distributions. ROMP also allowed for the incorporation of functional groups that were used to assemble the polymers into ordered structures. Charge-transfer motifs were exploited and shown to drive the assembly of random and alternating copolymers via intramolecular side-chain interactions. Incorporation of complementary hydrogen bonding motifs was shown to guide the single-chain folding of a multifunctional triblock copolymer into sheet-like structures. Precision over the size, shape, and monomer sequence were identified as key elements for efficient self-assembly. The self-assembly of colloids using DNA hybridization was also investigated. Previously, the majority of colloid-based research relied upon the self-assembly of spherical isotropic particles into closed-packed arrangements. In contrast, anisotropic particles may allow for the realization of open structures. By expanding upon a method to permanently cross-link DNA strands incubated on a colloidal surface, a new strategy to engineer patchy particles is described. These functional DNA-coated patches are demonstrated to direct particle assembly. The self-assembly of polymer and colloidal systems utilizing noncovalent interactions

  12. Collagen-like peptides and peptide-polymer conjugates in the design of assembled materials

    PubMed Central

    Luo, Tianzhi; Kiick, Kristi L.

    2013-01-01

    Collagen is the most abundant protein in mammals, and there has been long-standing interest in understanding and controlling collagen assembly in the design of new materials. Collagen-like peptides (CLP), also known as collagen-mimetic peptides (CMP) or collagen-related peptides (CRP), have thus been widely used to elucidate collagen triple helix structure as well as to produce higher-order structures that mimic natural collagen fibers. This mini-review provides an overview of recent progress on these topics, in three broad topical areas. The first focuses on reported developments in deciphering the chemical basis for collagen triple helix stabilization, which we review not with the intent of describing the basic structure and biological function of collagen, but to summarize different pathways for designing collagen-like peptides with high thermostability. Various approaches for producing higher-order structures via CLP self-assembly, via various types of intermolecular interaction, are then discussed. Finally, recent developments in a new area, the production of polymer-CLP bioconjugates, are summarized. Biological applications of collagen contained hydrogels are also included in this section. The topics may serve as a guide for the design of collagen-like peptides and their bioconjugates for targeted application in the biomedical arena. PMID:24039275

  13. Assembly and Characterization of Well Defined High Molecular Weight Poly(p-phenylene) Polymer Brushes

    SciTech Connect

    Alonzo Calderon, Jose E; Kilbey, II, S Michael; Ankner, John Francis; Britt, Phillip F; Chen, Jihua; Dadmun, Mark D; Deng, Suxiang; Hong, Kunlun; Mays, Jimmy; Messman, Jamie M; Sumpter, Bobby; Swader, Onome A; Yu, Xiang; Bredas, Jean-Luc E; Malagoli, Massimo

    2011-01-01

    The assembly and characterization of well-defined, end-tethered poly(p-phenylene) (PPP) brushes having high molecular weight, low polydispersity and high 1,4-stereoregularity are presented. The PPP brushes are formed using a precursor route that relies on either self-assembly or spin coating of high molecular weight (degrees of polymerizations 54, 146, and 238) end-functionalized poly(1,3-cyclohexadiene) (PCHD) chains from benzene solutions onto silicon or quartz substrates, followed by aromatization of the end-attached PCHD chains on the surface. The approach allows the thickness (grafting density) of the brushes to be easily varied. The dry brushes before and after aromatization are characterized by ellipsometry, atomic force microscopy, grazing angle attenuated total reflectance Fourier transform infrared spectroscopy, and UV-Vis spectroscopy. The properties of the PPP brushes are compared with those of films made using oligo-paraphenylenes and with ab initio density functional theory simulations of optical properties. Our results suggest conversion to fully aromatized, end-tethered PPP polymer brushes having effective conjugation lengths of 5 phenyl units.

  14. Long-Term Biostability of Self-Assembling Protein Polymers in the Absence of Covalent Crosslinking

    PubMed Central

    Sallach, Rory E.; Cui, Wanxing; Balderrama, Fanor; Martinez, Adam W.; Wen, Jing; Haller, Carolyn A.; Taylor, Jeannette V.; Wright, Elizabeth R.; Long, Robert C.; Chaikof, Elliot L.

    2009-01-01

    Unless chemically crosslinked, matrix proteins, such as collagen or silk, display a limited lifetime in vivo with significant degradation observed over a period of weeks. Likewise, amphiphilic peptides, lipopeptides, or glycolipids that self-assemble through hydrophobic interactions to form thin films, fiber networks, or vesicles do not demonstrate in vivo biostability beyond a few days. We report herein that a self-assembling, recombinant elastin-mimetic triblock copolymer elicited minimal inflammatory response and displayed robust in vivo stability for periods exceeding 1 year, in the absence of either chemical or ionic crosslinking. Specifically, neither a significant inflammatory response nor calcification was observed upon implantation of test materials into the peritoneal cavity or subcutaneous space of a mouse model. Moreover, serial quantitative magnetic resonance imaging, evaluation of pre- and post-explant ultrastructure by cryo-high resolution scanning electron microscopy, and an examination of implant mechanical responses revealed substantial preservation of form, material architecture, and biomechanical properties, providing convincing evidence of a non-chemically or ionically crosslinked protein polymer system that exhibits long-term stability in vivo. PMID:19854505

  15. Self-Assembling Nanoparticles of Amphiphilic Polymers for In Vitro and In Vivo FRET Imaging.

    PubMed

    Garcia-Amorós, Jaume; Tang, Sicheng; Zhang, Yang; Thapaliya, Ek Raj; Raymo, Françisco M

    2016-01-01

    Self-assembling nanoparticles of amphiphilic polymers are viable delivery vehicles for transporting hydrophobic molecules across hydrophilic media. Noncovalent contacts between the hydrophobic domains of their macromolecular components are responsible for their formation and for providing a nonpolar environment for the encapsulated guests. However, such interactions are reversible and, as a result, these supramolecular hosts can dissociate into their constituents amphiphiles to release the encapsulated cargo. Operating principles to probe the integrity of the nanocarriers and the dynamic exchange of their components are, therefore, essential to monitor the fate of these supramolecular assemblies in biological media. The co-encapsulation of complementary chromophores within their nonpolar interior offers the opportunity to assess their stability on the basis of energy transfer and fluorescence measurements. Indeed, the exchange of excitation energy between the entrapped chromophores can only occur if the nanoparticles retain their integrity to maintain donors and acceptors in close proximity. In fact, energy-transfer schemes are becoming invaluable protocols to elucidate the transport properties of these fascinating supramolecular constructs in a diversity of biological preparations and can facilitate the identification of strategies to deliver contrast agents and/or drugs to target locations in living organisms for potential diagnostic and/or therapeutic applications.

  16. Self-assembly of phospholipid-analogous hyperbranched polymers nanomicelles for drug delivery.

    PubMed

    Liu, Jinyao; Pang, Yan; Huang, Wei; Zhu, Xinyuan; Zhou, Yongfeng; Yan, Deyue

    2010-02-01

    A drug nanocarrier has been constructed through self-assembly of phospholipid analogous hyperbranched polymers (HPHEEP-alkyls) which contain a polar hyperbranched polyphosphate headgroup and many aliphatic tails. HPHEEP-alkyls were synthesized by self-condensing ring-opening polymerization of 2-(2-hydroxyethoxy)ethoxy-2-oxo-1,3,2-dioxaphospholane and then capped with palmitoyl chloride. Benefiting from the amphiphilic structure with the hydrophilic core and many hydrophobic tails, HPHEEP-alkyls were able to self-assemble into nanomicelles in aqueous media. Importantly, the size of the nanomicelles could be controlled conveniently from 98 to 215 nm by adjusting the capped fraction of the hydroxyl groups with hydrophobic palmityls. The excellent biocompatibility of these nanomicelles was confirmed by methyl tetrazolium assay and acridine orange/ethidium bromide double staining against COS-7 cells. Confocal laser scanning microscopy and flow cytometry analysis demonstrated their good cell permeability, i.e. these nanomicelles were easily internalized by vivid cells and mainly located in the cytoplasm rather than nucleolus. Chlorambucil-loaded nanomicelles were investigated for proliferation inhibition of a MCF-7 breast cancer cell line in vitro, and the chlorambucil dose required for 50% cellular growth inhibition was found to be 5 microg/mL. All of these results indicate that HPHEEP-alkyls nanomicelles can be used as safe and promising drug nanocarriers.

  17. Self-assembled nanoscale coordination polymers with trigger release properties for effective anticancer therapy

    NASA Astrophysics Data System (ADS)

    Liu, Demin; Poon, Christopher; Lu, Kuangda; He, Chunbai; Lin, Wenbin

    2014-06-01

    Nanoscale coordination polymers (NCPs) are self-assembled from metal ions and organic bridging ligands, and can overcome many drawbacks of existing drug delivery systems by virtue of tunable compositions, sizes and shapes, high drug loadings, ease of surface modification and intrinsic biodegradability. Here we report the self-assembly of zinc bisphosphonate NCPs that carry 48±3 wt% cisplatin prodrug and 45±5 wt% oxaliplatin prodrug. In vivo pharmacokinetic studies in mice show minimal uptake of pegylated NCPs by the mononuclear phagocyte system and excellent blood circulation half-lives of 16.4±2.9 and 12.0±3.9 h for the NCPs carrying cisplatin and oxaliplatin, respectively. In all tumour xenograft models evaluated, including CT26 colon cancer, H460 lung cancer and AsPC-1 pancreatic cancer, pegylated NCPs show superior potency and efficacy compared with free drugs. As the first example of using NCPs as nanotherapeutics with enhanced antitumour activities, this study establishes NCPs as a promising drug delivery platform for cancer therapy.

  18. Directed Self-Assembly of Block Copolymers in Thin Films on Polymer Nano-Stripes

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Eun; Kang, Ho-Jong; Lee, Dong Hyun; Nano Functional Materials Lab. Team

    In this study, we report directed self-assembly (DSA) of block copolymers in thin films on nano-stripes of polymers. Unique nano-stripes of poly(tetrafluoro ethylene) (PTFE) having ~20 nm of amplitude and ~200 nm of pitch were simply generated by physically rubbing a PTFE bar on various substrates like Si wafers, glass, and polyimide due to its low friction coefficient and high wear rate. The resulting nano-stripes were extremely oriented along the rubbing direction. Then, various asymmetric polystyrene-block-poly(2-vinylpyridine) copolymers (PS- b-P2VP) were directly self-assembled on the nano-stripes of PTFE by solvent-annealing in vapor of tetrahydrofuran (THF). As a result, PS- b-P2VP exhibited extremely ordered P2VP cylinders oriented normal to the surface in large area on the underlying nano-stripes of PTFE. In addition, as utilizing the BCPs as templates, hexagonal arrays of metal nanoparticles were generated in large area for further application. BCP thin films and arrays of metal nanoparticles were characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM).

  19. Self-assembled nanoscale coordination polymers with trigger release properties for effective anticancer therapy

    PubMed Central

    Liu, Demin; Poon, Christopher; Lu, Kuangda; He, Chunbai; Lin, Wenbin

    2014-01-01

    Nanoscale coordination polymers (NCPs) are self-assembled from metal ions and organic bridging ligands, and can overcome many drawbacks of existing drug delivery systems by virtue of tunable compositions, sizes, and shapes; high drug loadings; ease of surface modification; and intrinsic biodegradability. Here we report the self-assembly of zinc bisphosphonate NCPs that carry 48±3 wt% cisplatin prodrug and 45±5 wt% oxaliplatin prodrug. In vivo pharmacokinetic studies in mice show minimal uptake of pegylated NCPs by the mononuclear phagocyte system and excellent blood circulation half-lives of 16.4±2.9 and 12.0±3.9 h for the NCPs carrying cisplatin and oxaliplatin, respectively. In all tumor xenograft models evaluated, including CT26 colon cancer, H460 lung cancer, and AsPC-1 pancreatic cancer, pegylated NCPs show superior potency and efficacy compared to free drugs. As the first example of using NCPs as nanotherapeutics with enhanced antitumor activities, this study establishes NCPs as a promising drug delivery platform for cancer therapy. PMID:24964370

  20. Self-assembly through secondary interactions in formation of two-dimensional lead(II) supramolecular polymer with nanosheets morphology

    NASA Astrophysics Data System (ADS)

    Noori, Yasamin; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

    2017-02-01

    In order to study the role of self-assembly through secondary interactions in formation of [Pb(3-AB)2]n (1), [3-ABbar = 3-aminobenzoate], we designed some experiments and synthesized two samples of 1 under ultrasonic irradiations. Nanosheets of 1 were synthesized under these conditions. Compound 1 is a one-dimensional coordination polymer. Self-assembly through hydrogen bonding and π-π stacking interactions between these chains results in formation of two-dimensional supramolecular polymer. It seems that self-assembly through secondary interactions between these chain structures is responsible for formation of 1 with nanosheet morphology. Formation nanoparticles of [Pb(2,6-DHB)2]n (2), [2,6-DHBbar = 2,6-dihydroxybenzoate], under the same condition applied for 1, which has three-dimensional coordination network in its crystalline structure, approved our hypotheses. These microstructures were characterized by IR spectroscopy, X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM).

  1. An automated spin-assisted approach for molecular layer-by-layer assembly of crosslinked polymer thin films

    SciTech Connect

    Chan, Edwin P.; Chung, Jun Young; Stafford, Christopher M.; Lee, Jung-Hyun

    2012-11-15

    We present the design of an automated spin-coater that facilitates fabrication of polymer films based on molecular layer-by-layer (mLbL) assembly. Specifically, we demonstrate the synthesis of ultrathin crosslinked fully-aromatic polyamide (PA) films that are chemically identical to polymer membranes used in water desalination applications as measured by X-ray photoelectron spectroscopy. X-ray reflectivity measurements indicate that the automated mLbL assembly creates films with a constant film growth rate and minimal roughness compared with the traditional interfacial polymerization of PA. This automated spin-coater improves the scalability and sample-to-sample consistency by reducing human involvement in the mLbL assembly.

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

    PubMed

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

    2013-06-26

    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. Superhydrophobic Thin Films Fabricated by Reactive Layer-by-Layer Assembly of Azlactone-Functionalized Polymers

    PubMed Central

    Buck, Maren E.; Schwartz, Sarina C.

    2010-01-01

    We report an approach to the fabrication of superhydrophobic thin films that is based on the ‘reactive’ layer-by-layer assembly of azlactone-containing polymer multilayers. We demonstrate that films fabricated from alternating layers of the azlactone functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and poly(ethyleneimine) (PEI) exhibit micro- and nanoscale surface features that result in water contact angles in excess of 150º. Our results reveal that the formation of these surface features is (i) dependent upon film thickness (i.e., the number of layers of PEI and PVDMA deposited) and (ii) that it is influenced strongly by the presence (or absence) of cyclic azlactone-functionalized oligomers that can form upon storage of the 2-vinyl-4,4-dimethylazlactone (VDMA) used to synthesize PVDMA. For example, films fabricated using polymers synthesized in the presence of these oligomers exhibited rough, textured surfaces and superhydrophobic behavior (i.e., advancing contact angles in excess of 150º). In contrast, films fabricated from PVDMA polymerized in the absence of this oligomer (e.g., using freshly distilled monomer) were smooth and only moderately hydrophobic (i.e., advancing contact angles of ~75º). The addition of authentic, independently synthesized oligomer to samples of distilled VDMA at specified and controlled concentrations permitted reproducible fabrication of superhydrophobic thin films on the surfaces of a variety of different substrates. The surfaces of these films were demonstrated to be superhydrophobic immediately after fabrication, but they became hydrophilic after exposure to water for six days. Additional experiments demonstrated that it was possible to stabilize and prolong the superhydrophobic properties of these films (e.g., advancing contact angles in excess of 150° even after complete submersion in water for at least six weeks) by exploiting the reactivity of residual azlactones to functionalize the surfaces of the

  4. Nanowires: A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template-Assisted Assembly of Polyfluorene Nanowires (Small 31/2016).

    PubMed

    Bae, Dong Geun; Jeong, Ji-Eun; Kang, Seok Hee; Byun, Myunghwan; Han, Dong-Wook; Lin, Zhiqun; Woo, Han Young; Hong, Suck Won

    2016-08-01

    A simple yet robust strategy is developed to yield the self-assembly of DNA by exploiting controlled stick-slip motions and "coffee ring" effect of DNA solutions in a unique confined geometry, as H. Y. Woo, S. W. Hong, and co-workers report on page 4254. A number of highly ordered concentric ring-like superstructures composed of DNA are spontaneously formed, which can be employed as a "template" to tightly organize cationic conjugated polyelectrolytes alongside the DNA strands.

