Sample records for high level self-assembly

  1. Molecular recognition and self-assembly special feature: Integrative self-sorting is a programming language for high level self-assembly. (United States)

    Jiang, Wei; Schalley, Christoph A


    Starting from the basis of a simple 4-component self-sorting system of crown ethers and ammonium ions, we design 6 building blocks in which 2 identical or different binding sites are incorporated. These building blocks can be mixed in many different ways to yield quite distinctly different pseudorotaxane assemblies. The self-sorting process integrates all building blocks in specific places so that this approach permits us to exert positional control and can widely influence the resulting assemblies with respect to the details of their structures. At maximum, we report quadruply interlocked species with up to 5 subunits that form specific assemblies. Although NMR methods are limited to the analysis of simpler complexes, ESI-MS and, in particular, tandem mass spectrometry is highly useful to analyze the assemblies' connectivities.

  2. Purification of ethanol for highly sensitive self-assembly experiments

    Directory of Open Access Journals (Sweden)

    Kathrin Barbe


    Full Text Available Ethanol is the preferred solvent for the formation of self-assembled monolayers (SAMs of thiolates on gold. By applying a thin film sensor system, we could demonstrate that even the best commercial qualities of ethanol contain surface-active contaminants, which can compete with the desired thiolates for surface sites. Here we present that gold nanoparticles deposited onto zeolite X can be used to remove these contaminants by chemisorption. This nanoparticle-impregnated zeolite does not only show high capacities for surface-active contaminants, such as thiols, but can be fully regenerated via a simple pyrolysis protocol.

  3. Solvent-free, molecular-level modeling of self-assembling amphiphiles in water (United States)

    Dey, Somajit; Saha, Jayashree


    Aggregation mesophases of self-assembling amphiphiles in water are highly important in the context of biology (biomembranes), therapy (liposomes), industry (polymer surfactants), and condensed-matter physics (lyotropic liquid crystals). Besides helping to increase fundamental understanding of collective molecular behavior, simulations of these lyotropic phases are pivotal to technological and medical developments such as smart drug carriers for gene therapy. Implicit-solvent, coarse-grained, low resolution modeling with a simple pair potential is the key to realizing the larger length and time scales associated with such mesoscopic phenomena during a computer simulation. Modeling amphiphiles by directed, soft, ellipsoidal cores interacting via a computationally simple yet tunable anisotropic pair potential, we have come to such a single-site model amphiphile that can rapidly self-assemble to give diverse lyotropic phases (such as fluid bilayers, micelles, etc.) without requiring the explicit incorporation of solvent particles. The model directly represents a tunable packing parameter that manifests in the spontaneous curvature of the amphiphile aggregates. Besides the all-important hydrophobic interaction, the hydration force is also treated implicitly. Thanks to the efficient solvent-free molecular-level coarse graining, this model is suitable for generic mesoscale studies of phenomena such as self-assembly, amphiphile mixing, domain formation, fusion, elasticity, etc., in amphiphile aggregates.

  4. Self-assembly of Si-containing block copolymers with high-segregation strength: toward sub-10nm features in directed self-assembly (United States)

    Reboul, C.; Fleury, G.; Aissou, K.; Brochon, C.; Cloutet, E.; Nicolet, C.; Chevalier, X.; Navarro, C.; Tiron, R.; Cunge, G.; Hadziioannou, G.


    Ordered microstructures with nanometrically defined periodicity offer promising opportunities in microelectronic applications for the production of advanced CMOS digital logic circuits. To produce the features and arrays inherent to such technologies, the combination of the "bottom-up" block copolymer self-assembly with "top-down" guiding templates has been successfully introduced leading to new technological breakthroughs. Among the materials used in the direct self-assembly methodology, poly(styrene-b-methylmethacrylate) systems have reached an unprecedented level of maturity which will lead to their introduction into the next technological nodes. However, this system suffers from deficiencies such as a low Flory Huggins parameter (X = 0.04 at 25°C) and a low chemical contrast as regards to the etching processes which could be problematic for targeting sub-22 nm features. Consequently we have developed new systems based on Si-containing block copolymers which are characterized by high segregation strength as well as strong chemical etching contrast. In this contribution, we focus on a poly(lactic acid) / poly(dimethylsiloxane) system exhibiting a cylindrical mesostructure. By controlling the surface energy at the interface between the substrate and the block copolymer domains, we show the possibility to control the orientation of the mesostructure with a methodology comparable to the one used for poly(styrene) / poly(methyl methacrylate) system but with random copolymers having distinct monomers than the block copolymers.

  5. Modelling DNA origami self-assembly at the domain level

    Energy Technology Data Exchange (ETDEWEB)

    Dannenberg, Frits; Kwiatkowska, Marta [Department of Computer Science, University of Oxford, Wolfson Building, Parks Road, Oxford OX1 3QD (United Kingdom); Dunn, Katherine E. [Department of Physics, University of Oxford, Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Department of Electronics, University of York, York YO10 5DD (United Kingdom); Bath, Jonathan; Turberfield, Andrew J. [Department of Physics, University of Oxford, Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Ouldridge, Thomas E. [Department of Physics, University of Oxford, Rudolf Peierls Centre for Theoretical Physics, 1 Keble Road, Oxford OX1 3NP (United Kingdom); Department of Mathematics, Imperial College, 180 Queen’s Gate, London SW7 2AZ (United Kingdom)


    We present a modelling framework, and basic model parameterization, for the study of DNA origami folding at the level of DNA domains. Our approach is explicitly kinetic and does not assume a specific folding pathway. The binding of each staple is associated with a free-energy change that depends on staple sequence, the possibility of coaxial stacking with neighbouring domains, and the entropic cost of constraining the scaffold by inserting staple crossovers. A rigorous thermodynamic model is difficult to implement as a result of the complex, multiply connected geometry of the scaffold: we present a solution to this problem for planar origami. Coaxial stacking of helices and entropic terms, particularly when loop closure exponents are taken to be larger than those for ideal chains, introduce interactions between staples. These cooperative interactions lead to the prediction of sharp assembly transitions with notable hysteresis that are consistent with experimental observations. We show that the model reproduces the experimentally observed consequences of reducing staple concentration, accelerated cooling, and absent staples. We also present a simpler methodology that gives consistent results and can be used to study a wider range of systems including non-planar origami.

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

    KAUST Repository

    Kim, Gi-Hwan


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

  7. Controlling self-assembly of diphenylalanine peptides at high pH using heterocyclic capping groups (United States)

    Martin, Adam D.; Wojciechowski, Jonathan P.; Robinson, Andrew B.; Heu, Celine; Garvey, Christopher J.; Ratcliffe, Julian; Waddington, Lynne J.; Gardiner, James; Thordarson, Pall


    Using small angle neutron scattering (SANS), it is shown that the existence of pre-assembled structures at high pH for a capped diphenylalanine hydrogel is controlled by the selection of N-terminal heterocyclic capping group, namely indole or carbazole. At high pH, changing from a somewhat hydrophilic indole capping group to a more hydrophobic carbazole capping group results in a shift from a high proportion of monomers to self-assembled fibers or wormlike micelles. The presence of these different self-assembled structures at high pH is confirmed through NMR and circular dichroism spectroscopy, scanning probe microscopy and cryogenic transmission electron microscopy.

  8. Highly efficient chirality transfer from diamines encapsulated within a self-assembled calixarene-salen host


    Kleij, Arjan W.; Bandeira, Nuno A. G.; Luis Martínez-Rodríguez; Carles Bo


    Highly efficient chirality transfer from diamines encapsulated within a self-assembled calixarene-salen host A calix[4]arene host equipped with two bis-[Zn(salphen)] complexes self-assembles into a capsular complex in the presence of a chiral diamine guest with an unexpected 2:1 ratio between the host and the guest. Effective chirality transfer from the diamine to the calix-salen hybrid host is observed by circular dichroism (CD) spectroscopy, and a high stability constant K2,1 of 1.59×101...

  9. Self-assembled nanoparticle aggregates: Organizing disorder for high performance surface-enhanced spectroscopy (United States)

    Fasolato, C.; Domenici, F.; Brasili, F.; Mura, F.; Sennato, S.; De Angelis, L.; Mazzi, E.; Bordi, F.; Postorino, P.


    The coherent oscillations of the surface electron gas, known as surface plasmons, in metal nanostructures can give rise to the localization of intense electromagnetic fields at the metal-dielectric interface. These strong fields are exploited in surface enhanced spectroscopies, such as Surface Enhanced Raman Scattering (SERS), for the detection and characterization of molecules at very low concentration. Still, the implementation of SERS-based biosensors requires a high level of reproducibility, combined with cheap and simple fabrication methods. For this purpose, SERS substrates based on self-assembled aggregates of commercial metallic nanoparticles (Nps) can meet all the above requests. Following this line, we report on a combined micro-Raman and Atomic Force Microscopy (AFM) analysis of the SERS efficiency of micrometric silver Np aggregates (enhancement factors up to 109) obtained by self-assembly. Despite the intrinsic disordered nature of these Np clusters, we were able to sort out some general rules relating the specific aggregate morphology to its plasmonic response. We found strong evidences of cooperative effects among the NPs within the cluster and namely a clear dependence of the SERS-efficiency on both the cluster area (basically linear) and the number of stacked NPs layers. A cooperative action among the superimposed layers has been proved also by electromagnetic simulations performed on simplified nanostructures consisting of stacking planes of ordered Nps. Being clear the potentialities of these disordered self-assembled clusters, in terms of both easy fabrication and signal enhancement, we developed a specific nanofabrication protocol, based on electron beam lithography and molecular functionalization, that allowed for a fine control of the Np assemblies into designed shapes fixing their area and height. In particular, we fabricated 2D ordered arrays of disordered clusters choosing gold Nps owing to their high stability. AFM measurements confirmed

  10. Self-assembled nanoparticle aggregates: Organizing disorder for high performance surface-enhanced spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fasolato, C. [Dipartimento di Fisica, Università Sapienza, Rome (Italy); Center for Life Nanoscience@Sapienza, Istituto Italiano di Tecnologia, Rome (Italy); Domenici, F., E-mail: [Dipartimento di Fisica, Università Sapienza, Rome (Italy); Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Rome (Italy); Brasili, F.; Mazzi, E.; Postorino, P., E-mail: [Dipartimento di Fisica, Università Sapienza, Rome (Italy); Mura, F. [Center for Nanotechnology for Engineering (CNIS), Università Sapienza, Rome (Italy); Dipartimento di Scienze di Base Applicate all’Ingegneria, Università Sapienza, Rome (Italy); Sennato, S. [Dipartimento di Fisica, Università Sapienza, Rome (Italy); CNR-ISC UOS Sapienza, Università Sapienza, Rome (Italy); De Angelis, L. [Dipartimento di Fisica, Università Sapienza, Rome (Italy); Center for Nanophotonics, FOM Institute AMOLF, Amsterdam (Netherlands); Bordi, F. [Dipartimento di Fisica, Università Sapienza, Rome (Italy); CNR-IPCF UOS Roma, Dipartimento di Fisica, Università Sapienza, Rome (Italy)


    The coherent oscillations of the surface electron gas, known as surface plasmons, in metal nanostructures can give rise to the localization of intense electromagnetic fields at the metal-dielectric interface. These strong fields are exploited in surface enhanced spectroscopies, such as Surface Enhanced Raman Scattering (SERS), for the detection and characterization of molecules at very low concentration. Still, the implementation of SERS-based biosensors requires a high level of reproducibility, combined with cheap and simple fabrication methods. For this purpose, SERS substrates based on self-assembled aggregates of commercial metallic nanoparticles (Nps) can meet all the above requests. Following this line, we report on a combined micro-Raman and Atomic Force Microscopy (AFM) analysis of the SERS efficiency of micrometric silver Np aggregates (enhancement factors up to 10{sup 9}) obtained by self-assembly. Despite the intrinsic disordered nature of these Np clusters, we were able to sort out some general rules relating the specific aggregate morphology to its plasmonic response. We found strong evidences of cooperative effects among the NPs within the cluster and namely a clear dependence of the SERS-efficiency on both the cluster area (basically linear) and the number of stacked NPs layers. A cooperative action among the superimposed layers has been proved also by electromagnetic simulations performed on simplified nanostructures consisting of stacking planes of ordered Nps. Being clear the potentialities of these disordered self-assembled clusters, in terms of both easy fabrication and signal enhancement, we developed a specific nanofabrication protocol, based on electron beam lithography and molecular functionalization, that allowed for a fine control of the Np assemblies into designed shapes fixing their area and height. In particular, we fabricated 2D ordered arrays of disordered clusters choosing gold Nps owing to their high stability. AFM measurements

  11. Amphiphilic self-assembled polymeric copper catalyst to parts per million levels: click chemistry. (United States)

    Yamada, Yoichi M A; Sarkar, Shaheen M; Uozumi, Yasuhiro


    Self-assembly of copper sulfate and a poly(imidazole-acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and CuSO(4) via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO(4) to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5-45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h(-1), respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively.

  12. Fabrication of cellulose self-assemblies and high-strength ordered cellulose films. (United States)

    Yuan, Zaiwu; Zhang, Jingjing; Jiang, Anning; Lv, Wenting; Wang, Yuewen; Geng, Hongjuan; Wang, Jin; Qin, Menghua


    Based on the formation of cellulose hydrogels in NaOH/urea aqueous solvent media, cellulose self-assembly precursor is acquired. It is proved that the water uptake capability of the cellulose hydrogels depends highly on the cross-link degree (CLD) of cellulose. With varying CLD and concentration of cellulose, a variety of morphologies of cellulose self-assemblies, including sheets with perfect morphology, high-aspect-ratio fibers, and disorganized segments and network, are formed through evaporation. Furthermore, cellulose films are fabricated by diecasting and evaporating the cellulose hydrogels, resulting in a 3D-ordered structure of closely stacking of cellulose sheets. The mechanical test indicates both tensile strength and flexibility of the cellulose films are greatly improved, which is attributed to the formation of the orderly stacking of cellulose sheets. The study is expected to lay an important foundation on the preparation of ordered and high-strength cellulose materials. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. High-Density Liquid-Crystalline Polymer Brushes Formed by Surface Segregation and Self-Assembly. (United States)

    Mukai, Koji; Hara, Mitsuo; Nagano, Shusaku; Seki, Takahiro


    High-density polymer brushes on substrates exhibit unique properties and functions stemming from the extended conformations due to the surface constraint. To date, such chain organizations have been mostly attained by synthetic strategies of surface-initiated living polymerization. We show herein a new method to prepare a high-density polymer brush architecture using surface segregation and self-assembly of diblock copolymers containing a side-chain liquid-crystalline polymer (SCLCP). The surface segregation is attained from a film of an amorphous base polymer (polystyrene, PS) containing a minor amount of a SCLCP-PS diblock copolymer upon annealing above the glass-transition temperature. The polystyrene portion of the diblock copolymer can work as a laterally mobile anchor for the favorable self-assembly on the polystyrene base film. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Noncanonical Self-Assembly of Highly Asymmetric Genetically Encoded Polypeptide Amphiphiles into Cylindrical Micelles (United States)


    Elastin-like polypeptides (ELPs) are a class of biopolymers consisting of the pentameric repeat (VPGαG)n based on the sequence of mammalian tropoelastin that display a thermally induced soluble-to-insoluble phase transition in aqueous solution. We have discovered a remarkably simple approach to driving the spontaneous self-assembly of high molecular weight ELPs into nanostructures by genetically fusing a short 1.5 kDa (XGy)z assembly domain to one end of the ELP. Classical theories of self-assembly based on the geometric mass balance of hydrophilic and hydrophobic block copolymers suggest that these highly asymmetric polypeptides should form spherical micelles. Surprisingly, when sufficiently hydrophobic amino acids (X) are presented in a periodic sequence such as (FGG)8 or (YG)8, these highly asymmetric polypeptides self-assemble into cylindrical micelles whose length can be tuned by the sequence of the morphogenic tag. These nanostructures were characterized by light scattering, tunable resistive pulse sensing, fluorescence spectrophotometry, and thermal turbidimetry, as well as by cryogenic transmission electron microscopy (cryo-TEM) and small-angle neutron scattering (SANS). These short assembly domains provide a facile strategy to control the size, shape, and stability of stimuli responsive polypeptide nanostructures. PMID:25268037

  15. Drying-Mediated Self-Assembly of Highly Ordered Complex Structures: From Polymers to Nanoparticles (United States)

    Lin, Zhiqun


    Drying of a sessile drop containing nonvolatile solutes readily self-assembles into a number of concentric ``coffee rings'' by repetitive ``stick-slip'' motion of the three-phase contact line. However, due mainly to lack of control over the evaporation process of the drop, the challenge remains to use evaporative self-assembly to rationally ``synthesize'' ``coffee rings'' of different shapes and sizes of high regularity and fidelity. Here, we report a facile, robust, and one-step evaporation method for producing in a precisely controllable manner versatile microstructures possessing high regularity, dispensing with the need for lithographic techniques and externally applied fields. Polymer or nanocrystal solutions are confined in a simple geometry comprised of a curved surface placed upon a flat substrate. By changing the shape of the upper surface of the imposed geometry, the controlled, evaporative self-assembly of polymer or nanocrystal solutions yields a variety of complex, intriguing, and well-ordered structures over large areas. As such, this method represents a significant advance in creating regularly organized, complex structures with potential applications in microelectronics, optoelectronics, and biotechnology, among other areas.

  16. Peptide amphiphile self-assembly (United States)

    Iscen, Aysenur; Schatz, George C.


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

  17. Synthesis of Self-Assembled Multifunctional Nanocomposite Catalysts with Highly Stabilized Reactivity and Magnetic Recyclability (United States)

    Yu, Xu; Cheng, Gong; Zheng, Si-Yang


    In this paper, a multifunctional Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite catalyst with highly stabilized reactivity and magnetic recyclability was synthesized by a self-assembled method. The magnetic Fe3O4 nanoparticles were coated with a thin layer of the SiO2 to obtain a negatively charged surface. Then positively charged poly(ethyleneimine) polymer (PEI) was self-assembled onto the Fe3O4@SiO2 by electrostatic interaction. Next, negatively charged glutathione capped gold nanoparticles (GSH-AuNPs) were electrostatically self-assembled onto the Fe3O4@SiO2@PEI. After that, silver was grown on the surface of the nanocomposite due to the reduction of the dopamine in the alkaline solution. An about 5 nm thick layer of polydopamine (PDA) was observed to form the Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was carefully characterized by the SEM, TEM, FT-IR, XRD and so on. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite shows a high saturation magnetization (Ms) of 48.9 emu/g, which allows it to be attracted rapidly to a magnet. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was used to catalyze the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system. The reaction kinetic constant k was measured to be about 0.56 min-1 (R2 = 0.974). Furthermore, the as-prepared catalyst can be easily recovered and reused for 8 times, which didn’t show much decrease of the catalytic capability.

  18. High-performance and high-sensitivity applications of graphene transistors with self-assembled monolayers. (United States)

    Yeh, Chao-Hui; Kumar, Vinod; Moyano, David Ricardo; Wen, Shao-Hsuan; Parashar, Vyom; Hsiao, She-Hsin; Srivastava, Anchal; Saxena, Preeti S; Huang, Kun-Ping; Chang, Chien-Chung; Chiu, Po-Wen


    Charge impurities and polar molecules on the surface of dielectric substrates has long been a critical obstacle to using graphene for its niche applications that involve graphene's high mobility and high sensitivity nature. Self-assembled monolayers (SAMs) have been found to effectively reduce the impact of long-range scatterings induced by the external charges. Yet, demonstrations of scalable device applications using the SAMs technique remains missing due to the difficulties in the device fabrication arising from the strong surface tension of the modified dielectric environment. Here, we use patterned SAM arrays to build graphene electronic devices with transport channels confined on the modified areas. For high-mobility applications, both rigid and flexible radio-frequency graphene field-effect transistors (G-FETs) were demonstrated, with extrinsic cutoff frequency and maximum oscillation frequency enhanced by a factor of ~2 on SiO2/Si substrates. For high sensitivity applications, G-FETs were functionalized by monoclonal antibodies specific to cancer biomarker chondroitin sulfate proteoglycan 4, enabling its detection at a concentration of 0.01 fM, five orders of magnitude lower than that detectable by a conventional colorimetric assay. These devices can be very useful in the early diagnosis and monitoring of a malignant disease. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. A unique highly hydrophobic anticancer prodrug self-assembled nanomedicine for cancer therapy. (United States)

    Ren, Guolian; Jiang, Mengjuan; Xue, Peng; Wang, Jing; Wang, Yongjun; Chen, Bo; He, Zhonggui


    In contrast with common thought, we generated highly hydrophobic anticancer prodrug self-assembled nanoparticles without the aid of surface active substances, based on the conjugation of docetaxel to d-α-tocopherol succinate. The reduction-sensitive prodrug was synthesized with a disulfide bond inserted into the linker and was compared with a control reduction-insensitive prodrug. The morphology and stability of self-assembled nanoparticles were investigated. Cytotoxicity and apoptosis assays showed that the reduction-sensitive nanoparticles had higher anticancer activity than the reduction-insensitive nanoparticles. The reduction-sensitive nanoparticles exhibited favorable in vivo antitumor activity and tolerance compared with docetaxel Tween80-containing formulation and the reduction-insensitive nanoparticles. Taken together, the unique nanomedicine demonstrated a number of advantages: (i) ease and reproducibility of preparation, (ii) high drug payload, (iii) superior stability, (iv) prolonged circulation, and (v) improved therapeutic effect. This highly reproducible molecular assembly strategy should motivate the development of new nanomedicines. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. Self-assembly of a thin highly reduced graphene oxide film and its high electrocatalytic activity. (United States)

    Bai, Yan-Feng; Zhang, Yong-Fang; Zhou, An-Wei; Li, Hai-Wai; Zhang, Yu; Luong, John H T; Cui, Hui-Fang


    A thin highly reduced graphene oxide (rGO) film was self-assembled at the dimethyl formamide (DMF)-air interface through evaporation-induced water-assisted thin film formation at the pentane-DMF interface, followed by complete evaporation of pentane. The thin film was transferred onto various solid substrates for film characterization and electrochemical sensing. UV-visible spectrometry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemistry techniques were used to characterize the film. An rGO film showing 82.8% of the transmittance at 550 nm corresponds to a few layers of rGO nanosheets. The rGO nanosheets cross-stack with each other, lying approximately in the plane of the film. An rGO film collected on a glassy carbon (GC) electrode exhibited improved electrical conductivity compared to GC, with the electrode charge-transfer resistance (Rct) reduced from 31 Ω to 22 Ω. The as-formed rGO/GC electrode was mechanically very stable, exhibiting significantly enhanced electrocatalytic activity to H(2)O(2) and dopamine. Multiple layers of the rGO films on the GC electrode showed even stronger electrocatalytic activity to dopamine than that of the single rGO film layer. The controllable formation of a stable rGO film on various solid substrates has potential applications for nanoelectronics and sensors/biosensors.

  1. Self-assembly of gold nanoparticles to silver microspheres as highly efficient 3D SERS substrates (United States)

    Chen, Shouhui; Huang, Peng; Wang, Zhihua; Wang, Zhe; Swierczewska, Magdalena; Niu, Gang; Cui, Daxiang; Chen, Xiaoyuan


    Herein we report a simple, one-pot, surfactant-free synthesis of 3D Ag microspheres (AgMSs) in aqueous phase at room temperature. The 3D AgMSs act as supports to fix the gold nanoparticles (GNPs) in 3D space via the interaction between the carboxyl groups of GNPs and the Ag atoms of AgMSs. The ensemble of AgMSs@GNPs with high surface-enhanced Raman scattering (SERS) activity and sensitivity can be an ideal 3D substrate choice for practical SERS detection applications. The simple self-assembly strategy may be extended to other metallic materials with great potentials in SERS, catalysis, and photoelectronic devices.

  2. High-speed logic integrated circuits with solution-processed self-assembled carbon nanotubes (United States)

    Han, Shu-Jen; Tang, Jianshi; Kumar, Bharat; Falk, Abram; Farmer, Damon; Tulevski, George; Jenkins, Keith; Afzali, Ali; Oida, Satoshi; Ott, John; Hannon, James; Haensch, Wilfried


    As conventional monolithic silicon technology struggles to meet the requirements for the 7-nm technology node, there has been tremendous progress in demonstrating the scalability of carbon nanotube field-effect transistors down to the size that satisfies the 3-nm node and beyond. However, to date, circuits built with carbon nanotubes have overlooked key aspects of a practical logic technology and have stalled at simple functionality demonstrations. Here, we report high-performance complementary carbon nanotube ring oscillators using fully manufacturable processes, with a stage switching frequency of 2.82 GHz. The circuit was built on solution-processed, self-assembled carbon nanotube arrays with over 99.9% semiconducting purity, and the complementary feature was achieved by employing two different work function electrodes.

  3. 1-Dodecanethiol based highly stable self-assembled monolayers for germanium passivation

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Qi [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China); University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing 100049 (China); Xu, Baojian, E-mail: [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China); Shanghai Internet of Things Co., LTD, No. 1455, Pingcheng Road, Shanghai 201899 (China); Ye, Lin [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China); University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing 100049 (China); Di, Zengfeng [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China); Huang, Shanluo; Du, Xiaowei [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China); University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing 100049 (China); Zhang, Jishen; Jin, Qinghui [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China); Zhao, Jianlong, E-mail: [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, No. 865, Changning Road, Shanghai 200050 (China)


    Highlights: • A simple and effective approach for higly stable germanium passivation. • 1-Dodecanethiol self-assembled monolayers for germanium oxidation resistance. • The influence factors of germanium passivation were systematically studied. • The stability of the passivated Ge was more than 10 days even in water conditions. - Abstract: As a typical semiconductor material, germanium has the potential to replace silicon for future-generation microelectronics, due to its better electrical properties. However, the lack of stable surface state has limited its extensive use for several decades. In this work, we demonstrated highly stable self-assembled monolayers (SAMs) on Ge surface to prevent oxidization for further applications. After the pretreatment in hydrochloric acid, the oxide-free and Cl-terminated Ge could be further coated with 1-dodecanethiol (NDM) SAMs. The influence factors including reaction time, solvent component and reaction temperature were optimized to obtain stable passivated monolayer for oxidation resistance. Contact angle analysis, atomic force microscopy, ellipsometer and X-ray photoelectron spectroscopy were performed to characterize the functionalized Ge surface respectively. Meanwhile, the reaction mechanism and stability of thiols SAMs on Ge (1 1 1) surface were investigated. Finally, highly stable passivated NDM SAMs on Ge surface could be formed through immersing oxide-free Ge in mixture solvent (water/ethanol, v/v = 1:1) at appropriately elevated temperature (∼80 °C) for 24 h. And the corresponding optimized passivated Ge surface was stable for more than 10 days even in water condition, which was much longer than the data reported and paved the way for the future practical applications of Ge.

  4. Effects of High Pressure on Internally Self-Assembled Lipid Nanoparticles

    DEFF Research Database (Denmark)

    Kulkarni, Chandrashekhar V; Yaghmur, Anan; Steinhart, Milos


    We present the first report on the effects of hydrostatic pressure on colloidally stabilized lipid nanoparticles enveloping inverse nonlamellar self-assemblies in their interiors. These internal self-assemblies were systematically tuned into bicontinuous cubic (Pn3m and Im3m), micellar cubic (Fd3m......), hexagonal (H2), and inverse micellar (L2) phases by regulating the lipid/oil ratio as the hydrostatic pressure was varied from atmospheric pressure to 1200 bar and back to atmospheric pressure. The effects of pressure on these lipid nanoparticles were compared with those on their equilibrium bulk...... samples, whereas the internal self-assemblies of the corresponding lipid nanoparticles displayed only pressure-modulated single phases. Interestingly, both the lattice parameters and the linear pressure expansion coefficients were larger for the self-assemblies enveloped inside the lipid nanoparticles...

  5. Electronic structure of InAs/GaAs self-assembled quantum dots studied by high-excitation luminescence in magnetic fields up to 73 T

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, D.; Raymond, S.; Studenikin, S.; Babinski, A.; Leotin, J.; Frings, P.; Potemski, M.; Sachrajda, A


    We report on high-excitation photoluminescence (PL) measurements of an ensemble of InAs/GaAs self-assembled quantum dots with large inter-shell spacing (75 meV) in magnetic fields up to 73 T. The PL spectra show a complex picture of levels splitting and crossings. A simple two-band single-particle model provides a good approximation to explain the observed magneto-PL spectra.

  6. Hydrogen bonds induced supramolecular self-assembly of azobenzene derivatives on the highly oriented pyrolytic graphite surface (United States)

    Miao, Xinrui; Cheng, Zhiyu; Ren, Biye; Deng, Wenli


    The self-assembly of azobenzene derivatives (CnAzCOOH) with various lengths of peripheral alkyl chains (with carbon number of n = 8, 10, 12, 14, 16) were observed by scanning tunneling microscopy on highly oriented pyrolytic graphite (HOPG) surface. The effect of van der Waals interactions and the intermolecular hydrogen bonding on the two-dimensional self-assembly was systematically studied. No alkyl-chain length effect was observed according to the STM images. All kinds of CnAzCOOH adopting the same pattern self-assembled on the HOPG surface, suggesting the formation of the two-dimensional structures was dominated by the hydrogen bonding of the functional groups. It could be found that two CnAzCOOH molecules formed a hydrogen-bonded dimer with “head-to-head” fashion as expected; however, the dimers organized themselves in the form of relative complex lamellae. Three dimers as a group arranged side by side and formed a well-defined stripe with periodic dislocations due to the registry mechanism of the alkyl chain with the underlying HOPG surface. The hydrogen bonds between the adjacent dimers in one lamella were formed and dominated the self-assembled pattern.

  7. Highly Efficient Air Desulfurization on Self-Assembled Bundles of Copper Hydroxide Nanorods. (United States)

    Giannakoudakis, Dimitrios A; Jiang, Mingyung; Bandosz, Teresa J


    Copper hydroxide and copper hydroxyl nitrate were successfully synthesized from copper nitrate. A slight alteration of a base addition pathway led to entirely different chemical and crystal structures. Structural, morphological, and surface chemical features were analyzed using various physical and chemical methods. The copper hydroxide texture consists of self-assembled bundles of nanorods with a diameter between 15 and 40 nm. They are stack together forming platelet-like particles. In the case of the copper hydroxyl nitrate, platelet-like particles with a smooth surface were detected. The fully hydroxylated sample showed a considerably higher surface area and mesoporous volume than those of copper hydroxyl nitrate. Both synthesized materials were used as air desulfurization media at moist or dry conditions. The results indicate a supreme chemical adsorption of H2S on copper hydroxide. Moisture in air has a positive effect on the adsorption performance. In humid conditions, almost 0.9 mol H2S/mol of Cu(OH)2 was adsorbed. CuS with almost a stoichiometric ratio was a product of surface reactions. The color change of the powder from sapphire blue to dark brown during the adsorption can be used as a fast indication of the adsorbent exhaustion level.

  8. Highly Efficient Chirality Transfer from Diamines Encapsulated within a Self-Assembled Calixarene-Salen Host. (United States)

    Martínez-Rodríguez, Luis; Bandeira, Nuno A G; Bo, Carles; Kleij, Arjan W


    A calix[4]arene host equipped with two bis-[Zn(salphen)] complexes self-assembles into a capsular complex in the presence of a chiral diamine guest with an unexpected 2:1 ratio between the host and the guest. Effective chirality transfer from the diamine to the calix-salen hybrid host is observed by circular dichroism (CD) spectroscopy, and a high stability constant K2,1 of 1.59×10(11)  M(-2) for the assembled host-guest ensemble has been determined with a substantial cooperativity factor α of 6.4. Density functional calculations are used to investigate the origin of the stability of the host-guest system and the experimental CD spectrum compared with those calculated for both possible diastereoisomers showing that the M,M isomer is the one that is preferentially formed. The current system holds promise for the chirality determination of diamines, as evidenced by the investigated substrate scope and the linear relationship between the ee of the diamine and the amplitude of the observed Cotton effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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


    Amphiphile self-assembly materials, which contain both a hydrophilic and a hydrophobic domain, have great potential in high-throughput and combinatorial approaches to discovery and development. However, the materials chemistry community has not embraced these ideas to anywhere near the extent that the medicinal chemistry community has. While this situation is beginning to change, extracting the full potential of high-throughput approaches in the development of self-assembling materials will require further development in the synthesis, characterization, formulation, and application domains. One of the key factors that make small molecule amphiphiles prospective building blocks for next generation multifunctional materials is their ability to self-assemble into complex nanostructures through low-energy transformations. Scientists can potentially tune, control, and functionalize these structures, but only after establishing their inherent properties. Because both robotic materials handling and customized rapid characterization equipment are increasingly available, high-throughput solutions are now attainable. These address traditional development bottlenecks associated with self-assembling amphiphile materials, such as their structural characterization and the assessment of end-use functional performance. A high-throughput methodology can help streamline materials development workflows, in accord with existing high-throughput discovery pipelines such as those used by the pharmaceutical industry in drug discovery. Chemists have identified several areas that are amenable to a high-throughput approach for amphiphile self-assembly materials development. These allow an exploration of not only a large potential chemical, compositional, and structural space, but also material properties, formulation, and application variables. These areas of development include materials synthesis and preparation, formulation, characterization, and screening performance for the desired end

  10. High-Resolution Structure of a Self-Assembly-Competent Form of a Hydrophobic Peptide Captured in a Soluble [beta]-Sheet Scaffold

    Energy Technology Data Exchange (ETDEWEB)

    Makabe, Koki; Biancalana, Matthew; Yan, Shude; Tereshko, Valentina; Gawlak, Grzegorz; Miller-Auer, Hélène; Meredith, Stephen C.; Koide, Shohei (UC)


    {beta}-Rich self-assembly is a major structural class of polypeptides, but still little is known about its atomic structures and biophysical properties. Major impediments for structural and biophysical studies of peptide self-assemblies include their insolubility and heterogeneous composition. We have developed a model system, termed peptide self-assembly mimic (PSAM), based on the single-layer {beta}-sheet of Borrelia outer surface protein A. PSAM allows for the capture of a defined number of self-assembly-like peptide repeats within a water-soluble protein, making structural and energetic studies possible. In this work, we extend our PSAM approach to a highly hydrophobic peptide sequence. We show that a penta-Ile peptide (Ile{sub 5}), which is insoluble and forms {beta}-rich self-assemblies in aqueous solution, can be captured within the PSAM scaffold in a form capable of self-assembly. The 1.1-{angstrom} crystal structure revealed that the Ile{sub 5} stretch forms a highly regular {beta}-strand within this flat {beta}-sheet. Self-assembly models built with multiple copies of the crystal structure of the Ile5 peptide segment showed no steric conflict, indicating that this conformation represents an assembly-competent form. The PSAM retained high conformational stability, suggesting that the flat {beta}-strand of the Ile{sub 5} stretch primed for self-assembly is a low-energy conformation of the Ile{sub 5} stretch and rationalizing its high propensity for self-assembly. The ability of the PSAM to 'solubilize' an otherwise insoluble peptide stretch suggests the potential of the PSAM approach to the characterization of self-assembling peptides.

  11. Self-assembly of a highly organized, hexameric supramolecular architecture: formation, structure and properties. (United States)

    Schaeffer, Gaël; Fuhr, Olaf; Fenske, Dieter; Lehn, Jean-Marie


    Two derivatives, (3)L and (9)L, of a ditopic, multiply hydrogen-bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self-assembly into a complex supramolecular species. The solid-state molecular structure of (3)L, determined by single-crystal X-ray crystallography, revealed that it forms a highly organized hexameric entity (3)L6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen-bonding interactions. The complicated (1)H NMR spectra observed in o-dichlorobenzene (o-DCB) for (3)L and (9)L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen-bond-disrupting solvent, such as DMSO, the (1)H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature-dependent (1)H NMR studies in o-DCB showed that the L6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers (United States)

    An, Hyosung; Mike, Jared; Smith, Kendall A.; Swank, Lisa; Lin, Yen-Hao; L. Pesek, Stacy; Verduzco, Rafael; Lutkenhaus, Jodie L.


    Mechanically robust battery electrodes are desired for applications in wearable devices, flexible displays, and structural energy and power. In this regard, the challenge is to balance mechanical and electrochemical properties in materials that are inherently brittle. Here, we demonstrate a unique water-based self-assembly approach that incorporates a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT-b-PEO), with V2O5 to form a flexible, tough, carbon-free hybrid battery cathode. V2O5 is a promising lithium intercalation material, but it remains limited by its poor conductivity and mechanical properties. Our approach leads to a unique electrode structure consisting of interlocking V2O5 layers glued together with micellar aggregates of P3HT-b-PEO, which results in robust mechanical properties, far exceeding the those obtained from conventional fluoropolymer binders. Only 5 wt % polymer is required to triple the flexibility of V2O5, and electrodes comprised of 10 wt % polymer have unusually high toughness (293 kJ/m3) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes. Furthermore, addition of P3HT-b-PEO enhances lithium-ion diffusion, eliminates cracking during cycling, and boosts cyclability relative to V2O5 alone. These results highlight the importance of tradeoffs between mechanical and electrochemical performance, where polymer content can be used to tune both aspects. PMID:26391053

  13. Epidermal growth factor receptor-targeted lipid nanoparticles retain self-assembled nanostructures and provide high specificity (United States)

    Zhai, Jiali; Scoble, Judith A.; Li, Nan; Lovrecz, George; Waddington, Lynne J.; Tran, Nhiem; Muir, Benjamin W.; Coia, Gregory; Kirby, Nigel; Drummond, Calum J.; Mulet, Xavier


    Next generation drug delivery utilising nanoparticles incorporates active targeting to specific sites. In this work, we combined targeting with the inherent advantages of self-assembled lipid nanoparticles containing internal nano-structures. Epidermal growth factor receptor (EGFR)-targeting, PEGylated lipid nanoparticles using phytantriol and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-PEG-maleimide amphiphiles were created. The self-assembled lipid nanoparticles presented here have internal lyotropic liquid crystalline nano-structures, verified by synchrotron small angle X-ray scattering and cryo-transmission electron microscopy, that offer the potential of high drug loading and enhanced cell penetration. Anti-EGFR Fab' fragments were conjugated to the surface of nanoparticles via a maleimide-thiol reaction at a high conjugation efficiency and retained specificity following conjugation to the nanoparticles. The conjugated nanoparticles were demonstrated to have high affinity for an EGFR target in a ligand binding assay.Next generation drug delivery utilising nanoparticles incorporates active targeting to specific sites. In this work, we combined targeting with the inherent advantages of self-assembled lipid nanoparticles containing internal nano-structures. Epidermal growth factor receptor (EGFR)-targeting, PEGylated lipid nanoparticles using phytantriol and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-PEG-maleimide amphiphiles were created. The self-assembled lipid nanoparticles presented here have internal lyotropic liquid crystalline nano-structures, verified by synchrotron small angle X-ray scattering and cryo-transmission electron microscopy, that offer the potential of high drug loading and enhanced cell penetration. Anti-EGFR Fab' fragments were conjugated to the surface of nanoparticles via a maleimide-thiol reaction at a high conjugation efficiency and retained specificity following conjugation to the nanoparticles. The conjugated nanoparticles

  14. Microtubule Self- Assembly (United States)

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


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

  15. A highly controllable protein self-assembly system with morphological versatility induced by reengineered host-guest interactions. (United States)

    Li, Xiumei; Bai, Yushi; Huang, Zupeng; Si, Chengye; Dong, Zeyuan; Luo, Quan; Liu, Junqiu


    Manipulating proteins to self-assemble into highly ordered nanostructures not only provides insights into the natural protein assembly process but also allows access to advanced biomaterials. Host-guest interactions have been widely used in the construction of artificial protein assemblies in recent years. CB[8] can selectively associate with two tripeptide Phe-Gly-Gly (FGG) tags with an extraordinarily high binding affinity (Kter = 1.5 × 10(11) M(-2)). However, the FGG tags utilized before are all fixed to the N-termini via genetic fusion; this spatial limitation greatly confined the availability of the CB[8]/FGG pair in the construction of more sophisticated protein nanostructures. Here we first designed and synthesized a maleimide-functionalized Phe-Gly-Gly tag as a versatile site-specific protein modification tool; this designed tag can site-selectively introduce desired guest moieties onto protein surfaces for host-guest driven protein assembly. When regulating the self-assembly process of proteins and CB[8], the constructed protein nanosystem can exhibit distinctive morphological diversities ranging from nanorings, nanospirals, nanowires to superwires. This work developed a new strategy for site-specific protein modification of the CB[8] binding tag and provides a possible direction for the construction of 'smart', dynamic self-assembly systems.

  16. Efficient small molecule bulk heterojunction solar cells with high fill factors via pyrene-directed molecular self-assembly

    KAUST Repository

    Lee, Olivia P.


    Efficient organic photovoltaic (OPV) materials are constructed by attaching completely planar, symmetric end-groups to donor-acceptor electroactive small molecules. Appending C2-pyrene as the small molecule end-group to a diketopyrrolopyrrole core leads to materials with a tight, aligned crystal packing and favorable morphology dictated by π-π interactions, resulting in high power conversion efficiencies and high fill factors. The use of end-groups to direct molecular self-assembly is an effective strategy for designing high-performance small molecule OPV devices. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Self-assembled H-aggregation induced high performance poly (3-hexylthiophene) Schottky diode (United States)

    Chaudhary, Vivek; Pandey, Rajiv K.; Prakash, Rajiv; Singh, Arun Kumar


    The investigation of size confinement and chain orientation within the microstructure of a polymer thin film is very important for electronic device applications and fundamental research. Here, we present single step methodology for the synthesis of solution-processable poly (3-hexylthiophene) (P3HT) nanofibers via a self-assembly process. The formation of P3HT nanofibers is confirmed by atomic force microscopy. The synthesized nanofibers are characterized by UV-visible absorption, photoluminescence, and Raman spectroscopy. The aggregation type of self-assembled P3HT is studied by both UV-visible absorbance and photoluminescence spectroscopy. The exciton bandwidth in polymer films is calculated by following the Spano's H-aggregate model and found to be 28 meV. Raman spectroscopy is used to identify the various stretching modes present in nanofibers. The structural investigation using grazing angle X-ray diffraction of nanofibers reveals the presence of alkyl chain ordering. We have fabricated organic Schottky diodes with P3HT nanofibers on indium tin oxide (ITO) coated glass with configuration Al/P3HT/ITO, and current density-voltage characteristics are subsequently used for extracting the electronic parameters of the device. We have also discussed the charge transport mechanism at the metal/polymer interface.

  18. Scanning Tunneling Microscopic Observation of Adatom-Mediated Motifs on Gold-Thiol Self-assembled Monolayers at High Coverage

    DEFF Research Database (Denmark)

    Wang, Yun; Chi, Qijin; Hush, Noel S.


    Self-assembled monolayers (SAMs) formed by chemisorption of a branched-chain alkanethiol, 2-methyl-1-propanethiol, on Au(111) surfaces were studied by in situ scanning tunneling microscopy (STM) under electrochemical potential control and analyzed using extensive density functional theory (DFT...... the structural motifs observed on surfaces at low coverage and on gold nanoparticles to the observed spectroscopic properties of high-coverage SAMs formed by methanethiol. However, the significant role attributed to intermolecular steric packing effects suggests a lack of generality for the adatom-mediated motif...

  19. Functionalization at the central position of vinyl polymer chains: highly associable multipoint hydrogen bonds for complementary self-assemblies. (United States)

    Lee, Sang-Ho; Ouchi, Makoto; Sawamoto, Mitsuo


    This paper deals with the precision introduction of a multiple hydrogen-bonding site of a high association constant at the central position of a vinyl polymer chain for complementary self-assemblies. The interactive site consists of an array of hydrogen donors (D) and acceptors (A) to induce a multiple and highly associable interaction with a complementary counterpart. A bifunctional initiator (Cl-DADDAD-Cl) for metal-catalyzed living radical polymerization is thus designed and synthesized to embed a "Hamilton receptor" (DADDAD) between two terminal chlorides (Cl). In the presence of a ruthenium complex, the dichloride gives controlled polymers (Cl∼∼∼DADDAD∼∼∼Cl, ∼ ∼ ∼: polymer backbone) of narrow molecular weight distributions (Mw/Mn MMA). The receptor-decorated polystyrene recognizes complementary associable molecules and polymers carrying an ADADA unit (ADADA-Anthracene and ADADA-PMMA) to form self-assemblies where the association constant is as high as K(ass) ≈ 8000 m(-1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Self-assembly of highly charged polyelectrolyte complexes with superior proton conductivity and methanol barrier properties for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Yilmaztuerk, Serpil; Deligoez, Hueseyin; Yilmazoglu, Mesut; Damyan, Hakan; Oeksuezoemer, Faruk; Koc, S. Naci; Durmus, Ali; Ali Guerkaynak, M. [Istanbul University, Engineering Faculty, Chemical Engineering Dept., 34320 Avcilar-Istanbul (Turkey)


    The paper is concerned with the formation of Layer-by-Layer (LbL) self-assembly of highly charged polyvinyl sulfate potassium salt (PVS) and polyallylamine hydrochloride (PAH) on Nafion membrane to obtain the multilayered composite membranes with both high proton conductivity and methanol blocking properties. Also, the influences of the salt addition to the polyelectrolyte solutions on membrane selectivity (proton conductivity/methanol permeability) are discussed in terms of controlled layer thickness and charge density. The deposition of the self-assembly of PAH/PVS is confirmed by SEM analysis and it is observed that the polyelectrolyte layers growth on each side of Nafion membrane regularly. (PAH/PVS){sub 10}-Na{sup +} and (PAH/PVS){sub 10}-H{sup +} with 1.0 M NaCl provide 55.1 and 43.0% reduction in lower methanol permittivity in comparison to pristine Nafion, respectively, while the proton conductivities are 12.4 and 78.3 mS cm{sup -1}. Promisingly, it is found that the membrane selectivity values ({phi}) of all multilayered composite membranes in H{sup +} form are much higher than those of Na{sup +} form and perfluorosulfonated ionomers reported in the literature. These encouraging results indicate that composite membranes having both superior proton conductivity and improved methanol barrier properties can be prepared from highly charged polyelectrolytes including salt for fuel cell applications. (author)

  1. Self-Assembled Dendritic Pt Nanostructure with High-Index Facets as Highly Active and Durable Electrocatalyst for Oxygen Reduction. (United States)

    Jang, Youngjin; Choi, Kwang-Hyun; Chung, Dong Young; Lee, Ji Eun; Jung, Namgee; Sung, Yung-Eun


    The durability issues of Pt catalyst should be resolved for the commercialization of proton exchange membrane fuel cells. Nanocrystal structures with high-index facets have been recently explored to solve the critical durability problem of fuel cell catalysts as Pt catalysts with high-index facets can preserve the ordered surfaces without change of the original structures. However, it is very difficult to develop effective and practical synthetic methods for Pt-based nanostructures with high-index facets. The current study describes a simple one-pot synthesis of self-assembled dendritic Pt nanostructures with electrochemically active and stable high-index facets. Pt nanodendrites exhibited 2 times higher ORR activity and superior durability (only 3.0 % activity loss after 10 000 potential cycles) than a commercial Pt/C. The enhanced catalytic performance was elucidated by the formation of well-organized dendritic structures with plenty of reactive interfaces among 5 nm-sized Pt particles and the coexistence of low- and high-index facets on the particles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. High Order in a Self-Assembled Iridium(III) Complex Gelator Towards Nanostructured IrO2 Thin Films. (United States)

    Scarpelli, Francesca; Ionescu, Andreea; Aiello, Iolinda; La Deda, Massimo; Crispini, Alessandra; Ghedini, Mauro; Brunelli, Elvira; Sesti, Settimio; Godbert, Nicolas


    The preparation and characterization of a new metallogelator based on the Ir(III) discrete cyclometalated complex [(ppy)2 Ir(bpy)](CH3 CH2 OCH2 CO2 ) are reported, where H(ppy) is 2-phenylpiridine and bpy is 2,2'-bipyridine, which is used as an ancillary ligand. The compound is able to self-assemble in water in a range of concentrations between 3 % and 6 % w/w, creating a luminescent ordered supramolecular gel. The gel and xerogel architectures were investigated through polarized optical microscopy (POM), SEM and TEM microscopies coupled with powder X-ray diffraction. The gel supramolecular organization is characterized by columnar tetragonal strands, already present at high dilution conditions, of cations surrounded by counteranions. These strands, in turn, are self-assembled in an oblique columnar cell upon gelification. The xerogel thin films obtained upon complete dehydration maintained the gel supramolecular order and can be used as a precursor for the preparation of nanostructured IrO2 thin films. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. High frequency magneto-dielectric effects in self-assembled ferrite-ferroelectric core-shell nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Popov


    Full Text Available Magneto-dielectric effects in self-assembled core-shell nanoparticles of nickel ferrite (NFO and barium titanate (BTO have been investigated in the millimeter wave frequencies. The core-shell nano-composites were synthesized by coating 100 nm nickel ferrite and 50 nm barium titanate nanoparticles with complementary coupling groups and allowing them to self-assemble in the presence of a catalyst forming heterogeneous nanocomposites. Magneto-electric (ME characterization of as-assembled particles has been carried out by measurements of the relative permittivity ɛr as a function of frequency f under an applied static magnetic field H over 16–24 GHz. Measurements show an H-induced decrease in ɛr of 1 to 1.5%. But a giant magneto-dielectric effect with an H-induced change in permittivity as high as 28% is measured under dielectric resonance in the samples. A strong ME coupling was also evident from H-tuning of dielectric resonance in the composites. A theory for the high frequency magneto-dielectric effect has been developed and consists of the following steps. First the Bruggeman model is used to estimate the effective dielectric constant for the shell consisting of the BTO particles and voids considered as spherical air-pores. Then the permittivity for the core and shell is estimated taking into consideration the sample porosity. Finally the H-dependence of the permittivity due to ME interactions is calculated from the free energy considerations. Estimated ɛr vs. H and dielectric resonance frequency vs. H characteristics are in general agreement with the data.

