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Sample records for assembled polymer nanowires

  1. Two-fold odd-even effect in self-assembled nanowires from oligopeptide-polymer-substituted perylene bisimides.

    PubMed

    Marty, Roman; Nigon, Robin; Leite, Deborah; Frauenrath, Holger

    2014-03-12

    Organic nanowires are important building blocks for nanoscopic organic electronic devices. In order to ensure efficient charge transport through such nanowires, it is important to understand in detail the molecular parameters that guide self-assembly of π-conjugated molecules into one-dimensional stacks with optimal constructive π-π overlap. Here, we investigated the subtle relationship between molecular structure and supramolecular arrangement of the chromophores in self-assembled nanowires prepared from perylene bisimides with oligopeptide-polymer side chains. We observed a "two-fold" odd-even effect in circular dichroism spectra of these derivatives, depending on both the number of l-alanine units in the oligopeptide segments and length of the alkylene spacer between chromophore and oligopeptide substituents. Our results indicate that there is a complex interplay between the translation of molecular chirality into supramolecular helicity and the molecules' inherent propensity for well-defined one-dimensional aggregation into β-sheet-like superstructures in the presence of a central chromophore. Strong excitonic coupling as expressed by the appearance of hypsochromically and bathochromically shifted UV-vis absorptions and strong CD signals was systematically observed for molecules with an odd number of l-alanines in the side chains. The latter derivatives gave rise to nanowires with a significantly higher electron mobility. Our results, hence, provide an important design rule for self-assembled organic nanowires.

  2. Soluble polymer-based, blown bubble assembly of single- and double-layer nanowires with shape control.

    PubMed

    Wu, Shiting; Huang, Kai; Shi, Enzheng; Xu, Wenjing; Fang, Ying; Yang, Yanbing; Cao, Anyuan

    2014-04-22

    We present here an efficient blown bubble method for large-scale assembly of semiconducting nanowires, with simultaneous control on the material shape. As-synthesized Te nanowires in powder form are dispersed in a polymethylmethacrylate (PMMA) solution, assembled in a large size bubble blown from the solution, and then transferred (repeatedly) to arbitrary substrates. By this way, we have obtained single-layer (aligned) and double-layer (crossed) Te nanowires as well as buckled Te nanosprings which are converted from initially straight nanowires in situ during bubble blowing. The PMMA bubble film can be removed by direct dissolution in acetone to expose nanostructures with clean surface while maintaining original configuration. After matrix removal, these clean nanowire and nanospring arrays can be fabricated into functional nanoelectronic devices such as photodetectors and gas sensors with high performance.

  3. Macroscopic nanowire networks from hierarchically assembled mesostructures

    NASA Astrophysics Data System (ADS)

    Wang, Donghai

    Nanoscale building blocks, such as nanocrystals and one-dimensional (1D) nanostructures, have attracted tremendous attention due to their peculiar and fascinating properties. It is necessary to assemble the low dimensional nanoscale building blocks into macroscopic nanostructured architectures for potential applications in energy storage, separation, catalysis, computation, sensing, etc. This dissertation demonstrates synthesis, characterization and applications of macroscopic hierarchical metal or semiconductor (e.g., Pt, CdSe) nanowire networks. These nanowire networks were synthesized by electrodeposition within the pores of highly-ordered mesoporous silica template followed by removal of the silica template, resulting in robust nanowire networks with replicated mesopore structure. The nanowire diameter (3-10 nm) and network mesostructures (e.g. 2D, 3D and superstructures) are controlled by the pore size and the mesostructure of the silica template. As-synthesized metal nanowires self support to form networks with high electrochemical active surface area, which are further applied in enzymatic glucose sensing. Semiconductor CdSe nanowire networks show tunable optical properties dependent on nanowire diameter and have been demonstrated as a good electron acceptor in CdSe nanowire network/polymer photovoltaic devices. The dissertation also describes self-assembly behavior of composite mesostructures under physical confined environment. Novel mesostructures and mesostructured nanowire superstructures have been achieved by the confined assembly and the replication procedure mentioned above. Our approach provides an easy and efficient way to synthesize macroscopic hierarchical nanowire networks with well-controlled diameter and mesoscale arrangement, which will be of great interest for sensor, photovoltaic, and other applications.

  4. Single conducting polymer nanowire based conductometric sensors

    NASA Astrophysics Data System (ADS)

    Bangar, Mangesh Ashok

    The detection of toxic chemicals, gases or biological agents at very low concentrations with high sensitivity and selectivity has been subject of immense interest. Sensors employing electrical signal readout as transduction mechanism offer easy, label-free detection of target analyte in real-time. Traditional thin film sensors inherently suffered through loss of sensitivity due to current shunting across the charge depleted/added region upon analyte binding to the sensor surface, due to their large cross sectional area. This limitation was overcome by use of nanostructure such as nanowire/tube as transducer where current shunting during sensing was almost eliminated. Due to their benign chemical/electrochemical fabrication route along with excellent electrical properties and biocompatibility, conducting polymers offer cost-effective alternative over other nanostructures. Biggest obstacle in using these nanostructures is lack of easy, scalable and cost-effective way of assembling these nanostructures on prefabricated micropatterns for device fabrication. In this dissertation, three different approaches have been taken to fabricate individual or array of single conducting polymer (and metal) nanowire based devices and using polymer by itself or after functionalization with appropriate recognition molecule they have been applied for gas and biochemical detection. In the first approach electrochemical fabrication of multisegmented nanowires with middle functional Ppy segment along with ferromagnetic nickel (Ni) and end gold segments for better electrical contact was studied. This multi-layered nanowires were used along with ferromagnetic contact electrode for controlled magnetic assembly of nanowires into devices and were used for ammonia gas sensing. The second approach uses conducting polymer, polypyrrole (Ppy) nanowires using simple electrophoretic alignment and maskless electrodeposition to anchor nanowire which were further functionalized with antibodies against

  5. Synthesis and characterization of nanowire coils of organometallic coordination polymers for controlled cargo release.

    PubMed

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing

    2014-06-12

    Nanowire coils of organometallic coordination polymers have been synthesized for the first time by using the emulsion periphery polymerization technique. An amphiphilic triblock copolymer terminated with inclusion complex of β-cyclodextrin and 4,4'-bipyridine self-assembles into oil-in-water emulsion in a toluene/water mixture. Subsequent coordination of bipyridine with Ni(II) in periphery of emulsions results in the formation of coordination polymer nanowire coils. The nanowire coils are composed of nanowires with diameter of 2 nm. Nanowire coils exhibit enhanced thermal stability in contrast to their parent triblock copolymer. Interestingly, nanowire coils are capable of encapsulating organic cargoes. Encapsulated cargoes can be selectively extracted from nanowire coils without damaging nanowire coils. Nanowire coils are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24842771

  6. Maskless electrodeposited contact for conducting polymer nanowires

    NASA Astrophysics Data System (ADS)

    Hangarter, Carlos M.; Bangar, Mangesh; Hernandez, Sandra C.; Chen, Wilfred; Deshusses, Marc A.; Mulchandani, Ashok; Myung, Nosang V.

    2008-02-01

    This letter reports a simple and scalable method to create mechanical joints and electrical contacts of conducting polymer nanowires to electrodes by selective maskless metal electrodeposition on electrodes. This is an attractive route for contacting nanowires as it bypasses harsh processing conditions of conventional methods. The electrodeposition conditions and initial resistance of the nanowires were found to have a significant impact on the selective maskless deposition. Different dopants were also investigated to understand the polymer reduction during cathodic deposition of metal. A single dodecyl sulfate doped polypyrrole nanowire with maskless electrodeposited nickel contacts was shown to have improved sensitivity toward ammonia gas.

  7. Shape-Controlled Deterministic Assembly of Nanowires.

    PubMed

    Zhao, Yunlong; Yao, Jun; Xu, Lin; Mankin, Max N; Zhu, Yinbo; Wu, Hengan; Mai, Liqiang; Zhang, Qingjie; Lieber, Charles M

    2016-04-13

    Large-scale, deterministic assembly of nanowires and nanotubes with rationally controlled geometries could expand the potential applications of one-dimensional nanomaterials in bottom-up integrated nanodevice arrays and circuits. Control of the positions of straight nanowires and nanotubes has been achieved using several assembly methods, although simultaneous control of position and geometry has not been realized. Here, we demonstrate a new concept combining simultaneous assembly and guided shaping to achieve large-scale, high-precision shape controlled deterministic assembly of nanowires. We lithographically pattern U-shaped trenches and then shear transfer nanowires to the patterned substrate wafers, where the trenches serve to define the positions and shapes of transferred nanowires. Studies using semicircular trenches defined by electron-beam lithography yielded U-shaped nanowires with radii of curvature defined by inner surface of the trenches. Wafer-scale deterministic assembly produced U-shaped nanowires for >430,000 sites with a yield of ∼90%. In addition, mechanistic studies and simulations demonstrate that shaping results in primarily elastic deformation of the nanowires and show clearly the diameter-dependent limits achievable for accessible forces. Last, this approach was used to assemble U-shaped three-dimensional nanowire field-effect transistor bioprobe arrays containing 200 individually addressable nanodevices. By combining the strengths of wafer-scale top-down fabrication with diverse and tunable properties of one-dimensional building blocks in novel structural configurations, shape-controlled deterministic nanowire assembly is expected to enable new applications in many areas including nanobioelectronics and nanophotonics. PMID:26999059

  8. Mesoscale Polymer Assemblies

    NASA Astrophysics Data System (ADS)

    Choudhary, Satyan; Pham, Jonathan; Crosby, Alfred

    2015-03-01

    Materials encompassing structural hierarchy and multi-functionality allow for remarkable physical properties across different length scales. Mesoscale Polymer (MSP) assemblies provide a critical link, from nanometer to centimeter scales, in the definition of such hierarchical structures. Recent focus has been on exploiting these MSP assemblies for optical, electronic, photonics and biological applications. We demonstrate a novel fabrication method for MSP assemblies. Current fabrication methods restrict the length scale and volume of such assemblies. A new method developed uses a simple piezo-actuated motion for de-pinning of a polymer solution trapped by capillary forces between a flexible blade and a rigid substrate. The advantages of new method include ability to make MSP of monodisperse length and to fabricate sufficient volumes of MSP to study their physical properties and functionality in liquid dispersions. We demonstrate the application of MSP as filler for soft materials, providing rheological studies of the MSP with surrounding matrices.

  9. 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

  10. 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.

  11. Interfacing conjugated polymers with magnetic nanowires.

    PubMed

    Callegari, Vincent; Demoustier-Champagne, Sophie

    2010-05-01

    A variety of new multisegmented nanowires based on magnetic metals and conjugated polymers, polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT), were synthesized by an all-electrochemical template method for precise control over segment lengths. To overcome the major problem occurring when performing direct electrodeposition of PPy or PEDOT on active metals, such as nickel, the concomitant metal oxidation and redissolution at the positive potentials required for polymer formation, we developed a two-step chemical process. Prior to electropolymerization, the Ni surface was pretreated with 3-(pyrrol-1-yl) propanoic acid. This strategy allowed the improvement of the polymer adhesion, resulting in the formation of mechanically robust Ni/conjugated polymer interfaces. By this way, we successfully prepared various original trisegmented nanostructures, such as systems containing one magnetic segment, Ni-PPy-Pt and Ni-PEDOT-Au nanowires, and systems containing two different magnetic metals, Ni-PPy-Co and Ni-PEDOT-Co nanowires. All these one-dimensional multicomponent nanostructures present both fundamental interest and potential applications in nanoelectronics and in biomedical field.

  12. Manufacturing a nanowire-based sensing system via flow-guided assembly in a microchannel array template

    NASA Astrophysics Data System (ADS)

    Chen, Juan; Zu, Yingbo; Rajagopalan, Kartik Kumar; Wang, Shengnian

    2015-06-01

    A novel flow-guided assembly approach is presented to accurately align and position nanowire arrays in pre-defined locations with high throughput and large-scale manufacturing capability. In this approach, a polymer solution is first filled in an array of microfluidic channels. Then a gas flow is introduced to blow out most of the solution while pushing a little leftover against the channel wall for assembly into polymer nanowires. In this way, highly ordered nanowires are conveniently aligned in the flow direction and patterned along both sides of the microchannels. In this study, we demonstrated this flow-guided assembly process by producing millimetre-long nanowires across a 5 × 12 mm area in the same orientation and with basic ‘I-shape’, ‘T-shape’, and ‘cross’ patterns. The assembled polymer nanowires were further converted to conductive carbon nanowires through a standard carbonization process. After being integrated into electronic sensors, high sensitivity was found in model protein sensing tests. This new nanowire manufacturing approach is anticipated to open new doors to the fabrication of nanowire-based sensing systems and serve as good manufacturing practice for its simplicity, low cost, alignment reliability, and high throughput.

  13. Manufacturing a nanowire-based sensing system via flow-guided assembly in a microchannel array template.

    PubMed

    Chen, Juan; Zu, Yingbo; Kumar Rajagopalan, Kartik; Wang, Shengnian

    2015-06-12

    A novel flow-guided assembly approach is presented to accurately align and position nanowire arrays in pre-defined locations with high throughput and large-scale manufacturing capability. In this approach, a polymer solution is first filled in an array of microfluidic channels. Then a gas flow is introduced to blow out most of the solution while pushing a little leftover against the channel wall for assembly into polymer nanowires. In this way, highly ordered nanowires are conveniently aligned in the flow direction and patterned along both sides of the microchannels. In this study, we demonstrated this flow-guided assembly process by producing millimetre-long nanowires across a 5 × 12 mm area in the same orientation and with basic 'I-shape', 'T-shape', and 'cross' patterns. The assembled polymer nanowires were further converted to conductive carbon nanowires through a standard carbonization process. After being integrated into electronic sensors, high sensitivity was found in model protein sensing tests. This new nanowire manufacturing approach is anticipated to open new doors to the fabrication of nanowire-based sensing systems and serve as good manufacturing practice for its simplicity, low cost, alignment reliability, and high throughput.

  14. 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. PMID:27556354

  15. 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.

  16. Functional Nanoscale Electronic Devices Assembled Using Silicon Nanowire Building Blocks

    NASA Astrophysics Data System (ADS)

    Cui, Yi; Lieber, Charles M.

    2001-02-01

    Because semiconductor nanowires can transport electrons and holes, they could function as building blocks for nanoscale electronics assembled without the need for complex and costly fabrication facilities. Boron- and phosphorous-doped silicon nanowires were used as building blocks to assemble three types of semiconductor nanodevices. Passive diode structures consisting of crossed p- and n-type nanowires exhibit rectifying transport similar to planar p-n junctions. Active bipolar transistors, consisting of heavily and lightly n-doped nanowires crossing a common p-type wire base, exhibit common base and emitter current gains as large as 0.94 and 16, respectively. In addition, p- and n-type nanowires have been used to assemble complementary inverter-like structures. The facile assembly of key electronic device elements from well-defined nanoscale building blocks may represent a step toward a ``bottom-up'' paradigm for electronics manufacturing.

  17. Functional nanoscale electronic devices assembled using silicon nanowire building blocks.

    PubMed

    Cui, Y; Lieber, C M

    2001-02-01

    Because semiconductor nanowires can transport electrons and holes, they could function as building blocks for nanoscale electronics assembled without the need for complex and costly fabrication facilities. Boron- and phosphorous-doped silicon nanowires were used as building blocks to assemble three types of semiconductor nanodevices. Passive diode structures consisting of crossed p- and n-type nanowires exhibit rectifying transport similar to planar p-n junctions. Active bipolar transistors, consisting of heavily and lightly n-doped nanowires crossing a common p-type wire base, exhibit common base and emitter current gains as large as 0.94 and 16, respectively. In addition, p- and n-type nanowires have been used to assemble complementary inverter-like structures. The facile assembly of key electronic device elements from well-defined nanoscale building blocks may represent a step toward a "bottom-up" paradigm for electronics manufacturing.

  18. 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.

  19. 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.

  20. Electrokinetic assembly of selenium and silver nanowires into macroscopic fibers.

    PubMed

    Wang, Michael C P; Zhang, Xin; Majidi, Elham; Nedelec, Kevin; Gates, Byron D

    2010-05-25

    Solution-phase synthesized nanowires with high aspect ratios can be a challenge to assemble into desired structures. As synthesized, these nanostructures readily bend and entangle with each other to form larger aggregates. This manuscript reports a general procedure for directing the assembly of semiconducting and metallic nanowires into fibers that can easily span distances >1 cm. Dispersions of these nanostructures in a low dielectric solution are organized by electrokinetic techniques into fibers that can be isolated from solution. Theoretical studies suggest that the assembled fibers adopt an orientation along electric field lines in the solution. The number of assembled fibers is a function of the duration of the assembly process, the magnitude of the electric potential, and the initial concentration of nanowires dispersed in solution. These findings offer a general method for the assembly of nanowires into macroscopic fibers of tunable dimensions. Fibers of selenium nanowires isolated from solution can reversibly bend in response to a source of electrostatic charges positioned in close proximity to the free-standing fiber. These flexible selenium fibers also exhibit a photoconductive response when illuminated with white light.

  1. Self-Assembled PbSe Nanowire:Perovskite Hybrids.

    PubMed

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

    2015-12-01

    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.

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

    PubMed

    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. PMID:25316926

  3. 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.

  4. Substrateless Welding of Self-Assembled Silver Nanowires at Air/Water Interface.

    PubMed

    Hu, Hang; Wang, Zhongyong; Ye, Qinxian; He, Jiaqing; Nie, Xiao; He, Gufeng; Song, Chengyi; Shang, Wen; Wu, Jianbo; Tao, Peng; Deng, Tao

    2016-08-10

    Integrating connected silver nanowire networks with flexible polymers has appeared as a popular way to prepare flexible electronics. To reduce the contact resistance and enhance the connectivity between silver nanowires, various welding techniques have been developed. Herein, rather than welding on solid supporting substrates, which often requires complicated transferring operations and also may pose damage to heat-sensitive substrates, we report an alternative approach to prepare easily transferrable conductive networks through welding of self-assembled silver nanowires at the air/water interface using plasmonic heating. The intriguing welding behavior of partially aligned silver nanowires was analyzed with combined experimental observation and theoretical modeling. The underlying water not only physically supports the assembled silver nanowires but also buffers potential overheating during the welding process, thereby enabling effective welding within a broad range of illumination power density and illumination duration. The welded networks could be directly integrated with PDMS substrates to prepare high-performance stable flexible heaters that are stretchable, bendable, and can be easily patterned to explore selective heating applications. PMID:27437907

  5. Substrateless Welding of Self-Assembled Silver Nanowires at Air/Water Interface.

    PubMed

    Hu, Hang; Wang, Zhongyong; Ye, Qinxian; He, Jiaqing; Nie, Xiao; He, Gufeng; Song, Chengyi; Shang, Wen; Wu, Jianbo; Tao, Peng; Deng, Tao

    2016-08-10

    Integrating connected silver nanowire networks with flexible polymers has appeared as a popular way to prepare flexible electronics. To reduce the contact resistance and enhance the connectivity between silver nanowires, various welding techniques have been developed. Herein, rather than welding on solid supporting substrates, which often requires complicated transferring operations and also may pose damage to heat-sensitive substrates, we report an alternative approach to prepare easily transferrable conductive networks through welding of self-assembled silver nanowires at the air/water interface using plasmonic heating. The intriguing welding behavior of partially aligned silver nanowires was analyzed with combined experimental observation and theoretical modeling. The underlying water not only physically supports the assembled silver nanowires but also buffers potential overheating during the welding process, thereby enabling effective welding within a broad range of illumination power density and illumination duration. The welded networks could be directly integrated with PDMS substrates to prepare high-performance stable flexible heaters that are stretchable, bendable, and can be easily patterned to explore selective heating applications.

  6. Viral assembly of oriented quantum dot nanowires

    NASA Astrophysics Data System (ADS)

    Mao, Chuanbin; Flynn, Christine E.; Hayhurst, Andrew; Sweeney, Rozamond; Qi, Jifa; Georgiou, George; Iverson, Brent; Belcher, Angela M.

    2003-06-01

    The highly organized structure of M13 bacteriophage was used as an evolved biological template for the nucleation and orientation of semiconductor nanowires. To create this organized template, peptides were selected by using a pIII phage display library for their ability to nucleate ZnS or CdS nanocrystals. The successful peptides were expressed as pVIII fusion proteins into the crystalline capsid of the virus. The engineered viruses were exposed to semiconductor precursor solutions, and the resultant nanocrystals that were templated along the viruses to form nanowires were extensively characterized by using high-resolution analytical electron microscopy and photoluminescence. ZnS nanocrystals were well crystallized on the viral capsid in a hexagonal wurtzite or a cubic zinc blende structure, depending on the peptide expressed on the viral capsid. Electron diffraction patterns showed single-crystal type behavior from a polynanocrystalline area of the nanowire formed, suggesting that the nanocrystals on the virus were preferentially oriented with their [001] perpendicular to the viral surface. Peptides that specifically directed CdS nanocrystal growth were also engineered into the viral capsid to create wurtzite CdS virus-based nanowires. Lastly, heterostructured nucleation was achieved with a dual-peptide virus engineered to express two distinct peptides within the same viral capsid. This work represents a genetically controlled biological synthesis route to a semiconductor nanoscale heterostructure.

  7. 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.

  8. Thermodynamics of the adsorption of flexible polymers on nanowires

    DOE PAGESBeta

    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

  9. 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.

  10. Silver nanowire array-polymer composite as thermal interface material

    NASA Astrophysics Data System (ADS)

    Xu, Ju; Munari, Alessio; Dalton, Eric; Mathewson, Alan; Razeeb, Kafil M.

    2009-12-01

    Silver nanowire arrays embedded inside polycarbonate templates are investigated as a viable thermal interface material for electronic cooling applications. The composite shows an average thermal diffusivity value of 1.89×10-5 m2 s-1, which resulted in an intrinsic thermal conductivity of 30.3 W m-1 K-1. The nanowires' protrusion from the film surface enables it to conform to the surface roughness to make a better thermal contact. This resulted in a 61% reduction in thermal impedance when compared with blank polymer. An ˜30 nm Au film on the top of the composite was found to act as a heat spreader, reducing the thermal impedance further by 35%. A contact impedance model was employed to compare the contact impedance of aligned silver nanowire-polymer composites with that of aligned carbon nanotubes, which showed that the Young's modulus of the composite is the defining factor in the overall thermal impedance of these composites.

  11. 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.

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

    PubMed

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

    2015-09-10

    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.

  13. 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

  14. Size dependent nanomechanics of coil spring shaped polymer nanowires

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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.

  15. Size dependent nanomechanics of coil spring shaped polymer nanowires.

    PubMed

    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

  16. Size dependent nanomechanics of coil spring shaped polymer nanowires.

    PubMed

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

    2015-11-27

    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.

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

    PubMed

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

    2010-11-18

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

  18. Energy harvesting performance of piezoelectric ceramic and polymer nanowires

    NASA Astrophysics Data System (ADS)

    Crossley, Sam; Kar-Narayan, Sohini

    2015-08-01

    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

  19. 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

  20. Mechanism of formation of supramolecular DNA-templated polymer nanowires.

    PubMed

    Watson, Scott M D; Galindo, Miguel A; Horrocks, Benjamin R; Houlton, Andrew

    2014-05-01

    Details of the mechanism of formation of supramolecular polymer nanowires by templating on DNA are revealed for the first time using AFM. Overall these data reveal that the smooth, regular, structures produced are rendered by highly dynamic supramolecular transformations occurring over the micrometre scale. In the initial stages of the process a low density of conducting polymer (CP) binds to the DNA as, essentially, spherical particles. Further reaction time produces DNA strands which are more densely packed with particles giving a beads-on-a-string appearance. The particles subsequently undergo dynamic reconfiguration so as to elongate along the template axis and merge to yield the highly regular, smooth morphology of the final nanowire. MD simulations illustrate the early stages of the process showing the binding of globular CP to duplex DNA, while the latter stages can be modeled effectively by a linear thermodynamic description based on the balance between the line energy, which accounts for adhesion of the material to the template, and its surface tension. This model accounts for the phenomena observed in the AFM studies: the relative success of DNA templating of polymers compared to metals; the slow approach to equilibrium; and the observed thinning and 'necking' phenomena as the structures transform from beads-on-a-string to smooth nanowire. PMID:24712548

  1. Development of self-assembling nanowires containing electronically active oligothiophenes

    NASA Astrophysics Data System (ADS)

    Tsai, Wei-Wen

    This dissertation discusses the development of conductive one-dimensional nanowires from self-assembling oligothiophene molecules. Self-assembly has been demonstrated to be a promising alternative approach towards high performance, solution processable, and low-cost organic electronics. One of the many challenges in this field is the control of supramolecular morphologies of ordered structures containing pi-conjugated moieties. This research demonstrated several successful strategies to achieve self assembly of conductive nanowires using synergistic interactions combining pi stacking and hydrogen bonding. The first approach used was to develop a hairpin-shaped sexithiophene molecule, which features two arms of the conjugated structure. The diamidocyclohexyl headgroup of this molecule successfully directs the self-assembly from hydrogen bonding among the amides, forming high-aspect-ratio one-dimensional nanowires with well-defined diameters of 3.0 +/- 0.3 nm. The molecular orientation in the nanostructures promotes formation of sexithiophene H and J aggregates that facilitate efficient charge transport. Organic field-effect transistors were fabricated to reveal improved intrinsic hole mobility from films of the nanostructures, 3.46 x 10-6 cm2V-1s-1, which is one order of magnitude higher than films cast from unassembled molecules. Bulk heterojunction solar cells were developed from this molecule and fullerenes utilizing solution-phase fabrication methods. Intimate mix of the molecule and phenyl-C61-butyric acid methyl ester creates structured interfaces for efficient exciton splitting. The charge carrier mobilities of each material are improved by self-assembly in solution and thermal-energy assisted phase separation.The photovoltaic devices achieved the highest open-circuit voltage of 0.62 V, short-circuit current of 1.79 mA/cm2, fill factor of 35%, and power conversion efficiency of 0.48%. Another strategy to one-dimensional nanowires studied here involved the

  2. Polymer Self-assembly on Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Giulianini, Michele; Motta, Nunzio

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

  3. Composite Layer-by-Layer (LBL) assembly with inorganic nanoparticles and nanowires.

    PubMed

    Srivastava, Sudhanshu; Kotov, Nicholas A

    2008-12-01

    New assembly techniques are required for creating advanced materials with enough structural flexibility to be tuned for specific applications, and to be practical, the techniques must be implemented at relatively low cost. Layer-by-layer (LBL) assembly is a simple, versatile, and significantly inexpensive approach by which nanocomponents of different groups can be combined to coat both macroscopically flat and non-planar (e.g., colloidal core-shell particles) surfaces. Compared with other available assembly methods, LBL assembly is simpler and more universal and allows more precise thickness control at the nanoscale. LBL can be used to combine a wide variety of species--including nanoparticles (NPs), nanosheets, and nanowires (NWs)--with polymers, thus merging the properties of each type of material. This versatility has led to recent exceptional growth in the use of LBL-generated nanocomposites. This Account will focus on the materials and biological applications of introducing inorganic nanocrystals into polymer thin films. Combining inorganic NPs and NWs with organic polymers allows researchers to manipulate the unique properties in the nanomaterial. We describe the LBL assembly technique for introducing metallic NPs into polymers in order to generate a material with combined optomechanical properties. Similarly, LBL assembly of highly luminescent semiconductor NPs like HgTe or CdTe with poly(diallyldimethylammonium chloride) (PDDA) was used to create uniform optical-quality coatings made on optical fibers and tube interiors. In addition, LBL assembly with inorganic nanosheets or clay molecules is reported for fabricating films with strong mechanical and ion transport properties, and the technique can also be employed to prepare Au/TiO(2) core/sheath NWs. The LBL approach not only will be useful for assembly of inorganic nanocrystals with various polymers but can be further applied to introduce specific functions. We discuss how the expanded use of NWs and

  4. Polymer blends for directed self-assembly

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  5. Investigation of functionalized silicon nanowires by self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Hemed, Nofar Mintz; Convertino, Annalisa; Shacham-Diamand, Yosi

    2016-03-01

    The functionalization using self assembled monolayer (SAM) of silicon nanowires (SiNW) fabricated by plasma enhanced chemical vapor deposition (PECVD) is reported here. The SAM is being utilized as the first building block in the functionalization process. The morphology of the SiNW comprises a polycrystalline core wrapped by an hydrogenated amorphous silicon (α-Si:H) shell. Since most of the available methods for SAM verification and characterization are suitable only for flat substrates; therefore, in addition to the SiNW α-Si:H on flat samples were produced in the same system as the SiNWs. First we confirmed the SAM's presence on the flat α-Si:H samples using the following methods: contact angle measurement to determine the change in surface energy; atomic force microscopy (AFM) to determine uniformity and molecular coverage. Spectroscopic ellipsometry and X-ray reflectivity (XRR) were performed to measure SAM layer thickness and density. X-ray photoelectron spectroscopy (XPS) was applied to study the chemical states of the surface. Next, SiNW/SAM were tested by electrochemical impedance spectroscopy (EIS), and the results were compared to α-Si:H/SAM. The SAM electrical coverage on SiNW and α-Si:H was found to be ∼37% and ∼65 ± 3%, respectively. A model, based on transmission line theory for the nanowires is presented to explain the disparity in results between the nanowires and flat surface of the same materials.

  6. 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.

  7. 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.

  8. Manipulating assembly of nanoparticles by polymer tethers

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenli; Horsch, Mark; Iacovella, Christopher; Glotzer, Sharon

    2006-03-01

    A major challenge in nanoscience and nanotechnology is the ability to control and guide the self-assembly of nano building blocks into target structures in a predictable way. In this talk, we use molecular simulation to show how polymer tethers can be used to manipulate the assembly of nanoparticles into various one-dimensional, two-dimensional, and three-dimensional structures. We present results on the self-assembly of polymer-tethered nanospheres, nanorods, and more exotic shapes, and present temperature versus concentration phase diagrams for the nanosphere and nanorod systems. For polymer-tethered nanorods we predict tetragonally perforated lamellar and honeycomb phases, which have been observed experimentally but have not been predicted by any previous theory. We also predict a new phase---a racemic mixture of hexagonally ordered chiral cylinders that self-assemble from these achiral building blocks. For the system of polymer-tethered nanospheres we predict that in contrast to flexible amphiphiles, the nanospheres are locally ordered and there is an increase in the local ordering with an increase in concentration or relative nanoparticle diameter. [1] Zhang, Mark A. Horsch, Monica H. Lamm, and Sharon C. Glotzer, Nano Lett., 3(10), 1341-1346, 2003. [2] Mark A. Horsch, Zhenli Zhang and Sharon C. Glotzer, Phys. Rev. Lett., 95(5), 056106, 2005. [3] Christopher R. Iacovella, Mark A. Horsch, Zhenli Zhang and Sharon C. Glotzer, Langmuir, 21(21), 9488, 2005.

  9. 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.

  10. Investigation of fluidic assembly of nanowires using a droplet inside microchannels

    NASA Astrophysics Data System (ADS)

    Salalha, Wael; Zussman, Eyal

    2005-06-01

    Nanowires are common building blocks for the bottom-up assembly of electronic and photonic devices. A significant challenge is to introduce a single nanowire into an oriented assembly in order to express its unique anisotropic properties or to fabricate a nanodevice. In this work we focused on the development of a micrometer length scale approach, based on a fluidic method for alignment and assembling of nanowires. The alignment is achieved by manipulating a droplet composed of a dilute nanowire suspension by creating thermocapillary motion inside a microchannel. Our purpose is to explore the nanowires' alignment mechanism in the middle region between the droplet's front and rear menisci, and their interaction with the free surface and the contact lines. Experimental results show that nanowires which are found in the middle region of the droplet are generally aligned with the flow direction. Nanowires which reach the front meniscus move together with the displacing fluid which undergoes a "rolling" type motion, and are finally adsorbed to the surface of the microchannel. The adsorbed nanowires were found in most cases to align with the droplet's flow direction. However, in certain cases nanowires may become reoriented by the passage of the rear-contact line.

  11. Directed Assembly of Biological Polymers

    NASA Astrophysics Data System (ADS)

    Miller, Aline

    2009-03-01

    The self-assembly of polypeptides into beta-sheet rich nanofibrils has attracted considerable attention in recent years to both understand amyloidgenesis and for their potential biomaterials applications. This self-assembly process is generic to all proteins where fibrillation is typically induced under harsh conditions of low pH and/or high temperature, which are of course not suitable for biomaterials applications. Here we will outline the method developed in our laboratory to create thermo-reversible fibrillar hydrogels from aqueous solutions of a series of proteins by adding a reductant. Proteins studied include beta-lactoglobulin, ovalbimum, lysozyme and bovine serum albimum; all contain an increasing number of disulfide bridges that are disrupted by the reductant. Such disruption destabilises the native state of the protein and this allows us to form transparent, self-supporting hydrogels under physiological conditions. The potential to control and manipulate the gel properties, including mechanical strength and structure (fibre diameter and mesh size of hydrogel) has been explored by varying the protein (consequently the number of disulfide bridges), protein concentration, reductant concentration and ionic strength of the matrix. Our results will be presented here and similarities and differences highlighted. Furthermore we will present both our 2- and 3-dimensional cell culture experiments that show the gel matrix promotes both fibroblast and chondrocyte cell spreading, attachment and proliferation; indicating our hydrogels gels are biocompatible and they can provide a viable support for different cell types.

  12. Collaborative Investigations of Supramolecular Polymer Assembly Processes.

    NASA Astrophysics Data System (ADS)

    Wooley, Karen

    2007-03-01

    It is a pleasure to participate in this symposium, honoring Darrin J. Pochan's awarding of the John H. Dillon Medal for advancing our understanding of the physics of assembly and chain conformation of synthetic polypeptides. Assemblies of polypeptides, polysaccharides and polymers of nucleic acids are, of course, complex natural systems that form the bases of life. Over the past three years, we have worked together as a highly interdisciplinary team of investigators, to investigate the self assembly behaviors and resulting morphologies for synthetic amphiphilic block copolymer systems. This presentation will highlight the findings from these collaborative studies, including the importance of the block copolymer composition and topology and the significance of the assembly conditions.

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  14. Tailoring Dielectric Properties and Energy Density of Ferroelectric Polymer Nanocomposites by High-k Nanowires.

    PubMed

    Wang, Guanyao; Huang, Xingyi; Jiang, Pingkai

    2015-08-19

    High dielectric constant (k) polymer nanocomposites have shown great potential in dielectric and energy storage applications in the past few decades. The introduction of high-k nanomaterials into ferroelectric polymers has proven to be a promising strategy for the fabrication of high-k nanocomposites. One-dimensional large-aspect-ratio nanowires exhibit superiority in enhancing k values and energy density of polymer nanocomposites in comparison to their spherical counterparts. However, the impact of their intrinsic properties on the dielectric properties of polymer nanocomposites has been seldom investigated. Herein, four kinds of nanowires (Na2Ti3O7, TiO2, BaTiO3, and SrTiO3) with different inherent characteristics are elaborately selected to fabricate high-k ferroelectric polymer nanocomposites. Dopamine functionalization facilitates the excellent dispersion of these nanowires in the ferroelectric polymer matrix because of the strong polymer/nanowire interfacial adhesion. A thorough comparative study on the dielectric properties and energy storage capability of the nanowires-based nanocomposites has been presented. The results reveal that, among the four types of nanowires, BaTiO3 NWs show the best potential in improving the energy storage capability of the proposed nanocomposites, resulting from the most signficant increase of k while retaining the rather low dielectric loss and leakage current.

  15. Directed Assembly of Nanofilled Polymer Thin Films

    NASA Astrophysics Data System (ADS)

    Karim, Alamgir

    Facile directed self-assembly (DSA) of multicomponent thin films is important for potential technological applications. This requires a fine control of a complex interplay of processing parameters that need to be properly optimized for different organized structures. This talk will discuss some of our recent success towards realizing tunable DSA of soft matter multicomponent systems involving a dispersion of polymer-grafted nanoparticles in block copolymer or homopolymer matrices. DSA methods for such multicomponent films will be discussed. These include the use of zone-annealing with soft-shear to create highly anisotropic nanoparticle arrays, while direct immersion annealing (DIA) has been used to order nanoparticle filled films by dipping the films into controlled solvent quality solvent mixtures. A recently observed phenomena of confinement driven entropic order and phase segregation of polymer grafted nanoparticles in similar and dissimilar polymer matrices in melt state will be discussed. A high density of nano particles of different types ranging from metallic to inorganic to organic were patterned almost exclusively into channels via topographical soft confinement using entropic forces. Enthalpic interactions between the nanoparticle grafted layer and the polymer matrix could be used as a further handle to tune the directed assembly of the nanoparticles. The phenomena will be discussed in terms of confinement parameters, partition coefficient, free energy gain and entropic versus enthalpic interactions.

  16. Electrical Conductivity Studies on Individual Conjugated Polymer Nanowires: Two-Probe and Four-Probe Results

    PubMed Central

    2010-01-01

    Two- and four-probe electrical measurements on individual conjugated polymer nanowires with different diameters ranging from 20 to 190 nm have been performed to study their conductivity and nanocontact resistance. The two-probe results reveal that all the measured polymer nanowires with different diameters are semiconducting. However, the four-probe results show that the measured polymer nanowires with diameters of 190, 95–100, 35–40 and 20–25 nm are lying in the insulating, critical, metallic and insulting regimes of metal–insulator transition, respectively. The 35–40 nm nanowire displays a metal–insulator transition at around 35 K. In addition, it was found that the nanocontact resistance is in the magnitude of 104Ω at room temperature, which is comparable to the intrinsic resistance of the nanowires. These results demonstrate that four-probe electrical measurement is necessary to explore the intrinsic electronic transport properties of isolated nanowires, especially in the case of metallic nanowires, because the metallic nature of the measured nanowires may be coved by the nanocontact resistance that cannot be excluded by a two-probe technique. PMID:20652139

  17. 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

  18. Self-assembly mechanism of Ni nanowires prepared with an external magnetic field

    PubMed Central

    Li, Xiaoyu; Wang, Hu; Xie, Kenan; Long, Qin; Lai, Xuefei

    2015-01-01

    Summary Nickel nanowires with a mean diameter of about 95 nm and lengths of up to 26 μm were prepared by a chemical reduction method in aqueous solution under an external magnetic field. The self-assembly mechanism was investigated in detail. The results indicate that the self-assembly process of Ni nanowires consists of three stages: nucleation and growth, ordered alignment and self-assembly, and deposition on the surface and gaps between the nickel particles. The self-assembly phenomenon occurs only when nickel particles grow to a size of about 60 nm in the reaction system. This critical size, which is proposed for the first time, is very important to comprehend the self-assembly mechanism of Ni nanowires prepared with an external magnetic field. PMID:26665084

  19. 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.