  5. Supramolecular polymers constructed by orthogonal self-assembly based on host-guest and metal-ligand interactions.

    PubMed

    Wei, Peifa; Yan, Xuzhou; Huang, Feihe

    2015-02-07

    Supramolecular polymers constructed by orthogonal self-assembly based on host-guest and metal-ligand interactions are attracting increasing attention currently because of their interesting properties and potential applications. Host-guest interactions impart these polymers with good selectivity and convenient enviro-responsiveness, and metal-ligand interactions endow them with various coordination geometries, strong yet tunable coordination binding abilities, as well as magnetic, redox, photophysical, and electrochromic properties. Therefore, supramolecular polymers constructed by orthogonal host-guest and metal-ligand interactions have wide applications in the fields of soft matter, fluorescence sensing, heterocatalysis, electronics, gas storage, etc. In this critical review, we will address the recent development of supramolecular polymeric systems involving metal-ligand interactions and host-guest molecular recognition. Specifically, we classify the related supramolecular polymers depending on the types of macrocyclic hosts, and highlight their intriguing properties originating from the elegant combination of host-guest complexation and metal centers.

  6. Thermo-reversible morphology and conductivity of a conjugated polymer network embedded in polymeric self-assembly

    NASA Astrophysics Data System (ADS)

    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 opportunities to create nano hybrid materials, utilizing self-assembled micro-domains with a variety of morphology and periodic architectures as templates for functional nano-fillers. Here we report new progress towards the fabrication of a thermally responsive conducting polymer self-assembly made from a water-soluble poly(thiophene) derivative with short PEO side chains and Pluronic L62 solution in water. The structural and electrical properties of conjugated polymer-embedded nanostructures were investigated by combining SANS, SAXS, CGMD 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. 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. The research was sponsored by the Scientific User Facilities Division, Office of BES, U.S. DOE and Laboratory Directed Research and Development Program of ORNL, managed by UT-Battelle, LLC.

  7. Surface-Directed Assembly of Sequence-Defined Synthetic Polymers into Networks of Hexagonally Patterned Nanoribbons with Controlled Functionalities.

    PubMed

    Chen, Chun-Long; Zuckermann, Ronald N; DeYoreo, James J

    2016-05-24

    The exquisite self-assembly of proteins and peptides in nature into highly ordered functional materials has inspired innovative approaches to the design and synthesis of biomimetic materials. While sequence-defined polymers hold great promise to mimic proteins and peptides for functions, controlled assembly of them on surfaces still remains underdeveloped. Here, we report the assembly of 12-mer peptoids containing alternating acidic and aromatic monomers into networks of hexagonally patterned nanoribbons on mica surfaces. Ca(2+)-carboxylate coordination creates peptoid-peptoid and peptoid-mica interactions that control self-assembly. In situ atomic force microscopy (AFM) shows that peptoids first assemble into discrete nanoparticles; these particles then transform into hexagonally patterned nanoribbons on mica surfaces. AFM-based dynamic force spectroscopy studies show that peptoid-mica interactions are much stronger than peptoid-peptoid interactions, illuminating the driving forces for mica-directed peptoid assembly. We further demonstrate the display of functional domains at the N-terminus of assembling peptoids to produce extended networks with similar hierarchical structures. This research demonstrates that surface-directed peptoid assembly can be used as a robust platform to develop biomimetic coating materials for applications.

  8. Improved performance of nanowire-quantum-dot-polymer solar cells by chemical treatment of the quantum dot with ligand and solvent materials.

    PubMed

    Nadarajah, A; Smith, T; Könenkamp, R

    2012-12-07

    We report a nanowire-quantum-dot-polymer solar cell consisting of a chemically treated CdSe quantum dot film deposited on n-type ZnO nanowires. The electron and hole collecting contacts are a fluorine-doped tin-oxide/zinc oxide layer and a P3HT/Au layer. This device architecture allows for enhanced light absorption and an efficient collection of photogenerated carriers. A detailed analysis of the chemical treatment of the quantum dots, their deposition, and the necessary annealing processes are discussed. We find that the surface treatment of CdSe quantum dots with pyridine, and the use of 1,2-ethanedithiol (EDT) ligands, critically improves the device performance. Annealing at 380 °C for 2 h is found to cause a structural conversion of the CdSe from its initial isolated quantum dot arrangement into a polycrystalline film with excellent surface conformality, thereby resulting in a further enhancement of device performance. Moreover, long-term annealing of 24 h leads to additional increases in device efficiency. Our best conversion efficiency reached for this type of cell is 3.4% under 85 mW cm(-2) illumination.

  9. Improved performance of nanowire-quantum-dot-polymer solar cells by chemical treatment of the quantum dot with ligand and solvent materials

    NASA Astrophysics Data System (ADS)

    Nadarajah, A.; Smith, T.; Könenkamp, R.

    2012-12-01

    We report a nanowire-quantum-dot-polymer solar cell consisting of a chemically treated CdSe quantum dot film deposited on n-type ZnO nanowires. The electron and hole collecting contacts are a fluorine-doped tin-oxide/zinc oxide layer and a P3HT/Au layer. This device architecture allows for enhanced light absorption and an efficient collection of photogenerated carriers. A detailed analysis of the chemical treatment of the quantum dots, their deposition, and the necessary annealing processes are discussed. We find that the surface treatment of CdSe quantum dots with pyridine, and the use of 1,2-ethanedithiol (EDT) ligands, critically improves the device performance. Annealing at 380 °C for 2 h is found to cause a structural conversion of the CdSe from its initial isolated quantum dot arrangement into a polycrystalline film with excellent surface conformality, thereby resulting in a further enhancement of device performance. Moreover, long-term annealing of 24 h leads to additional increases in device efficiency. Our best conversion efficiency reached for this type of cell is 3.4% under 85 mW cm-2 illumination.

  10. Bio-Inspired Fluoro-polydopamine Meets Barium Titanate Nanowires: A Perfect Combination to Enhance Energy Storage Capability of Polymer Nanocomposites.

    PubMed

    Wang, Guanyao; Huang, Xingyi; Jiang, Pingkai

    2017-03-01

    Rapid evolution of energy storage devices expedites the development of high-energy-density materials with excellent flexibility and easy processing. The search for such materials has triggered the development of high-dielectric-constant (high-k) polymer nanocomposites. However, the enhancement of k usually suffers from sharp reduction of breakdown strength, which is detrimental to substantial increase of energy storage capability. Herein, the combination of bio-inspired fluoro-polydopamine functionalized BaTiO3 nanowires (NWs) and a fluoropolymer matrix offers a new thought to prepare polymer nanocomposites. The elaborate functionalization of BaTiO3 NWs with fluoro-polydopamine has guaranteed both the increase of k and the maintenance of breakdown strength, resulting in significantly enhanced energy storage capability. The nanocomposite with 5 vol % functionalized BaTiO3 NWs discharges an ultrahigh energy density of 12.87 J cm(-3) at a relatively low electric field of 480 MV m(-1), more than three and a half times that of biaxial-oriented polypropylene (BOPP, 3.56 J cm(-3) at 600 MV m(-1)). This superior energy storage capability seems to rival or exceed some reported advanced nanoceramics-based materials at 500 MV m(-1). This new strategy permits insights into the construction of polymer nanocomposites with high energy storage capability.

  11. Supramolecular self-assembly of 1D and 3D heterometallic coordination polymers with triruthenium building blocks.

    PubMed

    Chan, Sharon Lai-Fung; Gao, Song; Chui, Stephen Sin-Yin; Shek, Lam; Huang, Jie-Sheng; Che, Chi-Ming

    2012-09-03

    Ru(3)(TSA)(6) (1; H(2)TSA=2-thiosalicylic acid), which bears six peripheral carboxylate groups and was isolated in the form [NEt(4)](1.5)[Ru(3)(HTSA)(2)(TSA)(4)](OAc)(0.5)·3.5H(2)O, serves as a building block for assembly of heterometallic coordination polymers. Treatment of 1 with [Fe(acac)(3)] (acac=acetylacetonate) in EG/H(2)O (EG=ethylene glycol) afforded 1D Ru(3)-Fe coordination polymer 2 by means of the connection of the building block 1 through iron centers. Treatment of 1 with MnCl(2) in EG resulted in the formation of 1D Ru(3)-Mn(3) coordination polymer 3, which features self-assembled polynuclear linking units Mn(3)(OCH(2)CH(2)O)(3), each of which contains a planar Mn(3)O(3) ring. By treating 1 with Gd(NO(3))(3) and NaHCO(3) in EG, a 3D Ru(3)-Gd(6) coordination polymer 4 was obtained; this 3D coordination polymer features unprecedented Gd(6)(μ(3)-CO(3))(4) units. The magnetic properties of 1-4, along with DFT calculations on the electronic structure of 1, are also described.

  12. Cobalt oxide 2D nano-assemblies from infinite coordination polymer precursors mediated by a multidentate pyridyl ligand.

    PubMed

    Li, Guo-Rong; Xie, Chen-Chao; Shen, Zhu-Rui; Chang, Ze; Bu, Xian-He

    2016-05-04

    In this work, the construction of Co3O4 two dimensional (2D) nano-assemblies utilizing infinite coordination polymers (ICPs) as precursors was investigated, aiming at the morphology targeted fabrication and utilization of 2D materials. Based on the successful modulation of morphology, a rose-like Co based ICP precursor was obtained, which was further transformed into porous Co3O4 nanoflake assemblies with a well-preserved 2D morphology and a large surface area. The mechanism of the morphology modulation was illustrated by systematic investigation, which demonstrated the crucial role of a modulating agent in the formation of 2D nano-assemblies. In addition, the cobalt oxide 2D nano-assemblies are fabricated into a lithium anode combined with graphene, and the remarkable capacity and stability (900 mA h g(-1) after 50 cycles) of the resulting Co3O4/G nanocomposite indicates its potential in lithium battery applications.

  13. Towards bulk syntheses of nanomaterials: a homeostatically supersaturated synthesis of polymer-like Bi2S3 nanowires with nearly 100% yield and no injection

    DOE PAGES

    Yuan, Bin; Brandt, Jordan Aaron; Shaw, Santosh; ...

    2016-11-25

    This article reports the implementation of a one-pot strategy for the synthesis of polymer-like Bi2S3 nanowires from supersaturated precursors. These conditions result in (i) a homeostatically regulated supersaturation of the growing phase during most of the reaction, (ii) a nearly 100% conversion of the limiting reagent, and (iii) an improved colloidal stability and polydispersity of the product (when compared to the hot-injection product) that allows the identification of three new exciton transitions in the absorption spectrum (one of them, importantly, being a weakly absorbing ground state at 1.64 eV). Three different commercial sources of ligands do not yield significantly differentmore » conversion rates. Scalability is further improved by lack of stirring after the initial stage of reaction and a lower reaction temperature (90 °C).« less

  14. RF/Microwave properties and applications of directly assembled nanotubes and nanowires: LDRD project 102662 final report.

    SciTech Connect

    Mayer, Theresa (The Pennyslvania State University, University Park, PA 16802); Vallett, Aaron (The Pennyslvania State University, University Park, PA 16802); Lee, Mark; Shaner, Eric Arthur; Jones, Frank E.; Talin, Albert Alec; Highstrete, Clark

    2006-11-01

    LDRD Project 102662 provided support to pursue experiments aimed at measuring the basic electrodynamic response and possible applications of carbon nanotubes and silicon nanowires at radiofrequency to microwave frequencies, approximately 0.01 to 50 GHz. Under this project, a method was developed to integrate these nanomaterials onto high-frequency compatible co-planar waveguides. The complex reflection and transmission coefficients of the nanomaterials was studied as a function of frequency. From these data, the high-frequency loss characteristics of the nanomaterials were deduced. These data are useful to predict frequency dependence and power dissipation characteristics in new rf/microwave devices incorporating new nanomaterials.

  15. Nanowire sensors and arrays for chemical/biomolecule detection

    NASA Technical Reports Server (NTRS)

    Yun, Minhee; Lee, Choonsup; Vasquez, Richard P.; Ramanathan, K.; Bangar, M. A.; Chen, W.; Mulchandan, A.; Myung, N. V.

    2005-01-01

    We report electrochemical growth of single nanowire based sensors using e-beam patterned electrolyte channels, potentially enabling the controlled fabrication of individually addressable high density arrays. The electrodeposition technique results in nanowires with controlled dimensions, positions, alignments, and chemical compositions. Using this technique, we have fabricated single palladium nanowires with diameters ranging between 75 nm and 300 nm and conducting polymer nanowires (polypyrrole and polyaniline) with diameters between 100 nm and 200 nm. Using these single nanowires, we have successfully demonstrated gas sensing with Pd nanowires and pH sensing with polypirrole nanowires.

  16. Single-Crystalline Gold Nanowires Synthesized from Light-Driven Oriented Attachment and Plasmon-Mediated Self-Assembly of Gold Nanorods or Nanoparticles.

    PubMed

    Yu, Shang-Yang; Gunawan, Hariyanto; Tsai, Shiao-Wen; Chen, Yun-Ju; Yen, Tzu-Chen; Liaw, Jiunn-Woei

    2017-03-16

    Through the light-driven geometrically oriented attachment (OA) and self-assembly of Au nanorods (NRs) or nanoparticles (NPs), single-crystalline Au nanowires (NWs) were synthesized by the irradiation of a linearly-polarized (LP) laser. The process was conducted in a droplet of Au colloid on a glass irradiated by LP near-infrared (e.g. 1064 nm and 785 nm) laser beam of low power at room temperature and atmospheric pressure, without any additive. The FE-SEM images show that the cross sections of NWs are various: tetragonal, pentagonal or hexagonal. The EDS spectrum verifies the composition is Au, and the pattern of X-ray diffraction identifies the crystallinity of NWs with the facets of {111}, {200}, {220} and {311}. We proposed a hypothesis for the mechanism that the primary building units are aligned and coalesced by the plasmon-mediated optical torque and force to form the secondary building units. Subsequently, the secondary building units undergo the next self-assembly, and so forth the tertiary ones. The LP light guides the translational and rotational motions of these building units to perform geometrically OA in the side-by-side, end-to-end and T-shaped manners. Consequently, micron-sized ordered mesocrystals are produced. Additionally, the concomitant plasmonic heating causes the annealing for recrystallizing the mesocrystals in water.

  17. Single-Crystalline Gold Nanowires Synthesized from Light-Driven Oriented Attachment and Plasmon-Mediated Self-Assembly of Gold Nanorods or Nanoparticles

    PubMed Central

    Yu, Shang-Yang; Gunawan, Hariyanto; Tsai, Shiao-Wen; Chen, Yun-Ju; Yen, Tzu-Chen; Liaw, Jiunn-Woei

    2017-01-01

    Through the light-driven geometrically oriented attachment (OA) and self-assembly of Au nanorods (NRs) or nanoparticles (NPs), single-crystalline Au nanowires (NWs) were synthesized by the irradiation of a linearly-polarized (LP) laser. The process was conducted in a droplet of Au colloid on a glass irradiated by LP near-infrared (e.g. 1064 nm and 785 nm) laser beam of low power at room temperature and atmospheric pressure, without any additive. The FE-SEM images show that the cross sections of NWs are various: tetragonal, pentagonal or hexagonal. The EDS spectrum verifies the composition is Au, and the pattern of X-ray diffraction identifies the crystallinity of NWs with the facets of {111}, {200}, {220} and {311}. We proposed a hypothesis for the mechanism that the primary building units are aligned and coalesced by the plasmon-mediated optical torque and force to form the secondary building units. Subsequently, the secondary building units undergo the next self-assembly, and so forth the tertiary ones. The LP light guides the translational and rotational motions of these building units to perform geometrically OA in the side-by-side, end-to-end and T-shaped manners. Consequently, micron-sized ordered mesocrystals are produced. Additionally, the concomitant plasmonic heating causes the annealing for recrystallizing the mesocrystals in water. PMID:28300218

  18. Single-Crystalline Gold Nanowires Synthesized from Light-Driven Oriented Attachment and Plasmon-Mediated Self-Assembly of Gold Nanorods or Nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, Shang-Yang; Gunawan, Hariyanto; Tsai, Shiao-Wen; Chen, Yun-Ju; Yen, Tzu-Chen; Liaw, Jiunn-Woei

    2017-03-01

    Through the light-driven geometrically oriented attachment (OA) and self-assembly of Au nanorods (NRs) or nanoparticles (NPs), single-crystalline Au nanowires (NWs) were synthesized by the irradiation of a linearly-polarized (LP) laser. The process was conducted in a droplet of Au colloid on a glass irradiated by LP near-infrared (e.g. 1064 nm and 785 nm) laser beam of low power at room temperature and atmospheric pressure, without any additive. The FE-SEM images show that the cross sections of NWs are various: tetragonal, pentagonal or hexagonal. The EDS spectrum verifies the composition is Au, and the pattern of X-ray diffraction identifies the crystallinity of NWs with the facets of {111}, {200}, {220} and {311}. We proposed a hypothesis for the mechanism that the primary building units are aligned and coalesced by the plasmon-mediated optical torque and force to form the secondary building units. Subsequently, the secondary building units undergo the next self-assembly, and so forth the tertiary ones. The LP light guides the translational and rotational motions of these building units to perform geometrically OA in the side-by-side, end-to-end and T-shaped manners. Consequently, micron-sized ordered mesocrystals are produced. Additionally, the concomitant plasmonic heating causes the annealing for recrystallizing the mesocrystals in water.