  4. Self-assembled core-polyethylene glycol-lipid shell nanoparticles demonstrate high stability in shear flow. (United States)

    Shen, Zhiqiang; Ye, Huilin; Kröger, Martin; Li, Ying


    A core-polyethylene glycol-lipid shell (CPLS) nanoparticle consists of an inorganic core coated with polyethylene glycol (PEG) polymers, surrounded by a lipid bilayer shell. It can be self-assembled from a PEGylated core with surface-tethered PEG chains, where all the distal ends are covalently bonded to lipid molecules. Upon adding free lipids, a complete lipid bilayer shell can be formed on the surface driven by the hydrophobic nature of lipid tails, leading to the formation of a CPLS nanoparticle. The stability of CPLS nanoparticles in shear flow has been systematically studied through large scale dissipative particle dynamics simulations. CPLS nanoparticles demonstrate higher stability and less deformation in shear flow, compared with lipid vesicles. Burst leakage of drug molecules inside lipid vesicles and CPLS NPs can be induced by the large pores at their tips. These pores are initiated by the maximum stress in the waist region. It further grows along with the tank-treading motion of vesicles or CPLS NPs in shear flow. However, due to the constraints applied by PEG polymers, CPLS NPs are less deformed than vesicles with comparable size under the same flow conditions. Thus, the less deformed CPLS NPs express a smaller maximum stress at waists, demonstrating higher stability. Pore formation at waists, evolving into large pores on vesicles, leads to the burst leakage of drug molecules and complete rupture of vesicles. In contrast, although similar drug leakage in CPLS nanoparticles can occur at high shear rates, pores initiated at moderate shear rates tend to be short-lived and close due to the constraints mediated by PEG polymers. This kind of 'self-healing' capability can be observed over a wide range of shear rates for CPLS nanoparticles. Our results suggest self-assembled CPLS nanoparticles to exhibit high stability during blood circulation without rapid drug leakage. These features make CPLS nanoparticles candidates for a promising drug delivery platform.

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

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


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

  6. High Circular Polarization of Electroluminescence Achieved via Self-Assembly of a Light-Emitting Chiral Conjugated Polymer into Multidomain Cholesteric Films. (United States)

    Di Nuzzo, Daniele; Kulkarni, Chidambar; Zhao, Baodan; Smolinsky, Eilam; Tassinari, Francesco; Meskers, Stefan C J; Naaman, Ron; Meijer, E W; Friend, Richard H


    We demonstrate a facile route to obtain high and broad-band circular polarization of electroluminescence in single-layer polymer OLEDs. As a light-emitting material we use a donor-acceptor polyfluorene with enantiomerically pure chiral side-chains. We show that upon thermal annealing the polymer self-assembles into a multidomain cholesteric film. By varying the thickness of the polymer emitting layer, we achieve high levels of circular polarization of electroluminescence (up to 40% excess of right-handed polarization), which are the highest reported for polymer OLEDs not using chiral dopants or alignment layers. Mueller matrix ellipsometry shows strong optical anisotropies in the film, indicating that the circular polarization of luminescence arises mainly after the photon has been generated, through selective scattering and birefringence correlated in the direction of the initial linear polarization of the photon. Our work demonstrates that chirally substituted conjugated polymers can combine photonic and semiconducting properties in advanced optoelectronic devices.

  7. High quality factor whispering gallery modes from self-assembled hexagonal GaN rods grown by metal-organic vapor phase epitaxy. (United States)

    Tessarek, C; Sarau, G; Kiometzis, M; Christiansen, S


    Self-assembled GaN rods were grown on sapphire by metal-organic vapor phase epitaxy using a simple two-step method that relies first on a nitridation step followed by GaN epitaxy. The mask-free rods formed without any additional catalyst. Most of the vertically aligned rods exhibit a regular hexagonal shape with sharp edges and smooth sidewall facets. Cathodo- and microphotoluminescence investigations were carried out on single GaN rods. Whispering gallery modes with quality factors greater than 4000 were measured demonstrating the high morphological and optical quality of the self-assembled GaN rods.

  8. Self-Assembled NiO/Ni(OH)2 Nanoflakes as Active Material for High-Power and High-Energy Hybrid Rechargeable Battery. (United States)

    Lee, Dong Un; Fu, Jing; Park, Moon Gyu; Liu, Hao; Ghorbani Kashkooli, Ali; Chen, Zhongwei


    Herein, a proof-of-concept of novel hybrid rechargeable battery based on electrochemical reactions of both nickel-zinc and zinc-air batteries is demonstrated using NiO/Ni(OH)2 nanoflakes self-assembled into mesoporous spheres as the active electrode material. The hybrid battery operates on two sets of fundamentally different battery reactions combined at the cell level, unlike in other hybrid systems where batteries of different reactions are simply connected through an external circuitry. As a result of combining nickel-zinc and zinc-air reactions, the hybrid battery demonstrates both remarkably high power density (volumetric, 14 000 W L(-1); gravimetric, 2700 W kg(-1)) and energy density of 980 W h kg(-1), significantly outperforming the performances of a conventional zinc-air battery. Furthermore, the hybrid battery demonstrates excellent charge rate capability up to 10 times faster than the rate of discharge without any capacity and voltage degradations, which makes it highly suited for large-scale applications such as electric vehicle propulsion and smart-grid energy storage.

  9. Highχ block copolymers for directed self-assembly patterning without the need for topcoat or solvent annealing (United States)

    Xu, Kui; Hockey, Mary Ann; Calderas, Eric; Guerrero, Douglas; Sweat, Daniel; Fiehler, Jeffrey


    High-χ block copolymers for directed self-assembly (DSA) patterning that do not need topcoat or solvent annealing have been developed. A variety of functionalities have been successfully added into the block copolymers, such as balanced surface energy between the polymer blocks, outstandingly high χ, tunable glass transition temperature (Tg), and selective crosslinking. Perpendicular orientation control, as desired for patterning, of the block copolymers can be simply achieved by thermal annealing due to the equal surface energy of the polymer blocks at the annealing temperatures, which allows avoiding solvent annealing or top-coat. The χ value can be tuned up to achieve L0 as low as 8-10 nm for lamellar-structured block copolymers and hole/pillar size as small as 5-6 nm for cylinder-structured block copolymers. The Tg of the block copolymers can be tuned to improve the kinetics of thermal annealing by enhancing the polymer chain mobility. Block-selective crosslinking facilitates the pattern transfer by mitigating pattern collapse during wet etching and improving oxygen plasma etching selectivity between the polymer blocks. This paper provides an introductory review of our high-χ block copolymer materials with various functionalities for achieving improved DSA performance.

  10. Three-Dimensional Self-Assembly of Core/Shell-Like Nanostructures for High-Performance Nanocomposite Permanent Magnets. (United States)

    Li, Hailing; Li, Xiaohong; Guo, Defeng; Lou, Li; Li, Wei; Zhang, Xiangyi


    Core/shell nanostructures are fascinating for many advanced applications including strong permanent magnets, magnetic recording, and biotechnology. They are generally achieved via chemical approaches, but these techniques limit them to nanoparticles. Here, we describe a three-dimensional (3D) self-assembly of core/shell-like nanocomposite magnets, with hard-magnetic Nd2Fe14B core of ∼45 nm and soft-magnetic α-Fe shell of ∼13 nm, through a physical route. The resulting Nd2Fe14B/α-Fe core/shell-like nanostructure allows both large remanent magnetization and high coercivity, leading to a record-high energy product of 25 MGOe which reaches the theoretical limit for isotropic Nd2Fe14B/α-Fe nanocomposite magnets. Our approach is based on a sequential growth of the core and shell nanocrystals in an alloy melt. These results make an important step toward fabricating core/shell-like nanostructure in 3D materials.

  11. Self-assembled structures of N-alkylated bisbenzimidazolyl naphthalene in aqueous media for highly sensitive detection of picric acid. (United States)

    Wu, Yan-Cheng; Luo, Shi-He; Cao, Liang; Jiang, Kai; Wang, Ling-Yun; Xie, Jie-Chun; Wang, Zhao-Yang


    A 2,6-dibenzimidazole-appended naphthalene derivative flanking with two N-alkyl chains (sensor 4) was designed and applied for highly sensitive detection of picric acid (PA) in aqueous media. Driven by the hydrophobicity of alkyl chain and π-π stacking effect of aryl, sensor 4 can undergo self-assembly to form an orderly rod-like structure in H2O/THF (v/v, 90/10) solution, as shown by the dynamic light scattering (DLS) and scanning electron microscopy (SEM) studies. Sensor 4 shows high selectivity and sensitivity toward PA over other nitroaromatic explosives. DFT calculations and 1H NMR, the time-correlated single photon counting (TCSPC) experiments confirm that the quenching mechanism is due to both electron and energy transfer from the electron-rich sensor 4 to the electron-deficient PA. Sensor 4 can detect as low as 0.57 ppb PA in aqueous media and 11.46 ag cm-2 PA by contact mode. Importantly, sensor 4 exhibits low interference against common solvents, metal ions and anions. Thus, it is practically applicable for sensing PA in real environmental samples and vapor phase. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Preparation and high-performance microwave absorption of hierarchical dendrite-like Co superstructures self-assembly of nanoflakes (United States)

    Yu, Miao; Wang, Lirui; Yang, Pingan; Fu, Jie


    Dendritic-like Co superstructures based on the self-assembly of nanoflakes that could efficiently suppress the eddy current were successfully synthesized via a facile, rapid, and energy-saving chemical reduction method. Since crystal structure, size, and special geometrical morphology, magnetism have a vital influence on microwave absorption properties, the as-obtained products were characterized by x-ray diffraction, scanning electron microscopy, vibrating sample magnetometry, and vector network analysis. The prepared dendritic Co possesses abundant secondary branches that extend to the 3D space. Their dimensions, spacing, sheet-like blocks, and high-ordering microstructures all contribute to the penetration, scattering, and attenuation of EM waves. The composites present attractive microwave absorption performances in the X band, as well as in the whole S band (2–4 GHz). This work investigates the mechanism of absorption for the as-obtained Co, offers a promising strategy for the fabrication of hierarchical Co microstructure assemblies by multi-leaf flakes and introduces the application of dendritic-like Co as a highly efficient absorber in the S band and X band.

  13. Self-assembled nanostructures

    CERN Document Server

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


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

  14. Robust Self-Assembly of Highly Ordered Complex Structures by Controlled Evaporation of Confined Microfluids (United States)

    Lin, Zhiqun; Byun, Myunghwan; Hong, Suck Won


    We demonstrate a robust, one-step method of evaporating polymer solutions in curve-on-flat geometries to create versatile, highly regular microstructures in a precisely controlled environment, as well as offering a comprehensive study of the influence of different upper surfaces on complex structure formation via controlled evaporation. Our method further enhances current fabrication approaches to creating highly ordered structures in a simple and cost-effective manner, with the potential to be tailored for use in photonics, electronics, optoelectronics, microfluidic devices, nanotechnology, and biotechnology.

  15. Highly permeable artificial water channels that can self-assemble into two-dimensional arrays


    Shen, Yue-xiao; Si, Wen; Erbakan, Mustafa; Decker, Karl; De Zorzi, Rita; Saboe, Patrick O.; Kang, You Jung; Majd, Sheereen; Butler, Peter J.; Walz, Thomas; Aksimentiev, Aleksei; Hou, Jun-Li; Kumar, Manish


    This study focuses on the design of highly permeable artificial water channels for the use in membrane-based separation materials. A platform was developed for the systematic characterization of the single-channel water conduction of artificial channels, which is based on permeability measurement by stopped-flow light-scattering experiments and single-molecule counting by fluorescence correlation spectroscopy. With this platform the water conduction of the redesigned peptide-appended pillar[5...

  16. Self-assembled Ti3C2Tx MXene film with high gravimetric capacitance. (United States)

    Hu, Minmin; Li, Zhaojin; Zhang, Hui; Hu, Tao; Zhang, Chao; Wu, Zhen; Wang, Xiaohui


    Binder-free MXene films comprising Ti3C2Tx nanoflakes in a face-to-face fashion, achieved by a simple dropping-mild baking approach, exhibit high gravimetric capacitances up to 499 F g(-1) with excellent cyclability and rate performances. The entire electrode system including Ni-foam and MXene film shows volumetric capacitances in the range of 84-226 F cm(-3) depending on the loadings of MXene as active material.

  17. High Frequency Magneto Dielectric Effects In Self Assembled Ferrite Ferroelectric Core Shell Nanoparticles (United States)


    estimate the magneto-capacitance effect in BTO or PZT films on substrates of ferromagnetic alloys.25 This work is on the observation and theory of MDE...The sample shows ferromagnetic behavior with hysteresis and remnance and the magnetization compared favorably with reported value for...samples. A strong ME coupling was also evident from H-tuning of dielectric resonance in the composites. A theory for the high frequency magneto

  18. Design of Introspective Circuits for Analysis of Cell-Level Dis-orientation in Self-Assembled Cellular Systems

    Directory of Open Access Journals (Sweden)

    Nicholas Jesse Macias


    Full Text Available This paper discusses a novel approach to managing complexity in a large self-assembled system, by employing the self-assembling components themselves to address the complexity. Challenges are discussed, including the question of how to deal with elements that are assembled in different orientations from each other, and a solution based on the idea of introspective circuits is described. A methodology for determining a single cell’s orientation from an adjacent cell is given. An algorithm is then described for using such re-oriented edge cells to determine orientation of more-interior cells, thus allowing re-orientation of an entire 2D region of cells. Test procedures are described, and results are presented to show better-than-linear time performance (O(sqrt(n. The significance of this work is discussed, not only in terms of managing arrays of dis-oriented cells, but more importantly as an example of the usefulness of local, distributed self-configuration to create and use introspective circuitry. Finally, future work is discussed, including extension to 3D collections of cells.

  19. Sub-10-nm patterning process using directed self-assembly with high χ block copolymers (United States)

    Kihara, Naoko; Seino, Yuriko; Sato, Hironobu; Kasahara, Yusuke; Kobayashi, Katsutoshi; Miyagi, Ken; Minegishi, Shinya; Yatsuda, Koichi; Fujiwara, Tomoharu; Hirayanagi, Noriyuki; Kanai, Hideki; Kawamonzen, Yoshiaki; Kodera, Katsuyoshi; Azuma, Tsukasa; Hayakawa, Teruaki


    The perpendicularly orientated lamellar structure of the self-organized diblock copolymer is an attractive template for sub-10-nm line-and-space pattern formation. We propose a method of evaluating the neutral layer (NL) whose performance has an important bearing on the perpendicular orientation of the lamellar structure. The random copolymer of methyl methacrylate and i-butyl POSS methacrylate (MAIBPOSS) has been investigated as an NL for a polymethylmethacrylate-b-polymethacrylethylPOSS (PMMA-b-PMAIBPOSS) lamellar structure. PMMA-b-PMAIBPOSS material has the potential to form sub-10 nm line-and-space pattern, in addition to high etch selectivity due to its POSS structure. Under the free surface, PMMA-b-PMAIBPOSS film on the random copolymer layer showed horizontal orientation. However, a half-pitch of a 7-nm finger pattern structure was observed by peeling off the horizontally oriented layer. The upper portion of the PMMA-b-PMAIBPOSS film was eliminated till proximity of the random copolymer layer by CF4 gas etching. From the result, it was revealed that the PMMA-r-PMAIBPOSS works as an NL. It was confirmed that the contact angle analysis using an appropriate polymer is a suitable method for evaluation of the surface energy performance of the copolymer with the attribute of high segregation energy.

  20. Self-assembly of thiophene derivatives on highly oriented pyrolytic graphite: hydrogen bond effect. (United States)

    Xu, Li-Ping; Liu, Yibiao; Zhao, Jing; Wang, Shuqi; Lin, Chen-Sheng; Zhang, Rui-Qin; Wen, Yongqiang; Du, Hongwu; Zhang, Xueji


    In this paper, to elucidate the hydrogen bond effect on the assembly behavior, we studied the assembly structures of two carboxylic substituted thiophene derivatives on highly oriented pyrolytic graphite (HOPG) by scanning tunneling microscopy. Here thiophene-2-carboxylic acid (TCA) and thiophene-2,5-dicarboxylic acid (TDA) were employed. TDA molecules spontaneously adsorb on the HOPG surface and self-organize into a two-dimensional (2D) assembly with well-defined structure. Two types of domain could be observed. Each TDA molecule appears as a round circle with two small faint dots and forms hydrogen bonds with neighbours. Besides monolayer structure, a bilayer structure of TDA adlayer on HOPG was also observed in this research. Remnant TDA molecules adsorb on the monolayer of TDA and bilayer structure is formed. In contrast to TDA, no ordered structure of TCA on HOPG can be observed. TCA molecules have high propensity to form dimers through H-bond between carboxylic groups. But TCA dimer is not stable enough for either adsorption or imaging. Our result provides a new example for understanding hydrogen effect on stabilizing and controlling two-dimensional assembly structure and is helpful for surface nanofabrication and development of electric nanodevices.

  1. WO3 nanorods created by self-assembly of highly crystalline nanowires under hydrothermal conditions. (United States)

    Navarro, Julien R G; Mayence, Arnaud; Andrade, Juliana; Lerouge, Frédéric; Chaput, Frédéric; Oleynikov, Peter; Bergström, Lennart; Parola, Stephane; Pawlicka, Agnieszka


    WO3 nanorods and wires were obtained via hydrothermal synthesis using sodium tungstate as a precursor and either oxalic acid, citric acid, or poly(methacrylic acid) as a stabilizing agent. Transmission electron microscopy images showed that the organic acids with different numbers of carboxylic groups per molecule influence the final sizes and stacking nanostructures of WO3 wires. Three-dimensional electron diffraction tomography of a single nanocrystal revealed a hexagonal WO3 structure with preferential growth along the c-axis, which was confirmed by high-resolution transmission electron microscopy. WO3 nanowires were also spin-coated onto an indium tin oxide/glass conducting substrate, resulting in the formation of a film that was characterized by scanning electron microscopy. Finally, cyclic voltammetry measurements performed on the WO3 thin film showed voltammograms typical for the WO3 redox process.

  2. The high frequency magnetic properties of self assembled Fe-Co-Si-N nanogranular thin films

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yan [National University of Singapore, Centre for Superconducting and Magnetic Materials, Department of Physics, Singapore (Singapore); Nanyang Technological University, School of Materials Science and Engineering, Singapore (Singapore); Ramanujan, R.V. [Nanyang Technological University, School of Materials Science and Engineering, Singapore (Singapore); Liu, Z.W. [National University of Singapore, Centre for Superconducting and Magnetic Materials, Department of Physics, Singapore (Singapore); Nanyang Technological University, School of Materials Science and Engineering, Singapore (Singapore); South China University of Technology, School of Materials Science and Engineering, Guangzhou (China); Tan, C.Y. [National University of Singapore, Centre for Superconducting and Magnetic Materials, Department of Physics, Singapore (Singapore); Institute of Materials Research and Engineering, Singapore (Singapore); Zhao, Xing; Liu, Erjia [Nanyang Technological University, School of Mechanical and Aerospace Engineering, Singapore (Singapore); Ong, C.K. [National University of Singapore, Centre for Superconducting and Magnetic Materials, Department of Physics, Singapore (Singapore)


    The effect of a variation in Si and N concentration on the microstructure, crystal structure and high-frequency magnetic properties of Fe-Co-Si-N nanogranular thin films was investigated. The films, prepared by rf magnetron sputtering, consisted of nanosized grains of FeCo as well as a Si and N rich intergranular amorphous phase. The Si concentration had a significant effect on the crystal structure of the FeCo phase. The resistivities of the Fe-Co-Si-N films were significantly enhanced by an increase in Si concentration. The resonant frequency of the Fe-Co-Si-N films could be tuned from 0.45 GHz to 2.1 GHz by controlling Si concentration. The N concentration greatly influenced magnetic properties and the variation in resonant frequency is in agreement with Kittel's equation. (orig.)

  3. Photovoltaic self-assembly.

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Self-assembly of suspended graphene wrinkles with high pre-tension and elastic property (United States)

    Yang, Liusi; Niu, Tianxiao; Zhang, Hui; Xu, Wenjing; Zou, Mingchu; Xu, Lu; Cao, Guoxin; Cao, Anyuan


    Wrinkles exist universally in graphene-based structures, yet their controlled fabrication remains challenging; most graphene wrinkles have been produced either in attachment to elastic substrates or limited in small single sheets. Here, we utilize the phenomenon of gel-cracking to generate uniaxial strains locally on solution-precipitated graphene oxide (GO) sheets, thus creating suspended and aligned wrinkles over the trenches between cracked TiO2 islands. In particular, those GO wrinkles are subjected to a high pre-tension, which is important for making stable suspended configuration, as confirmed by theoretical calculations based on the wrinkle geometry and measured spring constants, respectively. As a result, in situ atomic force microscope indentation reveals elastic deformation with tunable spring constants depending on the gap width. We further obtain chemically reduced GO wrinkles with enhanced spring constants and reversible behavior after 1000 indentation cycles. Our suspended and aligned graphene wrinkles have potential applications in many areas such as sensors, actuators, and micro/nano electromechanical systems.

  5. Self-assembly of ultrathin Cu2MoS4 nanobelts for highly efficient visible light-driven degradation of methyl orange (United States)

    Zhang, Ke; Chen, Wenxing; Lin, Yunxiang; Chen, Haiping; Haleem, Yasir A.; Wu, Chuanqiang; Ye, Fei; Wang, Tianxing; Song, Li


    We demonstrate ultrathin self-assembled Cu2MoS4 nanobelts synthesized by using Cu2O as the starting sacrificial template via a hydrothermal method. The nanobelts exhibit strong light absorption over a broad wavelength spectrum, suggesting their potential application as photocatalysts. The photocatalytic activity of nanobelts is evaluated by the degradation of Methyl Orange (MO) dye under visible light irradiation. Notably, the nanobelts can completely degrade 100 mL of 15 mg mL-1 MO in 20 minutes with excellent recycling and structural stability, suggesting their excellent photocatalytic performance. In comparison with a sheet-like sample, the high efficiency of the self-assembled Cu2MoS4 nanobelts is attributed to a high surface area and a unique band gap, agreeing with the nitrogen adsorption analysis and photoluminescence spectra. This study offers a self-assembled synthetic route to create new multifunctional nanoarchitectures composed of atomic layers, and thus may open a window for greatly extending potential applications in water pollution treatment, photocatalytic water-splitting, solar cells and other related fields.We demonstrate ultrathin self-assembled Cu2MoS4 nanobelts synthesized by using Cu2O as the starting sacrificial template via a hydrothermal method. The nanobelts exhibit strong light absorption over a broad wavelength spectrum, suggesting their potential application as photocatalysts. The photocatalytic activity of nanobelts is evaluated by the degradation of Methyl Orange (MO) dye under visible light irradiation. Notably, the nanobelts can completely degrade 100 mL of 15 mg mL-1 MO in 20 minutes with excellent recycling and structural stability, suggesting their excellent photocatalytic performance. In comparison with a sheet-like sample, the high efficiency of the self-assembled Cu2MoS4 nanobelts is attributed to a high surface area and a unique band gap, agreeing with the nitrogen adsorption analysis and photoluminescence spectra. This study

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

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


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

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

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


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

  8. Self-assembly of ultrathin Cu2MoS4 nanobelts for highly efficient visible light-driven degradation of methyl orange. (United States)

    Zhang, Ke; Chen, Wenxing; Lin, Yunxiang; Chen, Haiping; Haleem, Yasir A; Wu, Chuanqiang; Ye, Fei; Wang, Tianxing; Song, Li


    We demonstrate ultrathin self-assembled Cu2MoS4 nanobelts synthesized by using Cu2O as the starting sacrificial template via a hydrothermal method. The nanobelts exhibit strong light absorption over a broad wavelength spectrum, suggesting their potential application as photocatalysts. The photocatalytic activity of nanobelts is evaluated by the degradation of Methyl Orange (MO) dye under visible light irradiation. Notably, the nanobelts can completely degrade 100 mL of 15 mg mL(-1) MO in 20 minutes with excellent recycling and structural stability, suggesting their excellent photocatalytic performance. In comparison with a sheet-like sample, the high efficiency of the self-assembled Cu2MoS4 nanobelts is attributed to a high surface area and a unique band gap, agreeing with the nitrogen adsorption analysis and photoluminescence spectra. This study offers a self-assembled synthetic route to create new multifunctional nanoarchitectures composed of atomic layers, and thus may open a window for greatly extending potential applications in water pollution treatment, photocatalytic water-splitting, solar cells and other related fields.

  9. Mechanical Self-Assembly Science and Applications

    CERN Document Server


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

  10. Highly Sensitive Aluminium(III) Ion Sensor Based on a Self-assembled Monolayer on a Gold Nanoparticles Modified Screen-printed Carbon Electrode. (United States)

    See, Wong Pooi; Heng, Lee Yook; Nathan, Sheila


    A new approach for the development of a highly sensitive aluminium(III) ion sensor via the preconcentration of aluminium(III) ion with a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode and current mediation by potassium ferricyanide redox behavior during aluminium(III) ion binding has been attempted. A monolayer of mercaptosuccinic acid served as an effective complexation ligand for the preconcentration of trace aluminium; this led to an enhancement of aluminium(III) ion capture and thus improved the sensitivity of the sensor with a detection limit of down to the ppb level. Under the optimum experimental conditions, the sensor exhibited a wide linear dynamic range from 0.041 to 12.4 μM. The lower detection limit of the developed sensor was 0.037 μM (8.90 ppb) using a 10 min preconcentration time. The sensor showed excellent selectivity towards aluminium(III) ion over other interference ions.

  11. Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions (United States)

    Wang, Shaofei; Jiang, Jiaolai; Wu, Haoxi; Jia, Jianping; Shao, Lang; Tang, Hao; Ren, Yiming; Chu, Mingfu; Wang, Xiaolin


    A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of Odbnd Udbnd O resulting from two kinds of adsorption of uranyl species (;strong; and ;weak; adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of Odbnd Udbnd O shifted from 871 cm- 1 (normal Raman) to 720 cm- 1 and 826 cm- 1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at 826 cm- 1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10- 7 to 10- 3 mol L- 1 with an excellent linear relation (R2 = 0.998), and the detection limit was 10- 7 mol L- 1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

  12. A self-assembled ionophore (United States)

    Tirumala, Sampath K.


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

  13. Ge nanobelts with high compressive strain fabricated by secondary oxidation of self-assembly SiGe rings

    DEFF Research Database (Denmark)

    Lu, Weifang; Li, Cheng; Lin, Guangyang


    Curled Ge nanobelts were fabricated by secondary oxidation of self-assembly SiGe rings, which were exfoliated from the SiGe stripes on the insulator. The Ge-rich SiGe stripes on insulator were formed by hololithography and modified Ge condensation processes of Si0.82Ge0.18 on SOI substrate. Ge...... nanobelts under a residual compressive strain of 2% were achieved, and the strain should be higher before partly releasing through bulge islands and breakage of the curled Ge nanobelts during the secondary oxidation process. The primary factor leading to compressive strain is thermal shrinkage of Ge...

  14. Determination of low levels of cadmium ions by the under potential deposition on a self-assembled monolayer on gold electrode

    Energy Technology Data Exchange (ETDEWEB)

    Noyhouzer, Tomer [Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel); Mandler, Daniel, E-mail: [Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel)


    The electrochemical determination of low levels of Cd using a self-assembled monolayer (SAM) modified Au electrode is reported. Determination was based on the stripping of Cd, which was deposited by under potential deposition (UPD). A series of short alkanethiol SAMs bearing different end groups, i.e., sulfonate, carboxylate and ammonium, were examined. Lowest level of detection (ca. 50 ng L{sup -1}) was achieved with a 3-mercaptopropionic acid (MPA) monolayer using subtractive anodic square wave voltammetry (SASV). Additional surface methods, namely, reductive desorption and X-ray photoelectron spectroscopy, were applied to determine the interfacial structure of the electrodeposited Cd on the modified electrodes. We conclude that the deposited Cd forms a monoatomic layer, which bridges between the gold surface and the alkanethiol monolayer associating with both the gold and the sulfur atoms.

  15. Self-Assembly at the Colloidal Scale (United States)

    Zhong, Xiao

    The existence of self-assembly, the phenomenon of spontaneous structural formation from building blocks, transcends many orders of magnitude, ranging from molecular to cosmic. It is arguably the most common, important, and complex question in science. This thesis aims for understanding a spectrum of self-assembly-self assembly at the colloidal scale. Of the whole spectrum of self-assembly, the colloidal scale is of particular interest and importance to researchers, for not only comprehensive tools for colloidal scale studies have been well established, but also the various promising applications colloidal self-assembly can facilitate. In this thesis, a high throughput technique-Polymer Pen Lithography (PPL) is modified and its potential for creating corrals for colloidal assembly is evaluated. Then two different approaches of assembling colloids are explored in depth. One of them is by using a phenomenon called dielectrophoresis (DEP) as driving force to manipulate colloidal nucleation and crystal growth. And the other takes advantage of the Pt-catalyzed H2O 2 redox reaction to drive micrometer-scaled, rod-shaped colloids to swim and assemble. Lastly, an optical method called Holographic Video Microscopy (HVM) is used to monitor and characterize "bad" self-assembly of proteins, that is their aggregations. The four studies discussed in this thesis represent advancements in the colloidal scale from different aspects. The PPL technique enriched the toolbox for colloidal self-assembly. The DEP driven colloidal nucleation and crystal growth shed light on deeper understanding the mechanism of crystallization. And the swimming and assembly of micro-scale rods leads to kinetics reminiscent of bacterial run-and-tumble motion. Finally, the HVM technique for monitoring and understanding protein aggregation could potentially lead to better quality assurance for therapeutic proteins and could be a powerful tool for assessing their shelf lives.

  16. High resolution patterning of nanoparticles by evaporative self-assembly enabled by in situ creation and mechanical lift-off of a polymer template (United States)

    Demko, Michael T.; Choi, Sun; Zohdi, Tarek I.; Pisano, Albert P.


    High-resolution patterning of nanostructured materials into open templates is limited by the processes of creation and removal of the necessary template. In this work, a process for forming a micropatterned template from cellulose acetate polymer in situ on the substrate is demonstrated. Nanoparticles are patterned by evaporative self-assembly, and the template is removed by mechanical means. The process is demonstrated by patterning zinc oxide nanoparticles on silicon and cyclic olefin copolymer substrates and by creating a highly sensitive ultraviolet light detector.

  17. Self-assembly of self-assembled molecular triangles

    Indian Academy of Sciences (India)

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

  18. Peptide Self-Assembled Nanostructures for Drug Delivery Applications

    Directory of Open Access Journals (Sweden)

    Taotao Fan


    Full Text Available Peptide self-assembled nanostructures are very popular in many biomedical applications. Drug delivery is one of the most promising applications among them. The tremendous advantages for peptide self-assembled nanostructures include good biocompatibility, low cost, tunable bioactivity, high drug loading capacities, chemical diversity, specific targeting, and stimuli responsive drug delivery at disease sites. Peptide self-assembled nanostructures such as nanoparticles, nanotubes, nanofibers, and hydrogels have been investigated by many researchers for drug delivery applications. In this review, the underlying mechanisms for the self-assembled nanostructures based on peptides with different types and structures are introduced and discussed. Peptide self-assembled nanostructures associated promising drug delivery applications such as anticancer drug and gene drug delivery are highlighted. Furthermore, peptide self-assembled nanostructures for targeted and stimuli responsive drug delivery applications are also reviewed and discussed.

  19. Electrostatic Self-Assembly of Fe3O4 Nanoparticles on Graphene Oxides for High Capacity Lithium-Ion Battery Anodes

    Directory of Open Access Journals (Sweden)

    Jung Kyoo Lee


    Full Text Available Magnetite, Fe3O4, is a promising anode material for lithium ion batteries due to its high theoretical capacity (924 mA h g−1, high density, low cost and low toxicity. However, its application as high capacity anodes is still hampered by poor cycling performance. To stabilize the cycling performance of Fe3O4 nanoparticles, composites comprising Fe3O4 nanoparticles and graphene sheets (GS were fabricated. The Fe3O4/GS composite disks of mm dimensions were prepared by electrostatic self-assembly between negatively charged graphene oxide (GO sheets and positively charged Fe3O4-APTMS [Fe3O4 grafted with (3-aminopropyltrimethoxysilane (APTMS] in an acidic solution (pH = 2 followed by in situ chemical reduction. Thus prepared Fe3O4/GS composite showed an excellent rate capability as well as much enhanced cycling stability compared with Fe3O4 electrode. The superior electrochemical responses of Fe3O4/GS composite disks assure the advantages of: (1 electrostatic self-assembly between high storage-capacity materials with GO; and (2 incorporation of GS in the Fe3O4/GS composite for high capacity lithium-ion battery application.

  20. S-Layer Protein Self-Assembly (United States)

    Pum, Dietmar; Toca-Herrera, Jose Luis; Sleytr, Uwe B.


    Crystalline S(urface)-layers are the most commonly observed cell surface structures in prokaryotic organisms (bacteria and archaea). S-layers are highly porous protein meshworks with unit cell sizes in the range of 3 to 30 nm, and thicknesses of ~10 nm. One of the key features of S-layer proteins is their intrinsic capability to form self-assembled mono- or double layers in solution, and at interfaces. Basic research on S-layer proteins laid foundation to make use of the unique self-assembly properties of native and, in particular, genetically functionalized S-layer protein lattices, in a broad range of applications in the life and non-life sciences. This contribution briefly summarizes the knowledge about structure, genetics, chemistry, morphogenesis, and function of S-layer proteins and pays particular attention to the self-assembly in solution, and at differently functionalized solid supports. PMID:23354479

  1. A novel molybdenum disulfide nanosheet self-assembled flower-like monolithic sorbent for solid-phase extraction with high efficiency and long service life. (United States)

    Ran, Fanpeng; Liu, Hongmei; Wang, Xiaoqi; Guo, Yong


    A novel material consisting of molybdenum disulfide (MoS2) nanosheet that self-assemble into flower-like microspheres which aggregate to form a monolithic matrix with a micro or nano-scaled mesopore structure was successfully synthesized and used as an efficient sorbent for solid-phase extraction (SPE) due to its large specific adsorption area and good stability. The extraction properties of the as-prepared sorbent were evaluated by high-performance liquid chromatography with variable wavelength detection (HPLC-VWD) by analyzing four flavonoids (apigenin, quercetin, luteolin, and kaempferol). Under optimal conditions, the LODs and LOQs were found to be in the ranges of 0.1-0.25 and 0.4-0.5μgL-1, respectively, and wide linear ranges were obtained with correlation coefficients (R) ranging from 0.9991 to 0.9996. Compared with commercial C18 and Alumina-N sorbents, the as-prepared sorbent showed high extraction efficiency at different concentrations of flavonoids. After 100 uses, the extraction ability of the self-assembled MoS2 nanosheet monolithic sorbent had no evident decline, denoting a long service life. Finally, the SPE-HPLC-VWD method using the as-prepared sorbent was applied to flavonoid analysis in beverage samples with satisfactory results. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Sub-15 nm nano-pattern generation by spacer width control for high density precisely positioned self-assembled device nanomanufacturing

    KAUST Repository

    Rojas, Jhonathan Prieto


    We present a conventional micro-fabrication based thin film vertical sidewall (spacer) width controlled nano-gap fabrication process to create arrays of nanopatterns for high density precisely positioned self-assembled nanoelectronics device integration. We have used conventional optical lithography to create base structures and then silicon nitride (Si 3N4) based spacer formation via reactive ion etching. Control of Si3N4 thickness provides accurate control of vertical sidewall (spacer) besides the base structures. Nano-gaps are fabricated between two adjacent spacers whereas the width of the gap depends on the gap between two adjacent base structures minus width of adjacent spacers. We demonstrate the process using a 32 nm node complementary metal oxide semiconductor (CMOS) platform to show its compatibility for very large scale heterogeneous integration of top-down and bottom-up fabrication as well as conventional and selfassembled nanodevices. This process opens up clear opportunity to overcome the decade long challenge of high density integration of self-assembled devices with precise position control. © 2012 IEEE.

  3. Signal amplification by a self-assembled biosensor system designed on the principle of dockerin-cohesin interactions in a cellulosome complex. (United States)

    Hyeon, Jeong Eun; Kang, Dae Hee; Han, Sung Ok


    To construct a self-assembled biosensor with signal amplification, a cellulosome system, comprising type I and type II dockerin-cohesin interactions with different specificities, from the anaerobic Clostridia bacterium was applied. The self-assembled biosensor was highly sensitive and achieved 128.1-fold increase in detection levels compared to the control.

  4. Mixed Self-Assembly of Polyethylene Glycol and Aptamer on Polydopamine Surface for Highly Sensitive and Low-Fouling Detection of Adenosine Triphosphate in Complex Media. (United States)

    Wang, Guixiang; Xu, Qingjun; Liu, Lei; Su, Xiaoli; Lin, Jiehua; Xu, Guiyun; Luo, Xiliang


    Detection of disease biomarkers within complex biological media is a substantial outstanding challenge because of severe biofouling and nonspecific adsorptions. Herein, a reliable strategy for sensitive and low-fouling detection of a biomarker, adenosine triphosphate (ATP) in biological samples was developed through the formation of a mixed self-assembled sensing interface, which was constructed by simultaneously self-assembling polyethylene glycol (PEG) and ATP aptamer onto the self-polymerized polydopamine-modified electrode surface. The developed aptasensor exhibited high selectivity and sensitivity toward the detection of ATP, and the linear range was 0.1-1000 pM, with a detection limit down to 0.1 pM. Moreover, owing to the presence of PEG within the sensing interface, the aptasensor was capable of sensing ATP in complex biological media such as human plasma with significantly reduced nonspecific adsorption effect. Assaying ATP in real biological samples including breast cancer cell lysates further proved the feasibility of this biosensor for practical application.

  5. Application of Self-Assembled Monolayers to the Electroless Metallization of High Aspect Ratio Vias for Microelectronics (United States)

    Bernasconi, R.; Molazemhosseini, A.; Cervati, M.; Armini, S.; Magagnin, L.


    All-wet electroless metallization of through-silicon vias (TSVs) with a width of 5 μm and a 1:10 aspect ratio was carried out. Immersion in a n-(2-aminoethyl) 3-aminopropyl-trimethoxysilane (AEAPTMS) self-assembled monolayer (SAM) was used to enhance the adhesion between the metal film and substrate. Contact angle variation and atomic force microscopy were used to verify the formation of a SAM layer. A PdCl2 solution was later used to activate the silanized substrates, exploiting the affinity of the -NH3 functional group of AEAPTMS to palladium. A nickel-phosphorus-boron electroless bath was employed to deposit the first barrier layer onto silicon. The NiPB growth rate was evaluated on flat silicon wafers, while the structure of the coating obtained was investigated via glow discharge optical emission spectroscopy. Cross-sectional scanning electron microscope observations were carried out on metallized TSVs to characterize the NiPB seed, the Cu seed layer deposited with a second electroless step, and the Cu superfilling obtained with a commercial solution. Complete filling of TSV was achieved.

  6. Canine parvovirus VP2 protein expressed in silkworm pupae self-assembles into virus-like particles with high immunogenicity. (United States)

    Feng, Hao; Hu, Gui-qiu; Wang, Hua-lei; Liang, Meng; Liang, Hongru; Guo, He; Zhao, Pingsen; Yang, Yu-jiao; Zheng, Xue-xing; Zhang, Zhi-fang; Zhao, Yong-kun; Gao, Yu-wei; Yang, Song-tao; Xia, Xian-zhu


    The VP2 structural protein of parvovirus can produce virus-like particles (VLPs) by a self-assembly process in vitro, making VLPs attractive vaccine candidates. In this study, the VP2 protein of canine parvovirus (CPV) was expressed using a baculovirus expression system and assembled into parvovirus-like particles in insect cells and pupae. Electron micrographs of VLPs showed that they were very similar in size and morphology when compared to the wild-type parvovirus. The immunogenicity of the VLPs was investigated in mice and dogs. Mice immunized intramuscularly with purified VLPs, in the absence of an adjuvant, elicited CD4(+) and CD8(+) T cell responses and were able to elicit a neutralizing antibody response against CPV, while the oral administration of raw homogenates containing VLPs to the dogs resulted in a systemic immune response and long-lasting immunity. These results demonstrate that the CPV-VLPs stimulate both cellular and humoral immune responses, and so CPV-VLPs may be a promising candidate vaccine for the prevention of CPV-associated disease.

  7. Canine parvovirus VP2 protein expressed in silkworm pupae self-assembles into virus-like particles with high immunogenicity.

    Directory of Open Access Journals (Sweden)

    Hao Feng

    Full Text Available The VP2 structural protein of parvovirus can produce virus-like particles (VLPs by a self-assembly process in vitro, making VLPs attractive vaccine candidates. In this study, the VP2 protein of canine parvovirus (CPV was expressed using a baculovirus expression system and assembled into parvovirus-like particles in insect cells and pupae. Electron micrographs of VLPs showed that they were very similar in size and morphology when compared to the wild-type parvovirus. The immunogenicity of the VLPs was investigated in mice and dogs. Mice immunized intramuscularly with purified VLPs, in the absence of an adjuvant, elicited CD4(+ and CD8(+ T cell responses and were able to elicit a neutralizing antibody response against CPV, while the oral administration of raw homogenates containing VLPs to the dogs resulted in a systemic immune response and long-lasting immunity. These results demonstrate that the CPV-VLPs stimulate both cellular and humoral immune responses, and so CPV-VLPs may be a promising candidate vaccine for the prevention of CPV-associated disease.

  8. Peptide Self-Assembled Biofilm with Unique Electron Transfer Flexibility for Highly Efficient Visible-Light-Driven Photocatalysis. (United States)

    Pan, Yun-Xiang; Cong, Huai-Ping; Men, Yu-Long; Xin, Sen; Sun, Zheng-Qing; Liu, Chang-Jun; Yu, Shu-Hong


    Inspired by natural photosynthesis, biomaterial-based catalysts are being confirmed to be excellent for visible-light-driven photocatalysis, but are far less well explored. Herein, an ultrathin and uniform biofilm fabricated from cold-plasma-assisted peptide self-assembly was employed to support Eosin Y (EY) and Pt nanoparticles to form an EY/Pt/Film catalyst for photocatalytic water splitting to H2 and photocatalytic CO2 reduction with water to CO, under irradiation of visible light. The H2 evolution rate on EY/Pt/Film is 62.1 μmol h(-1), which is about 5 times higher than that on Pt/EY and 1.5 times higher than that on the EY/Pt/TiO2 catalyst. EY/Pt/Film exhibits an enhanced CO evolution rate (19.4 μmol h(-1)), as compared with Pt/EY (2.8 μmol h(-1)) and EY/Pt/TiO2 (6.1 μmol h(-1)). The outstanding activity of EY/Pt/Film results from the unique flexibility of the biofilm for an efficient transfer of the photoinduced electrons. The present work is helpful for designing efficient biomaterial-based catalysts for visible-light-driven photocatalysis and for imitating natural photosynthesis.

  9. Directed self-assembly of lamellae-forming block copolymer with density multiplication for high aspect ratio structures (United States)

    Chen, Xuanxuan; Rincon Delgadillo, Paulina; Jiang, Zhang; Wang, Jin; Strzalka, Joseph; Nealey, Paul; IMEC Collaboration; Advanced Photon Source, Argonne National Labratory Collaboration


    Directed self-assembly (DSA) of block copolymers provides the means to control structure over micro- and macroscopic dimensions. We investigate the potential for DSA to control nanostructure through sub-micron film thickness and realize near perfect structure in the plane of the film over macroscopic areas. Lamellae-forming poly (styrene) - block - poly (methyl methacrylate) (L0 = 28.5nm) was directed to assemble on chemical patterns with a pitch (LS) of 84nm. The three-dimensional structure of the films was characterized by SEM and GISAXS as a function of the geometry and chemistry of the chemical pattern, film thickness, and thermal annealing time. At optimal conditions, perpendicular through film structures was achieved with aspect ratio of 12 over 5 x 8 mm2 areas in 3 hours at 250 C. At non-optimal boundary conditions, time for assembly increases, and the maximum film thickness decreases, suggesting an assembly mechanism involving nucleation of structure at the pattern and free surface and differing governance of the pattern-directed structure in both the thermodynamics and kinetics of the system. GISAXS experiments reveals that a significant number of defect structures persist within the films even after the surface structures are perfectly aligned.

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

    Shetye, Sheetal B.

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

  11. Mesoporous Bragg reflectors: block-copolymer self-assembly leads to building blocks with well defined continuous pores and high control over optical properties

    KAUST Repository

    Guldin, S.


    Mesoporous distributed Bragg re ectors (MDBRs) exhibit porosity on the sub-optical length scale. This makes them ideally suited as sensing platforms in biology and chemistry as well as for light management in optoelectronic devices. Here we present a new fast forward route for the fabrication of MDBRs which relies on the self-assembling properties of the block copolymer poly(isoprene-block -ethylene oxide) (PI-b -PEO) in combination with sol-gel chemistry. The interplay between structure directing organic host and co-assembled inorganic guest allows the ne tuning of refractive index in the outcome material. The refractive index dierence between the high and low porosity layer can be as high as 0.4, with the optical interfaces being well dened. Following a 30 min annealing protocol after each layer deposition enables the fast and reliable stacking of MDBRs which exhibit a continuous TiO2 network with large accessible pores and high optical quality.

  12. Self-Assembled Hierarchical Formation of Conjugated 3D Cobalt Oxide Nanobead-CNT-Graphene Nanostructure Using Microwaves for High-Performance Supercapacitor Electrode. (United States)

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


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

  13. A facile self-assembled film assisted preparation of CuGaS{sub 2} ultrathin films and their high sensitivity to L-noradrenaline

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Qin; Kang, Shi-Zhao, E-mail:; Li, Xiangqing; Qin, Lixia; Mu, Jin, E-mail:


    Graphical abstract: A dense CuGaS{sub 2} ultrathin film was prepared in an improved layer-by-layer self-assembled process following heat treatment. And, the as-prepared CuGaS{sub 2} ultrathin film possesses high sensitivity to L-noradrenaline. - Highlights: • Tetragonal CuGaS{sub 2} film was prepared in a simple process. • CuGaS{sub 2} film exhibits a narrow emission. • High sensitivity to LNE with a detection limit of 2.83 ng cm{sup −2}. - Abstract: A dense CuGaS{sub 2} ultrathin film was prepared in an improved layer-by-layer self-assembled process followed by heat treatment and characterized with X-ray diffraction, scanning electron microscopy, UV–vis spectroscopy, and fluorescence spectroscopy. Meanwhile, the application of the as-prepared CuGaS{sub 2} ultrathin film in the trace detection of L-noradrenaline was explored as a photoluminescent probe. The results show that the tetragonal phase CuGaS{sub 2} film fabricated on the glass substrate is smooth and dense. And this CuGaS{sub 2} ultrathin film can exhibit a strong emission at 829 nm with full width at half maximum of approximate 12 nm. Furthermore, the as-prepared CuGaS{sub 2} ultrathin film possesses high sensitivity to L-noradrenaline with a detectable concentration of 2.83 ng cm{sup −2} when it is used as a photoluminescent probe, implying that it is a promising candidate in the field of biological and chemical sensing in future.