  20. Synergistic Assembly of Covalent and Supramolecular Polymers.

    PubMed

    Bai, Linyi; Zhao, Yanli

    2016-06-01

    Integrating irreplaceable features of both covalent chemistry and noncovalent interactions into a single entity to maximize the applicability is highly desired. Here, a discovery of this type of hybrid, developed by Stupp and co-workers, is developed, where a synergistic combination of covalent and noncovalent compartments enables them to assemble by each other perfectively. The covalent compartments can grow into polymer chains assisted by a supramolecular compartment. The supramolecular compartments can be reversibly removed and re-formed to reconstitute the hybrid structure. The obtained soft materials can serve as functional platforms for molecular delivery or self-repairing materials. PMID:27076255

  1. CO2-stimulated diversiform deformations of polymer assemblies.

    PubMed

    Yan, Qiang; Zhao, Yue

    2013-11-01

    Use of a given physiological stimulus to delicately deform polymer assemblies is a challenging topic. Here we develop synthetic block copolymers to construct a series of CO2-sensitive self-assembled nanostructures that can simulate controllable deformations of the organelles in different ways. By controlling the CO2 stimulation levels, one can modulate the size, shape, and morphology of the polymer aggregates, which is conducive to understanding the stimuli-triggered dynamic reshaping process of polymer assemblies in aqueous solution.

  2. Flow-enabled self-assembly of large-scale aligned nanowires.

    PubMed

    Li, Bo; Zhang, Chuchu; Jiang, Beibei; Han, Wei; Lin, Zhiqun

    2015-03-27

    One-dimensional nanowires enable the realization of optical and electronic nanodevices that may find applications in energy conversion and storage systems. Herein, large-scale aligned DNA nanowires were crafted by flow-enabled self-assembly (FESA). The highly oriented and continuous DNA nanowires were then capitalized on either as a template to form metallic nanowires by exposing DNA nanowires that had been preloaded with metal salts to an oxygen plasma or as a scaffold to direct the positioning and alignment of metal nanoparticles and nanorods. The FESA strategy is simple and easy to implement and thus a promising new method for the low-cost synthesis of large-scale one-dimensional nanostructures for nanodevices.

  3. 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. PMID:26784743

  4. 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

    2014-04-01

    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.

  5. Ultrathin W18O49 nanowire assemblies for electrochromic devices.

    PubMed

    Liu, By Jian-Wei; Zheng, Jing; Wang, Jin-Long; Xu, Jie; Li, Hui-Hui; Yu, Shu-Hong

    2013-08-14

    Ordered W18O49 nanowire thin films were fabricated by Langmuir-Blodgett (LB) technique in the presence of poly(vinyl pyrrolidone) coating. The well-organized monolayer of W18O49 nanowires with periodic structures can be readily used as electrochromic sensors, showing reversibly switched electrochromic properties between the negative and positive voltage. Moreover, the electrochromism properties of the W18O49 nanowire films exhibit significant relationship with their thickness. The coloration/bleaching time was around 2 s for the W18O49 nanowire monolayer, which is much faster than the traditional tungsten oxide nanostructures. Moreover, the nanowire devices display excellent stability when color switching continues, which may provide a versatile and promising platform for electrochromism device, smart windows, and other applications. PMID:23869487

  6. 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.

  7. Evaporation-Induced Self-Assembly of Ultrathin Tungsten Oxide Nanowires over a Large Scale for Ultraviolet Photodetector.

    PubMed

    Cheng, Wei; Niederberger, Markus

    2016-03-15

    Self-assembly of inorganic nanowires on a large scale directly on a substrate represents a great challenge. Starting from colloidally stable dispersions of ultrathin tungsten oxide nanowires, we successfully assemble the nanowires on a centimeter scale on flat or patterned substrates by a simple evaporation-induced self-assembly method. The capillary flow generated during the evaporation is responsible for the assembly of the nanowires. The concentration of the nanowire dispersion has a significant influence on the self-assembly behavior. Well-aligned tungsten oxide nanowire thin films are achieved when the concentration of the dispersion is in the range from 0.5 to 3.0 mg/mL. While at higher concentrations disordered nanowire thin films with cracks are formed, lower concentrations do not result in the formation of a continuous thin film. A macroscopic device based on the self-assembled tungsten oxide nanowires is fabricated, exhibiting good performance for UV light detection. Our results may pave the road for integrating aligned ultrathin semiconductor nanowires into macroscopic devices for optoelectronic applications. PMID:26900019

  8. 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.

  9. 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)). PMID:27551657

  10. Enzymatic activatable self-assembled peptide nanowire for targeted therapy and fluorescence imaging of tumors.

    PubMed

    Tang, Ying; Wu, Zhan; Zhang, Chong-Hua; Zhang, Xiao-Li; Jiang, Jian-Hui

    2016-03-01

    We developed novel activatable probe using self-assembled peptide nanowires with low affinity and toxicity to tumor cells in the absence of matrix metalloproteinase that showed activated high affinity and toxicity and provided a highly selective and efficient platform for targeted therapy and tumor imaging. PMID:26854263

  11. 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.

  12. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    DOE PAGESBeta

    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 wellmore » dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  14. 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. PMID:23377293

  15. Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes.

    PubMed

    Nam, Ki Tae; Kim, Dong-Wan; Yoo, Pil J; Chiang, Chung-Yi; Meethong, Nonglak; Hammond, Paula T; Chiang, Yet-Ming; Belcher, Angela M

    2006-05-12

    The selection and assembly of materials are central issues in the development of smaller, more flexible batteries. Cobalt oxide has shown excellent electrochemical cycling properties and is thus under consideration as an electrode for advanced lithium batteries. We used viruses to synthesize and assemble nanowires of cobalt oxide at room temperature. By incorporating gold-binding peptides into the filament coat, we formed hybrid gold-cobalt oxide wires that improved battery capacity. Combining virus-templated synthesis at the peptide level and methods for controlling two-dimensional assembly of viruses on polyelectrolyte multilayers provides a systematic platform for integrating these nanomaterials to form thin, flexible lithium ion batteries.

  16. Wafer-scale assembly of highly ordered semiconductor nanowire arrays by contact printing.

    PubMed

    Fan, Zhiyong; Ho, Johnny C; Jacobson, Zachery A; Yerushalmi, Roie; Alley, Robert L; Razavi, Haleh; Javey, Ali

    2008-01-01

    Controlled and uniform assembly of "bottom-up" nanowire (NW) materials with high scalability presents one of the significant bottleneck challenges facing the integration of nanowires for electronic applications. Here, we demonstrate wafer-scale assembly of highly ordered, dense, and regular arrays of NWs with high uniformity and reproducibility through a simple contact printing process. The assembled NW pitch is shown to be readily modulated through the surface chemical treatment of the receiver substrate, with the highest density approaching approximately 8 NW/mum, approximately 95% directional alignment, and wafer-scale uniformity. Such fine control in the assembly is attained by applying a lubricant during the contact printing process which significantly minimizes the NW-NW mechanical interactions, therefore enabling well-controlled transfer of nanowires through surface chemical binding interactions. Furthermore, we demonstrate that our printing approach enables large-scale integration of NW arrays for various device structures on both rigid silicon and flexible plastic substrates, with a controlled semiconductor channel width ranging from a single NW ( approximately 10 nm) up to approximately 250 microm, consisting of a parallel array of over 1250 NWs and delivering over 1 mA of ON current.

  17. 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

  18. 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.

  19. 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. PMID:20355800

  20. 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.

  1. 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

  2. Non-resonant Mie scattering: emergent optical properties of core-shell polymer nanowires.

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    Khudiyev, Tural; Huseyinoglu, Ersin; Bayindir, Mehmet

    2014-04-01

    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.

  4. 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

  5. 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.

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

    PubMed

    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 cm(2)V(-1)s(-1)), on/off ratio (10(7)), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  7. 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

  8. 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

  9. Suppression of Low-Frequency Electronic Noise in Polymer Nanowire Field-Effect Transistors.

    PubMed

    Lezzi, Francesca; Ferrari, Giorgio; Pennetta, Cecilia; Pisignano, Dario

    2015-11-11

    The authors report on the reduction of low-frequency noise in semiconductor polymer nanowires with respect to thin-films made of the same organic material. Flicker noise is experimentally investigated in polymer nanowires in the range of 10-10(5) Hz by means of field-effect transistor architectures. The noise in the devices is well described by the Hooge empirical model and exhibits an average Hooge constant, which describes the current power spectral density of fluctuations, suppressed by 1-2 orders of magnitude compared to thin-film devices. To explain the Hooge constant reduction, a resistor network model is developed, in which the organic semiconducting nanostructures or films are depicted through a two-dimensional network of resistors with a square-lattice structure, accounting for the different anisotropy and degree of structural disorder of the active nanowires and films. Results from modeling agree well with experimental findings. These results support enhanced structural order through size-confinement in organic nanostructures as effective route to improve the noise performance in polymer electronic devices. PMID:26479330

  10. Large-scale parallel arrays of silicon nanowires via block copolymer directed self-assembly.

    PubMed

    Farrell, Richard A; Kinahan, Niall T; Hansel, Stefan; Stuen, Karl O; Petkov, Nikolay; Shaw, Matthew T; West, Laetitia E; Djara, Vladimir; Dunne, Robert J; Varona, Olga G; Gleeson, Peter G; Jung, Soon-Jung; Kim, Hye-Young; Koleśnik, Maria M; Lutz, Tarek; Murray, Christopher P; Holmes, Justin D; Nealey, Paul F; Duesberg, Georg S; Krstić, Vojislav; Morris, Michael A

    2012-05-21

    Extending the resolution and spatial proximity of lithographic patterning below critical dimensions of 20 nm remains a key challenge with very-large-scale integration, especially if the persistent scaling of silicon electronic devices is sustained. One approach, which relies upon the directed self-assembly of block copolymers by chemical-epitaxy, is capable of achieving high density 1 : 1 patterning with critical dimensions approaching 5 nm. Herein, we outline an integration-favourable strategy for fabricating high areal density arrays of aligned silicon nanowires by directed self-assembly of a PS-b-PMMA block copolymer nanopatterns with a L(0) (pitch) of 42 nm, on chemically pre-patterned surfaces. Parallel arrays (5 × 10(6) wires per cm) of uni-directional and isolated silicon nanowires on insulator substrates with critical dimension ranging from 15 to 19 nm were fabricated by using precision plasma etch processes; with each stage monitored by electron microscopy. This step-by-step approach provides detailed information on interfacial oxide formation at the device silicon layer, the polystyrene profile during plasma etching, final critical dimension uniformity and line edge roughness variation nanowire during processing. The resulting silicon-nanowire array devices exhibit Schottky-type behaviour and a clear field-effect. The measured values for resistivity and specific contact resistance were ((2.6 ± 1.2) × 10(5)Ωcm) and ((240 ± 80) Ωcm(2)) respectively. These values are typical for intrinsic (un-doped) silicon when contacted by high work function metal albeit counterintuitive as the resistivity of the starting wafer (∼10 Ωcm) is 4 orders of magnitude lower. In essence, the nanowires are so small and consist of so few atoms, that statistically, at the original doping level each nanowire contains less than a single dopant atom and consequently exhibits the electrical behaviour of the un-doped host material. Moreover this indicates that the processing

  11. 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.

  12. Self-assembled polymer nanocomposites and their networks

    NASA Astrophysics Data System (ADS)

    Patil, Nitin Vikas

    This dissertation describes new routes to synthesize polymer nanocomposite networks via self-assembly. Polymerizable structure directing agents (referred to as surfmers) obtained by end-group functionalization preserves the structure-directing capabilities of the surfactant for templating ordered mesoporous silica particle growth, while simultaneously generating a reactive matrix for polymer network formation through reactive end groups in the presence of intimately mixed mesoporous silicates. A combination of small angle X-ray scattering, surface area, and microscopy experiments on mesoporous silica indicated the structure directing capabilities of surfmers. Free-radical polymerization of the surfmer leads to novel crosslinked nanocomposites networks. Multiple experiments, including gel permeation chromatography, swelling, and solid state NMR experiments on polymer nanocomposites gave evidence of the polymerization of surfmer leading to formation of crosslink networks. Polymer nanocomposites with varied silica content were prepared. Effects of silica content on polymer nanocomposites were studied on rheometer. Results obtained from rheological experiments indicate that the storage (G') and loss modulus (G") increases with increase in the content of mesoporous silica. In this way, the nanocomposites networks obtained via self-assembly shows independent behavior with respect to frequency in rheological experiments. Additionally, this self-assembled route was extended to synthesize biodegradable and biocompatible polymer nanocomposites networks. The nanocomposite networks obtained with 15% of silica content showed the increase in storage modulus by two orders of magnitude in rheological experiments.

  13. Self-assembling of molecular nanowires for enhancing the conducting properties of discotic liquid crystals

    NASA Astrophysics Data System (ADS)

    Park, Ji Hyun; Kim, Kyung Ho; Takanishi, Yoichi; Yamamoto, Jun; Park, Yung Woo; Kim, Youn Sang; Scalia, Giusy

    2015-08-01

    The self-organization of discotic liquid crystal molecules in columns has enormous interest for soft nanoelectronic applications. A great advantage of discotic liquid crystal is that defects can be self-annealed in contrast to typical organic materials. Through the overlap of molecular orbitals, the aromatic cores assemble into long range ordered one-dimensional structures. Very thin structured films can be obtained by spin-coating from solution and the resulting morphologies are strongly dependent on the interaction between discotics and solvent molecules. Toluene produces films formed by very long nanowires, spontaneously aligned along a common direction and over fairly large areas. These nanostructured films are a result of the interplay between liquid crystal self-organization and solvent driven assembly. The ordered nanowire structures exhibit improvement in the electrical properties compared to misaligned structures and even to pristine HAT5, deposited without the aid of solvent. In this study we show that the toluene-based deposition of discotic liquid crystals is advantageous because it allows a uniform coverage of the substrate, unlike pristine HAT5 but also thanks to the type of induced structures exhibiting one order of magnitude higher conductivity, in the aligned nanowire films, compared to bare HAT5 ones.

  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. Nanowire polarizers by guided self-assembly of block copolymers

    NASA Astrophysics Data System (ADS)

    Roberts, Philip M. S.; Baum, Alexandra; Karamath, James; Evans, Allan; Shibata, Satoshi; Walton, Harry

    2014-01-01

    Wire-grid polarizers (WGPs) are currently limited by their wafer-scale manufacturing methods to sizes of approximately 12 to 18 in. For large-size displays, a new method for the production of large-area WGPs is required. Large-area WGPs were simulated using the finite-difference-time-domain method, and a scaleable method for their production based on a block copolymer (BCP)-nanostructured template was implemented. The nanostructured template is globally aligned through the use of a cylinder-forming liquid crystal (LC) diblock copolymer, which is first aligned on a rubbed polyimide substrate. A surface-relief template is produced using the differential dry etch rates of the cylinder-forming component and LC polymer matrix component of the BCP. The template is metalized to produce a WGP. Polarizers of arbitrary size with polarization efficiency up to 0.6 have been made in close agreement with calculated values for idealized structures. The choice of the cylinder-forming polymer is critical to the degree of alignment of the template, and the thermal stability of the LC polymer matrix is critical to the stability of the template during etching.

  16. 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. PMID:27440174

  17. Convective polymer assembly for the deposition of nanostructures and polymer thin films on immobilized particles

    NASA Astrophysics Data System (ADS)

    Richardson, Joseph J.; Björnmalm, Mattias; Gunawan, Sylvia T.; Guo, Junling; LiangPresent Address: Csiro Process Science; Engineering, Clayton, Victoria 3168, Australia, Kang; Tardy, Blaise; SekiguchiPresent Address: Graduate School Of Chemical Sciences; Engineering, Hokkaido University, Sapporo, Japan, Shota; Noi, Ka Fung; Cui, Jiwei; EjimaPresent Address: Institute Of Industrial Science, The University Of Tokyo, Tokyo, Japan, Hirotaka; Caruso, Frank

    2014-10-01

    We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules.We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules. Electronic supplementary information (ESI) available: Detailed experimental/instrumental information and supporting figures. See DOI: 10.1039/c4nr04348k

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Efficient Multiscale Models of Polymer Assembly.

    PubMed

    Ruiz-Martinez, Alvaro; Bartol, Thomas M; Sejnowski, Terrence J; Tartakovsky, Daniel M

    2016-07-12

    Protein polymerization and bundling play a central role in cell physiology. Predictive modeling of these processes remains an open challenge, especially when the proteins involved become large and their concentrations high. We present an effective kinetics model of filament formation, bundling, and depolymerization after GTP hydrolysis, which involves a relatively small number of species and reactions, and remains robust over a wide range of concentrations and timescales. We apply this general model to study assembly of FtsZ protein, a basic element in the division process of prokaryotic cells such as Escherichia coli, Bacillus subtilis, or Caulobacter crescentus. This analysis demonstrates that our model outperforms its counterparts in terms of both accuracy and computational efficiency. Because our model comprises only 17 ordinary differential equations, its computational cost is orders-of-magnitude smaller than the current alternatives consisting of up to 1000 ordinary differential equations. It also provides, to our knowledge, a new insight into the characteristics and functioning of FtsZ proteins at high concentrations. The simplicity and versatility of our model render it a powerful computational tool, which can be used either as a standalone descriptor of other biopolymers' assembly or as a component in more complete kinetic models. PMID:27410746

  5. Ultralong Ordered Nanowires from the Concerted Self-Assembly of Discotic Liquid Crystal and Solvent Molecules.

    PubMed

    Park, Ji Hyun; Kim, Kyung Ho; Park, Yung Woo; Lagerwall, Jan P F; Scalia, Giusy

    2015-09-01

    The realization of long, aligned molecular wires is a great challenge, and a variety of approaches have been proposed. Interestingly, hexapentyloxytriphenylene (HAT5) discotic liquid crystal molecules, a model system of molecules with flat and aromatic cores, can spontaneously form well-aligned, micrometer long, yet only tens of nanometers thick, nanowires on solid surfaces. We have investigated the formation mechanism of these wires using different solvents with selected characteristics, including chemical structure, boiling point, vapor pressure, and surface tension. When casting from toluene and benzene solutions, atomic force microscopy reveals that the discotics spontaneously form very long and thin wires, self-aligning along a common orientation. If instead dodecane or heptane are used, different and in general thicker structures are obtained. The chemical structure of the solvent appears to have a key role, coupling to the liquid crystal self-assembly by allowing solvent molecules to enter the ordered structure if their design matches the core of HAT5 molecules, thereby guiding the assembly. However, other aspects are also relevant in the assembly, including the nature of the substrate and the rate of solvent evaporation, and these can favor or interfere with the self-assembly into long structures. The use of solvents with aromatic structure is advantageous not only because it affects the geometry of the assembly, promoting long wire formation, but it is also compatible with good quality of the intermolecular order, as suggested by a high anisotropy of the Raman spectra of the nanowires formed from these solvents. Finally, the electrical properties of ordered systems show a clearly higher electrical conductivity compared to the disorganized aggregates. PMID:26079283

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. Monolithic and assembled polymer-ceramic composites for bone regeneration.

    PubMed

    Nandakumar, Anandkumar; Cruz, Célia; Mentink, Anouk; Tahmasebi Birgani, Zeinab; Moroni, Lorenzo; van Blitterswijk, Clemens; Habibovic, Pamela

    2013-03-01

    The rationale for the use of polymer-ceramic composites for bone regeneration stems from the natural composition of bone, with collagen type I and biological apatite as the main organic and inorganic constituents, respectively. In the present study composite materials of PolyActive™ (PA), a poly(ethylene oxide terephthalate)/poly(butylene terephtalate) co-polymer, and hydroxyapatite (HA) at a weight ratio of 85:15 were prepared by rapid prototyping (RP) using two routes. In the first approach pre-extruded composite filaments of PA-HA were processed using three-dimensional fibre deposition (3DF) (conventional composite scaffolds). In the second approach PA scaffolds were fabricated using 3DF and combined with HA pillars produced inside stereolithographic moulds that fitted inside the pores of the PA three-dimensional structure (assembled composite scaffolds). Analysis of calcium and phosphate release in a simulated physiological solution, not containing calcium or phosphate, revealed significantly higher values for the HA pillars compared with other scaffolds. Release in simulated body fluid saturated with respect to HA did not show significant differences among the different scaffolds. Human mesenchymal stromal cells were cultured on polymer (3DF), conventional composite (3DF-HA) and assembled composite (HA assembled in 3DF) scaffolds and assessed for morphology, metabolic activity, DNA amount and gene expression of osteogenic markers using real time quantitative polymerase chain reaction (PCR). Scanning electron microscopy images showed that the cells attached to and infiltrated all the scaffolds. Assembled composites had a higher metabolic activity compared with 3DF-HA scaffolds while no significant differences were observed in DNA amounts. Gene expression of osteopontin in the assembled composite was significantly higher compared with the conventional composites. The strategy of composite fabrication by assembly appears to be a promising alternative to the

  12. Cross-Linked Conjugated Polymer Fibrils: Robust Nanowires from Functional Polythiophene Diblock Copolymers

    SciTech Connect

    Hammer, Brenton A. G.; Bokel, Felicia A.; Hayward, Ryan C.; Emrick, Todd

    2011-09-27

    A series of poly(3-hexyl thiophene) (P3HT)-based diblock copolymers were prepared and examined in solution for their assembly into fibrils, and post-assembly cross-linking into robust nanowire structures. P3HT-b-poly(3-methanol thiophene) (P3MT), and P3HT-b-poly(3-aminopropyloxymethyl thiophene) (P3AmT) diblock copolymers were synthesized using Grignard metathesis (GRIM) polymerization. Fibrils formed from solution assembly of these copolymers are thus decorated with hydroxyl and amine functionality, and cross-linking is achieved by reaction of diisocyanates with the hydroxyl and amine groups. A variety of cross-linked structures, characterized by transmission electron microscopy (TEM), were produced by this method, including dense fibrillar sheets, fibril bundles, or predominately individual fibrils, depending on the chosen reaction conditions. In solution, the cross-linked fibrils maintained their characteristic vibronic structure in solvents that would normally disrupt (dissolve) the structures.

  13. Conjugated polymer particles: towards self-assembling organic photonics

    NASA Astrophysics Data System (ADS)

    Kuehne, Alexander J. C.; Luelf, Tobias; Wessling, Matthias; Sprakel, Joris

    2013-09-01

    The preparation of conjugated polymer particles with uniform size is presented and discussed. The particles can selfassemble into photonic crystal arrangements exhibiting a photonic band-gap. This way, active optical assemblies with an optical stop-band and an independent fluorescence band can be fabricated. To showcase the applicability of the particles, which can be processed from dispersion, optical core sheath fibers are presented. The particles can be extruded into the core of the fiber with polyacrylonitrile as the cladding material. The particle dispersions can be easily processed by dryspinning and are confined to only the core of the fiber, where they assemble into a random close packing.

  14. 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. PMID:26985790

  15. Mesoporous Silicia Nanowires by Space-Confined Organic-Inorganic Hybrid Self-Assembly

    SciTech Connect

    Lai, Peng

    2007-10-01

    This research focuses on the space-confined self-assembly of P123-silica hybrid solution inside nano-scale channels. Mesoporous silica nanowires with various diameters (10-400nm) were synthesized via sol-gel combined evaporation-induced self-assembly in channels of both anodized aluminum oxide (AAO) and etched polycarbonate (EPC) substrate. Scanning transmission electron microscope (STEM) was utilized to characterize the samples in terms of nanopore size, ordering, and orientation. The mesoporous structures of silica wires formed in EPC channels with diameter less than 400 nm are investigated and reported for the first time. Substrate effect (EPC vs. AAO) and processing condition effect on the morphology of the mesoporous structure of silica wires are presented and discussed. The more ordered and uniform mesoporous structure is preferentially formed in narrower substrate channel confinement. A critical diameter of hard template channels is around 30-50 nm, below which the space confinement effect leads to more uniform nanostructured nanowires, and above which mixed meso-structures usually exist. The formation of various meso-structures of silica wires is sensitive to process conditions.

  16. Co-assembled thin films of Ag nanowires and functional nanoparticles at the liquid-liquid interface by shaking

    NASA Astrophysics Data System (ADS)

    Zhang, Shao-Yi; Liu, Jian-Wei; Zhang, Chuan-Ling; Yu, Shu-Hong

    2013-05-01

    In this paper, we report the fabrication of co-assembled thin films composed of silver nanowires (NWs) and Au nanoparticles (NPs) at the liquid-liquid interface (water-chloroform) by vigorous shaking. The composition of co-assembled thin films can be controlled by adjusting the concentration of the nanosized building blocks. As a versatile interfacial assembly method, other nanoparticles such as Ag2S and Fe3O4 NPs can also be co-assembled with Ag NWs using the same procedure. Meanwhile, the co-assembly state of the obtained Au NPs and Ag NWs makes a significant contribution to the high sensitivity of surface-enhanced Raman scattering (SERS) to model the molecule 3,3'-diethylthiatricarbocyanine iodide (DTTCI). The SERS intensities show high dependence on the molar ratio of Au NPs and Ag NWs and the layer number of the co-assembled thin films. This shaking-assisted liquid-liquid assembly system has been proved to be a facile way for co-assembling nanowires and nanoparticles, and will pave a way for further applications of the macroscopic co-assemblies with novel functionalities.In this paper, we report the fabrication of co-assembled thin films composed of silver nanowires (NWs) and Au nanoparticles (NPs) at the liquid-liquid interface (water-chloroform) by vigorous shaking. The composition of co-assembled thin films can be controlled by adjusting the concentration of the nanosized building blocks. As a versatile interfacial assembly method, other nanoparticles such as Ag2S and Fe3O4 NPs can also be co-assembled with Ag NWs using the same procedure. Meanwhile, the co-assembly state of the obtained Au NPs and Ag NWs makes a significant contribution to the high sensitivity of surface-enhanced Raman scattering (SERS) to model the molecule 3,3'-diethylthiatricarbocyanine iodide (DTTCI). The SERS intensities show high dependence on the molar ratio of Au NPs and Ag NWs and the layer number of the co-assembled thin films. This shaking-assisted liquid-liquid assembly system

  17. 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

  18. 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.

  19. Assembly and Integration of Nanowires and Graphene for Nanoelectronics and Nanobiotechnology

    NASA Astrophysics Data System (ADS)

    Nam, Sungwoo

    Flexible bottom-up assembly and integration of nanoscale materials with tunable composition and structure could make possible the development and advancement of novel fabrication strategies and unconventional integrated electronics/sensors not previously achievable with top-down approaches. We demonstrate contact-printing assembly and integration of semiconducting nanowires for three-dimensional (3D), multilayer nanowire (NW) electronics and large-scale complementary SiNW biosensor arrays, and monolithic integration of graphene-graphite for flexible bioprobes and integrated graphene electronics. First, we achieved the assembly of highly-ordered NW arrays by contact-printing with well-controlled shear process between growth and target substrates. We show the capability of uniform and patterned automated contact-printing from single chip to a 4-inch wafer scale. We also demonstrate the power of our assembly approach with the creation of 3D NW electronics and large-scale, complementary SiNW biosensor arrays. We show, first, multilayer assembly of semiconducting NWs for 3D, multi-functional electronics, which includes (1) 10 layers of Ge/Si NW field-effect transistor (FET) arrays, (2) two-layer, multi-functional circuits assembled onto flexible plastic substrates and (3) vertically-interconnected complementary metal-oxide-semiconductor (CMOS) circuits based on heterogeneous n-InAs and p-Ge/Si NW FETs with a record high ring oscillation frequency of ca. 110 MHz. Furthermore, we present the assembly and integration of large-scale, complementary SiNW biosensor arrays capable of simultaneous, multi-channel detections with femtomolar sensitivity of prostate-specific antigen (PSA). Second, we report monolithic integration of graphene-graphite to realize flexible, electrically-active nanoprobes, and a single-step synthesis of monolithic graphene-graphite structure to realize the integration of a whole circuit. We demonstrate that monolithically-integrated graphene

  20. Solution assembly behaviors of 3-hexylthiophene polymer based rod-coil graft copolymer

    NASA Astrophysics Data System (ADS)

    Kim, Youngkwon; Kim, Jin-Sung; Kim, Hyeong Jun; Kim, Bumjoon

    Solution assembly of conjugated polymer based block copolymers (BCPs) is an attractive approach for achieving conducting nanowires (NWs) with nanometer-scale cross-sectional dimensions. In particular, conjugated block offers one-dimensional self-growth of crystalline NWs, and secondary block gives rise to stable dispersion of NWs and additional tuning parameter for the structures of NWs. Herein, we developed a series of poly(3-hexylthiophene)-graft-poly(2-vinylpyridine) (P3HT-g-P2VP) rod-coil copolymers with systematically controlled crystallinity by modifying both grafting density and molecular weight (Mn) of coil block, and their solution assembly behaviors were carefully examined. As increasing the volume fraction and grafting density of the secondary blocks, melting temperatures, crystallization temperatures, and the crystallinity were gradually decreased by hindering rod-rod interaction between P3HT backbones, resulting in the formation of short NWs. Furthermore, the length of NMs was relatively shorter for the densely grafted copolymer despite same volume fraction of secondary block. These results suggested that controlling Mn and the number of branched coil block was critical to regulate the crystalline properties and new approach for determining the NWs growth.

  1. 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

  2. Nanoscale Control of Polymer Assembly on a Synthetic Catalyst-Bilayer System.

    PubMed

    Gorgoll, Ricardo M; Harano, Koji; Nakamura, Eiichi

    2016-08-01

    The use of the interior of self-assembled membrane as a template for polymer synthesis and assembly has long attracted the interest of chemists. However, it is difficult to utilize a lipid membrane as a chemical reactor for controlled assembly for polymers because lipid membrane is easily destabilized by loading of extraneous molecules. We found that a several-nanometer-thick bilayer vesicle made by self-assembly of an organic fullerene amphiphile doped with a metathesis catalyst serves as a nanosized chemical reactor in water, where a polymer is synthesized and assembled, depending on the affinity of the growing polymer to the organic groups on the amphiphile. This catalyst-bilayer system can thus control supramolecular assembly of the ester-functionalized polymer product into different nanoscale structures: a nanoparticle made of a single polymer chain and a nanocapsule made of several tens of polymer chains. PMID:27404736

  3. Nanowires formed by the co-assembly of a negatively charged low-molecular weight gelator and a zwitterionic polythiophene.

    PubMed

    Li, Feng; Palaniswamy, Ganesan; de Jong, Menno R; Aslund, Andreas; Konradsson, Peter; Marcelis, Antonius T M; Sudhölter, Ernst J R; Stuart, Martien A Cohen; Leermakers, Frans A M

    2010-06-21

    Conjugated organic nanowires have been prepared by co-assembling a carboxylate containing low-molecular weight gelator (LMWG) and an amino acid substituted polythiophene derivative (PTT). Upon introducing the zwitterionic polyelectrolyte PTT to a basic molecular solution of the organogelator, the negative charges on the LMWG are compensated by the positive charges of the PTT. As a result, nanowires form through co-assembly. These nanowires are visualized by both transmission electron microscopy (TEM) and atomic force microscopy (AFM). Depending on the concentration and ratio of the components these nanowires can be micrometers long. These measurements further suggest that the aggregates adopt a helical conformation. The morphology of these nanowires are studied with fluorescent confocal laser scanning microscopy (CLSM). The interactions between LMWG and PTT are characterized by steady-state and time-resolved fluorescence spectroscopy studies. The steady-state spectra indicate that the backbone of the PTT adopts a more planar and more aggregated conformation when interacting with LMWG. The time- resolved fluorescence decay studies confirm this interpretation.

  4. 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.

  5. Self-assembled GaN quantum wires on GaN/AlN nanowire templates.

    PubMed

    Arbiol, Jordi; Magen, Cesar; Becker, Pascal; Jacopin, Gwénolé; Chernikov, Alexey; Schäfer, Sören; Furtmayr, Florian; Tchernycheva, Maria; Rigutti, Lorenzo; Teubert, Jörg; Chatterjee, Sangam; Morante, Joan R; Eickhoff, Martin

    2012-12-01

    We present a novel approach for self-assembled growth of GaN quantum wires (QWRs) exhibiting strong confinement in two spatial dimensions. The GaN QWRs are formed by selective nucleation on {112[combining macron]0} (a-plane) facets formed at the six intersections of {11[combining macron]00} (m-plane) sidewalls of AlN/GaN nanowires used as a template. Based on microscopy observations we have developed a 3D model explaining the growth mechanism of QWRs. We show that the QWR formation is governed by self-limited pseudomorphic growth on the side facets of the nanowires (NWs). Quantum confinement in the QWRs is confirmed by the observation of narrow photoluminescence lines originating from individual QWRs with emission energies up to 4.4 eV. Time-resolved photoluminescence studies reveal a short decay time (~120 ps) of the QWR emission. Capping of the QWRs with AlN allows enhancement of the photoluminescence, which is blue-shifted due to compressive strain. The emission energies from single QWRs are modelled assuming a triangular cross-section resulting from self-limited growth on a-plane facets. Comparison with the experimental results yields an average QWR diameter of about 2.7 nm in agreement with structural characterization. The presented results open a new route towards controlled realization of one-dimensional semiconductor quantum structures with a high potential both for fundamental studies and for applications in electronics and in UV light generation.

  6. A facile synthesis of novel nanorod-assembling hollow nanowires of cadmium sulfide/DBTU nanocomposite

    SciTech Connect

    Tang, Yu; Mo, Yan-mei; Yang, Kui; Chen, Tie-shi; Yang, Jun; Zhang, Yuan-ming

    2010-11-15

    Novel nanorod-assembling hollow nanowires of cadmium sulfide/DBTU (N,N'-dibutylthiourea) nanocomposite were synthesized by reacting CdCl{sub 2} with in situ produced H{sub 2}S from reaction of butylamine and carbon disulfide at molar ratio 3:3 of CS{sub 2}:BuNH{sub 2} at 50 {sup o}C. This product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), energy dispersive X-ray spectroscopy (EDAX), thermogravimetric (TG), Fourier transform infrared (FTIR) and UV-vis absorption spectra. A plausible mechanism that the extending DBTU molecules in solvent of CS{sub 2} induce the formation of CdS/DBTU nanorods by coordinating with the formed CdS particles, and construct these nanorods to hollow nanowires via molecular interactions is proposed and discussed on the basis of experimental results. Photoluminescence (PL) of CdS/DBTU nanocomposite exhibits increasing emission intensity largely.

  7. 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.

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

    PubMed

    Chakraborty, A K; Golumbfskie, A J

    2001-01-01

    Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context. PMID:11326074

  9. 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.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    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.

  12. 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.

  13. Directed Assembly of Nanoparticle Catalysts on Nanowire Photoelectrodes for Photoelectrochemical CO2 Reduction.

    PubMed

    Kong, Qiao; Kim, Dohyung; Liu, Chong; Yu, Yi; Su, Yude; Li, Yifan; Yang, Peidong

    2016-09-14

    Reducing carbon dioxide with a multicomponent artificial photosynthetic system, closely mimicking nature, represents a promising approach for energy storage. Previous works have focused on exploiting light-harvesting semiconductor nanowires (NW) for photoelectrochemical water splitting. With the newly developed CO2 reduction nanoparticle (NP) catalysts, direct interfacing of these nanocatalysts with NW light absorbers for photoelectrochemical reduction of CO2 becomes feasible. Here, we demonstrate a directed assembly of NP catalysts on vertical NW substrates for CO2-to-CO conversion under illumination. Guided by the one-dimensional geometry, well-dispersed assembly of Au3Cu NPs on the surface of Si NW arrays was achieved with facile coverage tunability. Such Au3Cu NP decorated Si NW arrays can readily serve as effective CO2 reduction photoelectrodes, exhibiting high CO2-to-CO selectivity close to 80% at -0.20 V vs RHE with suppressed hydrogen evolution. A reduction of 120 mV overpotential compared to the planar (PL) counterpart was observed resulting from the optimized spatial arrangement of NP catalysts on the high surface area NW arrays. In addition, this system showed consistent photoelectrochemical CO2 reduction capability up to 18 h. This simple photoelectrode assembly process will lead to further progress in artificial photosynthesis, by allowing the combination of developments in each subfield to create an efficient light-driven system generating carbon-based fuels. PMID:27494433

  14. Directed Assembly of Nanoparticle Catalysts on Nanowire Photoelectrodes for Photoelectrochemical CO2 Reduction.

    PubMed

    Kong, Qiao; Kim, Dohyung; Liu, Chong; Yu, Yi; Su, Yude; Li, Yifan; Yang, Peidong

    2016-09-14

    Reducing carbon dioxide with a multicomponent artificial photosynthetic system, closely mimicking nature, represents a promising approach for energy storage. Previous works have focused on exploiting light-harvesting semiconductor nanowires (NW) for photoelectrochemical water splitting. With the newly developed CO2 reduction nanoparticle (NP) catalysts, direct interfacing of these nanocatalysts with NW light absorbers for photoelectrochemical reduction of CO2 becomes feasible. Here, we demonstrate a directed assembly of NP catalysts on vertical NW substrates for CO2-to-CO conversion under illumination. Guided by the one-dimensional geometry, well-dispersed assembly of Au3Cu NPs on the surface of Si NW arrays was achieved with facile coverage tunability. Such Au3Cu NP decorated Si NW arrays can readily serve as effective CO2 reduction photoelectrodes, exhibiting high CO2-to-CO selectivity close to 80% at -0.20 V vs RHE with suppressed hydrogen evolution. A reduction of 120 mV overpotential compared to the planar (PL) counterpart was observed resulting from the optimized spatial arrangement of NP catalysts on the high surface area NW arrays. In addition, this system showed consistent photoelectrochemical CO2 reduction capability up to 18 h. This simple photoelectrode assembly process will lead to further progress in artificial photosynthesis, by allowing the combination of developments in each subfield to create an efficient light-driven system generating carbon-based fuels.