  19. Free-standing, single-monomer-thick two-dimensional polymers through covalent self-assembly in solution.

    PubMed

    Baek, Kangkyun; Yun, Gyeongwon; Kim, Youngkook; Kim, Dongwoo; Hota, Raghunandan; Hwang, Ilha; Xu, Dan; Ko, Young Ho; Gu, Gil Ho; Suh, Ju Hyung; Park, Chan Gyung; Sung, Bong June; Kim, Kimoon

    2013-05-01

    The design and synthesis of two-dimensional (2D) polymers is a challenging task, hitherto achieved in solution only through the aid of a solid surface "template" or preorganization of the building blocks in a 2D confined space. We present a novel approach for synthesizing free-standing, covalently bonded, single-monomer-thick 2D polymers in solution without any preorganization of building blocks on solid surfaces or interfaces by employing shape-directed covalent self-assembly of rigid, disk-shaped building blocks having laterally predisposed reactive groups on their periphery. We demonstrate our strategy through a thiol-ene "click" reaction between (allyloxy)12CB[6], a cucurbit[6]uril (CB[6]) derivative with 12 laterally predisposed reactive alkene groups, and 1,2-ethanedithiol to synthesize a robust and readily transferable 2D polymer. We can take advantage of the high binding affinity of fully protonated spermine (positive charges on both ends) to CB[6] to keep each individual polymer sheet separated from one another by electrostatic repulsion during synthesis, obtaining, for the first-time ever, a single-monomer-thick 2D polymer in solution. The arrangement of CB[6] repeating units in the resulting 2D polymer has been characterized using gold nanoparticle labeling and scanning transmission electron microscopy. Furthermore, we have confirmed the generality of our synthetic approach by applying it to different monomers to generate 2D polymers. Novel 2D polymers, such as our CB[6] derived polymer, may be useful in selective transport, controlled drug delivery, and chemical sensing and may even serve as well-defined 2D scaffolds for ordered functionalization and platforms for bottom-up 3D construction.

  20. Kinetic Effects on Self-Assembly and Function of Protein-Polymer Bioconjugates in Thin Films Prepared by Flow Coating.

    PubMed

    Chang, Dongsook; Huang, Aaron; Olsen, Bradley D

    2017-01-01

    The self-assembly of nanostructured globular protein arrays in thin films is demonstrated using protein-polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self-assembled cylindrical nanostructures with POEGA domains selectively segregating to the air-film interface. Long-range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long-range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.

  1. Kinetic Effects on Self-Assembly and Function of Protein-Polymer Bioconjugates in Thin Films Prepared by Flow Coating

    SciTech Connect

    Chang, Dongsook; Huang, Aaron; Olsen, Bradley D.

    2016-11-04

    The self-assembly of nanostructured globular protein arrays in thin films is demonstrated using protein–polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self-assembled cylindrical nanostructures with POEGA domains selectively segregating to the air–film interface. Long-range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long-range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.

  2. Lithium-ion polymer cells assembled with a reactive composite separator containing vinyl-functionalized SiO2 particles

    NASA Astrophysics Data System (ADS)

    Yoo, Ji-Hyun; Shin, Won-Kyung; Koo, Sang Man; Kim, Dong-Won

    2015-11-01

    Vinyl-functionalized SiO2 particles of different sizes are synthesized and coated onto both sides of a polyethylene separator to prepare a reactive composite separator for lithium-ion polymer cells. The SiO2-coated composite separators exhibit excellent thermal stability due to the presence of heat-resistant silica particles. By using these reactive composite separators and a gel electrolyte precursor, lithium-ion polymer cells composed of a graphite negative electrode and a LiNi1/3Co1/3Mn1/3O2 positive electrode are assembled by in-situ chemical cross-linking, and their cycling performance is evaluated. The cells assembled with a reactive composite separator exhibit superior cycling performance to cell prepared with a conventional polyethylene separator due to the strong interfacial adhesion between the electrodes and separator, as well as suppression of deleterious reactions during cycling.

  3. Responsive Hydrogels and Ion Gels by Self-Assembly of ABA and ABC Triblock Polymers

    NASA Astrophysics Data System (ADS)

    Lodge, Timothy

    2014-03-01

    Gels - polymeric networks swollen with a substantial amount of solvent - represent a fascinating class of soft materials, with wide-ranging applications in fields as diverse as biomedicine, pharmaceutics, personal care products, foods, sensors, actuators, flexible electronics, oil recovery, and adhesives. Physical gels are held together by non-covalent interactions, which may be as specific as hydrogen bonds, or as general as solvophobic association of insoluble blocks. Among the attractive features of physical gels are reversibility, stimuli-responsiveness, and tunability of macroscopic properties. In this talk two classes of physical gels will be highlighted. In one, the ability of ABC block terpolymers to form novel structures will be demonstrated, where blocks A and C are mutually immiscible and solvophobic, while B is solvophilic. In particular, the formation of gels by sequential association (first A, then C) leads to a remarkably sharp gelation transition, at a relatively low polymer concentration, compared to analogous gels formed from ABA systems. In the second class, gels formed by self-assembly of a variety of ABA systems in ionic liquids will be described, and in particular how gelation can be controlled through factors such as block chemistry, temperature, choice of ionic liquid, and application of light.

  4. Facile hierarchical assembly of gold particle decorated conductive polymer nanofibers for electrochemical sensing

    NASA Astrophysics Data System (ADS)

    Dai, Minhui; Chen, Juhong; Goddard, Julie M.; Nugen, Sam R.

    2017-02-01

    In this study, we successfully applied vapor-phase polymerization towards the synthesis of PEDOT nanofibers which were subsequently functionalized with gold particles and used as electrodes for electrochemical sensing. Two methods were used to synthesize the PEDOT nanofibers including (1) electrospinning followed by vapor-phase polymerization (EVP), and (2) one-step vapor-phase polymerization (OSVP). The average diameter of EVP fibers was approximately 350 nm, and OSVP was approximately 200 nm. Gold particles (∼500 nm) were synthesized by an oxidation-reduction reaction between gold precursors and residue EDOT monomers on the surface of the PEDOT nanofibers. In order to investigate the electrochemical performance of these electrodes, ascorbic acid was chosen as an analyte model. Our results indicated that PEDOT nanofiber electrodes showed an enhanced response with respect to bare gold electrodes. Furthermore, the OSVP PEDOT nanofibers with gold particles demonstrated the highest sensitivity at low ascorbic acid concentrations. These hierarchically assembled, gold particle-decorated, conductive polymer nanofibers were further fabricated into flexible electrodes, demonstrating a potential in advanced applications such as wearable electronics.

  5. Tunable Gas Permeability of Polymer-Clay Nano Brick Wall Thin Film Assemblies

    NASA Astrophysics Data System (ADS)

    Gamboa, Daniel; Priolo, Morgan; Grunlan, Jaime

    2010-03-01

    Thin films of anionic natural montmorrilonite (MMT) clay and cationic polyethylenimine (PEI) have been produced by alternately dipping a plastic substrate into dilute aqueous mixtures containing each ingredient. After 40 polymer-clay layers have been deposited, the resulting transparent film exhibits an oxygen transmission rate (OTR) below 0.35 cm^3/m^2 . day when the pH of PEI solution is 10. This low permeability is due to a brick wall nanostructure comprised of completely exfoliated clay bricks in polymeric mortar. This brick wall creates an extremely tortuous path at thicknesses below 250 nm and clay concentration above 80 wt%. A 70-bilayer PEI-MMT assembly has an undetectable OTR (< 0.005 cm^3/m^2 . day), which equates to a permeability below SiOx when multiplied by its film thickness of 231 nm. With optical transparency greater than 86% and the ability to be microwaved, these thin film composites are good candidates for flexible electronics packaging and foil replacement for food.

  6. Multi-colored fibers by self-assembly of DNA, histone proteins, and cationic conjugated polymers.

    PubMed

    Wang, Fengyan; Liu, Zhang; Wang, Bing; Feng, Liheng; Liu, Libing; Lv, Fengting; Wang, Yilin; Wang, Shu

    2014-01-07

    The development of biomolecular fiber materials with imaging ability has become more and more useful for biological applications. In this work, cationic conjugated polymers (CCPs) were used to construct inherent fluorescent microfibers with natural biological macromolecules (DNA and histone proteins) through the interfacial polyelectrolyte complexation (IPC) procedure. Isothermal titration microcalorimetry results show that the driving forces for fiber formation are electrostatic and hydrophobic interactions, as well as the release of counterions and bound water molecules. Color-encoded IPC fibers were also obtained based on the co-assembly of DNA, histone proteins, and blue-, green-, or red- (RGB-) emissive CCPs by tuning the fluorescence resonance energy-transfer among the CCPs at a single excitation wavelength. The fibers could encapsulate GFP-coded Escherichia coli BL21, and the expression of GFP proteins was successfully regulated by the external environment of the fibers. These multi-colored fibers show a great potential in biomedical applications, such as biosensor, delivery, and release of biological molecules and tissue engineering.

  7. Water-Based Assembly of Polymer-Metal Organic Framework (MOF) Functional Coatings

    SciTech Connect

    De, Souvik; Nandasiri, Manjula I.; Schaef, Herbert T.; McGrail, Benard Peter; Nune, Satish K.; Lutkenhaus, Jodie L.

    2016-12-27

    Metal organic frameworks (MOFs) have gained tremendous attention for their porosity, size selectivity, and structural diversity. There is a need for MOF-based coatings, particularly in applications such as separations, electronics and energy; yet forming thin, functional, conformal coatings is prohibitive because MOFs exist as a powder. Layer-by- layer assembly, a versatile thin film coating approach, offers a unique solution to this problem, but this approach requires MOFs that are water-dispersible and bear a surface charge. Here, we address these issues by examining water-based dispersions of MIL-101(Cr) that facilitate the formation of robust polymer-MOF hybrid coatings. Specifically, the substrate to be coated is alternately exposed to an aqueous solution of poly(styrene sulfonate) and dispersion MIL-101(Cr), yielding linear film growth and coatings with a MOF content as high as 77 wt%.This approach is surface-agnostic, in which the coating is successfully applied to silicon, glass, flexible plastic, and even cotton fabric, conformally coating individual fibers. In contrast, prior attempts at forming MOF-coatings were severely limited to a handful of surfaces, required harsh chemical treatment, and were not conformal. The approach presented here unambiguously confirms that MOFs can be conformally coated onto complex and unusual surfaces, opening the door for a wide variety of applications.

  8. Ternary blend polymer solar cells with self-assembled structure for enhancing power conversion efficiency

    NASA Astrophysics Data System (ADS)

    Yang, Zhenhua; Li, Hongfei; Nam, Chang-Yong; Kisslinger, Kim; Satija, Sushil; Rafailovich, Miriam

    Bulk heterojunction (BHJ) polymer solar cells are an area of intense interest due to their advantages such as mechanical flexibility. The active layer is typically spin coated from the solution of polythiophene derivatives (donor) and fullerenes (acceptor) and interconnected domains are formed because of phase separation. However, the power conversion efficiency (PCE) of BHJ solar cell is restricted by the disordered inner structures in the active layer, donor or acceptor domains isolated from electrodes. Here we report a self-assembled columnar structure formed by phase separation between (PCDTBT) and polystyrene (PS) for the active layer morphology optimization. The BHJ solar cell device based on this structure is promising for exhibiting higher performance due to the shorter carrier transportation pathway and larger interfacial area between donor and acceptor. The surface morphology is investigated with atomic force microscopy (AFM) and the columnar structure is studied by investigation of cross-section of the blend thin film of PCDTBT and PS under the transmission electron microscopy (TEM). The different morphological structures formed via phase segregation are correlated with the performance of the BHJ solar cells.

  9. Conductive Nanowires Templated by Molecular Brushes.

    PubMed

    Raguzin, Ivan; Stamm, Manfred; Ionov, Leonid

    2015-10-21

    In this paper, we report the fabrication of conductive nanowires using polymer bottle brushes as templates. In our approach, we synthesized poly(2-dimethylamino)ethyl methacrylate methyl iodide quaternary salt brushes by two-step atom transfer radical polymerization, loaded them with palladium salt, and reduced them in order to form metallic nanowires with average lengths and widths of 300 and 20 nm, respectively. The obtained nanowires were deposited between conductive gold pads and were connected to them by sputtering of additional pads to form an electric circuit. We connected the nanowires in an electric circuit and demonstrated that the conductivity of these nanowires is around 100 S·m(-1).

  10. Probing the self-assembled nanostructures of functional polymers with synchrotron grazing incidence X-ray scattering.

    PubMed

    Ree, Moonhor

    2014-05-01

    For advanced functional polymers such as biopolymers, biomimic polymers, brush polymers, star polymers, dendritic polymers, and block copolymers, information about their surface structures, morphologies, and atomic structures is essential for understanding their properties and investigating their potential applications. Grazing incidence X-ray scattering (GIXS) is established for the last 15 years as the most powerful, versatile, and nondestructive tool for determining these structural details when performed with the aid of an advanced third-generation synchrotron radiation source with high flux, high energy resolution, energy tunability, and small beam size. One particular merit of this technique is that GIXS data can be obtained facilely for material specimens of any size, type, or shape. However, GIXS data analysis requires an understanding of GIXS theory and of refraction and reflection effects, and for any given material specimen, the best methods for extracting the form factor and the structure factor from the data need to be established. GIXS theory is reviewed here from the perspective of practical GIXS measurements and quantitative data analysis. In addition, schemes are discussed for the detailed analysis of GIXS data for the various self-assembled nanostructures of functional homopolymers, brush, star, and dendritic polymers, and block copolymers. Moreover, enhancements to the GIXS technique are discussed that can significantly improve its structure analysis by using the new synchrotron radiation sources such as third-generation X-ray sources with picosecond pulses and partial coherence and fourth-generation X-ray laser sources with femtosecond pulses and full coherence.

  11. Highly-ordered supportless three-dimensional nanowire networks with tunable complexity and interwire connectivity for device integration.

    PubMed

    Rauber, Markus; Alber, Ina; Müller, Sven; Neumann, Reinhard; Picht, Oliver; Roth, Christina; Schökel, Alexander; Toimil-Molares, Maria Eugenia; Ensinger, Wolfgang

    2011-06-08

    The fabrication of three-dimensional assemblies consisting of large quantities of nanowires is of great technological importance for various applications including (electro-)catalysis, sensitive sensing, and improvement of electronic devices. Because the spatial distribution of the nanostructured material can strongly influence the properties, architectural design is required in order to use assembled nanowires to their full potential. In addition, special effort has to be dedicated to the development of efficient methods that allow precise control over structural parameters of the nanoscale building blocks as a means of tuning their characteristics. This paper reports the direct synthesis of highly ordered large-area nanowire networks by a method based on hard templates using electrodeposition within nanochannels of ion track-etched polymer membranes. Control over the complexity of the networks and the dimensions of the integrated nanostructures are achieved by a modified template fabrication. The networks possess high surface area and excellent transport properties, turning them into a promising electrocatalyst material as demonstrated by cyclic voltammetry studies on platinum nanowire networks catalyzing methanol oxidation. Our method opens up a new general route for interconnecting nanowires to stable macroscopic network structures of very high integration level that allow easy handling of nanowires while maintaining their connectivity.

  12. High-efficiency solid-state dye-sensitized solar cells: fast charge extraction through self-assembled 3D fibrous network of crystalline TiO2 nanowires.