  14. Self-assembly of Fe{sub 2}O{sub 3}/reduced graphene oxide hydrogel for high Li-storage

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Weiwei, E-mail:; Ding, Chunyan; Jia, Xingtao; Tian, Ye; Guan, Qiaotian; Wen, Guangwu, E-mail:


    Highlights: • A new composite hydrogel consisted of Fe{sub 2}O{sub 3} nanotubes and graphene has been prepared via hydrothermal method. • In this composite hydrogel, RGO sheets self-assemble into an interconnected macroporous framework and Fe{sub 2}O{sub 3} nanotubes encapsulate into RGO layers. • The resulting composite hydrogel exhibits high specific capacity (850 mAh/g at 200 mA/g), good rate capability and cycling stability. - Abstract: A novel three-dimensional (3D) Fe{sub 2}O{sub 3}/reduced graphene oxide (RGO) hydrogel (FGH) is prepared by a facile hydrothermal strategy. In this composite hydrogel, RGO sheets self-assemble into an interconnected macroporous framework and Fe{sub 2}O{sub 3} nanotubes encapsulate into RGO layers. The FGH delivers high rate capacities of 850, 780, 550, and 400 mAh/g at current densities of 200, 400, 600, and 800 mA/g, respectively. The specific capacity can still maintain at ∼600 mAh/g after 70 cycles, which greatly outperforms that of pure Fe{sub 2}O{sub 3} nanotubes (∼60 mAh/g after 70 cycles). The improved electrochemical performance is ascribed to the unique macroscopic structure which is beneficial for enlarging the active surface area, shortening the electron/ion pathway, accommodating the volume change of Fe{sub 2}O{sub 3} nanotubes, and preventing the aggregation of both Fe{sub 2}O{sub 3} nanoparticles and RGO sheets.

  15. A facile and general preparation of high-performance noble-metal-based free-standing nanomembranes by a reagentless interfacial self-assembly strategy (United States)

    Wu, Haoxi; He, Haili; Zhai, Yujuan; Li, Haijuan; Lai, Jianping; Jin, Yongdong


    As a simple and flexible 2D platform, the water-air interface is envisioned as an environmentally-friendly approach to prepare ultrathin free-standing nanomembranes (FNMs) of monolayered nanoparticles of interest via interfacial self-assembly. However, attempts so far have been rather rare due to the lack of efficient methods. In this article, we report on a facile and general strategy for fabrication of a family of noble metal-based FNMs by a simple and reagentless interfacial self-assembly tactics to prepare functional (plasmonic or catalytic) FNMs, such as Au, Ag, Pd, Pt-FNMs and their bimetallic hybrids, Ag/Au-FNMs and Pd/Pt-FNMs. The organic solvent-free process, varying somewhat from metal to metal only in precursors, reducing agents and dosage of reagents used, is found to be a general phenomenon and ligand-independent (irrespective of the monolayer quality of the resulting FNMs), allowing the growth of high-quality noble metal-based FNMs with well-defined nanoparticulate and monolayer morphology as large as several square centimeters. Heat treatment (boiling) is performed to accelerate the formation of FNMs within 15 min. More significantly, the as-prepared plasmonic Au-FNMs acting as a SERS substrate show a superior activity; whereas the resulting catalytic Pd-FNMs, except for their excellent ethanol electrooxidation performance, exhibit higher electrocatalytic activity for formic acid oxidation than commercial catalysts.As a simple and flexible 2D platform, the water-air interface is envisioned as an environmentally-friendly approach to prepare ultrathin free-standing nanomembranes (FNMs) of monolayered nanoparticles of interest via interfacial self-assembly. However, attempts so far have been rather rare due to the lack of efficient methods. In this article, we report on a facile and general strategy for fabrication of a family of noble metal-based FNMs by a simple and reagentless interfacial self-assembly tactics to prepare functional (plasmonic or

  16. Deep level transient spectroscopy of hole traps related to CdTe self-assembled quantum dots embedded in ZnTe matrix. (United States)

    Zielony, E; Placzek-Popko, E; Dyba, P; Gumienny, Z; Szatkowski, J; Dobaczewski, L; Karczewski, G


    The capacitance-voltage (C-V) and deep level transient spectroscopy (DLTS) measurements have been made on a Schottky Ti-ZnTe (p-type) diode containing CdTe self-assembled quantum dots (QD) and control diode without dots. The C-V curve of the QD diode exhibits a characteristic step associated with the QD states whereas the reference diode shows ordinary bulk behavior. A quasistatic model based on the self-consistent solution of the Poisson's equation is used to simulate the capacitance. By comparison of the calculated C-V curve with the experimental one, hole binding energy at the QD states is found to be equal about 0.12 eV. The results of DLTS measurements for the sample containing QDs reveal the presence of a low-temperature peak which is not observed for the control diode. Analysis of its behavior at different bias conditions leads to the conclusion that this peak may be related to the hole emission from the QD states to the ZnTe valence band. Its thermal activation energy obtained from related Arrhenius plot equals to 0.12 eV in accordance with the energy obtained from the Poisson's equation. Thus based on the C-V and DLTS studies it may be concluded that the thermal activation energy of holes from the QD states to the ZnTe valence band in the CdTe/ZnTe QD system is equal about 0.12 eV.

  17. Smart Self-Assembled Hybrid Hydrogel Biomaterials


    Kopeček, Jindřich; Yang, Jiyuan


    Hybrid biomaterials are systems created from components of at least two distinct classes of molecules, for example, synthetic macromolecules and proteins or peptide domains. The synergistic combination of two types of structures may produce new materials that possess unprecedented levels of structural organization and novel properties. This Review focuses on biorecognition-driven self-assembly of hybrid macromolecules into functional hydrogel biomaterials. First, basic rules that govern the s...

  18. Self-assembly of cyclodextrins

    DEFF Research Database (Denmark)

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


    that increases upon formation of inclusion complexes with lipophilic drugs. However, the stability of such aggregates is not sufficient for parenteral administration. In this review CD polymers and CD containing nanoparticles are categorized, with focus on self-assembled CD nanoparticles. It is described how......The design of functional cyclodextrin (CD) nanoparticles is a developing area in the field of nanomedicine. CDs can not only help in the formation of drug carriers but also increase the local concentration of drugs at the site of action. CD monomers form aggregates by self-assembly, a tendency...

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

    Liang, Hongjun

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

  20. Programming protein self assembly with coiled coils

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, Hendrik; Bornschloegl, Thomas; Heym, Roland; Koenig, Frauke; Rief, Matthias [Physik Department E22, Technische Universitaet Muenchen, James-Franck-Strasse 1, 85748 Garching (Germany)


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

  1. Porous NiCo{sub 2}S{sub 4}-halloysite hybrid self-assembled from nanosheets for high-performance asymmetric supercapacitor applications

    Energy Technology Data Exchange (ETDEWEB)

    Chai, Hui, E-mail:; Dong, Hong; Wang, Yucheng; Xu, Jiayu; Jia, Dianzeng


    Highlights: • The NiCo{sub 2}S{sub 4}-HL nanomaterial is achieved via two-step hydrothermal approach. • The unique structures are assembled self-assembly by nanosheets. • The obtained electrode exhibits high capacitance and excellent retention. • An asymmetric supercapacitor also displays high energy density and outstanding cycling stability. • The high-performance of the device is possibly due to the introduction of HL and formation of composed nanosheets. - Abstract: The porous nanostructures have drawn considerable attention because of their abundant pore volume and unique properties that provide outstanding performance in catalysis and energy storage applications. This study proposes the growth mechanism of porous NiCo{sub 2}S{sub 4} composited with halloysite (HL) via a self-assembly method using halloysite as a template and component. Electrochemical tests showed that the NiCo{sub 2}S{sub 4}-HL exhibited an ultrahigh specific capacitance (Csp) (589C g{sup −1} at 1A g{sup −1}) and good cycle stability (Csp retention of 86% after 1000 cycles). The desirable capacitive performance of the NiCo{sub 2}S{sub 4}-HL can be attributed to the large specific surface area and short diffusion path for electrons and ions in the hierarchical porous structure. The superior electrochemical performances with the energy density of 35.48 W h kg{sup −1} at a power density of 199.9 W kg{sup −1} were achieved in an assembled aqueous asymmetric supercapacitor (ASC) device using NiCo{sub 2}S{sub 4}-HL as a positive electrode and N-doped graphene (NG) as a negative electrode. Moreover, the NiCo{sub 2}S{sub 4}-HL//NG asymmetric supercapacitor achieved outstanding cycle stability (also retained 83.2% after 1700 cycles). The high-performance of the ASC device will undoubtedly make the porous NiCo{sub 2}S{sub 4}-HL as potential electrode materials attractive in energy storage systems.

  2. Chiral recognition and selection during the self-assembly process of protein-mimic macroanions

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Panchao; Zhang, Zhi-Ming; Lv, Hongjin; Li, Tao; Haso, Fadi; Hu, Lang; Zhang, Baofang; Basca, John; Wei, Yongge; Gao, Yanqing; Hou, Yu; Li, Yang-Guang; Hill, Craig L.; Wang, En-Bo; Liu, Tianbo


    The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe28(μ3-O)8(Tart)16(HCOO)24]20- (Tart=D- or L-tartaric acid tetra-anion). The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis of the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection.

  3. Coded nanoscale self-assembly

    Indian Academy of Sciences (India)

    the number of starting particles. Figure 6. Coded self-assembly results in specific shapes. When the con- stituent particles are coded to only combine in a certain defined rules, it al- ways manages to generate the same shape. The simplest case of linear coding with multiseed option is presented here. in place the resultant ...

  4. Self-assembly of cobalt-centered metal organic framework and multiwalled carbon nanotubes hybrids as a highly active and corrosion-resistant bifunctional oxygen catalyst (United States)

    Fang, Yiyun; Li, Xinzhe; Li, Feng; Lin, Xiaoqing; Tian, Min; Long, Xuefeng; An, Xingcai; Fu, Yan; Jin, Jun; Ma, Jiantai


    Metal organic frameworks (MOF) derived carbonaceous materials have emerged as promising bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts for electrochemical energy conversion and storage. But previous attempts to overcome the poor electrical conductivity of MOFs hybrids involve a harsh high-template pyrolytic process to in situ form carbon, which suffer from extremely complex operation and inevitable carbon corrosion at high positive potentials when OER is operated. Herein, a self-assembly approach is presented to synthesize a non-precious metal-based, high active and strong durable Co-MOF@CNTs bifunctional catalyst for OER and ORR. CNTs not only improve the transportation of the electrons but also can sustain the harsh oxidative environment of OER without carbon corrosion. Meanwhile, the unique 3D hierarchical structure offers a large surface area and stable anchoring sites for active centers and CNTs, which enables the superior durability of hybrid. Moreover, a synergistic catalysis of Co(II), organic ligands and CNTs will enhance the bifunctional electrocatalytic performance. Impressively, the hybrid exhibits comparable OER and ORR catalytic activity to RuO2 and 20 wt% Pt/C catalysts and superior stability. This facile and versatile strategy to fabricating MOF-based hybrids may be extended to other electrode materials for fuel cell and water splitting applications.

  5. Building unique surface structure on aramid fibers through a green layer-by-layer self-assembly technique to develop new high performance fibers with greatly improved surface activity, thermal resistance, mechanical properties and UV resistance

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Lifang; Yuan, Li; Guan, Qingbao; Gu, Aijuan, E-mail:; Liang, Guozheng, E-mail:


    Highlights: • A green technology is setup to build unique surface structure on aramid fiber (AF). • The method is layer-by-layer self-assembling SiO{sub 2} and layered double hydroxide. • The surface of AF is adjustable by controlling the self-assembly cycle number. • New AF has excellent surface activity, anti-UV, thermal and mechanical properties. • The origin behind attractive performances of new AFs was intensively studied. - Abstract: Combining green preparation and high performance is becoming the direction of sustainable development of materials. How to simultaneously overcome the two bottlenecks (poor surface activity and UV resistance) of aramid fibers (AFs) while improving thermal and mechanical properties through a green process is still an interesting issue with big challenge. Herein, new AFs (BL-AFs) were prepared by alternately self-assembling SiO{sub 2} and MgAlFe layered double hydroxide (LDH) on surfaces of AFs, successively, through a green layer-by-layer (LBL) self-assembly technique without using high temperature and organic solvent. The structures and properties of BL-AFs were systematically studied, which are controllable by adjusting the number of self-assembly cycle. The new fibers with three or more self-assembly cycles have remarkably improved surface activity, thermal resistance, mechanical properties and UV resistance compared with AFs. Typically, with three self-assembly cycles, the initial degradation temperature and char yield of the new fiber (3BL-AF) are as high as 552.9 °C and 81.2%, about 92 °C and 25.2% higher than those of AF, respectively; after 168 h-UV irradiation, the retention of tensile performances of 3BL-AF fiber is as high as 91–95%, about 29–14% higher than that of AF, showing the best overall performances among all modified AFs prepared using a green technique reported so far. The origin behind the attractive performances of BL-AFs is revealed through correlating with structures of original and

  6. Building unique surface structure on aramid fibers through a green layer-by-layer self-assembly technique to develop new high performance fibers with greatly improved surface activity, thermal resistance, mechanical properties and UV resistance (United States)

    Zhou, Lifang; Yuan, Li; Guan, Qingbao; Gu, Aijuan; Liang, Guozheng


    Combining green preparation and high performance is becoming the direction of sustainable development of materials. How to simultaneously overcome the two bottlenecks (poor surface activity and UV resistance) of aramid fibers (AFs) while improving thermal and mechanical properties through a green process is still an interesting issue with big challenge. Herein, new AFs (BL-AFs) were prepared by alternately self-assembling SiO2 and MgAlFe layered double hydroxide (LDH) on surfaces of AFs, successively, through a green layer-by-layer (LBL) self-assembly technique without using high temperature and organic solvent. The structures and properties of BL-AFs were systematically studied, which are controllable by adjusting the number of self-assembly cycle. The new fibers with three or more self-assembly cycles have remarkably improved surface activity, thermal resistance, mechanical properties and UV resistance compared with AFs. Typically, with three self-assembly cycles, the initial degradation temperature and char yield of the new fiber (3BL-AF) are as high as 552.9 °C and 81.2%, about 92 °C and 25.2% higher than those of AF, respectively; after 168 h-UV irradiation, the retention of tensile performances of 3BL-AF fiber is as high as 91-95%, about 29-14% higher than that of AF, showing the best overall performances among all modified AFs prepared using a green technique reported so far. The origin behind the attractive performances of BL-AFs is revealed through correlating with structures of original and modified fibers. The excellent comprehensive properties of BL-AFs demonstrate that the green method provided in this study is facile and effective to completely solve the bottlenecks of aramid fibers, and developing higher performance organic fibers.

  7. Triblock-Terpolymer-Directed Self-Assembly of Mesoporous TiO2: High-Performance Photoanodes for Solid-State Dye-Sensitized Solar Cells

    KAUST Repository

    Docampo, Pablo


    A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO 2 films is presented, based on the triblock terpolymer poly(isoprene - b - styrene - b - ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solidstate dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Novel collaboration and situational awareness environment for leaders and their support staff via self assembling software.

    Energy Technology Data Exchange (ETDEWEB)

    Bouchard, Ann Marie; Osbourn, Gordon Cecil (Org. 1001 : Complex Systems Science Department); Bartholomew, John Warren


    This is the final report on the Sandia Fellow LDRD, project 117865, 08-0281. This presents an investigation of self-assembling software intended to create shared workspace environment to allow online collaboration and situational awareness for use by high level managers and their teams.

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

    Shieh, Aileen

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

  10. A facile self-assembled film assisted preparation of CuGaS2 ultrathin films and their high sensitivity to L-noradrenaline (United States)

    Zhou, Qin; Kang, Shi-Zhao; Li, Xiangqing; Qin, Lixia; Mu, Jin


    A dense CuGaS2 ultrathin film was prepared in an improved layer-by-layer self-assembled process followed by heat treatment and characterized with X-ray diffraction, scanning electron microscopy, UV-vis spectroscopy, and fluorescence spectroscopy. Meanwhile, the application of the as-prepared CuGaS2 ultrathin film in the trace detection of L-noradrenaline was explored as a photoluminescent probe. The results show that the tetragonal phase CuGaS2 film fabricated on the glass substrate is smooth and dense. And this CuGaS2 ultrathin film can exhibit a strong emission at 829 nm with full width at half maximum of approximate 12 nm. Furthermore, the as-prepared CuGaS2 ultrathin film possesses high sensitivity to L-noradrenaline with a detectable concentration of 2.83 ng cm-2 when it is used as a photoluminescent probe, implying that it is a promising candidate in the field of biological and chemical sensing in future.

  11. Self-Assembly of Chip-Size Components with Cavity Structures: High-Precision Alignment and Direct Bonding without Thermal Compression for Hetero Integration

    Directory of Open Access Journals (Sweden)

    Mitsumasa Koyanagi


    Full Text Available New surface mounting and packaging technologies, using self-assembly with chips having cavity structures, were investigated for three-dimensional (3D and hetero integration of complementary metal-oxide semiconductors (CMOS and microelectromechanical systems (MEMS. By the surface tension of small droplets of 0.5 wt% hydrogen fluoride (HF aqueous solution, the cavity chips, with a side length of 3 mm, were precisely aligned to hydrophilic bonding regions on the surface of plateaus formed on Si substrates. The plateaus have micro-channels to readily evaporate and fully remove the liquid from the cavities. The average alignment accuracy of the chips with a 1 mm square cavity was found to be 0.4 mm. The alignment accuracy depends, not only on the area of the bonding regions on the substrates and the length of chip periphery without the widths of channels in the plateaus, but also the area wetted by the liquid on the bonding regions. The precisely aligned chips were then directly bonded to the substrates at room temperature without thermal compression, resulting in a high shear bonding strength of more than 10 MPa.

  12. Synthesis and Self-Assembly of Rod2Coil Miktoarm Star Copolymers of Poly(3-dodecxylthiophene) and Poly(methyl methacrylate) with high rod fractions (United States)

    Park, Jicheol; Moon, Hong Chul; Choi, Chung-Royng; Kim, Jin Kon


    Poly(3-dodecylthiophene)-b-poly(methyl methacrylate) diblock copolymer (P3DDT- b-PMMA) can self-assembled into various microdomains such as spheres, cylinders, and lamellae depending on weight fraction of P3DDT. However, only filbril morphology was formed when weight fraction of P3DDT (wP 3 DDT) was major (wP 3 DDT ~ 0.76). Here, we introduce a new approach to obtain microdomain structures even at high wP 3 DDT by using well-defined A2B miktoarm star copolymer composed of P3DDT and PMMA ((P3DDT)2PMMA. We found via small angle X-ray scattering and transmission electron microscopy that (P3DDT)2PMMA showed PMMA cylinder packed hexagonally in the matrix of P3DDT and body-centered-cubic spheres of PMMA for wP 3 DDT of 0.66 and 0.75, respectively. This because of much reduction of the rod-rod interaction in (P3DDT)2PMMA compared with P3DDT- b-PMMA diblock copolymers.

  13. Self-assembled NiCo2O4-anchored reduced graphene oxide nanoplates as high performance anode materials for lithium ion batteries (United States)

    Yang, Juan; Tian, Hangyu; Tang, Jingjing; Bai, Tao; Xi, Lihua; Chen, Sanmei; Zhou, Xiangyang


    The NiCo2O4-anchored reduced graphene oxide (NiCo2O4@rGO) nanoplates have been synthesized by a facile self-assembly process. The morphology, crystalline structure and electrochemical performance of the materials have been investigated comprehensively. The results of SEM manifest that NiCo2O4 particles have been densely anchored on the surface of rGO with a mesoporous structure, and the morphology is tunable via altering concentration of urea during the preparation process. Due to the high ratio of NiCo2O4 in the composite and the plate structure, the electrochemical performance of as-prepared material has been greatly improved. When evaluated as anode materials in lithium ion batteries (LIBs), the as-prepared NiCo2O4@rGO nanocomposite delivers a reversible capacity of 994 mAh g-1 at a current density of 200 mA g-1 with outstanding rate capability, revealing that it could be a promising anode for LIBs.

  14. Synthesis of frost-like CuO combined graphene-TiO2 by self-assembly method and its high photocatalytic performance (United States)

    Nguyen, Dinh Cung Tien; Cho, Kwang-Youn; Oh, Won-Chun


    A novel material, frost-like CuO combined-graphene-TiO2 composite, was successfully synthesized using a self-assembly method. During the reaction, the loading of CuO and TiO2 nanoparticles on graphene sheets was achieved. The obtained CuO-graphene-TiO2 composite photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), and X-ray photoelectron spectroscopy (XPS). The frost-like CuO nanoparticles combined with the small TiO2 rods were successfully loaded on the transparent graphene sheets. The photocatalytic degradation of rhodamine B (RhB), methylene blue trihydrate (MB), and reactive black B (RBB) in an aqueous solution under visible light irradiation was observed by UV spectrophotometry after measurement of the decrease of their concentrations. Through the photocatalytic test and TOC results, the CuO-graphene-TiO2 is expected to become a new potential material for photodegradation activity with excellent photodegradation. The scavenging experiments confirmed that rad OH and h+ play a major role in the photocatalytic reaction than O2rad - or both hydroxyl and holes are the active species responsible for the RBB degradation under visible light irradiation. After five repeated cycles to investigate the stability of photocatalytic performance, the CuO-graphene-TiO2 had high stability under visible light irradiation.

  15. Self-assembly synthesis of 3D graphene-encapsulated hierarchical Fe3O4 nano-flower architecture with high lithium storage capacity and excellent rate capability (United States)

    Ma, Yating; Huang, Jian; Lin, Liang; Xie, Qingshui; Yan, Mengyu; Qu, Baihua; Wang, Laisen; Mai, Liqiang; Peng, Dong-Liang


    Graphene-encapsulated hierarchical metal oxides architectures can efficiently combine the merits of graphene and hierarchical metal oxides, which are deemed as the potential anode material candidates for the next-generation lithium-ion batteries due to the synergistic effect between them. Herein, a cationic surfactant induced self-assembly method is developed to construct 3D Fe3O4@reduction graphene oxide (H-Fe3O4@RGO) hybrid architecture in which hierarchical Fe3O4 nano-flowers (H-Fe3O4) are intimately encapsulated by 3D graphene network. Each H-Fe3O4 particle is constituted of rod-shaped skeletons surrounded by petal-like nano-flakes that are made up of enormous nanoparticles. When tested as the anode material in lithium-ion batteries, a high reversible capacity of 2270 mA h g-1 after 460 cycles is achieved under a current density of 0.5 A g-1. More impressively, even tested at a large current density of 10 A g-1, a decent reversible capacity of 490 mA h g-1 can be retained, which is still higher than the theoretical capacity of traditional graphite anode, demonstrating the remarkable lithium storage properties. The reasons for the excellent electrochemical performance of H-Fe3O4@RGO electrode have been discussed in detail.

  16. Self-assembly of 2D sandwich-structured MnFe{sub 2}O{sub 4}/graphene composites for high-performance lithium storage

    Energy Technology Data Exchange (ETDEWEB)

    Li, Songmei, E-mail:; Wang, Bo; Li, Bin; Liu, Jianhua; Yu, Mei; Wu, Xiaoyu


    Highlights: • MFO/GN composites were synthesized by a facile in situ solvothermal approach. • The MFO microspheres are sandwiched between the graphene layers. • Each MFO microsphere is an interstitial cluster of nanoparticles. • The MFO/GN electrode exhibits an enhanced cyclability for Li-ion batteries anodes. - Abstract: In this study, two-dimensional (2D) sandwich-structured MnFe{sub 2}O{sub 4}/graphene (MFO/GN) composites are synthesized by a facile in situ solvothermal approach, using cetyltrimethylammonium bromide (CTAB) as cationic surfactant. As a consequence, the nanocomposites of MFO/GN self-assembled into a 2D sandwich structure, in which the interstitial cluster structure of microsphere-type MnFe{sub 2}O{sub 4} is sandwiched between the graphene layers. This special structure of the MFO/GN composites used as anodes for lithium-ion batteries will be favorable for the maximum accessible surface of electroactive materials, fast diffusion of lithium ions and migration of electron, and elastomeric space to accommodate volume changes during the discharge–charge processes. The as-synthesized MFO/GN composites deliver a high specific reversible capacity of 987.95 mA h g{sup −1} at a current density of 200 mA g{sup −1}, a good capacity retention of 69.27% after 80 cycles and excellent rate performance for lithium storage.

  17. A Theoretical and Experimental Study of DNA Self-assembly (United States)

    Chandran, Harish

    The control of matter and phenomena at the nanoscale is fast becoming one of the most important challenges of the 21st century with wide-ranging applications from energy and health care to computing and material science. Conventional top-down approaches to nanotechnology, having served us well for long, are reaching their inherent limitations. Meanwhile, bottom-up methods such as self-assembly are emerging as viable alternatives for nanoscale fabrication and manipulation. A particularly successful bottom up technique is DNA self-assembly where a set of carefully designed DNA strands form a nanoscale object as a consequence of specific, local interactions among the different components, without external direction. The final product of the self-assembly process might be a static nanostructure or a dynamic nanodevice that performs a specific function. Over the past two decades, DNA self-assembly has produced stunning nanoscale objects such as 2D and 3D lattices, polyhedra and addressable arbitrary shaped substrates, and a myriad of nanoscale devices such as molecular tweezers, computational circuits, biosensors and molecular assembly lines. In this dissertation we study multiple problems in the theory, simulations and experiments of DNA self-assembly. We extend the Turing-universal mathematical framework of self-assembly known as the Tile Assembly Model by incorporating randomization during the assembly process. This allows us to reduce the tile complexity of linear assemblies. We develop multiple techniques to build linear assemblies of expected length N using far fewer tile types than previously possible. We abstract the fundamental properties of DNA and develop a biochemical system, which we call meta-DNA, based entirely on strands of DNA as the only component molecule. We further develop various enzyme-free protocols to manipulate meta-DNA systems and provide strand level details along with abstract notations for these mechanisms. We simulate DNA circuits by

  18. Self-Assembly of Large Amyloid Fibers (United States)

    Ridgley, Devin M.

    Functional amyloids found throughout nature have demonstrated that amyloid fibers are potential industrial biomaterials. This work introduces a new "template plus adder" cooperative mechanism for the spontaneous self-assembly of micrometer sized amyloid fibers. A short hydrophobic template peptide induces a conformation change within a highly alpha-helical adder protein to form beta-sheets that continue to assemble into micrometer sized amyloid fibers. This study utilizes a variety of proteins that have template or adder characteristics which suggests that this mechanism may be employed throughout nature. Depending on the amino acid composition of the proteins used the mixtures form amyloid fibers of a cylindrical ( 10 mum diameter, 2 GPa Young's modulus) or tape (5- 10 mum height, 10-20 mum width and 100-200 MPa Young's modulus) morphology. Processing conditions are altered to manipulate the morphology and structural characteristics of the fibers. Spectroscopy is utilized to identify certain amino acid groups that contribute to the self-assembly process. Aliphatic amino acids (A, I, V and L) are responsible for initiating conformation change of the adder proteins to assemble into amyloid tapes. Additional polyglutamine segments (Q-blocks) within the protein mixtures will form Q hydrogen bonds to reinforce the amyloid structure and form a cylindrical fiber of higher modulus. Atomic force microscopy is utilized to delineate the self-assembly of amyloid tapes and cylindrical fibers from protofibrils (15-30 nm width) to fibers (10-20 mum width) spanning three orders of magnitude. The aliphatic amino acid content of the adder proteins' alpha-helices is a good predictor of high density beta-sheet formation within the protein mixture. Thus, it is possible to predict the propensity of a protein to undergo conformation change into amyloid structures. Finally, Escherichia coli is genetically engineered to express a template protein which self-assembles into large amyloid

  19. Enzymatic Self-Assembly of Nanostructures for Theranostics


    Yue Chen, Gaolin Liang


    Self-assembly of small molecules or macromolecules through non-covalent or covalent bonds to build up supramolecular nanostructures is a prevalent and important process in nature. While most chemists use small molecules to assemble nanostructures with physical or chemical perturbations, nature adopts enzymes to catalyze the reaction to assemble biological, functional nanostructures with high efficiency and specificity. Although enzymatic self-assembly of nanostructures has been remained chall...

  20. Self-assembled tunable networks of sticky colloidal particles

    Energy Technology Data Exchange (ETDEWEB)

    Demortiere, Arnaud; Snezhko, Oleksiy Alexey; Sapozhnikov, Maksim; Becker, Nicholas G.; Proslier, Thomas; Aronson, Igor S.


    Self-assembled tunable networks of microscopic polymer fibers ranging from wavy colloidal "fur" to highly interconnected networks are created from polymer systems and an applied electric field. The networks emerge via dynamic self-assembly in an alternating (ac) electric field from a non-aqueous suspension of "sticky" polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles.

  1. Enzymatic self-assembly of nanostructures for theranostics. (United States)

    Chen, Yue; Liang, Gaolin


    Self-assembly of small molecules or macromolecules through non-covalent or covalent bonds to build up supramolecular nanostructures is a prevalent and important process in nature. While most chemists use small molecules to assemble nanostructures with physical or chemical perturbations, nature adopts enzymes to catalyze the reaction to assemble biological, functional nanostructures with high efficiency and specificity. Although enzymatic self-assembly of nanostructures has been remained challenging for chemists, there are still a few examples of using important enzymes to initiate the self-assembly of nanostructures for diagnosis or therapy of certain diseases because down-regulation or overexpression of certain enzymes always associates with abnormalities of tissues/organs or diseases in living body. Herein, we introduce the concept of enzymatic self-assembly and illustrate the design and application of enzyme-catalyzed or -regulated formation of nanostructures for theranostics.

  2. Design of Highly Sensitive C2H5OH Sensors Using Self-Assembled ZnO Nanostructures

    Directory of Open Access Journals (Sweden)

    Jong-Heun Lee


    Full Text Available Various ZnO nanostructures such as porous nanorods and two hierarchical structures consisting of porous nanosheets or crystalline nanorods were prepared by the reaction of mixtures of oleic-acid-dissolved ethanol solutions and aqueous dissolved Zn-precursor solutions in the presence of NaOH. All three ZnO nanostructures showed sensitive and selective detection of C2H5OH. In particular, ultra-high responses (Ra/Rg = ~1,200, Ra: resistance in air, Rg: resistance in gas to 100 ppm C2H5OH was attained using porous nanorods and hierarchical structures assembled from porous nanosheets, which is one of the highest values reported in the literature. The gas response and linearity of gas sensors were discussed in relation to the size, surface area, and porosity of the nanostructures.

  3. Rapid high-throughput analysis of ochratoxin A by the self-assembly of DNAzyme-aptamer conjugates in wine. (United States)

    Yang, Cheng; Lates, Vasilica; Prieto-Simón, Beatriz; Marty, Jean-Louis; Yang, Xiurong


    We report a new label-free colorimetric aptasensor based on DNAzyme-aptamer conjugate for rapid and high-throughput detection of Ochratoxin A (OTA, a possible human carcinogen, group 2B) in wine. Two oligonucleotides were designed for this detection. One is N1 for biorecognition, which includes two adjacent sequences: the OTA-specific aptamer sequence and the horseradish peroxidase (HRP)-mimicking DNAzyme sequence. The other is a blocking DNA (B2), which is partially complementary to a part of the OTA aptamer and partially complementary to a part of the DNAzyme. The existence of OTA reduces the hybridization between N1 and B2. Thus, the activity of the non-hybridized DNAzyme is linearly correlated with the concentration of OTA up to 30 nM with a limit of detection of 4 nM (3σ). Meanwhile, a double liquid-liquid extraction (LLE) method is accordingly developed to purify OTA from wine. Compared with the existing HPLC-FD or immunoassay methods, the proposed strategy presents the most appropriate balance between accuracy and facility, resulting in a considerable improvement of real-time quality control, and thereby, preventing chronic poisoning caused by OTA contained red wine. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Transferrable Plasmonic Au Thin Film Containing Sub-20 nm Nanohole Array Constructed via High-Resolution Polymer Self-Assembly and Nanotransfer Printing. (United States)

    Yim, Soonmin; Jeon, Suwan; Kim, Jong Min; Baek, Kwang Min; Lee, Gun Ho; Kim, Hyowook; Shin, Jonghwa; Jung, Yeon Sik


    The fabrication and characterization of nanoscale hole arrays (NHA) have been extensively performed for a variety of unique characteristics including extraordinary optical transmission phenomenon observed for plasmonic NHAs. Although the size miniaturization and hole densification are strongly required for enhancement of high-frequency optical responses, from a practical point-of-view, it is still not straightforward to manufacture NHA using conventional lithography techniques. Herein, a facile, cost-effective, and transferrable fabrication route for high-resolution and high-density NHA with sub-50 nm periodicity is demonstrated. Solvent-assisted nanotransfer printing with ultrahigh-resolution combined with block copolymer self-assembly is used to fabricate well-defined Si nanomesh master template with 4-fold symmetry. An Au NHA film on quartz substrate is then obtained by thermal-evaporation on the Si master and subsequent transfer of the sample, resulting in NHA structure having a hole with a diameter of 18 nm and a density over 400 holes/μm2. A resonance peak at the wavelength of 650 nm, which is not present in the transmittance spectrum of a flat Au film, is observed for the Au NHA film. Finite-difference time-domain (FDTD) simulation results propose that the unexpected peak appears because of plasmonic surface guiding mode. The position of the resonance peak shows the sensitivity toward the change of the refractive index of surrounding medium, suggesting it as a promising label-free sensor application. In addition, other types of Au nanostructure arrays such as geometry-controlled NHA and nanoparticle arrays (NPAs) shows the outstanding versatility of our approach.

  5. Human papillomavirus L1 protein expressed in Escherichia coli self-assembles into virus-like particles that are highly immunogenic. (United States)

    Chen, Yumei; Liu, Yunchao; Zhang, Gaiping; Wang, Aiping; Dong, Ziming; Qi, Yanhua; Wang, Jucai; Zhao, Baolei; Li, Ning; Jiang, Min


    HPV vaccines based on L1 virus-like particles (VLPs) provided a high degree of protection against HPVs infection. In this study, the codon optimized HPV16 L1 gene were sub-cloned into five procaryotic expression vectors (pET-28a, pET-32a, pGEX-4T-2, pE-sumo and pHSIE), and fused with different protein tags. No recombinant proteins were expressed in pET-28a-L1 and pHSIE-L1, and the proteins expressed by pET-32a-L1 plasmid with TRX-tag were in the form of inclusion body. Only SUMO-tagged and GST-tagged L1 proteins expressed by pE-Sumo-L1 or pGEX-4T-L1 were soluble. The yield of SUMO-L1 protein reached 260mg/L fermentation medium in shake flask. After SUMO tags were eliminated, a 90% purity of L1 proteins was generated by ion-exchange and Ni-NTA affinity chromatography. The purified HPV16 L1 protein self-assembled into virus-like particles (VLPs) and showed a haemagglutination activity. High titers specific and neutralizing antibodies were detected in HPV 16 L1VLPs vaccinated mice. Cytokines such as IFN-γ and IL-2 showed significant higher in VLPs vaccinated mice compared with negative control (p<0.05, p=0.055). Thus, the expression of recombinant HPV16 L1 VLPs in Escherichia coli was feasible, which could potentially be used for a VLP-based HPV vaccine. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Self-assembly of NiO/graphene with three-dimension hierarchical structure as high performance electrode material for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Bing; Zhuang, Hua; Fang, Tao; Jiao, Zheng; Liu, Ruizhe; Ling, Xuetao [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Lu, Bo [Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444 (China); Jiang, Yong, E-mail: [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)


    Highlights: • 3D hierarchical NiO/graphene is prepared by a refluxing method with aqua-based solvent. • Time-dependent experiments are carried out to investigate formation mechanism. • Hierarchical sphere is formed through self-assembly of NiO grown on disc-shaped CTAB micelles. • It delivers a capacitance of 555 F g{sup −1} at 1 A g{sup −1} with 90.8% retention after 2000 cycles. - Abstract: This article reports a facile preparation of NiO/graphene composite by the combination of a controlled refluxing method with water based solvent in the presence of cetyltrimethylammonium bromide and subsequent annealing. X-ray diffraction and scanning electron microscopy reveal that the graphene nanosheets are uniformly wrapped by hierarchical porous NiO spheres with three-dimension hierarchical structure in the product. The composite shows highly improved electrochemical performance as electrode material for supercapacitor. The three-dimension hierarchical structure NiO/graphene composite delivers a first discharge capacitance of 555 F g{sup −1} and remains a reversible capacitance up to 504 F g{sup −1} after 2000 cycles at a current of 1 A g{sup −1} in three-electrode system. Contrarily, the pure NiO shows only a first discharge capacitance of 166 F g{sup −1} and remains only a reversible capacitance of 107 F g{sup −1} after 2000 cycles. The NiO/graphene composite also exhibits ameliorative rate capacitance of 402.9 F g{sup −1} at the current density of 5 A g{sup −1}. The enhanced electrochemical performances are ascribed to the higher surface area, the stable three-dimension hierarchical structure and the synergistic effects between the conductive graphene and porous NiO spheres.

  7. KH2PO4-Assisted Synthesis and Electrochemical Performance of Highly Uniform CuBi2O4 Microspheres Hierarchically Self-Assembled by Nanoparticles (United States)

    Wang, Fei; Yang, Hua; Zhang, Yunchuan; Zhang, Haimin


    The effect of KH2PO4 on the synthesis of CuBi2O4 microstructures was investigated. The samples were characterized by powder x-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) analysis, x-ray photoelectron spectroscopy (XPS) and ultraviolet (UV)-visible diffuse reflectance spectroscopy. It is demonstrated that the use of KH2PO4 leads to the production of highly uniform CuBi2O4 microspheres hierarchically self-assembled by nanoparticles. With increasing the KH2PO4 concentration from 0.5 M to 1.4 M, the average diameter of the resultant microspheres decreases gradually from 3.3 μm to 1.4 μm. However, further increase in the KH2PO4 concentration up to 1.5 M leads to a sudden increase in the average diameter of the resultant microspheres up to 2.3 μm. In addition, a minor amount of bamboo leaf- or pine needle-like structures are visible in the samples prepared at the KH2PO4 concentrations of 1.0-1.5 M. The bandgap energy of the as-prepared samples is measured to be 1.89 eV by UV-visible diffuse reflectance spectroscopy. The electrochemical performance of the samples was investigated by cyclic voltammetry, galvanostatic charge-discharge measurements, and electrochemical impedance spectroscopy in 2 M KOH electrolyte. Among the hierarchical microspheres, those prepared at the KH2PO4 concentration of 1.4 M deliver a relatively higher specific capacitance due to their smaller size (1284 F g-1 at a current density of 2 A g-1).

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

    Directory of Open Access Journals (Sweden)

    Kitae Ryu


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

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

    KAUST Repository

    Tétreault, Nicolas


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

  10. Self-assembly of nitrogen-doped carbon nanoparticles: a new ratiometric UV-vis optical sensor for the highly sensitive and selective detection of Hg(2+) in aqueous solution. (United States)

    Ruan, Yudi; Wu, Lie; Jiang, Xiue


    Water-soluble nitrogen-doped carbon nanoparticles (N-CNPs) prepared by the one-step hydrothermal treatment of uric acid were found to show ratiometric changes in their UV-vis spectra due to Hg(2+)-mediated self-assembly. For the first time, such a property was developed into a UV-vis optical sensor for detecting Hg(2+) in aqueous solutions with high sensitively and selectively (detection limit = 1.4 nM). More importantly, this novel sensor exhibits a higher linear sensitivity over a wider concentration range compared with the fluorescence sensor based on the same N-CNPs. This work opens an exciting new avenue to explore the use of carbon nanoparticles in constructing UV-vis optical sensors for the detection of metal ions and the use of carbon nanoparticles as a new building block to self-assemble into superlattices.

  11. Self-assembly of C60 into highly ordered chain-like structures on HOPG observed at ambient conditions

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Haahr, Lærke Thorlund


    The observation of chain-like structures of self-assembled C-60 Molecules on HOPG surfaces at room temperature in aerial atmosphere by means of scanning tunneling microscopy is reported. The ca. 2.5 nm center-to-center distance between two fullerene molecules is much larger than in the close......-packed layered or film structures Of C-60 usually found on HOPG surfaces. (c) 2007 Elsevier B.V. All rights reserved....

  12. Self-assembly of various Au nanocrystals on functionalized water-stable PVA/PEI nanofibers: a highly efficient surface-enhanced Raman scattering substrates with high density of "hot" spots. (United States)

    Zhu, Han; Du, MingLiang; Zhang, Ming; Wang, Pan; Bao, ShiYong; Zou, Meiling; Fu, YaQin; Yao, JuMing


    We have demonstrated a facile approach for the fabrication of flexible and reliable sulfydryl functionalized PVA/PEI nanofibers with excellent water stability for the self-assembly of Au nanocrystals, such as Au nanoparticles (AuNPs), Au nanoflowers (AuNFs) and Au nanorods (AuNRs), used as the highly efficient surface-enhanced Raman scattering (SERS) substrates for the detection of rhodamine B (RhB). Various methods were employed to cross-link the PVA nanofibers with better morphology and porous structures after immersing in water for desired times. Various SERS-active Au nanocrystals, such as AuNPs, AuNFs, and AuNRs have been successfully synthesized. After the grafting of MPTES on the cross-linked PVA/PEI nanofibers, the Au nanocrystals can easily be self-assembled on the surfaces of the nanofibers because of the strong interactions of the Au-S chemical bondings. The Au nanocrystals self-assembled throughout the PVA/PEI nanofibers used as SERS substrates all exhibit enhanced SERS signals of RhB compared with their individual nanocrystals. It is mainly due to the close interparticle distance, mutual orientation and high density of "hot" spots, that can strongly affect the overall optical response and the SERS enhancement. By changing the amounts of the self-assembled AuNFs on the nanofibers, we can control the density of the "hot" spots. With the increased amounts of the AuNFs throughout the nanofibers, the SERS substrates show enhanced Raman signals of the RhB, indicating that the increased density of "hot" spots can directly lead to the SERS enhancement. The AuNFs/(PVA/PEI) SERS substrates show good sensitivity, reliability and low detection limit (10(-9) M). The presented approach can be broadly applicable to the assembly of different types of plasmonic nanostructures and these novel materials with strong SERS enhancement can be applied in bioanalysis and biosensors. © 2013 Published by Elsevier B.V.

  13. Self-assembled nanostructured metamaterials (United States)

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


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

  14. Self-assembled nanostructures on vicinal surfaces (United States)

    Petrovykh, Dmitri Yourievich


    One of the first methods for visualizing crystal planes and atomic steps has been step decoration with gold on alkali-halide surfaces. An impressive body of work has been conducted since then on the role of steps in controlling surface diffusion and adsorption rates, catalytic and chemical activity, and other physical and chemical surface properties. Due to these special characteristics, vicinal surfaces offer an approach for creating self-assembled structures with one or more dimensions on nanometer scale. The storage and communications industries have been revolutionized by applications of two-dimensional electron gas confined in thin films, so an interest in one and zero-dimensional systems is not surprising. This work demonstrates how macroscopic amounts of low-dimensional structures can be produced by self-assembly using stepped surfaces as nanometer-scale templates. High-quality templates of step arrays can be prepared on vicinal Si(111) surfaces. Sub-monolayer CaF2/Si(111) heteroepitaxial growth is examined in a series of experiments. A new growth mode is observed in addition to the ones typical in three dimensions. With increasing coverage, the growth front changes from rough to smooth geometry, driven by the elastic interactions between the multiple growth fronts and the surface steps. The mechanism is thus unique to the two-dimensional growth on stepped surfaces. The possible arrangements of the CaF2 self-assembled nanostructures are arrays of stripes or islands, both interesting as potential masks for silicon nanolithography. Anisotropic surface reconstructions, such as Ca and Au induced 3 x 1 and 5 x 2 on Si(111), are effectively self-assembled one-dimensional atomic chains. Reconstructions are single-domain on vicinal surfaces and with odd electron count a metallic one-dimensional state is expected in both the above examples. However in angular-resolved photoemission both appear as semiconductors, and Au-Si(111)5 x 2 exhibits a continuous one

  15. Facile Layer-by-Layer Self-Assembly toward Enantiomeric Poly(lactide) Stereocomplex Coated Magnetite Nanocarrier for Highly Tunable Drug Deliveries. (United States)

    Li, Zibiao; Yuan, Du; Jin, Guorui; Tan, Beng H; He, Chaobin


    A highly tunable nanoparticle (NP) system with multifunctionalities was developed as drug nanocarrier via a facile layer-by-layer (LbL) stereocomplex (SC) self-assembly of enantiomeric poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) in solution using silica-coated magnetite (Fe3O4@SiO2) as template. The poly(lactide) (PLA) SC coated NPs (Fe3O4@SiO2@-SC) were further endowed with different stimuli-responsiveness by controlling the outermost layer coatings with respective pH-sensitive poly(lactic acid)-poly(2-dimethylaminoethyl methacrylate) (PLA-D) and temperature-sensitive poly(lactic acid)-poly(N-isopropylacrylamide) (PLA-N) diblock copolymers to yield Fe3O4@SiO2@SC-D and Fe3O4@SiO2@SC-N NPs, respectively, while the superparamagnetic properties of Fe3O4 were maintained. TEM images show a clearly resolved core-shell structure with a silica layer and sequential PLA SC co/polymer coating layers in the respective NPs. The well-designed NPs possess a size distribution in a range of 220-270 nm and high magnetization of 70.8-72.1 emu/g [Fe3O4]. More importantly, a drug release study from the as-constructed stimuli-responsive NPs exhibited sustained release profiles and the rates of release can be tuned by variation of external environments. Further cytotoxicity and cell culture studies revealed that PLA SC coated NPs possessed good cell biocompatibility and the doxorubicin (DOX)-loaded NPs showed enhanced drug delivery efficiency toward MCF-7 cancer cells. Together with the strong magnetic sensitivity, the developed hybrid NPs demonstrate a great potential of control over the drug release at a targeted site. The developed coating method can be further optimized to finely tune the nanocarrier size and operating range of pHs and temperatures for in vivo applications.