  15. Preparation of Nanowire Silica Inside Self-Assembled Sodium Bis(2-ethylhexyl) Sulfosuccinate (AOT) Gels.

    PubMed

    Lai, Wei-Chi; Hong, Li-Tzuen

    2016-09-22

    In conventional sol-gel methods, gel formation occurs due to aggregation of particles into irregular shapes of larger size. In this study, we conducted hydrolysis-condensation reactions of tetraethyl orthosilicate (TEOS) within water-laden channels inside the space created by self-assembled AOT molecules to prepare regular and nanosized silica in self-assembled sodium bis(2-ethylhexyl) sulfosuccinate (AOT) gels. The AOT gels were obtained by adding small amounts of water to organic solvents containing high concentrations of AOT. Adding silica significantly influenced the rheological properties and microstructures of these AOT/silica gels. Rheological studies showed that the storage modulus G' and loss modulus G″ of the AOT gel systems became very close and even crossed, indicating that the gel is "weak"; however, for the AOT/silica gel systems, the rheological data demonstrated that G' is greater than G″ at all frequencies, indicative of a real gel with a G' of approximately 10(5) pa. Small-angle X-ray scattering (SAXS) results showed that the gels initially had a hexagonal close-packed cylindrical structure with long-range order and transitioned to nonclose-packed cylindrical structures without long-range order as the silica formed. The cylinder is expected to comprise stacks of silica molecules surrounded by AOT molecules, and the radius of the cylinder is close to the sum of the length of one AOT molecule and half the size of one silica molecule. The rheological and SAXS data show that silica in the AOT/silica systems grew in the axial direction due to the confinement of these cylindrical structures, leading to nanowire silica structures. After removal of the AOT components, the nanowire silica was approximately 5-10 nm in diameter, as observed using transmission electron microscopy (TEM). PMID:27602986

  16. Preparation of Nanowire Silica Inside Self-Assembled Sodium Bis(2-ethylhexyl) Sulfosuccinate (AOT) Gels.

    PubMed

    Lai, Wei-Chi; Hong, Li-Tzuen

    2016-09-22

    In conventional sol-gel methods, gel formation occurs due to aggregation of particles into irregular shapes of larger size. In this study, we conducted hydrolysis-condensation reactions of tetraethyl orthosilicate (TEOS) within water-laden channels inside the space created by self-assembled AOT molecules to prepare regular and nanosized silica in self-assembled sodium bis(2-ethylhexyl) sulfosuccinate (AOT) gels. The AOT gels were obtained by adding small amounts of water to organic solvents containing high concentrations of AOT. Adding silica significantly influenced the rheological properties and microstructures of these AOT/silica gels. Rheological studies showed that the storage modulus G' and loss modulus G″ of the AOT gel systems became very close and even crossed, indicating that the gel is "weak"; however, for the AOT/silica gel systems, the rheological data demonstrated that G' is greater than G″ at all frequencies, indicative of a real gel with a G' of approximately 10(5) pa. Small-angle X-ray scattering (SAXS) results showed that the gels initially had a hexagonal close-packed cylindrical structure with long-range order and transitioned to nonclose-packed cylindrical structures without long-range order as the silica formed. The cylinder is expected to comprise stacks of silica molecules surrounded by AOT molecules, and the radius of the cylinder is close to the sum of the length of one AOT molecule and half the size of one silica molecule. The rheological and SAXS data show that silica in the AOT/silica systems grew in the axial direction due to the confinement of these cylindrical structures, leading to nanowire silica structures. After removal of the AOT components, the nanowire silica was approximately 5-10 nm in diameter, as observed using transmission electron microscopy (TEM).

  17. Self-assembly of ordered, conjugated polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    McCaughey, Byron

    This research aims to control the configuration and properties of functional, conjugated polymer systems by tuning the composite nanostructure and molecular interactions. This is accomplished by self-assembly of specific organic and inorganic building blocks. New nanocomposite synthesis schemes are demonstrated for poly(2,5-thienylene ethynylene) (PTE) and polydiacetylene (PDA) that focus on the combination of amphiphiles with hydrophobic and hydrophilic components. The weak molecular interactions between these building blocks result in spontaneous organization into highly ordered amorphous and crystalline structures. Emulsion polymerization, simultaneous monomer incorporation during self-assembly, and PDA supramolecular assembly synthesis paradigms will be discussed. By controlling the interactions, synthesis conditions, and building blocks; this research tunes the structure, molecular conformation, and therefore the optical properties of the resultant composites. Notable results include control of PTE particle size; direction of PTE/silica nanocomposite mesostructure; synthesis of free-standing mesoporous PTE; completely reversible thermochromatic and structural transitions in PDA assemblies; chemical and solvent sensing with PDA; and tunable mechanochromatic response with PDA composites. The synthesis schemes developed in this dissertation research program provide a general route to prepare functional materials with beneficial properties such as thermally controlled optical adsorption, self-healing mesostructure, molecular recognition, and mechanically induced color changes for the detection of damage in plastic composites.

  18. Using Polymer Conformation to Control Architecture in Semiconducting Polymer/Viral Capsid Assemblies

    PubMed Central

    Ng, Benny C.; Chan, Stephanie T.; Lin, Jason; Tolbert, Sarah H.

    2011-01-01

    Cowpea Chlorotic Mottle Virus is a single-stranded RNA plant virus with a diameter of 28 nm. The proteins comprising the capsid of this virus can be purified and reassembled either by themselves to form hollow structures, or with polyanions like double-stranded DNA or single-stranded RNA. Depending on pH and ionic strength, a diverse range of structures and shapes can form. The work presented here focuses on using these proteins to encapsulate a fluorescent polyanionic semiconducting polymer, MPS-PPV (poly-2-methoxy-5-propyloxy sulfonate phenylene vinlyene), in order to obtain optically active virus-like particles. After encapsulation, fluorescence from MPS-PPV shows two distinct peaks, which suggests the polymer may be in two conformations. A combination of TEM, fluorescence anisotropy, and sucrose gradient separation indicate that the blue peak arises from polymer encapsulated into spherical particles, while the redder peak corresponds to polymers contained in rod-like cages. Ionic strength during assembly can be used to tune the propensity to form rods or spheres. The results illustrate the synergy of hybrid synthetic/biological system – polymer conformation drives the structure of this composite material, which in turn modifies the polymer optical properties. This synergy could be useful for the future development of synthetic/biological hybrid materials with designated functionality. PMID:21942298

  19. 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. PMID:22775468

  20. 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. PMID:25961419

  1. Polymer-template-assisted growth of gold nanowires using a novel flow-stream technique.

    PubMed

    Metwalli, E; Moulin, J-F; Perlich, J; Wang, W; Diethert, A; Roth, S V; Müller-Buschbaum, P

    2009-10-01

    By utilizing a fluidic device, a gold nanoparticle dispersion is cast onto a nanostructured polymer template using solution subjected to hydrodynamic flow. With in situ grazing incidence small-angle X-ray scattering (GISAXS), the progressive gold deposition from a stream of gold solution onto the polymer template of a diblock copolymer with parallel cylinder morphology arranged into powder-like domains is investigated. The continuously flowing solution causes a systematic increase in the X-ray contrast between both of the microphase-separated blocks of the block copolymer film, indicating flow-induced selective gold immobilization on one block. Both in situ GISAXS data and atomic force microscopy of the metal-deposited polymer film prove the 1D coalescence of nanoparticles into continuous nanowires. With additional gold nanoparticle upload by the continuous flow-stream method, the selectivity of the nanoparticle deposition diminishes as a result of the formation of a pseudo uniform gold layer. Consequently, this flow-stream deposition technique introduces an easy alternative method to the vapor deposition technique for surface gold nanopatterning. PMID:19572494

  2. 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. PMID:25405589

  3. 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.

  4. 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

  5. Effect of ion beam energy and polymer weight on the thickness of nanowires produced by ion bombardment of polystyrene thin films

    SciTech Connect

    Tsukuda, Satoshi; Seki, Shu; Tagawa, Seiichi; Sugimoto, Masaki

    2005-12-05

    Exposure of polystyrene to MeV-order heavy-ion beams produces nanowires by cross-linking along ion tracks. The chemical core of these ion tracks is visualized, and the dependence of the diameter of the nanowires on the linear energy transfer of the ion beam and molecular weight of the polymer are investigated precisely based on the model of transformation of a nanowire cross section into an ellipse. an equation is derived to predict the radius (5.6-27.6 nm) of the chemical core considering the energy density required for gelation of the polymer, and the validity of the relation is confirmed against experimental results.

  6. 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.

  7. Synthesis, phase composition, and magnetic properties of iron nanowires prepared in the pores of polymer track-etched membranes

    NASA Astrophysics Data System (ADS)

    Frolov, K. V.; Zagorskii, D. L.; Lyubutin, I. S.; Korotkov, V. V.; Bedin, S. A.; Sulyanov, S. N.; Artemov, V. V.; Mchedlishvili, B. V.

    2014-07-01

    Arrays of iron nanowires prepared by the method of galvanic filling of polymer track-etched membrane pores (matrix synthesis) under different electrolysis modes and electrolyte temperatures have been studied. The conditions of the synthesis have been analyzed. The optimal composition and electrolyte temperature have been found. The phase composition and magnetic properties of nanowires have been studied using the methods of electron microscopy, X-ray diffraction, elemental energy-dispersive microanalysis, and Mössbauer spectroscopy. The average nanowire diameter is 100-200 nm. The length varies from 6 to 10 μm. The surface density is ˜108 cm-2 at the average distance to each other of about 1 μm. It has been established that the basis of nanowires is formed by the metal iron nanocomposite that manifests the magnetic properties of bulk α-Fe. It has been found that the preferred orientation of the magnetization inside the iron nanowires arises for an array prepared at a potential of -750 mV.

  8. 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.

  9. 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.

  10. 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.

  11. 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. PMID:24039099

  12. 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

  13. 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

  14. Surface reconstruction of ZnO nanowire arrays via solvent-evaporation-induced self-assembly

    NASA Astrophysics Data System (ADS)

    Fang, Fang; Zhao, Dongxu; Li, Binghui; Zhang, Zhenzhong; Shen, Dezhen; Wang, Xiaohua

    2011-02-01

    Vertically aligned ZnO nanowires (NWs) can be reconstructed on large scales by a solvent-evaporation-induced method. The morphologies of the nanowires are regulated by changing the concentration of the solution. Possible mechanism, which the compressive residual stresses and wires/wires self-attraction can be responsible for the surface reconstruction, is addressed. Furthermore, we compare the structural properties of ZnO nanowires before and after reconstructed.

  15. 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.

  16. Enhancing Crystalline Structural Orders of Polymer Semiconductors for Efficient Charge Transport via Polymer-Matrix-Mediated Molecular Self-Assembly.

    PubMed

    Lei, Yanlian; Deng, Ping; Lin, Ming; Zheng, Xuelin; Zhu, Furong; Ong, Beng S

    2016-08-01

    A facile polymer-matrix-mediated molecular self-assembly of polymer semiconductors into highly crystalline orders for efficient charge transport in organic thin-film transistors is demonstrated. Phenomenal enhancements in field-effect mobility of about one order of magnitude and current on/off ratio of two to three orders of magnitude are realized with polyacrylonitrile-incorporated polymer semiconductor compositions via solution deposition. PMID:27168128

  17. 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

  18. Intraband absorption in self-assembled Ge-doped GaN/AlN nanowire heterostructures.

    PubMed

    Beeler, M; Hille, P; Schörmann, J; Teubert, J; de la Mata, M; Arbiol, J; Eickhoff, M; Monroy, E

    2014-03-12

    We report the observation of transverse-magnetic-polarized infrared absorption assigned to the s-p(z) intraband transition in Ge-doped GaN/AlN nanodisks (NDs) in self-assembled GaN nanowires (NWs). The s-p(z) absorption line experiences a blue shift with increasing ND Ge concentration and a red shift with increasing ND thickness. The experimental results in terms of interband and intraband spectroscopy are compared to theoretical calculations of the band diagram and electronic structure of GaN/AlN heterostructured NWs, accounting for their three-dimensional strain distribution and the presence of surface states. From the theoretical analysis, we conclude that the formation of an AlN shell during the heterostructure growth applies a uniaxial compressive strain which blue shifts the interband optical transitions but has little influence on the intraband transitions. The presence of surface states with density levels expected for m-GaN plane charge-deplete the base of the NWs but is insufficient to screen the polarization-induced internal electric field in the heterostructures. Simulations show that the free-carrier screening of the polarization-induced internal electric field in the NDs is critical to predicting the photoluminescence behavior. The intraband transitions, on the other hand, are blue-shifted due to many-body effects, namely, the exchange interaction and depolarization shift, which exceed the red shift induced by carrier screening. PMID:24502703

  19. 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

  20. Low operating voltage single ZnO nanowire field-effect transistors enabled by self-assembled organic gate nanodielectrics.

    PubMed

    Ju, Sanghyun; Lee, Kangho; Janes, David B; Yoon, Myung-Han; Facchetti, Antonio; Marks, Tobin J

    2005-11-01

    The development of nanowire transistors enabled by appropriate dielectrics is of great interest for flexible electronic and display applications. In this study, nanowire field-effect transistors (NW-FETs) composed of individual ZnO nanowires are fabricated using a self-assembled superlattice (SAS) as the gate insulator. The 15-nm SAS film used in this study consists of four interlinked layer-by-layer self-assembled organic monolayers and exhibits excellent insulating properties with a large specific capacitance, 180 nF/cm2, and a low leakage current density, 1 x 10(-8) A/cm2. SAS-based ZnO NW-FETs display excellent drain current saturation at Vds = 0.5 V, a threshold voltage (Vth) of -0.4 V, a channel mobility of approximately 196 cm2/V s, an on-off current ratio of approximately 10(4), and a subthreshold slope of 400 mV/dec. For comparison, ZnO NW-FETs are also fabricated using 70-nm SiO2 as the gate insulator. Implementation of the SAS gate dielectric reduces the NW-FET operating voltage dramatically with more than 1 order of magnitude enhancement of the on-current. These results strongly indicate that SAS-based ZnO NW-FETs are promising candidates for future flexible display and logic technologies.

  1. Template directed assembly of nanoelements in viscous polymer environments

    NASA Astrophysics Data System (ADS)

    Modi, Satyamkumar

    Polymer melt-based manufacturing methods, such as injection molding, offer the potential of directly fabricating three-dimensional parts with nanostructured surfaces in a one-step, high-rate, and solventless process. Electrophoretic deposition has the potential to produce in-mold assembly of nanoparticles during injection molding. The process is fast, is cost effective and can be automated. This electrophoretic deposition, however, has been performed from low-viscosity media and polymer melts are far more viscous. This research provided a fundamental understanding of the electrophoretic deposition process in viscous media. Electrophoresis was performed using a model system of carbon black and polystyrene in tetrahydrofuran (THF). Examined were the effects of processing parameters, polystyrene molecular weight, and carbon black charge. The presence of polystyrene did not prevent deposition of carbon black, but deposition rates decreased at shorter deposition times; deposition was not linear with increasing applied voltage; and greater solution concentrations reduced the critical voltages. A comparison of experimental data with Hamaker's model showed that about 1.6% of the available polystyrene was initially deposited with the carbon black. At voltages above the critical voltage, the deposited mass indicated formation of electrically insulating layers on the electrodes. Increases in polystyrene molecular weight reduced the electrophoretic deposition of the carbon black particles due to increases in suspension viscosity and preferential adsorption of the longer polystyrene chains on the carbon black particles. At low deposition times (≤ 5 seconds), only carbon black deposited onto the electrodes. For longer deposition times, polystyrene co-deposited with the carbon black, with the amount of polystyrene increasing with molecular weight and decreasing with greater charge on the polystyrene molecules. The additional of function groups to the carbon black surface

  2. 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.

  3. 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.

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

    PubMed

    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.

  5. 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.

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

    PubMed

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-08-01

    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

  7. Highly efficient flexible optoelectronic devices using metal nanowire-conducting polymer composite transparent electrode

    NASA Astrophysics Data System (ADS)

    Jung, Eui Dae; Nam, Yun Seok; Seo, Houn; Lee, Bo Ram; Yu, Jae Choul; Lee, Sang Yun; Kim, Ju-Young; Park, Jang-Ung; Song, Myoung Hoon

    2015-09-01

    Here, we report a comprehensive analysis of the electrical, optical, mechanical, and surface morphological properties of composite nanostrutures based on silver nanowires (AgNW) and PEDOT:PSS conducting polymer for the use as flexible and transparent electrodes. Compared to ITO or the single material of AgNW or PEDOT:PSS, the AgNW/PEDOT:PSS composite electrode showed high electrical conductivity with a low sheet resistance of 26.8 Ω/sq at 91% transmittance (at 550 nm), improves surface smoothness, and enhances mechanical properties assisted by an amphiphilic fluoro-surfactant. The polymeric light-emitting diodes (PLEDs) and organic solar cells (OSCs) using the AgNW/PEDOT:PSS composite electrode showed higher device performances than those with AgNW and PEDOT:PSS electrodes and excellent flexibility under bending test. These results indicates that the AgNW/PEDOT:PSS composite presented is a good candidate as next-generation transparent elelctrodes for applications into flexible optoelectronic devices. [Figure not available: see fulltext.

  8. 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).

  9. Sn-Seeded GaAs Nanowires as Self-Assembled Radial p–n Junctions

    PubMed Central

    2015-01-01

    The widespread use of Au as a seed particle in the fabrication of semiconductor nanowires presents a fundamental limitation to the potential incorporation of such nanostructures into electronic devices. Although several other growth techniques have been demonstrated, the use of alternative seed particle metals remains an underexplored but potentially very promising way to influence the properties of the resulting nanowires while simultaneously avoiding gold. In this Letter, we demonstrate the use of Sn as a seed particle metal for GaAs nanowires grown by metal–organic vapor phase epitaxy. We show that vertically aligned and stacking defect-free GaAs nanowires can be grown with very high yield. The resulting nanowires exhibit Esaki diode behavior, attributed to very high n-doping of the nanowire core with Sn, and simultaneous C-doping of the radial overgrowth. These results demonstrate that the use of alternative seed particle metals is a potentially important area to explore for developing nanowire materials with controlled material properties. PMID:25989532

  10. 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.

  11. 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.

  12. Temporal and Triggered Evolution of Host-Guest Characteristics in Amphiphilic Polymer Assemblies.

    PubMed

    Rangadurai, Poornima; Molla, Mijanur Rahaman; Prasad, Priyaa; Caissy, Matthew; Thayumanavan, S

    2016-06-22

    An amphiphilic polymer with cleavable side chain and main chain functional groups has been designed and synthesized. Specific cleavage of either of its functional groups was found to have an effect on the morphology of the assembly. Degradation of the main chain is shown to cause morphology of the supramolecular assembly to evolve with time from a micelle-like assembly to a vesicular assembly. On the other hand, stimulus-induced cleavage of the side chains causes these nanoassemblies to disassemble. These temporal (main chain) and triggered (side chain) degradation processes have implications in the design of degradable polymers as supramolecular scaffolds for biological applications. PMID:27258854

  13. A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template-Assisted Assembly of Polyfluorene Nanowires.

    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

    DNA molecules have been widely recognized as promising building blocks for constructing functional nanostructures with two main features, that is, self-assembly and rich chemical functionality. The intrinsic feature size of DNA makes it attractive for creating versatile nanostructures. Moreover, the ease of access to tune the surface of DNA by chemical functionalization offers numerous opportunities for many applications. Herein, a simple yet robust strategy is developed to yield the self-assembly of DNA by exploiting controlled evaporative assembly of DNA solution in a unique confined geometry. Intriguingly, depending on the concentration of DNA solution, highly aligned nanostructured fibrillar-like arrays and well-positioned concentric ring-like superstructures composed of DNAs are formed. Subsequently, the ring-like negatively charged DNA superstructures are employed as template to produce conductive organic nanowires on a silicon substrate by complexing with a positively charged conjugated polyelectrolyte poly[9,9-bis(6'-N,N,N-trimethylammoniumhexyl)fluorene dibromide] (PF2) through the strong electrostatic interaction. Finally, a monolithic integration of aligned arrays of DNA-templated PF2 nanowires to yield two DNA/PF2-based devices is demonstrated. It is envisioned that this strategy can be readily extended to pattern other biomolecules and may render a broad range of potential applications from the nucleotide sequence and hybridization as recognition events to transducing elements in chemical sensors. PMID:27351291

  14. 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.

  15. Polymeric microtubules that breathe: CO2 -driven polymer controlled-self-assembly and shape transformation.

    PubMed

    Yan, Qiang; Zhao, Yue

    2013-09-16

    Tubular breathing motion: Polymer tubules self-assembled from a gas-sensitive triblock copolymer can undergo shape evolution. A sequence from microtubes through submicroscopic vesicles to nanosized spherical micelles is modulated by CO2 stimulation levels.

  16. 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. PMID:24446808

  17. Fabrication of Pt nanoparticle incorporated polymer nanowires by high energy ion and electron beam irradiation

    NASA Astrophysics Data System (ADS)

    Tsukuda, Satoshi; Takahasi, Ryouta; Seki, Shu; Sugimoto, Masaki; Idesaki, Akira; Yoshikawa, Masahito; Tanaka, Shun-Ichiro

    2016-01-01

    Polyvinylpyrrolidone (PVP)-Pt nanoparticles (NPs) hybrid nanowires were fabricated by high energy ion beam irradiation to PVP thin films including H2PtCl6. Single ion hitting caused crosslinking reactions of PVP and reduction of Pt ions within local cylindrical area along an ion trajectory (ion track); therefore, the PVP nanowires including Pt NPs were formed and isolated on Si substrate after wet-development procedure. The number of Pt NPs was easily controlled by the mixed ratio of PVP and H2PtCl6. However, increasing the amount of H2PtCl6 led to decreasing the radial size and separation of the hybrid nanowires during the wet-development. Additional electron beam irradiation after ion beam improved separation of the nanowires and controlled radial sizes due to an increase in the density of crosslinking points inner the nanowires.

  18. 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

  19. 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.

  20. Chemical Sensing with Nanowires

    NASA Astrophysics Data System (ADS)

    Penner, Reginald M.

    2012-07-01

    Transformational advances in the performance of nanowire-based chemical sensors and biosensors have been achieved over the past two to three years. These advances have arisen from a better understanding of the mechanisms of transduction operating in these devices, innovations in nanowire fabrication, and improved methods for incorporating receptors into or onto nanowires. Nanowire-based biosensors have detected DNA in undiluted physiological saline. For silicon nanowire nucleic acid sensors, higher sensitivities have been obtained by eliminating the passivating oxide layer on the nanowire surface and by substituting uncharged protein nucleic acids for DNA as the capture strands. Biosensors for peptide and protein cancer markers, based on both semiconductor nanowires and nanowires of conductive polymers, have detected these targets at physiologically relevant concentrations in both blood plasma and whole blood. Nanowire chemical sensors have also detected several gases at the parts-per-million level. This review discusses these and other recent advances, concentrating on work published in the past three years.

  1. The cluster-assembled nanowires based on M12N12 (M = Al and Ga) clusters as potential gas sensors for CO, NO, and NO2 detection.

    PubMed

    Yong, Yongliang; Jiang, Huai; Li, Xiaohong; Lv, Shijie; Cao, Jingxiao

    2016-08-01

    The advances in cluster-assembled materials where clusters serve as building blocks have opened new opportunities to develop ever more sensitive gas sensors. Here, using density functional theory calculations, the structural and electronic properties of cluster-assembled nanowires based on M12N12 (M = Al and Ga) clusters and their application as gas sensors have been investigated. Our results show that the nanowires can be produced via the coalescence of stable M12N12 fullerene-like clusters. The M12N12-based nanowires have semiconducting electrical properties with direct energy gaps, and are particularly stable at room temperature for long enough to allow for their characterization and applications. Furthermore, we found that the CO, NO, and NO2 molecules are chemisorbed on the M12N12-based nanowires with reasonable adsorption energies and apparent charge transfer. The electronic properties of the M12N12-based nanowires present dramatic changes after the adsorption of the CO, NO, and NO2 molecules, especially their electric conductivity. However, the adsorption of NO2 on the Al12N12-based nanowire is too strong, indicating an impractical recovery time as NO2 sensors. In addition to this, due to reasonable adsorption energies, apparent charge transfer, change in the electric conductivity, and the short recovery time, the Al12N12-based nanowire should be a good CO and NO sensor with quick response as well as short recovery time, while the Ga12N12-based nanowire should be a promising gas sensor for CO, NO, and NO2 detection. PMID:27424739

  2. 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

    2016-04-01

    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. PMID:26998893

  3. 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

  4. Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host-guest complexation.

    PubMed

    Wang, Jie; Qiu, Zhiqiang; Wang, Yiming; Li, Li; Guo, Xuhong; Pham, Duc-Truc; Lincoln, Stephen F; Prud'homme, Robert K

    2016-01-01

    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

  5. 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

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

    PubMed

    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

  7. Langevin dynamics simulation of polymer-assisted virus-like assembly

    NASA Astrophysics Data System (ADS)

    Mahalik, J. P.; Muthukumar, M.

    2012-04-01

    Starting from a coarse grained representation of the building units of the minute virus of mice and a flexible polyelectrolyte molecule, we have explored the mechanism of assembly into icosahedral structures with the help of Langevin dynamics simulations and the parallel tempering technique. Regular icosahedra with appropriate symmetry form only in a narrow range of temperature and polymer length. Within this region of parameters where successful assembly would proceed, we have systematically investigated the growth kinetics. The assembly of icosahedra is found to follow the classical nucleation and growth mechanism in the absence of the polymer, with the three regimes of nucleation, linear growth, and slowing down in the later stage. The calculated average nucleation time obeys the laws expected from the classical nucleation theory. The linear growth rate is found to obey the laws of secondary nucleation as in the case of lamellar growth in polymer crystallization. The same mechanism is seen in the simulations of the assembly of icosahedra in the presence of the polymer as well. The polymer reduces the nucleation barrier significantly by enhancing the local concentration of subunits via adsorbing them on their backbone. The details of growth in the presence of the polymer are also found to be consistent with the classical nucleation theory, despite the smallness of the assembled structures.

  8. Spectral Modifications and Polarization Dependent Coupling in Tailored Assemblies of Quantum Dots and Plasmonic Nanowires

    PubMed Central

    2013-01-01

    The coupling of optical emitters with a nanostructured environment is at the heart of nano- and quantum optics. We control this coupling by the lithographic positioning of a few (1–3) quantum dots (QDs) along plasmonic silver nanowires with nanoscale resolution. The fluorescence emission from the QD-nanowire systems is probed spectroscopically, by microscopic imaging and decay time measurements. We find that the plasmonic modes can strongly modulate the fluorescence emission. For a given QD position, the local plasmon field dictates the coupling efficiency, and thus the relative weight of free space radiation and emission into plasmon modes. Simulations performed with a generic few-level model give very good agreement with experiment. Our data imply that the 2D degenerate emission dipole orientation of the QD can be forced to predominantly emit to one polarization component dictated by the nanowire modes. PMID:23968490

  9. 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.

  10. 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.

  11. 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.

  12. 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. PMID:27167577

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    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.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

  14. Holey polymer films templated by growth and self-assembly of water drops over evaporating polymer solutions

    NASA Astrophysics Data System (ADS)

    Sharma, Vivek; Srinivasarao, Mohan

    2010-03-01

    Water drops that nucleate and grow over evaporating polymer solutions exhibit non-coalescence and pack like hard spheres. In this study, we elucidate how the growth and self-organization of a population of close packed drops occur in response to the heat and mass fluxes involved in water condensation and evaporation of organic solvent. We examine the role of solvent and polymer in controlling the kinetics of growth and assembly of droplets, which eventually evaporate away, producing a polymer film with ordered array of pores. We describe a rich array of experimental observations and theoretical considerations about water droplet growth, noncoalescence and assembly that have not been reported in the published literature so far. Most importantly, we provide insights into how the porous, microstructure is generated and how the size of pore can be controlled.

  15. 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

  16. 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

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    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.

  19. Evaporation-induced Nanoparticle Self-Assembly in a Polymer Matrix

    NASA Astrophysics Data System (ADS)

    Cheng, Shengfeng

    A critical challenge in many applications of polymer nanocomposites is to control the dispersion of nanoparticles in a polymer matrix. We employ large-scale molecular dynamics simulations to study the assembly of nanoparticles as the solvent evaporates from a polymer solution containing nanoparticles. Results show that the organization of nanoparticles can be controlled by varying the strength of the polymer-nanoparticle interactions. When the nanoparticles and polymers strongly attract, as the solvent evaporates, a concentrated polymer film forms at the surface and entraps a layer of nanoparticles, which assemble into a close-packed hexagonal lattice. This dense film of polymers and nanoparticles dramatically reduce the rate of evaporation as the solvent has to transverse the film to reach the surface. If the nanoparticle-polymer interactions are weak, then as the solvent evaporates, the surface layer is almost entirely made of polymers. The nanoparticles are largely excluded from the surface and dispersed randomly in the region below the surface layer. In this case the slowing-down of the evaporation by the surface layer is less dramatic. Also of interest is the case of a nanoparticle solution in contact with polymers that are end grafted to a flat surface to form a polymer brush. For a relatively weak nanoparticle-brush attraction, after evaporation of the solvent the nanoparticles straddle the brush surface and form an ordered lattice. For a strong nanoparticle-polymer attraction, however, the nanoparticles are engulfed inside the brush and the packing quality diminishes because the lateral diffusion of the nanoparticles is suppressed. To better understand the nanoparticle-brush interactions, our calculations to quantify the free energy penalty of inserting a nanoparticle into a polymer brush will also be discussed.

  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

    2014-01-01

    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. Nanoparticle Self-Assembly in a Polymer Matrix and Its Impact on Phase Separation

    NASA Astrophysics Data System (ADS)

    Douglas, Jack

    2011-03-01

    The ubiquitous clustering of nanoparticles (NPs) in solutions and polymer melts depends sensitively on the strength and directionality of the effective NP-NP interactions, as well as on the molecular geometry and interactions of the dispersing fluid. Surface functionalization apparently can also lead to emergent anisotropic interactions that can influence NP dispersion. Since NP clustering can strongly influence the properties of polymer nanocomposites and NP solutions, we investigate the reversible self-assembly of model NPs into clusters under equilibrium conditions through a combination of simulation and analytic methods. First, we performed molecular dynamics simulations of polyhedral NPs in a coarse-grained dense bead--spring polymer melt and find a transition from a dispersed to clustered NP state, consistent with the thermodynamic models of equilibrium particle association such as equilibrium polymerization. We also describe the competition between self-assembly and phase separation in an analytic lattice model of a mixture of polymers and NPs. We then focus on the particularly interesting situation where the associating ``monomeric'' NP species form high molecular mass dynamic polymeric clusters and where the assembly process then transforms the phase boundary from a form typical of a polymer solution to one that more resembles a polymer blend with increasing association near the critical point for phase separation. The model calculations elucidate basic physical principles governing the coupling of self-assembly and phase behavior in these complex mixtures.

  2. 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.

  3. Assembly of microspheres with polymers by evaporating emulsion droplets

    NASA Astrophysics Data System (ADS)

    Lin, Keng-Hui; Lai, Liang-Jie; Chang, Chih-Chung; Chen, Hui

    2008-10-01

    We study the packing of colloidal microspheres mixed with polymers in oil-in-water emulsion droplets by evaporation. The addition of polymers produces non-unique configurations of final clusters when the number of particles N inside the droplet is larger than 4. The cluster configurations are classified into three categories based on symmetry. Stablized colloidal clusters of spherical packings are observed. Our observations on packing process suggest the mechanisms which cause different and nonunique structures. The osmotic pressure and the interparticle interaction due to polymers changes the force balance between microspheres and result in different structures.

  4. 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. PMID:26953514

  5. Effective chiral behavior on self-assembled tilted gold nanowires metasurface by means of linear and nonlinear optical techniques

    NASA Astrophysics Data System (ADS)

    Belardini, A.; Leahu, G.; Centini, M.; Li Voti, R.; Fazio, E.; Sibilia, C.; Haus, Joseph W.; Sarangan, Andrew; Hooper, D.; Valev, V. K.

    2016-04-01

    Even non-chiral objects can exhibit effective optical chiral response due to particular symmetry breaking of the investigating light and the sample morphology. Here we show linear and nonlinear optical measurements performed on a metasurface composed by self-assembled tilted golden nanowires on silicon substrate. The measurements are performed in three different schemes: optical reflectance, photoacoustic absorbance and second harmonic generation. In all these schemes circular polarized light was used in order to evidence the optical chiral behavior in different reciprocal disposition of the wires and light direction. The circular dichroism results to be present in all schemes when the three directions formed by i) the wires orientation, ii) the impinging light wave vector and iii) the normal to the metasurface forms a non-planar triad. Indeed non-planar triad of vectors represents a system that cannot be superposed to its mirror image, thus it is chiral system. We measured a sample obtained by vacuum evaporation of gold at glancing angle on a silicon substrate maintained at the temperature of 300K. The gold nanowires form a forest homogeneously distributed on 1 square inch substrate. Even if the chirality was detected both in linear and nonlinear optical measurements, the second harmonic generation process results to be more sensitive.

  6. 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

  7. 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.

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

    DOEpatents

    Wang Zhong L.; Wang, Xudong; Morber, Jenny R.; Liu, Jin

    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.

  9. Bioinspired assemblies of plant cell wall polymers unravel the affinity properties of carbohydrate-binding modules.

    PubMed

    Paës, Gabriel; von Schantz, Laura; Ohlin, Mats

    2015-09-01

    Lignocellulose-acting enzymes play a central role in the biorefinery of plant biomass to make fuels, chemicals and materials. These enzymes are often appended to carbohydrate binding modules (CBMs) that promote substrate targeting. When used in plant materials, which are complex assemblies of polymers, the binding properties of CBMs can be difficult to understand and predict, thus limiting the efficiency of enzymes. In order to gain more information on the binding properties of CBMs, some bioinspired model assemblies that contain some of the polymers and covalent interactions found in the plant cell walls have been designed. The mobility of three engineered CBMs has been investigated by FRAP in these assemblies, while varying the parameters related to the polymer concentration, the physical state of assemblies and the oligomerization state of CBMs. The features controlling the mobility of the CBMs in the assemblies have been quantified and hierarchized. We demonstrate that the parameters can have additional or opposite effects on mobility, depending on the CBM tested. We also find evidence of a relationship between the mobility of CBMs and their binding strength. Overall, bioinspired assemblies are able to reveal the unique features of affinity of CBMs. In particular, the results show that oligomerization of CBMs and the presence of ferulic acid motifs in the assemblies play an important role in the binding affinity of CBMs. Thus we propose that these features should be finely tuned when CBMs are used in plant cell walls to optimise bioprocesses. PMID:26189625

  10. Building Nanowires from Micelles: Hierarchical Self-Assembly of Alternating Amphiphilic Glycopolypeptide Brushes with Pendants of High-Mannose Glycodendron and Oligophenylalanine.

    PubMed

    Liu, Yijiang; Zhang, Yufei; Wang, Zheyu; Wang, Jue; Wei, Kongchang; Chen, Guosong; Jiang, Ming

    2016-09-28

    Mimicking the diverse glyco-conjugate structures in nature is always the dream of scientists. Right now, hierarchical self-assembled structures of natural conjugates of peptides and sugars could not easily be achieved via linear glycopolypeptide with monosaccharides as attachments. In this work, by using a series of well-designed alternating amphiphilic glycopolypeptide brushes (AAGBs) with pendants of glycodendrons and short peptides, various self-assembled morphologies were achieved, including nanowires, nanoribbon, and compound micelles mainly depending on the number ratio of the sugar units to the amino acids species (S/F). Among these morphologies, nanowire attracted our great attention. TEM studies demonstrated that it is formed via a hierarchical self-assembly, i.e., a series of successive processes, including micellization, micelles alignment forming nanofilament, branching of the nanofilaments by micelles, and finally nanowire formation. As far as we know, such hierarchical self-assembly process with high complexity has not been observed in literature for glycopolypeptides even polypeptides, which will deepen our understanding on self-assembly mechanism of natural glyco-conjugates and expand the library of biomimetic materials.

  11. 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.

  12. Facile synthesis of SnO2 nanocrystals coated conducting polymer nanowires for enhanced lithium storage

    NASA Astrophysics Data System (ADS)

    Du, Zhijia; Zhang, Shichao; Jiang, Tao; Wu, Xiaomeng; Zhang, Lan; Fang, Hua

    2012-12-01

    SnO2 nanoparticles uniformly decorated polypyrrole (PPy) nanowires are synthesized by a facile two-step electrochemical reaction method: electropolymerization and electrodeposition. The nanostructured SnO2-PPy hybrids show porous reticular morphology and homogenous distributions. The reticular SnO2-PPy nanowires can increase the electrode/electrolyte interface and accommodate the volume variation of SnO2. When applied as anode materials for lithium ion batteries, the unique nanostructured hybrids deliver meaningfully improved Li+ storage performance with the first reversible capacity of 690 mAh g-1. This facile synthesis procedure can also be simply grafted to other inorganic-organic hybrid composites.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  15. 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.

  16. 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. PMID

  17. Self-assembled and highly selective sensors based on air-bridge-structured nanowire junction arrays.

    PubMed

    Park, Won Jeong; Choi, Kyung Jin; Kim, Myung Hwa; Koo, Bon Hyeong; Lee, Jong-Lam; Baik, Jeong Min

    2013-08-14

    We describe a strategy for creating an air-bridge-structured nanowire junction array platform that capable of reliably discriminating between three gases (hydrogen, carbon monoxide, and nitrogen dioxide) in air. Alternatively driven dual nanowire species of ZnO and CuO with the average diameter of ∼30 nm on a single substrate are used and decorated with metallic nanoparticles to form two-dimensional microarray, which do not need to consider the post fabrications. Each individual nanowires in the array form n-n, p-p, and p-n junctions at the micro/nanoscale on single substrate and the junctions act as electrical conducting path for carriers. The adsorption of gas molecules to the surface changes the potential barrier height formed at the junctions and the carrier transport inside the straight semiconductors, which provide the ability of a given sensor array to differentiate among the junctions. The sensors were tested for their ability to distinguish three gases (H2, CO, and NO2), which they were able to do unequivocally when the data was classified using linear discriminant analysis. PMID:23841667

  18. 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.

  19. Under-Liquid Self-Assembly of Submerged Buoyant Polymer Particles.

    PubMed

    Multanen, Victor; Pogreb, Roman; Bormashenko, Yelena; Shulzinger, Evgeny; Whyman, Gene; Frenkel, Mark; Bormashenko, Edward

    2016-06-14

    The self-assembly of submerged cold-plasma-treated polyethylene beads (PBs) is reported. The plasma-treated immersed millimetrically sized PBs formed well-ordered 2D quasicrystalline structures. The submerged floating of "light" (buoyant) PBs is possible because of the energy gain achieved by the wetting of the high-energy plasma-treated polymer surface prevailing over the energy loss due to the upward climb of the liquid over the beads. The capillary "immersion" attraction force is responsible for the observed self-assembly. The observed 2D quasicrystalline structures demonstrate "dislocations" and "point defects". The mechanical vibration of self-assembled rafts built of PBs leads to the healing of point defects. The immersion capillary lateral force governs the self-assembly, whereas the elastic force is responsible for the repulsion of polymer beads. PMID:27193509

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

    PubMed

    Liu, Jing; Mao, Yiwu; Ge, Jianping

    2012-03-01

    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. PMID:22297654

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

    DOE PAGESBeta

    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).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

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

    PubMed

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

    2015-07-01

    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.

  3. 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.