    PubMed

    Tétreault, Nicolas; Horváth, Endre; Moehl, Thomas; Brillet, Jérémie; Smajda, Rita; Bungener, Stéphane; Cai, Ning; Wang, Peng; Zakeeruddin, Shaik M; Forró, László; Magrez, Arnaud; Grätzel, Michael

    2010-12-28

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

  13. Pulse electrodeposition and electrochemical quartz crystal microbalance techniques for high perpendicular magnetic anisotropy cobalt nanowire arrays

    SciTech Connect

    Ursache, Andrei; Goldbach, James T.; Russell, Thomas P.; Tuominen, Mark T.

    2005-05-15

    This research is focused on the development of pulse electrodeposition techniques to fabricate a high-density array of vertically oriented, high-magnetic anisotropy cobalt nanowires using a porous polymer film template. This type of array is a competitive candidate for future perpendicular magnetic media capable of storage densities exceeding 1 Terabit/in.{sup 2} The polymer template, derived from a self-assembling P(S-b-MMA) diblock copolymer film, provides precise control over the nanowire diameter (15 nm) and interwire spacing (24 nm), whereas nanowire length (typically 50 to 1000 nm) is controlled accurately with the aid of real-time electrochemical quartz crystal monitoring. Pulse and pulse-reversed electrodeposition techniques, as compared to dc, are shown to significantly enhance the perpendicular magnetic anisotropy of the magnetic nanowire array and ultimately result in coercivity as large as 2.7 kOe at 300 K. Magnetic and structural characterizations suggest that these properties arise from an improved degree of magnetocrystalline anisotropy (due to c-axis oriented crystal growth and improvements in crystal quality) that strongly supplements the basic shape anisotropy of the nanowires. Low temperature magnetometry is used to investigate exchange bias effects due to the incorporation of CoO antiferromagnetic impurities during the electrodeposition process and subsequent Co oxidation in air.

  14. Self-Assembly of Telechelic Tyrosine End-Capped PEO and Poly(alanine) Polymers in Aqueous Solution.

    PubMed

    Kirkham, Steven; Castelletto, Valeria; Hamley, Ian William; Reza, Mehedi; Ruokolainen, Janne; Hermida-Merino, Daniel; Bilalis, Panayiotis; Iatrou, Hermis

    2016-03-14

    The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(L-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers--in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide-polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped "associative polymers". Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-groups.

  15. Self-Assembled ROS-Sensitive Polymer-Peptide Therapeutics Incorporating Built-in Reporters for Evaluation of Treatment Efficacy.

    PubMed

    Qiao, Zeng-Ying; Zhao, Wen-Jing; Cong, Yong; Zhang, Di; Hu, Zhiyuan; Duan, Zhong-Yu; Wang, Hao

    2016-05-09

    One of the major challenges in current cancer therapy is to maximize therapeutic effect and evaluate tumor progression under the scheduled treatment protocol. To address these challenges, we synthesized the cytotoxic peptide (KLAKLAK)2 (named KLAK) conjugated amphiphilic poly(β-thioester)s copolymers (H-P-K) composed of reactive oxygen species (ROS) sensitive backbones and hydrophilic polyethylene glycol (PEG) side chains. H-P-K could self-assemble into micelle-like nanoparticles by hydrophobic interaction with copolymer backbones as cores and PEG and KLAK as shells. The assembled polymer-peptide nanoparticles remarkably improved cellular internalization and accumulation of therapeutic KLAK in cells. Compared to free KLAK peptide, the antitumor activity of H-P-K was significantly enhanced up to ∼400 times, suggesting the effectiveness of the nanoscaled polymer-peptide conjugation as biopharmaceuticals. The higher antitumor activity of nanoparticles was attributed to the efficient disruption of mitochondrial membranes and subsequent excessive ROS production in cells. To realize the ROS monitoring and treatment evaluation, we encapsulated squaraine (SQ) dyes as built-in reporters in ROS-sensitive H-P-K micelles. The overgenerated ROS around mitochondria stimulated the swelling of nanoparticles and subsequent release of SQ, which formed H-aggregates and significantly increased the photoacoustic (PA) signal. We believed that this self-assembled polymer-peptide nanotherapeutics incorporating built-in reporters has great potential for high antitumor performance and in situ treatment evaluation.

  16. Furan-functionalized co-polymers for targeted drug delivery: characterization, self-assembly and drug encapsulation.

    PubMed

    Shi, Meng; Shoichet, Molly S

    2008-01-01

    We have previously reported furan-maleimide Diels-Alder chemistry as a new methodology to couple maleimide-modified antibodies on furan-functionalized polymeric carriers in the preparation of immuno-nanoparticles for targeted drug delivery. In this report, we focus on the characterization, self-assembly behavior and drug encapsulation of two types of furan-functionalized co-polymers: poly(2-methyl, 2-carboxytrimethylene carbonate-co-D,L-lactide)-furan (poly(TMCC-co-LA)-furan) and poly(2-methyl, 2-carboxytrimethylene carbonate-co-D,L-lactide)-graft-poly(ethylene glycol)-furan (poly(TMCC-co-LA)-g-PEG-furan). The co-polymers were synthesized by modifying the carboxylic acid groups on the poly(TMCC-co-LA) backbone by either furfurylamine or PEG-furan to generate either linear co-polymers of poly(TMCC-co-LA)-furan with furan pendant groups or graft co-polymers of poly(TMCC-co-LA)-g-PEG-furan with furan-terminated PEG grafts, respectively. Using a membrane dialysis method, both of the co-polymers were self-assembled into nanoparticles in aqueous environments driven by the hydrophobic association among polymer chains. The hydrophobic domains in the nanoparticles were confirmed by the incorporation of pyrene molecules and the critical aggregation concentrations were determined to be approximately 5 x 10(-5) mM for poly(TMCC-co-LA)-furan and 2 x 10(-4) mM for poly(TMCC-co-LA)-g-PEG-furan. By the addition of borate buffer in the organic solvent used to dissolve the co-polymers in the dialysis procedure, we were able to control the size of the nanoparticles: 54-169 nm for poly(TMCC-co-LA)-furan and 28-283 nm for poly(TMCC-co-LA)-g-PEG-furan. This unique feature can be explained by the ionization of carboxylic acid groups along the co-polymer backbone. A hydrophobic anticancer drug, doxorubicin (DOX), was encapsulated within the nanoparticles, with the larger size nanoparticles incorporating greater amounts of DOX. Combining the strategy of antibody-mediated targeting, these

  17. High-efficiency si/polymer hybrid solar cells based on synergistic surface texturing of Si nanowires on pyramids.

    PubMed

    He, Lining; Lai, Donny; Wang, Hao; Jiang, Changyun; Rusli

    2012-06-11

    An efficient Si/PEDOT:PSS hybrid solar cell using synergistic surface texturing of Si nanowires (SiNWs) on pyramids is demonstrated. A power conversion efficiency (PCE) of 9.9% is achieved from the cells using the SiNW/pyramid binary structure, which is much higher than similar cells based on planar Si, pyramid-textured Si, and SiNWs. The PCE is the highest reported to-date for hybrid cells based on Si nanostructures and PEDOT.

  18. Functionalization at the central position of vinyl polymer chains: highly associable multipoint hydrogen bonds for complementary self-assemblies.

    PubMed

    Lee, Sang-Ho; Ouchi, Makoto; Sawamoto, Mitsuo

    2014-02-01

    This paper deals with the precision introduction of a multiple hydrogen-bonding site of a high association constant at the central position of a vinyl polymer chain for complementary self-assemblies. The interactive site consists of an array of hydrogen donors (D) and acceptors (A) to induce a multiple and highly associable interaction with a complementary counterpart. A bifunctional initiator (Cl-DADDAD-Cl) for metal-catalyzed living radical polymerization is thus designed and synthesized to embed a "Hamilton receptor" (DADDAD) between two terminal chlorides (Cl). In the presence of a ruthenium complex, the dichloride gives controlled polymers (Cl∼∼∼DADDAD∼∼∼Cl, ∼ ∼ ∼: polymer backbone) of narrow molecular weight distributions (Mw/Mn < 1.2) from common monomers such as styrene and methyl methacrylate (MMA). The receptor-decorated polystyrene recognizes complementary associable molecules and polymers carrying an ADADA unit (ADADA-Anthracene and ADADA-PMMA) to form self-assemblies where the association constant is as high as K(ass) ≈ 8000 m(-1).

  19. Switchable supramolecular polymers from the self-assembly of a small monomer with two orthogonal binding interactions.

    PubMed

    Gröger, Gerd; Meyer-Zaika, Wolfgang; Böttcher, Christoph; Gröhn, Franziska; Ruthard, Christian; Schmuck, Carsten

    2011-06-15

    The low molecular weight heteroditopic monomer 1 forms supramolecular polymers in polar solution as shown, for example, by infrared laser-based dynamic light scattering (DLS), small-angle neutron scattering (SANS), electron microscopy (TEM, cryo-TEM), and viscosity measurements. Self-assembly of 1 is based on two orthogonal binding interactions, the formation of a Fe(II)-terpyridine 1:2 metal-ligand complex and the dimerization of a self-complementary guanidiniocarbonyl pyrrole carboxylate zwitterion. Both binding interactions have a sufficient stability in polar (DMSO) and even aqueous solutions to ensure formation of linear polymers of considerable length (up to 100 nm). The supramolecular polymerization follows a ring-chain mechanism causing a significant increase in the viscosity of the solutions at millimolar concentrations and above. The linear polymers then further aggregate in solution into larger globular aggregates with a densely packed core and a loose shell. Both binding interactions can be furthermore switched on and off either by adding a competing ligand to remove the metal ion and subsequent readdition of Fe(II) or by reversible protonation and deprotonation of the zwitterion upon addition of acid or base. The self-assembly of 1 can therefore be switched back and forth between four different states, the monomer, a metal-complexed dimer or an ion paired dimer, and finally the polymer.

  20. Single-step microfluidic synthesis of various nonspherical polymer nanoparticles via in situ assembling: dominating role of polyelectrolytes molecules.

    PubMed

    Visaveliya, Nikunjkumar; Köhler, J Michael

    2014-07-23

    In this paper, a microfluidic approach has been used for the synthesis of ellipsoidal, dumbbell, rodlike, and necklacelike polymer nanoparticles. High yields of special types of nonspherical nanoparticles have been achieved by the implementation of an emulsion polymerization into microfluidic arrangement with a micro hole-plate reactor for the formation of monomer droplets. Here, in particular, the formation of nonspherical polymer nanoparticles is dependent on the presence of polyelectrolyte surface active molecules such as poly(4-styrenesulfonic acid-co-maleic acid) sodium salt (PSS-co-PM), poly(sodium-p-styrenesulfonate) (PSSS), and polyanetholesulfonic acid sodium salt (PAES). The shapes and sizes of the interparticle nanoassemblies are precisely controlled by adjusting the concentration of polyelectrolytes in the aqueous phase, and by choosing suitable flow rate ratios (aqueous to monomer phase), respectively. The formation of polymer nanoparticles with different morphologies can be explained by a spontaneous in situ assembling under partial electrostatic repulsive control in the single step synthesis. The effect of particle charge and the competition between thermal motion of particles and electrostatic repulsion on the spontaneous assembling under the condition of a limited polarizability are discussed here as an important factor for the formation process of nonspherical polymer nanoparticles.

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

    PubMed

    Xu, Wen-Sheng; Freed, Karl F

    2016-06-07

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

  2. Synthesis and self-assembly behavior of POSS-embedded hyperbranched polymers.

    PubMed

    Li, Dawei; Niu, Yuguang; Yang, Yanyu; Wang, Xing; Yang, Fei; Shen, Hong; Wu, Decheng

    2015-05-14

    Here we demonstrate a simple and straightforward approach to prepare POSS-embedded hyperbranched (HB-POSS) polymers with customized molecular weights and sizes just by controlling the polymerization time. The polymers can be further used for building amphiphilic polymers, presenting morphological transition from micelle to vesicle in aqueous solution.

  3. Quantum dots as templates for self-assembly of photoswitchable polymers: small, dual-color nanoparticles capable of facile photomodulation.

    PubMed

    Díaz, Sebastián A; Giordano, Luciana; Azcárate, Julio C; Jovin, Thomas M; Jares-Erijman, Elizabeth A

    2013-02-27

    A photomodulatable amphiphilic polymer has been synthesized with a backbone of poly[isobutylene-alt-maleic anhydride] and pendant dodecyl alkyl chains, Lucifer Yellow (LY) fluorescent probes, and diheteroarylethenes photochromic (PC) groups. The latter serve as reversible UV-activated FRET acceptors for the LY donors. We characterized the spectral and switching properties of the polymer in an organic solvent (CHCl(3)). In an aqueous medium the polymer forms polymersomes, constituting fluorescence probes ~75 nm in diameter. Self-assembly of the polymer on the surface of a quantum dot (QD) serving as a template creates a dual-color photoswitchable nanoparticle (psNP) with improved properties due to the increase in polymer density and efficiency of PC photoconversion. The psNP exhibits a second QD red emission band that functions as an internal standard requiring only a single excitation wavelength, and is much reduced in size (<20 nm diameter) compared to the polymersomes. The QD template also greatly increases the depth of modulation by photochromic FRET of the LY emission monitored by both steady-state and time-resolved (lifetime) fluorescence (from 20%→70%, and from 12%→55%, respectively).

  4. Multifunctional metal-polymer nanoagglomerates from single-pass aerosol self-assembly

    NASA Astrophysics Data System (ADS)

    Byeon, Jeong Hoon

    2016-08-01

    In this study, gold (Au)-iron (Fe) nanoagglomerates were capped by a polymer mixture (PM) consisting of poly(lactide-co-glycolic acid), protamine sulfate, and poly-l-lysine via floating self-assembly in a single-pass aerosol configuration as multibiofunctional nanoplatforms. The Au-Fe nanoagglomerates were directly injected into PM droplets (PM dissolved in dichloromethane) in a collison atomizer and subsequently heat-treated to liberate the solvent from the droplets, resulting in the formation of PM-capped Au-Fe nanoagglomerates. Measured in vitro, the cytotoxicities of the nanoagglomerates (>98.5% cell viability) showed no significant differences compared with PM particles alone (>98.8%), thus implying that the nanoagglomerates are suitable for further testing of biofunctionalities. Measurements of gene delivery performance revealed that the incorporation of the Au-Fe nanoagglomerates enhanced the gene delivery performance (3.2 × 106 RLU mg‑1) of the PM particles alone (2.1 × 106 RLU mg‑1), which may have been caused by the PM structural change from a spherical to a hairy structure (i.e., the change followed the agglomerated backbone). Combining the X-ray-absorbing ability of Au and the magnetic property of Fe led to magnetic resonance (MR)-computed tomography (CT) contrast ability in a phantom; and the signal intensities [which reached 64 s‑1 T2-relaxation in MR and 194 Hounsfield units (HUs) in CT at 6.0 mg mL‑1] depended on particle concentration (0.5–6.0 mg mL‑1).

  5. Multifunctional metal-polymer nanoagglomerates from single-pass aerosol self-assembly

    PubMed Central

    Byeon, Jeong Hoon

    2016-01-01

    In this study, gold (Au)-iron (Fe) nanoagglomerates were capped by a polymer mixture (PM) consisting of poly(lactide-co-glycolic acid), protamine sulfate, and poly-l-lysine via floating self-assembly in a single-pass aerosol configuration as multibiofunctional nanoplatforms. The Au-Fe nanoagglomerates were directly injected into PM droplets (PM dissolved in dichloromethane) in a collison atomizer and subsequently heat-treated to liberate the solvent from the droplets, resulting in the formation of PM-capped Au-Fe nanoagglomerates. Measured in vitro, the cytotoxicities of the nanoagglomerates (>98.5% cell viability) showed no significant differences compared with PM particles alone (>98.8%), thus implying that the nanoagglomerates are suitable for further testing of biofunctionalities. Measurements of gene delivery performance revealed that the incorporation of the Au-Fe nanoagglomerates enhanced the gene delivery performance (3.2 × 106 RLU mg−1) of the PM particles alone (2.1 × 106 RLU mg−1), which may have been caused by the PM structural change from a spherical to a hairy structure (i.e., the change followed the agglomerated backbone). Combining the X-ray-absorbing ability of Au and the magnetic property of Fe led to magnetic resonance (MR)-computed tomography (CT) contrast ability in a phantom; and the signal intensities [which reached 64 s−1 T2-relaxation in MR and 194 Hounsfield units (HUs) in CT at 6.0 mg mL−1] depended on particle concentration (0.5–6.0 mg mL−1). PMID:27507668

  6. Diffusion-coupled molecular assembly: structuring of coordination polymers across multiple length scales.

    PubMed

    Hirai, Kenji; Reboul, Julien; Morone, Nobuhiro; Heuser, John E; Furukawa, Shuhei; Kitagawa, Susumu

    2014-10-22

    Porous coordination polymers (PCPs) are an intriguing class of molecular-based materials because of the designability of framework scaffolds, pore sizes and pore surface functionalities. Besides the structural designability at the molecular scale, the structuring of PCPs into mesoscopic/macroscopic morphologies has attracted much attention due to the significance for the practical applications. The structuring of PCPs at the mesoscopic/macroscopic scale has been so far demonstrated by the spatial localization of coordination reactions on the surface of templates or at the phase boundaries. However, these methodologies have never been applied to the fabrication of solid-solution or multivariate metal-organic frameworks (MOFs), in which multiple components are homogeneously mixed. Herein, we demonstrate the structuring of a box-type superstructure comprising of a solid-solution PCP by integrating a bidirectional diffusion of multiple organic ligands into molecular assembly. The parent crystals of [Zn2(ndc)2(bpy)]n were placed in the DMF solution of additional organic component of H2bdc, and the temperature was rapidly elevated up to 80 °C (ndc = 1,4-naphthalenedicarboxylate, bpy = 4,4'-bipyridyl, bdc = 1,4-benzenedicarboxylate). The dissolution of the parent crystals induced the outward diffusion of components; contrariwise, the accumulation of the other organic ligand of H2bdc induced the inward diffusion toward the surface of the parent crystals. This bidirectional diffusion of multiple components spatially localized the recrystallization at the surface of cuboid parent crystals; therefore, the nanocrystals of a solid-solution PCP ([Zn2(bdc)1.5(ndc)0.5(bpy)]n) were organized into a mesoscopic box superstructure. Furthermore, we demonstrated that the box superstructures enhanced the mass transfer kinetics for the separation of hydrocarbons.