  16. Synthesis of frost-like CuO combined graphene-TiO{sub 2} by self-assembly method and its high photocatalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Dinh Cung Tien [Department of Advanced Materials Science & Engineering, Hanseo University, Seosan, Chungnam, 356-706 (Korea, Republic of); Cho, Kwang-Youn [Korea Institutes of Ceramic Engineering and Technology, Soho-ro, Jinju-Si, Gyeongsangnam-do (Korea, Republic of); Oh, Won-Chun, E-mail: [Department of Advanced Materials Science & Engineering, Hanseo University, Seosan, Chungnam, 356-706 (Korea, Republic of)


    Highlights: • The frost-like CuO nanoparticles (3–5 nm) combined with the small TiO{sub 2} rods (50–100 nm) are expected to have a high charge transfer effect from TiO{sub 2} to CuO. • In this study, ·OH and h{sup +} play a major role in the photocatalytic reaction than O{sub 2}·{sup –} or both hydroxyl and holes are the active species responsible under visible light irradiation. • The photocatalytic degradation of rhodamine B (RhB), methylene blue trihydrate (MB), and reactive black B (RBB) in an aqueous solution under visible light irradiation was observed by UV spectrophotometry after measurement of the decrease of their concentrations. CuO-graphene-TiO{sub 2} is expected to become a new potential material for photodegradation activity with excellent photodegradation. - Graphical abstract: TEM image of CuO-graphene (a and b), and CuO-graphene-TiO{sub 2} (c and d) composites. - Abstract: A novel material, frost-like CuO combined-graphene-TiO{sub 2} composite, was successfully synthesized using a self-assembly method. During the reaction, the loading of CuO and TiO{sub 2} nanoparticles on graphene sheets was achieved. The obtained CuO-graphene-TiO{sub 2} composite photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), and X-ray photoelectron spectroscopy (XPS). The frost-like CuO nanoparticles combined with the small TiO{sub 2} rods were successfully loaded on the transparent graphene sheets. The photocatalytic degradation of rhodamine B (RhB), methylene blue trihydrate (MB), and reactive black B (RBB) in an aqueous solution under visible light irradiation was observed by UV spectrophotometry after measurement of the decrease of their concentrations. Through the photocatalytic test and TOC results, the CuO-graphene-TiO{sub 2} is expected to

  17. Controllable self-assembly of RNA dendrimers. (United States)

    Sharma, Ashwani; Haque, Farzin; Pi, Fengmei; Shlyakhtenko, Lyudmila S; Evers, B Mark; Guo, Peixuan


    We report programmable self-assembly of branched, 3D globular, monodisperse and nanoscale sized dendrimers using RNA as building blocks. The central core and repeating units of the RNA dendrimer are derivatives of the ultrastable three-way junction (3WJ) motif from the bacteriophage phi29 motor pRNA. RNA dendrimers were constructed by step-wise self-assembly of modular 3WJ building blocks initiating with a single 3WJ core (Generation-0) with overhanging sticky end and proceeding in a radial manner in layers up to Generation-4. The final constructs were generated under control without any structural defects in high yield and purity, as demonstrated by gel electrophoresis and AFM imaging. Upon incorporation of folate on the peripheral branches of the RNA dendrimers, the resulting constructs showed high binding and internalization into cancer cells. RNA dendrimers are envisioned to have a major impact in targeting, disease therapy, molecular diagnostics and bioelectronics in the near future. Dendrimers are gaining importance as a carrier platform for diagnosis and therapeutics. The authors here reported building of their dendrimer molecules using RNA as building blocks. The addition of folate also allowed recognition and subsequent binding to tumor cells. This new construct may prove to be useful in many clinical settings. Copyright © 2015 Elsevier Inc. All rights reserved.

  18. Two-dimensional porous architecture of protonated GCN and reduced graphene oxide via electrostatic self-assembly strategy for high photocatalytic hydrogen evolution under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Pu, Chenchen; Wan, Jun; Liu, Enzhou; Yin, Yunchao; Li, Juan; Ma, Yongning [School of Chemical Engineering, Northwest University, Xi’an 710069 (China); Fan, Jun, E-mail: [School of Chemical Engineering, Northwest University, Xi’an 710069 (China); Hu, Xiaoyun, E-mail: [School of Physics, Northwest University, Xi’an 710069 (China)


    Highlights: • The protonated GCN (pGCN) is prepared by acidic cutting and hydrothermal process. • The pGCN coupled with rGO are synthesized via electrostatic self-assembly strategy. • The pGCN-5 wt% rGO is obtained with a high specific surface area of 115.64 m{sup 2}g{sup −1}. • The pGCN-5 wt% rGO photocatalysts exhibit superb photocatalytic reduction capacity. - Abstract: Herein, porous protonated graphitic carbon nitride (pGCN) is prepared from bulk g-C{sub 3}N{sub 4} (GCN) directly by acidic cutting and hydrothermal process. The holey structure not only provides a lot of bounds on the accelerated and photo induced charge transfer and thus reduce the aggregation, but also endows the GCN with more exposure to the active site. The pGCN is obtained with an increased band gap of 2.91 eV together with a higher specific surface area of 82.76 m{sup 2}g{sup −1}. Meanwhile, the positively charged GCN resulted from the protonation pretreatment is beneficial for improving the interaction with negatively charged GO sheets. Compared with GCN, pGCN-rGO displays a significant decrease of PL intensities and an apparently enhancement of visible-light absorption, resulting a lower charge recombination rate and a better light absorption. Besides, the enhanced charge separation is demonstrated by photoluminescence emission spectroscopy and the transient photocurrent measurement. The photocatalytic performance studies for the degradation of MB indicate that pGCN-rGO exhibits the highest adsorption ability towards dye molecules. In addition, the pGCN-5 wt% rGO composite shows the optimal photocatalytic activity, the photodegradation rate of MB is 99.4% after 80 min of irradiation and the H{sub 2} evolution performance up to 557 μmol g{sup −1}h{sup −1} under visible light, which is much higher than the other control samples.

  19. Self-assembled flat-faceted nanoparticles chains as a highly-tunable platform for plasmon-enhanced spectroscopy in the infrared. (United States)

    Aguirregabiria, Garikoitz; Aizpurua, Javier; Esteban, Ruben


    Self-assembly fabrication methods can produce aggregates of metallic nanoparticles separated by nanometer distances which act as versatile platforms for field-enhanced spectroscopy due to the strong fields induced at the interparticle gaps. In this letter we show the advantages of using particles with large flat facets at the gap as the building elements of the aggregates. For this purpose, we analyze theoretically the plasmonic response of chains of metallic particles of increasing length. These chains may be a direct product of the chemical synthesis and can be seen as the key structural unit behind the plasmonic response of two and three dimensional self-assembled aggregates. The longitudinal chain plasmon that dominates the optical response redshifts following an exponential dependence on the number of particles in the chain for all facets studied, with a saturation wavelength and a characteristic decay length depending linearly on the diameter of the facet. According to our calculations, for small Au particles of 50 nm size separated by a 1 nanometer gap, the saturation wavelength for the largest facets considered correspond to a wavelength shift of ≈ 1200 nm with respect to the single particle resonance, compared to shifts of only ≈ 200 nm for the equivalent configuration of perfectly spherical particles. The corresponding decay lengths are 11.8 particles for the faceted nanoparticles and 3.5 particles for the spherical ones. Thus, large flat facets lead to an excellent tunability of the longitudinal chain plasmon, covering the whole biological window and beyond. Furthermore, the maximum near-field at the gap is only moderately weaker for faceted gaps than for spherical particles, while the region of strong local field enhancement extends over a considerably larger volume, allowing to accommodate more target molecules. Our results indicate that flat facets introduce significant advantages for spectroscopic and sensing applications using self-assembled

  20. Integrating top-down and self-assembly in the fabrication of peptide and protein-based biomedical materials. (United States)

    Smith, Katherine H; Tejeda-Montes, Esther; Poch, Marta; Mata, Alvaro


    The capacity to create an increasing variety of bioactive molecules that are designed to assemble in specific configurations has opened up tremendous possibilities in the design of materials with an unprecedented level of control and functionality. A particular challenge involves guiding such self-assembling interactions across scales, thus precisely positioning individual molecules within well-organized, highly-ordered structures. Such hierarchical control is essential if peptides and proteins are to serve as both structural and functional building blocks of biomedical materials. To achieve this goal, top-down techniques are increasingly being used in combination with self-assembling systems to reproducibly manipulate, localize, orient and assemble peptides and proteins to form organized structures. In this tutorial review we provide insight into how both standard and novel top-down techniques are being used in combination with peptide or protein self-assembly to create a new generation of functional materials. This journal is © The Royal Society of Chemistry 2011

  1. Self-assembled monolayers on silicon oxide

    Energy Technology Data Exchange (ETDEWEB)

    Belgardt, Christian; Graaf, Harald; Baumgaertel, Thomas; Borczyskowski, Christian von [Center for Nanostructured Materials and Analytics, Institute of Physics, Chemnitz University of Technology, Reichenhainer Str. 70, 09107 Chemnitz (Germany)


    We evaluated the wet-chemical formation of octa-decyltrichlorosilane (OTS) self-assembled monolayers on silicon substrates with a silicon oxide layer. Our investigations were focussed on the influence of the reaction time on the surface energy. The surface energy was thereby calculated by measuring the static contact angle of two probe liquids on the surface. We found that only high reaction times of several hundred minutes yield a high quality monolayer with a minimal surface energy. A clear increase of the dispersive part of the surface energy for short reaction times is found. This can be explained by a high ratio of gauche-conformation within the alkyl chains accompanied by a rather slow rearrangement of the chains inside the monolayer to form a densely packed all-trans conformation. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Leveraging symmetry to predict self-assembly of multiple polymers (United States)

    Lin, Milo M.


    Protein self-assembly is fundamental to biological function and disease. Experimentally, the atomic-level structure is difficult to obtain and the assembly mechanism is poorly understood. The large number of possible states accessible to such systems limits computational prediction. Here, I introduce a new computational approach that enforces conformational symmetry, whereby all chains in the system adopt the same conformation. Using this approach on a 2D lattice, a designed multi-chain conformation is found more than four orders of magnitude faster than existing approaches. Furthermore, the free energy landscape can be efficiently computed, showing potential for enabling atomistic prediction of protein self-assembly.

  3. Self-assembly patterning of organic molecules on a surface (United States)

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


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

  4. Design principles for nonequilibrium self-assembly. (United States)

    Nguyen, Michael; Vaikuntanathan, Suriyanarayanan


    We consider an important class of self-assembly problems, and using the formalism of stochastic thermodynamics, we derive a set of design principles for growing controlled assemblies far from equilibrium. The design principles constrain the set of configurations that can be obtained under nonequilibrium conditions. Our central result provides intuition for how equilibrium self-assembly landscapes are modified under finite nonequilibrium drive.

  5. Molecular self-assembly advances and applications

    CERN Document Server

    Dequan, Alex Li


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

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

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


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

  7. Self-Assembly in Biosilicification and Biotemplated Silica Materials

    Directory of Open Access Journals (Sweden)

    Francisco M. Fernandes


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

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

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


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

  9. Self-assembly of model proteins into virus capsids (United States)

    Wołek, Karol; Cieplak, Marek


    We consider self-assembly of proteins into a virus capsid by the methods of molecular dynamics. The capsid corresponds either to SPMV or CCMV and is studied with and without the RNA molecule inside. The proteins are flexible and described by the structure-based coarse-grained model augmented by electrostatic interactions. Previous studies of the capsid self-assembly involved solid objects of a supramolecular scale, e.g. corresponding to capsomeres, with engineered couplings and stochastic movements. In our approach, a single capsid is dissociated by an application of a high temperature for a variable period and then the system is cooled down to allow for self-assembly. The restoration of the capsid proceeds to various extent, depending on the nature of the dissociated state, but is rarely complete because some proteins depart too far unless the process takes place in a confined space.

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

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


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

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

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


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

  12. Smart self-assembled hybrid hydrogel biomaterials. (United States)

    Kopeček, Jindřich; Yang, Jiyuan


    Hybrid biomaterials are systems created from components of at least two distinct classes of molecules, for example, synthetic macromolecules and proteins or peptide domains. The synergistic combination of two types of structures may produce new materials that possess unprecedented levels of structural organization and novel properties. This Review focuses on biorecognition-driven self-assembly of hybrid macromolecules into functional hydrogel biomaterials. First, basic rules that govern the secondary structure of peptides are discussed, and then approaches to the specific design of hybrid systems with tailor-made properties are evaluated, followed by a discussion on the similarity of design principles of biomaterials and macromolecular therapeutics. Finally, the future of the field is briefly outlined. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)

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

  14. Interfacial self-assembly of amino acids and peptides: Scanning tunneling microscopy investigation (United States)

    Xu, Li-Ping; Liu, Yibiao; Zhang, Xueji


    Proteins play important roles in human daily life. To take advantage of the lessons learned from nature, it is essential to investigate the self-assembly of subunits of proteins, i.e., amino acids and polypeptides. Due to its high resolution and versatility of working environment, scanning tunneling microscopy (STM) has become a powerful tool for studying interfacial molecular assembly structures. This review is intended to reflect the progress in studying interfacial self-assembly of amino acids and peptides by STM. In particular, we focus on environment-induced polymorphism, chiral recognition, and coadsorption behavior with molecular templates. These studies would be highly beneficial to research endeavors exploring the mechanism and nanoscale-controlling molecular assemblies of amino acids and polypeptides on surfaces, understanding the origin of life, unravelling the essence of disease at the molecular level and deeming what is necessary for the ``bottom-up'' nanofabrication of molecular devices and biosensors being constructed with useful properties and desired performance.

  15. The Self-Assembly Properties of a Benzene-1,3,5-tricarboxamide Derivative (United States)

    Stals, Patrick J. M.; Haveman, Jan F.; Palmans, Anja R. A.; Schenning, Albertus P. H. J.


    A series of experiments involving the synthesis and characterization of a benzene-1,3,5-tricarboxamide derivative and its self-assembly properties are reported. These laboratory experiments combine organic synthesis, self-assembly, and physical characterization and are designed for upper-level undergraduate students to introduce the topic of…

  16. Shape Restoration by Active Self-Assembly

    Directory of Open Access Journals (Sweden)

    D. Arbuckle


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

  17. Tetrahymena dynamin related protein 6 self assembles independent ...

    Indian Academy of Sciences (India)

    eluted as small oligomeric forms. Absence of any peak in the void volume suggests that human dynamin 1 does not form self-assembled structure under high ionic strength condition. Supplementary figure 3: Size exclusion chromatography profile of Drp6-R414A. His6-Drp6-. R414A expressed and purified from bacteria ...

  18. Directed Self-Assembly of Nanodispersions

    Energy Technology Data Exchange (ETDEWEB)

    Furst, Eric M [University of Delaware


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

  19. Biocatalytic Self-Assembly on Magnetic Nanoparticles. (United States)

    Conte, Maria P; Sahoo, Jugal Kishore; Abul-Haija, Yousef M; Lau, K H Aaron; Ulijn, Rein V


    Combining (bio)catalysis and molecular self-assembly provides an effective approach for the production and processing of self-assembled materials by exploiting catalysis to direct the assembly kinetics and hence controlling the formation of ordered nanostructures. Applications of (bio)catalytic self-assembly in biologically interfacing systems and in nanofabrication have recently been reported. Inspired by self-assembly in biological cells, efforts to confine catalysts on flat or patterned surfaces to exert spatial control over molecular gelator generation and nanostructure self-assembly have also emerged. Building on our previous work in the area, we demonstrate in this report the use of enzymes immobilized onto magnetic nanoparticles (NPs) to spatially localize the initiation of peptide self-assembly into nanofibers around NPs. The concept is generalized for both an equilibrium biocatalytic system that forms stable hydrogels and a nonequilibrium system that normally has a preset lifetime. Characterization of the hydrogels shows that self-assembly occurs at the site of enzyme immobilization on the NPs to give rise to gels with a "hub-and-spoke" morphology, where the nanofibers are linked through the enzyme-NP conjugates. This NP-controlled arrangement of self-assembled nanofibers enables both remarkable enhancements in the shear strength of hydrogel systems and a dramatic extension of the hydrogel stability in the nonequilibrium system. We are also able to show that the use of magnetic NPs enables the external control of both the formation of the hydrogel and its overall structure by application of an external magnetic field. We anticipate that the enhanced properties and stimuli-responsiveness of our NP-enzyme system will have applications ranging from nanomaterial fabrication to biomaterials and biosensing.

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

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


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

  1. Polymer Self-Assembled Nanostructures as Innovative Drug Nanocarrier Platforms. (United States)

    Pippa, Natassa; Pispas, Stergios; Demetzos, Costas


    Polymer self-assembled nanostructures are used in pharmaceutical sciences as bioactive molecules' delivery systems for therapeutic and diagnostic purposes. Micelles, polyelectrolyte complexes, polymersomes, polymeric nanoparticles, nanogels and polymer grafted liposomes represent delivery vehicles that are marketed and/or under clinical development, as drug formulations. In this mini-review, these, recently appeared in the literature, innovative polymer drug nanocarrier platforms are discussed, starting from their technological development in the laboratory to their potential clinical use, through studies of their biophysics, thermodynamics, physical behavior, morphology, bio-mimicry, therapeutic efficacy and safety. The properties of an ideal drug delivery system are the structural control over size and shape of drug or imaging agent cargo/domain, biocompatibility, nontoxic polymer/ pendant functionality and the precise, nanoscale container and/or scaffolding properties with high drug or imaging agent capacity features. Self-assembled polymer nanostructures exhibit all these properties and could be considered as ideal drug nanocarriers through control of their size, structure and morphology, with the aid of a large variety of parameters, in vitro and in vivo. These modern trends reside at the interface of soft matter self-assembly and pharmaceutical sciences and the technologies for health. Great advantages related to basic science and applications are expected by understanding the self-assembly behavior of these polymeric nanotechnological drug delivery systems, created through bio-inspiration and biomimicry and have potential utilization into clinical applications.

  2. Self-assembly of various silver nanocrystals on PmPD/PAN nanofibers as a high-performance 3D SERS substrate. (United States)

    Jia, Peng; Cao, Bing; Wang, Jianqiang; Qu, Jin; Liu, Yuxuan; Pan, Kai


    We report a facile method to synthesise flexible 3D surface-enhanced Raman scattering (SERS) substrates, using poly-m-phenylenediamine/polyacrylonitrile (PmPD/PAN) nanofiber mats as templates to self-assemble citrate-stabilized Ag nanocrystals (AgNCs), such as Ag nanoparticles (AgNPs), Ag nanotriangles (AgNTs) or Ag nanodisks (AgNDs). The SERS performances of AgNC@2D and AgNC@3D substrates were compared using 4-MBA as the probe molecule. The effect of the extinction wavelength as well as the density and morphology of the AgNCs on the SERS enhancement effect was explored. The results suggest that the 3D AgNT@PmPD/PAN nanofiber mat exhibits the highest SERS sensitivity and the lowest relative standard deviation (RSD) value. The detection limit of 4-MBA is as low as 10(-8) M, making the nanofiber mat a promising candidate for the SERS detection of chemical molecules. In addition, this study provides a simple route for the fabrication of SERS substrates with different types of noble metals and materials with strong SERS enhancement performance.

  3. Fabrication of electrophoretically deposited, self-assembled three-dimensional porous Al/CuO nanothermite films for highly enhanced energy output

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Yanjun [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Li, Xueming, E-mail: [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Shu, Yuanjie [Xi’an Modern Chemistry Research Institute, Xi’an 71000 (China); Guo, Xiaogang; Bao, Hebin; Li, Wulin; Zhu, Yuhua; Li, Yu; Huang, Xinyue [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China)


    A novel porous Al/CuO nanothermite was successfully synthetized by utilizing the controllable electrophoretic deposition (EPD) method. The morphology and phase composition of the CuO and Al/CuO films were investigated in detail by field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD). When the pH of the solution was 2.0, the surface area of the Al/CuO film was able to reach 495.6 m{sup 2}/g, which was much higher than that of films grown at pH 1.0, 3.0 or 4.0. Meanwhile, the combustion performance and energy outputs were coincident with the results mentioned above. At pH 2.0, bright flames were observed after ignition, and the released heat of the nanothermite reaction reached 3.49 kJ/g, exhibiting excellent combustion performance and enhanced energy output. - Highlights: • Porous CuO films were synthesized without using templates. • The self-assembled porous Al/CuO nanothermite had a specific surface area of 495.6 m{sup 2}/g. • The energy output and combustion performance of Al/CuO nanothermite were significantly enhanced.

  4. In situ self-assembled reduced graphene oxide aerogel embedded with nickel oxide nanoparticles for the high-efficiency separation of ovalbumin. (United States)

    Chen, Lei; Zheng, Dong-Hua; Zhang, Ying; Wang, Ya-Ning; Xu, Zhang-Run


    A three-dimensional reduced graphene oxide aerogel with embedded nickel oxide nanoparticles was prepared by a one-step self-assembly reaction in a short time. The nanoparticles could be captured into the interior of reduced graphene oxide network during the formation of the three-dimensional architecture. The composite exhibited porosity, good biocompatibility, and abundant metal affinity binding sites. The aerogel was used to isolate ovalbumin selectively from egg white, and favorable adsorption was achieved at pH 3. An adsorption efficiency of 90.6% was obtained by using 1 mg of the composite for adsorbing 70 μg/mL of ovalbumin in 1.0 mL of sample solution, and afterwards a recovery of 90.7% was achieved by using an eluent of 1.0 mL Britton-Robinson buffer solution at pH 5. After the adsorption/desorption, ovalbumin showed no change in the conformation. The adsorption behavior of ovalbumin on the reduced graphene oxide composite well fitted to the Langmuir adsorption model, and a corresponding theoretical maximum adsorption capacity was 1695.2 mg/g. A sodium dodecyl sulfate polyacrylamide gel electrophoresis assay demonstrated that the aerogel could selectively isolate ovalbumin from chicken egg white. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Greiner, A.; Wendorff, J. H.

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

  6. On the influence of the aliphatic linker on fabrication of highly ordered and orientated self-assembled monolayers of aromatic selenols on AU(111)

    KAUST Repository

    Azzam, Waleed


    Self-assembled monolayers (SAMs) formed by adsorption of 1,2-dibenzyldiselenide (DPMSe) and 1,2-diphenyldiselenide (DBSe) on Au(111) substrates at room temperature have been characterized using scanning tunnelling microscopy, X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and low-energy electron diffraction. Upon adsorption, the Se-Se bonds in DPMSe and DBSe were cleaved on the gold surface to form phenylmethaneselenolate (PMSe) and benzeneselenolate (BSe) species, respectively. Although both PMSe and BSe molecular entities only differ in their structure (an additional methyl group in PMSe), the resulting monolayer films revealed noteworthy dissimilarities regarding their adlayer SAM structure and surface morphology. The molecular adlayer structure and orientation of PMSe and BSe species were found to vary significantly with the immersion time (IT). The resulting PMSe films were poorly organized, and the structure was described by a (4√3 × 2) rectangular unit cell for the SAMs prepared with 24 h of IT. Moreover, the PMSe-SAMs were found to be unstable upon exposure to air for a long time. Our results showed that exposure to air for 48 h results in the formation of small bright ad-islands, which have a height corresponding to that of a single atomic step on the Au(111). Contrary, BSe-SAMs exhibited densely packed and well-ordered monolayers, and two different structural phases were resolved at short and long ITs. The most densely packed structure was obtained for SAMs prepared with very short ITs (10 min). Upon increasing the IT, the SAMs exhibited structural changes to a lower density of molecular packing structure. The spectroscopic data also confirmed this structural transformation by suggesting an upright orientation for BSe-SAMs prepared after short ITs and strongly inclined adsorption geometry for SAMs prepared after long ITs. © 2014 American Chemical Society.

  7. Trace Water as Prominent Factor to Induce Peptide Self-Assembly: Dynamic Evolution and Governing Interactions in Ionic Liquids. (United States)

    Wang, Juan; Yuan, Chengqian; Han, Yuchun; Wang, Yilin; Liu, Xiaomin; Zhang, Suojiang; Yan, Xuehai


    The interaction between water and biomolecules including peptides is of critical importance for forming high-level architectures and triggering life's functions. However, the bulk aqueous environment has limitations in detecting the kinetics and mechanisms of peptide self-assembly, especially relating to interactions of trace water. With ionic liquids (ILs) as a nonconventional medium, herein, it is discovered that trace amounts of water play a decisive role in triggering self-assembly of a biologically derived dipeptide. ILs provide a suitable nonaqueous environment, enabling us to mediate water content and follow the dynamic evolution of peptide self-assembly. The trace water is found to be involved in the assembly process of dipeptide, especially leading to the formation of stable noncovalent dipeptide oligomers in the early stage of nucleation, as evident by both experimental studies and theoretical simulations. The thermodynamics of the growth process is mainly governed by a synergistic effect of hydrophobic interaction and hydrogen bonds. Each step of assembly presents a different trend in thermodynamic energy. The dynamic evolution of assembly process can be efficiently mediated by changing trace water content. The decisive role of trace water in triggering and mediating self-assembly of biomolecules provides a new perspective in understanding supramolecular chemistry and molecular self-organization in biology. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Evaporation-induced self-assembled silica colloidal particle-assisted nanoporous structural evolution of poly(ethylene terephthalate) nonwoven composite separators for high-safety/high-rate lithium-ion batteries (United States)

    Lee, Jung-Ran; Won, Ji-Hye; Kim, Jong Hun; Kim, Ki Jae; Lee, Sang-Young


    A facile approach to the fabrication of nanoporous structure-tuned nonwoven composite separators is demonstrated for application in high-safety/high-rate lithium-ion batteries. This strategy is based on the construction of silica (SiO2) colloidal particle-assisted nanoporous structure in a poly(ethylene terephthalate) (PET) nonwoven substrate. The nanoparticle arrangement arising from evaporation-induced self-assembly of SiO2 colloidal particles allows the evolution of the unusual nanoporous structure, i.e. well-connected interstitial voids formed between close-packed SiO2 particles adhered by styrene-butadiene rubber (SBR) binders. Meanwhile, the PET nonwoven serves as a mechanical support that contributes to suppressing thermal shrinkage of the nonwoven composite separator. The aforementioned structural novelty of the nonwoven composite separator plays a key role in providing the separator with advantageous characteristics (specifically, good electrolyte wettability, high ionic conductivity, and benign compatibility with electrodes), which leads to the better cell performance than a commercialized polyethylene (PE) separator.

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

    Grabow, Wade W; Jaeger, Luc


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

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

    KAUST Repository

    Zhu, Jia


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

  11. Self-assembly programming of DNA polyominoes. (United States)

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


    Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Optical orientation in self assembled quantum dots

    CERN Document Server

    Stevens, G C


    We examined Zeeman splitting in a series of ln sub x Ga sub ( sub 1 sub - sub x sub ) As/GaAs self assembled quantum dots (SAQD's) with different pump polarisations. All these measurements were made in very low external magnetic fields where direct determination of the Zeeman splitting energy is impossible due to its small value in comparison to the photoluminescence linewidths. The use of a technique developed by M. J. Snelling allowed us to obtain the Zeeman splitting and hence the excitonic g-factors indirectly. We observed a linear low field splitting, becoming increasingly non-linear at higher fields. We attribute this non-linearity to field induced level mixing. It is believed these are the first low field measurements in these structures. A number of apparent nuclear effects in the Zeeman splitting measurements led us onto the examination of nuclear effects in these structures. The transverse and oblique Hanie effects then allowed us to obtain the sign of the electronic g-factors in two of our samples,...

  13. Self-assembly of nanocomposite materials (United States)

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


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

  14. Self-Assembly Modularity and Physical Complexity (United States)

    Ahnert, S. E.


    Self-assembly is ubiquitous in physics, chemistry and biology, and has many applications in materials science and engineering. Here we present a general approach for finding the simplest set of building blocks that will assemble into a given physical structure. Our procedure can be adapted to any given geometry, and thus to any given type of physical system. The amount of information required to describe this simplest set of building blocks provides a quantitative measure of the structure's physical complexity, which is capable of detecting any symmetry or modularity in the underlying structure.We also introduce the notions of joint, mutual and conditional complexity for self-assembling structures. We illustrate our approach using self-assembling polyominoes, and demonstrate the breadth of its potential applications by using it to quantify the physical complexity of protein complexes.

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

    Olvera de La Cruz, Monica


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

  16. Transparent 1T-MoS2 nanofilm robustly anchored on substrate by layer-by-layer self-assembly and its ultra-high cycling stability as supercapacitors. (United States)

    Li, Danqin; Zhou, Weiqiang; Zhou, Qianjie; Ye, Guo; Wang, Tongzhou; Wu, Jing; Chang, Yanan; Xu, Jingkun


    Two-dimensional MoS2 materials have attracted more and more interest and been applied to the field of energy storage because of its unique physical, optical, electronic and electrochemical properties. However, there are no reports on high-stable transparent MoS2 nanofilms as supercapacitors electrode. Here, we describe a transparent 1T-MoS2 nanofilm electrode with super-long stability anchored on the indium tin oxide (ITO) glass by a simple alternate layer-by-layer (LBL) self-assembly of a highly charged cationic poly(diallyldimethylammonium chloride) (PDDA) and negative single-/few-layer 1T MoS2 nanosheets. The ITO/(PDDA/MoS2)20 electrode shows a transmittance of 51.6% at 550 nm and obviously exhibits excellent transparency by naked eye observation. Ultrasonic damage test validates that the (PDDA/MoS2)20 film with the average thickness about 50 nm is robustly anchored on ITO substrate. Additionally, the electrochemical results indicate that the ITO/(PDDA/MoS2)20 film shows areal capacitance of 1.1 mF cm(-2) and volumetric capacitance of 220 F cm(-3) at 0.04 mA cm(-2), 130.6% retention of the original capacitance value after 5000 cycles. Further experiments indicate that the formation of transparent (PDDA/MoS2) x nanofilm by LBL self-assembly can be extended to other substrates, e.g., slide glass and flexible polyethylene terephthalate (PET). Thus, the easily available (PDDA/MoS2) x nanofilm electrode has great potential for application in transparent and/or flexible optoelectronic and electronics devices.

  17. Nondeterministic self-assembly with asymmetric interactions (United States)

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


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

  18. Self-assembling segmented coiled tubing

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, David W.


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

  19. Dynamic covalent chemistry in aid of peptide self-assembly. (United States)

    Sadownik, Jan W; Ulijn, Rein V


    Self-assembled peptide systems have been widely studied in the context of gaining understanding of the rules that govern biomolecular processes and increasingly as new bio-inspired nanomaterials. Such materials may be designed to be highly dynamic, displaying adaptive and self-healing properties. This review focuses on recent approaches, which exploit reversible covalent and noncovalent chemistry in combination with peptide-based self-assembly. Selected examples of recent advances include sulphur and nitrogen-based reversible reactions, metal-ligand coordination and enzyme-assisted transamidation that lead to structures such as catenanes, nanofibres, β-hairpins and coiled-coil assemblies. It is demonstrated that these structures give rise to nanomaterials with emergent properties that are highly sensitive and adaptive to external conditions and may allow for in vitro evolution of novel peptide nanostructures via templating or self-recognition. Copyright © 2010 Elsevier Ltd. All rights reserved.

  20. J-aggregation of cyanine dyes by self-assembly. (United States)

    Steiger, Rolf; Pugin, Raphaël; Heier, Jakob


    The importance of highly ordered surfaces, containing adsorptive surface states, is discussed for J-aggregation by self-assembly. Such nucleating surfaces are nanometer-sized edges and corners of cubic AgBr microcrystals, or surface iodide-clusters located along edges and corners of AgBr:I microcrystals. Of particular interest are dendrimers, monoatomic steps on terraced silver halide microcrystals and fullerene derivatives as nucleating surfaces. Molecular organisation into J-aggregates by self-assembly was realized using aprotic, apolar solvents for fullerenes, and polar solvents for dendrimers and monoatomic surface steps. By using dendrimers as nucleating agents in mesopores of metal oxide nanoparticle coatings, size-controlled and stable J-aggregates with high optical densities and strong fluorescence were obtained reproducibly. Such films may be useful for sensors, opto-electronics, lighting and photovoltaics.

  1. Protein-directed self-assembly of a fullerene crystal (United States)

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


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

  2. Synthesis and Self-Assembly of Triangulenium Salts

    DEFF Research Database (Denmark)

    Shi, Dong

    This thesis describes the design and synthesis of asymmetrically substituted amphiphilic tis(dialkylamino)trioxiatriangulenium (ATOTA+) salts with different counter ions. Attention was focused on exploring the assembling properties of the ATOTA+ salts in aqueous media. A direct vortexing-processed...... in influencing the assembling process and morphology of the assembled nanostructures. Tailoring the ATOTA+ system with alkyl chains of different length showed large effect on the final morphology of assembled supramolecular structures. The first two chapters give a brief introduction to molecular self......, highly ordered, and free-floating bilayer nanosheets through prolonged vigorous shaking. In this study, a mechanism for the self-assembly process agitated by prolonged vigorous shaking is proposed. It is proposed that the self-assembly is realized via a intermediated monolayer formed at the dynamic air...

  3. Optical nanoimaging for block copolymer self-assembly. (United States)

    Yan, Jie; Zhao, Ling-Xi; Li, Chong; Hu, Zhe; Zhang, Guo-Feng; Chen, Ze-Qiang; Chen, Tao; Huang, Zhen-Li; Zhu, Jintao; Zhu, Ming-Qiang


    One approach toward optical nanoimaging involves sequential molecular localization of photoswitchable fluorophores to achieve high resolution beyond optical limit of diffraction. Block copolymer micelles assembled from polystryrene-block-poly(ethylene oxide) block copolymers (PSt-b-PEO) are visualized in optical nanoimaging by staining the polystyrene blocks with spiropyrans (SPs). SPs localized in hydrophobic phase of block copolymer micelles exhibit reversible fluorescence on-off switching at alternating irradiation of UV and visible light. Phase-selective distribution of SPs in block copolymer micelles enables optical nanoimaging of microphase structures of block copolymer self-assembly at 50-nm resolution. To date, this is the sturdiest realization of optical nanoimaging with subdiffraction resolution for solution self-assembly of block copolymers.

  4. Self-assembly of hyperbranched polymers and its biomedical applications. (United States)

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


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

  5. Stabilization of Self-Assembled Alumina Mesophases

    NARCIS (Netherlands)

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


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

  6. Self-assembly of hyperbranched spheres

    NARCIS (Netherlands)

    Huck, W.T.S.; Huck, Wilhelm T.S.; van Veggel, F.C.J.M.; Reinhoudt, David


    A new type of building block with two coordinatively unsaturated palladium centres has been described that self-assembles in nitromethane solution and disassembles when acetonitrile is added. The resulting hyperbranched, organopalladium spheres have a remarkably narrow size distribution as was

  7. Self-assembled nanogaps for molecular electronics

    DEFF Research Database (Denmark)

    Tang, Qingxin; Tong, Yanhong; Jain, Titoo


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

  8. Efficient exciton transport in layers of self-assembled porphyrin derivatives

    NARCIS (Netherlands)

    Huijser, A.; Suijkerbuijk, B.M.J.M.; Klein Gebbink, R.J.M.; Savenije, T.J.; Siebbeles, D.A.


    The photosynthetic apparatus of green sulfur bacteria, the chlorosome, is generally considered as a highly efficient natural light-harvesting system. The efficient exciton transport through chlorosomes toward the reaction centers originates from self-assembly of the bacteriochlorophyll molecules.

  9. Molecular Effects on Coacervate-Driven Block Copolymer Self Assembly (United States)

    Lytle, Tyer; Radhakrishna, Mithun; Sing, Charles

    Two oppositely charged polymers can undergo associative phase separation in a salt solution in a process known as \\x98complex coacervation. Recent work has used this as a motif to control the self-assembly behavior of a mixture of oppositely-charged block copolymers which form nanoscale structures. The materials formed from these complex coacervate-block copolymers (BCPs) have potential use as drug delivery systems, gels, and sensors. We have developed a hybrid Monte Carlo-Single Chain in a Mean Field (MC-SCMF) simulation method that is able to determine morphological phase diagrams for BCPs. This technique is an efficient way to calculate morphological phase diagrams and provides a clear link between molecular level features and self-assembly behaviors. Morphological phase diagrams showing the effects of polymer concentration, salt concentration, chain length, and charge-block fraction at large charge densities on self-assembly behavior have been determined. An unexpected phase transition from disorder to hexagonal packing at large salt concentrations has been observed for charge-block fractions equal to and larger than 0.5. This is attributed to the salt filling space stabilizing the morphology of the BCP.

  10. Functionalized fullerenes in self-assembled monolayers. (United States)

    Gimenez-Lopez, Maria del Carmen; Räisänen, Minna T; Chamberlain, Thomas W; Weber, Uli; Lebedeva, Maria; Rance, Graham A; Briggs, G Andrew D; Pettifor, David; Burlakov, Victor; Buck, Manfred; Khlobystov, Andrei N


    Anisotropy of intermolecular and molecule-substrate interactions holds the key to controlling the arrangement of fullerenes into 2D self-assembled monolayers (SAMs). The chemical reactivity of fullerenes allows functionalization of the carbon cages with sulfur-containing groups, thiols and thioethers, which facilitates the reliable adsorption of these molecules on gold substrates. A series of structurally related molecules, eight of which are new fullerene compounds, allows systematic investigation of the structural and functional parameters defining the geometry of fullerene SAMs. Scanning tunnelling microscopy (STM) measurements reveal that the chemical nature of the anchoring group appears to be crucial for the long-range order in fullerenes: the assembly of thiol-functionalized fullerenes is governed by strong molecule-surface interactions, which prohibit formation of ordered molecular arrays, while thioether-functionalized fullerenes, which have a weaker interaction with the surface than the thiols, form a variety of ordered 2D molecular arrays owing to noncovalent intermolecular interactions. A linear row of fullerene molecules is a recurring structural feature of the ordered SAMs, but the relative alignment and the spacing between the fullerene rows is strongly dependent on the size and shape of the spacer group linking the fullerene cage and the anchoring group. Careful control of the chemical functionality on the carbon cages enables positioning of fullerenes into at least four different packing arrangements, none of which have been observed before. Our new strategy for the controlled arrangement of fullerenes on surfaces at the molecular level will advance the development of practical applications for these nanomaterials. © 2011 American Chemical Society

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

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


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

  12. Molecular Motions in Functional Self-Assembled Nanostructures

    Directory of Open Access Journals (Sweden)

    Jean-Marc Saiter


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

  13. Self-assembled peptide-based nanostructures: Smart nanomaterials toward targeted drug delivery. (United States)

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


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

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

    Schade, Nicholas Benjamin

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

  15. Self-assembled dopamine nanolayers wrapped carbon nanotubes as carbon-carbon bi-functional nanocatalyst for highly efficient oxygen reduction reaction and antiviral drug monitoring (United States)

    Khalafallah, Diab; Akhtar, Naeem; Alothman, Othman Y.; Fouad, H.; Abdelrazek khalil, Khalil


    Oxygen reduction reaction (ORR) catalysts are the heart of eco-friendly energy resources particularly low temperature fuel cells. Although valuable efforts have been devoted to synthesize high performance catalysts for ORR, considerable challenges are extremely desirable in the development of energy technologies. Herein, we report a simple self-polymerization method to build a thin film of dopamine along the tubular nanostructures of multi-walled carbon nanotubes (CNT) in a weak alkaline solution. The dopamine@CNT hybrid (denoted as DA@CNT) reveals an enhanced electrocatalytic activity towards ORR with highly positive onset potential and cathodic current as a result of their outstanding features of longitudinal mesoporous structure, high surface area, and ornamentation of DA layers with nitrogen moieties, which enable fast electron transport and fully exposed electroactive sites. Impressively, the as-obtained hybrid afford remarkable electrochemical durability for prolonged test time of 60,000 s compared to benchmark Pt/C (20 wt%) catalyst. Furthermore, the developed DA@CNT electrode was successfully applied to access the quality of antiviral drug named Valacyclovir (VCR). The DA@CNT electrode shows enhanced sensing performance in terms of large linear range (3-75 nM), low limit of detection (2.55 nM) than CNT based electrode, indicating the effectiveness of the DA coating. Interestingly, the synergetic effect of nanostructured DA and CNT can significantly boost the electronic configuration and exposure level of active species for ORR and biomolecule recognition. Therefore, the existing carbon-based porous electrocatalyst may find numerous translational applications as attractive alternative to noble metals in polymer electrolyte membrane fuel cells and quality control assessment of pharmaceutical and therapeutic drugs.

  16. Tribological characteristics of self-assembled nanometer film ...

    Indian Academy of Sciences (India)

    APTES) self-assembled mono- layer (SAM) were prepared on the hydroxylated silicon substrate by a self-assembling process from specially for- mulated solution. Chemical compositions of the films and chemical state of the elements were ...

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

    NARCIS (Netherlands)

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


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

  18. Molecular self-assembly into one-dimensional nanostructures. (United States)

    Palmer, Liam C; Stupp, Samuel I


    Self-assembly of small molecules into one-dimensional nanostructures offers many potential applications in electronically and biologically active materials. The recent advances discussed in this Account demonstrate how researchers can use the fundamental principles of supramolecular chemistry to craft the size, shape, and internal structure of nanoscale objects. In each system described here, we used atomic force microscopy (AFM) and transmission electron microscopy (TEM) to study the assembly morphology. Circular dichroism, nuclear magnetic resonance, infrared, and optical spectroscopy provided additional information about the self-assembly behavior in solution at the molecular level. Dendron rod-coil molecules self-assemble into flat or helical ribbons. They can incorporate electronically conductive groups and can be mineralized with inorganic semiconductors. To understand the relative importance of each segment in forming the supramolecular structure, we synthetically modified the dendron, rod, and coil portions. The self-assembly depended on the generation number of the dendron, the number of hydrogen-bonding functions, and the length of the rod and coil segments. We formed chiral helices using a dendron-rod-coil molecule prepared from an enantiomerically enriched coil. Because helical nanostructures are important targets for use in biomaterials, nonlinear optics, and stereoselective catalysis, researchers would like to precisely control their shape and size. Tripeptide-containing peptide lipid molecules assemble into straight or twisted nanofibers in organic solvents. As seen by AFM, the sterics of bulky end groups can tune the helical pitch of these peptide lipid nanofibers in organic solvents. Furthermore, we demonstrated the potential for pitch control using trans-to-cis photoisomerization of a terminal azobenzene group. Other molecules called peptide amphiphiles (PAs) are known to assemble in water into cylindrical nanostructures that appear as nanofiber

  19. Ternary self-assemblies in water

    DEFF Research Database (Denmark)

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


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

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

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


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

  1. Biological Nanoplatforms for Self-Assembled Electronics (United States)


    AFRL-RV-PS- AFRL-RV-PS- TR-2015-0024 TR-2015-0024 BIOLOGICAL NANOPLATFORMS FOR SELF- ASSEMBLED ELECTRONICS Stephen Jett University of New Mexico 1...University of New Mexico Albuquerque, NM 87131-0001 24 Mar 2015 Final Report APPROVED FOR PUBLIC RELEASE; DISTRIBUTION IS UNLIMITED. AIR FORCE...RESEARCH LABORATORY Space Vehicles Directorate 3550 Aberdeen Ave SE AIR FORCE MATERIEL COMMAND KIRTLAND AIR FORCE BASE, NM 87117-5776 NOTICE AND

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

    Indian Academy of Sciences (India)


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

  3. Ni foam supported quasi-core-shell structure of ultrathin Ti3C2 nanosheets through electrostatic layer-by-layer self-assembly as high rate-performance electrodes of supercapacitors (United States)

    Tian, Yapeng; Yang, Chenhui; Que, Wenxiu; He, Yucheng; Liu, Xiaobin; Luo, Yangyang; Yin, Xingtian; Kong, Ling Bing


    Supercapacitor, as an important energy storage device, is a critical component for next generation electric power system, due to its high power density and long cycle life. In this study, a novel electrode material with quasi-core-shell structure, consisting of negatively charged few layer Ti3C2 nanosheets (FL-Ti3C2) and positively charged polyethyleneimine as building blocks, has been prepared by using an electrostatic layer-by-layer self-assembly method, with highly conductive Ni foam to be used as the skeleton. The unique quasi-core-shell structured ultrathin Ti3C2 nanosheets provide an excellent electron channel, ion transport channel and large effective contact area, thus leading to a great improvement in electrochemical performance of the material. The specific capacitance of the binder-free FL-Ti3C2@Ni foam electrodes reaches 370 F g-1 at the scan rate of 2 mV s-1 and a specific capacitance of 117 F g-1 is obtained even at the scan rate of 1000 mV s-1 in the electrolyte of Li2SO4, indicating a high rate performance. In addition, this electrode shows a long-term cyclic stability with a loss of only 13.7% after 10,000 circles. Furthermore, quantitative analysis has been conducted to ensure the relationship between the capacitive contribution and the rate performance of the as-fabricated electrode.

  4. Self-assembled monolayers in organic electronics. (United States)

    Casalini, Stefano; Bortolotti, Carlo Augusto; Leonardi, Francesca; Biscarini, Fabio


    Self-assembly is possibly the most effective and versatile strategy for surface functionalization. Self-assembled monolayers (SAMs) can be formed on (semi-)conductor and dielectric surfaces, and have been used in a variety of technological applications. This work aims to review the strategy behind the design and use of self-assembled monolayers in organic electronics, discuss the mechanism of interaction of SAMs in a microscopic device, and highlight the applications emerging from the integration of SAMs in an organic device. The possibility of performing surface chemistry tailoring with SAMs constitutes a versatile approach towards the tuning of the electronic and morphological properties of the interfaces relevant to the response of an organic electronic device. Functionalisation with SAMs is important not only for imparting stability to the device or enhancing its performance, as sought at the early stages of development of this field. SAM-functionalised organic devices give rise to completely new types of behavior that open unprecedented applications, such as ultra-sensitive label-free biosensors and SAM/organic transistors that can be used as robust experimental gauges for studying charge tunneling across SAMs.

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

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


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

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

    Lombardo, Michael T.

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

  7. Self assembly of rectangular shapes on concentration programming and probabilistic tile assembly models. (United States)

    Kundeti, Vamsi; Rajasekaran, Sanguthevar


    Efficient tile sets for self assembling rectilinear shapes is of critical importance in algorithmic self assembly. A lower bound on the tile complexity of any deterministic self assembly system for an n × n square is [Formula: see text] (inferred from the Kolmogrov complexity). Deterministic self assembly systems with an optimal tile complexity have been designed for squares and related shapes in the past. However designing [Formula: see text] unique tiles specific to a shape is still an intensive task in the laboratory. On the other hand copies of a tile can be made rapidly using PCR (polymerase chain reaction) experiments. This led to the study of self assembly on tile concentration programming models. We present two major results in this paper on the concentration programming model. First we show how to self assemble rectangles with a fixed aspect ratio (α:β), with high probability, using Θ(α + β) tiles. This result is much stronger than the existing results by Kao et al. (Randomized self-assembly for approximate shapes, LNCS, vol 5125. Springer, Heidelberg, 2008) and Doty (Randomized self-assembly for exact shapes. In: proceedings of the 50th annual IEEE symposium on foundations of computer science (FOCS), IEEE, Atlanta. pp 85-94, 2009)-which can only self assembly squares and rely on tiles which perform binary arithmetic. On the other hand, our result is based on a technique called staircase sampling. This technique eliminates the need for sub-tiles which perform binary arithmetic, reduces the constant in the asymptotic bound, and eliminates the need for approximate frames (Kao et al. Randomized self-assembly for approximate shapes, LNCS, vol 5125. Springer, Heidelberg, 2008). Our second result applies staircase sampling on the equimolar concentration programming model (The tile complexity of linear assemblies. In: proceedings of the 36th international colloquium automata, languages and programming: Part I on ICALP '09, Springer-Verlag, pp 235-253, 2009

  8. Amphiphiles Self-Assembly: Basic Concepts and Future Perspectives of Supramolecular Approaches

    Directory of Open Access Journals (Sweden)

    Domenico Lombardo


    Full Text Available Amphiphiles are synthetic or natural molecules with the ability to self-assemble into a wide variety of structures including micelles, vesicles, nanotubes, nanofibers, and lamellae. Self-assembly processes of amphiphiles have been widely used to mimic biological systems, such as assembly of lipids and proteins, while their integrated actions allow the performance of highly specific cellular functions which has paved a way for bottom-up bionanotechnology. While amphiphiles self-assembly has attracted considerable attention for decades due to their extensive applications in material science, drug and gene delivery, recent developments in nanoscience stimulated the combination of the simple approaches of amphiphile assembly with the advanced concept of supramolecular self-assembly for the development of more complex, hierarchical nanostructures. Introduction of stimulus responsive supramolecular amphiphile assembly-disassembly processes provides particularly novel approaches for impacting bionanotechnology applications. Leading examples of these novel self-assembly processes can be found, in fact, in biosystems where assemblies of different amphiphilic macrocomponents and their integrated actions allow the performance of highly specific biological functions. In this perspective, we summarize in this tutorial review the basic concept and recent research on self-assembly of traditional amphiphilic molecules (such as surfactants, amphiphile-like polymers, or lipids and more recent concepts of supramolecular amphiphiles assembly which have become increasingly important in emerging nanotechnology.