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

    DOE PAGESBeta

    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 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

  5. Development of palladium nanowires

    NASA Astrophysics Data System (ADS)

    Cheng, Chuanding

    Inherent limitations of traditional lithography have prompted the search for means of achieving self-assembly of nano-scale structures and networks for the next generation of electronic and photonic devices. The nanowire, the basic building block of a nanocircuit, has recently become the focus of intense research. Reports on nanowire synthesis and assembly have appeared in the scientific literature, which include Vapor-Liquid-Solid mechanism, template-based electrochemical fabrication, solvothermal or wet chemistry, and assembly by fluid alignment or microchannel networks. An ideal approach for practical application of nanowires would circumvent technical and economic constraints of templating. Here we report on the self-assembly of highly-ordered metallic nanowires directly from a palladium acetate solution under an applied alternating current (AC) electric field of relatively high intensity and frequency. DNA-templated nanowires are first presented here. DNA molecules were stretched and positioned by electric field, followed by metallization by palladium acetate solution. Palladium nanowire arrays have been found to grow directly between microelectrodes without any template, under an alternating electric field of relatively high intensity and frequency. The wires grew spontaneously along the direction of the electric field and have high uniformity and conductivity. Single 75 nm-diameter palladium nanowires have also been self-assembled from aqueous solution at predefined locations between 15 mum-gap electrodes built on a SiO2 substrate. Nanowire assembly was initiated by application an electric field, and it occurred only along the direction of field lines where the field is strongest. Related metals did not support single nanowire assembly under comparable conditions. Current-limiting circuits for controlled nanowire synthesis, electric field simulation, and growth mechanism were studied. The simple and straightforward approach to nanowire assembly outlined here

  6. Polymer lasers assembled by suspending membranes on a distributed feedback grating.

    PubMed

    Zhai, Tianrui; Tong, Fei; Wang, Yonglu; Wu, Xiaofeng; Li, Songtao; Wang, Meng; Zhang, Xinping

    2016-09-19

    Polymer lasers are fabricated by an assembly method. A polymer membrane is directly attached on the one- or two- dimensional grating. The suspended membrane acts as an active waveguide, which is supported by the grating ridge, leaving air gaps in the grating valley. Most of the radiation is effectively confined within the active waveguide due to the strong reflection at the membrane/air interfaces. So, low threshold lasing can be achieved when the sample is optically pumped. This fabrication method provides an alternative to investigate low-threshold polymer lasers. PMID:27661937

  7. Fabrication of hybrid ultraviolet photodetector using organic polymer thin-film-coated TiO2 nanowires

    NASA Astrophysics Data System (ADS)

    Saha, Saptadip; Das, Priyanath; Chakraborty, Ajoy Kumar; Sarkar, Sharmistha; Debbarma, Ruchira

    2016-04-01

    Poly (methyl methacrylate) (PMMA) thin film (TF) was employed on TiO2 nanowires (NWs) to fabricate organic-inorganic hybrid UV photodetector (PD), and its properties were studied and compared with bare TiO2 NW-based PD. A maximum photoresponsivity of 20×10-3 A/W and a maximum external quantum efficiency of ˜3.15% were observed in the UV region at 370 nm (˜3.35 eV). Enhanced photon absorption was observed in the hybrid detector. The TF of PMMA, which is a π-conjugated polymer, increased the carrier lifetime and reduced recombination rate. The PMMA TF:TiO2 NWs hybrid UV detector shows excellent rectification, and light current/dark current ratio was measured to be ˜1.46 times in comparison to bare TiO2 NWs photodetector in the reverse bias condition from -1 to -10 V.

  8. 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. PMID:24533638

  9. Highly Ordered Single Crystalline Nanowire Array Assembled Three-Dimensional Nb3O7(OH) and Nb2O5 Superstructures for Energy Storage and Conversion Applications.

    PubMed

    Zhang, Haimin; Wang, Yun; Liu, Porun; Chou, Shu Lei; Wang, Jia Zhao; Liu, Hongwei; Wang, Guozhong; Zhao, Huijun

    2016-01-26

    Three-dimensional (3D) metal oxide superstructures have demonstrated great potentials for structure-dependent energy storage and conversion applications. Here, we reported a facile hydrothermal method for direct growth of highly ordered single crystalline nanowire array assembled 3D orthorhombic Nb3O7(OH) superstructures and their subsequent thermal transformation into monoclinic Nb2O5 with well preserved 3D nanowire superstructures. The performance of resultant 3D Nb3O7(OH) and Nb2O5 superstructures differed remarkably when used for energy conversion and storage applications. The thermally converted Nb2O5 superstructures as anode material of lithium-ion batteries (LiBs) showed higher capacity and excellent cycling stability compared to the Nb3O7(OH) superstructures, while directly hydrothermal grown Nb3O7(OH) nanowire superstructure film on FTO substrate as photoanode of dye-sensitized solar cells (DSSCs) without the need for further calcination exhibited an overall light conversion efficiency of 6.38%, higher than that (5.87%) of DSSCs made from the thermally converted Nb2O5 film. The high energy application performance of the niobium-based nanowire superstructures with different chemical compositions can be attributed to their large surface area, superior electron transport property, and high light utilization efficiency resulting from a 3D superstructure, high crystallinity, and large sizes. The formation process of 3D nanowire superstructures before and after thermal treatment was investigated and discussed based on our theoretical and experimental results. PMID:26579783

  10. 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

  11. 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.

  12. Sensitive pseudobienzyme electrocatalytic DNA biosensor for mercury(II) ion by using the autonomously assembled hemin/G-quadruplex DNAzyme nanowires for signal amplification.

    PubMed

    Yuan, Yali; Gao, Min; Liu, Guangpeng; Chai, Yaqin; Wei, Shiqing; Yuan, Ruo

    2014-02-01

    Herein, a novel sensitive pseudobienzyme electrocatalytic DNA biosensor was proposed for mercury ion (Hg(2+)) detection by using autonomously assembled hemin/G-quadruplex DNAzyme nanowires for signal amplification. Thiol functionalized capture DNA was firstly immobilized on a nano-Au modified glass carbon electrode (GCE). In presence of Hg(2+), the specific coordination between Hg(2+) and T could result in the assembly of primer DNA on the electrode, which successfully triggered the HCR to form the hemin/G-quadruplex DNAzyme nanowires with substantial redox probe thionine (Thi). In the electrolyte of PBS containing NADH, the hemin/G-quadruplex nanowires firstly acted as an NADH oxidase to assist the concomitant formation of H2O2 in the presence of dissolved O2. Then, with the redox probe Thi as electron mediator, the hemin/G-quadruplex nanowires acted as an HRP-mimicking DNAzyme that quickly bioelectrocatalyzed the reduction of produced H2O2, which finally led to a dramatically amplified electrochemical signal. This method has demonstrated a high sensitivity of Hg(2+) detection with the dynamic concentration range spanning from 1.0 ng L(-1) to 10 mg L(-1) Hg(2+) and a detection limit of 0.5 ng L(-1) (2.5 pM) at the 3Sblank level, and it also demonstrated excellent selectivity against other interferential metal ions.

  13. Assembly of optical fibers for the connection of polymer-based waveguide

    NASA Astrophysics Data System (ADS)

    Ansel, Yannick; Grau, Daniel; Holzki, Markus; Kraus, Silvio; Neumann, Frank; Reinhard, Carsten; Schmitz, Felix

    2003-03-01

    This paper describes the realization of polymer-based optical structures and the assembly and packaging strategy to connect optical fiber ribbons to the waveguides. For that a low cost fabrication process using the SU-8TM thick photo-resist is presented. This process consists in the deposition of two photo-structurized resist layers filled up with epoxy glue realising the core waveguide. For the assembly, a new modular vacuum gripper was realised and installed on an automatic pick and place assembly robot to mount precisely and efficiently the optical fibers in the optical structures. First results have shown acceptable optical propagation loss for the complete test structure.

  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. 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.

  16. Self-assembly in a polymer matrix and its impact on phase separation.

    PubMed

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

    2009-03-26

    Molecular self-assembly often occurs in the presence of long chain polymers, and we develop a theory to describe the competition between self-assembly and phase separation that generally occurs in these complex fluid mixtures. The theory includes a description of the particularly interesting situation where the associating "monomeric" species form high molecular mass polymeric structures and where the assembly process transforms the phase boundary from a form typical of a polymer solution to one that more resembles a polymer blend. We consider both self-assembly upon cooling and upon heating, but the van der Waals interactions are chosen so that phase separation occurs only upon cooling in the absence of association. Systems that associate upon heating prove to be particularly rich, and closed loop and ordinary (upper solution critical) phase boundaries are found to coexist over a wide range of interaction parameter values. Each critical temperature in the limit of a large polymerization index for the matrix polymers approaches its respective theta temperature. The calculations elucidate basic physical principles governing the phase behavior of these complex mixtures.

  17. A pillar[5]arene-fused cryptand: from orthogonal self-assembly to supramolecular polymer.

    PubMed

    Wang, Qi; Cheng, Ming; Zhao, Yue; Wu, Lin; Jiang, Juli; Wang, Leyong; Pan, Yi

    2015-02-28

    A pillar[5]arene-fused cryptand with two different cavities was synthesized successfully. It was found that the novel tricyclic host could associate with two different guest species in an orthogonal manner. And based on this orthogonal self-assembly of two host-guest interactions, a novel type of supramolecular polymer was constructed easily and conveniently. PMID:25636005

  18. 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.

  19. Halogen-bonded mesogens direct polymer self-assemblies up to millimetre length scale

    PubMed Central

    Houbenov, Nikolay; Milani, Roberto; Poutanen, Mikko; Haataja, Johannes; Dichiarante, Valentina; Sainio, Jani; Ruokolainen, Janne; Resnati, Giuseppe; Metrangolo, Pierangelo; Ikkala, Olli

    2014-01-01

    Aligning polymeric nanostructures up to macroscale in facile ways remains a challenge in materials science and technology. Here we show polymeric self-assemblies where nanoscale organization guides the macroscopic alignment up to millimetre scale. The concept is shown by halogen bonding mesogenic 1-iodoperfluoroalkanes to a star-shaped ethyleneglycol-based polymer, having chloride end-groups. The mesogens segregate and stack parallel into aligned domains. This leads to layers at ~10 nm periodicity. Combination of directionality of halogen bonding, mesogen parallel stacking and minimization of interfacial curvature translates into an overall alignment in bulk and films up to millimetre scale. Upon heating, novel supramolecular halogen-bonded polymeric liquid crystallinity is also shown. As many polymers present sites capable of receiving halogen bonding, we suggest generic potential of this strategy for aligning polymer self-assemblies. PMID:24893843

  20. 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.

  1. Electrochemically Directed Self-Assembly and Conjugated Polymer Semiconductors for Organic Electronic Applications

    NASA Astrophysics Data System (ADS)

    Pillai, Rajesh Gopalakrishna

    2011-07-01

    The research work presented in this thesis investigates the mechanistic details of conventional as well as electrochemically directed self-assembly of alkylthiosulfates and explores the use of conjugated semiconducting polymers for organic electronic applications. Here, the significance of the use of conjugated polymers is twofold; first, to explore their applications in nanoelectronics and second, the possibility of using them as a top contact on the self-assembled monolayers (SAMs) for molecular electronic applications. Throughout this work, deposition of the organic materials was performed on prefabricated device structures that required no further lithographic or metal deposition steps after modification of the electrodes with the organic molecules. Self-assembly of alkylthiosulfates on gold are reported to form monolayers identical to those formed from the corresponding alkanethiols. However, these self-assembly processes follow more complex mechanisms of monolayer formation than originally recognized. Studies on the mechanism of alkylthiosulfate chemisorption on gold shows that the self-assembly process is influenced by electrolyte and solvent. Plausible mechanisms have been proposed for the role of trace water in the solvent on conventional as well as electrochemically assisted self-assembly of alkylthiosulfates on gold. Electroanalytical and spectroscopic techniques have been used to explore the mechanistic details of electrochemically directed self-assembly of alkylthiosulfates on gold. It has been found that the self-assembly process is dynamic under electrochemical conditions and the heterogeneous electron transfer process between the organosulfur compound and gold is mediated through gold surface oxide and accompanied by corrosion. Conducting polymers are serious candidates for organic electronic applications since their properties can be controlled by the manipulation of molecular architecture. Unique electronic properties of conjugated polypyrrole

  2. High Modulus Silicates/poly L-Lactic Acid) Based Polymers Assemblies for Potential Applications in Tissue Engineering

    NASA Astrophysics Data System (ADS)

    Ma, Hui; Xu, Ronghua; Xu, Hong; Zhang, Linping; Zhong, Yi; Jiang, Qiuran; Yang, Yiqi; Mao, Zhiping

    2013-08-01

    In this paper, silicates/poly (l-lactic acid)-co-bisphenol A epoxy resin assemblies with high modulus were developed by in situ polymerization of l-lactic acid and surface-modified lamellar vermiculites for potential applications in tissue engineering. These assemblies represented advances in the mechanical properties that can be hardly obtained in other assemblies formed via physical interactions. The covalent grafting of the PLLA based polymers onto the vermiculites surface was confirmed by X-ray photon spectroscopy. The elastic moduli of the assemblies measured by an atomic force microscope were around 7 GPa, and higher than the elastic moduli of the pure polymer (3.2 GPa) and unmodified vermiculites (1.5 GPa), respectively. Images demonstrated that cells proliferated and reached confluence on both the assemblies and pure polymer materials, which indicated that the assemblies exhibited the similar cytocompatibility with pure polymer. With the addition of 5 wt.% assemblies, the polymer and assemblies blended-composites exhibited a 118% improvement in compressive strength and 117% improvement in modulus compared with pure polymer. The present work demonstrated a strategy for the assembly of biomacromolecules and inorganic layers and fabrication of biomaterials high in modulus for tissue engineering applications.

  3. 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.

  4. 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

    2013-06-01

    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.

  5. Synthesis of Discrete Alkyl-Silica Hybrid Nanowires and Their Assembly into Nanostructured Superhydrophobic Membranes.

    PubMed

    Yi, Deliang; Xu, Chenglong; Tang, Ruidie; Zhang, Xuehua; Caruso, Frank; Wang, Yajun

    2016-07-11

    We report the synthesis of highly flexible and mechanically robust hybrid silica nanowires (NWs) which can be used as novel building blocks to construct superhydrophobic functional materials with three-dimensional macroporous networks. The hybrid silica NWs, with an average diameter of 80 nm and tunable length of up to 12 μm, are prepared by anisotropic deposition of the hydrolyzed tetraethylorthosilicate in water/n-pentanol emulsions. A mechanistic investigation reveals that the trimethoxy(octadecyl)silane introduced to the water-oil interface in the synthesis plays key roles in stabilizing the water droplets to sub-100 nm and also growing a layer of octadecyl groups on the NW surface. This work opens a solution-based route for the one-pot preparation of monodisperse, hydrophobic silica NWs and represents an important step toward the bottom-up construction of 3D superhydrophobic materials and macroporous membranes. PMID:27278242

  6. Assessment of Polarity in GaN Self-Assembled Nanowires by Electrical Force Microscopy.

    PubMed

    Minj, A; Cros, A; Garro, N; Colchero, J; Auzelle, T; Daudin, B

    2015-10-14

    In this work, we demonstrate the capabilities of atomic force microscopies (AFMs) for the nondestructive determination of the polarity of GaN nanowires (NWs). Three complementary AFMs are analyzed here: Kelvin probe force microscopy (KPFM), light-assisted KPFM, and piezo-force microscopy (PFM). These techniques allow us to assess the polarity of individual NWs over an area of tens of μm(2) and provide statistics on the polarity of the ensemble with an accuracy hardly reachable by other methods. The precise quantitative analysis of the tip-sample interaction by multidimensional spectroscopic measurements, combined with advanced data analysis, has allowed the separate characterization of electrostatic and van der Waals forces as a function of tip-sample distance. Besides their polarity, the net surface charge density of individual NWs was estimated.

  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. Synthesis of Discrete Alkyl-Silica Hybrid Nanowires and Their Assembly into Nanostructured Superhydrophobic Membranes.

    PubMed

    Yi, Deliang; Xu, Chenglong; Tang, Ruidie; Zhang, Xuehua; Caruso, Frank; Wang, Yajun

    2016-07-11

    We report the synthesis of highly flexible and mechanically robust hybrid silica nanowires (NWs) which can be used as novel building blocks to construct superhydrophobic functional materials with three-dimensional macroporous networks. The hybrid silica NWs, with an average diameter of 80 nm and tunable length of up to 12 μm, are prepared by anisotropic deposition of the hydrolyzed tetraethylorthosilicate in water/n-pentanol emulsions. A mechanistic investigation reveals that the trimethoxy(octadecyl)silane introduced to the water-oil interface in the synthesis plays key roles in stabilizing the water droplets to sub-100 nm and also growing a layer of octadecyl groups on the NW surface. This work opens a solution-based route for the one-pot preparation of monodisperse, hydrophobic silica NWs and represents an important step toward the bottom-up construction of 3D superhydrophobic materials and macroporous membranes.

  9. 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.

  10. 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.

  11. Microbial nanowires for bioenergy applications.

    PubMed

    Malvankar, Nikhil S; Lovley, Derek R

    2014-06-01

    Microbial nanowires are electrically conductive filaments that facilitate long-range extracellular electron transfer. The model for electron transport along Shewanella oneidensis nanowires is electron hopping/tunneling between cytochromes adorning the filaments. Geobacter sulfurreducens nanowires are comprised of pili that have metal-like conductivity attributed to overlapping pi-pi orbitals of aromatic amino acids. The nanowires of Geobacter species have been implicated in direct interspecies electron transfer (DIET), which may be an important mode of syntrophy in the conversion of organic wastes to methane. Nanowire networks confer conductivity to Geobacter biofilms converting organic compounds to electricity in microbial fuel cells (MFCs) and increasing nanowire production is the only genetic manipulation shown to yield strains with improved current-producing capabilities. Introducing nanowires, or nanowire mimetics, might improve other bioenergy strategies that rely on extracellular electron exchange, such as microbial electrosynthesis. Similarities between microbial nanowires and synthetic conducting polymers suggest additional energy-related applications.

  12. 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

  13. The nature of protein interactions governing globular protein-polymer block copolymer self-assembly.

    PubMed

    Lam, Christopher N; Kim, Minkyu; Thomas, Carla S; Chang, Dongsook; Sanoja, Gabriel E; Okwara, Chimdimma U; Olsen, Bradley D

    2014-04-14

    The effects of protein surface potential on the self-assembly of protein-polymer block copolymers are investigated in globular proteins with controlled shape through two approaches: comparison of self-assembly of mCherry-poly(N-isopropylacrylamide) (PNIPAM) bioconjugates with structurally homologous enhanced green fluorescent protein (EGFP)-PNIPAM bioconjugates, and mutants of mCherry with altered electrostatic patchiness. Despite large changes in amino acid sequence, the temperature-concentration phase diagrams of EGFP-PNIPAM and mCherry-PNIPAM conjugates have similar phase transition concentrations. Both materials form identical phases at two different coil fractions below the PNIPAM thermal transition temperature and in the bulk. However, at temperatures above the thermoresponsive transition, mCherry conjugates form hexagonal phases at high concentrations while EGFP conjugates form a disordered micellar phase. At lower concentration, mCherry shows a two-phase region while EGFP forms homogeneous disordered micellar structures, reflecting the effect of changes in micellar stability. Conjugates of four mCherry variants with changes to their electrostatic surface patchiness also showed minimal change in phase behavior, suggesting that surface patchiness has only a small effect on the self-assembly process. Measurements of protein/polymer miscibility, second virial coefficients, and zeta potential show that these coarse-grained interactions are similar between mCherry and EGFP, indicating that coarse-grained interactions largely capture the relevant physics for soluble, monomeric globular protein-polymer conjugate self-assembly. PMID:24654888

  14. 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. PMID:26235000

  15. 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.

  16. Amphiphilic invertible polymers: Self-assembly into functional materials driven by environment polarity

    NASA Astrophysics Data System (ADS)

    Hevus, Ivan

    Stimuli-responsive polymers adapt to environmental changes by adjusting their chain conformation in a fast and reversible way. Responsive polymeric materials have already found use in electronics, coatings industry, personal care, and bio-related areas. The current work aims at the development of novel responsive functional polymeric materials by manipulating environment-dependent self-assembly of a new class of responsive macromolecules strategically designed in this study,—amphiphilic invertible polymers (AIPs). Environment-dependent micellization and self-assembly of three different synthesized AIP types based on poly(ethylene glycol) as a hydrophilic fragment and varying hydrophobic constituents was demonstrated in polar and nonpolar solvents, as well as on the surfaces and interfaces. With increasing concentration, AIP micelles self-assemble into invertible micellar assemblies composed of hydrophilic and hydrophobic domains. Polarity-responsive properties of AIPs make invertible micellar assemblies functional in polar and nonpolar media including at interfaces. Thus, invertible micellar assemblies solubilize poorly soluble substances in their interior in polar and nonpolar solvents. In a polar aqueous medium, a novel stimuli-responsive mechanism of drug release based on response of AIP-based drug delivery system to polarity change upon contact with the target cell has been established using invertible micellar assemblies loaded with curcumin, a phytochemical drug. In a nonpolar medium, invertible micellar assemblies were applied simultaneously as nanoreactors and stabilizers for size-controlled synthesis of silver nanoparticles stable in both polar and nonpolar media. The developed amphiphilic nanosilver was subsequently used as seeds to promote anisotropic growth of CdSe semiconductor nanoparticles that have potential in different applications ranging from physics to medicine. Amphiphilic invertible polymers were shown to adsorb on the surface of silica

  17. Importance of capillary forces in the assembly of carbon nanotubes in a polymer colloid lattice.

    PubMed

    Jurewicz, Izabela; Keddie, Joseph L; Dalton, Alan B

    2012-05-29

    We highlight the significance of capillary pressure in the directed assembly of nanorods in ordered arrays of colloidal particles. Specifically, we discuss mechanisms for the assembly of carbon nanotubes at the interstitial sites between latex polymer particles during composite film formation. Our study points to general design rules to be considered to optimize the ordering of nanostructures within such polymer matrices. In particular, gaining an understanding of the role of capillary forces is critical. Using a combination of electron microscopy and atomic force microscopy, we show that the capillary forces acting on the latex particles during the drying process are sufficient to bend carbon nanotubes. The extent of bending depends on the flexural rigidity of the carbon nanotubes and whether or not they are present as bundled ensembles. We also show that in order to achieve long-range ordering of the nanotubes templated by the polymer matrix, it is necessary for the polymer to be sufficiently mobile to ensure that the nanotubes are frozen into the ordered network when the film is formed and the capillary forces are no longer dominant. In our system, the polymer is plasticized by the addition of surfactant, so that it is sufficiently mobile at room temperature. Interestingly, the carbon nanotubes effectively act as localized pressure sensors, and as such, the study agrees well with previous theoretical predictions calculating the magnitude of capillary forces during latex film formation.

  18. Growth of self-assembled copper nanostructure on conducting polymer by electrodeposition

    NASA Astrophysics Data System (ADS)

    Sarkar, D. K.; Zhou, X. J.; Tannous, A.; Louie, M.; Leung, K. T.

    2003-02-01

    In the present work, self-assembled nanostructures of copper are grown by electrodeposition on a thin conducting polymer (polypyrrole) film electropolymerized on a gold electrode. The shapes, sizes and the densities of the nanostructures are found to depend on the thickness of the polypyrrole thin film, which provides an easy means to control the morphology of these nanostructures. In particular, for the same applied potential on the gold electrode, smaller nanocrystals with a higher density are observed on thinner polymer films while bigger nanocrystals at a lower density are found on thicker films.

  19. Ultrasensitive and selective nitrogen dioxide sensor based on self-assembled graphene/polymer composite nanofibers.

    PubMed

    Yuan, Wenjing; Huang, Liang; Zhou, Qinqin; Shi, Gaoquan

    2014-10-01

    Reduced graphene oxide (rGO) sheets were self-assembled onto the surfaces of electrospun polymer nanofibers to form an ultrathin coating. These rGO/polymer composite nanofibers were used to fabricate nitrogen dioxide (NO2) sensor. This sensor can be performed at room temperature, and it exhibited a high sensitivity of 1.03 ppm(-1) with excellent selectivity and good reversibility. Furthermore, the limit of detection was experimentally measured to be as low as 150 ppb, and this value is much lower than the threshold exposure limit proposed by American Conference of Governmental Industrial Hygienists (200 ppb). PMID:25208097

  20. Microwave synthesis of branched silver nanowires and their use as fillers for high thermal conductivity polymer composites

    NASA Astrophysics Data System (ADS)

    Seshadri, Indira; Esquenazi, Gibran L.; Cardinal, Thomas; Borca-Tasciuc, Theodorian; Ramanath, Ganpati

    2016-04-01

    We report a rapid synthesis approach to obtain branched Ag nanowires by microwave-stimulated polyvinylpyrrolidone-directed polyol-reduction of silver nitrate. Microwave exposure results in micrometer-long nanowires passivated with polyvinylpyrrolidone. Cooling the reaction mixture by interrupting microwave exposure promotes nanocrystal nucleation at low-surfactant coverage sites. The nascent nuclei grow into nanowire branches upon further microwave exposure. Dispersions of low fractions of the branched nanowires in polydimethylsiloxane yield up to 60% higher thermal conductivity than that obtained using unbranched nanowire fillers. Our findings should be useful for realizing nanocomposites with tailored thermal transport properties for applications.

  1. 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.

  2. Formation of gold nanoparticle assemblies in responsive polymer brushes

    NASA Astrophysics Data System (ADS)

    Christau, Stephanie; von Klitzing, Regine; Genzer, Jan

    2014-03-01

    The modification of surfaces by means of polymer brushes has become an active area of research during the past few years due to numerous potential applications of such systems in nano- and biotechnology. The structure and conformation of a brush depends on external stimuli such as pH, temperature or solvent type and can be manipulated by varying these attributes. This stimulus-response can be exploited for the development of smart surfaces and for sensor applications. Furthermore, brushes can be used as 3D matrices for immobilization of nanoparticles. In this study, responsive brushes are used as a matrix for the attachment of gold nanoparticles (AuNPs); this hybrid system exhibits intriguing optical properties due to the surface plasmon resonance of the AuNPs. We address the effect of some system parameters such as synthetic procedure, brush thickness, brush grafting density, particle size and particle incubation time on the characteristics of the resultant particle-impregnated brushes. We also discuss the spatial distribution of the AuNPs inside the brush with regard to the particle size, brush density and brush molecular weight.

  3. 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.

  4. 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

    2016-10-01

    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 × 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.

  5. 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

    2016-10-01

    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 × 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. PMID:27578613

  6. Polymer based planar coupling of self-assembled bottle microresonators

    NASA Astrophysics Data System (ADS)

    Grimaldi, I. A.; Berneschi, S.; Testa, G.; Baldini, F.; Nunzi Conti, G.; Bernini, R.

    2014-12-01

    The investigation of a simple and self-assembling method for realizing polymeric micro-bottle resonators is reported. By dispensing precise amounts of SU-8 onto a cleaved optical fiber, employed as mechanical support, bottle microcavities with different shapes and diameters are fabricated. The balancing of surface energy between glass fiber and polymeric microresonator with surface tension of SU-8 confers different shape to these microstructures. Planar single-mode SU-8 based waveguide, realized on polymethylmethacrylate, is chosen for exciting the micro-bottle resonators by evanescent wave. The reliability of the fabrication process and the shape of the bottle microcavities are investigated through optical analysis. We observe whispering gallery modes in these resonant microstructures by a robust coupling with single mode planar waveguides around 1.5 μm wavelength. The resonance spectra of micro-bottle resonators and the spectral characteristics, such as Quality-factor (Q factor) and free spectral range, are evaluated for all the realized microstructures. SU-8 micro-bottle resonators show high Q-factors up to 3.8 × 104 and present a good mechanical stability. These features make these microcavities attractive for sensing and/or lasing applications in a planar platform.

  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. PMID:25760226

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

    DOE PAGESBeta

    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 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

  10. Synthesis, characterization, and multilayer assembly of pH sensitive graphene-polymer nanocomposites.

    PubMed

    Liu, Jingquan; Tao, Lei; Yang, Wenrong; Li, Dan; Boyer, Cyrille; Wuhrer, Richard; Braet, Filip; Davis, Thomas P

    2010-06-15

    pH sensitive graphene-polymer composites have been prepared by the modification of graphene basal planes with pyrene-terminated poly(2-N,N'-(dimethyl amino ethyl acrylate) (PDMAEA) and poly(acrylic acid) (PAA) via pi-pi stacking. The pyrene-terminal PDMAEA and PAA were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization with a pyrene-functional RAFT agent. The graphene-polymer composites were found to demonstrate phase transfer behavior between aqueous and organic media at different pH values. Atomic force microscopy (AFM) analysis revealed that the thicknesses of the graphene-polymer sheets were approximately 3.0 nm when prepared using PDMAEA (M(n): 6800 and PDI: 1.12). The surface coverage of polymer chains on the graphene basal plane was calculated to be 5.3 x 10(-11) mol cm(-2) for PDMAEA and 1.3 x 10(-10) mol cm(-2) for PAA. The graphene-polymer composites were successfully characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and thermogravimetric analysis (TGA). Self-assembly of the two oppositely charged graphene-polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements.

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

    PubMed

    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 decomposition 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. PMID:25428569

  12. Water-Soluble Conjugated Polymers: Self-Assembly and Biosensor Applications

    NASA Astrophysics Data System (ADS)

    Bazan, Guillermo

    2005-03-01

    Homogeneous assays can be designed which take advantage of the optical amplification of conjugated polymers and the self-assembly characteristic of aqueous polyelectrolytes. For example, a ssDNA sequence sensor comprises an aqueous solution containing a cationic water soluble conjugated polymer such as poly(9,9-bis(trimethylammonium)-hexyl)-fluorene phenylene) with a peptide nucleic acid (PNA) labeled with a dye (PNA-C*). Signal transduction is controlled by hybridization of the neutral PNA-C* probe and the negative ssDNA target, resulting in favorable electrostatic interactions between the hybrid complex and the cationic polymer. Distance requirements for Förster energy transfer are thus met only when ssDNA of complementary sequence to the PNA-C* probe is present. Signal amplification by the conjugated polymer provides fluorescein emission >25 times higher than that of the directly excited dye. Transduction by electrostatic interactions followed by energy transfer is a general strategy. Examples involving other biomolecular recognition events, such as DNA/DNA, RNA/protein and RNA/RNA, will also be provided. The mechanism of biosensing will be discussed, with special attention to the varying contributions of hydrophobic and electrostatic forces, polymer conformation, charge density, local concentration of C*s and tailored defect sites for aggregation-induced optical changes. Finally, the water solubility of these conjugated polymers opens possibilities for spin casting onto organic materials, without dissolving the underlying layers. This property is useful for fabricating multilayer organic optoelectronic devices by simple solution techniques.

  13. Three-dimensional triple hierarchy formed by self-assembly of wax crystals on CuO nanowires for nonwettable surfaces.

    PubMed

    Lee, Jun-Young; Pechook, Sasha; Jeon, Deok-Jin; Pokroy, Boaz; Yeo, Jong-Souk

    2014-04-01

    Novel hierarchical surfaces combining paraffin wax crystals and CuO nanowires are presented. We demonstrate a bioinspired hierarchical wax on nanowire (NW) structures having high water and ethylene glycol repellence. In general, vertically grown nanowire arrays can provide a superhydrophobic surface (SHS) due to extremely high surface roughness but cannot repel ethylene glycol. In this paper, C36H74 and C50H102 waxes are thermally evaporated on the surface of CuO NWs, forming highly ordered, three-dimensional (3D) hierarchical structures via self-assembly of wax crystals. These two and three level hierarchical structures provide perfect self-cleaning characteristics, with water contact angles (CAs) exceeding 170°. Furthermore, C36H74 and C50H102 wax crystals assembled perpendicularly to the longitudinal NW axis form a re-entrant (that is, a multivalued surface topography) curvature enabling high repellence to ethylene glycol (EG) with CAs exceeding 160°. We analyze the wettability dependence on wax crystal size and structure for the optimization of nonwettable hierarchical structured surfaces.

  14. 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. PMID:26942835

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

    DOE PAGESBeta

    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. 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

  16. 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.

  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. Self-assembly of nanoparticles in nanometer-thin polymer films

    NASA Astrophysics Data System (ADS)

    Liu, Zhen

    2005-12-01

    Using "soft" materials such as block copolymers to organize self-assembly of nanoparticles into specific, ordered geometries is a promising route to nanostructure fabrication. In the case of block copolymers, which are the materials used in this thesis, the usual attractiveness for creation of nanostructures stems from the nanometer scale structure of their ordered matrices composed of phase-separated microdomains. The characteristic length scale of ordered block copolymer matrices typically lies below the resolution of conventional lithography techniques. Another advantage of block copolymers as a templating tool is that the geometry and periodicity of their structure can be tuned by changing their molecular parameters such as overall length of the block copolymer chain or the relative size of the blocks. This thesis investigates the self-organization of thiol-passivated gold nanoparticles in polymer films with thickness comparable to the particle diameter. Various nanostructures were observed to form, and their fundamental origins were investigated. In most cases, the polymers comprising the films were attached by one end to an underlying surface, in a "polymer brush" motif. Chapter 1 gives an introduction of the work done by other groups on the self-assembly of nanometer components on substrates, especially on using block copolymers as manipulating tools for nanostructure fabrication. Chapter 2 describes experimental methods and sample characterization, such as nanoparticle synthesis, preparation of polymer/nanoparticle composite films and sample characterization with various techniques, including TEM, AFM, SEM, FTIR, and XPS. In Chapter 3, organization of nanoparticles deposited on top of a polymer brush is investigated experimentally. A physical understanding of how the constraint of end-attachment of the polymer chains affects the organization of the nanoparticles and determines the morphology of nanoparticle aggregation (elongated stripes, extensive circular

  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. Molecular junctions of self-assembled monolayers with conducting polymer contacts.

    PubMed

    Neuhausen, Alexander B; Hosseini, Ali; Sulpizio, Joseph A; Chidsey, Christopher E D; Goldhaber-Gordon, David

    2012-11-27

    We present a method to fabricate individually addressable junctions of self-assembled monolayers (SAMs) that builds on previous studies which have shown that soft conductive polymer top contacts virtually eliminate shorts through the SAMs. We demonstrate devices with nanoscale lateral dimensions, representing an order of magnitude reduction in device area, with high yield and relatively low device-to-device variation, improving several features of previous soft contact devices. The devices are formed in pores in an inorganic dielectric layer with features defined by e-beam lithography and dry etching. We replace the aqueous PEDOT:PSS conductive polymer used in prior devices with Aedotron P, a low-viscosity, amphiphilic polymer, allowing incorporation of self-assembled monolayers with either hydrophobic or hydrophilic termination with the same junction geometry and materials. We demonstrate the adaptability of this new design by presenting transport measurements on SAMs composed of alkanethiols with methyl, thiol, carboxyl, and azide terminations. We establish that the observed room-temperature tunnel barrier is primarily a function of monolayer thickness, independent of the terminal group's hydrophilicity. Finally, we investigate the temperature dependence of transport and show that the low-temperature behavior is based on the energy distribution of sites from which carriers can tunnel between the polymer and gold contacts, as described by a model of variable-range hopping transport in a disordered conductor.

  1. Modeling the Assembly of Polymer-Grafted Nanoparticles at Oil-Water Interfaces.

    PubMed

    Yong, Xin

    2015-10-27

    Using dissipative particle dynamics (DPD), I model the interfacial adsorption and self-assembly of polymer-grafted nanoparticles at a planar oil-water interface. The amphiphilic core-shell nanoparticles irreversibly adsorb to the interface and create a monolayer covering the interface. The polymer chains of the adsorbed nanoparticles are significantly deformed by surface tension to conform to the interface. I quantitatively characterize the properties of the particle-laden interface and the structure of the monolayer in detail at different surface coverages. I observe that the monolayer of particles grafted with long polymer chains undergoes an intriguing liquid-crystalline-amorphous phase transition in which the relationship between the monolayer structure and the surface tension/pressure of the interface is elucidated. Moreover, my results indicate that the amorphous state at high surface coverage is induced by the anisotropic distribution of the randomly grafted chains on each particle core, which leads to noncircular in-plane morphology formed under excluded volume effects. These studies provide a fundamental understanding of the interfacial behavior of polymer-grafted nanoparticles for achieving complete control of the adsorption and subsequent self-assembly. PMID:26439456

  2. Molecular junctions of self-assembled monolayers with conducting polymer contacts.

    PubMed

    Neuhausen, Alexander B; Hosseini, Ali; Sulpizio, Joseph A; Chidsey, Christopher E D; Goldhaber-Gordon, David

    2012-11-27

    We present a method to fabricate individually addressable junctions of self-assembled monolayers (SAMs) that builds on previous studies which have shown that soft conductive polymer top contacts virtually eliminate shorts through the SAMs. We demonstrate devices with nanoscale lateral dimensions, representing an order of magnitude reduction in device area, with high yield and relatively low device-to-device variation, improving several features of previous soft contact devices. The devices are formed in pores in an inorganic dielectric layer with features defined by e-beam lithography and dry etching. We replace the aqueous PEDOT:PSS conductive polymer used in prior devices with Aedotron P, a low-viscosity, amphiphilic polymer, allowing incorporation of self-assembled monolayers with either hydrophobic or hydrophilic termination with the same junction geometry and materials. We demonstrate the adaptability of this new design by presenting transport measurements on SAMs composed of alkanethiols with methyl, thiol, carboxyl, and azide terminations. We establish that the observed room-temperature tunnel barrier is primarily a function of monolayer thickness, independent of the terminal group's hydrophilicity. Finally, we investigate the temperature dependence of transport and show that the low-temperature behavior is based on the energy distribution of sites from which carriers can tunnel between the polymer and gold contacts, as described by a model of variable-range hopping transport in a disordered conductor. PMID:23035989

  3. 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

    2016-08-01

    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. PMID:27410517

  4. Supramolecular self-assembly of amphiphilic hyperbranched polymers at all scales and dimensions: progress, characteristics and perspectives.

    PubMed

    Zhou, Yongfeng; Yan, Deyue

    2009-03-14

    This feature article describes the supramolecular self-assembly of hyperbranched polymers (HBPs), including the progress, unique characteristics and future perspectives. HBPs are irregular in molecular structure compared with that of linear block copolymers and dendrimers. However, similar to these well-defined polymer tectons, HBPs have displayed great potential to be excellent precursors in solution self-assembly, interfacial self-assembly and hybrid self-assembly. Many impressive supramolecular aggregates and hybrids at all scales and dimensions, such as macroscopic tubes, micro- or nano-vesicles, fibers, spherical micelles and honeycomb films, have been generated. In addition, HBPs also demonstrate unique characteristics or advantages in supramolecular self-assembly behaviours, including controllable morphologies and structures, special properties, characteristic self-assembly mechanism and facile functionalization process. Although still being at the early stage, self-assembly of HBPs has provided a new avenue for the development of supramolecular chemistry.

  5. Silicon Nanowire Devices

    NASA Astrophysics Data System (ADS)

    Kamins, Theodore

    2006-03-01

    Metal-catalyzed, self-assembled, one-dimensional semiconductor nanowires are being considered as possible device elements to augment and supplant conventional electronics and to extend the use of CMOS beyond the physical and economic limits of conventional technology. Such nanowires can create nanostructures without the complexity and cost of extremely fine scale lithography. The well-known and controllable properties of silicon make silicon nanowires especially attractive. Easy integration with conventional electronics will aid their acceptance and incorporation. For example, connections can be formed to both ends of a nanowire by growing it laterally from a vertical surface formed by etching the top silicon layer of a silicon-on-insulator structure into isolated electrodes. Field-effect structures are one class of devices that can be readily built in silicon nanowires. Because the ratio of surface to volume in a thin nanowire is high, conduction through the nanowire is very sensitive to surface conditions, making it effective as the channel of a field-effect transistor or as the transducing element of a gas or chemical sensor. As the nanowire diameter decreases, a greater fraction of the mobile charge can be modulated by a given external charge, increasing the sensitivity. Having the gate of a nanowire transistor completely surround the nanowire also enhances the sensitivity. For a field-effect sensor to be effective, the charge must be physically close to the nanowire so that the majority of the compensating charge is induced in the nanowire and so that ions in solution do not screen the charge. Because only induced charge is being sensed, a coating that selectively binds the target species should be added to the nanowire surface to distinguish between different species in the analyte. The nanowire work at Hewlett-Packard Laboratories was supported in part by the Defense Advanced Research Projects Agency.