  7. Electrostatic Assembly of Polymers and Nanoparticles at Liquid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Hoagland, David

    The electrostatic attraction between charged solutes on opposite sides of the interface between immiscible liquids offers an efficient route to the self-assembly of two-dimensional films. As implemented by us, a hydrophobic polymer with amine end(s) or block(s) is presented in an oil phase, and a negatively charged nanoparticle is presented in an aqueous phase; both solutes are insoluble in the opposite phase but efficiently driven to the liquid-liquid interface by mutual electrostatically attraction to the solute in the opposite phase. Depending on experimental conditions (salt concentration, pH, solute concentrations, etc.), a continuous, nanoscopically thin composite film builds at the oil-water interface over the timescale of minutes, often accompanied by a dramatic reduction of interfacial tension akin to that observed for a surfactant. Film formation and properties by the new route will be discussed, as principally probed through pendant drop interfacial tensiometry and pendant drop interfacial rheometry. Components of model system are toluene-dissolved amine end-capped polystyrene and water-dispersed acid-treated carbon nanotubes or citrate-treated gold nanospheres. Film structures are complicated, as are crucial electrostatic interactions near the interface. With amine end-capped polystyrene partnered with acid-treated carbon nanotubes, high pH (above 5) and high polystyrene molecular weight (above 5000 g/mol) strongly hinder film formation. These films, which are liquid-like, show two viscoelastic relaxations, a fast relaxation (about 10 s) associated with polystyrene chain rearrangements (slightly impacted by carbon nanotube association) and a slow relaxation (about 20 min) associated with polystyrene adsorption/desorption; at intermediate times (or frequencies), the two-dimensional storage and loss moduli follow approximately the same power law dependences. Support by NSF through the Univ. of Massachusetts MRSEC.

  8. Assembled core-shell nanostructures of gold nanoparticles with biocompatible polymers toward biology.

    PubMed

    Li, Dongxiang; Li, Qianru; Hao, Xiongwen; Zhang, Yaojun; Zhang, Zhupeng; Li, Chunfang

    2014-03-01

    The present review focuses on core-shell nanostructures of spherical gold nanoparticles (Au NPs) and biocompatible polymers mainly from the view points of preparation approaches, nanocomposite properties and potential applications for biology. The preparation approaches are assorted into direct-reduction, covalent "graft-to", "graft-from" approach, surface bonding and physical adsorption. Various biocompatible polymers are involved such as the thermosensitive polymers, pH-responsive polymers, antibiofouling polymers, conductive polymers and several natural polymers. The encapsulating and loading properties, cellular uptake and drug release control, as well as biorecognition, targeting and sensing potential are discussed in connection with biological systems. These polymeric gold nanocomposites will have a great potential in biotechnology and life science but also face enormous challenge in future applications.

  9. Silver nanowire percolation network soldered with graphene oxide at room temperature and its application for fully stretchable polymer light-emitting diodes.

    PubMed

    Liang, Jiajie; Li, Lu; Tong, Kwing; Ren, Zhi; Hu, Wei; Niu, Xiaofan; Chen, Yongsheng; Pei, Qibing

    2014-02-25

    Transparent conductive electrodes with high surface conductivity, high transmittance in the visible wavelength range, and mechanical compliance are one of the major challenges in the fabrication of stretchable optoelectronic devices. We report the preparation of a transparent conductive electrode (TCE) based on a silver nanowire (AgNW) percolation network modified with graphene oxide (GO). The monatomic thickness, mechanical flexibility, and strong bonding with AgNWs enable the GO sheets to wrap around and solder the AgNW junctions and thus dramatically reduce the inter-nanowire contact resistance without heat treatment or high force pressing. The GO-soldered AgNW network has a figure-of-merit sheet resistance of 14 ohm/sq with 88% transmittance at 550 nm. Its storage stability is improved compared to a conventional high-temperature annealed AgNW network. The GO-soldered AgNW network on polyethylene terephthalate films was processed from solutions using a drawdown machine at room temperature. When bent to 4 mm radius, its sheet resistance was increased by only 2-3% after 12,000 bending cycles. GO solder can also improve the stretchability of the AgNW network. Composite TCE fabricated by inlaying a GO-soldered AgNW network in the surface layer of polyurethane acrylate films is stretchable, by greater than 100% linear strain without losing electrical conductivity. Fully stretchable white polymer light-emitting diodes (PLEDs) were fabricated for the first time, employing the stretchable TCE as both the anode and cathode. The PLED can survive after 100 stretching cycles between 0 and 40% strain and can be stretched up to 130% linear strain at room temperature.

  10. Bottom-up/top-down high resolution, high throughput lithography using vertically assembled block bottle brush polymers

    NASA Astrophysics Data System (ADS)

    Trefonas, Peter; Thackeray, James W.; Sun, Guorong; Cho, Sangho; Clark, Corrie; Verkhoturov, Stanislav V.; Eller, Michael J.; Li, Ang; Pavía-Jiménez, Adriana; Schweikert, Emile A.; Wooley, Karen L.

    2013-03-01

    We describe a novel deterministic bottom-up / top-down approach to sub-30 nm photolithography using a film composed of assembled block brush polymers of highly uniform composition and chain length. The polymer architecture consists of a rigid backbone of polymerized norbornene, each linked to flexible short side brush chains. The resultant `bottle brush' topology has a cylindrical shape with short brush chains arranged concentrically around the backbone, in which the cylinder radius is determined by the number of monomers within the brush fragment, while the cylinder length is determined by the degree of backbone polymerization. The modularity of the synthetic system allows a wide diversity of lithographically useful monomers, sequencing, dimension and property variation. Sequential grafting of pre-synthesized blocks allows for facile formation of either concentric or lengthwise block copolymers. Placement of brush chains of different compositions along different regions of the cylinder, along with variation of the relative concentric and lengthwise dimensions, provides mechanisms to align and control placement of the cylinders. These polymers are compatible with photoacid generators (PAGs) and crosslinker functionality. Our results are consistent with a model that the bottle brush polymers assemble (bottom-up) in the film to yield a `forest' of vertically arranged cylindrical block brush polymers, with the film thickness determined by the coherence lengths of the cylinders. Subsequent imaging via electron beam (EB or ebeam) or optical radiation yields a (top-down) mechanism for acid catalyzed crosslinking of adjacent cylinders. Uncrosslinked cylinders are removed in developer to yield negative photoresist patterns. Exposure doses are very low and throughputs are amenable to the requirements of Extreme Ultraviolet (EUV) lithography. The limiting resolution with ebeam exposure is potentially about two cylinder diameters width (< 8 nm), with the smallest observed

  11. Bottom-up/top-down, high-resolution, high-throughput lithography using vertically assembled block bottle brush polymers

    NASA Astrophysics Data System (ADS)

    Trefonas, Peter; Thackeray, James W.; Sun, Guorong; Cho, Sangho; Clark, Corrie; Verkhoturov, Stanislav V.; Eller, Michael J.; Li, Ang; Pavia-Sanders, Adriana; Schweikert, Emile A.; Wooley, Karen L.

    2013-10-01

    We describe a novel deterministic bottom-up/top-down approach to sub-30-nm photolithography using a film composed of assembled block brush polymers of highly uniform composition and chain length. The polymer architecture consists of a rigid backbone of polymerized norbornene, each linked to flexible short side brush chains. The resultant bottle brush topology has a cylindrical shape with short brush chains arranged concentrically around the backbone, in which the cylinder radius is determined by the number of monomers within the brush fragment, while the cylinder length is determined by the degree of backbone polymerization. The modularity of the synthetic system allows a wide diversity of lithographically useful monomers, sequencing, dimension, and property variation. Sequential grafting of presynthesized blocks allows for facile formation of either concentric or lengthwise block copolymers. Placement of brush chains of different compositions along different regions of the cylinder, along with variation of the relative concentric and lengthwise dimensions, provides mechanisms to align and control placement of the cylinders. These polymers are compatible with photoacid generators and crosslinker functionality. Our results are consistent with a model that the bottle brush polymers assemble (bottom-up) in the film to yield a forest of vertically arranged cylindrical block brush polymers, with the film thickness determined by the coherence lengths of the cylinders. Subsequent imaging via electron beam (e-beam) or optical radiation yields a (top-down) mechanism for acid catalyzed crosslinking of adjacent cylinders. Uncrosslinked cylinders are removed in developer to yield negative photoresist patterns. Exposure doses are very low and throughputs are amenable to the requirements of extreme ultraviolet lithography. The limiting resolution with e-beam exposure is potentially about two cylinder diameters width (<8 nm), with the smallest observed patterns approaching 10 nm.

  12. Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.

    PubMed

    Zhang, Ren; Lee, Bongjoon; Bockstaller, Michael R; Douglas, Jack F; Stafford, Christopher M; Kumar, Sanat K; Raghavan, Dharmaraj; Karim, Alamgir

    The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.

  13. Inorganic molecular-scale MoSI nanowire-gold nanoparticle networks exhibit self-organized critical self-assembly.

    PubMed

    Strle, Jure; Vengust, Damjan; Mihailovic, Dragan

    2009-03-01

    We investigate for the first time the topological characteristics of large molecular-scale inorganic networks self-assembled in solution using the unique sulfur-bonding chemistry of conducting MoSI molecular wires and gold nanoparticles (GNPs). The network self-assembly is shown to display power-law distribution of graph edges, indicating an intrinsic tendency to self-organize into scale-invariant critical state, without any external control parameter. We discuss the electronic transport properties of such networks particularly with regard to the possibility of data processing.

  14. Self-assembled Fe nanowires using organometallic chemical vapor deposition and CaF2 masks on stepped Si(111)

    NASA Astrophysics Data System (ADS)

    Lin, J.-L.; Petrovykh, D. Y.; Kirakosian, A.; Rauscher, H.; Himpsel, F. J.; Dowben, P. A.

    2001-02-01

    Linear arrays of 3 nm wide Fe stripes with 15 nm spacing are fabricated by self-assembly. They are formed by photolysis of ferrocene that is selectively adsorbed between CaF2 stripes. An ultraviolet nitrogen laser removes the organic ligands from ferrocene. Arrays of CaF2 stripes serve as masks, which are self-assembled on a stepped Si(111) surface. Scanning tunneling microscopy is used to investigate the surface morphology during growth. A generalization of this method to other wire materials is discussed.

  15. Synthesis of high crystallinity ZnO nanowire array on polymer substrate and flexible fiber-based sensor.

    PubMed

    Liu, Jinmei; Wu, Weiwei; Bai, Suo; Qin, Yong

    2011-11-01

    Well aligned ZnO nanowire (NW) arrays are grown on Kevlar fiber and Kapton film via the chemical vapor deposition (CVD) method. These NWs have better crystallinity than those synthesized through the low-temperature hydrothermal method. The average length and diameter of ZnO NWs grown on Kevlar fiber can be controlled from 0.5 to 2.76 μm and 30 to 300 nm, respectively. A flexible ultraviolet (UV) sensor based on Kevlar fiber/ZnO NWs hybrid structure is made to detect UV illumination quantificationally.

  16. Microtubule-based gold nanowires and nanowire arrays.

    PubMed

    Zhou, Jing C; Gao, Yao; Martinez-Molares, Alfredo A; Jing, Xiaoye; Yan, Dong; Lau, Joseph; Hamasaki, Toshikazu; Ozkan, Cengiz S; Ozkan, Mihrimah; Hu, Evelyn; Dunn, Bruce

    2008-09-01

    Biological structures are attractive as templates to form nanoscale architectures for electronics because of their dimensions and the ability to interact with inorganic materials. In this study, we report the fabrication and electrical properties of microtubule (MT)-templated Au nanowires, and methods for assembling Au nanowire arrays based on these templates. The adsorption of MTs on silicon substrates is an effective means for preserving the conformation of the MT and provides a convenient platform for electrical measurements. To improve the metallization of MTs, a photochemical route for gold reduction is adapted, which leads to continuous coverage. The conductivity values measured on micrometer-long nanowires are similar to those reported for other biotemplated gold nanowires. A protocol for fabricating arrays of MT-templated gold nanowires is demonstrated.

  17. Patterned Fabrication of Zinc Oxide Nanowire Arrays

    NASA Astrophysics Data System (ADS)

    Khan, Sahar; Lamson, Thomas; Xu, Huizhong

    Zinc oxide nanowires possess desirable mechanical, thermodynamic, electrical, and optical properties. Although the hydrothermal growth process can be applied in tolerable growth conditions, the dimension and density of nanowires has a complex dependence on substrate pre-treatment, precursor concentrations, and growth conditions. Precise control of the geometry and density of nanowires as well as the location of nanowires would allow for the fabrication of useful nanowaveguide devices. In this work, we used electron beam lithography to pattern hole arrays in a polymer layer on gold-coated glass substrates and synthesized zinc oxide nanowires inside these holes. Arrays of nanowires with diameters ranging from 50 nm to 140 nm and various spacings were obtained. The transmission of light through these zinc oxide nanowire arrays in a silver film was also studied. This research was supported by the Seed Grant Program of St. John's University and the National Science Foundation under Grant No. CBET-0953645.

  18. Sandwiched assembly of ZnO nanowires between graphene layers for a self-powered and fast responsive ultraviolet photodetector

    NASA Astrophysics Data System (ADS)

    Deka Boruah, Buddha; Mukherjee, Anwesha; Misra, Abha

    2016-03-01

    A heterostructure of graphene and zinc oxide (ZnO) nanowires (NWs) is fabricated by sandwiching an array of ZnO NWs between two graphene layers for an ultraviolet (UV) photodetector. This unique structure allows NWs to be in direct contact with the graphene layers, minimizing the effect of the substrate or metal electrodes. In this device, graphene layers act as highly conducting electrodes with a high mobility of the generated charge carriers. An excellent sensitivity is demonstrated towards UV illumination, with a reversible photoresponse even for a short period of UV illumination. Response and recovery times of a few milliseconds demonstrated a much faster photoresponse than most of the conventional ZnO nanostructure-based photodetectors. It is shown that the generation of a built-in electric field between the interface of graphene and ZnO NWs effectively contributes to the separation of photogenerated electron-hole pairs for photocurrent generation without applying any external bias. Upon application of external bias voltage, the electric field further increases the drift velocity of photogenerated electrons by reducing the charge recombination rates, and results in an enhancement of the photocurrent. Therefore, the graphene-based heterostructure (G/ZnO NW/G) opens avenues to constructing a novel heterostructure with a combination of two functionally dissimilar materials.

  19. A supramolecular Janus hyperbranched polymer and its photoresponsive self-assembly of vesicles with narrow size distribution.

    PubMed

    Liu, Yong; Yu, Chunyang; Jin, Haibao; Jiang, Binbin; Zhu, Xinyuan; Zhou, Yongfeng; Lu, Zhongyuan; Yan, Deyue

    2013-03-27

    Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host-guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups. In addition, the obtained vesicles could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. The dynamics and mechanism for the self-assembly of vesicles as well as the bilayer structure have been disclosed by a dissipative particle dynamics simulation.