  9. Microstructure and Phase Behavior of a Quinquethiophene-Based Self-Assembled Monolayer as a Function of Temperature

    NARCIS (Netherlands)

    Flesch, Heinz-Georg; Mathijssen, Simon G. J.; Gholamrezaie, Fatemeh; Moser, Armin; Neuhold, Alfred; Novak, Jiri; Ponomarenko, Sergei A.; Shen, Quan; Teichert, Christian; Hlawacek, Gregor; Puschnig, Peter; Ambrosch-Draxl, Claudia; Resel, Roland; de Leeuw, Dago M.


    The self-assembly of monolayers is a highly promising approach in organic electronics, but most systems show weak device performances, probably because of a lack of long-range order of the molecules. The present self-assembled monolayer was formed by a molecule that contains a dimethyl-chlorosilyl

  10. A self-assembled microbonded germanium/silicon heterojunction photodiode for 25 Gb/s high-speed optical interconnects (United States)

    Tseng, Chih-Kuo; Chen, Wei-Ting; Chen, Ku-Hung; Liu, Han-Din; Kang, Yimin; Na, Neil; Lee, Ming-Chang M.


    A novel technique using surface tension to locally bond germanium (Ge) on silicon (Si) is presented for fabricating high performance Ge/Si photodiodes. Surface tension is a cohesive force among liquid molecules that tends to bring contiguous objects in contact to maintain a minimum surface energy. We take advantage of this phenomenon to fabricate a heterojunction optoelectronic device where the lattice constants of joined semiconductors are different. A high-speed Ge/Si heterojunction waveguide photodiode is presented by microbonding a beam-shaped Ge, first grown by rapid-melt-growth (RMG) method, on top of a Si waveguide via surface tension. Excellent device performances such as an operating bandwidth of 17 GHz and a responsivity of 0.66 and 0.70 A/W at the reverse bias of −4 and −6 V, respectively, are demonstrated. This technique can be simply implemented via modern complementary metal-oxide-semiconductor (CMOS) fabrication technologies for integrating Ge on Si devices. PMID:24232956

  11. Self-Assembly of 3D Fennel-Like Co3O4 with Thirty-Six Surfaces for High Performance Supercapacitor

    Directory of Open Access Journals (Sweden)

    Yanfang Li


    Full Text Available Three-dimensional (3D fennel-like cobalt oxide (II, III (Co3O4 particles with thirty-six surfaces on nickel foams were prepared via a simple hydrothermal synthesis method and its growth process was also researched. The crystalline structure and morphology were investigated by X-ray diffraction (XRD, scanning electron microscopy (SEM, and Raman spectroscopy. The Brunauer-Emmett-Teller (BET analysis revealed that 3D fennel-like Co3O4 particles have high specific surface area. Therefore, the special structure with thirty-six surfaces indicates the good electrochemical performance of the micron-nanometer material as electrode material for supercapacitors. The cyclic voltammetry (CV, galvanostatic charge-discharge, and electrochemical impedance spectroscopy (EIS were conducted to evaluate the electrochemical performances. Compared with other morphological materials of the similar sizes, the Co3O4 particles on nickel foam exhibit a high specific capacitance of 384.375 F·g−1 at the current density of 3 A·g−1 and excellent cycling stability of a capacitance retention of 96.54% after 1500 galvanostatic charge-discharge cycles in 6 M potassium hydroxide (KOH electrolyte.

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

    Directory of Open Access Journals (Sweden)

    Eugen Stulz


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

  13. Self-assembled organic microfibers for nonlinear optics. (United States)

    Xu, Jialiang; Semin, Sergey; Niedzialek, Dorota; Kouwer, Paul H J; Fron, Eduard; Coutino, Eduardo; Savoini, Matteo; Li, Yuliang; Hofkens, Johan; Uji-I, Hiroshi; Beljonne, David; Rasing, Theo; Rowan, Alan E


    While highly desired in integrated optical circuits, multiresponsive and tunable nonlinear optical (NLO) active 1D (sub)wavelength scale superstructures from organic materials are rarely reported due to the strong tendency of organic molecules to self-assembly in centrosymmetric modes. Here a solution-processed assembly approach is reported to generate non-centrosymmetric single-crystalline organic microfibers with a cumulative dipole moment for anisotropic combined second- and third-order NLO. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Chengzhou [School of Mechanical and Materials Engineering, Washington State University, Pullman WA 99164 USA; Fu, Shaofang [School of Mechanical and Materials Engineering, Washington State University, Pullman WA 99164 USA; Song, Junhua [School of Mechanical and Materials Engineering, Washington State University, Pullman WA 99164 USA; Shi, Qiurong [School of Mechanical and Materials Engineering, Washington State University, Pullman WA 99164 USA; Su, Dong [Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton NY 11973 USA; Engelhard, Mark H. [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Li, Xiaolin [Energy and Environmental Directory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Xiao, Dongdong [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Li, Dongsheng [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Estevez, Luis [Energy and Environmental Directory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Du, Dan [School of Mechanical and Materials Engineering, Washington State University, Pullman WA 99164 USA; Lin, Yuehe [School of Mechanical and Materials Engineering, Washington State University, Pullman WA 99164 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA


    Finely controlled synthesis of high active and robust non-precious metal catalysts with excellent electrocatalytic efficiency towards oxygen reduction reaction is extremely vital for successful implementation of fuel cells and metal batteries. Unprecedented oxygen reduction reaction electrocatalytic performances and the diversified synthetic procedure in term of favorable structure/morphology characteristics make transition metals-derived M–N–C (M=Fe, Co) structures the most promising nanocatalysts. Herein, using the nitrogen-containing small molecular and inorganic salt as precursors and ultrathin tellurium nanowires as templates, we successfully synthesized a series of well-defined M-N-doped hollow carbon nanowire aerogels through one step hydrothermal route and subsequent facile annealing treatment. Taking advantage of the porous nanostructures, one-dimensional building block as well as homogeneity of active sites, the resultant Fe-N-doped carbon hollow nanowire aerogels exhibited excellent ORR electrocatalytic performance even better than commercial Pt/C in alkaline solution, holding great potential in fuel cell applications.

  15. Self-assembly of high-nuclearity metal clusters: programmed expansion of a metallasiloxane cage to an octacopper(II) cluster. (United States)

    Abbati, Gian Luca; Cornia, Andrea; Caneschi, Andrea; Fabretti, Antonio C; Mortalo, Cecilia


    The novel octanuclear copper(II) cluster [Cu6[(PhSiO2)6]2[NCCu(Me6tren)]2(MeOH)4]2+ (1) has been isolated as a perchlorate salt by reacting the hexacopper(II) metallasiloxane cage [Cu6[(PhSiO2)6]2(nBuOH)x] (x = 4, 6) with [Cu(Me6tren)CN]ClO4 in a methanol/chloroform mixture (Me6tren = tris(2-(dimethylamino)ethyl) amine). Crystal data for 1(ClO4)2 x MeOH: monoclinic, space group P2(1)/n (no. 14), a = 16.8490(3) angstroms, b = 22.2966(4) angstroms, c = 17.2508(3) angstroms, beta = 94.7658(5) degrees, V = 6458.3(2) angstroms3, Z = 2. The structure comprises a highly distorted hexagonal Cu6 array linked to two [Cu(Me6tren)] units via cyanide bridges. Magnetic measurements reveal that the addition of the copper cyanide complexes dramatically affects the magnetism of the Cu6 unit, whose ground spin state changes from S = 3 to S = 0. Copyright 2004 American Chemical Society

  16. Tetrameric Self-Assembly of a Cu(II) Complex Containing Schiff-Base Ligand and Its Unusually High Catecholase-like Activity

    Energy Technology Data Exchange (ETDEWEB)

    Sarkar, Shuranjan; Lee, Hongin [Kyungpook National Univ., Daegu (Korea, Republic of); Lee, Woo Ram; Hong, Chang Seop [Korea Univ., Seoul (Korea, Republic of)


    We report a new tetrameric supramolecular Cu(II) complex (Cu{sub 4}L{sub 4} = tetrakis(N,N'-bis(salicylidene)-2,2'-ethylenedianiline) Copper(II)) with a Schiff-base ligand (H{sub 2}L = N,N'-bis (salicylaldimine)-1,2-ethylenediamine) containing two N,O-bidentate chelate groups. Though the copper sites of Cu{sub 4}L{sub 4} are non-coupled, the complex exhibits a unusually high catecholase-like activity (k{sub cat} = 935 h{sup -1}) when the Cu{sub 4}L{sub 4} solution is treated with 3,5-di-tert-butylcatechol (3,5-DTBC) at basic condition in the presence of air. Combined information obtained from UV-VIS and EPR measurements could lead the suggestion of the reaction pathway in which the substrate may bind to Cu(II) ions by anti-anti didentate bridging mode.

  17. Layer-by-layer self-assembled graphene oxide/silica microsphere composites as stationary phase for high performance liquid chromatography. (United States)

    Liang, Xiaojing; Liu, Shujuan; Song, Xinwang; Zhu, Yangwen; Jiang, Shengxiang


    Graphene oxide (GO) has been layer-by-layer assembled onto silica microspheres to form a GO/SiO(2) composite stationary phase. All the characterizations of GO/SiO(2) by elemental analysis, Raman spectroscopy and Fourier transformed infrared spectrometry confirmed that with the increase of the assembled layer, GO gradually increases on the silica surface. The chromatographic properties of bare SiO(2) and GO/SiO(2) with different GO assembled layers show that the amount of GO plays an important role in the separation of analytes. Only the appropriate amount of GO on SiO(2) can perform a good chromatographic separation. The comparison between chromatographic performances of bare SiO(2) column, GO/SiO(2)-2 column and C18 commercial column clearly show that GO/SiO(2)-2 and C18 columns obtained a better separation; GO/SiO(2)-2 exhibits a large π-electron system and C18 exhibits hydrophobicity. The eluting order, peak width and resolution of analyte on GO/SiO(2)-2 column was highly dependent on the size of its π-electron system, while on the C18 column the decisive factor is its hydrophobic property.

  18. Heterogeneous self-assembled media for biopolymerization

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain


    compartments and lipid-bilayer lattices. Another kind of media is represented by self-assembled phases in the reaction medium, e.g., in water-ice matrices that are formed by two co-existing aqueous phases (a solid phase and a concentrated liquid phase) when an aqueous solution is cooled below its freezing...... point, but above the eutectic point. These media have the capacity to assemble chemical molecules or complex catalytic assemblies into unique configurations that are unstable or unavailable in bulk aqueous phases. Reactions can then proceed which do not readily occur in homogeneous solutions. To gauge...

  19. Nanoscale spirals by directed self-assembly (United States)

    Choi, Hong Kyoon; Chang, Jae-Byum; Hannon, Adam F.; Yang, Joel K. W.; Berggren, Karl K.; Alexander-Katz, Alfredo; Ross, Caroline A.


    Archimedean spiral patterns are formed by the directed self-assembly of diblock copolymer thin films within a circular template. The presence of a notch in the template promotes the formation of a spiral compared to concentric rings, and the notch shape determines the chirality of the spiral. Double spirals occur when the notch width is increased or when there are two notches. The spiral followed an Archimedean form with exponent ≈0.9. Self-consistent field theory reproduces the experimentally observed morphologies and demonstrates the templating of spirals in cylindrical-morphology block copolymer films.

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

    Kegel, Willem


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

  1. Self-assembling protein nanoparticles in the design of vaccines

    Directory of Open Access Journals (Sweden)

    Jacinto López-Sagaseta


    Full Text Available For over 100 years, vaccines have been one of the most effective medical interventions for reducing infectious disease, and are estimated to save millions of lives globally each year. Nevertheless, many diseases are not yet preventable by vaccination. This large unmet medical need demands further research and the development of novel vaccines with high efficacy and safety. Compared to the 19th and early 20th century vaccines that were made of killed, inactivated, or live-attenuated pathogens, modern vaccines containing isolated, highly purified antigenic protein subunits are safer but tend to induce lower levels of protective immunity. One strategy to overcome the latter is to design antigen nanoparticles: assemblies of polypeptides that present multiple copies of subunit antigens in well-ordered arrays with defined orientations that can potentially mimic the repetitiveness, geometry, size, and shape of the natural host-pathogen surface interactions. Such nanoparticles offer a collective strength of multiple binding sites (avidity and can provide improved antigen stability and immunogenicity. Several exciting advances have emerged lately, including preclinical evidence that this strategy may be applicable for the development of innovative new vaccines, for example, protecting against influenza, human immunodeficiency virus, and respiratory syncytial virus. Here, we provide a concise review of a critical selection of data that demonstrate the potential of this field. In addition, we highlight how the use of self-assembling protein nanoparticles can be effectively combined with the emerging discipline of structural vaccinology for maximum impact in the rational design of vaccine antigens.

  2. Semiconducting Self-Assembled Nanofibers Prepared from Photostable Octafluorinated Bisanthene Derivatives. (United States)

    Hayashi, Hironobu; Aratani, Naoki; Yamada, Hiroko


    Bisanthene is an important class of small two-dimensional polycyclic aromatic hydrocarbons with a zigzag-edged graphene nanoribbon character. Therefore, the functionalization and deep understanding of the structure-property relationship of bisanthene would provide an effective design for small organic molecular devices. In this study, octa- and tetrafluorinated bisanthene derivatives were synthesized for investigating the effect of electronegative fluorine substitution on the structure and physical property of bisanthene. Firstly, the octafluorinated bisanthene derivative has a twisted structure due to the steric repulsion of fluorine atoms at the bay region. Secondly, the absorption and fluorescence peak maxima are blueshifted with an increase in the degree of fluorine substitution. Notably, a triisopropylsilylethynyl-substituted octafluorinated derivative (F8) exhibited strong fluorescence at 657 nm with high fluorescence quantum yield (84 %). Additionally, cyclic voltammograms indicate the positive effect of fluorine substitution on the high highest occupied molecular orbital energy level of the molecules; thus, F8 molecule exhibited a remarkably increased photostability. Finally, the self-assembled behavior of fluorinated compounds was investigated by scanning electron microscopy and X-ray diffraction analysis. Specifically, F8 self-assembled to form bundles of long semicrystalline nanofibers exhibiting hole-transporting properties (3.4×10(-3)  cm(2)  V(-1)  s(-1) ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Development of self-assembling nanowires containing electronically active oligothiophenes (United States)

    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

  4. Physical principles of filamentous protein self-assembly kinetics (United States)

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


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

  5. Gold(I) catalysis at extreme concentrations inside self-assembled nanospheres. (United States)

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


    Homogeneous transition-metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mM or μM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M, inside well-defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mM levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular CO and CC bond-forming cyclization reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Novel Self-Assembly-Induced Gelation for Nanofibrous Collagen/Hydroxyapatite Composite Microspheres

    Directory of Open Access Journals (Sweden)

    Jae-Won Choi


    Full Text Available This study demonstrates the utility of the newly developed self-assembly-induced gelation technique for the synthesis of porous collagen/hydroxyapatite (HA composite microspheres with a nanofibrous structure. This new approach can produce microspheres of a uniform size using the droplets that form at the nozzle tip before gelation. These microspheres can have a highly nanofibrous structure due to the immersion of the droplets in a coagulation bath (water/acetone, in which the collagen aggregates in the solution can self-assemble into fibrils due to pH-dependent precipitation. Bioactive HA particles were incorporated into the collagen solutions, in order to enhance the bioactivity of the composite microspheres. The composite microspheres exhibited a well-defined spherical morphology and a uniform size for all levels of HA content (0 wt %, 10 wt %, 15 wt %, and 20 wt %. Collagen nanofibers—several tens of nanometers in size—were uniformly present throughout the microspheres and the HA particles were also well dispersed. The in vitro apatite-forming ability, assessed using the simulated body fluid (SBF solution, increased significantly with the incorporation of HA into the composite microspheres.

  7. Self-assembly of octadecyltrichlorosilane: Surface structures formed using different protocols of particle lithography

    Directory of Open Access Journals (Sweden)

    ChaMarra K. Saner


    Full Text Available Particle lithography offers generic capabilities for the high-throughput fabrication of nanopatterns from organosilane self-assembled monolayers, which offers the opportunity to study surface-based chemical reactions at the molecular level. Nanopatterns of octadecyltrichlorosilane (OTS were prepared on surfaces of Si(111 using designed protocols of particle lithography combined with either vapor deposition, immersion, or contact printing. Changing the physical approaches for applying molecules to masked surfaces produced OTS nanostructures with different shapes and heights. Ring nanostructures, nanodots and uncovered pores of OTS were prepared using three protocols, with OTS surface coverage ranging from 10% to 85%. Thickness measurements from AFM cursor profiles were used to evaluate the orientation and density of the OTS nanostructures. Differences in the thickness and morphology of the OTS nanostructures are disclosed based on atomic force microscopy (AFM images. Images of OTS nanostructures prepared on Si(111 that were generated by the different approaches provide insight into the self-assembly mechanism of OTS, and particularly into the role of water and solvents in hydrolysis and silanation.

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

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


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

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

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


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

  10. Self-Assembly of Human Serum Albumin: A Simplex Phenomenon (United States)

    Thakur, Garima; Prashanthi, Kovur; Jiang, Keren; Thundat, Thomas


    Spontaneous self-assemblies of biomolecules can generate geometrical patterns. Our findings provide an insight into the mechanism of self-assembled ring pattern generation by human serum albumin (HSA). The self-assembly is a process guided by kinetic and thermodynamic parameters. The generated protein ring patterns display a behavior which is geometrically related to a n-simplex model and is explained through thermodynamics and chemical kinetics. PMID:28930179

  11. Probabilistic Performance Guarantees for Distributed Self-Assembly

    KAUST Repository

    Fox, Michael J.


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

  12. Synthesis and self-assembly of complex hollow materials

    KAUST Repository

    Zeng, Hua Chun


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

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

    Bouchard, Ann M.; Osbourn, Gordon C.


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

  14. Protein-directed self-assembly of a fullerene crystal (United States)

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


    Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design. PMID:27113637

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

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


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

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

    Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor


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

  17. Nanostructured functional hybrid materials via self-assembly of brush block copolymers (United States)

    Song, Dong-Po; Gai, Yue; Yavitt, Benjamin; Watkins, James

    The self-assembly of well-ordered nanoparticle (NP) / block copolymer (BCP) composites enables precise control over the spatial distribution of NP arrays, providing a simple route to the low-cost ``bottom-up'' fabrication of hybrid materials with enhanced mechanical, optical and electric properties. Here we summarize the fabrication of nanocomposites via the self-assembly of brush BCPs (BBCPs). In comparison to conventional materials based on linear BCPs, the BBCP hybrids exhibit many attractive features, including rapid supramolecular self-assembly (100 nm), and high loading of functional additives (>70 wt%). Both the self-assembled structures and the compositions of the nanocomposites can be widely tuned for applications such as photonic crystals or coatings, nonlinear optics, and metamaterials. In addition, BBCPs were employed as templates for the mesoporous hybrid materials that have large mesopores (up to 40 nm) and high loadings of functional NPs (up to 50 wt%). Simple solutionbased processing and rapid self-assembly of brush BCP nanocomposites are promising for roll-to-roll manufacturing of low-cost and flexible devices. This work was supported by NSF Center for Hierarchical Manufacturing at the University of Massachusetts, Amherst.

  18. Self-Assembly through Noncovalent Preorganization of Reactants: Explaining the Formation of a Polyfluoroxometalate. (United States)

    Schreiber, Roy E; Avram, Liat; Neumann, Ronny


    High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H2 F6 NaW18 O56 ]7- from simple tungstate Na2 WO2 F4 was demonstrated by using 2D 19 F-19 F NOESY, 2D 19 F-19 F COSY NMR spectroscopy, a new 2D 19 F{183 W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Chemical and entropic control on the molecular self-assembly process (United States)

    Packwood, Daniel M.; Han, Patrick; Hitosugi, Taro


    Molecular self-assembly refers to the spontaneous assembly of molecules into larger structures. In order to exploit molecular self-assembly for the bottom-up synthesis of nanomaterials, the effects of chemical control (strength of the directionality in the intermolecular interaction) and entropic control (temperature) on the self-assembly process should be clarified. Here we present a theoretical methodology that unambiguously distinguishes the effects of chemical and entropic control on the self-assembly of molecules adsorbed to metal surfaces. While chemical control simply increases the formation probability of ordered structures, entropic control induces a variety of effects. These effects range from fine structure modulation of ordered structures, through to degrading large, amorphous structures into short, chain-shaped structures. Counterintuitively, the latter effect shows that entropic control can improve molecular ordering. By identifying appropriate levels of chemical and entropic control, our methodology can, therefore, identify strategies for optimizing the yield of desired nanostructures from the molecular self-assembly process. PMID:28195175

  20. Self-assembling multimeric nucleic acid constructs (United States)

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


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

  1. Self assembled structures for 3D integration (United States)

    Rao, Madhav

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

  2. Self-assembly of granular crystals (United States)

    Shattuck, Mark


    Acoustic meta-materials are engineered materials with the ability to control, direct, and manipulate sound waves. Since the 1990s, several groups have developed acoustic meta-materials with novel capabilities including negative index materials for acoustic super-lenses, phononic crystals with acoustic band gaps for wave guides and mirrors, and acoustic cloaking device. Most previous work on acoustic meta-materials has focused on continuum solids and fluids. In contrast, we report on coordinated computational and experimental studies to use macro-self-assembly of granular materials to produce acoustic meta-materials. The advantages of granular acoustic materials are three-fold: 1) Microscopic control: The discrete nature of granular media allows us to optimize acoustic properties on both the grain and network scales. 2) Tunability: The speed of sound in granular media depends strongly on pressure due to non-linear contact interactions and contact breaking. 3) Direct visualization: The macro-scale size of the grains enables visualization of the structure and stress propagation within granular assemblies. We report simulations and experiments of vibrated particles that form a variety of self-assembled ordered structures in two- and three-dimensions. In the simplest case of mono-disperse spheres, using a combination of pressure and vibration we produce crystals with long-range order on the scale of 100's of particles. Using special particle shapes that form ``lock and key'' structures we are able to make binary crystals with prescribed stoichiometries. We discuss the mechanical properties of these structures and methods to create more complicated structures.

  3. Quantifying the Self-Assembly Behavior of Anisotropic Nanoparticles Using Liquid-Phase Transmission Electron Microscopy. (United States)

    Luo, Binbin; Smith, John W; Ou, Zihao; Chen, Qian


    For decades, one of the overarching objectives of self-assembly science has been to define the rules necessary to build functional, artificial materials with rich and adaptive phase behavior from the bottom-up. To this end, the computational and experimental efforts of chemists, physicists, materials scientists, and biologists alike have built a body of knowledge that spans both disciplines and length scales. Indeed, today control of self-assembly is extending even to supramolecular and molecular levels, where crystal engineering and design of porous materials are becoming exciting areas of exploration. Nevertheless, at least at the nanoscale, there are many stones yet to be turned. While recent breakthroughs in nanoparticle (NP) synthesis have amassed a vast library of nanoscale building blocks, NP-NP interactions in situ remain poorly quantified, in large part due to technical and theoretical impediments. While increasingly many applications for self-assembled architectures are being demonstrated, it remains difficult to predict-and therefore engineer-the pathways by which these structures form. Here, we describe how investigations using liquid-phase transmission electron microscopy (TEM) have begun to play a role in pursuing some of these long-standing questions of fundamental and far-reaching interest. Liquid-phase TEM is unique in its ability to resolve the motions and trajectories of single NPs in solution, making it a powerful tool for studying the dynamics of NP self-assembly. Since 2012, liquid-phase TEM has been used to investigate the self-assembly behavior of a variety of simple, metallic NPs. In this Account, however, we focus on our work with anisotropic NPs, which we show to have very different self-assembly behavior, and especially on how analysis methods we and others in the field are developing can be used to convert their motions and trajectories revealed by liquid-phase TEM into quantitative understanding of underlying interactions and dynamics

  4. Self-assembly of tris(ureidobenzyl)amines: flexible bricks for robust architectures. (United States)

    Alajarin, Mateo; Orenes, Raul-Angel; Steed, Jonathan W; Pastor, Aurelia


    Despite their high degree of flexibility, tribenzylamine molecules endowed with one ureido group in every arm are avid self-assemblers with a high capacity for self-recognition. Narcissistic self-sorting or chiral self-discrimination events take place when two modules associate giving capsular aggregates. The size of the cavity may be modulated by the relative position of the ureido group and the amino function works as a pH switch of the rupture-reassembly process. When chiral racemic triureas are present the self-assembly is highly diastereoselective.

  5. Self-Assembly in the Ferritin Nano-Cage Protein Superfamily

    Directory of Open Access Journals (Sweden)

    Yu Zhang


    Full Text Available Protein self-assembly, through specific, high affinity, and geometrically constraining protein-protein interactions, can control and lead to complex cellular nano-structures. Establishing an understanding of the underlying principles that govern protein self-assembly is not only essential to appreciate the fundamental biological functions of these structures, but could also provide a basis for their enhancement for nano-material applications. The ferritins are a superfamily of well studied proteins that self-assemble into hollow cage-like structures which are ubiquitously found in both prokaryotes and eukaryotes. Structural studies have revealed that many members of the ferritin family can self-assemble into nano-cages of two types. Maxi-ferritins form hollow spheres with octahedral symmetry composed of twenty-four monomers. Mini-ferritins, on the other hand, are tetrahedrally symmetric, hollow assemblies composed of twelve monomers. This review will focus on the structure of members of the ferritin superfamily, the mechanism of ferritin self-assembly and the structure-function relations of these proteins.

  6. Self-Assembled Polyelectrolyte Nanoparticles as Fluorophore-Free Contrast Agents for Multicolor Optical Imaging

    Directory of Open Access Journals (Sweden)

    Da Hye Shin


    Full Text Available In this work, we describe the fabrication of self-assembled polyelectrolyte nanoparticles that provide a multicolor optical imaging modality. Poly(γ-glutamic acid(γ-PGA formed self-assembled nanoparticles through electrostatic interactions with two different cationic polymers: poly(L-lysine(PLL and chitosan. The self-assembled γ-PGA/PLL and γ-PGA/chitosan nanoparticles were crosslinked by glutaraldehyde. Crosslinking of the ionic self-assembled nanoparticles with glutaraldehyde not only stabilized the nanoparticles but also generated a strong autofluorescence signal. Fluorescent Schiff base bonds (C=N and double bonds (C=C were generated simultaneously by crosslinking of the amine moiety of the cationic polyelectrolytes with monomeric glutaraldehyde or with polymeric glutaraldehyde. The unique optical properties of the nanoparticles that resulted from the crosslinking by glutaraldehyde were analyzed using UV/Vis and fluorescence spectroscopy. We observed that the fluorescence intensity of the nanoparticles could be regulated by adjusting the crosslinker concentration and the reaction time. The nanoparticles also exhibited high performance in the labeling and monitoring of therapeutic immune cells (macrophages and dendritic cells. These self-assembled nanoparticles are expected to be a promising multicolor optical imaging contrast agent for the labeling, detection, and monitoring of cells.

  7. Biomimetic Branched Hollow Fibers Templated by Self-assembled Fibrous Polyvinylpyrrolidone (PVP) Structures in Aqueous Solution (United States)

    Qiu, Penghe; Mao, Chuanbin


    Branched hollow fibers are common in nature, but to form artificial fibers with a similar branched hollow structure is still a challenge. We discovered that polyvinylpyrrolidone (PVP) could self-assemble into branched hollow fibers in an aqueous solution after aging the PVP solution for about two weeks. Based on this finding, we demonstrated two approaches by which the self-assembly of PVP into branched hollow fibers could be exploited to template the formation of branched hollow inorganic fibers. First, inorganic material such as silica with high affinity against the PVP could be deposited on the surface of the branched hollow PVP fibers to form branched hollow silica fibers. To extend the application of PVP self-assembly in templating the formation of hollow branched fibers, we then adopted a second approach where the PVP molecules bound to inorganic nanoparticles (using gold nanoparticles as a model) co-self-assemble with the free PVP molecules in an aqueous solution, resulting in the formation of the branched hollow fibers with the nanoparticles embedded in the PVP matrix constituting the walls of the fibers. Heating the resultant fibers above the glass transition temperature of PVP led to the formation of branched hollow gold fibers. Our work suggests that the self-assembly of the PVP molecules in the solution can serve as a general method for directing the formation of branched hollow inorganic fibers. The branched hollow fibers may find potential applications in microfluidics, artificial blood vessel generation, and tissue engineering. PMID:20158250

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

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


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

  9. Ionic self-assembly for functional hierarchical nanostructured materials. (United States)

    Faul, Charl F J


    , specifically deoxyguanosine monophosphate. This approach proved, in combination with block copolymer (BCP) self-assembly, very fruitful for the construction of complex and hierarchical functional materials across multiple length scales. Molecular frustration and incommensurability, which played a major role in structure formation in combination with nucleotide assembly, have now become important tools to tune supramolecular structure formation. These concepts, that is, the use of BCP assembly and incommensurability, in combination with metal-containing polymeric materials, have provided access to novel supramolecular morphologies and, more importantly, design rules to prepare such constructs. These design rules are now also being applied to the assembly of electroactive oligo(aniline)-based materials for the preparation of highly ordered functional soft materials, and present an opportunity for materials development for applications in energy storage. In this Account, we therefore discuss investigations into (i) the inclusion and preparation of supramolecular photoactive and electroactive materials; (ii) the exploitation and control over multiple noncovalent interactions to fine-tune function, internal structure, and long-range order and (iii) exploration of construction over multiple length scales by combination of ISA with well-known BCP self-assembly. Combination of ISA with tuning of volume fractions, mutual compatibility, and molecular frustration now provides a versatile tool kit to construct complex and hierarchical functional materials in a facile noncovalent way. A direct challenge for future ISA activities would certainly be the construction of functional mesoscale objects. However, within a broader scientific context, the challenge would be to exploit this powerful assembly tool for application in areas of research with societal impact, for example, energy storage and generation. The hope is that this Account will provide a platform for such future research

  10. Aromatic Cross-Strand Ladders Control the Structure and Stability of [beta]-Rich Peptide Self-Assembly Mimics

    Energy Technology Data Exchange (ETDEWEB)

    Biancalana, Matthew; Makabe, Koki; Koide, Akiko; Koide, Shohei (UC)


    Though {beta}-rich self-assemblies comprise a major structural class of polypeptides, a detailed understanding of the determinants of their structure and stability is lacking. In particular, the roles of repetitive stretches of side chains running the long axis of these {beta}-sheets, termed 'cross-strand ladders,' remain poorly characterized due to the inherently insoluble and heterogeneous nature of self-assemblies. To overcome these experimental challenges, we have established a complementary experimental system termed 'peptide self-assembly mimics' (PSAMs). The PSAMs capture a defined number of self-assembly-like peptide repeats within a soluble {beta}-rich protein, making structural and energetic studies possible. In this work, we investigated the role of cross-strand ladders containing aromatic residues, which are prominent in self-assembling peptides. A combination of solution data and high-resolution crystal structures revealed that a single cross-strand ladder consisting solely of Tyr significantly stabilized, rigidified, and flattened the PSAM {beta}-sheet. These characteristics would stabilize each {beta}-sheet layer of a self-assembly and direct sheet conformations compatible with lamination. Our results therefore provide a rationale for the abundance of aromatic amino acids in fibril-forming peptides and establish important roles of cross-strand Tyr ladders in the structure and stability of {beta}-rich peptide self-assemblies.

  11. Topological defects in liquid crystals as templates for molecular self-assembly (United States)

    Wang, Xiaoguang; Miller, Daniel S.; Bukusoglu, Emre; de Pablo, Juan J.; Abbott, Nicholas L.


    Topological defects in liquid crystals (LCs) have been widely used to organize colloidal dispersions and template polymerization, leading to a range of assemblies, elastomers and gels. However, little is understood about molecular-level assembly processes within defects. Here, we report that nanoscopic environments defined by LC topological defects can selectively trigger processes of molecular self-assembly. By using fluorescence microscopy, cryogenic transmission electron microscopy and super-resolution optical microscopy, we observed signatures of molecular self-assembly of amphiphilic molecules in topological defects, including cooperativity, reversibility and controlled growth. We also show that nanoscopic o-rings synthesized from Saturn-ring disclinations and other molecular assemblies templated by defects can be preserved by using photocrosslinkable amphiphiles. Our results reveal that, in analogy to other classes of macromolecular templates such as polymer-surfactant complexes, topological defects in LCs are a versatile class of three-dimensional, dynamic and reconfigurable templates that can direct processes of molecular self-assembly.

  12. Electronic structure and self-assembling processes in platinum metalloporphyrins: photoemission and AFM studies (United States)

    Belogorokhov, A. I.; Bozhko, S. I.; Chaika, A. N.; Ionov, A. M.; Trophimov, S. A.; Rumiantseva, V. D.; Vyalikh, D.


    The main goal of this paper is to investigate the electronic structure of valence band and core levels as well as surface topography of pristine tetraphenylporphyrin and Pt-based compounds Pt-TPP(p-COOH3)4, Pt-TPP(m-OCH3)4, PtCl2-TPP(m-OCH3)4 thin films. The electronic structure of various Pt-based metalloporphyrins which were investigated in dependence on their chemical structure and spectra were measured by high-resolution X-ray photoelectron spectroscopy (XPS) of valence band and Pt4f, Pt4d, C1s, O1s, N1s core levels. Results of atomic force microscopy (AFM) studies of topography and self-assembling processes in thin films of porphyrines are presented and discussed.

  13. Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy (United States)

    Lin, Tao

    Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin

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

    NARCIS (Netherlands)

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


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

  15. Self-assembled Nanomaterials for Hybrid Electronic and Photonic Systems (United States)


    Self-assembled Nanomaterials for Hybrid Electronic and Photonic Systems This grant studied DNA nanostructures and their applications in a variety of...Number of Papers published in non peer-reviewed journals: Final Report: Self-assembled Nanomaterials for Hybrid Electronic and Photonic Systems Report

  16. Combinatoric and mean field analysis of heterogeneous self assembly (United States)


    REPORT Combinatoric and mean-field analysis of heterogeneous self-assembly 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: We present a stochastic analysis... Combinatoric and mean-field analysis of heterogeneous self-assembly Report Title ABSTRACT We present a stochastic analysis of heterogeneous

  17. Mechanisms of formation of self-assembled nanostructures in heteroepitaxy

    NARCIS (Netherlands)

    Kotrla, M.; Much, F.; Volkmann, T.; Biehl, M.; Sandera, P.


    We briefly review the recent results on formation of self-assembled nanostructures during heteroepitaxy of immiscible metals. The methods of microscopic modelling of multicomponent growth are described. Results of simulation of self-assembled structures with alternating strips using both lattice and

  18. Scalable Directed Self-Assembly Using Ultrasound Waves (United States)


    at Aberdeen Proving Grounds (APG), to discuss a possible collaboration. The idea is to integrate the ultrasound directed self- assembly technique ...difference between the ultrasound technology studied in this project, and other directed self-assembly techniques is its scalability and...deliverable: A scientific tool to predict particle organization, pattern, and orientation, based on the operating and design parameters of the ultrasound

  19. Self-Assembly of Magnetic Colloids in Soft Confinement

    NARCIS (Netherlands)

    Liu, P.


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

  20. Self-assembly of hydrolysed α-lactalbumin into nanotubes

    NARCIS (Netherlands)

    Graveland-Bikker, Johanna Frederike


    Self-assembly of proteins, peptides and DNA is a powerful approach for fabricating novel supramolecular architectures. Via this "bottom-up" approach many new nanomaterials have been and will be produced. Building blocks that self-assemble into fibrous materials are of special interest, because

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

    Indian Academy of Sciences (India)

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

  2. An approach to self-assembling swarm robots using multitree genetic programming. (United States)

    Lee, Jong-Hyun; Ahn, Chang Wook; An, Jinung


    In recent days, self-assembling swarm robots have been studied by a number of researchers due to their advantages such as high efficiency, stability, and scalability. However, there are still critical issues in applying them to practical problems in the real world. The main objective of this study is to develop a novel self-assembling swarm robot algorithm that overcomes the limitations of existing approaches. To this end, multitree genetic programming is newly designed to efficiently discover a set of patterns necessary to carry out the mission of the self-assembling swarm robots. The obtained patterns are then incorporated into their corresponding robot modules. The computational experiments prove the effectiveness of the proposed approach.

  3. Self-assembly of three-legged patchy particles into polyhedral cages (United States)

    den Otter, Wouter K.; Renes, Marten R.; Briels, W. J.


    The self-assembly of rigid three-legged building blocks into polyhedral cages is investigated by patchy particle simulations. A four-site anisotropic interaction potential is introduced to make pairs of overlapping legs bind in an anti-parallel fashion, thereby forming the edges of a polyhedron of pentagons and hexagons. A torsional potential, reflecting an asymmetry or polarity in the legs' binding potential, proves crucial for the successful formation of closed fullerene-like cages. Self-assembly proceeds by a nucleation-and-growth mechanism, with a high success rate of cage closure. The size distribution of the self-assembled buckyballs is largely determined by the pucker angle of the particle. Nature explores a similar building block, the clathrin triskelion, to regulate vesicle formation at the cell membrane during endocytosis.

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

    KAUST Repository

    Yu, Haizhou


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

  5. Solvent mediated self-assembly of solids

    Energy Technology Data Exchange (ETDEWEB)

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


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

  6. Charge conduction and breakdown mechanisms in self-assembled nanodielectrics. (United States)

    DiBenedetto, Sara A; Facchetti, Antonio; Ratner, Mark A; Marks, Tobin J


    Developing alternative high dielectric constant (k) materials for use as gate dielectrics is essential for continued advances in conventional inorganic CMOS and organic thin film transistors (OTFTs). Thicker films of high-k materials suppress tunneling leakage currents while providing effective capacitances comparable to those of thin films of lower-k materials. Self-assembled monolayers (SAMs) and multilayers offer attractive options for alternative OTFT gate dielectrics. One class of materials, organosilane-based self-assembled nanodielectrics (SANDs), has been shown to form robust films with excellent insulating and surface passivation properties, enhancing both organic and inorganic TFT performance and lowering device operating voltages. Since gate leakage current through the dielectric is one factor limiting continued TFT performance improvements, we investigate here the current (voltage, temperature) (I (V,T)) transport characteristics of SAND types II (pi-conjugated layer) and III (sigma-saturated + pi-conjugated layers) in Si/native SiO(2)/SAND/Au metal-insulator-metal (MIS) devices over the temperature range -60 to +100 degrees C. It is found that the location of the pi-conjugated layer with respect to the Si/SiO(2) substrate surface in combination with a saturated alkylsilane tunneling barrier is crucial in controlling the overall leakage current through the various SAND structures. For small applied voltages, hopping transport dominates at all temperatures for the pi-conjugated system (type II). However, for type III SANDs, the sigma- and pi-monolayers dominate the transport in two different transport regimes: hopping between +25 degrees C and +100 degrees C, and an apparent switch to tunneling for temperatures below 25 degrees C. The sigma-saturated alkylsilane tunneling barrier functions to reduce type III current leakage by blocking injected electrons, and by enabling bulk-dominated (Poole-Frenkel) transport vs electrode-dominated (Schottky) transport

  7. Charge Conduction and Breakdown Mechanisms in Self-Assembled Nanodielectrics

    Energy Technology Data Exchange (ETDEWEB)

    DiBenedetto, S.; Facchetti, A; Ratner, M; Marks, T


    Developing alternative high dielectric constant (k) materials for use as gate dielectrics is essential for continued advances in conventional inorganic CMOS and organic thin film transistors (OTFTs). Thicker films of high-k materials suppress tunneling leakage currents while providing effective capacitances comparable to those of thin films of lower-k materials. Self-assembled monolayers (SAMs) and multilayers offer attractive options for alternative OTFT gate dielectrics. One class of materials, organosilane-based self-assembled nanodielectrics (SANDs), has been shown to form robust films with excellent insulating and surface passivation properties, enhancing both organic and inorganic TFT performance and lowering device operating voltages. Since gate leakage current through the dielectric is one factor limiting continued TFT performance improvements, we investigate here the current (voltage, temperature) (I (V,T)) transport characteristics of SAND types II ({Pi}-conjugated layer) and III ({sigma}-saturated + {Pi}-conjugated layers) in Si/native SiO{sub 2}/SAND/Au metal-insulator-metal (MIS) devices over the temperature range -60 to +100 C. It is found that the location of the {Pi}-conjugated layer with respect to the Si/SiO{sub 2} substrate surface in combination with a saturated alkylsilane tunneling barrier is crucial in controlling the overall leakage current through the various SAND structures. For small applied voltages, hopping transport dominates at all temperatures for the {Pi}-conjugated system (type II). However, for type III SANDs, the {sigma}- and {Pi}- monolayers dominate the transport in two different transport regimes: hopping between +25 C and +100 C, and an apparent switch to tunneling for temperatures below 25 C. The {sigma}-saturated alkylsilane tunneling barrier functions to reduce type III current leakage by blocking injected electrons, and by enabling bulk-dominated (Poole-Frenkel) transport vs electrode-dominated (Schottky) transport in

  8. Self-assembled fibre optoelectronics with discrete translational symmetry. (United States)

    Rein, Michael; Levy, Etgar; Gumennik, Alexander; Abouraddy, Ayman F; Joannopoulos, John; Fink, Yoel


    Fibres with electronic and photonic properties are essential building blocks for functional fabrics with system level attributes. The scalability of thermal fibre drawing approach offers access to large device quantities, while constraining the devices to be translational symmetric. Lifting this symmetry to create discrete devices in fibres will increase their utility. Here, we draw, from a macroscopic preform, fibres that have three parallel internal non-contacting continuous domains; a semiconducting glass between two conductors. We then heat the fibre and generate a capillary fluid instability, resulting in the selective transformation of the cylindrical semiconducting domain into discrete spheres while keeping the conductive domains unchanged. The cylindrical-to-spherical expansion bridges the continuous conducting domains to create ∼10 4 self-assembled, electrically contacted and entirely packaged discrete spherical devices per metre of fibre. The photodetection and Mie resonance dependent response are measured by illuminating the fibre while connecting its ends to an electrical readout.

  9. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers (United States)

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping


    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10-15 cm2 s-1, 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value.

  10. Principles Governing the Self Assembly of Polypeptide Nanoparticles (United States)

    Wahome, Newton

    Self assembling systems on the nanometer scale afford the advantage of being able to control submicron level events. In this study, we focus on the self-assembling polypeptide nanoparticles (SAPN). The SAPN scaffold is made up of oligomerizing domains that align along the principle rotational axes of icosahedral symmetry. By aligning them along these axes, a particle with spherical geometry can be achieved. This particle can be utilized as a vaccine, as a drug delivery vehicle, or as a biomedical imaging device. This research will try to answer why the SAPN self-assembles into distinct molecular weight ranges while mostly maintaining a spherical morphology. The first means will be theoretical and computational, where we will utilize a mathematical formalism to find out how the packing of SAPN's monomeric units can occur within symmetric space. Then molecular dynamics will be run within this symmetric space to test the per amino acid residue susceptibility of SAPN towards becoming polymorphic in nature. Means for examining the aggregation propensity of SAPN will be also be tested. Specifically, the relationship of different sequences of SAPN with pH will be elucidated. Co-assembly of SAPN to reduce the surface density of an aggregation prone epitope will be tested. Also, aggregation reduction consisting of the exchange of an anionic denaturant with a positively charged suppressor in order to mitigate a priori peptide association and misfolding, will also be attempted. SAPN has been shown to be an immunogenic platform for the presentation of pathogen derived antigens. We will attempt to show the efficacy of presenting an antigen from HIV-1 which is structurally restrained to best match the native conformation on the virus. Immunological studies will be performed to test the effect of this approach, as well testing the antigenicity of the nanoparticle in the absence of adjuvant. Finally, the antigen presenting nanoparticles will undergo formulation testing, to measure

  11. Hypermodular Self-Assembling Space Solar Power -- Design Option for Mid-Term GEO Utility-Scale Power Plants

    CERN Document Server

    Leitgab, Martin


    This paper presents a design for scaleable space solar power systems based on free-flying reflectors and module self-assembly. Lower system cost of utility-scale space solar power is achieved by design independence of yet-to-be-built in-space assembly or transportation infrastructure. Using current and expected near-term technology, this study describe a design for mid-term utility-scale power plants in geosynchronous orbits. High-level economic considerations in the context of current and expected future launch costs are given as well.

  12. Characterization of self-assembled electrodes based on Au-Pt nanoparticles for PEMFC application

    Energy Technology Data Exchange (ETDEWEB)

    Valenzuela, E. [Politecnica Univ. de Chiapas, Tuxtla Gutierrez, Chiapas (Mexico). Energia y Sustentabilidad; Sebastian, P.J. [Politecnica Univ. de Chiapas, Chiapas (Mexico). Energia y Sustentabilidad; Centro de Investigacion en Energia, UNAM, Morelos (Mexico); Gamboa, S.A. [Centro de Investigacion en Energia, UNAM, Morelos (Mexico); Pal, U. [Inst. de Fisica, Universidad Autonoma de Puebla Univ., Puebla (Mexico). Inst. de Fisica; Gonzalez, I. [Autonoma Metropolitana Univ. (Mexico). Dept. de Quimica


    This paper reported on a study in which membrane electrode assemblies (MEAs) were fabricated by depositing Au, Pt and AuPt nanoparticles on Nafion 115 membrane for use in a proton exchange membrane fuel cell (PEMFC). A Rotating Disc Electrode (RDE) was used to measure the nanoparticle catalyst activity. After deposition of the nanoparticles on the membrane, the surface was studied by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The membrane proton conduction process was studied by Electrochemical Impedance Spectroscopy (EIS) with the 4 probe technique. The MEAs fabricated with Nafion/Metal membranes were evaluated in a PEMFC under standard conditions. Colloidal solutions were used to prepare self-assembled electrodes with nanoparticles deposited on Nafion membrane. The particles deposited on Nafion showed good stability and had homogeneous distribution along the membrane surface. The impedance results revealed an increase in the membrane proton resistance of the self-assembled electrodes compared to unmodified Nafion. The Au-Pt nanoparticles were obtained by chemical reduction. The nanoparticle size in the three systems was about 2 nm. The self-assembled electrodes performed well in standard conditions. The optimum colloidal concentration and immersion time must be determined in order to obtain good catalytic activity and high membrane conductance. The self-assembled Nafion/AuPt had the best open circuit potential (887 mV). The Au and Pt self-assemblies showed a similar performance in terms of maximum power and maximum current density. The performance of the Nafion/Au self-assembly was influenced more by ohmic losses, particularly in the membrane. The maximum power generation was obtained at 0.35 V. The mass transport losses increased after this value, thereby affecting the efficiency of the PEMFC. 2 figs.

  13. Initial condition of stochastic self-assembly. (United States)

    Davis, Jason K; Sindi, Suzanne S


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

  14. What promotes derected self assembly (DSA)?

    Energy Technology Data Exchange (ETDEWEB)

    Nakagawa, S.T.


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

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

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


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

  16. Self-assembly models for lipid mixtures (United States)

    Singh, Divya; Porcar, Lionel; Butler, Paul; Perez-Salas, Ursula


    Solutions of mixed long and short (detergent-like) phospholipids referred to as ``bicelle'' mixtures in the literature, are known to form a variety of different morphologies based on their total lipid composition and temperature in a complex phase diagram. Some of these morphologies have been found to orient in a magnetic field, and consequently bicelle mixtures are widely used to study the structure of soluble as well as membrane embedded proteins using NMR. In this work, we report on the low temperature phase of the DMPC and DHPC bicelle mixture, where there is agreement on the discoid structures but where molecular packing models are still being contested. The most widely accepted packing arrangement, first proposed by Vold and Prosser had the lipids completely segregated in the disk: DHPC in the rim and DMPC in the disk. Using data from small angle neutron scattering (SANS) experiments, we show how radius of the planar domain of the disks is governed by the effective molar ratio qeff of lipids in aggregate and not the molar ratio q (q = [DMPC]/[DHPC] ) as has been understood previously. We propose a new quantitative (packing) model and show that in this self assembly scheme, qeff is the real determinant of disk sizes. Based on qeff , a master equation can then scale the radii of disks from mixtures with varying q and total lipid concentration.