  6. Self-Assembling of Polymer-Enzyme Conjugates at Oil/water Interfaces

    NASA Astrophysics Data System (ADS)

    Zhang Newby, Bi-Min

    2005-03-01

    Interface-binding enzymes are desirable for biphasic reactions in that they offer simultaneous access to substrates dissolved in both phases across the interface. It has been shown that conjugating water-soluble enzymes with hydrophobic polymers facilitated the assembling of enzymes at oil/water interfaces. In this work, the interfacial assembling of alpha-chymotrypsin conjugated with polystyrene, poly(methyl methacrylate) and poly(L-latic acid) was examined using the pendant drop method. The interface-assembling process of the conjugates from the organic phase followed a similar pattern of that of native alpha-chymotrypsin from the aqueous buffer phase, i.e., the interfacial tension decreased gradually with time. However, when the conjugates were dispersed in the form of particulates in the aqueous phase, in which the conjugate was insoluble, the assembling occurred faster and the interfacial tension approached zero quickly. It was suspected that the assembling in this case involved two steps, i.e. the adsorption of the particulates and the subsequent rearrangement, dissociation and re-dispersion of the conjugates at the interface. The effect of other factors including the polarity of organic solvent, pH value and ionic strength of the aqueous phase was evaluated. It was found that the polar solvent slightly facilitated the assembling, whereas pH and ionic strength showed minimal effects.

  7. Self-Assembly of Differently Shaped Protein-Polymer Conjugates through Modification of the Bioconjugation Site.

    PubMed

    Huang, Aaron; Olsen, Bradley D

    2016-08-01

    Self-assembly of protein-polymer block copolymers is an attractive route for preparing biocatalytic materials. To clarify the effect of bioconjugate shape on self-assembly without changing the chemical details of either block, four different conjugation sites are selected on the surface of the model globular protein mCherry at residues 3, 108, 131, and 222 to alter the colloidal shape of the bioconjugate. All four mCherry-b-poly(N-isopropylacrylamide) bioconjugates show qualitatively similar phase diagrams, indicating that self-assembly is robust with respect to changes in conjugation site. However, protein orientation has an effect on the location of the order-disorder transition concentration, and the stability of the disordered micellar phase is shown to be different for each conjugate. Differences in domain spacing also suggest changes in protein orientation within the lamellae.

  8. Self-assembly of novel lipid-mimicking brush polymers in nanoscale thin films.

    PubMed

    Jung, Jungwoon; Kim, Heesoo; Ree, Moonhor

    2014-02-01

    A series of well-defined poly(oxy(11-phosphorylcholineundecylthiomethyl)ethylene-ran-oxy(n-dodecylthiomethyl)ethylene) (PECH-PCm: m = 0-100 mol% phosphorylcholine (PC)) polymers were used to prepare nanoscale thin films that were characterized by synchrotron X-ray reflectivity (XR) analysis. The quantitative XR analysis provided structural insights into the PECH-PCm thin films. The PECH-PC0 polymer film formed a well-ordered in-plane oriented molecular multibilayer structure, whose individual layers consisted of two sublayers. One sublayer was composed of the fully extended backbones and inner part of the bristles, exhibiting a relatively low electron density, whereas the other sublayer was composed of a bilayer of the outer parts of the bristles without interdigitation. The PECH-PC100 polymer film also formed a well-ordered in-plane oriented molecular multibilayer structure, the individual layers of which were composed of four sublayers rather than two. The bristles in the layer were interdigitated in part via the zwitterionic interactions of the PC end groups. Surprisingly, regardless of the copolymer composition, the PECH-PCm random copolymer molecules in the thin films self-assembled to form a multilayered structure that resembled the structure formed by the PECH-PC100 polymer. These properties have not been observed in other conventional random brush copolymer films. The remarkable multibilayer structures originated from the zwitterionic PC end groups and their favorable interactions and interdigitated structures, which overcame any negative contributions caused by the heterogeneity of the bristles. The unique self-assembly properties of the PECH-PCm polymers always provide a PC-rich surface. The PECH-PCm random copolymers successfully mimicked the molecular bilayer structures formed by natural lipids. PMID:24838200

  9. 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.

  10. 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.

  11. The Nitrosopumilus maritimus CdvB, but Not FtsZ, Assembles into Polymers

    PubMed Central

    Ng, Kian-Hong; Srinivas, Vinayaka; Srinivasan, Ramanujam; Balasubramanian, Mohan

    2013-01-01

    Euryarchaeota and Crenarchaeota are two major phyla of archaea which use distinct molecular apparatuses for cell division. Euryarchaea make use of the tubulin-related protein FtsZ, while Crenarchaea, which appear to lack functional FtsZ, employ the Cdv (cell division) components to divide. Ammonia oxidizing archaeon (AOA) Nitrosopumilus maritimus belongs to another archaeal phylum, the Thaumarchaeota, which has both FtsZ and Cdv genes in the genome. Here, we used a heterologous expression system to characterize FtsZ and Cdv proteins from N. maritimus by investigating the ability of these proteins to form polymers. We show that one of the Cdv proteins in N. maritimus, the CdvB (Nmar_0816), is capable of forming stable polymers when expressed in fission yeast. The N. maritimus CdvB is also capable of assembling into filaments in mammalian cells. However, N. maritimus FtsZ does not assemble into polymers in our system. The ability of CdvB, but not FtsZ, to polymerize is consistent with a recent finding showing that several Cdv proteins, but not FtsZ, localize to the mid-cell site in the dividing N. maritimus. Thus, we propose that it is Cdv proteins, rather than FtsZ, that function as the cell division apparatus in N. maritimus. PMID:23818813

  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. 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. PMID:27455678

  14. Growth of hydrophilic CuS nanowires via DNA-mediated self-assembly process and their use in fabricating smart hybrid films for adjustable chemical release.

    PubMed

    Zhou, Li; Li, Wei; Chen, Zhaowei; Ju, Enguo; Ren, Jinsong; Qu, Xiaogang

    2015-02-01

    Facile growth of CuS nanowires through self-assembly and their application as building blocks for near-infrared light-responsive functional films have been demonstrated. It is found that DNA is a key factor in preparing the CuS material with defined nanostructure. An exclusive oriented self-aggregate growth mechanism is proposed for the growth of the nanowires, which might have important implications for preparing advanced, sophisticated nanostructures based on DNA nanotechnology. By employing the hydrophilic CuS nanowire as an optical absorber and thermosensitive nanogel as guest reservoir inside alginate film, a new platform for the release of functional molecules has been set up. In vitro studies have shown that the hybrid film possesses excellent biocompatibility and the release rate of chemical molecules from the film could be controlled with high spatial and temporal precision. Our novel approach and the resulting outstanding combination of properties may advance both the fields of DNA nanotechnology and light-responsive devices. PMID:25504567

  15. 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.

  16. General strategy for self-assembly of highly oriented nanocrystalline semiconducting polymers with high mobility.

    PubMed

    Luo, Chan; Kyaw, Aung Ko Ko; Perez, Louis A; Patel, Shrayesh; Wang, Ming; Grimm, Bruno; Bazan, Guillermo C; Kramer, Edward J; Heeger, Alan J

    2014-05-14

    Solution processable semiconducting polymers with excellent film forming capacity and mechanical flexibility are considered among the most progressive alternatives to conventional inorganic semiconductors. However, the random packing of polymer chains and the disorder of the polymer matrix typically result in low charge transport mobilities (10(-5)-10(-2) cm(2) V(-1) s(-1)). These low mobilities compromise their performance and development. Here, we present a strategy, by utilizing capillary action, to mediate polymer chain self-assembly and unidirectional alignment on nanogrooved substrates. We designed a sandwich tunnel system separated by functionalized glass spacers to induce capillary action for controlling the polymer nanostructure, crystallinity, and charge transport. Using capillary action, we demonstrate saturation mobilities with average values of 21.3 and 18.5 cm(2) V(-1 )s(-1) on two different semiconducting polymers at a transistor channel length of 80 μm. These values are limited by the source-drain contact resistance, Rc. Using a longer channel length of 140 μm where the contact resistance is less important, we measured μh = 36.3 cm(2) v(-1) s(-1). Extrapolating to infinite channel length where Rc is unimportant, the intrinsic mobility for poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]thiadiazolo[3,4-c]pyridine] (Mn = 140 kDa) at this degree of chain alignment and structural order is μh ≈ 47 cm(2 )v(-1) s(-1). Our results create a promising pathway toward high performance, solution processable, and low-cost organic electronics. PMID:24712578

  17. 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.

  18. Observation of the Chiral and Achiral Hexatic Phases of Self-assembled Micellar polymers.

    PubMed

    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

  19. Single-step assembly of polymer-lipid hybrid nanoparticles for mitomycin C delivery

    PubMed Central

    2014-01-01

    Mitomycin C is one of the most effective chemotherapeutic agents for a wide spectrum of cancers, but its clinical use is still hindered by the mitomycin C (MMC) delivery systems. In this study, the MMC-loaded polymer-lipid hybrid nanoparticles (NPs) were prepared by a single-step assembly (ACS Nano 2012, 6:4955 to 4965) of MMC-soybean phosphatidyhlcholine (SPC) complex (Mol. Pharmaceutics 2013, 10:90 to 101) and biodegradable polylactic acid (PLA) polymers for intravenous MMC delivery. The advantage of the MMC-SPC complex on the polymer-lipid hybrid NPs was that MMC-SPC was used as a structural element to offer the integrity of the hybrid NPs, served as a drug preparation to increase the effectiveness and safety and control the release of MMC, and acted as an emulsifier to facilitate and stabilize the formation. Compared to the PLA NPs/MMC, the PLA NPs/MMC-SPC showed a significant accumulation of MMC in the nuclei as the action site of MMC. The PLA NPs/MMC-SPC also exhibited a significantly higher anticancer effect compared to the PLA NPs/MMC or free MMC injection in vitro and in vivo. These results suggested that the MMC-loaded polymer-lipid hybrid NPs might be useful and efficient drug delivery systems for widening the therapeutic window of MMC and bringing the clinical use of MMC one step closer to reality. PMID:25324707

  20. 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. PMID:22747256

  1. Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

    PubMed

    Hui, Joseph K-H; Kishida, Hiroyuki; Ishiba, Keita; Takemasu, Kenta; Morikawa, Masa-Aki; Kimizuka, Nobuo

    2016-09-26

    A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.

  2. 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

  3. Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

    PubMed

    Hui, Joseph K-H; Kishida, Hiroyuki; Ishiba, Keita; Takemasu, Kenta; Morikawa, Masa-Aki; Kimizuka, Nobuo

    2016-09-26

    A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics. PMID:27527513

  4. Engineering hybrid polymer/metal-oxide interfaces by self-assembled molecular interlayers

    NASA Astrophysics Data System (ADS)

    Mattoni, Alessandro

    2014-03-01

    Hybrid organic heterojunctions are of great technological interest as both optically active layers as well as hole blocking interfaces in organic or hybrid solar cells. Despite the potential of combining processable organic polymers with inorganic components, they have not yet demonstrated high efficiencies. promising approach towards more efficient systems consists in engineering the interface by self-assembled molecular interlayers that can selectively affect the interactions of the donor and acceptor components. a combination of molecular dynamics and electronic structure calculations we study thermodynamic and optoelectronic properties of polymer/metaloxide interfaces in presence of several molecular interlayers such as metal-organic macrocyclic complexes or pyridine derivatives. The theoretical results are tested on specifically designed hybrid solar cells providing evidence of impressive enhancement of interface properties.

  5. Self-assembly of 2D membranes from mixtures of hard rods and depleting polymers().

    PubMed

    Yang, Yasheng; Barry, Edward; Dogic, Zvonimir; Hagan, Michael F

    2012-01-01

    We combine simulations and experiments to elucidate the molecular forces leading to the assembly of two dimensional membrane-like structures composed of a one rod-length thick monolayer of aligned rods from an immiscible suspension of hard rods and depleting polymers. Computer simulations predict that monolayer membranes are thermodynamically stable above a critical rod aspect ratio and below a critical depletion interaction length scale. Outside of these conditions alternative structures such as stacked smectic columns or nematic droplets are thermodynamically stable. These predictions are confirmed by subsequent experiments using a model system of virus rod-like molecules and non-adsorbing polymer. Our work demonstrates that collective molecular protrusion fluctuations alone are sufficient to stabilize membranes composed of homogenous rods with simple excluded volume interactions.

  6. Self-assembly of DNA-polymer complexes using template polymerization.

    PubMed Central

    Trubetskoy, V S; Budker, V G; Hanson, L J; Slattum, P M; Wolff, J A; Hagstrom, J E

    1998-01-01

    The self-assembly of supramolecular complexes of nucleic acids and polymers is of relevance to several biological processes including viral and chromatin formation as well as gene therapy vector design. We now show that template polymerization facilitates condensation of DNA into particles that are <150 nm in diameter. Inclusion of a poly(ethylene glycol)-containing monomer prevents aggregation of these particles. The DNA within the particles remains biologically active and can express foreign genes in cells. The formation or breakage of covalent bonds has until now not been employed to compact DNA into artificial particles. PMID:9722638

  7. Self-assembly of DNA-polymer complexes using template polymerization.

    PubMed

    Trubetskoy, V S; Budker, V G; Hanson, L J; Slattum, P M; Wolff, J A; Hagstrom, J E

    1998-09-15

    The self-assembly of supramolecular complexes of nucleic acids and polymers is of relevance to several biological processes including viral and chromatin formation as well as gene therapy vector design. We now show that template polymerization facilitates condensation of DNA into particles that are <150 nm in diameter. Inclusion of a poly(ethylene glycol)-containing monomer prevents aggregation of these particles. The DNA within the particles remains biologically active and can express foreign genes in cells. The formation or breakage of covalent bonds has until now not been employed to compact DNA into artificial particles.

  8. 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.

  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

    2012-12-01

    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. Polymer surface interacts with calcium in aqueous media to induce stem cell assembly.

    PubMed

    Hung, Kun-Che; Hsu, Shan-Hui

    2015-10-28

    Bioinspired surface with functional group rearrangement abilities are highly desirable for designing functional materials. Calcium ion (Ca(2+) ) is a pivotal life element and the ion transport is tightly regulated through calcium channels. It is demonstrated here that Ca(2+) can be transported by polymer surface to induce cell assembly. A series of polyurethane materials is synthesized with different abilities to rearrange the surface functional groups in response to aqueous environment. It is observed that surface recruitment of carboxyl and amino groups from the bulk material can interact with Ca(2+) and facilitate its translocation from aqueous media into cells. The surface rearrangement of functional group triggers the calcium trafficking and turns on signals involving cell merging and assembly. This observation provides an insight on adjusting material-calcium interaction to design nature-inspired smart interfaces to induce cell organization and tissue regeneration.

  11. 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

  12. 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.

  13. Lithographic stress control for the self-assembly of polymer MEMS structures

    NASA Astrophysics Data System (ADS)

    Lee, S.-W.; Sameoto, D.; Mahanfar, A.; Parameswaran, M.

    2008-07-01

    We present a novel self-assembly mechanism to produce an assortment of predetermined three-dimensional micromechanical structures in polymer MEMS technology using lithographically defined areas of stress and mechanical reinforcement within a single structural material. This self-assembly technology is based on the tensile stress that arises during the cross-linking of the negative tone, epoxy-based photoresist SU-8. Two different thicknesses of SU-8 are used in a single compliant structure. The first SU-8 layer forms the main structural element and the second SU-8 layer determines the aspects of self-assembly. The second SU-8 layer thickness acts to both to create a stress differential within the structure as well as define the direction in which the induced stress will cause the structure to deform. In this manner, both the magnitude and direction of self-assembled structures can be controlled using a single lithographic step. Although this technique uses a single structural material, the basic concept may be adapted for other processes, with different material choices, for a wide variety of applications.

  14. 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).

  15. Performance of dielectric nanocomposites: matrix-free, hairy nanoparticle assemblies and amorphous polymer-nanoparticle blends.

    PubMed

    Grabowski, Christopher A; Koerner, Hilmar; Meth, Jeffrey S; Dang, Alei; Hui, Chin Ming; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Durstock, Michael F; Vaia, Richard A

    2014-12-10

    Demands to increase the stored energy density of electrostatic capacitors have spurred the development of materials with enhanced dielectric breakdown, improved permittivity, and reduced dielectric loss. Polymer nanocomposites (PNCs), consisting of a blend of amorphous polymer and dielectric nanofillers, have been studied intensely to satisfy these goals; however, nanoparticle aggregates, field localization due to dielectric mismatch between particle and matrix, and the poorly understood role of interface compatibilization have challenged progress. To expand the understanding of the inter-relation between these factors and, thus, enable rational optimization of low and high contrast PNC dielectrics, we compare the dielectric performance of matrix-free hairy nanoparticle assemblies (aHNPs) to blended PNCs in the regime of low dielectric contrast to establish how morphology and interface impact energy storage and breakdown across different polymer matrices (polystyrene, PS, and poly(methyl methacrylate), PMMA) and nanoparticle loadings (0-50% (v/v) silica). The findings indicate that the route (aHNP versus blending) to well-dispersed morphology has, at most, a minor impact on breakdown strength trends with nanoparticle volume fraction; the only exception being at intermediate loadings of silica in PMMA (15% (v/v)). Conversely, aHNPs show substantial improvements in reducing dielectric loss and maintaining charge/discharge efficiency. For example, low-frequency dielectric loss (1 Hz-1 kHz) of PS and PMMA aHNP films was essentially unchanged up to a silica content of 50% (v/v), whereas traditional blends showed a monotonically increasing loss with silica loading. Similar benefits are seen via high-field polarization loop measurements where energy storage for ∼15% (v/v) silica loaded PMMA and PS aHNPs were 50% and 200% greater than respective comparable PNC blends. Overall, these findings on low dielectric contrast PNCs clearly point to the performance benefits of

  16. Self-assembly and magnetic properties of MnAs nanowires on GaAs(001) substrate

    SciTech Connect

    Xu, F.; Huang, P. W.; Huang, J. H.; Lee, W. N.; Chin, T. S.; Ku, H. C.; Du, Y. W.

    2010-03-15

    The in-plane aligned MnAs nanowires have been grown by molecular-beam epitaxy on GaAs(001) substrates at high growth temperature ({>=}450 deg. C). A discontinuous growth with break intervals (50 s' interval per 10 s' growth) was employed. The obtained nanowires were identified to be mainly type-B hexagonal MnAs. The influences of growth temperature and As{sub 4}/Mn flux ratio on the nanowires' morphology were investigated. Both high growth temperature and high As{sub 4}/Mn flux ratio are necessary for the growth of uniaxially aligned MnAs nanowires with high aspect ratio. The magnetic anisotropy of the nanowires and their multimodal size distributions contribute to the large coercivity and special shape of the M-H loops along the magnetic easy axis, which is [1102]MnAs||[110]GaAs. However, the longer growth time would lead to the both azimuthal alignments of the MnAs wires and the weakening of the magnetic anisotropy.

  17. 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

  18. 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.

  19. Largely enhanced efficiency in ZnO nanowire/p-polymer hybridized inorganic/organic ultraviolet light-emitting diode by piezo-phototronic effect.

    PubMed

    Yang, Qing; Liu, Ying; Pan, Caofeng; Chen, Jun; Wen, Xiaonan; Wang, Zhong Lin

    2013-02-13

    ZnO nanowire inorganic/organic hybrid ultraviolet (UV) light-emitting diodes (LEDs) have attracted considerable attention as they not only combine the high flexibility of polymers with the structural and chemical stability of inorganic nanostructures but also have a higher light extraction efficiency than thin film structures. However, up to date, the external quantum efficiency of UV LED based on ZnO nanostructures has been limited by a lack of efficient methods to achieve a balance between electron contributed current and hole contributed current that reduces the nonradiative recombination at interface. Here we demonstrate that the piezo-phototronic effect can largely enhance the efficiency of a hybridized inorganic/organic LED made of a ZnO nanowire/p-polymer structure, by trimming the electron current to match the hole current and increasing the localized hole density near the interface through a carrier channel created by piezoelectric polarization charges on the ZnO side. The external efficiency of the hybrid LED was enhanced by at least a factor of 2 after applying a proper strain, reaching 5.92%. This study offers a new concept for increasing organic LED efficiency and has a great potential for a wide variety of high-performance flexible optoelectronic devices.

  20. 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.

  1. 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.

  2. Observation of the Chiral and Achiral Hexatic Phases of Self-assembled Micellar polymers

    NASA Astrophysics Data System (ADS)

    Pal, Antara; Kamal, Md. Arif; Raghunathan, V. A.

    2016-08-01

    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.

  3. 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. PMID:27501117

  4. Kinetically Controlled Nanostructure Formation in Self-Assembled Globular Protein-Polymer Diblock Copolymers

    PubMed Central

    Thomas, Carla S.; Xu, Liza; Olsen, Bradley D.

    2014-01-01

    Aqueous processing of globular protein-polymer diblock copolymers into solid-state materials and subsequent solvent annealing enables kinetic and thermodynamic control of nanostructure formation to produce block copolymer morphologies that maintain a high degree of protein fold and function. Using model diblock copolymers composed of mCherry-b-poly(N-isopropylacrylamide), orthogonal control over solubility of the protein block through changes in pH and the polymer block through changes in temperature is demonstrated during casting and solvent annealing. Hexagonal cylinders, perforated lamellae, lamellae, or hexagonal and disordered micellar phases are observed depending upon the coil fraction of the block copolymer and the kinetic pathway used for self-assembly. Good solvents for the polymer block produce ordered structures reminiscent of coil-coil diblock copolymers, while an unfavorable solvent results in kinetically trapped micellar structures. Decreasing solvent quality for the protein improves long-range ordering, suggesting that the strength of protein interactions influences nanostructure formation. Subsequent solvent annealing results in evolution of the nanostructures, with the best ordering and the highest protein function observed when annealing in a good solvent for both blocks. While protein secondary structure was found to be almost entirely preserved for all processing pathways, UV-vis spectroscopy of solid-state films indicates that using a good solvent for the protein block enables up to 70% of the protein to be retained in its functional form. PMID:22924842

  5. Kinetically controlled nanostructure formation in self-assembled globular protein-polymer diblock copolymers.

    PubMed

    Thomas, Carla S; Xu, Liza; Olsen, Bradley D

    2012-09-10

    Aqueous processing of globular protein-polymer diblock copolymers into solid-state materials and subsequent solvent annealing enables kinetic and thermodynamic control of nanostructure formation to produce block copolymer morphologies that maintain a high degree of protein fold and function. When model diblock copolymers composed of mCherry-b-poly(N-isopropylacrylamide) are used, orthogonal control over solubility of the protein block through changes in pH and the polymer block through changes in temperature is demonstrated during casting and solvent annealing. Hexagonal cylinders, perforated lamellae, lamellae, or hexagonal and disordered micellar phases are observed, depending on the coil fraction of the block copolymer and the kinetic pathway used for self-assembly. Good solvents for the polymer block produce ordered structures reminiscent of coil-coil diblock copolymers, while an unfavorable solvent results in kinetically trapped micellar structures. Decreasing solvent quality for the protein improves long-range ordering, suggesting that the strength of protein interactions influences nanostructure formation. Subsequent solvent annealing results in evolution of the nanostructures, with the best ordering and the highest protein function observed when annealing in a good solvent for both blocks. While protein secondary structure was found to be almost entirely preserved for all processing pathways, UV-vis spectroscopy of solid-state films indicates that using a good solvent for the protein block enables up to 70% of the protein to be retained in its functional form. PMID:22924842

  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. Invertible micellar polymer assemblies for delivery of poorly water-soluble drugs.

    PubMed

    Hevus, Ivan; Modgil, Amit; Daniels, Justin; Kohut, Ananiy; Sun, Chengwen; Stafslien, Shane; Voronov, Andriy

    2012-08-13

    Strategically designed amphiphilic invertible polymers (AIPs) are capable of (i) self-assembling into invertible micellar assemblies (IMAs) in response to changes in polarity of environment, polymer concentration, and structure, (ii) accommodating (solubilizing) substances that are otherwise insoluble in water, and (iii) inverting their molecular conformation in response to changes in the polarity of the local environment. The unique ability of AIPs to invert the molecular conformation depending on the polarity of the environment can be a decisive factor in establishing the novel stimuli-responsive mechanism of solubilized drug release that is induced just in response to a change in the polarity of the environment. The IMA capability to solubilize lipophilic drugs and deliver and release the cargo molecules by conformational inversion of polymer macromolecules in response to a change of the polarity of the environment was demonstrated by loading IMA with a phytochemical drug, curcumin. It was demonstrated that four sets of micellar vehicles based on different AIPs were capable of delivering the curcumin from water to an organic medium (1-octanol) by means of unique mechanism: AIP conformational inversion in response to changing polarity from polar to nonpolar. The IMAs are shown to be nontoxic against human cells up to a concentration of 10 mg/L. On the other hand, the curcumin-loaded IMAs are cytotoxic to breast carcinoma cells at this concentration, which confirms the potential of IMA-based vehicles in controlled delivery of poorly water-soluble drug candidates and release by means of this novel stimuli-responsive mechanism.

  8. Self-assembled lamellar MoS2, SnS2 and SiO2 semiconducting polymer nanocomposites.

    PubMed

    Kirmayer, Saar; Aharon, Eyal; Dovgolevsky, Ekaterina; Kalina, Michael; Frey, Gitti L

    2007-06-15

    Lamellar nanocomposites based on semiconducting polymers incorporated into layered inorganic matrices are prepared by the co-assembly of organic and inorganic precursors. Semiconducting polymer-incorporated silica is prepared by introducing the semiconducting polymers into a tetrahydrofuran (THF)/water homogeneous sol solution containing silica precursor species and a surface-active agent. Semiconducting polymer-incorporated MoS(2) and SnS(2) are prepared by Li intercalation into the inorganic compound, exfoliation and restack in the presence of the semiconducting polymer. All lamellar nanocomposite films are organized in domains aligned parallel to the substrate surface plane. The incorporated polymers maintain their semiconducting properties, as evident from their optical absorption and photoluminescence spectra. The optoelectronic properties of the nanocomposites depend on the properties of both the inorganic host and the incorporated guest polymer as demonstrated by integrating the nanocomposite films into light-emitting diodes. Devices based on polymer-incorporated silica and polymer-incorporated MoS(2) show no diode behaviour and no light emission due to the insulating and metallic properties of the silica and MoS(2) hosts. In contrast, diode performance and electroluminescence are obtained from devices based on semiconducting polymer-incorporated semiconducting SnS(2), demonstrating that judicious selection of the composite components in combination with the optimization of material synthesis conditions allows new hierarchical structures to be tailored for electronic and optoelectronic applications.

  9. Self-Assembly Directed Organization of Nanodiamond During Ionic Liquid Crystalline Polymer Formation.

    PubMed

    Ringstrand, Bryan S; Seifert, Sönke; Podlesak, David W; Firestone, Millicent A

    2016-07-01

    The UV-initiated free radical polymerization of a lyotropic mesophase prepared by co-assembly of an aqueous mixture of an ionic liquid (IL) monomer, 3-decyl-1-vinylimidazolium chloride, in a dimethyl sulfoxide dispersion of an IL-monomer nanodiamond conjugate yields a well-ordered 2D hexagonally structured network-polymer composite. The IL monomer is covalently bound to carboxylated detonation diamond via ester-linked 3-decyl-1-vinylimidazolium bromide. Successful preparation of the amphiphile-functionalized nanodiamond is determined by ATR/FT-IR, thermogravimetric analysis, and small-angle X-ray scattering (SAXS). Mesophase and composite structure are evaluated by SAXS, revealing a columnar architecture composed of amphiphilic ionic liquid cylinders containing solvent-rich cores. Self-assembly directed site localization of the nanodiamond positions the particles in the alkyl chain continuum upon polymerization. The composite reversibly swells in ethanol allowing structural variation and modulation of the nanoparticle internal packing arrangement. This work demonstrates that through careful molecular design, self-organization and site-directed assembly of nanodiamond into chemically distinct regions of a nanostructured organogel can be achieved. PMID:27197942

  10. Self-assembled regular arrays of carbon nanotube and the route toward actuation of shape memory polymer

    NASA Astrophysics Data System (ADS)

    Lu, Haibao; Wu, Chunxia; Liu, Yanju; Gou, Jan; Leng, Jinsong

    2010-04-01

    The synthesis of massive arrays of monodispersed carbon nanotubes that are self-assembled on hydrophilic polycarbonate membrane is reported. This approach involves individual carbon nanotube manufacturing by non-ionic surfactant to aid in dispersion and nanotubes self-assembled for three-dimensional orientation by high press filtration. The inherent capability of carbon nanotube and microstructure of well-packed arrays predominate excellent conductive properties of massive arrays. These potential applications of nanometer-sized sensor, probe and energy resistor have been characterized in this study. Furthermore, the route toward application of self-assembled regular arrays, as heat transmission intermedium, has been carried out by activating shape-memory polymer. The electrical conductivity of insulating polymer is significantly improved by assembled carbon nanotubes, resulting in shape recovery behavior of nanocomposite being driven by electrical resistive heating.

  11. 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.

  12. 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

    2016-05-01

    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. PMID:27067311

  13. 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

  14. 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

  15. Designing Functionalized Nanoparticles for Controlled Assembly in Polymer Matrix: Self consistent PRISM Theory and Monte Carlo simulation Study

    NASA Astrophysics Data System (ADS)

    Jayaraman, Arthi; Nair, Nitish

    2011-03-01

    Significant interest has grown around the ability to create hybrid materials with controlled spatial arrangement of nanoparticles mediated by a polymer matrix. By functionalizing or grafting polymers on to nanoparticle surfaces and systematically tuning the composition, chemistry, molecular weight and grafting density of the grafted polymers one can tailor the inter-particle interactions and control the assembly/dispersion of the particles in the polymer matrix. In our recent work using self-consistent Polymer Reference Interaction Site Model (PRISM) theory- Monte Carlo simulations we have shown that tailoring the monomer sequences in the grafted copolymers provides a novel route to tuning the effective inter-particle interactions between the functionalized nanoparticles in a polymer matrix. In this talk I will present how monomer sequence and molecular weights (with and without polydispersity) of the grafted polymers, compatibility of the graft and matrix polymers, and nanoparticle size affect the chain conformations of the grafted polymers and the potential of mean force between the grafted nanoparticles in the matrix.

  16. Electrochemically Grown Single Nanowire Sensors

    NASA Technical Reports Server (NTRS)

    Yun, Minhee; Lee, Choonsup; Vasquez, Richard P.; Penner, Reginald; Bangar, Mangesh; Mulchandani, Ashok; Myung, Nosang V.

    2004-01-01

    We report a fabrication technique that is potentially capable of producing arrays of individually addressable nanowire sensors with controlled dimensions, positions, alignments, and chemical compositions. The concept has been demonstrated with electrodeposition of palladium wires with 75 nm to 350 nm widths. We have also fabricated single and double conducting polymer nanowires (polyaniline and polypyrrole) with 100nm and 200nm widths using electrochemical direct growth. Using single Pd nanowires, we have also demonstrated hydrogen sensing. It is envisioned that these are the first steps towards nanowire sensor arrays capable of simultaneously detecting multiple chemical species.

  17. Self-assembly of octapod-shaped colloidal nanocrystals into a hexagonal ballerina network embedded in a thin polymer film.

    PubMed

    Arciniegas, Milena P; Kim, Mee R; De Graaf, Joost; Brescia, Rosaria; Marras, Sergio; Miszta, Karol; Dijkstra, Marjolein; van Roij, René; Manna, Liberato

    2014-02-12

    Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which CdSe(core)/CdS(pods) octapods are initially dispersed, affects the octapod-polymer organization upon solvent evaporation. We show that a fast drop-drying process can induce a remarkable two-dimensional (2D) self-assembly of octapods at the polymer/air interface. In the resulting structure, each octapod is oriented like a "ballerina", that is, only one pod sticks out of the polymer film and is perpendicular to the polymer-air interface, while the opposite pod (with respect to the octapod's center) is fully immersed in the film and points toward the substrate, like a ballerina performing a grand battement. In some areas, a hexagonal-like pattern is formed by the ballerinas in which the six nonvertical pods, which are all embedded in the film, maintain a pod-pod parallel configuration with respect to neighboring particles. We hypothesize that the mechanism responsible for such a self-assembly is based on a fast adsorption of the octapods from bulk solution to the droplet/air interface during the early stages of solvent evaporation. At this interface, the octapods maintain enough rotational freedom to organize mutually in a pod-pod parallel configuration between neighboring octapods. As the solvent evaporates, the octapods form a ballerina-rich octapod-polymer composite in which the octapods are in close contact with the substrate. Finally, we found that the resulting octapod-polymer composite is less hydrophilic than the polymer-only film.

  18. Graft-through Synthesis and Assembly of Janus Bottlebrush Polymers from A-Branch-B Diblock Macromonomers.

    PubMed

    Kawamoto, Ken; Zhong, Mingjiang; Gadelrab, Karim R; Cheng, Li-Chen; Ross, Caroline A; Alexander-Katz, Alfredo; Johnson, Jeremiah A

    2016-09-14

    We report the synthesis of Janus bottlebrush block copolymers by graft-through polymerization of branched diblock macromonomers. Self-assembly of the bottlebrushes was characterized by small-angle X-ray scattering, atomic force microscopy, and scanning electron microscopy. Phase separation and packing models of the bottlebrushes were computed, and their self-assembly behavior was corroborated experimentally in bulk and in thin films. Lamellar, hexagonal cylinder, and gyroid phases were observed and modeled. The A-branch-B Janus bottlebrush structure provides several unique advantages in the context of bottlebrush polymer assembly, including access to the first examples of gyroid phases.

  19. Graft-through Synthesis and Assembly of Janus Bottlebrush Polymers from A-Branch-B Diblock Macromonomers.

    PubMed

    Kawamoto, Ken; Zhong, Mingjiang; Gadelrab, Karim R; Cheng, Li-Chen; Ross, Caroline A; Alexander-Katz, Alfredo; Johnson, Jeremiah A

    2016-09-14

    We report the synthesis of Janus bottlebrush block copolymers by graft-through polymerization of branched diblock macromonomers. Self-assembly of the bottlebrushes was characterized by small-angle X-ray scattering, atomic force microscopy, and scanning electron microscopy. Phase separation and packing models of the bottlebrushes were computed, and their self-assembly behavior was corroborated experimentally in bulk and in thin films. Lamellar, hexagonal cylinder, and gyroid phases were observed and modeled. The A-branch-B Janus bottlebrush structure provides several unique advantages in the context of bottlebrush polymer assembly, including access to the first examples of gyroid phases. PMID:27580971

  20. Ion current behaviors of mesoporous zeolite-polymer composite nanochannels prepared by water-assisted self-assembly.

    PubMed

    Zhang, Wenjuan; Meng, Zheyi; Zhai, Jin; Heng, Liping

    2014-04-01

    Inspired by the asymmetry of biological ion channels in structure and composition, we designed a novel type of artificial asymmetric nanochannels based on mesoporous zeolite (MCM-41) and polyimide (PI) by water-assisted self-assembly. Meanwhile, we studied ionic current behaviors and rectifying characteristics of the mesoporous zeolite-polymer composite nanochannels. PMID:24394328

  1. 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

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. An automated spin-assisted approach for molecular layer-by-layer assembly of crosslinked polymer thin films.

    PubMed

    Chan, Edwin P; Lee, Jung-Hyun; Chung, Jun Young; Stafford, Christopher M

    2012-11-01

    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.

  8. Development and study of high-Tc superconductor conductive polymer assemblies

    NASA Astrophysics Data System (ADS)

    Schougaard, Steen Brian

    2002-01-01

    This dissertation presents the development and study of organic polymeric conductor/High-Tc superconductor bilayers, for exploration of the superconductor proximity effect. A major obstacle to this research is the instability of the High-Tc superconductor towards H2O and CO2 as it is necessary to create hybrid structures where the two conductors have intimate contact. For this reason, a study of the corrosion characteristics of the RBa2Cu3O 7 (R=Y, Eu, Nd) series was undertaken. In this study, R=Nd was shown to have enhanced corrosion resistance. In an effort to develop chemical processing methods that allow for the production of intimate contact between the cuprate superconductor and the conductive polymer systems, a study of alkyl amine adsorbed onto the surface of the superconductor is presented. In the electrochemical part of the study, alkyl amine ferrocene adsorbed onto the surface revealed that the amines are strongly adhered to the superconductor while still allowing electrons to pass from the superconductor to the ferrocene moiety. The self-assembled monolayer (SAM) structure of CF3(CF2)3(CH2) 11NH2 atop the superconductor was elucidated by employing several techniques, including atomic scale atomic force microscopy (AFM). A novel multistep bilayer sample preparation protocol is presented involving thin film fabrication by pulsed laser deposition (PLD), patterning by shadow mask ablation, sample thinning by scanning probe and electropolymerization of the polymer. Scanning probe thinning yields a smooth superconductor surface, a known superconductor thickness, and if a blocking layer is employed prior to thinning, the localization of polymer growth. Studies of the response of a bilayer structure of Y0.6Ca 0.4Ba1.6La0.4 Cu3O7/poly pyrrole to polymer redox cycling showed a semi-reversible suppression of transition temperature qualitatively consistent with a combination of corrosion and superconductor proximity effect. Quantitative analysis in the framework of

  9. 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.

  10. 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. PMID:27510363

  11. 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.

  12. Simultaneous nano- and micro-scale control of nanofibrous microspheres self-assembled from star-shaped polymers

    PubMed Central

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

    2015-01-01

    The mechanism underlying the multi-scale self-assembly of star-shaped polymers into non-hollow, hollow, and spongy nanofibrous microspheres is reported. Star-shaped poly(L-lactic acid) polymers with varying arm-numbers and arm-lengths are synthesized, dissolved in tetrahydrofuran, emulsified in glycerol, and thermally-induced to phase separate, resulting in microspheres that are either smooth or fibrous on the nano-scale, and either non-hollow, hollow, or spongy on the micro-scale. Molecular architecture and the hydroxyl density are shown to control assembly and morphology at both nano- and micro-scales. Nanofibers form only when the arm length is sufficiently long, while an increase in hydroxyl density causes the microspheres to change from non-hollow to hollow to spongy. We demonstrate via both experiments of capping or doubling the hydroxyl end groups and dissipative particle dynamics simulations that the affinity of hydroxyl to glycerol is critical to stabilizing the micro-scale structure. A “phase diagram” was constructed for the six types of microspheres in relation to the molecular structures of the star-shaped polymers. The proposed mechanism explains how star-shaped polymers self-assemble into various microspheres, and guides us to simultaneously control both nano- and micro-features of the microspheres. PMID:26009995

  13. 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. PMID:27136277

  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. 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

    2012-09-01

    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.

  16. 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

    2016-05-01

    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. PMID:27064264

  17. 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

    2016-05-01

    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.

  18. Fabrication of Interdigitated Micropatterns of Self-Assembled Polymer Nanofilms Containing Cell-adhesive Materials

    PubMed Central

    Mohammed, Javeed Shaikh; DeCoster, Mark A.; McShane, Michael J.