  20. Sonication-induced formation of size-controlled self-assemblies of amphiphilic Janus-type polymers as optical tumor-imaging agents.

    PubMed

    Miki, Koji; Hashimoto, Hiroki; Inoue, Tatsuhiro; Matsuoka, Hideki; Harada, Hiroshi; Hiraoka, Masahiro; Ohe, Kouichi

    2014-08-13

    In this study, amphiphilic Janus-type polymers were synthesized via ring-opening metathesis polymerization (ROMP), multiple vicinal diol formation, and grafting of poly(ethylene glycol) monomethyl ether (mPEG). These amphiphilic polymers formed self-assemblies, which were a mixture of micelles and multimicellar aggregates, in water. By choosing suitable Janus-type polymers and irradiating an aqueous solution of polymers using a sonicator, either small micelles or large multimicellar aggregates were obtained selectively. Hydrophobic substituents controlled the aggregation-disaggregation behavior, leading to the formation of metastable self-assemblies by sonication. The formation of self-assemblies with a uniform size was affected by ultrasonic frequency, rather than power. In vivo optical tumor imaging revealed that the large-size multimicellar aggregates persisting for a long time in blood circulation slowly accumulated in tumor tissues. In contrast, the tumor site was rapidly, clearly visualized using the small-size micelles.

  1. Radiation Stability of Metal Nanowires

    NASA Astrophysics Data System (ADS)

    Bedin, S. A.; Makhin’ko, F. F.; Ovchinnikov, V. V.; Gerasimenko, N. N.; Zagorskiy, D. L.

    2017-01-01

    The aim of this work is to investigate the radiation stability of pure nickel and iron– nickel Fe0.56Ni0.44 alloy nanowires fabricated by matrix synthesis using polymer track membranes and Ar+ and Xe+ (E = 20 keV, j = 300 μA/cm2) beam irradiation. The dependence of the stability of nanowires on their diameter, fluence, and type of implanted ions is investigated. The assumption that the thermalized regions of dense cascades of atomic displacements (thermal spikes) play an important role in the nanowire structure change is made. These regions are nanosized zones of explosive energy release and heated to several thousands of degrees.

  2. Blown-Bubble Assembly and in Situ Fabrication of Sausage-like Graphene Nanotubes Containing Copper Nanoblocks.

    PubMed

    Wu, Shiting; Yang, Long; Zou, Mingchu; Yang, Yanbing; Du, Mingde; Xu, Wenjing; Yang, Liusi; Fang, Ying; Cao, Anyuan

    2016-08-10

    We use a blown-bubble method to assemble Cu nanowires and in situ fabricate graphene-based one-dimensional heterostructures, including versatile sausage-like configurations consisting of multilayer graphene nanotubes (GNTs) filled by single or periodically arranged Cu nanoblocks (CuNBs). This is done by first assembling Cu nanowires among a polymer-based blown-bubble film (BBF) and then growing graphene onto the nanowire substrate using the polymer matrix as a solid carbon source by chemical-vapor deposition. The formation of sausage-like GNT@CuNB nanostructures is due to the partial melting and breaking of embedded Cu nanowires during graphene growth, which is uniquely related to our BBF process. We show that the GNT skin significantly slows the oxidation process of CuNBs compared with that of bare Cu nanowires, and the presence of stuffed CuNBs also reduces the linear resistance along the GNTs. The large-scale assembled graphene-based heterostructures achieved by our BBF method may have potential applications in heterojunction electronic devices and high-stability transparent conductive electrodes.

  3. Harnessing the instabilities of soft matter: Dynamically tuning of wetting, assembly and pattern transformation in polymer microstructures

    NASA Astrophysics Data System (ADS)

    Zhang, Ying

    2008-10-01

    In this dissertation, we have investigated the fabrication, mechanical instability and applications of two kinds of polymer micro/nano-structures: high-aspect-ratio (HAR) polymer pillar arrays, and periodic porous elastomer membranes. For HAR polymer pillar arrays, we demonstrated the fabrication of high-aspect-ratio (up to 18) polymer micropillars with different shapes and dimensions by replica molding. Capillary force lithography (CFL) is also demonstrated as a simple and flexible method to fabricate microstructures with controlled aspect ratios. Meanwhile, by introducing conventional photoresist SU-8, CFL is successfully coupled with photolithography and used to create hierarchical 2D or 3D structures, which greatly expand the capability of current capillary force lithography. The mechanical stability of HAR structures with varied materials and different aspect ratio, density and shape were also studied and the results show that the adhesive forces from environment are the major cause of structure collapsing. When HAR polymer pillars are subjected to different solvents treatment, both capillary force and solvent swelling need to be considered to completely understand the structure instability. On HAR micropillar array, thermoresponsive polymer brushes, poly ( N-isopropylacrylamide) (PNIPAAm), were selectively grafted at different locations for dynamically tuning surface wetting or pattern assembly. When the temperature changed from 40°C to 20°, depending on the location of polymer brushes, different wetting transitions, either from a composite solid/air state (Cassie state) to a composite solid/liquid state (Hemi-wicking state) or a transition between two Cassie states were observed. Meanwhile, the dynamically tuning of water contact angle enables us to control capillary drying force and thus harness pattern collapse to create superlattice micropatterns. For periodic porous elastomer membrane, a novel pattern transformation effect is discovered due to the

  4. Recent Advances in Gas Barrier Thin Films via Layer-by-Layer Assembly of Polymers and Platelets.

    PubMed

    Priolo, Morgan A; Holder, Kevin M; Guin, Tyler; Grunlan, Jaime C

    2015-05-01

    Layer-by-layer (LbL) assembly has emerged as the leading non-vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide-based barrier films. This Feature Article is a mini-review of LbL-based multilayer thin films with a 'nanobrick wall' microstructure comprising polymeric mortar and nano-platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water-based thin films exhibit oxygen transmission rates below 5 × 10(-3) cm(3) m(-2) day(-1) atm(-1) and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake-filled polymers are briefly reviewed.

  5. Hierarchical Assembly of Model Cell Surfaces: Synthesis of Mucin Mimetic Polymers and their Display on Supported Bilayers

    PubMed Central

    Rabuka, David; Parthasarathy, Raghuveer; Lee, Goo Soo; Chen, Xing; Groves, Jay T.; Bertozzi, Carolyn R.

    2008-01-01

    Molecular level analysis of cell surface phenomena could benefit from model systems comprising structurally-defined components. Here we present the first step toward bottom-up assembly of model cell surfaces – the synthesis of mucin mimetics and their incorporation into artificial membranes. Natural mucins are densely glycosylated O-linked glycoproteins that serve numerous functions on cell surfaces. Their large size and extensive glycosylation makes the synthesis of these biopolymers impractical. We designed synthetically tractable glycosylated polymers that possess rod-like extended conformations similar to natural mucins. The glycosylated polymers were end-functionalized with lipid groups and embedded into supported lipid bilayers where they interact with protein receptors in a structure-dependent manner. Furthermore, their dynamic behavior in synthetic membranes mirrored that of natural biomolecules. This system provides a unique framework with which to study the behavior of mucin-like macromolecules in a controlled, cell surface-mimetic environment. PMID:17425309

  6. Role of redox centre in charge transport investigated by novel self-assembled conjugated polymer molecular junctions

    PubMed Central

    Wang, Zongrui; Dong, Huanli; Li, Tao; Hviid, Rune; Zou, Ye; Wei, Zhongming; Fu, Xiaolong; Wang, Erjing; Zhen, Yonggang; Nørgaard, Kasper; Laursen, Bo W.; Hu, Wenping

    2015-01-01

    Molecular electronics describes a field that seeks to implement electronic components made of molecular building blocks. To date, few studies have used conjugated polymers in molecular junctions despite the fact that they potentially transport charge more efficiently than the extensively investigated small-molecular systems. Here we report a novel type of molecular tunnelling junction exploring the use of conjugated polymers, which are self-assembled into ultrathin films in a distinguishable ‘planar' manner from the traditional vertically oriented small-molecule monolayers. Electrical measurements on the junctions reveal molecular-specific characteristics of the polymeric molecules in comparison with less conjugated small molecules. More significantly, we decorate redox-active functionality into polymeric backbones, demonstrating a key role of redox centre in the modulation of charge transport behaviour via energy level engineering and external stimuli, and implying the potential of employing tailor-made polymeric components as alternatives to small molecules for future molecular-scale electronics. PMID:26085081

  7. Fabrication of metallic nanowires and nanoribbons using laser interference lithography and shadow lithography

    SciTech Connect

    Park, Joong- Mok; Nalwa, Kanwar Singh; Leung, Wai; Constant, Kristen; Chaudhary, Sumit; Ho, Kai-Ming

    2010-04-30

    Ordered and free-standing metallic nanowires were fabricated by e-beam deposition on patterned polymer templates made by interference lithography. The dimensions of the nanowires can be controlled through adjustment of deposition conditions and polymer templates. Grain size, polarized optical transmission and electrical resistivity were measured with ordered and free-standing nanowires.

  8. Chemical reactivity of Ni-Rh nanowires.

    PubMed

    Schoiswohl, J; Mittendorfer, F; Surnev, S; Ramsey, M G; Andersen, J N; Netzer, F P

    2006-09-22

    The properties of bimetallic Ni-Rh nanowires, fabricated by decorating the steps of vicinal Rh(111) surfaces by stripes of self-assembled Ni adatoms, have been probed by STM, photoemission, and ab initio density functional theory calculations. These Ni-Rh nanowires have specific electronic properties that lead to a significantly enhanced chemical reactivity towards oxygen. As a result, the Ni-Rh nanowires can be oxidized exclusively, generating novel quasi-one-dimensional oxide structures.

  9. Influence of polymer aging on reliability indices of a typical printed-circuit assembly of radioelectronic equipment

    NASA Astrophysics Data System (ADS)

    Kuznetsov, G. V.; Kravchenko, E. V.

    2007-09-01

    Mathematical modeling of nonlinear nonstationary temperature fields of a typical printed-circuit assembly of radioelectronic equipment has been performed in a three-dimensional formulation with account for the convective and radiative heat exchange with the environment. On the basis of the data of the numerical experiment the “aging” (degradation) indices of polymer materials under prolonged thermal action have been determined. It has been established that the reliability of an object modeled with account for the real temperature fields is five times lower compared to the realization of normalized thermal conditions.

  10. Responsive polymer/gold nanoparticle composite thin films fabricated by solvent-induced self-assembly and spin-coating.

    PubMed

    Li, Dongxiang; Lee, Ji Yong; Kim, Dong Ha

    2011-02-15

    Self-assembled poly(4-vinylpyridine)-grafted gold (Au) nanoparticles (NPs) and polystyrene-b-poly(4-vinylpyridine) block copolymers were fabricated by the introduction of a selective solvent to a common solution. The assembled mixtures were spin-coated onto solid substrates to fabricate composite gold/polymer thin films composed of copolymer-hybridized Au NPs and independent copolymer micelles. The obtained composite Au thin films had variable localized surface plasmon resonance (LSPR) bands and microscopic morphologies upon vapor annealing with selective solvents because the adsorption and dissolving of solvent molecules into the films could rearrange the copolymer block. The hybrid nanostructured Au thin films may have potential in vapor sensing and organic assays.

  11. Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles.

    PubMed

    Gu, Haibin; Ciganda, Roberto; Castel, Patricia; Vax, Amélie; Gregurec, Danijela; Irigoyen, Joseba; Moya, Sergio; Salmon, Lionel; Zhao, Pengxiang; Ruiz, Jaime; Hernández, Ricardo; Astruc, Didier

    2015-12-07

    We report the first pentamethylferrocene (PMF) polymers and the redox chemistry of their robust polycationic pentamethylferricenium (PMFium) analogues. The PMF polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a PMF-containing norbornene derivative by using the third-generation Grubbs ruthenium metathesis catalyst. Cyclic voltammetry studies allowed us to determine confidently the number of monomer units in the polymers through the Bard-Anson method. Stoichiometric oxidation by using ferricenium hexafluorophosphate quantitatively and instantaneously provided fully stable (even in aerobic solutions) blue d(5) Fe(III) metallopolymers. Alternatively, oxidation of the PMF-containing polymers was conducted by reactions with Ag(I) or Au(III) , to give PMFium polymer-embedded Ag and Au nanoparticles (NPs). In the presence of I2 , oxidation by using Ag(I) gave polymer-embedded Ag/AgI NPs and AgNPs at the surface of AgI NPs. Oxidation by using Au(III) also produced an Au(I) intermediate that was trapped and characterized. Engineered single-electron transfer reactions of these redox-robust nanomaterial precursors appear to be a new way to control their formation, size, and environment in a supramolecular way.

  12. Investigating the energy harvesting capabilities of a hybrid ZnO nanowires/carbon fiber polymer composite beam.

    PubMed

    Masghouni, N; Burton, J; Philen, M K; Al-Haik, M

    2015-03-06

    Hybrid piezoelectric composite structures that are able to convert mechanical energy into electricity have gained growing attention in the past few years. In this work, an energy harvesting composite beam is developed by growing piezoelectric zinc oxide nanowires on the surface of carbon fiber prior to forming structural composites. The piezoelectric behavior of the composite beam was demonstrated under different vibration sources such as water bath sonicator and permanent magnet vibration shaker. The beam was excited at its fundamental natural frequency (43.2 Hz) and the open circuit voltage and the short circuit current were measured to be 3.1 mV and 23 nA, respectively. Upon connecting an optimal resistor (1.2 kΩ) in series with the beam a maximum power output 2.5 nW was achieved.

  13. Gold-coated silicon nanowire-graphene core-shell composite film as a polymer binder-free anode for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, Han-Jung; Lee, Sang Eon; Lee, Jihye; Jung, Joo-Yun; Lee, Eung-Sug; Choi, Jun-Hyuk; Jung, Jun-Ho; Oh, Minsub; Hyun, Seungmin; Choi, Dae-Geun

    2014-07-01

    We designed and fabricated a gold (Au)-coated silicon nanowires/graphene (Au-SiNWs/G) hybrid composite as a polymer binder-free anode for rechargeable lithium-ion batteries (LIBs). A large amount of SiNWs for LIB anode materials can be prepared by metal-assisted chemical etching (MaCE) process. The Au-SiNWs/G composite film on current collector was obtained by vacuum filtration using an anodic aluminum oxide (AAO) membrane and hot pressing method. Our experimental results show that the Au-SiNWs/G composite has a stable reversible capacity of about 1520 mA h/g which was maintained for 20 cycles. The Au-SiNWs/G composite anode showed much better cycling performance than SiNWs/polyvinylidene fluoride (PVDF)/Super-P, SiNWs/G composite, and pure SiNWs anodes. The improved electrochemical properties of the Au-SiNWs/G composite anode material is mainly ascribed to the composite's porous network structure.

  14. Direct laser fabrication of nanowires on semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Haghizadeh, Anahita; Yang, Haeyeon

    2016-03-01

    Periodic nanowires are observed from (001) orientation of Si and GaAs when the surfaces are irradiated interferentially by high power laser pulses. These nanowires are self-assembled and can be strain-free while their period is consistent with interference period. The nanowire morphologies are studied by atomic force microscopy. The observed period between nanowires depends on the wavelengths used and interference angle. The nanowire width increases with laser intensity. The narrowest nanowires observed have the width smaller than 20 nm, which is more than 10 times smaller than the interference period.

  15. Influence of metallic and dielectric nanowire arrays on the photoluminescence properties of P3HT thin films.

    PubMed

    Handloser, M; Dunbar, R B; Wisnet, A; Altpeter, P; Scheu, C; Schmidt-Mende, L; Hartschuh, A

    2012-08-03

    The optical properties of organic semiconductor thin films deposited on nanostructured surfaces are investigated using time-resolved two-photon photoluminescence (PL) microscopy. The surfaces consist of parallel aligned metallic or dielectric nanowires forming well-defined arrays on glass substrates. Keeping the nanowire dimensions constant and varying only their spacing from 40 to 400 nm, we study the range of different types of nanowire-semiconductor interactions. For silver nanowires and spacings below 100 nm, the PL intensity and lifetime of P3HT and MDMO-PPV decrease rapidly due to the short-ranged metal-induced quenching that dominates the PL response with respect to a possible plasmonic enhancement of optical transition rates. In the case of P3HT however, we observe an additional longer-ranged reduction of non-radiative losses for both metallic and dielectric nanowires that is not observed for MDMO-PPV. Excitation polarization dependent measurements indicate that this reduction is due to self-assembly of the P3HT polymer chains along the nanowires. In conclusion, nanostructured surfaces, when fabricated across large areas, could be used to control film morphologies and to improve energy transport and collection efficiencies in P3HT-based solar cells.