  17. Strongly coupled plasmonic modes on macroscopic areas via template-assisted colloidal self-assembly. (United States)

    Hanske, Christoph; Tebbe, Moritz; Kuttner, Christian; Bieber, Vera; Tsukruk, Vladimir V; Chanana, Munish; König, Tobias A F; Fery, Andreas


    We present ensembles of surface-ordered nanoparticle arrangements, which are formed by template-assisted self-assembly of monodisperse, protein-coated gold nanoparticles in wrinkle templates. Centimeter-squared areas of highly regular, linear assemblies with tunable line width are fabricated and their extinction cross sections can be characterized by conventional UV/vis/NIR spectroscopy. Modeling based on electrodynamic simulations shows a clear signature of strong plasmonic coupling with an interparticle spacing of 1-2 nm. We find evidence for well-defined plasmonic modes of quasi-infinite chains, such as resonance splitting and multiple radiant modes. Beyond elementary simulations on the individual chain level, we introduce an advanced model, which considers the chain length distribution as well as disorder. The step toward macroscopic sample areas not only opens perspectives for a range of applications in sensing, plasmonic light harvesting, surface enhanced spectroscopy, and information technology but also eases the investigation of hybridization and metamaterial effects fundamentally.

  18. Self assembled silicon nanowire Schottky junction assisted by collagen (United States)

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


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

  19. Characterization of the Casein/Keratin Self-Assembly Nanomicelles

    Directory of Open Access Journals (Sweden)

    Su Xiao-Zhou


    Full Text Available Complex nanomicelles were made from casein and keratin through electrostatic self-assembly and transglutaminase fixation that was proved to be harmless and green. The complex nanomicelles were characterized by dynamic light scattering, scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and steady-state florescence. The results show that the complex nanomcelles acquired at the neutral pH in the mass ratio of casein to keratin 4 : 1 exhibit an anomalous sphere shape with uniform size which the diameter is about 40–70 nm. The complex nanomicelles in solution possess excellent dilution and storage stability due to the fixation and their high ζ-potential (22.8 mV. The complex nanomicelles are relatively hydrophilic and have a good potential for industrial application.

  20. Toward Single Electron Nanoelectronics Using Self-Assembled DNA Structure. (United States)

    Tapio, Kosti; Leppiniemi, Jenni; Shen, Boxuan; Hytönen, Vesa P; Fritzsche, Wolfgang; Toppari, J Jussi


    DNA based structures offer an adaptable and robust way to develop customized nanostructures for various purposes in bionanotechnology. One main aim in this field is to develop a DNA nanobreadboard for a controllable attachment of nanoparticles or biomolecules to form specific nanoelectronic devices. Here we conjugate three gold nanoparticles on a defined size TX-tile assembly into a linear pattern to form nanometer scale isolated islands that could be utilized in a room temperature single electron transistor. To demonstrate this, conjugated structures were trapped using dielectrophoresis for current-voltage characterization. After trapping only high resistance behavior was observed. However, after extending the islands by chemical growth of gold, several structures exhibited Coulomb blockade behavior from 4.2 K up to room temperature, which gives a good indication that self-assembled DNA structures could be used for nanoelectronic patterning and single electron devices.

  1. Advantages of Catalysis in Self-Assembled Molecular Capsules. (United States)

    Catti, Lorenzo; Zhang, Qi; Tiefenbacher, Konrad


    Control over the local chemical environment of a molecule can be achieved by encapsulation in supramolecular host systems. In supramolecular catalysis, this control is used to gain advantages over classical homogeneous catalysis in bulk solution. Two of the main advantages concern influencing reactions in terms of substrate and product selectivity. Due to size and/or shape recognition, substrate selective conversion can be realized. Additionally, noncovalent interactions with the host environment facilitate alternative reaction pathways and can yield unusual products. This Concept article discusses and highlights literature examples utilizing self-assembled molecular capsules to achieve catalytic transformations displaying a high degree of substrate and/or product selectivity. Furthermore, the advantage of supramolecular hosts in multicatalyst tandem reactions is covered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Gold electrode modified by self-assembled monolayers of thiols to ...

    Indian Academy of Sciences (India)

    The process of immobilization of biological molecules is one of the most important steps in the construction of a biosensor. In the case of DNA, the way it exposes its bases can result in electrochemical signals to acceptable levels. The use of self-assembled monolayer that allows a connection to the gold thiol group and ...

  3. Fabrication of bioinspired nanostructured materials via colloidal self-assembly (United States)

    Huang, Wei-Han

    Through millions of years of evolution, nature creates unique structures and materials that exhibit remarkable performance on mechanicals, opticals, and physical properties. For instance, nacre (mother of pearl), bone and tooth show excellent combination of strong minerals and elastic proteins as reinforced materials. Structured butterfly's wing and moth's eye can selectively reflect light or absorb light without dyes. Lotus leaf and cicada's wing are superhydrophobic to prevent water accumulation. The principles of particular biological capabilities, attributed to the highly sophisticated structures with complex hierarchical designs, have been extensively studied. Recently, a large variety of novel materials have been enabled by natural-inspired designs and nanotechnologies. These advanced materials will have huge impact on practical applications. We have utilized bottom-up approaches to fabricate nacre-like nanocomposites with "brick and mortar" structures. First, we used self-assembly processes, including convective self-assembly, dip-coating, and electrophoretic deposition to form well oriented layer structure of synthesized gibbsite (aluminum hydroxide) nanoplatelets. Low viscous monomer was permeated into layered nanoplatelets and followed by photo-curing. Gibbsite-polymer composite displays 2 times higher tensile strength and 3 times higher modulus when compared with pure polymer. More improvement occurred when surface-modified gibbsite platelets were cross-linked with the polymer matrix. We observed ˜4 times higher strength and nearly 1 order of magnitude higher modulus than pure polymer. To further improve the mechanical strength and toughness of inorganicorganic nanocomposites, we exploited ultrastrong graphene oxide (GO), a single atom thick hexagonal carbon sheet with pendant oxidation groups. GO nanocomposite is made by co-filtrating GO/polyvinyl alcohol suspension on 0.2 im pore-sized membrane. It shows ˜2 times higher strength and ˜15 times higher

  4. Enzyme-assisted self-assembly under thermodynamic control. (United States)

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


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

  5. Nanosystem Self-Assembly Pathways Discovered via All-Atom Multiscale Analysis (United States)

    Pankavich, Stephen D.; Ortoleva, Peter J.


    We consider the self-assembly of composite structures from a group of nanocomponents, each consisting of particles within an N-atom system. Self-assembly pathways and rates for nanocomposites are derived via a multiscale analysis of the classical Liouville equation. From a reduced statistical framework, rigorous stochastic equations for population levels of beginning, intermediate, and final aggregates are also derived. It is shown that the definition of an assembly type is a self-consistency criterion that must strike a balance between precision and the need for population levels to be slowly varying relative to the timescale of atomic motion. The deductive multiscale approach is complemented by a qualitative notion of multicomponent association and the ensemble of exact atomic-level configurations consistent with them. In processes such as viral self-assembly from proteins and RNA or DNA, there are many possible intermediates so that it is usually difficult to predict the most efficient assembly pathway. However, in the current study rates of assembly of each possible intermediate can be predicted. This avoids the need, as in a phenomenological approach, for recalibration with each new application. The method accounts for the feedback across scales in space and time that is fundamental to nanosystem self-assembly. The theory has applications to bionanostructures, geomaterials, engineered composites, and nanocapsule therapeutic delivery systems. PMID:22372746

  6. Guided self-assembly of nanostructured titanium oxide (United States)

    Wang, Baoxiang; Rozynek, Zbigniew; Fossum, Jon Otto; Knudsen, Kenneth D.; Yu, Yingda


    A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiOx nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiOx nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiOx nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiOx nanorods with rough surfaces are formed by the self-assembly of TiOx nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiOx nanorods shows stronger ER properties than that of the other nanostructured TiOx particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.

  7. Self-assembling hybrid diamond-biological quantum devices (United States)

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


    The realization of scalable arrangements of nitrogen vacancy (NV) centers in diamond remains a key challenge on the way towards efficient quantum information processing, quantum simulation and quantum sensing applications. Although technologies based on implanting NV-centers in bulk diamond crystals or hybrid device approaches have been developed, they are limited by the achievable spatial resolution and by the intricate technological complexities involved in achieving scalability. We propose and demonstrate a novel approach for creating an arrangement of NV-centers, based on the self-assembling capabilities of biological systems and their beneficial nanometer spatial resolution. Here, a self-assembled protein structure serves as a structural scaffold for surface functionalized nanodiamonds, in this way allowing for the controlled creation of NV-structures on the nanoscale and providing a new avenue towards bridging the bio-nano interface. One-, two- as well as three-dimensional structures are within the scope of biological structural assembling techniques. We realized experimentally the formation of regular structures by interconnecting nanodiamonds using biological protein scaffolds. Based on the achievable NV-center distances of 11 nm, we evaluate the expected dipolar coupling interaction with neighboring NV-centers as well as the expected decoherence time. Moreover, by exploiting these couplings, we provide a detailed theoretical analysis on the viability of multiqubit quantum operations, suggest the possibility of individual addressing based on the random distribution of the NV intrinsic symmetry axes and address the challenges posed by decoherence and imperfect couplings. We then demonstrate in the last part that our scheme allows for the high-fidelity creation of entanglement, cluster states and quantum simulation applications.

  8. Rapid, Brushless Self-assembly of a PS-b-PDMS Block Copolymer for Nanolithography

    DEFF Research Database (Denmark)

    Rasappa, Sozaraj; Schulte, Lars; Borah, Dipu


    Block copolymers (BCP) are highly promising self-assembling precursors for scalable nanolithography. Very regular BCP nanopatterns can be used as on-chip etch masks. The first step in the processing of BCP thin films is usually the chemical modification of the substrate surface, typically by graf...

  9. Self-assembled monolayers with biospecific affinity for lactate dehydrogenase for the electroenzymatic oxidation of lactate

    NARCIS (Netherlands)

    Schlereth, Daniela D.; Kooyman, R.P.H.


    Surface modified gold electrodes with high biospecific affinity for NAD(H)-dependent lactate dehydrogenase have been prepared by covalent attachment of several traizine dyes to stepwise functionalized mixed alkanethiol self-assembled monolayers. The biospecific affinity of such ligand-anchored

  10. Selective self-organization of guest molecules in self-assembled molecular boxes

    NARCIS (Netherlands)

    Kerckhoffs, J.M.C.A.; ten Cate, M.G.J.; Mateos timoneda, Miguel; van Leeuwen, F.W.B.; Ruel, Bianca H.M.; Spek, Anthony L.; Kooijman, Huub; Crego Calama, Mercedes; Reinhoudt, David


    This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 13·(DEB)6 and 33·(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix[4]arene dimelamine derivative molecules (1 or

  11. Magnetic manipulation of self-assembled colloidal asters.

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

  13. Self-Assembly and Crystallization of Conjugated Block Copolymers (United States)

    Davidson, Emily Catherine

    This dissertation demonstrates the utility of molecular design in conjugated polymers to create diblock copolymers that robustly self-assemble in the melt and confine crystallization upon cooling. This work leverages the model conjugated polymer poly(3-(2'-ethyl)hexylthiophene) (P3EHT), which features a branched side chain, resulting in a dramatically reduced melting temperature (Tm 80°C) relative to the widely-studied poly(3-hexylthiophene) (P3HT) (Tm 200°C). This reduced melting temperature permits an accessible melt phase, without requiring that the segregation strength (chiN) be dramatically increased. Thus, diblock copolymers containing P3EHT demonstrate robust diblock copolymer self-assembly in the melt over a range of compositions and morphologies. Furthermore, confined crystallization in the case of both glassy (polystyrene (PS) matrix block) and soft (polymethylacrylate (PMA) matrix block) confinement is studied, with the finding that even in soft confinement, crystallization is constrained within the diblock microdomains. This success demonstrates the strategy of leveraging molecular design to decrease the driving force for crystallization as a means to achieving robust self-assembly and confined crystallization in conjugated block copolymers. Importantly, despite the relatively flexible nature of P3EHT in the melt, the diblock copolymer phase behavior appears to be significantly impacted by the stiffness (persistence length of 3 nm) of the P3EHT chain compared to the coupled amorphous blocks (persistence length 0.7 nm). In particular, it is shown that the synthesized morphologies are dominated by a very large composition window for lamellar geometries (favored at high P3EHT volume fractions); cylindrical geometries are favored when P3EHT is the minority fraction. This asymmetry of the composition window is attributed to impact of conformational asymmetry (the difference in chain stiffness, as opposed to shape) between conjugated and amorphous blocks

  14. Self-assembly and continuous growth of hexagonal graphene flakes on liquid Cu. (United States)

    Cho, Seong-Yong; Kim, Min-Sik; Kim, Minsu; Kim, Ki-Ju; Kim, Hyun-Mi; Lee, Do-Joong; Lee, Sang-Hoon; Kim, Ki-Bum


    Graphene growth on liquid Cu has received great interest, owing to the self-assembly behavior of hexagonal graphene flakes with aligned orientation and to the possibility of forming a single grain of graphene through a commensurate growth of these graphene flakes. Here, we propose and demonstrate a two-step growth process which allows the formation of self-assembled, completely continuous graphene on liquid Cu. After the formation of full coverage on the liquid Cu, grain boundaries were revealed via selective hydrogen etching and the original grain boundaries were clearly resolved. This result indicates that, while the flakes self-assembled with the same orientation, there still remain structural defects, gaps and voids that were not resolved by optical microscopy or scanning electron microscopy. To overcome this limitation, the two-step growth process was employed, consisting of a sequential process of a normal single-layer graphene growth and self-assembly process with a low carbon flux, followed by the final stage of graphene growth at a high degree of supersaturation with a high carbon flux. Continuity of the flakes was verified via hydrogen etching and a NaCl-assisted oxidation process, as well as by measuring the electrical properties of the graphene grown by the two-step process. Two-step growth can provide a continuous graphene layer, but commensurate stitching should be further studied.

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

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

  16. DNA Self-assembly Catalyzed by Artificial Agents. (United States)

    Shi, Chao; Wang, Yifan; Zhang, Menghua; Ma, Cuiping


    Nucleic acids have been shown to be versatile molecules and engineered to produce various nanostructures. However, the poor rate of these uncatalyzed nucleic acid reactions has restricted the development and applications. Herein, we reported a novel finding that DNA self-assembly could be nonenzymatically catalyzed by artificial agents with an increasing dissociation rate constant K2. The catalytic role of several artificial agents in DNA self-assembly was verified by real-time fluorescent detection or agarose gel electrophoresis. We found that 20% PEG 200 could significantly catalyze DNA self-assembly and increase the reaction efficiency, such as linear hybridization chain reaction (HCR) and exponential hairpin assembly (EHA). Therefore, we foresee that a fast and efficient DNA self-assembly in structural DNA nanotechnology will be desirable.

  17. A review on self-assembly in microfluidic devices (United States)

    Dou, Yingying; Wang, Bingsheng; Jin, Mingliang; Yu, Ying; Zhou, Guofu; Shui, Lingling


    Self-assembly is a process that operates over a vast range of length and time scales. Microfluidic technology has been proven to be a powerful tool to manipulate micro- and nano-scale substrates with precise control over size and speed using various fluidic materials and properties. In this review, we discuss the current status of microfluidic technology in manipulating fluid dynamics and interfacial phenomena which influence self-assembly process and resulted structures. The self-assembled materials/structures were summarized and discussed as the sequence of the objective size at the micro-, nano- and molecular scale. Overall, microfluidics is becoming a useful tool to manipulate various fluids regarding to physical and chemical properties, being inherently suitable for self-assembly process control.

  18. Self-assembling Venturi-like peptide nanotubes. (United States)

    Fuertes, Alberto; Ozores, Haxel Lionel; Amorín, Manuel; Granja, Juan R


    We describe the design and synthesis of self-assembling peptide nanotubes that have an internal filter area and whose length and internal diameters, at the entrance and in the constricted area, are precisely controlled.

  19. Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properties

    Directory of Open Access Journals (Sweden)

    Xiang Sun


    Full Text Available This paper reports the self-assembly of two new tetrathiafulvalene (TTF derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron microscopy (SEM and X-ray diffraction (XRD, which showed that the self-assembly ability of T1 was better than that of T2. The results revealed that more urethane groups in a molecule did not necessarily instigate self-assembly. UV–vis and FTIR spectra were measured to explore noncovalent interactions. The driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T1 and T2 films was tested by a four-probe method.

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

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


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

  1. Self-Assembled Nanostructured Health Monitoring Sensors Project (United States)

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

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

    DEFF Research Database (Denmark)

    Canning, John; Lindoy, Lachlan; Huyang, George


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

  3. Mesoscopic Self-Assembly: A Shift to Complexity

    Directory of Open Access Journals (Sweden)

    Massimo eMastrangeli


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

  4. Self-assembly of graphene nanostructures on nanotubes. (United States)

    Patra, Niladri; Song, Yuanbo; Král, Petr


    We demonstrate by molecular dynamics simulations that carbon nanotubes can activate and guide on their surfaces and in their interiors the self-assembly of planar graphene nanostructures of various sizes and shapes. Nanotubes can induce bending, folding, sliding, and rolling of the nanostructures in vacuum and in the presence of solvent, leading to stable graphene rings, helices, and knots. We investigate the self-assembly conditions and analyze the stability of the formed nanosystems, with numerous possible applications.

  5. Optimal control of electrostatic self-assembly of binary monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Shestopalov, N V; Henkelman, G; Powell, C T; Rodin, G J [Institute for Computational Engineering and Sciences, University of Texas at Austin, Austin, TX 78712 (United States)], E-mail:


    A simple macroscopic model is used to determine an optimal annealing schedule for self-assembly of binary monolayers of spherical particles. The model assumes that a single rate-controlling mechanism is responsible for the formation of spatially ordered structures and that its rate follows an Arrhenius form. The optimal schedule is derived in an analytical form using classical optimization methods. Molecular dynamics simulations of the self-assembly demonstrate that the proposed schedule outperforms other schedules commonly used for simulated annealing.

  6. Lipid self-assemblies and nanostructured emulsions for cosmetic formulations


    Kulkarni, C


    A majority of cosmetic products that we encounter on daily basis contain lipid constituents in solubilized or insolubilized forms. Due to their amphiphilic nature, the lipid molecules spontaneously self-assemble into a remarkable range of nanostructures when mixed with water. This review illustrates the formation and finely tunable properties of self-assembled lipid nanostructures and their hierarchically organized derivatives, as well as their relevance to the development of cosmetic formula...

  7. Self assembly of DNA nanoparticles with polycations for the delivery of genetic materials into cells. (United States)

    Hosseinkhani, Hossein; Tabata, Yasuhiko


    Increasing attention has been paid to technology used for the delivery of genetic materials into cells for gene therapy and the generation of genetically engineered cells. So far, viral vectors have been mainly used because of their inherently high transfection efficiency of gene. However, there are some problems to be resolved for the clinical applications, such as the pathogenicity and immunogenicity of viral vectors themselves. Therefore, many research trials with non-viral vectors have been performed to enhance their efficiency to a level comparable to the viral vector. Two directions of these trials exist: Material improvement of non-viral vectors and their combination with various external physical stimuli. In this study gelatin was selected as a non-viral carrier for DNA. To give a positive charge to gelatin, different extents introduction of ethylenediamine (Ed), spermidine (Sd), and spermine (Sm) were reacted with gelatin in the presence of a water-soluble carbodiimide. When positively charged gelatin derivatives (Ed, Sd, and Sm) were mixed with negatively charged DNA, a self assembly of DNA nanoparticle (complex) was formed within few minutes through electrostatic interaction. Irrespective of the type of gelatin derivatives, the apparent molecular size of DNA was reduced by increasing the gelatin/DNA mixing ratio to attain a saturated value of about 150 nm. The condensed gelatin/DNA complexes showed the zeta potential of 10-15 mV. The amount of DNA internalized into the cells was significantly increased by the complexation with every gelatin derivative. The cells incubated with the gelatin/DNA complexes exhibited significantly stronger luciferase activities than naked plasmid DNA. This study clearly demonstrates and self-assembled DNA complexes has potential as a gene delivery vechile and are stable to transfer genetic materials to cells.

  8. Swell Gels to Dumbbell Micelles: Construction of Materials and Nanostructure with Self-assembly (United States)

    Pochan, Darrin


    Bionanotechnology, the emerging field of using biomolecular and biotechnological tools for nanostructure or nanotecnology development, provides exceptional opportunity in the design of new materials. Self-assembly of molecules is an attractive materials construction strategy due to its simplicity in application. By considering peptidic or charged synthetic polymer molecules in the bottom-up materials self-assembly design process, one can take advantage of inherently biomolecular attributes; intramolecular folding events, secondary structure, and electrostatic interactions; in addition to more traditional self-assembling molecular attributes such as amphiphilicty, to define hierarchical material structure and consequent properties. Several molecular systems will be discussed. Synthetic block copolymers with charged corona blocks can be assembled in dilute solution containing multivalent organic counterions to produce micelle structures such as toroids. These ring-like micelles are similar to the toroidal bundling of charged semiflexible biopolymers like DNA in the presence of multivalent counterions. Micelle structure can be tuned between toroids, cylinders, and disks simply by using different concentrations or molecular volumes of organic counterion. In addition, these charged blocks can consist of amino acids as monomers producing block copolypeptides. In addition to the above attributes, block copolypeptides provide the control of block secondary structure to further control self-assembly. Design strategies based on small (less than 24 amino acids) beta-hairpin peptides will be discussed. Self-assembly of the peptides is predicated on an intramolecular folding event caused by desired solution properties. Importantly, the intramolecular folding event impart a molecular-level mechanism for environmental responsiveness at the material level (e.g. infinite change in viscosity of a solution to a gel with changes in pH, ionic strength, temperature).

  9. Design of fluidic self-assembly bonds for precise component positioning (United States)

    Ramadoss, Vivek; Crane, Nathan B.


    Self Assembly is a promising alternative to conventional pick and place robotic assembly of micro components. Its benefits include parallel integration of parts with low equipment costs. Various approaches to self assembly have been demonstrated, yet demanding applications like assembly of micro-optical devices require increased positioning accuracy. This paper proposes a new method for design of self assembly bonds that addresses this need. Current methods have zero force at the desired assembly position and low stiffness. This allows small disturbance forces to create significant positioning errors. The proposed method uses a substrate assembly feature to provide a high accuracy alignment guide to the part. The capillary bond region of the part and substrate are then modified to create a non-zero positioning force to maintain the part in the desired assembly position. Capillary force models show that this force aligns the part to the substrate assembly feature and reduces sensitivity of part position to process variation. Thus, the new configuration can substantially improve positioning accuracy of capillary self-assembly. This will result in a dramatic decrease in positioning errors in the micro parts. Various binding site designs are analyzed and guidelines are proposed for the design of an effective assembly bond using this new approach.

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

    Directory of Open Access Journals (Sweden)

    Holger Bußkamp


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

  11. In-capillary self-assembly and proteolytic cleavage of polyhistidine peptide capped quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jianhao; Li, Jingyan; Li, Jinchen; Liu, Feifei [School of Pharmaceutical Engineering and Life Science, Changzhou University, Changzhou, Jiangsu, 213164 (China); Zhou, Xiang; Yao, Yi [Changzhou Qianhong Bio-pharma Co. Ltd, Changzhou 213164, Jiangsu (China); Wang, Cheli [School of Pharmaceutical Engineering and Life Science, Changzhou University, Changzhou, Jiangsu, 213164 (China); Qiu, Lin, E-mail: [School of Pharmaceutical Engineering and Life Science, Changzhou University, Changzhou, Jiangsu, 213164 (China); Jiang, Pengju, E-mail: [School of Pharmaceutical Engineering and Life Science, Changzhou University, Changzhou, Jiangsu, 213164 (China); State Key Laboratory of Pharmaceutical Biotechnology, Nanjing, Jiangsu (China)


    A new method using fluorescence coupled capillary electrophoresis (CE-FL) for monitoring self-assembly and proteolytic cleavage of hexahistidine peptide capped quantum dots (QDs) inside a capillary has been developed in this report. QDs and the ATTO 590-labeled hexahistidine peptide (H6-ATTO) were injected into a capillary, sequentially. Their self-assembly inside the capillary was driven by a metal-affinity force which yielded a new fluorescence signal due to Förster resonance energy transfer (FRET). The highly efficient separation of fluorescent complexes and the FRET process were analyzed using CE-FL. The self-assembly of QDs and biomolecules was found to effectively take place inside the capillary. The kinetics of the assembly was monitored by CE-FL, and the approach was extended to the study of proteolytic cleavage of surface conjugated peptides. Being the first in-depth analysis of in-capillary nanoparticle–biomolecule assembly, the novel approach reported here provides inspiration to the development of QD-based FRET probes for biomedical applications. - Highlights: • We examined the self-assembly QDs with H6-ATTO inside a capillary. • We prove CE-FL to be a powerful method to resolve QDs-H6-ATTO complex. • We achieve chromatographic separation of QDs-H6-ATTO complex. • We discovered a novel strategy for the online detection of thrombin. • This technique integrated “injection, mixing, reaction, separation and detection”.

  12. Molecular design and synthesis of self-assembling camptothecin drug amphiphiles. (United States)

    Cheetham, Andrew G; Lin, Yi-An; Lin, Ran; Cui, Honggang


    The conjugation of small molecular hydrophobic anticancer drugs onto a short peptide with overall hydrophilicity to create self-assembling drug amphiphiles offers a new prodrug strategy, producing well-defined, discrete nanostructures with a high and quantitative drug loading. Here we show the detailed synthesis procedure and how the molecular structure can influence the synthesis of the self-assembling prodrugs and the physicochemical properties of their assemblies. A series of camptothecin-based drug amphiphiles were synthesized via combined solid- and solution-phase synthetic techniques, and the physicochemical properties of their self-assembled nanostructures were probed using a number of imaging and spectroscopic techniques. We found that the number of incorporated drug molecules strongly influences the rate at which the drug amphiphiles are formed, exerting a steric hindrance toward any additional drugs to be conjugated and necessitating extended reaction time. The choice of peptide sequence was found to affect the solubility of the conjugates and, by extension, the critical aggregation concentration and contour length of the filamentous nanostructures formed. In the design of self-assembling drug amphiphiles, the number of conjugated drug molecules and the choice of peptide sequence have significant effects on the nanostructures formed. These observations may allow the fine-tuning of the physicochemical properties for specific drug delivery applications, ie systemic vs local delivery.

  13. The nature of protein interactions governing globular protein-polymer block copolymer self-assembly. (United States)

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


    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.

  14. Tunable synthesis of self-assembled cyclic peptide nanotubes and nanoparticles. (United States)

    Sun, Leming; Fan, Zhen; Wang, Yongzhong; Huang, Yujian; Schmidt, Michael; Zhang, Mingjun


    While tremendous efforts have been made in investigating scalable approaches for fabricating nanoparticles, less progress has been made in scalable synthesis of cyclic peptide nanoparticles and nanotubes, despite their great potential for broader biomedical applications. In this paper, tunable synthesis of self-assembled cyclic peptide nanotubes and nanoparticles using three different methods, phase equilibrium, pH-driven, and pH-sensitive methods, were proposed and investigated. The goal is scalable nanomanufacturing of cyclic peptide nanoparticles and nanotubes with different sizes in large quality by controlling multiple process parameters. Cyclo-(L-Gln-D-Ala-L-Glu-D-Ala-)2 was applied to illustrate the proposed ideas. In the study, mass spectrometry and high performance liquid chromatography were employed to verify the chemical structures and purity of the cyclic peptides. Morphology and size of the synthesized nanomaterials were characterized using atomic force microscopy and dynamic light scattering. The dimensions of the self-assembled nanostructures were found to be strongly influenced by the cyclic peptide concentration, side chain modification, pH values, reaction time, stirring intensity, and sonication time. This paper proposed an overall strategy to integrate all the parameters to achieve optimal synthesis outputs. Mechanisms of the self-assembly of the cyclic peptide nanotubes and nanoparticles under variable conditions and tunable parameters were discussed. This study contributes to scalable nanomanufacturing of cyclic peptide based self-assembled nanoparticles and nanotubes for broader biomedical applications.

  15. Self-assembly of a functional electronic circuit directed by capillary interactions (United States)

    Reynolds, K.; O'Riordan, A.; Redmond, G.


    We report on the use of capillary interactions to drive the self-assembly of an electronic circuit based on mesoscale building blocks. The specific target structure is a linear heterotetramer comprising non-identical millimetre-scale cubic blocks that, following assembly, forms a functioning astable multivibrator circuit. Importantly, the self-assembly process is designed to be unconstrained, i.e., each of the blocks are free to move in any way during assembly. To this end, solder droplets are selectively patterned on the block faces. On contact, capillary interactions between shape complimentary solder patterns on the blocks cause the molten solder droplets to coalesce and the blocks to self-assemble. In this way, capillary forces direct the alignment, registration, linking and electrical interconnection of each block during the assembly process. This demonstration of mesoscale self-assembly mediated by capillary interactions illustrates that the application of unconventional assembly paradigms to complex structure fabrication is feasible and that these approaches may yet yield viable strategies for fabrication of highly integrated systems.

  16. A new building block for DNA network formation by self-assembly and polymerase chain reaction. (United States)

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


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

  17. Reversible Self-Assembly of 3D Architectures Actuated by Responsive Polymers. (United States)

    Zhang, Cheng; Su, Jheng-Wun; Deng, Heng; Xie, Yunchao; Yan, Zheng; Lin, Jian


    An assembly of three-dimensional (3D) architectures with defined configurations has important applications in broad areas. Among various approaches of constructing 3D structures, a stress-driven assembly provides the capabilities of creating 3D architectures in a broad range of functional materials with unique merits. However, 3D architectures built via previous methods are simple, irreversible, or not free-standing. Furthermore, the substrates employed for the assembly remain flat, thus not involved as parts of the final 3D architectures. Herein, we report a reversible self-assembly of various free-standing 3D architectures actuated by the self-folding of smart polymer substrates with programmed geometries. The strategically designed polymer substrates can respond to external stimuli, such as organic solvents, to initiate the 3D assembly process and subsequently become the parts of the final 3D architectures. The self-assembly process is highly controllable via origami and kirigami designs patterned by direct laser writing. Self-assembled geometries include 3D architectures such as "flower", "rainbow", "sunglasses", "box", "pyramid", "grating", and "armchair". The reported self-assembly also shows wide applicability to various materials including epoxy, polyimide, laser-induced graphene, and metal films. The device examples include 3D architectures integrated with a micro light-emitting diode and a flex sensor, indicting the potential applications in soft robotics, bioelectronics, microelectromechanical systems, and others.

  18. 3D self-assembly polyethyleneimine modified graphene oxide hydrogel for the extraction of uranium from aqueous solution (United States)

    Wang, Xue; Liu, Qi; Liu, Jingyuan; Chen, Rongrong; Zhang, Hongsen; Li, Rumin; Li, Zhanshuang; Wang, Jun


    3D self-assembly polyethyleneimine-modified graphene oxide hydrogel (PEI-GH) was successfully synthesized via a simple one-step method without using other harsh chemicals. The unique three-dimensional (3D) porous network of PEI-GHs is achieved by using polyethyleneimine (PEI) as the cross-linking agent which also facilitate the self-assembly of GO sheets. With unique porous structure, large surface area and sufficient active sites, the PEI-GH has outstanding adsorption capacity (898 mg/g), large removal rate (>90% at ppm level, or ∼85% for ppb level simulated seawater) and high selectivity of uranium. The adsorption process was described well with the pseudo-second-order kinetic model and Langmuir isotherm model. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic. Based on the above results, the PEI-GH materials exhibits promising adsorption performance and high removal rate for uranium (VI) from aqueous solution and simulated seawater.

  19. Cooperativity Scale: A Structure-Mechanism Correlation in the Self-Assembly of Benzene-1,3,5-tricarboxamides. (United States)

    Kulkarni, Chidambar; Meijer, E W; Palmans, Anja R A


    The self-assembly of small and well-defined molecules using noncovalent interactions to generate various nano- and microarchitectures has been extensively studied. Among various architectures, one-dimensional (1-D) nano-objects have garnered significant attention. It has become increasingly evident that a cooperative or nucleation-elongation mechanism of polymerization leads to highly ordered 1-D supramolecular polymers, analogous to shape-persistent biopolymers such as actin. With this in mind, achieving cooperativity in self-assembled structures has been actively pursued with significant success. Only recently, researchers are focusing on the origin of the mechanism at the molecular level in different synthetic systems. Taking a step further, a thorough quantitative structure-mechanism correlation is crucial to control the size, shape, and functions of supramolecular polymers, and this is currently lacking in the literature. Among a plethora of molecules, benzene-1,3,5-tricarboxamides (BTAs) provide a unique combination of important noncovalent interactions such as hydrogen bonding, π-stacking, and hydrophobic interactions, for self-assembly and synthetic ease. Due to the latter, a diverse range of BTA derivatives with all possible structural mutations have been synthesized and studied during the past decade, mainly from our group. With such a large body of experimental results on BTA self-assembly, it is time to embark on a structure-mechanism correlation in this family of molecules, and a first step toward this will form the main focus of this Account. The origin of the cooperative mechanism of self-assembly in BTAs has been ascribed to 3-fold intermolecular hydrogen bonding (HB) between monomers based on density-functional theory (DFT) calculations. The intermolecular hydrogen-bonding interaction forms the central premise of this work, in which we evaluate the effect of different moieties such as alkyl chains, and amino acids, attached to the core amides on

  20. Directed self-assembly of mesoscopic components for led applications (United States)

    Tkachenko, Anton

    Light-emitting diodes (LEDs) constitute a rapidly evolving and fast growing technology that promises to replace incandescent bulbs and compact fluorescent lights in many illumination applications. Large-area LED luminaires have a capability to transform lighting by providing a venue for development of smart lighting systems with additional benefits, such as visible light communications, sensing, health and productivity improvement through color temperature control, capability of creating "virtual sky" ceiling, and many others. The objective of this work is to explore directed self-assembly (DSA) approaches suitable for cost-effective assembly of large amount of LEDs and other mesoscopic (i.e. millimeter and sub-millimeter) electronic components and thus to enable manufacturing of smart lighting luminaires. Existing alternative approaches for assembly of semiconductor dies are examined including transfer printing, laser-assisted die transfer, and various directed self-assembly approaches using shape-recognition, magnetic and capillary forces, etc. After comparing their advantages and limitations, we developed two approaches to magnetic force-assisted DSA of LEDs on a large-area substrate in liquid and air medium. The first approach involves pick-up of buoyant and magnetic dies from the liquid surface onto the flexible substrate in a roll-to-roll process. The possibility of high-speed assembly of LED dies is demonstrated, but with a low yield due to the influence of the capillary force of the carrier liquid and the difficulty in ensuring reliable supply of dies to the assembly interface. To overcome the aforementioned challenges this process was modified to assemble the dies by sinking them onto the receiving substrate with a stencil mask on top, demonstrating LED assembly with a very low error rate but at a lower speed. A solder-assisted self-alignment is used to further improve placement precision and to ensure the proper orientation of the dies. The second

  1. Cryogenic Electron Microscopy Studies: Structure and Formation of Self-assembled Nanostructures in Solution (United States)

    Lee, Han Seung

    Cryogenic electron microscopy (Cryo-EM) techniques are among the most powerful to characterize self-assembling soft materials (colloids, polymers, and microemulsions, etc.) at the nanometer scale, without any need for implicit models or assumptions about the structure. We can even visualize structure under dynamic conditions, capturing each stage of development. In this thesis, cryo-EM has been used to investigate the formation and structure of a variety of self-assembling soft materials. Visualization is complemented by small angle X-ray scattering (SAXS), dynamic light scattering, and conductivity measurements. In each case, cryo-EM provides new insights, not otherwise available, into the nanostructure development. Self-assembly phenomena at the molecular level are critical to the performance of tremendous number of applied systems ranging from personal care products to industrial products. To evaluate these self-assembled materials, multiple characterization techniques are required. We investigated aggregation behavior of cesium dodecyl sulfate (CsDS) ionic surfactant in aqueous solution. Coupled with the real space data from cryogenic transmission electron microscopy (Cryo-TEM) and the inverse space data from SAXS, the experimental result of CsDS in aqueous solution gave a new insight in CsDS micellar structures and their development as a function of concentration. Cryo-TEM showed the presence of the liquid-like hydrocarbon core in the CsDS micelles and relatively thick shell structures at a low CsDS concentration. The core-shell sphere structure micelle shifted to core-shell cylindrical micelle structure at high concentration. The morphology and structure of paclitaxel silicate (PTX) prodrug, encapsulated with amphiphilic poly(ethylene glycol)-b-poly(lactic-co-glycolic acid) diblock copolymers were studied. The six different silicate PTX prodrug candidates were characterized with cryo-TEM. Direct imaging with cryo-TEM illustrated structure of prodrug

  2. Rotational diffusion affects the dynamical self-assembly pathways of patchy particles (United States)

    Newton, Arthur C.; Groenewold, Jan; Kegel, Willem K.; Bolhuis, Peter G.


    Predicting the self-assembly kinetics of particles with anisotropic interactions, such as colloidal patchy particles or proteins with multiple binding sites, is important for the design of novel high-tech materials, as well as for understanding biological systems, e.g., viruses or regulatory networks. Often stochastic in nature, such self-assembly processes are fundamentally governed by rotational and translational diffusion. Whereas the rotational diffusion constant of particles is usually considered to be coupled to the translational diffusion via the Stokes–Einstein relation, in the past decade it has become clear that they can be independently altered by molecular crowding agents or via external fields. Because virus capsids naturally assemble in crowded environments such as the cell cytoplasm but also in aqueous solution in vitro, it is important to investigate how varying the rotational diffusion with respect to transitional diffusion alters the kinetic pathways of self-assembly. Kinetic trapping in malformed or intermediate structures often impedes a direct simulation approach of a kinetic network by dramatically slowing down the relaxation to the designed ground state. However, using recently developed path-sampling techniques, we can sample and analyze the entire self-assembly kinetic network of simple patchy particle systems. For assembly of a designed cluster of patchy particles we find that changing the rotational diffusion does not change the equilibrium constants, but significantly affects the dynamical pathways, and enhances (suppresses) the overall relaxation process and the yield of the target structure, by avoiding (encountering) frustrated states. Besides insight, this finding provides a design principle for improved control of nanoparticle self-assembly. PMID:26621742

  3. Stable self-assembled nanostructured hen egg white lysozyme exhibits strong anti-proliferative activity against breast cancer cells. (United States)

    Mahanta, Sailendra; Paul, Subhankar; Srivastava, Ankit; Pastor, Ashutosh; Kundu, Bishwajit; Chaudhuri, Tapan K


    Chemotherapy side effects have long been a matter of great concern. Here we describe a structurally stable self-assembled nanostructured lysozyme (snLYZ) synthesized using a simple desolvation technique that exhibited anticancer activity, as well as excellent hemocompatibility. Field emission scanning electron microscopy; atomic force microscopy and dynamic particle size analyzer were used for analyzing the synthesized snLYZ. The analysis revealed spherical shape with an average size of 300 nm. Circular dichroism and tryptophan fluorescence spectroscopic analysis revealed its gross change in secondary as well as the tertiary level of the structure. snLYZ also demonstrated excellent structural as well as the functional stability of LYZ in a wide range of pH and temperature with a fair level of protection against proteinase K digestion. When applied to MCF-7 breast cancer cells, it exhibited approximately 95% cell death within 24h, involving a reactive oxygen species (ROS) based mechanism, and showed excellent hemocompatibility. Fluorescence microscopy imaging revealed distinct cellular internalization of snLYZ and the formation of cytoplasmic granules, which initiated a cell-killing process through membrane damage. In order to mimic targeted therapy, we tagged folic acid with snLYZ, which further enhanced cytotoxicity against MCF-7 cells. Therefore, this is the first report of its kind where we demonstrated the preparation of a highly stable self-assembled nanostructured lysozyme with a strong anti-proliferative activity against breast cancer cells. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Anandamide and analogous endocannabinoids: a lipid self-assembly study

    Energy Technology Data Exchange (ETDEWEB)

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Mulet, Xavier; Drummond, Calum J.


    Anandamide, the endogenous agonist of the cannabinoid receptors, has been widely studied for its interesting biological and medicinal properties and is recognized as a highly significant lipid signaling molecule within the nervous system. Few studies have, however, examined the effect of the physical conformation of anandamide on its function. The study presented herein has focused on characterizing the self-assembly behaviour of anandamide and four other endocannabinoid analogues of anandamide, viz., 2-arachidonyl glycerol, arachidonyl dopamine, 2-arachidonyl glycerol ether (noladin ether), and o-arachidonyl ethanolamide (virodhamine). Molecular modeling of the five endocannabinoid lipids indicates that the highly unsaturated arachidonyl chain has a preference for a U or J shaped conformation. Thermal phase studies of the neat amphiphiles showed that a glass transition was observed for all of the endocannabinoids at {approx} -110 C with the exception of anandamide, with a second glass transition occurring for 2-arachidonyl glycerol, 2-arachidonyl glycerol ether, and virodhamine (-86 C, -95 C, -46 C respectively). Both anandamide and arachidonyl dopamine displayed a crystal-isotropic melting point (-4.8 and -20.4 C respectively), while a liquid crystal-isotropic melting transition was seen for 2-arachidonyl glycerol (-40.7 C) and 2-arachidonyl glycerol ether (-71.2 C). No additional transitions were observed for virodhamine. Small angle X-ray scattering and cross polarized optical microscopy studies as a function of temperature indicated that in the presence of excess water, both 2-arachidonyl glycerol and anandamide form co-existing Q{sub II}{sup G} (gyroid) and Q{sub II}{sup D} (diamond) bicontinuous cubic phases from 0 C to 20 C, which are kinetically stable over a period of weeks but may not represent true thermodynamic equilibrium. Similarly, 2-arachidonyl glycerol ether acquired an inverse hexagonal (HII) phase in excess water from 0 C to 40 C, while

  5. Disulfide-induced self-assembled targets: A novel strategy for the label free colorimetric detection of DNAs/RNAs via unmodified gold nanoparticles (United States)

    Shokri, Ehsan; Hosseini, Morteza; Davari, Mehdi D.; Ganjali, Mohammad R.; Peppelenbosch, Maikel P.; Rezaee, Farhad


    A modified non-cross-linking gold-nanoparticles (Au-NPs) aggregation strategy has been developed for the label free colorimetric detection of DNAs/RNAs based on self-assembling target species in the presence of thiolated probes. Two complementary thiol- modified probes, each of which specifically binds at one half of the target introduced SH groups at both ends of dsDNA. Continuous disulfide bond formation at 3‧ and 5‧ terminals of targets leads to the self-assembly of dsDNAs into the sulfur- rich and flexible products with different lengths. These products have a high affinity for the surface of Au-NPs and efficiently protect the surface from salt induced aggregation. To evaluate the assay efficacy, a small part of the citrus tristeza virus (CTV) genome was targeted, leading to a detection limit of about 5 × 10-9 mol.L-1 over a linear ranged from 20 × 10-9 to 10 × 10-7 mol.L-1. This approach also exhibits good reproducibility and recovery levels in the presence of plant total RNA or human plasma total circulating RNA extracts. Self-assembled targets can be then sensitively distinguished from non-assembled or mismatched targets after gel electrophoresis. The disulfide reaction method and integrating self-assembled DNAs/RNAs targets with bare AuNPs as a sensitive indicator provide us a powerful and simple visual detection tool for a wide range of applications.

  6. Self-assembly studies of native and recombinant fibrous proteins (United States)

    Wilson, Donna Lucille

    The structure of silk proteins consists of alternating amorphous (glycine-rich) and ordered crystalline regions (poly(alanine) and poly(glycine-alanine) repeats), where the organized regions are typically beta-sheet assemblies. In collagen, the basic helical repeat (glycine-proline-hydroxyproline and variants on this repeat) drives hierarchical assembly. Three polypeptide chains form left-handed poly-proline II-like helices, these three chains then self-assemble to form a right-handed triple helix. The focus of this thesis is on these proteins and defined variations thereof to reveal features of fibrous protein self-assembly. The amino acid sequences of native silk and collagen and their respective assembly environments have been systematically manipulated. Spider silk protein, based on the consensus sequence of Nephila clavipes dragline-silk, was genetically engineered to include methionines flanking the beta-sheet forming polyalanine regions. These methionines could be selectively oxidized and reduced, altering the bulkiness and charge of a methionine-based sulfoxide group to control beta-sheet formation by steric hindrance. A second version of the sterical trigger included a recognition site for Protein Kinase A allowing for the selective phosphorylation of a serine. Patterning a monolayer of precursor "director" molecules on length scales ranging from nanometer- to micrometer-length scales simplifies the interpretation of supramolecular assembly. Utilizing the atomic force microscopy (AFM)-based technique of dip-pen nanolithography, thiolated collagen and a collagen-like peptide were patterned at 30--50 nm line widths on evaporated gold surfaces. These are the largest molecules thus far positively printed on a surface at such small-length scales. The method preserved the triple helical structure and biological activity of collagen and even fostered the formation of characteristic higher-levels of structural organization. Nanopatterns were also achieved for

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

    KAUST Repository

    Al-Rehili, Safa’a


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Katja Petkau-Milroy


    Full Text Available Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard to streptavidin. Next to tetravalent streptavidin, monovalent streptavidin was used to study the protein assembly along the supramolecular polymer in detail without the interference of cross-linking. Upon self-assembly of the monovalent biotinylated discotics, multivalent proteins can be assembled along the supramolecular polymer. The concentration of discotics, which influences the length of the final polymers at the same time dictates the amount of assembled proteins.

  11. Self-assembly of hydrofluorinated Janus graphene monolayer

    DEFF Research Database (Denmark)

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei


    der Waals (vdW) interaction and the coupling of C-H/π/C-F interaction and π/π interaction are proven to offer the continuous driving force of self-assembly of J-GN. The results show that J-GN can self-assemble into various J-NSs structures, including arcs, multi-wall J-NS and arm-chair-like J...... driving force of the self-assembly. Finally, we studied the hydrogen sorption over the formed J-NS with a considerable interlayer spacing, which reaches the US DOE target, indicating that J-NS is a promising candidate for hydrogen storage by controlling the temperature of system. Our theoretical results...

  12. Scratch Drive Actuator Driven Self-assembled Variable Optical Attenuator (United States)

    Lee, Chengkuo; Lai, Yen-Jyh; Wu, Chia-Yu; Lin, Yu-Shen; Tasi, Ming Hung; Huang, Ruey-Shing; Lin, Min-Shyong


    This paper describes the new concept and design for a self-assembled variable optical attenuator (VOA) derived by using surface micromachining technology. A residual stress-induced flexure curved beam with corrugated trench anchors can lift up the reflective mirror shutter. This self-assembled reflective shutter can be driven by a set of scratch drive actuator (SDA), then slides into the spacing between input and output fiber ends. The attenuation range of proposed microelectromechanical systems (MEMS) VOA is determined by the vertical position of self-assembled pop-up polysilicon reflective shutter in which it is controlled by the value of applied dc voltage. This new VOA demonstrates continuous attenuation capability and wide attenuation range based on using an electrostatic actuator that is a new residual stress-induced flexure curved beam with corrugated-trench anchors. This device exhibits attenuation range of 70 dB and insertion loss less than 1 dB.