    2008-01-01

    Micropatterns of different biomaterials with micro- and nanoscale features and defined spatial arrangement on a single substrate are useful tools for studying cellular-level interactions, and recent reports have highlighted the strong influence of scaffold compliance in determining cell behavior. In this paper, a simple yet versatile and precise patterning technique for the fabrication of interdigitated micropatterns of nanocomposite multilayer coatings on a single substrate is demonstrated through a combination of lithography and layer-by-layer (LbL) assembly processes, termed as Polymer Surface Micromachining (PSM). The first nanofilm pattern is constructed using lithography, followed by LbL multilayer assembly and lift-off, and the process is repeated with optical alignment to obtain interdigitated patterns on the same substrate. Thus, the method is analogous to surface micromachining, except that the deposition materials are polymers and biological materials that are used to produce multilayer nanocomposite structures. A key feature of the multilayers is the capability to tune properties such as stiffness by appropriate selection of materials, deposition conditions, and post-deposition treatments. Two- and four-component systems on glass coverslips are presented to demonstrate the versatility of the approach to construct precisely-defined, homogeneous nanofilm patterns. In addition, an example of a complex system used as a testbed for in vitro cell adhesion and growth is provided: micropatterns of poly(sodium 4-styrenesulfonate)/poly-L-lysine hydrobromide (PSS/PLL) and secreted phospholipase A2/poly(ethyleneimine) (PEI/sPLA2) multilayers. The interdigitated square nanofilm array patterns were obtained on a single coverslip with poly(diallyldimethyl ammonium chloride) (PDDA) as a cell-repellent background. Cell culture experiments show that cortical neurons respond and bind specifically to the sPLA2 micropatterns in competition with PLL micropatterns. The

  19. Hierarchical Polymer-Carbon Nanotube Hybrid Mesostructures by Crystallization-Driven Self-Assembly.

    PubMed

    Jia, Lin; Petretic, Amy; Molev, Gregory; Guerin, Gerald; Manners, Ian; Winnik, Mitchell A

    2015-11-24

    Multistep crystallization-driven self-assembly has great potential to enable the construction of sophisticated hybrid mesostructures. During the assembly procedure, each step modifies the properties of the overall structure. Here, we demonstrate the flexibility and efficiency of this approach by preparing polymer-carbon nanotube (CNT) hybrid mesostructures. We started by growing polyferrocenyldimethylsilane (PFS) homopolymer crystals onto multiwalled CNTs. This first step facilitated the redispersion of the coated CNTs in both polar (2-propanol) and nonpolar (decane) solvents. In the second step of hybrid construction, a unimer solution of a PFS block copolymer was added into the PFS-CNT solution. The PFS coating on the CNT initiated the growth of elongated micelles, resulting in structures that resembled hairy caterpillars. PFS-b-P2VP (P2VP = poly-2-vinylpyridine) micelles were grown from the surface of PFS-CNT hybrids in 2-propanol, and PFS-b-PI (PI = polyisoprene) micelles were grown from these hybrids in decane. These micelles, by transmission electron microscopy were seen to have an unusual wavy kinked structure, very different from the uniform smooth structures normally formed by both block copolymers. For hybrids with PFS-b-PI micelles, cross-linking of the micelle coronas locked the whole structure in place and allowed us to use the partial oxidation of PFS components to grow metal nanoparticles in the core of these micelles. We finally investigated the influence of the corona-forming block used to grow the micelles on the wettability of films made from these mesostructures. Films formed with CNT hybrids grafted with PFS-b-PI micelles were superhydrophobic (contact angle, 152°). In contrast, the surface of the films was much more hydrophilic (contact angle, 54°) when they were prepared from CNT hybrids grafted with PFS-b-P2VP micelles.

  20. Hierarchical Polymer-Carbon Nanotube Hybrid Mesostructures by Crystallization-Driven Self-Assembly.

    PubMed

    Jia, Lin; Petretic, Amy; Molev, Gregory; Guerin, Gerald; Manners, Ian; Winnik, Mitchell A

    2015-11-24

    Multistep crystallization-driven self-assembly has great potential to enable the construction of sophisticated hybrid mesostructures. During the assembly procedure, each step modifies the properties of the overall structure. Here, we demonstrate the flexibility and efficiency of this approach by preparing polymer-carbon nanotube (CNT) hybrid mesostructures. We started by growing polyferrocenyldimethylsilane (PFS) homopolymer crystals onto multiwalled CNTs. This first step facilitated the redispersion of the coated CNTs in both polar (2-propanol) and nonpolar (decane) solvents. In the second step of hybrid construction, a unimer solution of a PFS block copolymer was added into the PFS-CNT solution. The PFS coating on the CNT initiated the growth of elongated micelles, resulting in structures that resembled hairy caterpillars. PFS-b-P2VP (P2VP = poly-2-vinylpyridine) micelles were grown from the surface of PFS-CNT hybrids in 2-propanol, and PFS-b-PI (PI = polyisoprene) micelles were grown from these hybrids in decane. These micelles, by transmission electron microscopy were seen to have an unusual wavy kinked structure, very different from the uniform smooth structures normally formed by both block copolymers. For hybrids with PFS-b-PI micelles, cross-linking of the micelle coronas locked the whole structure in place and allowed us to use the partial oxidation of PFS components to grow metal nanoparticles in the core of these micelles. We finally investigated the influence of the corona-forming block used to grow the micelles on the wettability of films made from these mesostructures. Films formed with CNT hybrids grafted with PFS-b-PI micelles were superhydrophobic (contact angle, 152°). In contrast, the surface of the films was much more hydrophilic (contact angle, 54°) when they were prepared from CNT hybrids grafted with PFS-b-P2VP micelles. PMID:26418346

  1. Pulse electrodeposition and electrochemical quartz crystal microbalance techniques for high perpendicular magnetic anisotropy cobalt nanowire arrays

    NASA Astrophysics Data System (ADS)

    Ursache, Andrei; Goldbach, James T.; Russell, Thomas P.; Tuominen, Mark T.

    2005-05-01

    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 1Terabit/in.2 The polymer template, derived from a self-assembling P(S-b-MMA) diblock copolymer film, provides precise control over the nanowire diameter (15nm) and interwire spacing (24nm), whereas nanowire length (typically 50to1000nm) 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 2.7kOe at 300K. 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.

  2. 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.

  3. 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

    2014-01-01

    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.

  4. 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.

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

    PubMed

    Phillips, Carolyn L; Glotzer, Sharon C

    2012-09-14

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

  6. 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.

  7. Host-guest interactions mediated nano-assemblies using cyclodextrin-containing hydrophilic polymers and their biomedical applications

    PubMed Central

    Zhang, Jianxiang; Ma, Peter X

    2010-01-01

    Summary Supramolecular nanostructures assembled by polymeric amphiphiles have been intensively studied during the last two decades. Such nanocarriers may be engineered to possess on-demand bio-responsitivity for the prevention, diagnosis, and treatment of human diseases. The successful development of several nanoassembly-based polymer therapeutics further encouraged scientists to develop nano-vehicles to achieve controlled release, enhanced efficacy, improved specificity and reduced toxicity. Different from the abundant existing literatures on the hydrophobically or electrostatically driven self-assemblies and their therapeutic applications, this article reviews host-guest interaction mediated nanoassemblies, especially those constructed using cyclodextrins as the host entities. The excellent biocompatibility, complexation capacity, and chemical-sensitivity of cyclodextrin make cyclodextrin-containing polymers attractive to construct host-guest nanoassemblies. Such nanocarriers may be advantageous also because of the broad availability of cyclodextrins, their flexibility for structure/property modulation and their chemical-responsive characteristics. PMID:20725642

  8. 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.

  9. Purification and processing of carbon nanotubes using self-assembly and selective interaction with a semiconjugated polymer

    NASA Astrophysics Data System (ADS)

    Fournet, Patrick; McCarthy, Brendan; Dalton, Alan B.; Coleman, Jonathan N.; Murphy, Robert J.; Stephan, Christophe; Lefrant, Serge; Bernier, Patrick; Byrne, Hugh J.; Blau, Werner J.

    2001-12-01

    A new route for nanotube-based applications in molecular electronics was developed. Individual polymer strands were assembled onto single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT) by mechanical agitation. The SWNT hybrid systems have been characterized by electron microscopy (TEM, STM), optical absorption and Raman spectroscopy and a fully nondestructive technique, using electron paramagnetic resonance (EPR), has been developed to estimate the purity of MWNT soot and hybrids. It is demonstrated that solutions of the polymer are capable of suspending nanotubes indefinitely while the majority of the accompanying amorphous graphite precipitates out of solution. Electron microscopy and Raman scattering indicate that through an intercalation process, the ropes of SWNT are destroyed, resulting in individual nanotubes being well dispersed within the polymer matrix. Moreover, Raman and absorption studies suggest that the polymer interacts preferentially with nanotubes of specific diameters or a range of diameters. STM studies showed that the chiral angle of the underlying nanotube is reflected in the polymer coating, demonstrating that the lattice structure of the SWNT templates the ordering in the coating. This could lead to design of specific polymer architectures for selection of desired chiral angles, and hence specific electronic properties.

  10. 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. PMID:26867986

  11. Synthesis of genetically engineered protein polymers (recombinamers) as an example of advanced self-assembled smart materials.

    PubMed

    Rodríguez-Cabello, José Carlos; Girotti, Alessandra; Ribeiro, Artur; Arias, Francisco Javier

    2012-01-01

    In this chapter, we describe two methods for bio-producing recombinant repetitive polypeptide polymers for use in biomedical devices. These polymers, known as elastin-like recombinamers (ELRs), are derived from the repetition of selected amino acid domains of extracellular matrix proteins with the aim of recreating their mechanical and physiological features. The proteinaceous nature of ELRs allows us to make use of the natural biosynthetic machinery of heterologous hosts to express advanced and large polymers or "recombinamers." Despite the essentially unlimited possibilities for designing recombinamers, the production of synthetic genes to encode them should allow us to overcome the difficulties surrounding bioproduction of these non-natural monotonous DNA and protein sequences. The aim of this work is to supply the biotechnologist with fine-tuning methods to biosynthesize advanced self-assembled smart materials.

  12. 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

    2016-05-01

    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.

  13. 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. PMID:24471886

  14. Understanding the Structure of Reversible Coordination Polymers Based on Europium in Electrostatic Assemblies Using Time-Resolved Luminescence.

    PubMed

    Xu, Limin; Xie, Mengqi; Huang, Jianbin; Yan, Yun

    2016-06-14

    In situ characterization of the structure of reversible coordination polymers remains a challenge because of their dynamic and concentration-responsive nature. It is especially difficult to determine these structures in their self-assemblies where their degree of polymerization responds to the local concentration. In this paper, we report on the structure of reversible lanthanide coordination polymers in electrostatic assemblies using time-resolved luminescence (TRL) measurement. The reversible coordinating system is composed of the bifunctional ligand 1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9-trioxaundecane (L2EO4) and europium ion Eu(3+). Upon mixing with the positively charged diblock copolymer poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP41-b-PEO205), electrostatic polyion micelles are formed and the negatively charged L2EO4-Eu coordination complex simultaneously transforms into coordination "polymers" in the micellar core. By virtue of the water-sensitive luminescence of Eu(3+), we are able to obtain the structural information of the L2EO4-Eu coordination polymers before and after the formation of polyion micelles. Upon analyzing the fluorescence decay curves of Eu(3+) before and after micellization, the fraction of Eu(3+) fully coordinated with L2EO4 is found to increase from 32 to 83%, which verifies the occurrence of chain extension of the L2EO4-Eu coordination polymers in the micellar core. Our work provides a qualitative picture for the structure change of reversible coordination polymers, which allows us to look into these "invisible" structures.

  15. Understanding the Structure of Reversible Coordination Polymers Based on Europium in Electrostatic Assemblies Using Time-Resolved Luminescence.

    PubMed

    Xu, Limin; Xie, Mengqi; Huang, Jianbin; Yan, Yun

    2016-06-14

    In situ characterization of the structure of reversible coordination polymers remains a challenge because of their dynamic and concentration-responsive nature. It is especially difficult to determine these structures in their self-assemblies where their degree of polymerization responds to the local concentration. In this paper, we report on the structure of reversible lanthanide coordination polymers in electrostatic assemblies using time-resolved luminescence (TRL) measurement. The reversible coordinating system is composed of the bifunctional ligand 1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9-trioxaundecane (L2EO4) and europium ion Eu(3+). Upon mixing with the positively charged diblock copolymer poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP41-b-PEO205), electrostatic polyion micelles are formed and the negatively charged L2EO4-Eu coordination complex simultaneously transforms into coordination "polymers" in the micellar core. By virtue of the water-sensitive luminescence of Eu(3+), we are able to obtain the structural information of the L2EO4-Eu coordination polymers before and after the formation of polyion micelles. Upon analyzing the fluorescence decay curves of Eu(3+) before and after micellization, the fraction of Eu(3+) fully coordinated with L2EO4 is found to increase from 32 to 83%, which verifies the occurrence of chain extension of the L2EO4-Eu coordination polymers in the micellar core. Our work provides a qualitative picture for the structure change of reversible coordination polymers, which allows us to look into these "invisible" structures. PMID:27228142

  16. 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.

  17. Solid-State Nanostructured Materials from Self-Assembly of a Globular Protein-Polymer Diblock Copolymer

    PubMed Central

    Thomas, Carla S.; Glassman, Matthew J.; Olsen, Bradley D.

    2014-01-01

    Self-assembly of three-dimensional solid-state nanostructures containing approximately 33% by weight globular protein is demonstrated using a globular protein-polymer diblock copolymer, providing a route to direct nanopatterning of proteins for use in bioelectronic and biocatalytic materials. A mutant red fluorescent protein, mCherryS131C, was prepared by incorporation of a unique cysteine residue and site-specifically conjugated to end-functionalized poly(N-isopropylacrylamide) through thiol-maleimide coupling to form a well-defined model protein-polymer block copolymer. The block copolymer was self-assembled into bulk nanostructures by solvent evaporation from concentrated solutions. Small-angle X-ray scattering and transmission electron microscopy illustrated the formation of highly disordered lamellae or hexagonally perforated lamellae depending upon the selectivity of the solvent during evaporation. Solvent annealing of bulk samples resulted in a transition towards lamellar nanostructures with mCherry packed in a bilayer configuration and a large improvement in long range ordering. Wide-angle X-ray scattering indicated that mCherry did not crystallize within the block copolymer nanodomains and that the β-sheet spacing was not affected by self-assembly. Circular dichroism showed no change in protein secondary structure after self-assembly, while UV-vis spectroscopy indicated approximately 35% of the chromophore remained optically active. PMID:21696135

  18. Self-assembly of CdTe nanocrystals at the water/oil interface by amphiphilic hyperbranched polymers

    NASA Astrophysics Data System (ADS)

    Shi, Yunfeng; Tu, Chunlai; Zhu, Qi; Qian, Huifeng; Ren, Jicun; Liu, Cuihua; Zhu, Xinyuan; Yan, Deyue; Siu-Wai Kong, Eric; He, Peng

    2008-11-01

    A general strategy for realizing the self-assembly of aqueous CdTe nanocrystals (NCs) at the water/oil interface by means of an amphiphilic core-shell hyperbranched polymer has been proposed. Aqueous CdTe NCs were firstly transferred into the chloroform phase in the presence of palmityl chloride functionalized hyperbranched poly(amidoamine) (HPAMAM-PC), and then self-assembled at the water/chloroform interface by decreasing the pH value of the aqueous phase or introducing α-CDs to the aqueous phase. The resulting CdTe/HPAMAM-PC self-assembly film was characterized by fluorescence microscopy, UV-vis, PL, TEM, EDS, FT-IR, DSC and TGA.

  19. The synthesis and characterization of self-assembling peptides bearing organic-electronic units for the development of biologically active nanowires

    NASA Astrophysics Data System (ADS)

    Diegelmann, Stephen Robert

    The development of complex self-assembling supramolecular systems derived from single, and sometimes simple, molecules has become an area of vast interest. These molecules are specifically designed to foster favorable intermolecular interactions leading to highly ordered macromolecular assemblies through 'bottom-up' fabrication with size dimensions that are on the order of nanometers to tens of microns. Self-assembling amyloid-like nanostructures provide biologically relevant systems that can be harnessed for the development of novel nanobiomaterials. Amyloid-like materials are composed of well-defined one dimensional (1-D) structures that can be used as scaffolding for controlled organization of organic electronic materials in aqueous environments. We have developed and functionalized a wide array of organic semiconductors and incorporated them into oligopeptides designed to self-assemble into 1-D amyloid-like nanofibers. These nanofibers have internalized intermolecularly delocalized pi-stacked oligothiophenes as well as linearly conjugated polydiacetylene (PDA) polymers running along the nanofiber long axis. These nanofibers can be globally aligned and fabricated into electronic devices that have a high degree of directionally dependent charge mobility. Preliminary experiments have also shown that these materials can be interfaced with biological systems with potential use as electro-active cell culture matrices.

  20. Structure and Electronic Properties of Polymer Chains and Graphene Nanoribbon Formed by Molecular Self-Assembly on Au(111)

    NASA Astrophysics Data System (ADS)

    Ma, Chuanxu; Fuentes-Cabrera, Miguel A.; Sumpter, Bobby G.; Hong, Kunlun; Li, An-Ping; Xiao, Zhongcan; Lu, Wenchang; Bernholc, J.

    Graphene nanoribbons (GNRs) with bandgaps are promising building blocks for ultra-fast electronics. Bottom-up synthesis of GNRs from aromatic hydrocarbon molecules has been proven to be an effective way to control GNR's width with atomically precise edge structures. Using scanning tunneling microscopy (STM), we study the formation of both linear polymer chains and narrow GNRs in the bottom-up self-assembly process with the DBBA molecules as the precursor on Au(111). The linear polymer chains are formed after the deposition of DBBA and 200 °C annealing for 30 min. The polymers can be converted to 7-AGNRs (seven-carbon wide armchair GNRs) after 400 °C annealing. Interestingly, second-layer polymer is seen to survive on the GNRs during the annealing process. This result indicates that the Au(111) substrate plays an important role in the dehydrogenation process and the formation of GNRs, which is confirmed by our DFT calculations. Electronically, the polymers show a bandgap of 3.4 eV, much larger than that of GNRs. After annealing at 500 °C for 30 min, wider GNRs can form: 14-AGNR, 21-AGNR. The 7-AGNR shows a typical edge state at -1.1 eV, while for 14-AGNR it is at -1.35 eV. Moreover, junctions of GNRs with different widths can be formed with pronounced boundary states.

  1. 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).

  2. 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

  3. Role of block copolymer adsorption versus bimodal grafting on nanoparticle self-assembly in polymer nanocomposites.

    PubMed

    Zhao, Dan; Di Nicola, Matteo; Khani, Mohammad M; Jestin, Jacques; Benicewicz, Brian C; Kumar, Sanat K

    2016-09-14

    We compare the self-assembly of silica nanoparticles (NPs) with physically adsorbed polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymers (BCP) against NPs with grafted bimodal (BM) brushes comprised of long, sparsely grafted PS chains and a short dense carpet of P2VP chains. As with grafted NPs, the dispersion state of the BCP NPs can be facilely tuned in PS matrices by varying the PS coverage on the NP surface or by changes in the ratio of the PS graft to matrix chain lengths. Surprisingly, the BCP NPs are remarkably better dispersed than the NPs tethered with bimodal brushes at comparable PS grafting densities. We postulate that this difference arises because of two factors inherent in the synthesis of the NPs: In the case of the BCP NPs the adsorption process is analogous to the chains being "grafted to" the NP surface, while the BM case corresponds to "grafting from" the surface. We have shown that the "grafted from" protocol yields patchy NPs even if the graft points are uniformly placed on each particle. This phenomenon, which is caused by chain conformation fluctuations, is exacerbated by the distribution function associated with the (small) number of grafts per particle. In contrast, in the case of BCP adsorption, each NP is more uniformly coated by a P2VP monolayer driven by the strongly favorable P2VP-silica interactions. Since each P2VP block is connected to a PS chain we conjecture that these adsorbed systems are closer to the limit of spatially uniform sparse brush coverage than the chemically grafted case. We finally show that the better NP dispersion resulting from BCP adsorption leads to larger mechanical reinforcement than those achieved with BM particles. These results emphasize that physical adsorption of BCPs is a simple, effective and practically promising strategy to direct NP dispersion in a chemically unfavorable polymer matrix. PMID:27502154

  4. 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.

  5. 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).

  6. Multifunctional metal-polymer nanoagglomerates from single-pass aerosol self-assembly.

    PubMed

    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 × 10(6) RLU mg(-1)) of the PM particles alone (2.1 × 10(6) 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

  7. A density functional study of silver clusters on a stepped graphite surface: formation of self-assembled nano-wires.

    PubMed

    Singh, Akansha; Sen, Prasenjit

    2015-05-21

    Adsorption and diffusion of silver adatoms and clusters containing up to eight atoms on an HOPG substrate with an armchair step are studied using density functional methods. Step edges act as attractive sinks for adatoms and clusters. The diffusion barrier of an Ag adatom along the step edge is much larger than that on a clean terrace. At zero temperature, Ag clusters either distort or dissociate by forming covalent bonds with the edge C atoms. At 600 K, Ag5 and Ag8 clusters diffuse to the step edges, and then break up so as to maximize Ag-C bonds. The Ag atoms try to form a nanowire structure along the step edge. At such high temperatures, diffusion of clusters along the step edge involves diffusion of individual Ag atoms not bonded to the edge C atoms. Assumption of complete immobility of clusters trapped at step edges in the Gates-Robins model is not valid at high temperatures in this particular system. PMID:25903308

  8. 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.

  9. 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. PMID:23464832

  10. 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.

  11. 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. PMID:27414282

  12. DNA-programmed modular assembly of cyclic and linear nanoarrays for the synthesis of two-dimensional conducting polymers.

    PubMed

    Chen, Wen; Schuster, Gary B

    2012-01-18

    Nanometer-scale arrays of conducting polymers were prepared on scaffolds of self-assembling DNA modules. A series of DNA oligomers was prepared, each containing six 2,5-bis(2-thienyl)pyrrole (SNS) monomer units linked covalently to N4 atoms of alternating cytosines placed between leading and trailing 12-nucleobase recognition sequences. These DNA modules were encoded so the recognition sequences would uniquely associate through Watson-Crick assembly to form closed-cycle or linear arrays of aligned SNS monomers. The melting behavior and electrophoretic migration of these assemblies showed cooperative formation of multicomponent arrays containing two to five DNA modules (i.e., 12-30 SNS monomers). The treatment of these arrays with horseradish peroxidase and H(2)O(2) resulted in oxidative polymerization of the SNS monomers with concomitant ligation of the DNA modules. The resulting cyclic and linear arrays exhibited chemical and optical properties typical of conducting thiophene-like polymers, with a red-end absorption beyond 1250 nm. AFM images of the cyclic array containing 18 SNS units revealed highly regular 10 nm diameter objects. PMID:22242713

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

    PubMed

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

    2014-04-01

    A self-assembly approach to preparing iron phthalocyanine/single-walled carbon nanotube (FePc/SWNT) heterojunction nanowires as a new oxygen reduction reaction (ORR) electrocatalyst has been developed by virtue of water-adjusted dispersing in 1-cyclohexyl-pyrrolidone (CHP) of the two components. The FePc/SWNT nanowires have a higher Fermi level compared to pure FePc (d-band center, DFT=-0.69 eV versus -0.87 eV, respectively). Consequently, an efficient channel for transferring electron to the FePc surface is readily created, facilitating the interaction between FePc and oxygen, so enhancing the ORR kinetics. This heterojunction-determined activity in ORR illustrates a new stratagem to preparing non-noble ORR electrocatalysts of significant importance in constructing real-world fuel cells. PMID:24491331

  14. 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

  15. Self-assembled epoxy-modified polymer coating on a poly(dimethylsiloxane) microchip for EOF inhibition and biopolymers separation.

    PubMed

    Wu, Dapeng; Qin, Jianhua; Lin, Bingcheng

    2007-11-01

    A straightforward approach to generate a stable and protein-resistant poly(dimethylsiloxane) (PDMS) surface using self-assembled hydrophilic polymers is demonstrated in this work. Epoxy-modified polymers were directly adsorbed from aqueous solution onto plasma oxidized PDMS based on H-bond interaction, and epoxies of polymer and silanols on oxidized PDMS surface were crosslinked by heating at 110 degrees C. The coating process could be completed within half hour. Poly(dimethylacrylamide-co-glycidyl methacrylate) (PDMA-co-GMA), poly(vinyl pyrrolidone)-g-glycidyl methacrylate (PVP-g-GMA) and poly(vinyl alcohol)-g-glycidyl methacrylate (PVA-g-GMA) (D. P. Wu, B. X. Zhao, Z. P. Dai, J. H. Qin and B. C. Lin, Lab Chip, 2006, 6, 942) were employed as examples here. Unlike PDMA, PVP, and PVA themselves, these epoxy-modified hydrophilic polymers could be directly used as static surface coatings on oxidized PDMS, and inhibited electroosmotic flow (EOF) within pH 3-11. It was also found that hard baking of PDMS at 150 degrees C for 24 hours before surface coating could greatly retard surface hydrophobicity recovery after oxygen plasma exposure, which strengthened epoxy-modified polymer coatings on oxidized PDMS surface, and resulted in EOF less than 0.2 x 10(-4) cm(2) V(-1) s(-1) (pH 9.0) within two weeks. On epoxy-modified polymer coated PDMS microchips, basic proteins, peptides and DNA fragments could be separated satisfactorily, in which more than 2 x 10(4) plates per 2 cm and less than 3% RSD (>8 runs) for migration time were obtained for lysozyme. PMID:17960276

  16. Biocompatible polyester macroligands: new subunits for the assembly of star-shaped polymers with luminescent and cleavable metal cores.

    PubMed

    Corbin, P S; Webb, M P; McAlvin, J E; Fraser, C L

    2001-01-01

    The synthesis of a series of star-shaped, biocompatible polyesters--polylactides (PLAs), polycaprolactones (PCLs), and various copolymer analogues--with either labile iron(II) tris-bipyridyl or luminescent ruthenium(II) tris-bipyridyl cores is described. These polymers were readily assembled by a convergent, metal-template-assisted approach that entailed the synthesis of bipyridine (bpy) ligands incorporating PLA- and PCL-containing arms and subsequent chelation of the "macroligands" to iron(II) or ruthenium(II). Specifically, the polyester macroligands bpyPLA(2) and bpyPCL(2) were prepared by a stannous octoate catalyzed ring-opening polymerization of DL- or L-lactide and epsilon-caprolactone, using bis(hydroxymethyl)-2,2'-bipyridine as the initiator. Copolymers bpy(PCL-PLA)(2) and bpy(PLA-PCL)(2) were generated in an analogous manner using bpyPLA(2) and bpyPCL(2) as macroinitiators. Polymers with narrow molecular weight distributions and with molecular weights close to values expected based upon monomer/initiator loading were produced. The macroligands were subsequently chelated to iron(II) to afford six-armed, iron-core star polymers, which were characterized by UV-vis and (1)H NMR spectroscopy. Estimated chelation efficiencies for formation of the star polymers (M(n) calcd: 20-240 kDa) were high, as determined by UV-vis spectral analysis. Within the molecular weight range investigated, differential scanning calorimetry and thermogravimetric analysis revealed that the small amounts of metal in the polyester stars and differences in polymer architecture had little effect on the thermal properties of the PLA/PCL materials. However, thin films of the red-violet colored iron-core stars exhibited reversible, thermochromic bleaching. Solutions and films of the polymers also responded (with color loss) to a variety of chemical stimuli (e.g., acid, base, peroxides, ammonia), thus revealing potential for use in diverse sensing applications. Likewise, the polyester

  17. 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.

  18. Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

    NASA Astrophysics Data System (ADS)

    Lian, Chen; Liu, Liu; Guo, Xu; Long, Yinshuang; Jia, Shanshan; Li, Huanhuan; Yang, Lirong

    2016-01-01

    Two novel coordination polymers, namely, [Ca(NCP)2]∞ (I) and [Sr(NCP)2]∞ (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-)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- which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability.

  19. 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

    2015-12-01

    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.

  20. 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

    2015-12-01

    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. PMID:26494439

  1. Electrochemically grown single-nanowire sensors

    NASA Astrophysics Data System (ADS)

    Yun, Minhee; Lee, Choonsup; Vasquez, Richard P.; Penner, Reginald M.; Bangar, Mangesh; Mulchandani, Ashok; Myung, Nosang V.

    2004-12-01

    We report a fabrication technique that is potentially capable of producing arrays of individually addressable nanowire sensors with controlled dimensions, positions, alignments, and chemical compositions. The concept has been demonstrated with electrodeposition of palladium wires with 75 nm to 350 nm widths. We have also fabricated single and double conducting polymer nanowires (polyaniline and polypyrrole) with 100nm and 200nm widths using electrochemical direct growth. Using single Pd nanowires, we have also demonstrated hydrogen sensing. It is envisioned that these are the first steps towards nanowire sensor arrays capable of simultaneously detecting multiple chemical species.

  2. Polymer complexes. LVII. Supramolecular assemblies of novel polymer complexes of dioxouranium(VI) with some substituted allyl azo dye compounds

    NASA Astrophysics Data System (ADS)

    Diab, M. A.; El-Sonbati, A. Z.; El-Bindary, A. A.; Balboula, M. Z.

    2013-05-01

    A novel method to synthesize some dioxouranium(VI) polymer complexes of the general formula [UO2(Ln)2(OAc)2] (where HLn = azo allyl rhodanine). The structure of the novel mononuclear dioxoutranium(VI) polymer complexes was characterized using elemental analysis, spectral (electronic, infrared, 1H &13C NMR) studies, magnetic susceptibility measurements and thermal analysis. The molar conductivities show that all the polymer complexes are non-electrolytes. The IR showed that the ligand HLn act as bidentate neutral through carbonyl group and imine group nitrogen atom forming thereby a six-membered chelating ring and concomitant formation of an intramolecular hydrogen bond. The υ3 frequency of UO2+2 has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ3 of the prepared complexes containing UO2+2 were successfully used to calculate the force constant, FUO (10-8 N/Å) and the bond length RUO (Å) of the Usbnd O bond. A strategy based upon both theoretical and experimental investigations has been adopted. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the Usbnd O bond distances from the values of the stretching and interaction force constants. The most probable correlation between Usbnd O force constant to Usbnd O bond distance were satisfactorily discussed in term of Badger's rule and the equations suggested by Jones and El-Sonbati. The effect of Hammet constant is also discussed.

  3. Tube-graft-Sheet Nano-Objects Created by A Stepwise Self-Assembly of Polymer-Polyoxometalate Hybrids.

    PubMed

    Tang, Jing; Li, Xue-Ying; Wu, Han; Ren, Li-Jun; Zhang, Yu-Qi; Yao, Hai-Xia; Hu, Min-Biao; Wang, Wei

    2016-01-19

    In this work, we report the preparation of complex nano-objects by means of a stepwise self-assembly of two polymer-polyoxometalate hybrids (PPHs) in solution. The PPHs are designed and synthesized by tethering two linear poly(ε-caprolactone)s (PCL) of different molecular weights (MW) on a complex of a Wells-Dawson-type polyoxometalate (POM) cluster and its countraions. The higher MW PCL-POM self-assembled into nanosheets, while the lower MW PCL-POM assembled into nanotubes just by altering the ratio of water in the DMF-water mixed solvent system. The two nano-objects have a similar membrane structure in which a PCL layer is sandwiched by the two POM-based complex layers. The PCL layer in the nanosheets is semicrystalline, while the PCL layer in the nanotubes is amorphous. We further exploited this MW-dependence to self-assemble the nanotubes on the nanosheet edges to create complex tube-graft-sheet nano-objects. We found that the nanotubes nucleate on the four {110} faces of the PCL crystal and then further grow along the crystallographic b-axis of the PCL crystal. Our findings offer hope for the further development of nano-objects with increasing complexity.

  4. 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

    2013-02-01

    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. PMID:23241687

  5. 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.

  6. 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

  7. Stable and robust nanotubes formed from self-assembled polymer membranes

    NASA Astrophysics Data System (ADS)

    Helmerson, Kristian; Reiner, Joseph E.; Kishore, Rani B.; Jofre, Ana; Allegrini, Maria; Pfefferkorn, Candace; Wells, Jeffrey M.

    2006-08-01

    We create long polymer nanotubes by directly pulling on the membrane of polymersomes using either optical tweezers or a micropipette. The polymersomes are composed of amphiphilic diblock copolymers and the nanotubes formed have an aqueous core connected to the aqueous interior of the polymersome. We stabilize the pulled nanotubes by subsequent chemical cross-linking. The cross-linked nanotubes are extremely robust and can be moved to another medium for use elsewhere. We demonstrate the ability to form networks of polymer nanotubes and polymersomes by optical manipulation. The aqueous core of the polymer nanotubes together with their robust character makes them interesting candidates for nanofluidics and other applications in biotechnology.

  8. A label-free cyclic assembly of G-quadruplex nanowires for cascade amplification detection of T4 polynucleotide kinase activity and inhibition.

    PubMed

    Shi, Zhilu; Zhang, Xiafei; Cheng, Rui; Li, Baoxin; Jin, Yan

    2015-09-01

    Several fluorescence methods have been developed for sensitive detection of PNK activity based on signal amplification techniques, but they need fluorescently labeled DNA probes and superabundant assistant enzymes. We have addressed these limitations and report here a label-free and enzyme-free amplification strategy for sensitively and specifically studying PNK activity and inhibition via hybridization chain reaction (HCR). First, the phosphorylation of hairpin DNA H1 by T4 PNK makes it be specifically digested by lambda exonuclease (λ exo) from 5' to 3' direction to generate a single-stranded initiator which can successively open hairpins H2 and H3 to trigger an autonomous assembly of long DNA nanowires. Meanwhile, an intermolecular G-quadruplex is formed between H2 and H3, thereby providing fluorescence enhancement of N-methyl mesoporphyrin IX (NMM) which is a highly quadruplex-selective fluorophore. So, the PNK activity can be facilely and sensitively detected by using NMM as a signal probe which provides a low background signal to improve the overall sensitivity, resulting in the detection limit of 3.37 × 10(-4) U mL(-1). More importantly, its successful application for detecting PNK activity in a complex biological matrix and studying the inhibition effects of PNK inhibitors demonstrated that it provides a promising platform for screening PNK inhibitors as well as detecting PNK activity. Therefore, it is a highly sensitive, specific, reliable and cost-effective strategy which shows great potential for biological process research, drug discovery, and clinical diagnostics.

  9. Interfacial Rheology of Hydrogen-Bonded Polymer Multilayers Assembled at Liquid Interfaces: Influence of Anchoring Energy and Hydrophobic Interactions.

    PubMed

    Le Tirilly, Sandrine; Tregouët, Corentin; Reyssat, Mathilde; Bône, Stéphane; Geffroy, Cédric; Fuller, Gerald; Pantoustier, Nadège; Perrin, Patrick; Monteux, Cécile

    2016-06-21

    We study the 2D rheological properties of hydrogen-bonded polymer multilayers assembled directly at dodecane-water and air-water interfaces using pendant drop/bubble dilation and the double-wall ring method for interfacial shear. We use poly(vinylpyrrolidone) (PVP) as a proton acceptor and a series of polyacrylic acids as proton donors. The PAA series of chains with varying hydrophobicity was fashioned from poly(acrylic acid), (PAA), polymethacrylic acid (PMAA), and a homemade hydrophobically modified polymer. The latter consisted of a PAA backbone covalently grafted with C12 moieties at 1% mol (referred to as PAA-1C12). Replacing PAA with the more hydrophobic PMAA provides a route for combining hydrogen bonding and hydrophobic interactions to increase the strength and/or the number of links connecting the polyacid chains to PVP. This systematic replacement allows for control of the ability of the monomer units inside the absorbed polymer layer to reorganize as the interface is sheared or compressed. Consequently, the interplay of hydrogen bonding and hydrophobic interactions leads to control of the resistance of the polymer multilayers to both shear and dilation. Using PAA-1C12 as the first layer improves the anchoring energy of a few monomers of the chain without changing the strength of the monomer-monomer contact in the complex layer. In this way, the layer does not resist shear but resists compression. This strategy provides the means for using hydrophobicity to control the interfacial dynamics of the complexes adsorbed at the interface of the bubbles and droplets that either elongate or buckle upon compression. Moreover, we demonstrate the pH responsiveness of these interfacial multilayers by adding aliquots of NaOH to the acidic water subphase surrounding the bubbles and droplets. Subsequent pH changes can eventually break the polymer complex, providing opportunities for encapsulation/release applications. PMID:27176147

  10. 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.

  11. Molecular layer-by-layer self-assembly and mercury sensing characteristics of novel brush polymers bearing thymine moieties.

    PubMed

    Jung, Jungwoon; Kim, Jin Chul; Rho, Yecheol; Kim, Mihee; Kwon, Wonsang; Kim, Heesoo; Ree, Moonhor

    2011-07-01

    Two new brush polyoxyethylenes bearing thymine moieties at the bristle ends have been synthesized as model polymers in which the chemical loading of the thymine functional group into the polymer is maximized: poly(oxy(11-thyminoacetyloxyundecylthiomethyl)ethylene) (PECH(S)-T) and poly(oxy(11-thyminoacetyloxyundecylsulfonylmethyl)ethylene) (PECH(SO(2))-T). These brush polymers are thermally stable up to around 225 °C, and their glass transitions occur in the range 23-27 °C, but they have significantly different properties despite the similarity of their chemical structures. In particular, PECH(SO(2))-T films exhibit better performance in sensing mercury ions than PECH(S)-T films. These differences were found to originate in the differences between their morphological structures. The PECH(SO(2))-T film has a multi-bilayer structure without interdigitation, in which the layers stack along the out-of-plane of the film and provide a thymine-rich surface. In contrast, the PECH(S)-T film is amorphous with a relatively low population of thymine moieties at the surface. This study demonstrated that a thymine-rich surface is required for recyclable thymine-based polymers to provide highly improved sensitivity and selectivity as well as full reversibility in the sensing of mercury ions. A thymine-rich surface can be achieved with a brush polymer bearing thymine moieties that can self-assemble into a multi-bilayer structure. Because of the thymine-rich surface, the PECH(SO(2))-T thin films even in only 6 nm thickness demonstrate the detection of mercury ions in aqueous solutions with a detection limit of 10(-6) M. PMID:21650219

  12. Two-dimensional electronic excitations in self-assembled conjugated polymer nanocrystals

    PubMed

    Osterbacka; An; Jiang; Vardeny

    2000-02-01

    Several spectroscopic methods were applied to study the characteristic properties of the electronic excitations in thin films of regioregular and regiorandom polythiophene polymers. In the regioregular polymers, which form two-dimensional lamellar structures, increased interchain coupling strongly influences the traditional one-dimensional electronic properties of the polymer chains. The photogenerated charge excitations (polarons) show two-dimensional delocalization that results in a relatively small polaronic energy, multiple absorption bands in the gap where the lowest energy band becomes dominant, and associated infrared active vibrations with reverse absorption bands caused by electron-vibration interferences. The relatively weak absorption bands of the delocalized polaron in the visible and near-infrared spectral ranges may help to achieve laser action in nanocrystalline polymer devices using current injection.