  16. Self Assembled Spin Coated and Bulk Films of a Novel Polydiacetylene as Second Order NLO Polymers

    DTIC Science & Technology

    1994-05-31

    NLO Polymers 6. AUTHOm(m) R&T Code: 4132016 W.H. Kim, B. Bihari, R. Moody, N. B. Kodali , J.Kumar,S.K. Dr. JoAnn MilUiken Tripathy. 7. PERFORMING...Polymers by W.H. Kim, B. Bihari, R. Moody, N. B. Kodali , J.Kumar,S.K. Tripathy. Submitted to Macromolecules University of Massachusetts Lowell Department...FILMS OF A NOVEL POLYDIACETYLENE AS SECOND ORDER NLO POLYMERS W. H. Kim, B. Bihari+, R. Moody+, N. B. Kodali , J. Kumar+, and S. K. Tripathy, University

  17. Co-assembly of Zn(SPh){sub 2} and organic linkers into helical and zig-zag polymer chains

    SciTech Connect

    Liu Yi; Yu Lingmin; Loo, Say Chye Joachim; Blair, Richard G.; Zhang Qichun

    2012-07-15

    Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (EG=ethylene glycol) (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized under solvothermal conditions at 150 Degree-Sign C or room temperature by the co-assembly of Zn(SPh){sub 2} and organic linkers such as 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPyTA) and 1,3-bis(trans-4-pyridylvinyl)benzene (BPyVB). X-ray crystallography study reveals that both polymers 1 and 2 crystallize in space group P2{sub 1}/c of the monoclinic system. The solid-state UV-vis absorption spectra show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up to 110 Degree-Sign C and 210 Degree-Sign C. - Graphical abstract: Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized. Solid-state UV-vis absorptions show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up to 110 Degree-Sign C and 210 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Two novel one-dimensional coordination polymers have been synthesized. Black-Right-Pointing-Pointer TPyTA results in helical structures in 1 while BPyVB leads to zig-zag chains in 2. Black-Right-Pointing-Pointer Solid-state UV-vis absorption spectra and TGA analysis of the title polymers were studied.

  18. Coupling Infusion and Gyration for the Nanoscale Assembly of Functional Polymer Nanofibers Integrated with Genetically Engineered Proteins

    PubMed Central

    Zhang, Siqi; Karaca, Banu Taktak; VanOosten, Sarah Kay; Yuca, Esra; Mahalingam, Suntharavathanan

    2015-01-01

    Nanofibers featuring functional nanoassemblies show great promise as enabling constituents for a diverse range of applications in areas such as tissue engineering, sensing, optoelectronics, and nanophotonics due to their controlled organization and architecture. An infusion gyration method is reported that enables the production of nanofibers with inherent biological functions by simply adjusting the flow rate of a polymer solution. Sufficient polymer chain entanglement is obtained at Berry number > 1.6 to make bead‐free fibers integrated with gold nanoparticles and proteins, in the diameter range of 117–216 nm. Integration of gold nanoparticles into the nanofiber assembly is followed using a gold‐binding peptide tag genetically conjugated to red fluorescence protein (DsRed). Fluorescence microscopy analysis corroborated with Fourier transform infrared spectroscopy (FTIR) data confirms the integration of the engineered red fluorescence protein with the nanofibers. The gold nanoparticle decorated nanofibers having red fluorescence protein as an integral part keep their biological functionality including copper‐induced fluorescence quenching of the DsRed protein due to its selective Cu+2 binding. Thus, coupling the infusion gyration method in this way offers a simple nanoscale assembly approach to integrate a diverse repertoire of protein functionalities into nanofibers to generate biohybrid materials for imaging, sensing, and biomaterial applications. PMID:26033345

  19. STRUCTURE AND ELECTRONIC PROPERTIES OF SELF-ASSEMBLED MACROCYCLE AND POLYMER MULTILAYERS

    SciTech Connect

    L. S. LI; A. D. Q. LI

    2001-05-01

    Our results from optical absorption and surface external reflection FTIR reveal that we can grow self-assembled multilayers consisting of electron acceptors like OHBP and donors like NiPc. In order to investigate the evolution of the surface physical properties of self-assembled multilayers, we applied Kelvin probe techniques and surface photovoltage spectroscopy to monitor the growth of self-assembled OHBP and NiPc systems. Kelvin probe results indicate that the surface electronic potential is very sensitive to the presence of self-assembled molecular layers on surfaces. We find that there is an approximately constant gap of 350 meV between the surface work function of OHBP and NiPc terminated self-assembled multilayers. In other words, the surface work function or surface electronic potentials is a periodic function of the terminating layer, oscillating between {approximately}450 mV for OHBP layers and {approximately}100 mV for NiPc layers. On the other hand, the photo-induced effects can be also correlated to the terminating layer of the OHBP-NiPc system. This shows that the self-assembled layers also control the photo-induced effects to some extent. Over the whole excitation spectrum (300-710 nm), the photo-induced band bending change oscillates between two values mostly governed by the properties of the terminating layer of the self-assembled systems.

  20. Assembly Properties of an Alanine-Rich, Lysine-Containing Peptide and the Formation of Peptide/Polymer Hybrid Hydrogels

    PubMed Central

    Grieshaber, Sarah E.; Nie, Ting; Yan, Congqi; Zhong, Sheng; Teller, Sean S.; Clifton, Rodney J.; Pochan, Darrin J.

    2010-01-01

    We are interested in developing peptide/polymer hybrid hydrogels that are chemically diverse and structurally complex. Towards this end, an alanine-based peptide doped with charged lysines with a sequence of (AKA3KA)2 (AK2) was selected from the crosslinking regions of the natural elastin. Pluronic® F127, known to self-assemble into defined micellar structures, was employed as the synthetic building blocks. Fundamental investigations on the environmental effects on the secondary structure and assembly properties of AK2 peptide were carried out with or without the F-127 micelles. At a relatively low peptide concentration (~0.5 mg/mL), the F127 micelles are capable of not only increasing the peptide helicity but also stabilizing it against thermal denaturation. At a higher peptide concentration in basic media, the AK2 peptide developed a substantial amount of β-sheet structure that is conducive to the formation of nanofibrils. The fibril formation was confirmed collectively by atomic force microscopy (AFM), small angle neutron scattering (SANS) and transmission electron microscopy (TEM). The assembly kinetics is strongly dependent on solution temperature and pH; an increased temperature and a more basic environment led to faster fibril assembly. The self-assembled nanoscale structures were covalently interlocked via the Michael-type addition reaction between vinyl sulfone-decorated F127 micelles and the lysine amines exposed at the surface of the nanofibers. The crosslinked hybrid hydrogels were viscoelastic, exhibiting an elastic modulus of approximately 17 kPa and a loss tangent of 0.2. PMID:21359141

  1. Hierarchical Sol-Gel Transition Induced by Thermosensitive Self-Assembly of an ABC Triblock Polymer in an Ionic Liquid

    SciTech Connect

    Kitazawa, Yuzo; Ueki, Takeshi; McIntosh, Lucas D.; Tamura, Saki; Niitsuma, Kazuyuki; Imaizumi, Satoru; Lodge, Timothy P.; Watanabe, Masayoshi

    2016-04-29

    Here we investigate a hierarchical morphology change and accompanying sol–gel transition using a doubly thermosensitive ABC-triblock copolymer in an ionic liquid (IL). The triblock copolymer contains two different lower critical solution temperature (LCST) thermosensitive polymers, poly(benzyl methacrylate) (PBnMA) and poly(2-phenylethyl methacrylate) (PPhEtMA), as the end blocks and poly(methyl methacrylate) (PMMA) as the middle block (PBnMA-b-PMMA-b-PPhEtMA: BMP). BMP undergoes a hierarchical phase transition corresponding to the self-assembly of each of the thermosensitive blocks in the IL, and a sol–gel transition was observed in concentrated, above 10 wt %, polymer solutions. The gelation behavior was affected by polymer concentration, and at 20 wt %, the BMP/IL composite showed a phase transition, with increasing temperature, from solution through a jammed micelle suspension to a physically cross-linked gel. For each phase was formed reversibly and rapidly over the corresponding temperature range. Finally, the jammed micelle and cross-linked gel states were characterized using viscoelastic measurements and small-angle X-ray scattering (SAXS).

  2. Optimization and Characterization of Self-assembled Triblock Polymer Membranes with Chemically-Tunable Pore Walls for Nanofiltration Applications

    NASA Astrophysics Data System (ADS)

    Sargent, Jessica; Mulvenna, Ryan; Prato, Rafael; Weidman, Jacob; Phillip, William; Boudouris, Bryan

    2015-03-01

    The field of block polymer-based membranes for separation applications has grown considerably in the past several years. However, decreasing the domain sizes of these membranes to below 5 nm has proven to be a challenge in many instances. Here, we demonstrate that a triblock polymer, polyisoprene- b-polystyrene- b-poly(tert-butyl methacrylate) (PI-PS-PtBMA), can be utilized to form nanoporous membranes capable of high flux and high selectivity based on both size and chemical composition. By controlling the synthesis, solution self-assembly, and non-solvent induced phase separation of these polymers, a scalable fabrication process can produce thin-film membranes that feature monodisperse pores approaching 1 nm in diameter, tunable pore-wall chemistry, good mechanical stability, and chlorine degradation resistance. The PtBMA functionality can further be converted to a number of side chain functionalities through simple coupling chemistry to produce membranes with specific chemical and structural characteristics tailored to meet the needs of various applications. In particular, these membranes provide a promising, inexpensive platform for chlorine degradation and fouling-resistant membranes for water purification that can be produced on an industrial scale.

  3. A trigonal prismatic ligand in the metal-mediated self-assembly of one- and two-dimensional metallosupramolecular polymers.

    PubMed

    Hu, Wen-Jing; Liu, Long-Qing; Ma, Ming-Liang; Zhao, Xiao-Li; Liu, Yahu A; Mi, Xian-Qiang; Jiang, Biao; Wen, Ke

    2013-08-19

    A novel trispyrazine-pillared prismatic bicycooxacalixaromatic ligand L is synthesized, and its application in metal-mediated self-assembly is described. Under self-assembly conditions, single chain, double-stranded cross-linked coordination polymer and two-dimensional (2D) coordination polymeric networks were formed via M-L (Ag(+), Cu(2+), and Zn(2+)) coordinative interactions. Structural analyses revealed that the antiparallelly arranged one-dimensional coordination polymers (Cu(2+) and Zn(2+)) are arranged to generate well-defined voids to host aromatic guests (benzene) via C-H···π and π···π interactions, while the double-stranded cross-linked coordination polymer (Ag(+)) contains a rhomboidal [Ag2(L(3))2] (L(3): tridentate ligand) cage motif to include a benzene guest; the "thicker" (thickness: ac 5 Å) 2D coordination polymeric networks (Ag(+), Cu(2+), and Zn(2+)), however, are all formed by connection of one or two kinds of topologically different metallomacrocyclic cage units. These unique metallomacrocyclic cage units in the 2D coordination polymeric networks are capable of hosting different guest species. For instance, the rhomboidal [M2(L(3))2] (M = Ag(+), Cu(2+)) cage units were found to host a benzene or a nitrate anion; a hexahedral [M3(L(3))3] (M = Ag(+)) cage was found to host a ligand L or a DMF molecule; the hexahedral [M4(L(3))4] (M = Cu(2+)) cage was found to host four solvent molecules of benzene; and the rectangular [M3(L(3))3] (M = Cu(2+), Zn(2+)) cage units, however, were found to host two THF molecules. The results highlight the potential of ligand L for applications in the construction of "thicker" 2D coordination polymeric networks with well-defined metallomacrocyclic cage units capable of hosting various guest species.

  4. Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

    SciTech Connect

    Lian, Chen; Liu, Liu; Guo, Xu; Long, Yinshuang; Jia, Shanshan; Li, Huanhuan; Yang, Lirong

    2016-01-15

    Two novel coordination polymers, namely, [Ca(NCP){sub 2}]{sub ∞} (I) and [Sr(NCP){sub 2}]{sub ∞} (II) were synthesized under hydrothermal conditions based on 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (HNCP) and characterized by elemental analysis, infrared spectrometry, X-ray powder diffraction and single crystal X-ray diffraction. Findings indicate that I and II are isomorphous and isostructural, containing the unit of M(NCP{sup −}){sub 4} (M=Ca(II) and Sr(II)), based on which to assemble into three-dimensional (3D) porous 4-fold interpenetration honeycomb-shaped neutral coordination polymers (CPs). Between the adjacent lamellar structures in I and II, there exist π–π interactions between the pyridine rings belonging to phenanthroline of NCP{sup −} which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability. - Graphical abstract: One-dimensional nanotubular channels with the cross dimension of 37.1959(20)×23.6141(11)Å{sup 2} in the three-dimensional honeycomb-shaped coordination network of II are observed. The topological analysis of II indicates that there exists a typical diamond framework possessing large adamantanoid cages, which containing four cyclohexane-shaped patterns in chair conformations. - Highlights: • Two isomorphous and isostructural coordination polymers based on flexible ligand and two alkaline-earth metal salts have been synthesized and characterized. • Structural analysis indicates that I and II are assembled into 3D porous honeycomb-shaped metal-organic frameworks. • Both I and II display stronger fluorescence emissions and higher thermal stability.

  5. Constructing Novel Si@SnO2 Core-Shell Heterostructures by Facile Self-Assembly of SnO2 Nanowires on Silicon Hollow Nanospheres for Large, Reversible Lithium Storage.

    PubMed

    Zhou, Zheng-Wei; Liu, Yi-Tao; Xie, Xu-Ming; Ye, Xiong-Ying

    2016-03-23

    Developing an industrially viable silicon anode, featured by the highest theoretical capacity (4200 mA h g(-1)) among common electrode materials, is still a huge challenge because of its large volume expansion during repeated lithiation-delithiation as well as low intrinsic conductivity. Here, we expect to address these inherent deficiencies simultaneously with an interesting hybridization design. A facile self-assembly approach is proposed to decorate silicon hollow nanospheres with SnO2 nanowires. The two building blocks, hand in hand, play a wonderful duet by bridging their appealing functionalities in a complementary way: (1) The silicon hollow nanospheres, in addition to the major role as a superior capacity contributor, also act as a host material (core) to partially accommodate the volume expansion, thus alleviating the capacity fading by providing abundant hollow interiors, void spaces, and surface areas. (2) The SnO2 nanowires serve as a conductive coating (shell) to enable efficient electron transport due to a relatively high conductivity, thereby improving the cyclability of silicon. Compared to other conductive dopants, the SnO2 nanowires with a high theoretical capacity (790 mA h g(-1)) can contribute outstanding electrochemical reaction kinetics, further adding value to the ultimate electrochemical performances. The resulting novel Si@SnO2 core-shell heterostructures exhibit remarkable synergy in large, reversible lithium storage, delivering a reversible capacity as high as 1869 mA h g(-1)@500 mA g(-1) after 100 charging-discharging cycles.

  6. Silver Nanowire-IZO-Conducting Polymer Hybrids for Flexible and Transparent Conductive Electrodes for Organic Light-Emitting Diodes

    NASA Astrophysics Data System (ADS)

    Yun, Ho Jun; Kim, Se Jung; Hwang, Ju Hyun; Shim, Yong Sub; Jung, Sun-Gyu; Park, Young Wook; Ju, Byeong-Kwon

    2016-10-01

    Solution-processed silver nanowire (AgNW) has been considered as a promising material for next-generation flexible transparent conductive electrodes. However, despite the advantages of AgNWs, some of their intrinsic drawbacks, such as large surface roughness and poor interconnection between wires, limit their practical application in organic light-emitting diodes (OLEDs). Herein, we report a high-performance AgNW-based hybrid electrode composed of indium-doped zinc oxide (IZO) and poly (3,4-ethylenediowythiophene):poly(styrenesulfonate) [PEDOT:PSS]. The IZO layer protects the underlying AgNWs from oxidation and corrosion and tightly fuses the wires together and to the substrate. The PEDOT:PSS effectively reduces surface roughness and increases the hybrid films’ transmittance. The fabricated electrodes exhibited a low sheet resistance of 5.9 Ωsq‑1 with high transmittance of 86% at 550 nm. The optical, electrical, and mechanical properties of the AgNW-based hybrid films were investigated in detail to determine the structure-property relations, and whether optical or electrical properties could be controlled with variation in each layer’s thickness to satisfy different requirements for different applications. Flexible OLEDs (f-OLEDs) were successfully fabricated on the hybrid electrodes to prove their applicability; their performance was even better than those on commercial indium doped tin oxide (ITO) electrodes.