  13. INTRODUCTION: New trends in simulating colloids and self-assembling systems New trends in simulating colloids and self-assembling systems (United States)

    Foffi, Giuseppe; Kahl, Gerhard


    relatively high number of contributions as an indicator that the topics presented at these workshops represent substantial scientific developments. The particular motivation to organize these two workshops came from the fact that experimental work in colloidal physics is advancing rapidly around the globe. In contrast, theoretical and simulation approaches to investigate the wide range of new and surprising physical phenomena of colloidal systems is lagging behind this experimental progress. This is the more deploring since theory and simulation might provide a more profound understanding of many phenomena in soft and bio-related physics, such as phase behaviour, self-assembly strategies, or rheological properties, to name but a few. Furthermore this insight might help to guide experiment to design new colloid-based materials with desired properties. The declared aim of the two workshops was thus to bring together scientists who have contributed in recent time to new developments in colloidal physics and to share and discuss their latest innovations. While CECAM workshops traditionally bring together scientists from the theoretical and simulator communities, from the very beginning the organizers considered it an indispensable necessity to invite experimentalists. And indeed, the organizers are happy to confirm that the participation of experimentalists, theoreticians, and simulators was highly fruitful and mutually inspiring: discussions between all communities did help to understand the possibilities and limitations imposed by experiment, theory, and simulations. Reuniting thus all forces, the workshop did contribute to a deeper understanding in colloidal physics and has helped to address future aspects that might lead to more applied problems of technological relevance. The first workshop, entitled 'Computer Simulation Approaches to Study Self-Assembly: From Patchy Nano-Colloids to Virus Capsides', (organized by Jonathan Doye—University Of Oxford, Ard A Louis

  14. Robust aqua material. A pressure-resistant self-assembled membrane for water purification

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, Erez; Weissman, Haim; Rybtchinski, Boris [Department of Organic Chemistry, Weizmann Institute of Science, 234 Herzl Street, Rehovot, 7610001 (Israel); Shimoni, Eyal; Kaplan-Ashiri, Ifat [Department of Chemical Research Support, Weizmann Institute of Science, 234 Herzl Street, Rehovot, 7610001 (Israel); Werle, Kai; Wohlleben, Wendel [Department of Material Physics, Materials and Systems Research, BASF SE, 67056, Ludwigshafen (Germany)


    ''Aqua materials'' that contain water as their major component and are as robust as conventional plastics are highly desirable. Yet, the ability of such systems to withstand harsh conditions, for example, high pressures typical of industrial applications has not been demonstrated. We show that a hydrogel-like membrane self-assembled from an aromatic amphiphile and colloidal Nafion is capable of purifying water from organic molecules, including pharmaceuticals, and heavy metals in a very wide range of concentrations. Remarkably, the membrane can sustain high pressures, retaining its function. The robustness and functionality of the water-based self-assembled array advances the idea that aqua materials can be very strong and suitable for demanding industrial applications. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Modular Design of Self-Assembling Peptide-Based Nanotubes. (United States)

    Burgess, Natasha C; Sharp, Thomas H; Thomas, Franziska; Wood, Christopher W; Thomson, Andrew R; Zaccai, Nathan R; Brady, R Leo; Serpell, Louise C; Woolfson, Derek N


    An ability to design peptide-based nanotubes (PNTs) rationally with defined and mutable internal channels would advance understanding of peptide self-assembly, and present new biomaterials for nanotechnology and medicine. PNTs have been made from Fmoc dipeptides, cyclic peptides, and lock-washer helical bundles. Here we show that blunt-ended α-helical barrels, that is, preassembled bundles of α-helices with central channels, can be used as building blocks for PNTs. This approach is general and systematic, and uses a set of de novo helical bundles as standards. One of these bundles, a hexameric α-helical barrel, assembles into highly ordered PNTs, for which we have determined a structure by combining cryo-transmission electron microscopy, X-ray fiber diffraction, and model building. The structure reveals that the overall symmetry of the peptide module plays a critical role in ripening and ordering of the supramolecular assembly. PNTs based on pentameric, hexameric, and heptameric α-helical barrels sequester hydrophobic dye within their lumens.

  16. Polypeptide Multilayer Self-Assembly Studied by Ellipsometry

    Directory of Open Access Journals (Sweden)

    Marina Craig


    Full Text Available A polypeptide nanofilm made by layer-by-layer (LbL self-assembly was built on a surface that mimics nonwoven, a material commonly used in wound dressings. Poly-L-lysine (PLL and poly-L-glutamic acid (PLGA are the building blocks of the nanofilm, which is intended as an enzymatically degradable lid for release of bactericides to chronic wounds. Chronic wounds often carry infection originating from bacteria such as Staphylococcus aureus and a release system triggered by the degree of infection is of interest. The dry nanofilm was studied with ellipsometry. The thickness of the nanofilm was 60% less in its dry state than in its wet state. The measurements showed that a primer was not necessary to build a stable nanofilm, which is practically important in our case because a nondegradable primer is highly unwanted in a wound care dressing. Added V8 (glutamyl endopeptidase enzymes only showed adsorption on the nanofilm at room temperature, indicating that the PLL/PLGA “lid” may remain intact until the dressing has been filled with wound exudate at the elevated temperature typical of that of the wound.

  17. Polypeptide multilayer self-assembly studied by ellipsometry. (United States)

    Craig, Marina; Holmberg, Krister; Le Ru, Eric; Etchegoin, Pablo


    A polypeptide nanofilm made by layer-by-layer (LbL) self-assembly was built on a surface that mimics nonwoven, a material commonly used in wound dressings. Poly-L-lysine (PLL) and poly-L-glutamic acid (PLGA) are the building blocks of the nanofilm, which is intended as an enzymatically degradable lid for release of bactericides to chronic wounds. Chronic wounds often carry infection originating from bacteria such as Staphylococcus aureus and a release system triggered by the degree of infection is of interest. The dry nanofilm was studied with ellipsometry. The thickness of the nanofilm was 60% less in its dry state than in its wet state. The measurements showed that a primer was not necessary to build a stable nanofilm, which is practically important in our case because a nondegradable primer is highly unwanted in a wound care dressing. Added V8 (glutamyl endopeptidase) enzymes only showed adsorption on the nanofilm at room temperature, indicating that the PLL/PLGA "lid" may remain intact until the dressing has been filled with wound exudate at the elevated temperature typical of that of the wound.

  18. Polymer based planar coupling of self-assembled bottle microresonators (United States)

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


    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.

  19. Self-Assembly of Protein Nanostructures to Enhance Biosensor Sensitivity (United States)

    Olsen, Bradley; Dong, Xuehui; Obermeyer, Allie

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

  20. Magnetic Actuation of Self-assembled Bacteria Inspired Nanoswimmers (United States)

    Ali, Jamel; Cheang, U. Kei; Martindale, James D.; Jabbarzadeh, Mehdi; Fu, Henry C.; Kim, Min Jun


    Currently, there is growing interest in developing nanoscale swimmers for biological and biomedical tasks. Of particular interest is the development of soft stimuli-responsive nanorobots to probe cellular and sub-cellular environments. While there have been a few reports of nanoscale robotic swimmers, which have shown potential to be used for these tasks, they often lack multifuctionality. In particular, no man-made soft nanoscale material has been able to match the ability of natural bacterial flagella to undergo rapid and reversible morphological changes in response to multiple forms of environmental stimuli. Towards this end, we report self-assembled stimuli-responsive nanoscale robotic swimmers composed of single or multiple bacterial flagella and attached to magnetic nanoparticles. We visualize the movement of flagella using high resolution fluorescence microscopy while controlling these swimmers via a magnetic control system. Differences in in propulsion before and after the change in flagellar form are observed. Furthermore, we demonstrate the ability to induce flagellar bundling in multiflagellated nanoswimmers. This work was funded by the National Science Foundation (DMR 1712061 and CMMI 1737682 to M.J.K. and DMR 1650970 and CBET 1651031 to H.C.F.), and the Korea Evaluation Institute of Industrial Technology (MOTIE) (NO. 10052980) award to M.J.K.

  1. Self-Assembling Ability Determines the Activity of Enzyme-Instructed Self-Assembly for Inhibiting Cancer Cells. (United States)

    Feng, Zhaoqianqi; Wang, Huaimin; Chen, Xiaoyi; Xu, Bing


    Enzyme-instructed self-assembly (EISA) represents a dynamic continuum of supramolecular nanostructures that selectively inhibits cancer cells via simultaneously targeting multiple hallmark capabilities of cancer, but how to design the small molecules for EISA from the vast molecular space remains an unanswered question. Here we show that the self-assembling ability of small molecules controls the anticancer activity of EISA. Examining the EISA precursor analogues consisting of an N-capped d-tetrapeptide, a phosphotyrosine residue, and a diester or a diamide group, we find that, regardless of the stereochemistry and the regiochemistry of their tetrapeptidic backbones, the anticancer activities of these precursors largely match their self-assembling abilities. Additional mechanistic studies confirm that the assemblies of the small peptide derivatives result in cell death, accompanying significant rearrangement of cytoskeletal proteins and plasma membranes. These results imply that the diester or diamide derivatives of the d-tetrapeptides self-assemble pericellularly, as well as intracellularly, to result in cell death. As the first case to correlate thermodynamic properties (e.g., self-assembling ability) of small molecules with the efficacy of a molecule process against cancer cells, this work provides an important insight for developing a molecular dynamic continuum for potential cancer therapy, as well as understanding the cytotoxicity of pathogenic assemblies.

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

    Directory of Open Access Journals (Sweden)

    Øystein Stakkestad


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

  3. Hierarchical Formation of Fibrillar and Lamellar Self-Assemblies from Guanosine-Based Motifs (United States)

    Neviani, Paolo; Sarazin, Dominique; Schmutz, Marc; Blanck, Christian; Giuseppone, Nicolas; Spada, Gian Piero


    Here we investigate the supramolecular polymerizations of two lipophilic guanosine derivatives in chloroform by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties. PMID:20798860

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

    Directory of Open Access Journals (Sweden)

    Paolo Neviani


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

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

    Directory of Open Access Journals (Sweden)

    Cheng Zeng


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

  6. Interactions of main chain in folding and self assembly of unfolded protein structure: Enquiries with a serine solubilized nonapeptide

    Directory of Open Access Journals (Sweden)

    Kinshuk Raj Srivastava


    Full Text Available Interactions of the protein main chain are probed for their role in folding and self-assembly. The interactions are assessed with serine nonapeptide Ac-(Ser-Ala4-Ser-NH2 in poly-L and alternating-L,D structure variations. Being a neutral molecule, Serine nonapeptide has been found to display not only folding-unfolding equilibrium, but also association-dissociation equilibrium as a function of solvent and concentration. Thus scrutiny of intra- and inter-molecular interactions have been undertaken in water, methanol, and DMSO solvents. In water, poly-L peptide displays a PPII-helix conformation which unfolds to extended β-conformation with increase of temperature, apparently in a two-state equilibrium. Poly-L peptide at high concentration and on transfer to the low polarity solvent, methanol, displays ordering as a β-hairpin. This implies folding of the peptide by self assembly. Self assembly and ordering possibly as double-stranded β-helix is also evidence for alternating-L,D peptide. Both isomers were observed to be unfolded in high polarity solvent DMSO. Dynamic light scattering suggests that assembly in both isomers may involve large size aggregates. The results have established that folding and self-assembly can be coupled equilibria dependent upon solute structure, concentration, and solvent. The interactions of the protein main chain involved in folding and self assembly of unfolded structure are illuminated and have been discussed.

  7. Self-Assembled Hydrogel Nanoparticles for Drug Delivery Applications

    Directory of Open Access Journals (Sweden)

    Miguel Gama


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

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

    Energy Technology Data Exchange (ETDEWEB)

    van Swol, Frank B.; Medforth, Craig John (University of New Mexico, Albuquerque, NM)


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

  9. Self-assembly of active amphiphilic Janus particles (United States)

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


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

  10. Two dimensional self-assembly of inverse patchy colloids


    K, Remya Ann Mathews; Mani, Ethayaraja


    We report on the self-assembly of inverse patchy colloids (IPC) using Monte Carlo simulations in two-dimensions. The IPC model considered in this work corresponds to either bipolar colloids or colloids decorated with complementary DNA on their surfaces, where only patch and non-patch parts attract. The patch coverage is found to be a dominant factor in deciding equilibrium self-assembled structures. In particular, both regular square and triangular crystals are found to be stable at 0.5 patch...

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  12. A parameter estimation technique for stochastic self-assembly systems and its application to human papillomavirus self-assembly (United States)

    Senthil Kumar, M.; Schwartz, Russell


    Virus capsid assembly has been a key model system for studies of complex self-assembly but it does pose some significant challenges for modeling studies. One important limitation is the difficulty of determining accurate rate parameters. The large size and rapid assembly of typical viruses make it infeasible to directly measure coat protein binding rates or deduce them from the relatively indirect experimental measures available. In this work, we develop a computational strategy to deduce coat-coat binding rate parameters for viral capsid assembly systems by fitting stochastic simulation trajectories to experimental measures of assembly progress. Our method combines quadratic response surface and quasi-gradient descent approximations to deal with the high computational cost of simulations, stochastic noise in simulation trajectories and limitations of the available experimental data. The approach is demonstrated on a light scattering trajectory for a human papillomavirus (HPV) in vitro assembly system, showing that the method can provide rate parameters that produce accurate curve fits and are in good concordance with prior analysis of the data. These fits provide an insight into potential assembly mechanisms of the in vitro system and give a basis for exploring how these mechanisms might vary between in vitro and in vivo assembly conditions.

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

    KAUST Repository

    Zhao, Kui


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

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

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


    DNA based self-assembled nanostructures and DNA origami has proven useful for organizing nanomaterials with firm precision. However, for advanced applications like nanoelectronics and photonics, large-scale organization of self-assembled branched DNA (bDNA) into periodic lattices is desired. In this communication for the first time we report a facile method of self-assembly of Y-shaped bDNA nanostructures on the cationic surface of Aluminum (Al) foil to prepare periodic two dimensional (2D) bDNA lattice. Particularly those Y-shaped bDNA structures having smaller overhangs and unable to self-assemble in solution, they are easily assembled on the surface of Al foil in the absence of ligase. Field emission scanning electron microscopy (FESEM) analysis shows homogenous distribution of two-dimensional bDNA lattices across the Al foil. When the assembled bDNA structures were recovered from the Al foil and electrophoresed in nPAGE only higher order polymeric bDNA structures were observed without a trace of monomeric structures which confirms the stability and high yield of the bDNA lattices. Therefore, this enzyme-free economic and efficient strategy for developing bDNA lattices can be utilized in assembling various nanomaterials for functional molecular components towards development of DNA based self-assembled nanodevices. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Amphiphilic Perylene-Calix[4]arene hybrids:synthesis and tunable self-assembly


    Rodler, Fabian; Schade, Boris; Jaeger, Christof M.; Backes, Susanne; Hampel, Frank; Boettcher, Christoph; Clark, Timothy; Hirsch, Andreas


    The first highly water-soluble perylene–calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π–π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficien...

  16. Self-assembled silver nanoparticles in a bow-tie antenna configuration. (United States)

    Eskelinen, Antti-Pekka; Moerland, Robert J; Kostiainen, Mauri A; Törmä, Päivi


    The self-assembly of silver nanoparticles into a bow-tie antenna configuration is achieved with the DNA origami method. Instead of complicated particle geometries, spherical silver nanoparticles are used. Formation of the structures in high yields is verified with transmission electron microscopy and agarose gel electrophoresis. According to finite-difference time-domain simulations, the antenna configuration could be used as a DNA sensor.

  17. Fluorescent nanoparticles based on self-assembled pi-conjugated systems. (United States)

    Kaeser, Adrien; Schenning, Albertus P H J


    pi-Conjugated molecules are interesting components to prepare fluorescent nanoparticles. From the use of polymer chains that form small aggregates in water to the self-assembly of small chromophoric segments into highly ordered structures, the preparation of these materials allows to develop systems with applications as sensors or biolabels. The potential functionalization of the nanoparticles can lead to specific probing. This progress report describes the recent advances in the preparation of such emittive organic nanoparticles.

  18. Kinetics versus thermodynamics dichotomy and growth -mechanisms in linear self-assembly of mixed nanoblocks


    Keten, Sinan


    Self-assembly is a low energy synthesis process, prominent in biological systems, in which smaller building blocks spontaneously associate to form highly organized structures of great complexity. Thus, it is one of the most promising strategies to engineer hierarchical functional nanostructures. Of special interest are one-dimensional arrays of nanobuilding blocks (e.g., nanoparticles, peptides, colloids, etc.), such as nanowires, nanotubes or polymer-like structures, due to their potential a...

  19. TEM EDS analysis of epitaxially-grown self-assembled indium islands

    Directory of Open Access Journals (Sweden)

    Jasmine Sears


    Full Text Available Epitaxially-grown self-assembled indium nanostructures, or islands, show promise as nanoantennas. The elemental composition and internal structure of indium islands grown on gallium arsenide are explored using Transmission Electron Microscopy (TEM Energy Dispersive Spectroscopy (EDS. Several sizes of islands are examined, with larger islands exhibiting high (>94% average indium purity and smaller islands containing inhomogeneous gallium and arsenic contamination. These results enable more accurate predictions of indium nanoantenna behavior as a function of growth parameters.

  20. Self-assembly of electronically abrupt borophene/organic lateral heterostructures


    Liu, Xiaolong; Wei, Zonghui; Balla, Itamar; Mannix, Andrew J.; Guisinger, Nathan P.; Luijten, Erik; Hersam, Mark C.


    Two-dimensional boron sheets (that is, borophene) have recently been realized experimentally and found to have promising electronic properties. Because electronic devices and systems require the integration of multiple materials with well-defined interfaces, it is of high interest to identify chemical methods for forming atomically abrupt heterostructures between borophene and electronically distinct materials. Toward this end, we demonstrate the self-assembly of lateral heterostructures betw...

  1. Strongly Coupled Plasmonic Modes on Macroscopic Areas via Template-Assisted Colloidal Self-Assembly


    Hanske, Christoph; Tebbe, Moritz; Kuttner, Christian; Bieber, Vera; Tsukruk, Vladimir V.; Chanana, Munish; K?nig, Tobias A. F.; Fery, Andreas


    We present ensembles of surface-ordered nanoparticle arrangements, which are formed by template-assisted self-assembly of monodisperse, protein-coated gold nanoparticles in wrinkle templates. Centimeter-squared areas of highly regular, linear assemblies with tunable line width are fabricated and their extinction cross sections can be characterized by conventional UV/vis/NIR spectroscopy. Modeling based on electrodynamic simulations shows a clear signature of strong plasmonic coupling with an ...

  2. Synthesis and solution self-assembly of side-chain cobaltocenium-containing block copolymers. (United States)

    Ren, Lixia; Hardy, Christopher G; Tang, Chuanbing


    The synthesis of side-chain cobaltocenium-containing block copolymers and their self-assembly in solution was studied. Highly pure monocarboxycobaltocenium was prepared and subsequently attached to side chains of poly(tert-butyl acrylate)-block-poly(2-hydroxyethyl acrylate), yielding poly(tert-butyl acrylate)-block-poly(2-acryloyloxyethyl cobaltoceniumcarboxylate). The cobaltocenium block copolymers exhibited vesicle morphology in the mixture of acetone and water, while micelles of nanotubes were formed in the mixture of acetone and chloroform.

  3. Hierarchical Structures from Inorganic Nanocrystal Self-Assembly for Photoenergy Utilization


    Zhu, Yun-Pei; Ren, Tie-Zhen; Ma, Tian-Yi; Yuan, Zhong-Yong


    Self-assembly has emerged as a powerful strategy for controlling the structure and physicochemical properties of ensembles of inorganic nanocrystals. Hierarchical structures from nanocrystal assembly show collective properties that differ from individual nanocrystals and bulk samples. Incorporation of structural hierarchy into nanostructures is of great importance as a result of enhancing mass transportation, reducing resistance to diffusion, and high surface areas for adsorption and reaction...

  4. Helical fibrous nanostructures self-assembled from metal-free phthalocyanine with peripheral chiral menthol units. (United States)

    Lv, Wei; Wu, Xingcui; Bian, Yongzhong; Jiang, Jianzhuang; Zhang, Xiaomei


    (D)- and (L)-enantiomers of a novel metal-free 2(3),9(10),16(17),23(24)-tetrakis(2-isopropyl-5-methylcyclohexoxyl)phthalocyanine (1) with four chiral menthol units attached at the peripheral positions of a phthalocyanine ligand have been synthesized, and characterized. Neither the (D)-1 nor the (L)-1 enantiomer display a circular dichroism (CD) signal in the Soret and Q absorption region of the phthalocyanine ligand, indicating the lack of effective chiral information transfer from the chiral menthol tails to the phthalocyanine chromophore at the molecular level. Their self-assembly properties were systematically studied by CD spectroscopy, transmission electron microscopy, scanning electron microscopy, and atom force microscopy technique. Although four constitutional stereoisomers of each enantiomer were synthesized, because the four chiral menthol substituents are randomly located at peripheral positions of the phthalocyanine ring, cooperation of intermolecular pi-pi interactions between the phthalocyanine rings with chiral discrimination of the chiral side chains of the (D)-1 and the (L)-1 enantiomer induces the formation of one-dimensional helices with left- and right-handed helical molecular arrangement, respectively, according to the CD spectroscopic results. This reveals the effective chiral information transfer from the chiral menthol tails to the phthalocyanine chromophore at the supermolecular level. The formed one-dimensional helices twist around each other to maximize the van der Waals interaction, leading to the formation of highly ordered fibrous nanostructures with both right- and left-handed helicity according to the staggering angles between the neighboring phthalocyanine molecules, indicating the hierarchical formation of these fibrous nanostructures. Careful inspection of these nanofibers indicates the majority of nanofibers with right- and left-handed helicity formed from (D)-1 and (L)-1 enantiomer, respectively, with the ratio of approximately

  5. Mn-doped Ge self-assembled quantum dots via dewetting of thin films

    Energy Technology Data Exchange (ETDEWEB)

    Aouassa, Mansour, E-mail: [LMON, Faculté des Sciences de Monastir, Avenue de l’environnement Monastir 5019 (Tunisia); Jadli, Imen [LMON, Faculté des Sciences de Monastir, Avenue de l’environnement Monastir 5019 (Tunisia); Bandyopadhyay, Anup [Department of Mechanical Engineering, Texas A& M University, College Station, TX 77843 (United States); Kim, Sung Kyu [Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Yuseong-daero 1689-gil, Yuseong-gu, Daejeon (Korea, Republic of); Department of Materials Science and Engineering, KAIST 291 Daehak-ro, Yuseong-gu, Daejeon (Korea, Republic of); Karaman, Ibrahim [Department of Mechanical Engineering, Texas A& M University, College Station, TX 77843 (United States); Lee, Jeong Yong [Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Yuseong-daero 1689-gil, Yuseong-gu, Daejeon (Korea, Republic of); Department of Materials Science and Engineering, KAIST 291 Daehak-ro, Yuseong-gu, Daejeon (Korea, Republic of)


    Highlights: • We report the new fabrication approach for producing a self- assembled Mn dpoed Ge quantum dots (QDs) on SiO{sub 2} thin film with a Curie temperature above room temperature. These magnetic QDs are crystalline, monodisperse and have a well-defined shape and a controlled size. The investigation opens new routes for elaboration of self-assembled magnetic nanocrystals - Abstract: In this study, we demonstrate an original elaboration route for producing a Mn-doped Ge self-assembled quantum dots on SiO{sub 2} thin layer for MOS structure. These magnetic quantum dots are elaborated using dewetting phenomenon at solid state by Ultra-High Vacuum (UHV) annealing at high temperature of an amorphous Ge:Mn (Mn: 40%) nanolayer deposed at very low temperature by high-precision Solid Source Molecular Beam Epitaxy on SiO{sub 2} thin film. The size of quantum dots is controlled with nanometer scale precision by varying the nominal thickness of amorphous film initially deposed. The magnetic properties of the quantum-dots layer have been investigated by superconducting quantum interference device (SQUID) magnetometry. Atomic force microscopy (AFM), x-ray energy dispersive spectroscopy (XEDS) and transmission electron microscopy (TEM) were used to examine the nanostructure of these materials. Obtained results indicate that GeMn QDs are crystalline, monodisperse and exhibit a ferromagnetic behavior with a Curie temperature (TC) above room temperature. They could be integrated into spintronic technology.

  6. Light Scattering Strategy for the Investigation of Time-Evolving Heterogeneous Supramolecular Self-Assemblies (United States)

    Jouault, Nicolas; Moulin, Emilie; Giuseppone, Nicolas; Buhler, Eric


    Supramolecular self-assembly is a multiple length-scale and time-dependent process involving many coexisting components. Such complexity requires suitable strategies to extract quantitative dynamical and structural information on all involved species. Here, we detail an original light scattering method to study the kinetics of tailored triarylamine molecules capable of self-assembling in supramolecular highly conductive nanowires upon light exposure. These micrometric assemblies cause the emergence of intermittences in the scattered intensity and the construction of a predominant slow mode in the correlation function making separation between small-and large-size species impossible using conventional treatments. Our strategy is based on the time monitoring of intermittences and allows us to determine the fraction of nanowires as well as those of small critical nuclei and triarylamine building blocks as a function of time and light exposure, in good agreement with recent theoretical predictions.

  7. Effect of cationic/anionic organic surfactants on evaporation induced self assembled tin oxide nanostructured films

    Energy Technology Data Exchange (ETDEWEB)

    Khun Khun, Kamalpreet [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India); Mahajan, Aman, E-mail: [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India); Bedi, R.K. [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India)


    Tin oxide nanostructures with well defined morphologies have been obtained through an evaporation induced self assembly process. The technique has been employed using an ultrasonic nebulizer for production of aersol and its subsequent deposition onto a heated glass substrate. The precursor used for aersol production was modified by introducing cationic and anionic surfactants namely cetyl trimethyl ammonium bromide and sodium dodecyl sulphate respectively. The effect of surfactants on the structural, electrical and optical properties of self assembled tin oxide nanostructures were investigated by using X-ray diffraction, field emission scanning electroscope microscopy, two probe technique and photoluminiscence studies. The results reveal that high concentration of surfactants in the precursor solution leads to reduction in crystallite size with significant changes in the morphology of tin oxide nanostructures. Photoluminiscence studies of the nanostructures show emissions in the visible region which exhibit marked changes in the intensities upon variation of surfactants in the precursor solutions.

  8. Reconfigurable Chiral Self-Assembly of Peptides through Control of Terminal Charges. (United States)

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


    Self-assembly of chiral nanostructures is of considerable interest, since the ability to control the chirality of these structures has direct ramifications in biology and materials science. A new approach to design chiral nanostructures from self-assembly of N-(9-fluorenylmethoxycarbonyl)-protected phenylalanine-tryptophan-lysine tripeptides is reported. The terminal charges can induce helical twisting of the assembled β-sheets, enabling the formation of well-defined chiral nanostructures. The degree and direction of twisting in the β-sheets can be precisely tailored through in situ pH and temperature modulations. This enables the assembly of reconfigurable chiral nanomaterials with easily adjustable size and handedness. These results offer new insight into the mechanism of helical twist formation, which may enable the precise assembly of highly dynamical materials with potential applications in biomedicine, chiroptics, and chiral sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Metallacrowns as products of the aqueous medium self-assembly of histidinehydroxamic acid-containing polypeptides. (United States)

    Cal, Marta; Kotynia, Aleksandra; Jaremko, Łukasz; Jaremko, Mariusz; Lisowski, Marek; Cebo, Małgorzata; Brasuń, Justyna; Stefanowicz, Piotr


    Self-assembly is a widely studied, spontaneous, and reversible phenomenon leading to the formation of the ordered structures by non-covalent specific interactions among starting molecules. In this work, a new template for the self-assembly of polypeptides based on peptides containing the C-terminal histidinehydroxamic acid moiety and Cu(2+) ions is characterized. Two peptide (tripeptide and pentadecapeptide) hydroxamic acid systems were synthesized and their interactions with Cu(2+) ions were investigated, revealing a high stability of the supramolecular assemblies formed. The supramolecular metallacrown-based L4Cu5 complexes exist at physiological pH in the presence of Cu(2+) ions as is evidenced from the spectroscopic methods, ESI mass spectrometry, and physicochemical techniques.

  10. Preparation and Characterization of Self-Assembled Manganese Dioxide Thin Films

    Directory of Open Access Journals (Sweden)

    Suh Cem Pang


    Full Text Available Thin films of manganese dioxide (MnO2 were prepared by self-assembly of MnO2 nanoparticles directly unto nickel-coated poly(ethylene terephthalate flexible films using the newly developed horizontal submersion process. The thickness of deposited thin films was controllable by the deposition duration. This horizontal submersion deposition process for thin-film deposition is relatively easy, simple, and cost effective. Effects of deposition duration and calcination temperatures on the microstructure and electrochemical properties of self-assembled MnO2 thin films were investigated. Optimized MnO2 thin films exhibited high charge capacity, good cycling reversibility, and stability in a mild aqueous electrolyte and are thus promising electrode materials for the fabrication of thin-film electrochemical capacitors.

  11. Quantitative self-assembly of a purely organic three-dimensional catenane in water (United States)

    Li, Hao; Zhang, Huacheng; Lammer, Aaron D.; Wang, Ming; Li, Xiaopeng; Lynch, Vincent M.; Sessler, Jonathan L.


    Self-assembly by means of coordinative bond formation has opened up opportunities for the high-yield synthesis of molecules with complex topologies. However, the preparation of purely covalent molecular architectures in aqueous media has remained a challenging task. Here, we present the preparation of a three-dimensional catenane through a self-assembly process that relies on the formation of dynamic hydrazone linkages in an acidic aqueous medium. The quantitative synthesis process and the mechanically interlocked structure of the resulting catenane were established by NMR spectroscopy, mass spectrometry, X-ray crystallography and HPLC studies. In addition, the labile hydrazone linkages of the individual [2]catenane components may be ‘locked’ by increasing the pH of the solution, yielding a relatively kinetically stable molecule. The present study thus details a simple approach to the creation and control of complex molecular architectures under reaction conditions that mimic biological milieux.

  12. Cationic xylan adsorption onto self-assembled monolayers and model cellulose surfaces (United States)

    Esker, Alan; Kaya, Abdulaziz; Drazenovich, Daniel; Glasser, Wolfgang; Schwikal, Katrin; Heinze, Thomas


    Self-assembly of cationic hydroxypropyltrimethylammonium xylans (HPMAs) with different degrees of substitution (DS) onto self-assembled monolayers (SAMs) and model cellulose surfaces has been investigated by surface plasmon resonance (SPR). Maximal adsorption of HPMAs onto COOH-terminated SAMs occurs at an intermediate DS=0.10. Ionic strength effects on adsorbed amount follow different trends at low and high DS values which qualitatively agree with predictions of scaling theory for polyelectrolyte adsorption. For adsorption onto model cellulose surfaces and OH-terminated SAMs, surface excess values are relatively low compared to COOH-terminated SAMs. For adsorption onto CH3-terminated SAMs, solubility of the HPMAs plays an important role as HPMA adsorption decreases with increasing DS values.

  13. Engineering Globular Protein Vesicles through Tunable Self-Assembly of Recombinant Fusion Proteins. (United States)

    Jang, Yeongseon; Choi, Won Tae; Heller, William T; Ke, Zunlong; Wright, Elizabeth R; Champion, Julie A


    Vesicles assembled from folded, globular proteins have potential for functions different from traditional lipid or polymeric vesicles. However, they also present challenges in understanding the assembly process and controlling vesicle properties. From detailed investigation of the assembly behavior of recombinant fusion proteins, this work reports a simple strategy to engineer protein vesicles containing functional, globular domains. This is achieved through tunable self-assembly of recombinant globular fusion proteins containing leucine zippers and elastin-like polypeptides. The fusion proteins form complexes in solution via high affinity binding of the zippers, and transition through dynamic coacervates to stable hollow vesicles upon warming. The thermal driving force, which can be tuned by protein concentration or temperature, controls both vesicle size and whether vesicles are single or bi-layered. These results provide critical information to engineer globular protein vesicles via self-assembly with desired size and membrane structure. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Time lapse microscopy of temperature control during self-assembly of 3D DNA crystals (United States)

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


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

  15. Scalable self-assembled reduced graphene oxide transistors on flexible substrate (United States)

    Wang, Zhenxing; Eigler, Siegfried; Halik, Marcus


    To enable graphene oxide (GO) flakes for application based on solution processable technology, we show that they can be self-assembled from solution on flexible substrate driven by a Coulomb interaction with the self-assembled monolayer (SAM). Field-effect transistors exhibit a high hole mobility around 14 cm2/V.s after a reduction process from GO to reduced GO (rGO), and meanwhile the device resistance shows a linear scaling behavior with the channel length. Due to the flexibility of the SAM, the device parameters maintain stable, while different strains are applied to the substrate. This approach makes the combination of rGO and SAM suitable for low-cost flexible applications.

  16. Identifying the nature of surface chemical modification for directed self-assembly of block copolymers

    Directory of Open Access Journals (Sweden)

    Laura Evangelio


    Full Text Available In recent years, block copolymer lithography has emerged as a viable alternative technology for advanced lithography. In chemical-epitaxy-directed self-assembly, the interfacial energy between the substrate and each block copolymer domain plays a key role on the final ordering. Here, we focus on the experimental characterization of the chemical interactions that occur at the interface built between different chemical guiding patterns and the domains of the block copolymers. We have chosen hard X-ray high kinetic energy photoelectron spectroscopy as an exploration technique because it provides information on the electronic structure of buried interfaces. The outcome of the characterization sheds light onto key aspects of directed self-assembly: grafted brush layer, chemical pattern creation and brush/block co-polymer interface.

  17. Host-guest complexation driven dynamic supramolecular self-assembly. (United States)

    Zhang, Huacheng; Nguyen, Kim Truc; Ma, Xing; Yan, Hong; Guo, Junfei; Zhu, Liangliang; Zhao, Yanli


    Host-guest complexation between pillararene trimer 1 and biviologen 2 was used to fabricate the dynamic supramolecular self-assembly, which exhibits a reversible multidimensional transformation from 0D to 3D upon concentration changes. As a comparison, assemblies built by the complexation between 1,4-dimethoxypillar[5]arene and 2 only show spherical morphology under similar conditions.

  18. Photoinduced self-assembly of nanostructure in glass

    Directory of Open Access Journals (Sweden)

    Shimotsuma Y.


    Full Text Available Ultrashort-pulsed laser direct writing can be useful for a 3D material processing. Especially the localized form-birefringence originated from self-assembled nanostructure in isotropic material (i.e. SiO2 and GeO2 glass was demonstrated.

  19. Electronic functionalization of organic semiconductors with self-assembled monolayers (United States)

    Podzorov, Vitaly


    Self-assembled monolayers (SAM) are widely used in a variety of emerging applications for surface modification of metals and oxides. Here, we demonstrate a new type of molecular self-assembly: the growth of organosilane SAMs at the surface of organic semiconductors. Remarkably, SAM growth results in a pronounced increase of surface conductivity of organic materials, which can be very large for SAMs with a strong electron withdrawing ability. For example, the conductivity induced by perfluorinated alkyl silanes in organic molecular crystals approaches 10̂-5 S per square, two orders of magnitude greater than the maximum conductivity typically achieved in organic field-effect transistors (OFETs). The observed large electronic effect opens new opportunities for nanoscale surface functionalization of organic semiconductors with molecular self-assembly. In particular, SAM-induced conductivity exhibits sensitivity to different molecular species present in the environment, which makes this system very attractive for chemical sensing applications [1]. [1]. M. F. Calhoun, J. Sanchez, D. Olaya, M. E. Gershenson and V. Podzorov, ``Electronic functionalization of the surface of organic semiconductors with self-assembled monolayers'', Nature Materials, Nov. 18, (2007).

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

    Sengupta, Sanchita; Würthner, Frank


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

  1. Functional materials derived from block copolymer self-assembly

    DEFF Research Database (Denmark)

    Li, Tao

    The main objective of this project is to explore block copolymer self-assembly for generating functional materials with well-defined morphology on sub-20 nanometer length scale, which can be utilized in many important applications such as solar cells and nanolithography. One of the specific targe...

  2. Tailoring self-assembled monolayers at the electrochemical interface

    Indian Academy of Sciences (India)

    The main focus of this review is to illustrate the amenability of self-assembled monolayers (SAMs) for functionalisation with different receptors, catalytic materials, biomolecules, enzymes, antigen-antibody, etc for various applications. The review discusses initially about the preparation and characterization of SAMs and ...

  3. Electrostatic Self-Assembly of Polysaccharides into Nanofibers

    DEFF Research Database (Denmark)

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


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

  4. Multiphonon capture processes in self-assembled quantum dots

    DEFF Research Database (Denmark)

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


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

  5. Self-Assembled Microwires of Terephthalic Acid and Melamine

    Directory of Open Access Journals (Sweden)

    Hong Wang


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

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

    NARCIS (Netherlands)

    Vutukuri, H.R.


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

  7. Synthesis, characterization and self-assembly of Co complexes ...

    Indian Academy of Sciences (India)

    (H-bonded) assemblies and afford inclusion complexes with solvents serving as the guest molecules.12 Self- assembly of phenolic compounds show that the ...... Board (SERB), Govt. of India for the generous financial support and CIF-USIC of this university for the instru- mental facilities. AA and DB thank University Grant.

  8. Reactivity within a confined self-assembled nanospace

    NARCIS (Netherlands)

    Koblenz, T.S.; Wassenaar, J.; Reek, J.N.H.


    Confined nanospaces in which reactions can take place, have been created by various approaches such as molecular capsules, zeolites and micelles. In this tutorial review we focus on the application of self-assembled nanocapsules with well-defined cavities as nanoreactors for organic and metal

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

    African Journals Online (AJOL)

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

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

    NARCIS (Netherlands)

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


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

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

    Indian Academy of Sciences (India)

    Usha P Kar


    Dec 30, 2017 ... Self-assembly on target membranes is one of the important properties of all dynamin family proteins. Drp6, a dynamin- related protein in Tetrahymena, controls nuclear remodelling and undergoes cycles of assembly/disassembly on the nuclear envelope. To elucidate the mechanism of Drp6 function, we ...

  12. Chirality controlled responsive self-assembled nanotubes in water

    NARCIS (Netherlands)

    van Dijken, D. J.; Stacko, P.; Stuart, M. C. A.; Browne, W. R.; Feringa, B. L.


    The concept of using chirality to dictate dimensions and to store chiral information in self-assembled nanotubes in a fully controlled manner is presented. We report a photoresponsive amphiphile that co-assembles with its chiral counterpart to form nanotubes and demonstrate how chirality can be used

  13. Long lived coherence in self-assembled quantum dots

    DEFF Research Database (Denmark)

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


    We report measurements of ultralong coherence in self-assembled quantum dots. Transient four-wave mixing experiments at 5 K show an average dephasing time of 372 ps, corresponding to a homogeneous linewidth of 3.5 mu eV, which is significantly smaller than the linewidth observed in single-dot lum...

  14. Digital Imprinting of RNA Recognition and Processing on a Self-Assembled Nucleic Acid Matrix (United States)

    Redhu, Shiv K.; Castronovo, Matteo; Nicholson, Allen W.


    The accelerating progress of research in nanomedicine and nanobiotechnology has included initiatives to develop highly-sensitive, high-throughput methods to detect biomarkers at the single-cell level. Current sensing approaches, however, typically involve integrative instrumentation that necessarily must balance sensitivity with rapidity in optimizing biomarker detection quality. We show here that laterally-confined, self-assembled monolayers of a short, double-stranded(ds)[RNA-DNA] chimera enable permanent digital detection of dsRNA-specific inputs. The action of ribonuclease III and the binding of an inactive, dsRNA-binding mutant can be permanently recorded by the input-responsive action of a restriction endonuclease that cleaves an ancillary reporter site within the dsDNA segment. The resulting irreversible height change of the arrayed ds[RNA-DNA], as measured by atomic force microscopy, provides a distinct digital output for each dsRNA-specific input. These findings provide the basis for developing imprinting-based bio-nanosensors, and reveal the versatility of AFM as a tool for characterizing the behaviour of highly-crowded biomolecules at the nanoscale.

  15. Peptides at the Interface: Self-Assembly of Amphiphilic Designer Peptides and Their Membrane Interaction Propensity. (United States)

    Kornmueller, Karin; Lehofer, Bernhard; Meindl, Claudia; Fröhlich, Eleonore; Leitinger, Gerd; Amenitsch, Heinz; Prassl, Ruth


    Self-assembling amphiphilic designer peptides have been successfully applied as nanomaterials in biomedical applications. Understanding molecular interactions at the peptide-membrane interface is crucial, since interactions at this site often determine (in)compatibility. The present study aims to elucidate how model membrane systems of different complexity (in particular single-component phospholipid bilayers and lipoproteins) respond to the presence of amphiphilic designer peptides. We focused on two short anionic peptides, V4WD2 and A6YD, which are structurally similar but showed a different self-assembly behavior. A6YD self-assembled into high aspect ratio nanofibers at low peptide concentrations, as evidenced by synchrotron small-angle X-ray scattering and electron microscopy. These supramolecular assemblies coexisted with membranes without remarkable interference. In contrast, V4WD2 formed only loosely associated assemblies over a large concentration regime, and the peptide promoted concentration-dependent disorder on the membrane arrangement. Perturbation effects were observed on both membrane systems although most likely induced by different modes of action. These results suggest that membrane activity critically depends on the peptide's inherent ability to form highly cohesive supramolecular structures.

  16. Selective Area Control of Self-Assembled Pattern Architecture Using a Lithographically Patternable Block Copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Black, C.T.; Bosworth, J.K.; Obert C.K.


    We leverage distinctive chemical properties of the diblock copolymer poly({alpha}-methylstyrene)-block-poly(4-hydroxystyrene) to create for the first time high-resolution selective-area regions of two different block copolymer phase morphologies. Exposure of thin films of poly({alpha}-methylstyrene)-block-poly(4-hydroxystyrene) to nonselective or block-selective solvent vapors results in polymer phase separation and self-assembly of patterns of cylindrical-phase or kinetically trapped spherical-phases, respectively. Poly(4-hydroxystyrene) acts as a high-resolution negative-tone photoresist in the presence of small amounts of a photoacid generator and cross-linker, undergoing radiation-induced cross-linking upon exposure to ultraviolet light or an electron beam. We use lithographic exposure to lock one self-assembled phase morphology in specific sample areas as small as 100 nm in width prior to film exposure to a subsequent solvent vapor to form a second self-assembled morphology in unexposed wafer areas.

  17. Design and self-assembly of simple coat proteins for artificial viruses (United States)

    Hernandez-Garcia, Armando; Kraft, Daniela J.; Janssen, Anne F. J.; Bomans, Paul H. H.; Sommerdijk, Nico A. J. M.; Thies-Weesie, Dominique M. E.; Favretto, Marco E.; Brock, Roland; de Wolf, Frits A.; Werten, Marc W. T.; van der Schoot, Paul; Stuart, Martien Cohen; de Vries, Renko


    Viruses are among the simplest biological systems and are highly effective vehicles for the delivery of genetic material into susceptible host cells. Artificial viruses can be used as model systems for providing insights into natural viruses and can be considered a testing ground for developing artificial life. Moreover, they are used in biomedical and biotechnological applications, such as targeted delivery of nucleic acids for gene therapy and as scaffolds in material science. In a natural setting, survival of viruses requires that a significant fraction of the replicated genomes be completely protected by coat proteins. Complete protection of the genome is ensured by a highly cooperative supramolecular process between the coat proteins and the nucleic acids, which is based on reversible, weak and allosteric interactions only. However, incorporating this type of supramolecular cooperativity into artificial viruses remains challenging. Here, we report a rational design for a self-assembling minimal viral coat protein based on simple polypeptide domains. Our coat protein features precise control over the cooperativity of its self-assembly with single DNA molecules to finally form rod-shaped virus-like particles. We confirm the validity of our design principles by showing that the kinetics of self-assembly of our virus-like particles follows a previous model developed for tobacco mosaic virus. We show that our virus-like particles protect DNA against enzymatic degradation and transfect cells with considerable efficiency, making them promising delivery vehicles.

  18. Septipyridines as conformationally controlled substitutes for inaccessible bis(terpyridine-derived oligopyridines in two-dimensional self-assembly

    Directory of Open Access Journals (Sweden)

    Daniel Caterbow


    Full Text Available The position of the peripheral nitrogen atoms in bis(terpyridine-derived oligopyridines (BTPs has a strong impact on their self-assembly behavior at the liquid/HOPG (highly oriented pyrolytic graphite interface. The intermolecular hydrogen bonding interactions in these peripheral pyridine units show specific 2D structures for each BTP isomer. From nine possible constitutional isomers only four have been described in the literature. The synthesis and self-assembling behavior of an additional isomer is presented here, but the remaining four members of the series are synthetically inaccessible. The self-assembling properties of three of the missing four BTP isomers can be mimicked by making use of the energetically preferred N–C–C–N transoid conformation between 2,2'-bipyridine subunits in a new class of so-called septipyridines. The structures are investigated by scanning tunneling microscopy (STM and a combination of force-field and first-principles electronic structure calculations.

  19. Topological defects in liquid crystals and molecular self-assembly (Conference Presentation) (United States)

    Abbott, Nicholas L.


    Topological defects in liquid crystals (LCs) have been widely used to organize colloidal dispersions and template polymerizations, leading to a range of elastomers and gels with complex mechanical and optical properties. However, little is understood about molecular-level assembly processes within defects. This presentation will describe an experimental study that reveals that nanoscopic environments defined by LC topological defects can selectively trigger processes of molecular self-assembly. By using fluorescence microscopy, cryogenic transmission electron microscopy and super-resolution optical microscopy, key signatures of molecular self-assembly of amphiphilic molecules in topological defects are observed - including cooperativity, reversibility, and controlled growth of the molecular assemblies. By using polymerizable amphiphiles, we also demonstrate preservation of molecular assemblies templated by defects, including nanoscopic "o-rings" synthesized from "Saturn-ring" disclinations. Our results reveal that topological defects in LCs are a versatile class of three-dimensional, dynamic and reconfigurable templates that can direct processes of molecular self-assembly in a manner that is strongly analogous to other classes of macromolecular templates (e.g., polymer—surfactant complexes). Opportunities for the design of exquisitely responsive soft materials will be discussed using bacterial endotoxin as an example.

  20. Self-assembly of nucleic acids, silk and hybrid materials thereof (United States)

    Humenik, Martin; Scheibel, Thomas


    Top-down approaches based on etching techniques have almost reached their limits in terms of dimension. Therefore, novel assembly strategies and types of nanomaterials are required to allow technological advances. Self-assembly processes independent of external energy sources and unlimited in dimensional scaling have become a very promising approach. Here, we highlight recent developments in self-assembled DNA-polymer, silk-polymer and silk-DNA hybrids as promising materials with biotic and abiotic moieties for constructing complex hierarchical materials in ‘bottom-up’ approaches. DNA block copolymers assemble into nanostructures typically exposing a DNA corona which allows functionalization, labeling and higher levels of organization due to its specific addressable recognition properties. In contrast, self-assembly of natural silk proteins as well as their recombinant variants yields mechanically stable β-sheet rich nanostructures. The combination of silk with abiotic polymers gains hybrid materials with new functionalities. Together, the precision of DNA hybridization and robustness of silk fibrillar structures combine in novel conjugates enable processing of higher-order structures with nanoscale architecture and programmable functions.

  1. Hierarchically Self-Assembled Nanofiber Films from Amylose-Grafted Carboxymethyl Cellulose

    Directory of Open Access Journals (Sweden)

    Daisuke Hatanaka


    Full Text Available In this paper, we report the formation of hierarchically self-assembled nanofiber films from amylose-grafted sodium carboxymethyl celluloses (NaCMCs that were synthesized by a chemoenzymatic approach. First, maltooligosaccharide primer-grafted NaCMCs were prepared by a chemical reaction using two kinds of NaCMCs with different degrees of polymerization (DPs from Avicel and cotton sources. Then, phosphorylase-catalyzed enzymatic polymerization of α-d-glucose 1-phosphate from the nonreducing ends of the primer chains on the products was conducted to produce the prescribed amylose-grafted NaCMCs. The films were obtained by drying aqueous alkaline solutions of the amylose-grafted NaCMCs. The scanning electron microscopy (SEM image of the film fabricated from the material with the higher DP from the cotton source showed a clear, self-assembled, highly condensed tangle of nanofibers. The SEM image of the material with the lower DP from the Avicel source, on the other hand, showed an unclear nanofiber morphology. These results indicate that the DPs of the main chains in the materials strongly affected the hierarchically self-assembled nanofiber formation. The SEM images of the films after washing out the alkali, furthermore, showed that the fibers partially merged with each other at the interfacial area owing to the double helix formation between the amylose-grafted chains. The mechanical properties of the films under tensile mode also depended on the self-assembled morphologies of the amylose-grafted NaCMCs from the different sources.