  13. Two-Dimensional Electronic Excitations in Self-Assembled Conjugated Polymer Nanocrystals

    NASA Astrophysics Data System (ADS)

    Österbacka, R.; An, C. P.; Jiang, X. M.; Vardeny, Z. V.

    2000-02-01

    Several spectroscopic methods were applied to study the characteristic properties of the electronic excitations in thin films of regioregular and regiorandom polythiophene polymers. In the regioregular polymers, which form two-dimensional lamellar structures, increased interchain coupling strongly influences the traditional one-dimensional electronic properties of the polymer chains. The photogenerated charge excitations (polarons) show two-dimensional delocalization that results in a relatively small polaronic energy, multiple absorption bands in the gap where the lowest energy band becomes dominant, and associated infrared active vibrations with reverse absorption bands caused by electron-vibration interferences. The relatively weak absorption bands of the delocalized polaron in the visible and near-infrared spectral ranges may help to achieve laser action in nanocrystalline polymer devices using current injection.

  14. Linking homogeneous and heterogeneous enantioselective catalysis through a self-assembled coordination polymer.

    PubMed

    García, José I; López-Sánchez, Beatriz; Mayoral, José A

    2008-11-01

    Combining the advantages of homogeneous and heterogeneous enantioselective catalysis is possible through self-supported copper coordination polymers, based on a new kind of ditopic chiral ligand bearing two azabis(oxazoline) moieties. When the coordination polymer is used to catalyze a cyclopropanation reaction, it becomes soluble in reaction conditions but precipitates after reaction completion, allowing easy recovery and efficient reuse in the same reaction up to 14 times.

  15. Surfactant-Templated Mesoporous Metal Oxide Nanowires

    DOE PAGESBeta

    Luo, Hongmei; Lin, Qianglu; Baber, Stacy; Naalla, Mahesh

    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

  16. Growth of single conductive nanowires at prescribed loci

    NASA Astrophysics Data System (ADS)

    Cheng, Chuanding; Haynie, Donald T.

    2005-12-01

    Conductive 75 nm diameter nanowires have been self-assembled from aqueous solution between 15μm gap electrodes on a SiO2 substrate at predefined locations. Nanowire assembly was initiated by application an electric field, and it occurred along the direction of field lines where the field is strongest. Certain salts of palladium, but not of related metals, yielded nanowires under comparable conditions. The simple and straightforward approach to nanowire assembly outlined here could be used for nano/microscale device interconnection at precise positions at room temperature, important for device development, integration, and packaging.

  17. 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.

  18. Synthesis and characterization of cadmium telluride nanowire

    NASA Astrophysics Data System (ADS)

    Kum, Maxwell C.; Yoo, Bong Young; Rheem, Young Woo; Bozhilov, Krassimir N.; Chen, Wilfred; Mulchandani, Ashok; Myung, Nosang V.

    2008-08-01

    CdTe nanowires with controlled composition were cathodically electrodeposited using track-etched polycarbonate membrane as scaffolds and their material and electrical properties were systematically investigated. As-deposited CdTe nanowires show nanocrystalline cubic phase structures with grain sizes of up to 60 nm. The dark-field images of nanowires reveal that the crystallinity of nanowires was greatly improved from nanocrystalline to a few single crystals within nanowires upon annealing at 200 °C for 6 h in a reducing environment (5% H2+95% N2). For electrical characterization, a single CdTe nanowire was assembled across microfabricated gold electrodes using the drop-casting method. In addition to an increase in grain size, the electrical resistivity of an annealed single nanowire (a few 105 Ω cm) was one order of magnitude greater than in an as-deposited nanowire, indicating that crystallinity of nanowires improved and defects within nanowires were reduced during annealing. By controlling the dopants levels (e.g. Te content of nanowires), the resistivity of nanowires was varied from 104 to 100 Ω cm. Current-voltage (I-V) characteristics of nanowires indicated the presence of Schottky barriers at both ends of the Au/CdTe interface. Temperature-dependent I-V measurements show that the electron transport mode was determined by a thermally activated component at T>-50 °C and a temperature-independent component below -50 °C. Under optical illumination, the single CdTe nanowire exhibited enhanced conductance.

  19. Heparin as a Bundler in a Self-Assembled Fibrous Network of Functionalized Protein-Based Polymers.

    PubMed

    Włodarczyk-Biegun, Małgorzata K; Slingerland, Cornelis J; Werten, Marc W T; van Hees, Ilse A; de Wolf, Frits A; de Vries, Renko; Stuart, Martien A Cohen; Kamperman, Marleen

    2016-06-13

    Nature shows excellent control over the mechanics of fibrous hydrogels by assembling protein fibers into bundles of well-defined dimensions. Yet, obtaining artificial materials displaying controlled bundling remains a challenge. Here, we developed genetically engineered protein-based polymers functionalized with heparin-binding KRSR domains and show controlled bundling using heparin as a binder. The protein polymer forms fibers upon increasing the pH to physiological values and at higher concentrations fibrous gels. We show that addition of heparin to the protein polymer with incorporated KRSR domains, induces bundling, which results in faster gel formation and stiffer gels. The interactions are expected to be primarily electrostatic and fiber bundling has an optimum when the positive charges of KRSR are approximately in balance with the negative charges of the heparin. Our study suggests that, generally, a straightforward method to control the properties of fibrous gels is to prepare a fiber former with specific binding domains and then simply adding an appropriate amount of binder. PMID:27129090

  20. Assembly Properties of an Alanine-Rich, Lysine-Containing Peptide and the Formation of Peptide/Polymer Hybrid Hydrogels.

    PubMed

    Grieshaber, Sarah E; Nie, Ting; Yan, Congqi; Zhong, Sheng; Teller, Sean S; Clifton, Rodney J; Pochan, Darrin J; Kiick, Kristi L; Jia, Xinqiao

    2011-02-01

    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 (AKA(3)KA)(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. 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).

  2. Polymer-facilitated low temperature fusing of spray-coated silver nanowire networks as transparent top and bottom electrodes in small molecule organic photovoltaics (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Selzer, Franz; Weiß, Nelli; Kneppe, David; Bormann, Ludwig; Sachse, Christoph; Gaponik, Nikolai; Eychmüller, Alexander; Leo, Karl; Müller-Meskamp, Lars

    2015-10-01

    Networks of silver nanowires (AgNWs) are promising candidates for transparent conducting electrodes in organic photovoltaics (OPV), as they achieve similar performance as the commonly used indium tin oxide (ITO) at lower cost and increased flexibility. The initial sheet resistance (Rs) of AgNW electrodes typically needs to be reduced by a post-annealing step (90 min@200 °C), being detrimental for processing on polymeric substrates. We present novel low temperature-based methods to integrate AgNWs in organic small molecule-based photovoltaics, either as transparent and highly conductive bottom-electrode or, for the first time, as spray-coated AgNW top-electrode. The bottom-electrodes are prepared by organic matrix assisted low-temperature fusing. Here, selected polymers are coated below the AgNWs to increase the interaction between NWs and substrate. In comparison to networks without these polymeric sublayers, the Rs is reduced by two orders of magnitude. AgNW top-electrodes are realized by dispersing modified high-quality AgNWs in inert solvents, which do not damage small molecule layers. Accordingly, our AgNW dispersion can be spray-coated onto all kind of OPV devices. Both bottom- and top-electrodes show a Rs of <11 Ω/ at >87 % transparency directly after spray-coating at very low substrate temperatures of <80 °C. We also demonstrate the implementation of our AgNW electrodes in organic solar cells. The corresponding devices show almost identical performance compared to organic solar cells exploiting ITO as bottom or thermally evaporated thin-metal as top-electrode.

  3. Molecular self assembly of mixed comb-like dextran surfactant polymers for SPR virus detection.

    PubMed

    Mai-Ngam, Katanchalee; Kiatpathomchai, Wansika; Arunrut, Narong; Sansatsadeekul, Jitlada

    2014-11-01

    The synthesis of two comb-like dextran surfactant polymers, that are different in their dextran molecular weight (MW) distribution and the presence of carboxylic groups, and their characterization are reported. A bimodal carboxylic dextran surfactant polymer consists of poly(vinyl amine) (PVAm) backbone with carboxyl higher MW dextran, non-functionalized lower MW dextran and hydrophobic hexyl branches; while a monomodal dextran surfactant polymer is PVAm grafted with non-functionalized lower MW dextran and hexyl branches. Layer formation of non-covalently attached dextran chains with bimodal MW distributions on a surface plasmon resonance (SPR) chip was investigated from the perspective of mixed physisorption of the bimodal and monomodal surfactant polymers. Separation distances between the carboxylic longer dextran side chains within the bimodal surfactant polymer and between the whole bimodal surfactant molecules on the chip surface could be well-controlled. SPR analysis of shrimp yellow head virus using our mixed surfactant chips showed dependence on synergetic adjustment of these separation distances.

  4. 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

  5. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  6. 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.

  7. 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.

  8. Synthesis of silver nanowires using hydrothermal technique for flexible transparent electrode application

    NASA Astrophysics Data System (ADS)

    Vijila, C. V. Mary; Rahman, K. K. Arsina; Parvathy, N. S.; Jayaraj, M. K.

    2016-05-01

    Transparent conducting films are becoming increasingly interesting because of their applications in electronics industry such as their use in solar energy applications. In this work silver nanowires were synthesized using solvothermal method by reducing silver nitrate and adding sodium chloride for assembling silver into nanowires. Absorption spectra of nanowires in the form of a dispersion in deionized water, AFM and SEM images confirm the nanowire formation. Solution of nanowire was coated over PET films to obtain transparent conducting films.

  9. 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.

  10. 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

  11. Doxorubicin-loaded aromatic imine-contained amphiphilic branched star polymer micelles: synthesis, self-assembly, and drug delivery.

    PubMed

    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)(n)s, 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)(n)s (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

  12. The first biantennary bacterial secondary cell wall polymer and its influence on S-layer glycoprotein assembly.

    PubMed Central

    Steindl, Christian; Schäffer, Christina; Wugeditsch, Thomas; Graninger, Michael; Matecko, Irena; Müller, Norbert; Messner, Paul

    2002-01-01

    -layer glycoprotein in vitro. Initial crystallization experiments performed with the soluble S-layer glycoprotein revealed that the assembly property could be restored upon dissociation of the polymer by the addition of poly(ethylene glycols). The formed two-dimensional crystalline S-layer self-assembly products exhibited the same lattice symmetry as observed on intact bacterial cells. PMID:12201818

  13. pH sensitive polymer nanoparticles: effect of hydrophobicity on self-assembly.

    PubMed

    Filippov, Sergey K; Starovoytova, Larisa; Konák, Cestmír; Hrubý, Martin; Macková, Hana; Karlsson, Göran; Stepánek, Petr

    2010-09-21

    The influence of hydrophobicity on formation, stability, and size of pH-responsive methacryloylated oligopeptide-based polymer nanoparticles has been studied by dynamic light scattering (DLS), transmission electron microscopy (Cryo-TEM), and NMR. Different polyanions/surfactant systems have been studied at constant polymer concentration and within a broad range of surfactant concentrations. The two newly synthesized pH-sensitive hydrophobic polyanions, poly(N(ω)-methacryloyl glycyl-L-leucine) and poly(N(ω)-methacryloyl glycyl-L-phenylalanyl-L-leucinyl-glycine), and three nonionic surfactants (Brij97, Brij98, and Brij700) have been investigated. The surfactants were different in the length of hydrophilic poly(ethylene oxide) (PEO) chain. In surfactant-free solution at basic pH, the polyanions form hydrophobic domains. In the presence of a surfactant, our results prove the complex formation at high pH between the nonionic surfactant and the polyelectrolyte; a pearl-necklace structure is formed. At low pH below critical pH (pH(tr)), reversible nanoscale structures occur in solutions for all systems. The detailed mechanism of the formation of pH-sensitive nanoparticles from polymer-surfactant complex with varying pH is established. Our results suggest that the polymer hydrophobicity is of primary importance in pretransitional behavior of the complex. Once preliminary nanoparticle nuclei are formed, the hydrophobicity of the polymer plays a minor role on further behavior of formed nanostructures. The subsequent transformation of nanoparticles is determined by the surfactant hydrophilicity, the length of hydrophilic tail that prevents further aggregation due to steric repulsions.

  14. Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

    PubMed Central

    Yan, Xuzhou; Li, Shijun; Pollock, James Bryant; Cook, Timothy R.; Chen, Jianzhuang; Zhang, Yanyan; Ji, Xiaofan; Yu, Yihua; Huang, Feihe; Stang, Peter J.

    2013-01-01

    A powerful strategy to obtain complex supramolecular materials is the bottom-up construction of noncovalently bound materials by hierarchical self-assembly. This assembly process involves stepwise, uniform increases to the architectural complexity of a substrate, starting from discrete precursors and growing in dimensionality through controlled reactivity to a final product. Herein, two orthogonal processes are exploited: coordination-driven self-assembly and hydrogen bonding. The former relies on the predictable formation of metal–ligand bonds wherein the directionalities of the rigid precursors used determines the structural outcome. The latter uses 2-ureido-4-pyrimidinone interfaces that are structurally robust by virtue of the quadruple hydrogen bonding that can occur between subunits. By combining these two processes into a single system, it is possible to generate hierarchical materials that preserve the attractive tunability associated with discrete supramolecular coordination complexes. For instance, the synthesis of a one-dimensional chain comprising linked metalla-rhomboids is readily adapted to a 2D cross-linked hexagonal network by simply selecting a different metal acceptor precursor as an assembly component. The specific interactions between subunits, in this case platinum(II)-pyridyl bonds and the quadruple H-bonding of ureidopyrimidinone, are unchanged, establishing a unique strategy to obtain supramolecular polymers with marked topological differences with minimal synthetic redesign. In addition, the structural rigidity imposed by the inclusion of the platinum metallacycles serves to minimize the formation of cyclic oligomers, increasing the efficacy of formation and improving the properties of the resultant materials. Furthermore, this study taps the potential of organoplatinum(II) metallacycles in materials science. PMID:24019475

  15. Freestanding and Reactive Thin Films Fabricated by Covalent Layer-by-Layer Assembly and Subsequent Lift-Off of Azlactone-Containing Polymer Multilayers

    PubMed Central

    Buck, Maren E.

    2010-01-01

    We report an approach to the fabrication of freestanding and amine-reactive thin films that is based on the reactive layer-by-layer assembly and subsequent lift-off of azlactone-containing polymer multilayers. We demonstrate that covalently crosslinked multilayers fabricated using the azlactone-functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and a primary amine-containing polymer [poly(ethyleneimine) (PEI)] can be delaminated from planar glass and silicon surfaces by immersion in mildly acidic aqueous environments to yield flexible freestanding membranes. These freestanding membranes are robust and can withstand exposure to strong acid, strong base, or incubation in high ionic strength solutions that typically lead to the disruption and erosion of polymer multilayers assembled by reversible weak interactions (e.g., ‘polyelectrolyte multilayers’ assembled by electrostatic interactions or hydrogen bonding). We demonstrate further that these PEI/PVDMA assemblies contain residual reactive azlactone functionality that can be exploited to chemically modify the films (either directly after fabrication or after they have been lifted off of the substrates on which they were fabricated) using a variety of amine-functionalized small molecules. These freestanding membranes can also be transferred readily onto other objects (for example, onto the surfaces of planar substrates containing holes or pores) to fabricate suspended polymer membranes and other film-functionalized interfaces. In addition to planar, two-dimensional freestanding films, this approach can be used to fabricate and isolate three-dimensional freestanding membranes (e.g., curved films or tubes) by layer-by-layer assembly on, and subsequent lift-off from, the surfaces of topologically complex substrates (e.g., the curved ends of glass tubing, etc.). The results of this investigation, when combined, suggest the basis of methods for the fabrication of stable, chemically-reactive, and

  16. Self-assembly of a three-dimensional fibrous polymer sponge by electrospinning.

    PubMed

    Sun, Bin; Long, Yun-Ze; Yu, Fang; Li, Meng-Meng; Zhang, Hong-Di; Li, Wen-Jing; Xu, Tian-Xiang

    2012-03-21

    In this paper, we report a quick approach to self-assemble three-dimensional (3D) spongiform nanofiber stacks via electrospinning, which usually fabricates 2D non-woven fiber mats. Through controlling experimental conditions, cone-like polystyrene fiber stacks can be self-assembled on aluminum foil within 30 min. The stacks are able to reach a height of more than 10 cm. Moreover, conversion between the 3D fiber stack and 2D thin film can be controlled. The formation mechanism of the self-assembled fiber stacks and the influence of experimental conditions have also been explored. The 3D fiber stacks may be promising for applications in many fields such as tissue engineering, electrodes of battery, and filtration, etc.

  17. Toward a chemiresistive ammonia (NH3) gas sensor based on viral-templated gold nanoparticles embedded in polypyrrole nanowires

    NASA Astrophysics Data System (ADS)

    Yan, Yiran; Zhang, Miluo; Su, Heng Chia; Myung, Nosang V.; Haberer, Elaine D.

    2014-08-01

    Preliminary studies toward the assembly of a gold-polypyrrole (PPy) peapod-like chemiresistive ammonia (NH3) gas sensors are presented. The proposed synthesis process will use electropolymerization to embed gold nanoparticles in polypyrrole nanowires. Viral-templating of gold nanoparticles and PPy electrodeposition via cyclic voltammetry are the focus of this investigation. A gold-binding M13 bacteriophage was used as a bio-template to assemble continuous chains of gold nanoparticles on interdigitated Pt working electrodes. The dimensions of the resulting nanowire-like structures were examined and the electrical resistance measured. PPy films were electropolymerized using an interdigitated planar, Pt electrode integrated counter and reference electrode. Morphological characterization of the polymer films was completed.

  18. Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.

    PubMed

    Miyamura, Hiroyuki; Sonoyama, Arisa; Hayrapetyan, Davit; Kobayashi, Shū

    2015-09-01

    While water-compatible Lewis acids have great potential as accessible and environmentally benign catalysts for various organic transformations, efficient immobilization of such Lewis acids while keeping high activity and without leaching of metals even under aqueous conditions is a challenging task. Self-assembled nanocomposite catalysts of organic polymers, carbon black, aluminum reductants, and scandium salts as heterogeneous water-compatible Lewis acid catalysts are described. These catalysts could be successfully applied to various C-C bond-forming reactions without leaching of metals. Scanning transmission electron microscopy analyses revealed that the nanocomposite structure of Al and Sc was fabricated in these heterogeneous catalysts. It is noted that Al species, which are usually decomposed rapidly in the presence of water, are stabilized under aqueous conditions. PMID:26228075

  19. Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.

    PubMed

    Miyamura, Hiroyuki; Sonoyama, Arisa; Hayrapetyan, Davit; Kobayashi, Shū

    2015-09-01

    While water-compatible Lewis acids have great potential as accessible and environmentally benign catalysts for various organic transformations, efficient immobilization of such Lewis acids while keeping high activity and without leaching of metals even under aqueous conditions is a challenging task. Self-assembled nanocomposite catalysts of organic polymers, carbon black, aluminum reductants, and scandium salts as heterogeneous water-compatible Lewis acid catalysts are described. These catalysts could be successfully applied to various C-C bond-forming reactions without leaching of metals. Scanning transmission electron microscopy analyses revealed that the nanocomposite structure of Al and Sc was fabricated in these heterogeneous catalysts. It is noted that Al species, which are usually decomposed rapidly in the presence of water, are stabilized under aqueous conditions.

  20. Comb polymer architecture and particle size effects on the behavior of biphasic nanoparticle inks for direct-write assembly

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Jun

    Biphasic nanoparticle mixtures composed of attractive and repulsive colloidal species enable the direct-write assembly of 3D structures with much finer features than those produced by pure colloidal gels. These mixtures rely on the use of comb polymer dispersants to render one particle population stable, while the other population is attractive. In this thesis, we systematically investigate the effects of comb polymer architecture and particle size ratio on the behavior of biphasic nanoparticle inks with the overarching aim of further advancing the direct-write assembly of 3D colloidal structures. We first investigated the effects of both pure polyelectrolytes, poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA), and comb polymer dispersants composed of a PMAA backbone with methoxy-poly(ethylene oxide) (mPEO) teeth of varying molecular weights on the stability of barium titanate (BaTiO 3) suspensions. While each dispersant imparts stability to BaTiO 3 nanoparticles at low ionic strength (< 0.01 M), only the PMAA-mPEO comb polymer with the longest teeth (MWteeth = 2000) provides stability at higher ionic strengths over a broad range of particle sizes and counterion valencies. These results provide guidelines for tailoring the molecular architecture and functionality of comb polymer dispersants for optimal stabilization of the repulsive particle population within the biphasic inks. Next, particle size effects on the rheological properties of biphasic nanoparticle suspensions are studied. Shear elastic modulus, shear yield stress, and compressive yield stress are measured for mixtures of varying total volume fraction, attractive-to-repulsive volume fraction, and particle size ratio between attractive and repulsive species. Our observations indicate that the repulsive particles hinder the formation of the attractive gel network. The time required for shear elastic modulus to approach a steady-state value increases with the fraction of repulsive species

  1. Block copolymer assembly on nanoscale patterns of polymer brushes formed by electrohydrodynamic jet printing.

    PubMed

    Onses, M Serdar; Ramírez-Hernández, Abelardo; Hur, Su-Mi; Sutanto, Erick; Williamson, Lance; Alleyne, Andrew G; Nealey, Paul F; de Pablo, Juan J; Rogers, John A

    2014-07-22

    Fundamental understanding of the self-assembly of domains in block copolymers (BCPs) and capabilities in control of these processes are important for their use as nanoscale templates in various applications. This paper focuses on the self-assembly of spin-cast and printed poly(styrene-block-methyl methacrylate) BCPs on patterned surface wetting layers formed by electrohydrodynamic jet printing of random copolymer brushes. Here, end-grafted brushes that present groups of styrene and methyl methacrylate in geometries with nanoscale resolution deterministically define the morphologies of BCP nanostructures. The materials and methods can also be integrated with lithographically defined templates for directed self-assembly of BCPs at multiple length scales. The results provide not only engineering routes to controlled formation of complex patterns but also vehicles for experimental and simulation studies of the effects of chemical transitions on the processes of self-assembly. In particular, we show that the methodology developed here provides the means to explore exotic phenomena displayed by the wetting behavior of BCPs, where 3-D soft confinement, chain elasticity, interfacial energies, and substrate's surface energy cooperate to yield nonclassical wetting behavior. PMID:24882265

  2. Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles.

    PubMed

    Coelho, João Paulo; Tardajos, Gloria; Stepanenko, Vladimir; Rödle, Alexander; Fernández, Gustavo; Guerrero-Martínez, Andrés

    2015-11-24

    The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs. PMID:26493583

  3. Reversible morphology transitions of supramolecular polymer self-assemblies for switch-controlled drug release.

    PubMed

    Zhang, Haitao; Fan, Xiaodong; Suo, Rongtian; Li, Hui; Yang, Zhen; Zhang, Wanbin; Bai, Yang; Yao, Hao; Tian, Wei

    2015-10-28

    A novel method for switch-controlled drug release was developed through the reversible morphology transitions of supramolecular branched copolymer self-assemblies. The reversible transitions from vesicles to nanoparticles were successfully achieved by alternating UV and visible light irradiation to obtain morphology-controlled drug release in a switch mode. PMID:26343347

  4. Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles.

    PubMed

    Coelho, João Paulo; Tardajos, Gloria; Stepanenko, Vladimir; Rödle, Alexander; Fernández, Gustavo; Guerrero-Martínez, Andrés

    2015-11-24

    The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs.

  5. Conductive polymer nanocomposites with hierarchical multi-scale structures via self-assembly of carbon-nanotubes on graphene on polymer-microspheres

    NASA Astrophysics Data System (ADS)

    Tang, Changyu; Long, Gucheng; Hu, Xin; Wong, Ka-Wai; Lau, Woon-Ming; Fan, Meikun; Mei, Jun; Xu, Tao; Wang, Bin; Hui, David

    2014-06-01

    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).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

  6. Current-dependent anisotropic conductivity of locally assembled silver nanoparticles in hybrid polymer films.

    PubMed

    Goel, Pooja; Vinokur, Rostislav; Weichold, Oliver

    2010-12-15

    The electrical behaviour of hybrid poly(ethylene terephthalate) films containing localised, percolating networks of silver nanoparticles separated by pure polymer is studied. The films resemble an array of parallel wires in the submicron range and, thus, exhibit anisotropic conductivity. In the high-conductivity direction at low amplitudes, the films show Ohmic behaviour, while at moderate voltage, non-linearity and a decreasing resistance is observed. The samples were found to heat up during the measurements and the deviation from Ohm's law coincides with the Tg of the polymer. Microstructural analysis of the samples revealed an irreversible agglomeration of the particles at moderate voltages leading to the formation of filaments with higher metallic character than the random particle network.

  7. A membrane-less enzymatic fuel cell with layer-by-layer assembly of redox polymer and enzyme over graphite electrodes.

    PubMed

    Rengaraj, Saravanan; Mani, Vigneshwaran; Kavanagh, Paul; Rusling, James; Leech, Dónal

    2011-11-21

    Layer-by-layer (LBL) assembly of alternate osmium redox polymers and glucose oxidase, at anode, and laccase, at cathode, using graphite electrodes form a membrane-less glucose/O(2) enzymatic fuel cell providing a power density of 103 μW cm(-2) at pH 5.5. PMID:21975371

  8. Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes.

    PubMed

    Xu, Chao; Hedin, Niklas; Shi, Hua-Tian; Xin, ZhiFeng; Zhang, Qian-Feng

    2015-04-14

    Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

  9. Polymer complexes. LVIII. Structures of supramolecular assemblies of vanadium with chelating groups.

    PubMed

    El-Sonbati, A Z; Belal, A A M; Diab, M A; Balboula, M Z

    2011-03-01

    Oxovanadium(IV) polymer complexes of formulation {[(VO)L](2)}(n) (1) and [(VO)LB](n) (2-4), where H(2)L is tridentate and dianionic ligand (allylazorhodanine) and B is planar heterocyclic and aliphatic base have been prepared and characterized by elemental analyses, IR, (1)H NMR, electronic spin resonance spectra, magnetic susceptibility measurements, molar conductance and thermal studies. The molecular structure shows the presence of a vanadyl group in six-coordinate VNO(3)/VN(3)O(3) coordination geometry. The N,N-donor heterocyclic and aliphatic bas displays a chelating mode of binding with an N-donor site trans to the vanadyl oxo-group. In all polymeric complexes (1-4) the ligand coordinates through oxygen of phenolic/enolic and azodye nitrogen. The molar conductivity data show them to be non-electrolytes. All the polymer complexes are ESR active due to the presence of an unpaired electron. The calculated bonding parameters indicate that in-plane σ bonding is more covalent than in-plane π bonding. From the electronic, magnetic and ESR spectral data suggest that all the oxovanadium(IV) polymer complexes have distorted octahedral geometry. The thermal decomposition process of the polymeric complexes involves three decomposition steps. PMID:21227746

  10. Polymer complexes. LVIII. Structures of supramolecular assemblies of vanadium with chelating groups

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Belal, A. A. M.; Diab, M. A.; Balboula, M. Z.

    2011-03-01

    Oxovanadium(IV) polymer complexes of formulation {[(VO)L] 2} n (1) and [(VO)LB] n (2-4), where H 2L is tridentate and dianionic ligand (allylazorhodanine) and B is planar heterocyclic and aliphatic base have been prepared and characterized by elemental analyses, IR, 1H NMR, electronic spin resonance spectra, magnetic susceptibility measurements, molar conductance and thermal studies. The molecular structure shows the presence of a vanadyl group in six-coordinate VNO 3/VN 3O 3 coordination geometry. The N,N-donor heterocyclic and aliphatic bas displays a chelating mode of binding with an N-donor site trans to the vanadyl oxo-group. In all polymeric complexes (1-4) the ligand coordinates through oxygen of phenolic/enolic and azodye nitrogen. The molar conductivity data show them to be non-electrolytes. All the polymer complexes are ESR active due to the presence of an unpaired electron. The calculated bonding parameters indicate that in-plane σ bonding is more covalent than in-plane π bonding. From the electronic, magnetic and ESR spectral data suggest that all the oxovanadium(IV) polymer complexes have distorted octahedral geometry. The thermal decomposition process of the polymeric complexes involves three decomposition steps.

  11. Polymer-templated electrodeposition of Ag nanosheets assemblies array as reproducible surface-enhanced Raman scattering substrate.

    PubMed

    Liu, Sisi; Xu, Zhimou; Sun, Tangyou; Zhao, Wenning; Wu, Xinghui; Ma, Zhichao; Zhang, Xueming; He, Jian; Chen, Cunhua

    2014-06-01

    Position-configurable, reproducible, vertically aligned nanosheets assemblies (ANAs) arrays are fabricated by polymer-templated electrodeposition method at room temperature. Here, nanoimprint lithography is utilized to fabricate polymer template on the fluorine-doped tin oxide substrate for the purpose of evenly tuning the location of Ag nanostructures. Subsequently, vertically aligned ANAs can be achieved at the bottom of each hole via electrodeposition in a mixed aqueous solution of AgNO3 and citric acid. To obtain uniform ANAs array, we have systematically investigated the factors that influenced the electrodeposition. It was found that the formation of uniform ANAs arrays is strongly depended on the seeding layer, citric acid concentration, electrodeposition potential and time. The as-synthesized ANAs array exhibited a remarkable SERS activity and Raman signal reproducibility to rhodamine 6G, a concentration down to 10(-13) M can be identified. Our results revealed that the ANAs array is a highly desirable candidate as the reliable enhancer for high performance SERS analysis.

  12. Conducting Polymer Nanostructures and Nanocomposites with Carbon Nanotubes: Hierarchical Assembly by Molecular Electrochemistry, Growth Aspects and Property Characterization.

    PubMed

    Gupta, Sanju; Price, Carson; Heintzman, Eli

    2016-01-01

    Conducting (or π-conjugated) polymers are promising materials for preparing supramolecular nano-structures and nanocomposites. We report controlled nanostructure syntheses of polypyrrole (PPy) and poylaniline (PANi) via electropolymerization (i.e., in-situ electrochemical anodic oxidation). The density, shape, caliber and thickness of self-assembled PPy micro-containers are regulated by electrochemical potential window for H2 bubbles and number of cyclic voltammetric (potentiodynamic) scans. Likewise, we employed amperometry, chronopotentiometry and potentiodynamic modes using hydrochloric acid as oxidizing agent to prepare PANi nanoparticles and nanotubules. We present our findings from the viewpoint of molecular electrochemistry with growth kinetic aspects yielding mechanistic details (initially forming dimers and oligomers as nucleating agents followed by polymer growth). Also targeted is forming nanocomposites with functionalized single- and multi-walled carbon nanotubes (FSWCNTs and FMWCNTs) as reinforced agent to optimize structural and functional properties. All of these novel nanomaterials are characterized using a range of complementary techniques to establish microscopic structure-property-function relationship. PMID:27398466

  13. Free-Standing, Patternable Nanoparticle/Polymer Monolayer Arrays Formed by Evaporation Induced Self-Assembly at a Fluid Interface

    SciTech Connect

    Pang, Jiebin; Xiong, Shisheng; Jaeckel, Felix; Sun, Zaicheng; Dunphy, Darren; Brinker, C.Jeffrey

    2008-12-03

    We report a general and facile method to prepare free-standing, patternable nanoparticle/polymer monolayer arrays by interfacial NP assembly within a polymeric photoresist. The ultrathin monolayer nanoparticle/polymer arrays are sufficiently robust that they can be transferred to arbitrary substrates and suspended as free-standing membranes over cm-sized holes -- even with free edges. More importantly, the polymethylmethacrylate (PMMA) in the system serves as a photoresist enabling two modes of electron beam (e-beam) patterning. Lower e-beam doses direct differential nanoparticle solubility and result in nanoparticle patterns with somewhat diffuse interfaces. At higher e-beam doses the PMMA serves as a negative resist resulting in submicrometer patterns with edge roughness comparable to that of the nanoparticle diameter. These ultrathin 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 macroscale devices including photovoltaics, sensors, catalysis, and magnetic storage.

  14. Morphology control of polymer: Fullerene solar cells by nanoparticle self-assembly

    NASA Astrophysics Data System (ADS)

    Zhang, Wenluan

    During the past two decades, research in the field of polymer based solar cells has attracted great effort due to their simple processing, mechanical flexibility and potential low cost. A standard polymer solar cell is based on the concept of a bulk-heterojunction composed of a conducting polymer as the electron donor and a fullerene derivative as the electron acceptor. Since the exciton lifetime is limited, this places extra emphasis on control of the morphology to obtain improved device performance. In this thesis, detailed characterization and novel morphological design of polymer solar cells was studied, in addition, preliminary efforts to transfer laboratory scale methods to industrialized device fabrication was made. Magnetic contrast neutron reflectivity was used to study the vertical concentration distribution of fullerene nanoparticles within poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2- b]thiophene (pBTTT) thin film. Due to the wide space between the side chains of polymer, these fullerene nanoparticles intercalate between them creating a stable co-crystal structure. Therefore, a high volume fraction of fullerene was needed to obtain optimal device performance as phase separated conductive pathways are required and resulted in a homogeneous fullerene concentration profile through the film. Small angle neutron scattering was used to find there is amorphous fullerene even at lower concentration since it was previously believed that all fullerene formed a co-crystal. These fullerene molecules evolve into approximately 15 nm sized agglomerates at higher concentrations to improve electron transport. Unfortunately, thermal annealing gives these agglomerates mobility to form micrometer sized crystals and reduce the device performance. In standard poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCMBM) solar cells, a higher concentration of PCBM at the cathode interface is desired due to the band alignment structure. This was

  15. Multi-shape memory polymers achieved by the spatio-assembly of 3D printable thermoplastic building blocks.

    PubMed

    Li, Hongze; Gao, Xiang; Luo, Yingwu

    2016-04-01

    Multi-shape memory polymers were prepared by the macroscale spatio-assembly of building blocks in this work. The building blocks were methyl acrylate-co-styrene (MA-co-St) copolymers, which have the St-block-(St-random-MA)-block-St tri-block chain sequence. This design ensures that their transition temperatures can be adjusted over a wide range by varying the composition of the middle block. The two St blocks at the chain ends can generate a crosslink network in the final device to achieve strong bonding force between building blocks and the shape memory capacity. Due to their thermoplastic properties, 3D printing was employed for the spatio-assembly to build devices. This method is capable of introducing many transition phases into one device and preparing complicated shapes via 3D printing. The device can perform a complex action via a series of shape changes. Besides, this method can avoid the difficult programing of a series of temporary shapes. The control of intermediate temporary shapes was realized via programing the shapes and locations of building blocks in the final device. PMID:26924759

  16. Oil-in-Oil Emulsions Stabilized by Asymmetric Polymersomes Formed by AC + BC Block Polymer Co-Assembly.

    PubMed

    Asano, Itaru; So, Soonyong; Lodge, Timothy P

    2016-04-13

    We demonstrate a facile route to asymmetric polymersomes by blending AC and BC block copolymers in oil-in-oil emulsions containing polystyrene (PS) and polybutadiene (PB) in chloroform (CHCl3). Polymersomes were prepared by mixing polystyrene-b-poly(ethylene oxide) (SO) and polybutadiene-b-poly(ethylene oxide) (BO) in the oil-in-oil emulsion, where the droplets and continuous phase are PS- and PB-rich, respectively. The polymersome structure was directly visualized using dye-labeled SO and BO with confocal fluorescence microscopy; SO and BO with a high O block fraction co-assemble to produce asymmetric polymersomes. As the O block is insoluble in both PS and PB, we infer that the detailed structure of the polymersomes is a bilayer in which the S and B blocks face the PS-inner and PB-outer phases, respectively, while the common O blocks form the core membrane. This structure is only observed for sufficiently long O blocks. It is remarkable that although all the polymers are soluble in CHCl3, such elaborate structures are created by straightforward co-assembly. These asymmetric polymersomes should provide robust bilayer membranes around emulsion droplets, leading to stable nanoscopic dispersions of two fluids. PMID:27046136

  17. Oil-in-Oil Emulsions Stabilized by Asymmetric Polymersomes Formed by AC + BC Block Polymer Co-Assembly.

    PubMed

    Asano, Itaru; So, Soonyong; Lodge, Timothy P

    2016-04-13

    We demonstrate a facile route to asymmetric polymersomes by blending AC and BC block copolymers in oil-in-oil emulsions containing polystyrene (PS) and polybutadiene (PB) in chloroform (CHCl3). Polymersomes were prepared by mixing polystyrene-b-poly(ethylene oxide) (SO) and polybutadiene-b-poly(ethylene oxide) (BO) in the oil-in-oil emulsion, where the droplets and continuous phase are PS- and PB-rich, respectively. The polymersome structure was directly visualized using dye-labeled SO and BO with confocal fluorescence microscopy; SO and BO with a high O block fraction co-assemble to produce asymmetric polymersomes. As the O block is insoluble in both PS and PB, we infer that the detailed structure of the polymersomes is a bilayer in which the S and B blocks face the PS-inner and PB-outer phases, respectively, while the common O blocks form the core membrane. This structure is only observed for sufficiently long O blocks. It is remarkable that although all the polymers are soluble in CHCl3, such elaborate structures are created by straightforward co-assembly. These asymmetric polymersomes should provide robust bilayer membranes around emulsion droplets, leading to stable nanoscopic dispersions of two fluids.

  18. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    PubMed

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained. PMID:24621148

  19. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    PubMed

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained.

  20. Towards a comprehensive insight into efficient hydrogen production by self-assembled Ru(bpy)3(2+)-polymer-Pt artificial photosystems.

    PubMed

    Lin, Huan; Liu, Dan; Long, Jinlin; Zhang, Zizhong; Zhuang, Huaqiang; Zheng, Yi; Wang, Xuxu

    2015-04-28

    The role of polymers in artificial photosystems has been studied in detail. The photosystems were composed of tris(2,2'-bipyridyl) ruthenium(II) chloride as a photosensitizer (PS), colloidal Pt stabilized by polymer as a hydrogen-evolving catalyst and sodium ascorbate as an electron donor, without the addition of a traditional molecular electron mediator. Comprehensive insights into the production of hydrogen on irradiation with visible light were achieved. Several polymers, including neutral polyvinyl pyrrolidone, anionic poly(sodium 4-styrene sulfonate) and poly(acrylic acid) not only stabilized the nanoparticles, but were also effective in the production of hydrogen. Under the optimum conditions, an outstanding apparent quantum efficiency of 12.8% for the evolution of hydrogen was achieved. The formation of self-assembled and spatially separated donor-acceptor complexes via the non-covalent intermolecular interaction between PS and the polymer-Pt was pivotal in the efficient conversion of solar energy to hydrogen fuel. Important details of the photo-induced electron and energy transfer processes in the self-assembled artificial photosystems were determined by nanosecond transient absorption spectrometry and time-resolved fluorescence spectrometry. The initial step in the photo-catalytic production of hydrogen was a reductive quenching of the triplet excited state of the PS by sodium ascorbate, leading to a reduced form of PS, which could then be quickly quenched by the polymer. The rate-determining step was the electron transfer from PS to the catalyst via the polymer bridge. PMID:25811660

  1. Towards a comprehensive insight into efficient hydrogen production by self-assembled Ru(bpy)3(2+)-polymer-Pt artificial photosystems.