  7. Silver Nanowire-IZO-Conducting Polymer Hybrids for Flexible and Transparent Conductive Electrodes for Organic Light-Emitting Diodes

    PubMed Central

    Yun, Ho Jun; Kim, Se Jung; Hwang, Ju Hyun; Shim, Yong Sub; Jung, Sun-Gyu; Park, Young Wook; Ju, Byeong-Kwon

    2016-01-01

    Solution-processed silver nanowire (AgNW) has been considered as a promising material for next-generation flexible transparent conductive electrodes. However, despite the advantages of AgNWs, some of their intrinsic drawbacks, such as large surface roughness and poor interconnection between wires, limit their practical application in organic light-emitting diodes (OLEDs). Herein, we report a high-performance AgNW-based hybrid electrode composed of indium-doped zinc oxide (IZO) and poly (3,4-ethylenediowythiophene):poly(styrenesulfonate) [PEDOT:PSS]. The IZO layer protects the underlying AgNWs from oxidation and corrosion and tightly fuses the wires together and to the substrate. The PEDOT:PSS effectively reduces surface roughness and increases the hybrid films’ transmittance. The fabricated electrodes exhibited a low sheet resistance of 5.9 Ωsq−1 with high transmittance of 86% at 550 nm. The optical, electrical, and mechanical properties of the AgNW-based hybrid films were investigated in detail to determine the structure-property relations, and whether optical or electrical properties could be controlled with variation in each layer’s thickness to satisfy different requirements for different applications. Flexible OLEDs (f-OLEDs) were successfully fabricated on the hybrid electrodes to prove their applicability; their performance was even better than those on commercial indium doped tin oxide (ITO) electrodes. PMID:27703182

  8. Annealing-free, flexible silver nanowire-polymer composite electrodes via a continuous two-step spray-coating method.

    PubMed

    Choi, Dong Yun; Kang, Hyun Wook; Sung, Hyung Jin; Kim, Sang Soo

    2013-02-07

    For the realization of high-efficiency flexible optoelectronic devices, transparent electrodes should be fabricated through a low-temperature process and have the crucial feature of low surface roughness. In this paper, we demonstrated a two-step spray-coating method for producing large-scale, smooth and flexible silver nanowire (AgNW)-poly3,4-ethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS) composite electrodes. Without the high-temperature annealing process, the conductivity of the composite film was improved via the lamination of highly conductive PEDOT:PSS modified by dimethyl sulfoxide (DMSO). Under the room temperature process condition, we fabricated the AgNW-PEDOT:PSS composite film showing an 84.3% mean optical transmittance with a 10.76 Ω sq(-1) sheet resistance. The figure of merit Φ(TC) was higher than that obtained from the indium tin oxide (ITO) films. The sheet resistance of the composite film slightly increased less than 5.3% during 200 cycles of tensile and compression folding, displaying good electromechanical flexibility for use in flexible optoelectronic applications.

  9. Conductive polymer nanocomposites with hierarchical multi-scale structures via self-assembly of carbon-nanotubes on graphene on polymer-microspheres.

    PubMed

    Tang, Changyu; Long, Gucheng; Hu, Xin; Wong, Ka-wai; Lau, Woon-ming; Fan, Meikun; Mei, Jun; Xu, Tao; Wang, Bin; Hui, David

    2014-07-21

    A novel and highly conductive 3-dimensional (3D) hierarchical multi-scale structure is formed by a new, simple, facile, and water-based method that enables practical production of conductive carbon nanofiller/polymer composites. More specifically, the π-π interaction between CNTs and graphene oxide (GO) is exploited to disperse conductive but non-polar CNTs with amphiphilic GO sheets to form a stable aqueous colloidal solution. Aqueous-dispersible latex-polystyrene microspheres are then added to enable the self-assembly processes of anchoring CNTs on GO and wrapping microspheres with GO-stabilized CNTs for the formation of an intriguing 3D hierarchical multi-scale structure. During this process, GO is reduced to conductive reduced-graphene oxide (RGO). The resultant RGO sheets act as "nano-walls" to prevent CNTs from randomly diffusing into the polymer bulk during thermal pressing of RGO-CNT/microspheres, which results in the formation of a 3D foam-like network of RGO-CNTs with high quality. The resultant composite with such a structure gives an ultra-low percolation threshold (0.03 vol% RGO-CNTs) and a reasonably high conductivity (153 S m(-1) at 4 vol% RGO-CNTs), which could satisfy various applications requiring both transparency and electrical conduction characteristics (e.g. transparent antistatic coatings, capacitive touch-screens, and transparent electronic devices).

  10. Self-assembly of silk-elastinlike protein polymers into three-dimensional scaffolds for biomedical applications

    NASA Astrophysics Data System (ADS)

    Zeng, Like

    Production of brand new protein-based materials with precise control over the amino acid sequences at single residue level has been made possible by genetic engineering, through which artificial genes can be developed that encode protein-based materials with desired features. As an example, silk-elastinlike protein polymers (SELPs), composed of tandem repeats of amino acid sequence motifs from Bombyx mori (silkworm) silk and mammalian elastin, have been produced in this approach. SELPs have been studied extensively in the past two decades, however, the fundamental mechanism governing the self-assembly process to date still remains largely unresolved. Further, regardless of the unprecedented success when exploited in areas including drug delivery, gene therapy, and tissue augmentation, SELPs scaffolds as a three-dimensional cell culture model system are complicated by the inability of SELPs to provide the embedded tissue cells with appropriate biochemical stimuli essential for cell survival and function. In this dissertation, it is reported that the self-assembly of silk-elastinlike protein polymers (SELPs) into nanofibers in aqueous solutions can be modulated by tuning the curing temperature, the size of the silk blocks, and the charge of the elastin blocks. A core-sheath model was proposed for nanofiber formation, with the silk blocks in the cores and the hydrated elastin blocks in the sheaths. The folding of the silk blocks into stable cores -- affected by the size of the silk blocks and the charge of the elastin blocks -- plays a critical role in the assembly of silk-elastin nanofibers. The assembled nanofibers further form nanofiber clusters on the microscale, and the nanofiber clusters then coalesce into nanofiber micro-assemblies, interconnection of which eventually leads to the formation of three-dimensional scaffolds with distinct nanoscale and microscale features. SELP-Collagen hybrid scaffolds were also fabricated to enable independent control over the

  11. Oxide nanowires for solar cell applications.

    PubMed

    Zhang, Qifeng; Yodyingyong, Supan; Xi, Junting; Myers, Daniel; Cao, Guozhong

    2012-03-07

    Oxide nanowire arrays were studied for their applications to solar cells. It was demonstrated that the nanowires could provide direct pathways for electron transport in dye-sensitized solar cells and therefore, while forming photoelectrode films, they offered better suppression of charge recombination than nanoparticles. However, the photoelectron films consisting of nanowires suffered a disadvantage in giving large surface area for dye adsorption. Such a shortcoming of nanowires had been exemplified in this paper illustrating that it could be well compensated by incorporating with nanoparticles to form a nanoparticle-nanowire array hybrid photoelectrode film. The oxide nanowires were also demonstrated to be able to enhance the performance of inverted structure polymer solar cells as a cathode buffer layer by establishing a large interface with the polymers so as to facilitate the transport of photogenerated electrons from the polymer to the electron collecting electrode. Such an enhancement effect could be further boosted while the nanowires were replaced with nanotubes; the latter may build up larger interface with the polymers than the former and therefore facilitates the electron transport more efficiently.

  12. Surfactant-Templated Mesoporous Metal Oxide Nanowires

    DOE PAGES

    Luo, Hongmei; Lin, Qianglu; Baber, Stacy; ...

    2010-01-01

    We demore » monstrate two approaches to prepare mesoporous metal oxide nanowires by surfactant assembly and nanoconfinement via sol-gel or electrochemical deposition. For example, mesoporous Ta 2 O 5 and zeolite nanowires are prepared by block copolymer Pluronic 123-templated sol-gel method, and mesoporous ZnO nanowires are prepared by electrodeposition in presence of anionic surfactant sodium dodecyl sulfate (SDS) surfactant, in porous membranes. The morphologies of porous nanowires are studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses.« less

  13. Modeling of silica nanowires for optical sensing.

    PubMed

    Lou, Jingyi; Tong, Limin; Ye, Zhizhen

    2005-03-21

    Based on evanescent-wave guiding properties of nanowire waveguides, we propose to use single-mode subwavelength-diameter silica nanowires for optical sensing. Phase shift of the guided mode caused by index change is obtained by solving Maxwell's equation, and is used as a criterion for sensitivity estimation. Nanowire sensor employing a wire-assembled Mach-Zehnder structure is modeled. The result shows that optical nanowires, especially those fabricated by taper drawing of optical fibers, are promising for developing miniaturized optical sensors with high sensitivity.

  14. Steric hindrance regulated supramolecular assembly between β-cyclodextrin polymer and pyrene for alkaline phosphatase fluorescent sensing.

    PubMed

    Song, Chunxia; Yang, Xiaohai; Wang, Kemin; Wang, Qing; Liu, Jianbo; Huang, Jin; Zhou, Maogui; Guo, Xiaochen

    2016-03-05

    We herein report a strategy for sensitive alkaline phosphatase (ALP) fluorescent sensing based on steric hindrance regulated supramolecular assembly between β-cyclodextrin polymer (polyβ-CD) and pyrene. The fluorescence of pyrene was enhanced more than 10 times through supramolecular assembly with polyβ-CD. The 5'-phosphorylated dsDNA probe with pyrene attached on the 3'-terminal could be cleaved by λ exonuclease (λ exo), yielding pyrene attached on mononucleotides. Pyrene attached on mononucleotides could easily enter the cavity of polyβ-CD, resulting in fluorescence enhancement. When ALP was introduced, it could remove 5'-phosphate groups from dsDNA and then prevented the cleavage of dsDNA. Pyrene attached on dsDNA was difficult to enter the cavity of polyβ-CD because of steric hindrance, resulting in an inconspicuous fluorescence enhancement. Owing to the excellent fluorescence enhancement during steric hindrance regulated supramolecular assembly, excellent performance of the assay method was achieved for ALP with a detection limit of 0.04 Um L(-1). The detection limit was superior or comparable with the reported methods. Besides, this method was simple in design, avoiding double-labeling of probe.

  15. Steric hindrance regulated supramolecular assembly between β-cyclodextrin polymer and pyrene for alkaline phosphatase fluorescent sensing

    NASA Astrophysics Data System (ADS)

    Song, Chunxia; Yang, Xiaohai; Wang, Kemin; Wang, Qing; Liu, Jianbo; Huang, Jin; Zhou, Maogui; Guo, Xiaochen

    2016-03-01

    We herein report a strategy for sensitive alkaline phosphatase (ALP) fluorescent sensing based on steric hindrance regulated supramolecular assembly between β-cyclodextrin polymer (polyβ-CD) and pyrene. The fluorescence of pyrene was enhanced more than 10 times through supramolecular assembly with polyβ-CD. The 5‧-phosphorylated dsDNA probe with pyrene attached on the 3‧-terminal could be cleaved by λ exonuclease (λ exo), yielding pyrene attached on mononucleotides. Pyrene attached on mononucleotides could easily enter the cavity of polyβ-CD, resulting in fluorescence enhancement. When ALP was introduced, it could remove 5‧-phosphate groups from dsDNA and then prevented the cleavage of dsDNA. Pyrene attached on dsDNA was difficult to enter the cavity of polyβ-CD because of steric hindrance, resulting in an inconspicuous fluorescence enhancement. Owing to the excellent fluorescence enhancement during steric hindrance regulated supramolecular assembly, excellent performance of the assay method was achieved for ALP with a detection limit of 0.04 U mL- 1. The detection limit was superior or comparable with the reported methods. Besides, this method was simple in design, avoiding double-labeling of probe.

  16. Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

    PubMed

    Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

    2015-08-01

    Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts.

  17. Novel Polymer Nanocomposites Resulted from Melt Processing of Polystyrene-Based Substrates Coated with Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Soltani, Iman; Spontak, Richard J.

    The novel polymer nanocomposites (PNCs) prepared through two steps of coating polystyrene-based substrates with layer-by-layer (LBL) deposition of montmorillonite and alternative polyelectrolyte layers of polyethyleneimine and polyethylene terephthalate ionomer, followed by their cyclic melt pressing, demonstrated particular morphologies. Transmission electron microscopy images at high magnification scales showed the occurrence of swollen intercalation and flocculated exfoliations of clay platelets, down to a few nanometer thickness, inside and sometimes out of LBL assemblies crushed portions. In fact, intercalation and exfoliation of clay platelets, established in LBL assemblies, increased by shear applied through their repetitive melt pressing. Additionally, x-ray diffractometry traces confirmed the aforementioned increase in clay intercalation. These high aspect ratio LBL assemblies portions formed highly tortuous labyrinths, which may work as scavenging centers to promote barrier properties of the PNCs against transport of gases like oxygen and carbon dioxide. It is despite spontaneously low interaction between hydrophobic styrenic groups and almost hydrophilic natural clay and moderate efficiency of cyclic pressing for providing intensive shear stress on samples.

  18. Self-assembled breath figure arrays of conjugated conducting polymers for photovoltaic application

    NASA Astrophysics Data System (ADS)

    Routh, Prahlad Kumar; Venkatesh, T. A.; Cotlet, Mircea

    2014-03-01

    Ordered microporous polymer structures have potential application in catalysis, surface engineering and optoelectronics. The Breath Figure Technique (BFT) is a simple method of producing such ordered microporous structures. In this study BFT was applied to a series of commercial conjugated polymer polythiophene derivatives with varying side chain length (n =6,8,10,12). An in-depth study of processing parameters has been carried with the aim of controlling the morphology of the honeycomb film over large, PV relevant areas. Structural and spectroscopic characterization of honeycomb films were performed using Scanning Electron Microscopy (SEM), X-ray scattering, Fluorescence Lifetime Imaging (FLIM) and Spectroscopy. Blends of these polymers with a fullerene derivative, PCBM, were also subjected to BFT and characterized with similar methods to assess their potential use as active layers in PV solar cells. Center for Functional Nanomaterials, Brookhaven National Laboratory.

  19. Ferritin-Polymer Conjugates: Grafting Chemistry and Integration into Nanoscale Assemblies

    SciTech Connect

    Y Hu; D Samanta; S Parelkar; S Hong; Q Wang; T Russell; T Emrick

    2011-12-31

    Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylene oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.

  20. Doxorubicin-loaded aromatic imine-contained amphiphilic branched star polymer micelles: synthesis, self-assembly, and drug delivery

    PubMed Central

    Qiu, Liang; Hong, Chun-Yan; Pan, Cai-Yuan

    2015-01-01

    Redox-and pH-sensitive branched star polymers (BSPs), BP(DMAEMA-co-MAEBA-co-DTDMA)(PMAIGP)ns, have been successively prepared by two steps of reversible addition–fragmentation chain transfer (RAFT) polymerization. The first step is RAFT polymerization of 2-(N,N-dimethylaminoethyl)methacrylate (DMAEMA) and p-(methacryloxyethoxy) benzaldehyde (MAEBA) in the presence of divinyl monomer, 2,2′-dithiodiethoxyl dimethacrylate (DTDMA). The resultant branched polymers were used as a macro-RAFT agent in the subsequent RAFT polymerization. After hydrolysis of the BSPs to form BP(DMAEMA-co-MAEBA-co-DTDMA)(PMAGP)ns (BSP-H), the anticancer drug doxorubicin (DOX) was covalently linked to branched polymer chains by reaction of primary amine of DOX and aldehyde groups in the polymer chains. Their compositions, structures, molecular weights, and molecular weight distributions were respectively characterized by nuclear magnetic resonance spectra and gel permeation chromatography measurements. The DOX-loaded micelles were fabricated by self-assembly of DOX-containing BSPs in water, which were characterized by transmission electron microscopy and dynamic light scattering. Aromatic imine linkage is stable in neutral water, but is acid-labile; controlled release of DOX from the BSP-H-DOX micelles was realized at pH values of 5 and 6, and at higher acidic solution, fast release of DOX was observed. In vitro cytotoxicity experiment results revealed low cytotoxicity of the BSPs and release of DOX from micelles in HepG2 and HeLa cells. Confocal laser fluorescence microscopy observations showed that DOX-loaded micelles have specific interaction with HepG2 cells. Thus, this type of BSP micelle is an efficient drug delivery system. PMID:26056444