    PubMed

    Lin, Huan; Liu, Dan; Long, Jinlin; Zhang, Zizhong; Zhuang, Huaqiang; Zheng, Yi; Wang, Xuxu

    2015-04-28

    The role of polymers in artificial photosystems has been studied in detail. The photosystems were composed of tris(2,2'-bipyridyl) ruthenium(II) chloride as a photosensitizer (PS), colloidal Pt stabilized by polymer as a hydrogen-evolving catalyst and sodium ascorbate as an electron donor, without the addition of a traditional molecular electron mediator. Comprehensive insights into the production of hydrogen on irradiation with visible light were achieved. Several polymers, including neutral polyvinyl pyrrolidone, anionic poly(sodium 4-styrene sulfonate) and poly(acrylic acid) not only stabilized the nanoparticles, but were also effective in the production of hydrogen. Under the optimum conditions, an outstanding apparent quantum efficiency of 12.8% for the evolution of hydrogen was achieved. The formation of self-assembled and spatially separated donor-acceptor complexes via the non-covalent intermolecular interaction between PS and the polymer-Pt was pivotal in the efficient conversion of solar energy to hydrogen fuel. Important details of the photo-induced electron and energy transfer processes in the self-assembled artificial photosystems were determined by nanosecond transient absorption spectrometry and time-resolved fluorescence spectrometry. The initial step in the photo-catalytic production of hydrogen was a reductive quenching of the triplet excited state of the PS by sodium ascorbate, leading to a reduced form of PS, which could then be quickly quenched by the polymer. The rate-determining step was the electron transfer from PS to the catalyst via the polymer bridge.

  2. Highly ordered self-assembling polymer/clay nanocomposite barrier film.

    PubMed

    Cook, Ray; Chen, Yihong; Beall, Gary W

    2015-05-27

    Efforts to mimic complex-structured biologically based materials such as abalone shell have occupied substantial research time and effort in science and engineering. The majority of the efforts involve tedious and expensive techniques and processes. Layer-by-layer (LBL) is one such technique that can produce materials with quite unique physical properties, approaching, and in some cases surpassing, those seen in nature. The LBL technique, however, is quite tedious and difficult to implement commercially. We report here the discovery of an organic/inorganic spontaneous self-assembling system that forms a highly structured nanocomposite. The driving force behind this self-assembly appears to be entropy. This discovery should open up completely new avenues to designing hierarchical composites and structures. The films have been studied by X-ray diffraction and the barrier properties for oxygen diffusion measured. PMID:25946617

  3. A Robust Highly Aligned DNA Nanowire Array-Enabled Lithography for Graphene Nanoribbon Transistors.

    PubMed

    Kang, Seok Hee; Hwang, Wan Sik; Lin, Zhiqun; Kwon, Se Hun; Hong, Suck Won

    2015-12-01

    Because of its excellent charge carrier mobility at the Dirac point, graphene possesses exceptional properties for high-performance devices. Of particular interest is the potential use of graphene nanoribbons or graphene nanomesh for field-effect transistors. Herein, highly aligned DNA nanowire arrays were crafted by flow-assisted self-assembly of a drop of DNA aqueous solution on a flat polymer substrate. Subsequently, they were exploited as "ink" and transfer-printed on chemical vapor deposited (CVD)-grown graphene substrate. The oriented DNA nanowires served as the lithographic resist for selective removal of graphene, forming highly aligned graphene nanoribbons. Intriguingly, these graphene nanoribbons can be readily produced over a large area (i.e., millimeter scale) with a high degree of feature-size controllability and a low level of defects, rendering the fabrication of flexible two terminal devices and field-effect transistors.

  4. 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). PMID:26418290

  5. Interplay between polymer chain conformation and nanoparticle assembly in model industrial silica/rubber nanocomposites.

    PubMed

    Bouty, Adrien; Petitjean, Laurent; Chatard, Julien; Matmour, Rachid; Degrandcourt, Christophe; Schweins, Ralf; Meneau, Florian; Kwasńiewski, Paweł; Boué, François; Couty, Marc; Jestin, Jacques

    2016-01-01

    The question of the influence of nanoparticles (NPs) on chain dimensions in polymer nanocomposites (PNCs) has been treated mainly through the fundamental way using theoretical or simulation tools and experiments on well-defined model PNCs. Here we present the first experimental study on the influence of NPs on the polymer chain conformation for PNCs designed to be as close as possible to industrial systems employed in the tire industry. PNCs are silica nanoparticles dispersed in a styrene-butadiene-rubber (SBR) matrix whose NP dispersion can be managed by NP loading with interfacial coatings or coupling additives usually employed in the manufacturing mixing process. We associated specific chain (d) labeling, and the so-called zero average contrast (ZAC) method, with SANS, in situ SANS and SAXS/TEM experiments to extract the polymer chain scattering signal at rest for non-cross linked and under stretching for cross-linked PNCs. NP loading, individual clusters or connected networks, as well as the influence of the type, the quantity of interfacial agent and the influence of the elongation rate have been evaluated on the chain conformation and on its related deformation. We clearly distinguish the situations where the silica is perfectly matched from those with unperfected matching by direct comparison of SANS and SAXS structure factors. Whatever the silica matching situation, the additive type and quantity and the filler content, there is no significant change in the polymer dimension for NP loading up to 15% v/v within a range of 5%. One can see an extra scattering contribution at low Q, as often encountered, enhanced for non-perfect silica matching but also visible for perfect filler matching. This contribution can be qualitatively attributed to specific h or d chain adsorption on the NP surface inside the NP cluster that modifies the average scattering neutron contrast of the silica cluster. Under elongation, NPs act as additional cross-linking junctions

  6. Quartz resonator assembling with TSV interposer using polymer sealing or metal bonding

    PubMed Central

    2014-01-01

    This paper presents one wafer level packaging approach of quartz resonator based on through-silicon via (TSV) interposer with metal or polymer bonding sealing of frequency components. The proposed silicon-based package of quartz resonator adopts several three-dimensional (3D) core technologies, such as Cu TSVs, sealing bonding, and wafer thinning. It is different from conventional quartz resonator using ceramic-based package. With evaluation of mechanical structure design and package performances, this quartz resonator with advanced silicon-based package shows great manufacturability and excellent performance to replace traditional metal lid with ceramic-based interposer fabrication approach. PMID:25324705

  7. Interplay between polymer chain conformation and nanoparticle assembly in model industrial silica/rubber nanocomposites.

    PubMed

    Bouty, Adrien; Petitjean, Laurent; Chatard, Julien; Matmour, Rachid; Degrandcourt, Christophe; Schweins, Ralf; Meneau, Florian; Kwasńiewski, Paweł; Boué, François; Couty, Marc; Jestin, Jacques

    2016-01-01

    The question of the influence of nanoparticles (NPs) on chain dimensions in polymer nanocomposites (PNCs) has been treated mainly through the fundamental way using theoretical or simulation tools and experiments on well-defined model PNCs. Here we present the first experimental study on the influence of NPs on the polymer chain conformation for PNCs designed to be as close as possible to industrial systems employed in the tire industry. PNCs are silica nanoparticles dispersed in a styrene-butadiene-rubber (SBR) matrix whose NP dispersion can be managed by NP loading with interfacial coatings or coupling additives usually employed in the manufacturing mixing process. We associated specific chain (d) labeling, and the so-called zero average contrast (ZAC) method, with SANS, in situ SANS and SAXS/TEM experiments to extract the polymer chain scattering signal at rest for non-cross linked and under stretching for cross-linked PNCs. NP loading, individual clusters or connected networks, as well as the influence of the type, the quantity of interfacial agent and the influence of the elongation rate have been evaluated on the chain conformation and on its related deformation. We clearly distinguish the situations where the silica is perfectly matched from those with unperfected matching by direct comparison of SANS and SAXS structure factors. Whatever the silica matching situation, the additive type and quantity and the filler content, there is no significant change in the polymer dimension for NP loading up to 15% v/v within a range of 5%. One can see an extra scattering contribution at low Q, as often encountered, enhanced for non-perfect silica matching but also visible for perfect filler matching. This contribution can be qualitatively attributed to specific h or d chain adsorption on the NP surface inside the NP cluster that modifies the average scattering neutron contrast of the silica cluster. Under elongation, NPs act as additional cross-linking junctions

  8. High-field mobility in an assembly of conjugated polymer segments

    NASA Astrophysics Data System (ADS)

    Bussac, M. N.; Zuppiroli, L.

    1996-08-01

    We present a calculation of the hopping rate between the finite chains of a conjugated polymer. It is based on the optimization of the semiclassical hopping rates with respect to the possible widths and possible positions of the large polaron during the jump. For sufficient long chains and high enough fields, we arrive at an expression for the mobility which resembles a Fowler-Nordheim dependence with the field F, namely, exp-(F0/F). In this regime the mobility is weakly temperature dependent.

  9. Quartz resonator assembling with TSV interposer using polymer sealing or metal bonding.

    PubMed

    Shih, Jian-Yu; Chen, Yen-Chi; Chiu, Chih-Hung; Lo, Chung-Lun; Chang, Chi-Chung; Chen, Kuan-Neng

    2014-01-01

    This paper presents one wafer level packaging approach of quartz resonator based on through-silicon via (TSV) interposer with metal or polymer bonding sealing of frequency components. The proposed silicon-based package of quartz resonator adopts several three-dimensional (3D) core technologies, such as Cu TSVs, sealing bonding, and wafer thinning. It is different from conventional quartz resonator using ceramic-based package. With evaluation of mechanical structure design and package performances, this quartz resonator with advanced silicon-based package shows great manufacturability and excellent performance to replace traditional metal lid with ceramic-based interposer fabrication approach. PMID:25324705

  10. Controllable deformation of silicon nanowires with strain up to 24%

    SciTech Connect

    Walavalkar, Sameer S.; Homyk, Andrew P.; Henry, M. David; Scherer, Axel

    2010-06-15

    Fabricated silicon nanostructures demonstrate mechanical properties unlike their macroscopic counterparts. Here we use a force mediating polymer to controllably and reversibly deform silicon nanowires. This technique is demonstrated on multiple nanowire configurations, which undergo deformation without noticeable macroscopic damage after the polymer is removed. Calculations estimate a maximum of nearly 24% strain induced in 30 nm diameter pillars. The use of an electron activated polymer allows retention of the strained configuration without any external input. As a further illustration of this technique, we demonstrate nanoscale tweezing by capturing 300 nm alumina beads using circular arrays of these silicon nanowires.

  11. Template-free fabrication of Ag nanowire arrays/Al2O3 assembly with flexible collective longitudinal-mode resonance and ultrafast nonlinear optical response

    NASA Astrophysics Data System (ADS)

    Hui, Shuai; Gao, Junhua; Wu, Xingzhi; Li, Zhongguo; Zou, Yousheng; Song, Yinglin; Cao, Hongtao

    2016-06-01

    We utilized a co-sputtering technique without any templates, featuring growing and etching synchronously, to delicately fabricate dense and ultrafine Ag nanowire arrays/alumina matrix composite films. Both the diameter and separation distance of the Ag nanowire arrays in the composites are not only within the scope of sub-10 nm but also tunable, which is very hard to accomplish for the conventional optical lithography- or template-based method. It is exhibited that the collective longitudinal plasmon resonance of the composite films, covering a wide range from visible to the near infrared region, is extremely sensitive to the geometrical parameters of the Ag nanowires, owing to the strong plasmonic coupling among neighboring nanowires. The experimental observations were also theoretically supported by the near-field electromagnetic numerical simulation. More interestingly, the fabricated composite films demonstrated ultrafast nonlinear optical response in the visible light region under femtosecond laser excitation, possessing a short relaxation time of 1.45 ps for the longitudinal mode (L mode) resonance. These results indicate that the proposed composite films as a building block with exotic optical properties could provide an opportunity to construct integrated nanodevices for plasmonic optical applications.

  12. Computational Insight into Solvent Effects on Conformation and Assembly of Structured Ionic Polymer

    NASA Astrophysics Data System (ADS)

    Senanayake, Manjula; Aryal, Dipak; Perahia, Dvora; Grest, Gary

    Structured ionomers are in the core of numerous current and potential new applications including clean energy, water purification membranes and sensors. The ability to facilitate ions and solvents transport is a key to their function and is controlled by their structure. One effective path for structural control is tuning their conformation by solvent interactions. Here, the confirmation and association of an ABCBA co-polymer where C is a randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55, B is poly (ethylene-r-propylene), and A is poly (t-butyl styrene), in n-propanol are studied by molecular dynamic simulation. In contrast to the collapsed conformation of the ionizable block in hydrophobic solvents, we find that it remains swollen. Similar to hydrophobic solutions the co-polymers aggregate to form an ionizable core surrounded by extended hydrophobic chains. In contrast to the ``locked-in'' ionizable segments observed in cyclohexane/heptane, here the ionic clusters remain dynamic. Supported in part by DOE Grant No. DE-SC007908.

  13. Coordination polymers assembled from semirigid fluorene-based ligand: A couple of enantiomers

    NASA Astrophysics Data System (ADS)

    Li, Liang; Wang, Zihao; Chen, Qiang; Zhou, Xinhui; yang, Tao; Zhao, Qiang; Huang, Wei

    2015-11-01

    A couple of Mg(II)-based coordination polymer enantiomers [MgL(DMF)(H2O)3]n (R-MgL and S-MgL), and a Zn(II)-based coordination polymer [ZnL(DMF)]n (ZnL) have been synthesized by the solvothermal reactions between the achiral ligand 4,4‧-(9,9-dimethyl-9H-fluorene-2,7-diyl)dibenzoic acid (H2L) and the corresponding metal salts. The MgL was obtained as the racemic conglomerate from the one pot reaction. The single crystal X-ray structural analyses reveal that MgL crystallize in the chiral space group P21 and possesses the right- or left-handed homochiral 1D Mg-O-C helical chain. The ZnL crystallize in the non-centrosymmetrical space group Aba2 and possesses the 2D network comprised of 1D Zn-O-C meso-helical chains and ligands. The MgL and ZnL complexes exhibit strong coordination-perturbed ligand-centered blue emissions when excited at 320 nm. Their second-order nonlinear optical effects and thermal properties have also been studied.

  14. Structural diversity in binary superlattices self-assembled from polymer-grafted nanocrystals

    PubMed Central

    Ye, Xingchen; Zhu, Chenhui; Ercius, Peter; Raja, Shilpa N.; He, Bo; Jones, Matthew R.; Hauwiller, Matthew R.; Liu, Yi; Xu, Ting; Alivisatos, A. Paul

    2015-01-01

    Multicomponent nanocrystal superlattices represent an interesting class of material that derives emergent properties from mesoscale structure, yet their programmability can be limited by the alkyl-chain-based ligands decorating the surfaces of the constituent nanocrystals. Polymeric ligands offer distinct advantages, as they allow for more precise tuning of the effective size and ‘interaction softness' through changes to the polymer's molecular weight, chemical nature, architecture, persistence length and surrounding solvent. Here we show the formation of 10 different binary nanocrystal superlattices (BNSLs) with both two- and three-dimensional order through independent adjustment of the core size of spherical nanocrystals and the molecular weight of densely grafted polystyrene ligands. These polymer-brush-based ligands introduce new energetic contributions to the interparticle potential that stabilizes various BNSL phases across a range of length scales and interparticle spacings. Our study opens the door for nanocrystals to become modular elements in the design of functional particle brush solids with controlled nanoscale interfaces and mesostructures. PMID:26628256

  15. Lithographically patterned nanowire electrodeposition

    NASA Astrophysics Data System (ADS)

    Xiang, Chengxiang

    Lithographically patterned nanowire electrodeposition (LPNE) is a new method for fabricating polycrystalline metal nanowires using electrodeposition. In LPNE, a sacrificial metal (M1 = silver or nickel) layer, 5 - 100 nm in thickness, is first vapor deposited onto a glass, oxidized silicon, or Kapton polymer film. A photoresist (PR) layer is then deposited, photopatterned, and the exposed Ag or Ni is removed by wet etching. The etching duration is adjusted to produce an undercut ≈300 nm in width at the edges of the exposed PR. This undercut produces a horizontal trench with a precisely defined height equal to the thickness of theM1 layer. Within this trench, a nanowire of metal M2 is electrodeposited (M2 = gold, platinum, palladium, or bismuth). Finally the PR layer and M1 layer are removed. The nanowire height and width can be independently controlled down to minimum dimensions of 5 nm (h) and 11 nm (w), for example, in the case of platinum. These nanowires can be 1 cm in total length. We measure the temperature-dependent resistance of 100 um sections of Au and Pd wires in order to estimate an electrical grain size for comparison with measurements by X-ray diffraction and transmission electron microscopy. Nanowire arrays can be postpatterned to produce two-dimensional arrays of nanorods. Nanowire patterns can also be overlaid one on top of another by repeating the LPNE process twice in succession to produce, for example, arrays of low-impedance, nanowirenanowire junctions. The resistance, R, of single gold nanowires was measured in situ during electrooxidation in aqueous 0.10 M sulfuric acid. Electrooxidation caused the formation of a gold oxide that is approximately 0.8 monolayers (ML) in thickness at +1.1 V vs saturated mercurous sulfate reference electrode (MSE) based upon coulometry and ex situ X-ray photoelectron spectroscopic analysis. As the gold nanowires were electrooxidized, R increased by an amount that depended on the wire thickness, ranging from

  16. Solar heating of GaAs nanowire solar cells.

    PubMed

    Wu, Shao-Hua; Povinelli, Michelle L

    2015-11-30

    We use a coupled thermal-optical approach to model the operating temperature rise in GaAs nanowire solar cells. We find that despite more highly concentrated light absorption and lower thermal conductivity, the overall temperature rise in a nanowire structure is no higher than in a planar structure. Moreover, coating the nanowires with a transparent polymer can increase the radiative cooling power by 2.2 times, lowering the operating temperature by nearly 7 K. PMID:26698787

  17. Fiber Optic pH Sensor with Self-Assembled Polymer Multilayer Nanocoatings

    PubMed Central

    Shao, Li-Yang; Yin, Ming-Jie; Tam, Hwa-Yaw; Albert, Jacques

    2013-01-01

    A fiber-optic pH sensor based on a tilted fiber Bragg grating (TFBG) with electrostatic self-assembly multilayer sensing film is presented. The pH sensitive polymeric film, poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) was deposited on the circumference of the TFBG with the layer-by-layer (LbL) electrostatic self-assembly technique. The PDDA/PAA film exhibits a reduction in refractive index by swelling in different pH solutions. This effect results in wavelength shifts and transmission changes in the spectrum of the TFBG. The peak amplitude of the dominant spectral fringes over a certain window of the transmission spectrum, obtained by FFT analysis, has a near-linear pH sensitivity of 117 arbitrary unit (a.u.)/pH unit and an accuracy of ±1 a.u. (in the range of pH 4.66 to pH 6.02). The thickness and surface morphology of the sensing multilayer film were characterized to investigate their effects on the sensor's performance. The dynamic response of the sensor also has been studied (10 s rise time and 18 s fall time for a sensor with six bilayers of PDDA/PAA). PMID:23348031

  18. Electrode assembly for use in a solid polymer electrolyte fuel cell

    DOEpatents

    Raistrick, Ian D.

    1989-01-01

    A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

  19. Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide

    PubMed Central

    Zhao, Xiaoli; Xu, Zhen; Zheng, Bingna; Gao, Chao

    2013-01-01

    Nacre realizes strength and toughness through hierarchical designs with primary “brick and mortar” structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0–100%), and proposed an equation to depict the relationship. PMID:24196491

  20. Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaoli; Xu, Zhen; Zheng, Bingna; Gao, Chao

    2013-11-01

    Nacre realizes strength and toughness through hierarchical designs with primary ``brick and mortar'' structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0-100%), and proposed an equation to depict the relationship.

  1. Self-Assembled Silica Nano-Composite Polymer Electrolytes: Synthesis, Rheology & Electrochemistry

    SciTech Connect

    Khan, Saad A.: Fedkiw Peter S.; Baker, Gregory L.

    2007-01-24

    The ultimate objectives of this research are to understand the principles underpinning nano-composite polymer electrolytes (CPEs) and facilitate development of novel CPEs that are low-cost, have high conductivities, large Li+ transference numbers, improved electrolyte-electrode interfacial stability, yield long cycle life, exhibit mechanical stability and are easily processable. Our approach is to use nanoparticulate silica fillers to formulate novel composite electrolytes consisting of surface-modified fumed silica nano-particles in polyethylene oxides (PEO) in the presence of lithium salts. We intend to design single-ion conducting silica nanoparticles which provide CPEs with high Li+ transference numbers. We also will develop low-Mw (molecular weight), high-Mw and crosslinked PEO electrolytes with tunable properties in terms of conductivity, transference number, interfacial stability, processability and mechanical strength

  2. Hierarchical self-assembly of nanoparticles in polymer matrix and the nature of the interparticle interaction

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Chiao; Chen, Chun-Yu; Chen, Hsin-Lung; Hashimoto, Takeji; Chen, Show-An; Li, Yen-Cheng

    2015-06-01

    Using small angle X-ray scattering (SAXS), we elucidated the spatial organization of palladium (Pd) nanoparticles (NPs) in the polymer matrix of poly(2-vinylpyridine) (P2VP) and the nature of inter-nanoparticle interactions, where the NPs were synthesized in the presence of P2VP by the reduction of palladium acetylacetonate (Pd(acac)2). The experimental SAXS profiles were analysed on the basis of a hierarchical structure model considering the following two types of interparticle potential: (i) hard-core repulsion only (i.e., the hard-sphere interaction) and (ii) hard-core repulsion together with an attractive potential well (i.e., the sticky hard-sphere interaction). The corresponding theoretical scattering functions, which were used for analysing the experimental SAXS profiles, were obtained within the context of the Percus-Yevick closure and the Ornstein-Zernike equation in the fundamental liquid theory. The analyses revealed that existence of the attractive potential well is indispensable to account for the experimental SAXS profiles. Moreover, the morphology of the hybrids was found to be characterized by a hierarchical structure with three levels, where about six primary NPs with the diameter of ca. 1.8 nm (level one) formed local clusters (level two), and these clusters aggregated to build up a large-scale mass-fractal structure (level three) with the fractal dimension of ca. 2.3. The scattering function developed here is of general use for quantitatively characterizing the morphological structures of polymer/NP hybrids and, in particular, for exploring the interaction potential of the NPs on the basis of the fundamental liquid theory.

  3. Hierarchical assemblies of soft matters from polymers and liquid crystals on structured surfaces

    NASA Astrophysics Data System (ADS)

    Honglawan, Apiradee

    Hierarchical, multifunctional materials hold important keys to numerous advanced technologies, including electronics, optics, and medicine. This thesis encompasses generation of hierarchical structures with novel morphologies and functions through self-assembly directed by lithographically fabricated templates. Here, two soft materials, amphiphilic random copolymers of photopolymerized acryloyl chloride (ranPAC) and smectic-A liquid crystal (SmA-LC) molecule, 4'(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecaflu-orododecyloxy)-biphenyl-4-carboxylic acid ethyl ester, are synthesized as model systems to investigate the governing principles at the topographic surface/interface. The ranPAC can self-organize into nanomicelles with high regularity and stability, typically not possible in random copolymer systems. The morphology can be controlled by the photopolymerization conditions and solvent; the crosslinked shell makes the micelles robust against drying and storage. Using SU-8 micropillar arrays with spatially controlled surface chemistry as templates, we construct hierarchical microporous structures with tunable pore size and symmetry (e.g. square array), and uncover a new evaporative assembly method. By functionalizing the ranPAC nanovesicles with cationic poly(ethyleneimines), we encapsulate the anticancer drug, doxorubicin hydrochloride, and mRNA at a high payload, which are delivered to HEK 293T cells in vitro at a low cytotoxicity level. SmA-LC are characterized by arrangement of molecules into thin layers with the long molecular axis parallel to the layer normal, forming a close-packed hexagonal array of topological defects known as focal conic domains (FCDs) in a thin film. Using a series of SU-8 micropillar arrays with different size, shape, height, and symmetry as topological templates, we investigate the epitaxial and hierarchical assemblies of FCDs; whether the system favors confinement or "pillar edge-pinning" depends on balance of the elastic energy

  4. Isolation and detection of single molecules on paramagnetic beads using sequential fluid flows in microfabricated polymer array assemblies.

    PubMed

    Kan, Cheuk W; Rivnak, Andrew J; Campbell, Todd G; Piech, Tomasz; Rissin, David M; Mösl, Matthias; Peterça, Andrej; Niederberger, Hans-Peter; Minnehan, Kaitlin A; Patel, Purvish P; Ferrell, Evan P; Meyer, Raymond E; Chang, Lei; Wilson, David H; Fournier, David R; Duffy, David C

    2012-03-01

    We report a method for isolating individual paramagnetic beads in arrays of femtolitre-sized wells and detecting single enzyme-labeled proteins on these beads using sequential fluid flows in microfabricated polymer array assemblies. Arrays of femtolitre-sized wells were fabricated in cyclic olefin polymer (COP) using injection moulding based on DVD manufacturing. These arrays were bonded to a complementary fluidic structure that was also moulded in COP to create an enclosed device to allow delivery of liquids to the arrays. Enzyme-associated, paramagnetic beads suspended in aqueous solutions of enzyme substrate were delivered fluidically to the array such that one bead per well was loaded by gravity. A fluorocarbon oil was then flowed into the device to remove excess beads from the surface of the array, and to seal and isolate the femtolitre-sized wells containing beads and enzyme substrate. The device was then imaged using standard fluorescence imaging to determine which wells contained single enzyme molecules. The analytical performance of this device as the detector for digital ELISA compared favourably to the standard method, i.e., glass arrays mechanically sealed against a silicone gasket; prostate specific antigen (PSA) could be detected from 0.011 pg mL(-1) up to 100 pg mL(-1). The use of an enclosed fluidic device to isolate beads in single-molecule arrays offers a multitude of advantages for low-cost manufacturing, ease of automation, and instrument development to enable applications in biomarker validation and medical diagnosis. PMID:22179487

  5. Hydrophobic drug-triggered self-assembly of nanoparticles from silk-elastin-like protein polymers for drug delivery.

    PubMed

    Xia, Xiao-Xia; Wang, Ming; Lin, Yinan; Xu, Qiaobing; Kaplan, David L

    2014-03-10

    Silk-elastin-like protein polymers (SELPs) combine the mechanical and biological properties of silk and elastin. These properties have led to the development of various SELP-based materials for drug delivery. However, SELPs have rarely been developed into nanoparticles, partially due to the complicated fabrication procedures, nor assessed for potential as an anticancer drug delivery system. We have recently constructed a series of SELPs (SE8Y, S2E8Y, and S4E8Y) with various ratios of silk to elastin blocks and described their capacity to form micellar-like nanoparticles upon thermal triggering. In this study, we demonstrate that doxorubicin, a hydrophobic antitumor drug, can efficiently trigger the self-assembly of SE8Y (SELPs with silk to elastin ratio of 1:8) into uniform micellar-like nanoparticles. The drug can be loaded in the SE8Y nanoparticles with an efficiency around 6.5% (65 ng doxorubicin/μg SE8Y), S2E8Y with 6%, and S4E8Y with 4%, respectively. In vitro studies with HeLa cell lines demonstrate that the protein polymers are not cytotoxic (IC50 > 200 μg/mL), while the doxorubicin-loaded SE8Y nanoparticles showed a 1.8-fold higher cytotoxicity than the free drug. Confocal laser scanning microscopy (CLSM) and flow cytometry indicate significant uptake of the SE8Y nanoparticles by the cells and suggest internalization of the nanoparticles through endocytosis. This study provides an all-aqueous, facile method to prepare nanoscale, drug-loaded SELPs packages with potential for tumor cell treatments.

  6. TOPICAL REVIEW: DNA nanowire fabrication

    NASA Astrophysics Data System (ADS)

    Gu, Qun; Cheng, Chuanding; Gonela, Ravikanth; Suryanarayanan, Shivashankar; Anabathula, Sathish; Dai, Kun; Haynie, Donald T.

    2006-01-01

    Deoxyribonucleic acid (DNA) has been a key building block in nanotechnology since the earliest work on what is now called DNA-templated self-assembly (Alivisatos et al 1996 Nature 382 609; Mirkin et al 1996 Nature 382 607; Braun et al 1998 Nature 391 775). A range of different nanoparticles and nanoclusters have been assembled on single DNA molecules for a variety of purposes (Braun et al 1998 Nature 391 775; Richter et al 2001 Appl. Phys. Lett. 78 536; Park et al 2002 Science 295 1503; Mirkin 2000 Inorg. Chem. 39 2258; Keren et al 2003 Science 302 1380). Electrically conductive silver (Braun et al 1998 Nature 391 775) and palladium (Richter et al 2001 Appl. Phys. Lett. 78 536) nanowires, for example, have been fabricated by DNA templating for the development of interconnection of nanoelectric elements, and field effect transistors have been built by assembly of a single carbon nanotube and DNA-templated nanowires (Keren et al 2003 Science 302 1380). DNA is well suited for nanowire assembly because of its size, well organized structure, and exquisite molecular-recognition-ability-specific base pairing. This property has been used to detect nucleic acids (Park et al 2002 Science 295 1503) and anthrax (Mirkin 2000 Inorg. Chem. 39 2258) with high sensitivity and specificity. Molecular recognition can also be used to localize nanowires in electronics. Various methods, for example molecular combing, electrophoretic stretching, and hydrodynamic stretching, have been developed to orient DNA molecules on a solid support. This review focuses on methods used to manipulate and metallize DNA in nanowire fabrication. A novel approach based on a single-stranded DNA template and molecular recognition is also discussed.

  7. Supramolecular Chemistry And Self-assembly Special Feature: Virus-assisted loading of polymer nanocontainer

    NASA Astrophysics Data System (ADS)

    Graff, Alexandra; Sauer, Marc; van Gelder, Patrick; Meier, Wolfgang

    2002-04-01

    We present a DNA-containing polymeric nanocontainer using the self-assembled superstructure of amphiphilic block copolymers in aqueous solutions. To demonstrate that DNA translocation is possible across a completely synthetic block copolymer membrane, we have used a phage transfection strategy as a DNA-transfer model system. For this purpose the bacterial channel forming protein LamB was reconstituted in ABA-triblock copolymer vesicles. The outer membrane protein LamB is a specific transporter for maltodextrins but also serves as a receptor for phage to trigger the ejection of phage DNA. We demonstrate that the functionality of the LamB protein is fully preserved despite the artificial surrounding. This leads to a type of polymeric vehicle for DNA that could be useful for gene therapy.

  8. Supramolecular assembly of crosslinkable monomers for degradable and fluorescent polymer nanoparticles

    PubMed Central

    Yuan, Conghui; Chang, Ying; Mao, Jie; Yu, Shirong; Luo, Weiang; Xu, Yiting

    2015-01-01

    Intermolecular B-N coordination has been recognized as a promising driving force for molecular self-organization. However, direct utilization of this intermolecular interaction as building bridge for the supramolecular self-assembly of chemical functionalities to form nano-sized architectures remains a daunting challenge. Here, we outline a multiple intermolecular B-N coordination based supramolecular system, where small boronate molecules can be brought together in solution to form nanoparticles with controllable sizes and morphologies. We not only demonstrate the intrinsic switchable fluorescence and the stimuli-responsive capabilities of the designed boronate molecule, but also show that the stabilized or surface functionalized nanoparticles are degradable in response to pH and D-glucose and able to retain the fluorescence features of the boronate molecule. Additionally, the degraded nanoparticles can repair themselves through the reformation of B-N coordination. PMID:26413298

  9. Fabrication of a molecular-level multilayer film on organic polymer surfaces via chemical bonding assembly.

    PubMed

    Zhao, Hongchi; Yang, Peng; Deng, Jianping; Liu, Lianying; Zhu, Jianwu; Sui, Yuan; Lu, Jiaoming; Yang, Wantai

    2007-02-13

    A fresh multilayer film was fabricated on a molecular level and successfully tethered to the surface of a hydroxylated organic substrate via chemical bonding assembly (CBA). Sulfate anion groups (SO4-) were preintroduced onto the surface of biaxially oriented polypropylene (BOPP) films via a reference method. Upon hydrolysis of the SO4- groups, hydroxyl groups (--OH) were formed that subsequently acted as initial reagents for a series of alternate reactions with terephthalyl chloride (TPC) and bisphenol A (BPA). A stable and well-defined multilayer film was thus fabricated via the CBA method. As a result of the nanoscale multilayer fresh film being abundant with reactive groups, it is believed that the film and its fabrication method should provide a fundamental platform for further surface functionalization and direct the design of advanced materials with desired properties.

  10. Phase Change Nanodots Patterning using a Self-Assembled Polymer Lithography and Crystallization Analysis

    SciTech Connect

    Zhang, Y.; Raoux, S; Krebs, D; Krupp, L; Topuria, T; Caldwell, M; Milliron, D; Kellock, A; Rice, P; et. al.

    2008-01-01

    Crystallization behavior of scalable phase change materials can be studied on nanoscale structures. In this paper, high density ordered phase change nanodot arrays were fabricated using the lift-off technique on a self-assembled diblock copolymer template, polystyrene-poly(methyl-methacrylate). The size of the nanodots was less than 15 nm in diameter with 40 nm spacing. This method is quite flexible regarding the patterned materials and can be used on different substrates. The crystallization behavior of small scale phase change nanodot arrays was studied using time-resolved x-ray diffraction, which showed the phase transition for different materials such as Ge15Sb85, Ge2Sb2Te5, and Ag and In doped Sb2Te. The transition temperatures of these nanodot samples were also compared with their corresponding blanket thin films, and it was found that the nanodots had higher crystallization temperatures and crystallized over a broader temperature range.

  11. Bypassing multidrug resistance in human breast cancer cells with lipid/polymer particle assemblies

    PubMed Central

    Li, Bo; Xu, Hui; Li, Zhen; Yao, Mingfei; Xie, Meng; Shen, Haijun; Shen, Song; Wang, Xinshi; Jin, Yi

    2012-01-01

    Background Multidrug resistance (MDR) mediated by the overexpression of adenosine triphosphate (ATP)-binding cassette (ABC) transporters, such as P-glycoprotein (P-gp), remains one of the major obstacles to effective cancer chemotherapy. In this study, lipid/particle assemblies named LipoParticles (LNPs), consisting of a dimethyldidodecylammonium bromide (DMAB)-modified poly(lactic-co-glycolic acid) (PLGA) nanoparticle core surrounded by a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) shell, were specially designed for anticancer drugs to bypass MDR in human breast cancer cells that overexpress P-gp. Methods Doxorubicin (DOX), a chemotherapy drug that is a P-gp substrate, was conjugated to PLGA and encapsulated in the self-assembled LNP structure. Physiochemical properties of the DOX-loaded LNPs were characterized in vitro. Cellular uptake, intracellular accumulation, and cytotoxicity were compared in parental Michigan Cancer Foundation (MCF)-7 cells and P-gp-overexpressing, resistant MCF-7/adriamycin (MCF-7/ADR) cells. Results This study found that the DOX formulated in LNPs showed a significantly increased accumulation in the nuclei of drug-resistant cells relative to the free drug, indicating that LNPs could alter intracellular traffic and bypass drug efflux. The cytotoxicity of DOX loaded-LNPs had a 30-fold lower half maximal inhibitory concentration (IC50) value than free DOX in MCF-7/ADR, measured by the colorimetric cell viability (MTT) assay, correlated with the strong nuclear retention of the drug. Conclusion The results show that this core-shell lipid/particle structure could be a promising strategy to bypass MDR. PMID:22275834

  12. Layer-by-layer films assembled from natural polymers for sustained release of neurotrophin.

    PubMed

    Zhang, Zhiling; Li, Qianqi; Han, Lin; Zhong, Yinghui

    2015-09-01

    Cortical neural prostheses (CNPs) hold great promise for paralyzed patients by recording neural signals from the brain and translating them into movement commands. However, these electrodes normally fail to record neural signals weeks to months after implantation due to inflammation and neuronal loss around the implanted neural electrodes. Sustained local delivery of neurotrophins from biocompatible coatings on CNPs can potentially promote neuron survival and attract the nearby neurons to migrate toward the electrodes to increase neuron density at the electrode/brain interface, which is important for maintaining the recording quality and long-term performance of the implanted CNPs. However, sustained release of neurotrophins from biocompatible ultrathin coatings is very difficult to achieve. In this study, we investigated the potential of several biocompatible natural polyanions including heparin, dextran sulfate, and gelatin to form layer-by-layer (LbL) assembly with positively charged neurotrophin nerve growth factor (NGF) and its model protein lysozyme, and whether sustained release of NGF and lysozyme can be achieved from the nanoscale thin LbL coatings. We found that gelatin, which is less negatively charged than heparin and dextran sulfate, showed the highest efficacy in loading proteins into the LbL films because other interactions in addition to electrostatic interactions were involved in LbL assembly. Sustained release of NGF and lysozymes for approximately 2 weeks was achieved from the gelatin-based LbL coatings. Released NGF maintained the bioactivity to stimulate neurite outgrowth from PC12 cells. Gelatin is generally recognized as safe by the FDA. Thus, the biocompatible LbL coating developed in this study is highly promising to be used for implanted CNPs to improve their long-term performance in human patients. PMID:26358683

  13. Structure-Property Relationships in CO2-philic (Co)polymers: Phase Behavior, Self-Assembly, and Stabilization of Water/CO2 Emulsions.

    PubMed

    Girard, Etienne; Tassaing, Thierry; Marty, Jean-Daniel; Destarac, Mathias

    2016-04-13

    This Review provides comprehensive guidelines for the design of CO2-philic copolymers through an exhaustive and precise coverage of factors governing the solubility of different classes of polymers. Starting from computational calculations describing the interactions of CO2 with various functionalities, we describe the phase behavior in sc-CO2 of the main families of polymers reported in literature. The self-assembly of amphiphilic copolymers of controlled architecture in supercritical carbon dioxide and their use as stabilizers for water/carbon dioxide emulsions then are covered. The relationships between the structure of such materials and their behavior in solutions and at interfaces are systematically underlined throughout these sections.

  14. Lithographically patterned nanowire electrodeposition: a method for patterning electrically continuous metal nanowires on dielectrics.

    PubMed

    Xiang, Chenxiang; Kung, Sheng-Chin; Taggart, David K; Yang, Fan; Thompson, Michael A; Güell, Aleix G; Yang, Yongan; Penner, Reginald M

    2008-09-23

    Lithographically patterned nanowire electrodeposition (LPNE) is a new method for fabricating polycrystalline metal nanowires using electrodeposition. In LPNE, a sacrificial metal (M(1)=silver or nickel) layer, 5-100 nm in thickness, is first vapor deposited onto a glass, oxidized silicon, or Kapton polymer film. A (+) photoresist (PR) layer is then deposited, ph