  2. Depth profiling of APTES self-assembled monolayers using surface-enhanced confocal Raman microspectroscopy (United States)

    Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki


    The internal structure of self-assembled monolayers (SAMs) such as 3-aminopropyltriethoxysilane (APTES) fabricated on a glass substrate is difficult to characterize and analyze at nanometer level. In this study, we employed surface-enhanced Raman spectroscopy (SERS) to study the internal molecular structure of APTES SAMs. The sample APTES SAMs were deposited with Ag nanoparticles to enhance the Raman signal and to obtain subtler structure information, which were supported by density functional theory calculations. In addition, in order to carry out high-resolution analysis, especially for vertical direction, a fine piezo electric positioner was used to control the depth scanning with a step of 0.1 nm. We measured and distinguished the vertical Raman intensity variations of specific groups in APTES, such as Ag/NH2, CH2, and Sisbnd O, with high resolution. The interfacial bond at the two interfaces of Ag-APTES and APTES-SiO2 was identified. Moreover, APTES molecule orientation was demonstrated to be inhomogeneous from frequency shift.

  3. Hierarchical self-assembly: Self-organized nanostructures in a nematically ordered matrix of self-assembled polymeric chains (United States)

    Mubeena, Shaikh; Chatterji, Apratim


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

  4. Long-range ordered self-assembled InAs quantum dots epitaxially grown on (110) GaAs (United States)

    Bauer, J.; Schuh, D.; Uccelli, E.; Schulz, R.; Kress, A.; Hofbauer, F.; Finley, J. J.; Abstreiter, G.


    We report on a promising approach for positioning of self-assembled InAs quantum dots on (110) GaAs with nanometer precision. By combining self-assembly of quantum dots with molecular beam epitaxy on previously grown and in situ cleaved substrates (cleaved-edge overgrowth), arrays of long-range ordered InAs quantum dots have been fabricated. Both atomic force microscopy and micro-photoluminescence measurements demonstrate the ability to control size, position, and ordering of the quantum dots. Furthermore, single dot photoluminescence investigations confirm the high optical quality of the quantum dots fabricated.

  5. A Robust and Engineerable Self-Assembling Protein Template for the Synthesis and Patterning of Ordered Nanoparticle Arrays (United States)

    McMillan, R. Andrew; Howard, Jeanie; Zaluzec, Nestor J.; Kagawa, Hiromi K.; Li, Yi-Fen; Paavola, Chad D.; Trent, Jonathan D.


    Self-assembling biomolecules that form highly ordered structures have attracted interest as potential alternatives to conventional lithographic processes for patterning materials. Here we introduce a general technique for patterning materials on the nanoscale using genetically modified protein cage structures called chaperonins that self-assemble into crystalline templates. Constrained chemical synthesis of transition metal nanoparticles is specific to templates genetically functionalized with poly-Histidine sequences. These arrays of materials are ordered by the nanoscale structure of the crystallized protein. This system may be easily adapted to pattern a variety of materials given the rapidly growing list of peptide sequences selected by screening for specificity for inorganic materials.

  6. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration. (United States)

    Yu, Haizhou; Qiu, Xiaoyan; Moreno, Nicolas; Ma, Zengwei; Calo, Victor Manuel; Nunes, Suzana P; Peinemann, Klaus-Viktor


    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol(-1) in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Peptide-Modulated Self-Assembly of Chromophores toward Biomimetic Light-Harvesting Nanoarchitectonics. (United States)

    Zou, Qianli; Liu, Kai; Abbas, Manzar; Yan, Xuehai


    Elegant self-assembling complexes by the combination of proteins/peptides with functional chromophores are decisively responsible for highly efficient light-harvesting and energy transfer in natural photosynthetic systems. Mimicking natural light-harvesting complexes through synthetic peptides is attractive due to their advantanges of programmable primary structure, tunable self-assembly architecture and easy availability in comparison to naturally occuring proteins. Here, an overview of recent progresses in the area of biomimetic light-harvesting nanoarchitectonics based on peptide-modulated self-assembly of chromophores is provided. Adjusting the organization of chromophores, either by creating peptide-chromophore conjugates or by the non-covalent assembly of peptides and chromophores are highlighted. The light-harvesting properties, especially the energy transfer of the biomimetic complexes are critically discussed. The applications of such complexes in the mineralization of inorganic nanoparticles, generation of molecular hydrogen and oxygen, and photosynthesis of bioactive molecules are also included. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Meshing complex macro-scale objects into self-assembling bricks. (United States)

    Hacohen, Adar; Hanniel, Iddo; Nikulshin, Yasha; Wolfus, Shuki; Abu-Horowitz, Almogit; Bachelet, Ido


    Self-assembly provides an information-economical route to the fabrication of objects at virtually all scales. However, there is no known algorithm to program self-assembly in macro-scale, solid, complex 3D objects. Here such an algorithm is described, which is inspired by the molecular assembly of DNA, and based on bricks designed by tetrahedral meshing of arbitrary objects. Assembly rules are encoded by topographic cues imprinted on brick faces while attraction between bricks is provided by embedded magnets. The bricks can then be mixed in a container and agitated, leading to properly assembled objects at high yields and zero errors. The system and its assembly dynamics were characterized by video and audio analysis, enabling the precise time- and space-resolved characterization of its performance and accuracy. Improved designs inspired by our system could lead to successful implementation of self-assembly at the macro-scale, allowing rapid, on-demand fabrication of objects without the need for assembly lines.

  9. Recombinant production of self-assembling β-structured peptides using SUMO as a fusion partner

    Directory of Open Access Journals (Sweden)

    Prakash Abhinav


    Full Text Available Abstract Background Self-assembling peptides that form nanostructured hydrogels are important biomaterials for tissue engineering scaffolds. The P11-family of peptides includes, P11-4 (QQRFEWEFEQQ and the complementary peptides P11-13 (EQEFEWEFEQE and P11-14 (QQOrnFOrnWOrnFOrnQQ. These form self-supporting hydrogels under physiological conditions (pH 7.4, 140 mM NaCl either alone (P11-4 or when mixed (P11-13 and P11-14. We report a SUMO-peptide expression strategy suitable for allowing release of native sequence peptide by SUMO protease cleavage. Results We have expressed SUMO-peptide fusion proteins from pET vectors by using autoinduction methods. Immobilised metal affinity chromatography was used to purify the fusion protein, followed by SUMO protease cleavage in water to release the peptides, which were recovered by reverse phase HPLC. The peptide samples were analysed by electrospray mass spectrometry and self-assembly was followed by circular dichroism and transmission electron microscopy. Conclusions The fusion proteins were produced in high yields and the β-structured peptides were efficiently released by SUMO protease resulting in peptides with no additional amino acid residues and with recoveries of 46% to 99%. The peptides behaved essentially the same as chemically synthesised and previously characterised recombinant peptides in self-assembly and biophysical assays.

  10. Activated Carbon Fibers "Thickly Overgrown" by Ag Nanohair Through Self-Assembly and Rapid Thermal Annealing (United States)

    Yan, Xuefeng; Xu, Sijun; Wang, Qiang; Fan, Xuerong


    Anisotropic nanomaterial-modified carbon fibers attract increasing attention because of their superior properties over traditional ones. In this study, activated carbon fibers (ACFs) "thickly overgrown" by Ag nanohair were prepared through self-assembly and rapid thermal annealing. Viscose fibers with well-dispersed silver nanoparticles (AgNPs) on surfaces were first prepared through self-assembly of hyperbranched poly(amino-amine) (HBPAA)-capped AgNPs on viscose surfaces. HBPAA endowed the AgNP surfaces with negative charges and abundant amino groups, allowing AgNPs to monodispersively self-assemble to fiber surfaces. Ag nanohair-grown ACFs were prepared by sequential pre-oxidation and carbonization. Because the carbonization furnace was open-ended, ACFs are immediately transferrable to the outside of the furnace. Therefore, the Ag liquid adsorbed by ACF pores squeezed out to form Ag nanowires through thermal contraction. FESEM characterization indicated that Ag nanohairs stood on ACF surface and grew from ACF caps. XPS and XRD characterization showed that Ag successfully assembled to fiber surfaces and retained its metallic state even after high-temperature carbonization. TG analysis suggested that Ag nanohair-grown ACFs maintained their excellent thermal stabilities. Finally, the fabricated ACFs showed excellent and durable antibacterial activities, and the developed method may provide a potential strategy for preparing metal nanowire-grown ACFs.

  11. Activated Carbon Fibers "Thickly Overgrown" by Ag Nanohair Through Self-Assembly and Rapid Thermal Annealing. (United States)

    Yan, Xuefeng; Xu, Sijun; Wang, Qiang; Fan, Xuerong


    Anisotropic nanomaterial-modified carbon fibers attract increasing attention because of their superior properties over traditional ones. In this study, activated carbon fibers (ACFs) "thickly overgrown" by Ag nanohair were prepared through self-assembly and rapid thermal annealing. Viscose fibers with well-dispersed silver nanoparticles (AgNPs) on surfaces were first prepared through self-assembly of hyperbranched poly(amino-amine) (HBPAA)-capped AgNPs on viscose surfaces. HBPAA endowed the AgNP surfaces with negative charges and abundant amino groups, allowing AgNPs to monodispersively self-assemble to fiber surfaces. Ag nanohair-grown ACFs were prepared by sequential pre-oxidation and carbonization. Because the carbonization furnace was open-ended, ACFs are immediately transferrable to the outside of the furnace. Therefore, the Ag liquid adsorbed by ACF pores squeezed out to form Ag nanowires through thermal contraction. FESEM characterization indicated that Ag nanohairs stood on ACF surface and grew from ACF caps. XPS and XRD characterization showed that Ag successfully assembled to fiber surfaces and retained its metallic state even after high-temperature carbonization. TG analysis suggested that Ag nanohair-grown ACFs maintained their excellent thermal stabilities. Finally, the fabricated ACFs showed excellent and durable antibacterial activities, and the developed method may provide a potential strategy for preparing metal nanowire-grown ACFs.

  12. Hyperbranched polymer vesicles: from self-assembly, characterization, mechanisms, and properties to applications. (United States)

    Jiang, Wenfeng; Zhou, Yongfeng; Yan, Deyue


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

  13. Formation of self-assembled micro- and nano-domain structures in uniaxial ferroelectrics (United States)

    Shur, V. Ya; Shur, A. G.; Akhmatkhanov, A. R.


    We present the experimental study of appearance of domain wall shape instabilities and self-assembled domain structures in uniaxial ferroelectrics lithium niobate and lithium tantalate covered by artificial dielectric layer. The domain structure evolution has been considered as a manifestation of nucleation processes similar to the first order phase transformation. The necessary conditions for formation of self-assembled domain structures including the highly non-equilibrium switching conditions and stability of concave angles were proposed. The formation of the self-assembled domain shape instabilities under application of the uniform external electric field during switching (domain growth) and backswitching (domain shrinkage) has been studied experimentally with these conditions fulfilled. The formation of the bumps at the vortexes of hexagon domain for diameter above 3 - 5 μm with subsequent oriented growth was obtained in stoichiometric lithium tantalate. The formation of quasi-regular fish-bone domain structure has been revealed during spontaneous backswitching in Mg doped lithium niobate. The resulted structure consisted of the narrow residual domains with width from 200 to 500 nm appeared as a result of finger growth to the center of hexagon domain. The obtained decreasing of the number of the residual domains during growth has been attributed to strong electrostatic interaction of domain walls.

  14. Surface Mediated Self-Assembly of Amyloid Peptides (United States)

    Fakhraai, Zahra


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

  15. Two-Dimensional Fluidization of Nanomaterials via Biomimetic Membranes towards Assisted Self Assembly (United States)

    Kelly, Kathleen

    Materials that take advantage of the exceptional properties of nano-meter sized aggregates of atoms are poised to play an important role in future technologies. Prime examples for such nano-materials that have an extremely large surface to volume ratio and thus are physically determined by surface related effects are quantum dots (qdots) and carbon nanotubes (CNTs). The production of such manmade nano-objects has by now become routine and even commercialized. However, the controlled assembly of individual nano-sized building blocks into larger structures of higher geometric and functional complexity has proven to be much more challenging. Yet, this is exactly what is required for many applications that have transformative potential for new technologies. If the tedious procedure to sequentially position individual nano-objects is to be forgone, the assembly of such objects into larger structures needs to be implicitly encoded and many ways to bestow such self-assembly abilities onto nano objects are being developed. Yet, as overall size and complexity of such self-assembled structures increases, kinetic and geometric frustration begin to prevent the system to achieve the desired configuration. In nature, this problem is solved by relying on guided or forced variants of the self-assembly approach. To translate such concepts into the realm of man-made nano-technology, ways to dynamically manipulate nano-materials need to be devised. Thus, in the first part of this work, I provide a proof of concept that supported lipid bilayers (SLBs) that exhibit free lateral diffusion of their constituents can be utilized as a two-dimensional platform for active nano-material manipulation. We used streptavidin coated quantum dots (Q-dots) as a model nano-building-block. Q-dots are 0-dimensional nanomaterials engineered to be fluorescent based solely on their diameter making visualization convenient. Biotinylated lipids were used to tether Q-dots to a SLB and we observed that the 2

  16. Predicting supramolecular self-assembly on reconstructed metal surfaces (United States)

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


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

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

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


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

  18. Self-assembled micro-structured sensors for food safety in paper based food packaging

    Energy Technology Data Exchange (ETDEWEB)

    Hakovirta, M., E-mail:; Aksoy, B.; Hakovirta, J.


    Natural self-assembled microstructured particles (diatomaceous earth) were used to develop a gas sensor paper with detection mechanism based on visible and distinct color changes of the sensor paper when exposed to volatile basic nitrogen compounds. The coating formulation for paper was prepared by applying diatomites, polyvinyl alcohol (PVOH), and pH sensitive dyes on acidic paper substrate. The surface coating was designed to allow a maximum gas flow through the diatomite sensors. The produced sensor paper was tested for sensitivity using different ammonia concentrations and we observed a sensitivity lower limit at 63 ppm. As a comparison, the results show comparable sensitivity levels to carbon nanotube based sensor technologies reported in literature. - Highlights: • Novel sensor paper was developed using micro-structured diatomaceous earth and pH sensitive dye. • The functionality is based on pH sensitive dye to indicate spoilage of meat or fish by color change. • Diatomaceous earth was successfully immobilized to the polyvinyl alcohol coating. • The coating was engineered to maximize the exposure of the diatom morphology. • The sensor paper achieved very high sensitivities for ammonia gas detection.

  19. Selective detection of heavy metal ions by self assembled chemical field effect transistors

    Energy Technology Data Exchange (ETDEWEB)

    Ruan, Hang, E-mail:; Kang, Yuhong; Gladwin, Elizabeth; Claus, Richard O. [NanoSonic, Inc., 158 Wheatland Drive, Pembroke, Virginia 24136 (United States)


    Multiple layer-by-layer sensor material modifications were designed and implemented to achieve selectivity of semiconductor based chemical field effect transistors (ChemFETs) to particular heavy metal ions. The ChemFET sensors were fabricated and modified in three ways, with the intent to initially target first mercury and lead ions and then chromium ions, respectively. Sensor characterization was performed with the gate regions of the sensor elements exposed to different concentrations of target heavy metal ion solutions. A minimum detection level in the range of 0.1 ppm and a 10%–90% response time of less than 10 s were demonstrated. By combining layer-by-layer gold nanoparticles and lead ionophores, a sensor is produced that is sensitive and selective not only to chromium but also to Cr{sup 3+} and Cr{sup 6+}. This result supports the claim that high selectivity can be achieved by designing self-assembled bonding for lead, arsenic, chromium, cesium, mercury, and cadmium.

  20. Nonvolatile Transistor Memory with Self-Assembled Semiconducting Polymer Nanodomain Floating Gates. (United States)

    Wang, Wei; Kim, Kang Lib; Cho, Suk Man; Lee, Ju Han; Park, Cheolmin


    Organic field effect transistor based nonvolatile memory (OFET-NVM) with semiconducting nanofloating gates offers additional benefits over OFET-NVMs with conventional metallic floating gates due to the facile controllability of charge storage based on the energetic structure of the floating gate. In particular, an all-in-one tunneling and floating-gate layer in which the semiconducting polymer nanodomains are self-assembled in the dielectric tunneling layer is promising. In this study, we utilize crystals of a p-type semiconducting polymer in which the crystalline lamellae of the polymer are spontaneously developed and embedded in the tunneling matrix as the nanofloating gate. The widths and lengths of the polymer nanodomains are approximately 20 nm and a few hundred nanometers, respectively. An OFET-NVM containing the crystalline nanofloating gates exhibits memory performance with a large memory window of 10 V, programming/erasing switching endurance for over 500 cycles, and a long retention time of 5000 s. Moreover, the device performance is improved by comixing with an n-type semiconductor; thus, the solution-processed p- and n-type double floating gates capable of storing both holes and electrons allow for the multilevel operation of our OFET-NVM. Four highly reliable levels (two bits per cell) of charge trapping and detrapping are achieved using this OFET-NVM by accurately choosing the programming/erasing voltages.

  1. Heteromer Nanostars by Spontaneous Self-Assembly

    Directory of Open Access Journals (Sweden)

    Caitlin Brocker


    Full Text Available Heteromer star-shaped nanoparticles have the potential to carry out therapeutic agents, improve intracellular uptake, and safely release drugs after prolonged periods of residence at the diseased site. A one-step seed mediation process was employed using polylactide-co-glycolic acid (PLGA, polyvinyl alcohol (PVA, silver nitrate, and tetrakis(hydroxymethylphosphonium chloride (THPC. Mixing these reagents followed by UV irradiation successfully produced heteromer nanostars containing a number of arm chains attached to a single core with a high yield. The release of THPC from heteromer nanostars was tested for its potential use for breast cancer treatment. The nanostars present a unique geometrical design exhibiting a significant intracellular uptake by breast cancer cells but low cytotoxicity that potentiates its efficacy as drug carriers.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  3. Self-assembled carboxylate complexes of zinc, nickel and copper (United States)

    Deka, Kaustavmoni; Barooah, Nilotpal; Sarma, Rupam Jyoti; Baruah, Jubaraj B.


    A metallo-organic hybrid acid namely tetra-aquo bis-4-carboxy- N-phthaloylglycinato zinc(II) dihydrate is prepared and characterised. In this complex the hydrogen bonding by free carboxylic acid group and π-π interactions between the rings in crystal lattice contributes to the formation of self-assembled structure. A monomeric nickel complex from 2-carbomethoxy benzoic acid ( L2H) and pyridine [Ni( L2)(py) 3(H 2O) 2] L2 is prepared (where py = pyridine). This complex has ionic as well as monodentate carboxylates. It forms self-assembly by C-H⋯π as well as hydrogen-bonding interactions. The 2-carbomethoxy benzoic acid ( L2H) forms dimeric copper complex [Cu 2( L2) 4(H 2O) 2]2H 2O which has an extended chain structure through hydrogen-bond interactions.

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

    Directory of Open Access Journals (Sweden)

    Chandrashekhar V. Kulkarni


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

  5. Self-Assembly and Hydrogelation of Peptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Wahyudi Priyono Suwarso


    Full Text Available Seven peptide amphiphiles were successfully synthesized using solid phase peptide synthesis method. Peptide amphiphiles were characterized using matrix assisted laser desorption/ionization (MALDI. Atomic force microscopy (AFM study showed that peptide amphiphiles having glycine, valine, or proline as linker, self-assembled into 100-200 nm nanofibers structure. According to our research, both peptide amphiphile with positive and negative charges bear similar self-assembly properties. Peptide amphiphile also showed its capability as low molecular weight gelator (LMWG. Peptide amphiphiles bearing C-16 and C-12 as alkyl showed better hydrogelation properties than C-8 alkyl. Five out of seven peptide amphiphiles have minimum gelation concentration (MGC lower than 1% (w/v.

  6. Programmed self-assembly of a quadruplex DNA nanowire. (United States)

    Hessari, Nason Ma'ani; Spindler, Lea; Troha, Tinkara; Lam, Wan-Chi; Drevenšek-Olenik, Irena; da Silva, Mateus Webba


    The ability to produce, reproducibly and systematically, well-defined quadruplex DNA nanowires through controlled rational design is poorly understood despite potential utility in structural nanotechnology. The programmed hierarchical self-assembly of a long four-stranded DNA nanowire through cohesive self-assembly of GpC and CpG "sticky" ends is reported. The encoding of bases within the quadruplex stem allows for an uninterrupted π-stacking system with rectilinear propagation for hundreds of nanometers in length. The wire is mechanically stable and features superior nuclease resistance to double-stranded DNA. The study indicates the feasibility for programmed assembly of uninterrupted quadruplex DNA nanowires. This is fundamental to the systematic investigation of well-defined DNA nanostructures for uses in optoelectronic and electronic devices as well as other structural nanotechnology applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Thermomechanical Response of Self-Assembled Nanoparticle Membranes

    Energy Technology Data Exchange (ETDEWEB)

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


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

  8. Molecular Gels Materials with Self-Assembled Fibrillar Networks

    CERN Document Server

    Weiss, Richard G


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

  9. Catalysis of Transesterification Reactions by a Self-Assembled Nanosystem

    Directory of Open Access Journals (Sweden)

    Davide Zaramella


    Full Text Available Histidine-containing peptides self-assemble on the surface of monolayer protected gold nanoparticles to form a catalytic system for transesterification reactions. Self-assembly is a prerequisite for catalysis, since the isolated peptides do not display catalytic activity by themselves. A series of catalytic peptides and substrates are studied in order to understand the structural parameters that are of relevance to the catalytic efficiency of the system. It is shown that the distance between the His-residue and the anionic tail does not affect the catalytic activity. On the other hand, the catalytic His-residue is sensitive to the chemical nature of the flanking amino acid residues. In particular, the presence of polar Ser-residues causes a significant increase in activity. Finally, kinetic studies of a series of substrates reveal that substrates with a hydrophobic component are very suitable for this catalytic system.

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

    Barry, Rachael; Gitai, Zemer


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

  11. Artificial Photosynthesis at Dynamic Self-Assembled Interfaces in Water. (United States)

    Hansen, Malte; Troppmann, Stefan; König, Burkhard


    Artificial photosynthesis is one of the big scientific challenges of today. Self-assembled dynamic interfaces, such as vesicles or micelles, have been used as microreactors to mimic biological photosynthesis. These aggregates can help to overcome typical problems of homogeneous photocatalytic water splitting. Microheterogeneous environments organize catalyst-photosensitizer assemblies at the interface in close proximity and thus enhance intermolecular interactions. Thereby vesicles and micelles may promote photoinitiated charge separation and suppress back electron transfer. The dynamic self-assembled interfaces solubilize non-polar compounds and protect sensitive catalytic units and intermediates against degradation. In addition, vesicles provide compartmentation that was used to separate different redox environments needed for an overall water splitting system. This Minireview provides an overview of the applications of micellar and vesicular microheterogeneous systems for solar energy conversion by photosensitized water oxidation and hydrogen generation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Self-Assembled Monolayers of CdSe Nanocrystals on Doped GaAs Substrates

    DEFF Research Database (Denmark)

    Marx, E.; Ginger, D.S.; Walzer, Karsten


    This letter reports the self-assembly and analysis of CdSe nanocrystal monolayers on both p- and a-doped GaAs substrates. The self-assembly was performed using a 1,6-hexanedithiol self-assembled monolayer (SAM) to link CdSe nanocrystals to GaAs substrates. Attenuated total reflection Fourier tran...

  13. STM visualisation of counterions and the effect of charges on self-assembled monolayers of macrocycles

    NARCIS (Netherlands)

    Kudernac, Tibor; Shabelina, Natalia; Mamdouh, Wael; Höger, Sigurd; De Feyter, Steven


    Despite their importance in self-assembly processes, the influence of charged counterions on the geometry of self-assembled organic monolayers and their direct localisation within the monolayers has been given little attention. Recently, various examples of self-assembled monolayers composed of

  14. Carbonate linkage bearing naphthalenediimides: self-assembly and photophysical properties. (United States)

    Kulkarni, Chidambar; George, Subi J


    Self-assembly of carbonate linkage bearing naphthalene diimides (NDI) showed unusually red-shifted excimer emission at approximately 560 nm. On the other hand, the ether linkers showed usual excimers at around 520 nm, highlighting the role of the carbonate group in tuning the molecular organization and the resultant photophysical properties of NDI. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Coherence and dephasing in self-assembled quantum dots

    DEFF Research Database (Denmark)

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


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

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


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


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

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

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


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

  18. Molecular Self-Assembly into One-Dimensional Nanostructures


    Palmer, Liam C.; Stupp, Samuel I.


    Self-assembly of small molecules into one-dimensional nanostructures offers many potential applications in electronically and biologically active materials. The recent advances discussed in this Account demonstrate how researchers can use the fundamental principles of supramolecular chemistry to craft the size, shape, and internal structure of nanoscale objects. In each system described here, we used atomic force microscopy (AFM) and transmission electron microscopy (TEM) to study the assembl...

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


    and C. J. Brinker, "Photoresponsive nanocomposite formed by self-assembly of an azobenzene -modified silane," Angew. Chem.-Int. Edit. 42 (15), 1731...Responsive Materials: Azobenzene Containing Polymers and Liquid Crystals,U Yue Zhao and Tomiki Ikeda, eds., John Wiley & Sons, Inc., Hoboken, NJ...phagocyte- derived oxidants: New role for the NADPH oxidase in host defense. Proc Natl Acad Sci U S A. 101, 13867-13872 (2004). xviii. Iler, R.K

  20. Microtubule dynamics. II. Kinetics of self-assembly

    DEFF Research Database (Denmark)

    Flyvbjerg, H.; Jobs, E.


    dependence on initial conditions-except it is known to be impossible for equilibrium reactions. This article presents a case study of a far-from-equilibrium reaction: it presents a systematic phenomenological analysis of experimental time series for the amount of final product, a biopolymer, formed from...... to analyze the self-assembly of microtubules from tubulin are general, and many other reactions and processes may be studied as inverse problems with these methods when enough experimental data are available....

  1. Directly Addressable Sub-3 nm Gold Nanogaps Fabricated by Nanoskiving Using Self-Assembled Monolayers as Templates

    NARCIS (Netherlands)

    Pourhossein, Parisa; Chiechi, Ryan C.

    This paper describes the fabrication of electrically addressable, high-aspect-ratio (>10000:1) nanowires of gold with square cross sections of 100 nm on each side that are separated by gaps of 1.7-2.2 nm which were defined using self-assembled monolayers (SAMs) as templates. We fabricated these

  2. Towards neat methanol operation of direct methanol fuel cells: a novel self-assembled proton exchange membrane. (United States)

    Li, Jing; Cai, Weiwei; Ma, Liying; Zhang, Yunfeng; Chen, Zhangxian; Cheng, Hansong


    We report here a novel proton exchange membrane with remarkably high methanol-permeation resistivity and excellent proton conductivity enabled by carefully designed self-assembled ionic conductive channels. A direct methanol fuel cell utilizing the membrane performs well with a 20 M methanol solution, very close to the concentration of neat methanol.

  3. Low-voltage organic transistors based on solution processed semiconductors and self-assembled monolayer gate dielectrics

    NARCIS (Netherlands)

    Woebkenberg, Paul H.; Ball, James; Kooistra, Floris B.; Hummelen, Jan C.; de Leeuw, Dago M.; Bradley, Donal D. C.; Anthopoulos, Thomas D.


    Reduction in the operating voltage of organic transistors is of high importance for successful implementation in low-power electronic applications. Here we report on low-voltage n-channel transistors fabricated employing a combination of soluble organic semiconductors and a self-assembled gate

  4. Directed Self-Assembly of Micron-Sized Gold Nanoplatelets into Oriented Flexible Stacks with Tunable Interplate Distance

    NARCIS (Netherlands)

    Vutukuri, H.R.; Badaire, S; de Winter, Matthijs; Imhof, A.; van Blaaderen, A.


    A growing demand for control over the interparticle spacing and the orientation of anisotropic metallic particles into self-assembled structures is fuelled by their use in potential applications such as in plasmonics, catalysis, sensing, and optoelectronics. Here, we present an improved high yield

  5. Solution processed self-assembled monolayer gate dielectrics for low-voltage organic transistors. : Section Title: Electric Phenomena

    NARCIS (Netherlands)

    Ball, James; Wobkenberg, Paul H.; Colleaux, Florian; Kooistra, Floris B.; Hummelen, Jan C.; Bradley, Donal D. C.; Anthopoulos, Thomas D.


    Low-voltage org. transistors are sought for implementation in high vol. low-power portable electronics of the future. Here we assess the suitability of three phosphonic acid based self-assembling mols. for use as ultra-thin gate dielecs. in low-voltage soln. processable org. field-effect

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

    DEFF Research Database (Denmark)

    Zhu, Nan; Ulstrup, Jens; Chi, Qijin


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


    NARCIS (Netherlands)



    The SC3p hydrophobin of Schizophyllum commune is a small hydrophobic protein (100-101 amino acids with eight cysteine residues) that self-assembles at a water/air interface and coats aerial hyphae with an SDS-insoluble protein membrane, at the outer side highly hydrophobic and with a typical rodlet

  8. Rational synthesis of low-polydispersity block copolymer vesicles in concentrated solution via polymerization-induced self-assembly

    NARCIS (Netherlands)

    Gonzato, Carlo; Semsarilar, Mona; Jones, Elizabeth R.; Li, Feng; Krooshof, Gerard J P; Wyman, Paul; Mykhaylyk, Oleksandr O.; Tuinier, Remco|info:eu-repo/dai/nl/183514262; Armes, Steven P.


    Block copolymer self-assembly is normally conducted via post-polymerization processing at high dilution. In the case of block copolymer vesicles (or "polymersomes"), this approach normally leads to relatively broad size distributions, which is problematic for many potential applications. Herein we

  9. Algorithmic self-assembly of DNA Sierpinski triangles.

    Directory of Open Access Journals (Sweden)

    Paul W K Rothemund


    Full Text Available Algorithms and information, fundamental to technological and biological organization, are also an essential aspect of many elementary physical phenomena, such as molecular self-assembly. Here we report the molecular realization, using two-dimensional self-assembly of DNA tiles, of a cellular automaton whose update rule computes the binary function XOR and thus fabricates a fractal pattern--a Sierpinski triangle--as it grows. To achieve this, abstract tiles were translated into DNA tiles based on double-crossover motifs. Serving as input for the computation, long single-stranded DNA molecules were used to nucleate growth of tiles into algorithmic crystals. For both of two independent molecular realizations, atomic force microscopy revealed recognizable Sierpinski triangles containing 100-200 correct tiles. Error rates during assembly appear to range from 1% to 10%. Although imperfect, the growth of Sierpinski triangles demonstrates all the necessary mechanisms for the molecular implementation of arbitrary cellular automata. This shows that engineered DNA self-assembly can be treated as a Turing-universal biomolecular system, capable of implementing any desired algorithm for computation or construction tasks.

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

    Kotov, Nicholas A.


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

  11. Evolutionary dynamics in a simple model of self-assembly (United States)

    Johnston, Iain G.; Ahnert, Sebastian E.; Doye, Jonathan P. K.; Louis, Ard A.


    We investigate the evolutionary dynamics of an idealized model for the robust self-assembly of two-dimensional structures called polyominoes. The model includes rules that encode interactions between sets of square tiles that drive the self-assembly process. The relationship between the model’s rule set and its resulting self-assembled structure can be viewed as a genotype-phenotype map and incorporated into a genetic algorithm. The rule sets evolve under selection for specified target structures. The corresponding complex fitness landscape generates rich evolutionary dynamics as a function of parameters such as the population size, search space size, mutation rate, and method of recombination. Furthermore, these systems are simple enough that in some cases the associated model genome space can be completely characterized, shedding light on how the evolutionary dynamics depends on the detailed structure of the fitness landscape. Finally, we apply the model to study the emergence of the preference for dihedral over cyclic symmetry observed for homomeric protein tetramers.

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

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


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

  13. 2D analogues of the inverted hexagonal phase self-assembled from 4,6-dialkoxylated isophthalic acids at solid-liquid interfaces (United States)

    Klymchenko, Andrey S.; Furukawa, Shuhei; Balandina, Tanya; Müllen, Klaus; van der Auweraer, Mark; de Feyter, Steven


    Self-assembly of organic molecules at solid-liquid interfaces is a route for developing novel functional materials on surfaces and modeling assembly phenomena in 3D. 5-Alkoxylated isophthalic acids (ISA) are known to self-assemble into two-dimensional (2D) lamellae at the interface between a surface of Au(111) or HOPG (highly oriented pyrolytic graphite) and a solvent. Presently, the self-assembly of 4,6-dialkoxylated isophthalic acid derivatives with variable alkyl chain length is investigated at Au(111)-water, Au(111)-tetradecane and HOPG-tetradecane interfaces with a particular focus on the first one. The main aspect of this study is to evaluate the role of the molecular geometry and different interactions in the 2D assembly of amphiphilic molecules. In contrast to 5-alkoxylated ISA, 4,6-dialkoxylated ISA derivatives self-assemble preferentially into arrays of cyclic pentameric/hexameric structures, which appear as 2D analogues of the inverted hexagonal phase of lipids. As a general trend, the derivatives bearing shorter alkyl chains show a higher level of ordering at Au(111)-liquid interfaces. In particular, at the Au(111)-water interface, the 4,6-diheptyloxy ISA derivative forms exclusively pentamers, which are arranged in a quasi-hexagonal lattice. Moreover, the cyclic pentameric features are not empty but host a single isophthalic acid residue which is found to be dynamic. Finally, the packing of the diheptyloxy derivative shows a distinct potential dependence: while at more negative potentials the pentameric arrangement is converted into lamellae, at more positive potentials a loosely packed zig-zag pattern is formed. The present results show that at different solid-liquid interfaces 4,6-dialkoxylated ISA derivatives tend to form cyclic structures that are 2D analogues of an inverted hexagonal phase, akin to lipids having two hydrophobic alkyl chains and a small polar head group. Moreover, the substrate potential at the Au(111)-water interface can tune the

  14. Controlled Ordering of Long-range Perpendicular Lamellae by Block Copolymer Self-assembly (United States)

    Ryu, Du Yeol; Kim, Kyunginn; Park, Sungmin; Kim, Yeongsik; Yonsei Univ Team

    We introduce a simple approach to fabricating highly stable, perpendicularly oriented lamellae through the self-assembly of high-molecular-weight polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA). The desired morphology was achieved over a narrow annealing period (5 10 min) under solvent vapor, since the SVA process need to terminate immediately before the saturated BCP films begin to dewet the substrate. This narrow processing period impeded practical applications to continuous industrial processes. A controlled SVA process at a selected temperature gap was found to show the excellent long-term stability, at which highly ordered line-arrays of perpendicularly oriented lamellae were confined to topographic line patterns.

  15. Nanoscale click-reactive scaffolds from peptide self-assembly. (United States)

    Guttenplan, Alexander P M; Young, Laurence J; Matak-Vinkovic, Dijana; Kaminski, Clemens F; Knowles, Tuomas P J; Itzhaki, Laura S


    Due to their natural tendency to self-assemble, proteins and peptides are important components for organic nanotechnology. One particular class of peptides of recent interest is those that form amyloid fibrils, as this self-assembly results in extremely strong, stable quasi-one-dimensional structures which can be used to organise a wide range of cargo species including proteins and oligonucleotides. However, assembly of peptides already conjugated to proteins is limited to cargo species that do not interfere sterically with the assembly process or misfold under the harsh conditions often used for assembly. Therefore, a general method is needed to conjugate proteins and other molecules to amyloid fibrils after the fibrils have self-assembled. Here we have designed an amyloidogenic peptide based on the TTR105-115 fragment of transthyretin to form fibrils that display an alkyne functionality, important for bioorthogonal chemical reactions, on their surface. The fibrils were formed and reacted both with an azide-containing amino acid and with an azide-functionalised dye by the Huisgen cycloaddition, one of the class of "click" reactions. Mass spectrometry and total internal reflection fluorescence optical microscopy were used to show that peptides incorporated into the fibrils reacted with the azide while maintaining the structure of the fibril. These click-functionalised amyloid fibrils have a variety of potential uses in materials and as scaffolds for bionanotechnology. Although previous studies have produced peptides that can both form amyloid fibrils and undergo "click"-type reactions, this is the first example of amyloid fibrils that can undergo such a reaction after they have been formed. Our approach has the advantage that self-assembly takes place before click functionalization rather than pre-functionalised building blocks self-assembling. Therefore, the molecules used to functionalise the fibril do not themselves have to be exposed to harsh, amyloid

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

    Directory of Open Access Journals (Sweden)

    Savi Bhalkaran


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

  17. New physics and devices based on self-assembled semiconductor quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Mowbray, D J; Skolnick, M S [Department of Physics and Astronomy, University of Sheffield, Hounsfield Road, Sheffield, S3 7RH (United Kingdom)


    Self-assembled semiconductor quantum dots (QDs) exhibit fully quantized electronic states and high radiative efficiencies. This makes them highly suitable both for fundamental physics studies of zero-dimensionality, atomic-like semiconductor systems and applications in a range of novel electro-optical devices. This review discusses recent important advances in the study and application of semiconductor QDs. Using a wide range of optical spectroscopy techniques, it is possible to obtain a detailed understanding of the electronic structure and dynamical carrier processes. Such an understanding is required for the implementation of a wide range of QD-based devices.

  18. Aggregation Kinetics and Self-Assembly Mechanisms of Graphene Quantum Dots in Aqueous Solutions: Cooperative Effects of pH and Electrolytes. (United States)

    Li, Qingqing; Chen, Baoliang; Xing, Baoshan


    The cooperative effects of pH and electrolytes on the aggregation of GQDs and the aggregate morphologies are characterized. Because GQDs have an average size of 9 nm with abundant O-functionalized edges, their suspension was very stable even in a high electrolyte concentration and low pH solution. Divalent cations (Mg(2+) and Ca(2+)) excelled at aggregating the GQD nanoplates, while monovalent cations (Na(+) and K(+)) did not disturb the stability. For Na(+) and K(+), positive linear correlations were observed between the critical coagulation concentration (CCC) and pH levels. For Mg(2+) and Ca(2+), negative, but nonlinear, correlations between CCC and pH values could not be explained and predicted by the traditional DLVO theory. Three-step mechanisms are proposed for the first time to elucidate the complex aggregation of GQDs. The first step is the protonation/deprotonation of GQDs under different pH values and the self-assembly of GQDs into GQD-water-GQD. The second step is the self-assembly of small GQD pieces into large plates (graphene oxide-like) induced by the coexisting Ca(2+) and then conversion into 3D structures via π-π stacking. The third step is the aggregation of the 3D-assembled GQDs into precipitates via the suppression of the electric double layer. The self-assembly of GQDs prior to aggregation was supported by SEM and HRTEM imaging. Understanding of the colloidal behavior of ultrasmall nanoparticles like GQDs is significantly important for the precise prediction of their environmental fate and risk.

  19. Self-assembly as a design tool for the integration of photonic structures into excitonic solar cells

    KAUST Repository

    Guldin, S.


    One way to successfully enhance light harvesting of excitonic solar cells is the integration of optical elements that increase the photon path length in the light absorbing layer. Device architectures which incorporate structural order in form of one- or three-dimensional refractive index lattices can lead to the localization of light in specific parts of the spectrum, while retaining the cell\\'s transparency in others. Herein, we present two routes for the integration of photonic crystals (PCs) into dye-sensitized solar cells (DSCs). In both cases, the self-assembly of soft matter plays a key role in the fabrication process of the TiO2 electrode. One approach relies on a combination of colloidal self-assembly and the self-assembly of block copolymers, resulting in a double layer dye-sensitized solar cell with increased light absorption from the 3D PC element. An alternative route is based on the fact that the refractive index of the mesoporous layer can be finely tuned by the interplay between block copolymer self-assembly and hydrolytic TiO2 sol-gel chemistry. Alternating deposition of high and low refractive index layers enables the integration of a 1D PC into a DSC.

  20. In-capillary self-assembly study of quantum dots and protein using fluorescence coupled capillary electrophoresis. (United States)

    Wang, Jianhao; Li, Jingyan; Li, Jinchen; Qin, Yuqin; Wang, Cheli; Qiu, Lin; Jiang, Pengju


    As a vast number of novel materials in particular inorganic nanoparticles have been invented and introduced to all aspects of life, public concerns about how they might affect our ecosystem and human life continue to arise. Such incertitude roots at a fundamental question of how inorganic nanoparticles self-assemble with biomolecules in solution. Various techniques have been developed to probe the interaction between particles and biomolecules, but very few if any can provide advantages of both rapid and convenient. Herein, we report a systematic investigation on quantum dots (QDs) and protein self-assembly inside a capillary. QDs and protein were injected to a capillary one after another. They were mixed inside the capillary when a high voltage was applied. Online separation and detection were then achieved. This new method can also be used to study the self-assembly kinetics of QDs and protein using the Hill equation, the KD value for the self-assembly of QDs and protein was calculated to be 8.8 μM. The obtained results were compared with the previous out of-capillary method and confirmed the effectiveness of the present method. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Method for selective immobilization of macromolecules on self assembled monolayer surfaces (United States)

    Laskin, Julia [Richland, WA; Wang, Peng [Billerica, MA


    Disclosed is a method for selective chemical binding and immobilization of macromolecules on solid supports in conjunction with self-assembled monolayer (SAM) surfaces. Immobilization involves selective binding of peptides and other macromolecules to SAM surfaces using reactive landing (RL) of mass-selected, gas phase ions. SAM surfaces provide a simple and convenient platform for tailoring chemical properties of a variety of substrates. The invention finds applications in biochemistry ranging from characterization of molecular recognition events at the amino acid level and identification of biologically active motifs in proteins, to development of novel biosensors and substrates for stimulated protein and cell adhesion.

  2. Phosphorus ionization in silicon doped by self-assembled macromolecular monolayers (United States)

    Wu, Haigang; Li, Ke; Gao, Xuejiao; Dan, Yaping


    Individual dopant atoms can be potentially controlled at large scale by the self-assembly of macromolecular dopant carriers. However, low concentration phosphorus dopants often suffer from a low ionization rate due to defects and impurities introduced by the carrier molecules. In this work, we demonstrated a nitrogen-free macromolecule doping technique and investigated the phosphorus ionization process by low temperature Hall effect measurements. It was found that the phosphorus dopants diffused into the silicon bulk are in nearly full ionization. However, the electrons ionized from the phosphorus dopants are mostly trapped by deep level defects that are likely carbon interstitials.

  3. Adsorption Dynamics and Self-Assembled L-cysteine on Au(100)

    DEFF Research Database (Denmark)

    Engelbrekt, Christian; Nazmutdinov, Renat R.; Yan, Jiawei

    can be structurally mapped at the single - molecule level . In this work, we have followed the adsorption of L - cysteine on single - crystal Au(100) by measuring the electrode potential dynamics during the adsorption process. In situ STM revealed the structure of the self - assembled ordered layers....... The molecular assemblies were studied through simulated STM image contrast based on density functional theory (DFT) including solvation effects. The adsorption kinetics showed clearly a complex pattern with at least one intermediate state. The modelling disclosed details of the interaction of all functional...

  4. High-level verification

    CERN Document Server

    Lerner, Sorin; Kundu, Sudipta


    Given the growing size and heterogeneity of Systems on Chip (SOC), the design process from initial specification to chip fabrication has become increasingly complex. This growing complexity provides incentive for designers to use high-level languages such as C, SystemC, and SystemVerilog for system-level design. While a major goal of these high-level languages is to enable verification at a higher level of abstraction, allowing early exploration of system-level designs, the focus so far for validation purposes has been on traditional testing techniques such as random testing and scenario-based

  5. Real-time analysis of self-assembled nucleobases by Venturi easy ambient sonic-spray ionization mass spectrometry. (United States)

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


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

  6. Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting

    Directory of Open Access Journals (Sweden)

    Christian Benkhäuser


    Full Text Available A Tröger's base-derived racemic bis(1,10-phenanthroline ligand (rac-1 and a bis(2,2'-bipyridine ligand with a central 1,3-diethynylbenzene unit 2 were synthesized. Each of these ligands acts as a multivalent entity for the binding of two copper(I ions. Upon coordination to the metal ions these two ligands undergo selective self-assembly into heteroleptic dinuclear metallosupramolecular kites in a high-fidelity social self-sorting manner as evidenced by NMR spectroscopy and mass spectrometry.

  7. Self-assembled isoporous block copolymer membranes with tuned pore sizes

    KAUST Repository

    Yu, Haizhou


    The combination of nonsolvent-induced phase separation and the self-assembly of block copolymers can lead to asymmetric membranes with a thin highly ordered isoporous skin layer. The effective pore size of such membranes is usually larger than 15 nm. We reduced the pore size of these membranes by electroless gold deposition. We demonstrate that the pore sizes can be controlled precisely between 3 and 20 nm leading to a tunable sharp size discrimination in filtration processes. Besides fractionation of nanoparticles and biomaterials, controlled drug delivery is an attractive potential application. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. An introduction to ultrathin organic films from Langmuir-Blodgett to self-assembly

    CERN Document Server

    Ulman, Abraham


    The development of oriented organic monomolecular layers by the Langmuir-Blodgett (LB) and self-assembly (SA) techniques has led researchers toward their goal of assembling individual molecules into highly ordered architectures. Thus the continually growing contribution of LB and SA systems to the chemistry and physics of thin organic films is widely recognized. Equally well-known is the difficulty in keeping up to date with the burgeoning multidisciplinary research in this area. Dr. Ulman provides a massive survey of the available literature. The book begins with a section on analytical tools

  9. Tunable Mesoporous Bragg Reflectors Based on Block-Copolymer Self-Assembly

    KAUST Repository

    Guldin, Stefan


    Mesoporous Bragg reflectors are a promising materials platform for photovoltaics, light emission, and sensing. A fast and versatile fabrication route that relies on the self-assembly of the block copolymer poly(isoprene-b-ethylene oxide) in combination with simple sol-gel chemistry is reported. The method allows extended control over porosity and pore size in the resulting inorganic material and results in high-quality optical elements. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Cross-linked self-assembled micelle based nanosensor for intracellular pH measurements

    DEFF Research Database (Denmark)

    Ek, Pramod Kumar; Søndergaard, Rikke Vicki; Windschiegl, Barbara


    A micelle based nanosensor was synthesized and investigated as a ratiometric pH sensor for use in measurements in living cells by fluorescent microscopy. The nanosensor synthesis was based on self-assembly of an amphiphilic triblock copolymer, which was chemically cross-linked after micelle......-linked by an amidation reaction using 3,6,9-trioxaundecandioic acid cross-linker. The cross-linked micelle was functionalized with two pH sensitive fluorophores and one reference fluorophore, which resulted in a highly uniform ratiometric pH nanosensor with a diameter of 29 nm. The use of two sensor fluorophores...

  11. Highly efficient near-infrared-emitting lanthanide(III) complexes formed by heterogeneous self-assembly of Ag(I), Ln(III), and thiacalix[4]arene-p-tetrasulfonate in aqueous solution (Ln(III) = Nd(III), Yb(III)). (United States)

    Iki, Nobuhiko; Hiro-oka, Shouichi; Tanaka, Teppei; Kabuto, Chizuko; Hoshino, Hitoshi


    strategy via self-assembly of the multidentate ligand, Ln(III), and an auxiliary metal ion to obtain a highly efficient NIR-emissive Ln(III) complex that usually relies on elaborate covalent linkage of a chromophore and multidentate ligands to expel coordinating water.

  12. PLGA nanofibers blended with designer self-assembling peptides for peripheral neural regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Nune, Manasa; Krishnan, Uma Maheswari; Sethuraman, Swaminathan, E-mail:


    Electrospun nanofibers are attractive candidates for neural regeneration due to similarity to the extracellular matrix. Several synthetic polymers have been used but they lack in providing the essential biorecognition motifs on their surfaces. Self-assembling peptide nanofiber scaffolds (SAPNFs) like RADA16 and recently, designer SAPs with functional motifs RADA16-I-BMHP1 areexamples, which showed successful spinal cord regeneration. But these peptide nanofiber scaffolds have poor mechanical properties and faster degradation rates that limit their use for larger nerve defects. Hence, we have developed a novel hybrid nanofiber scaffold of polymer poly(L-lactide-co-glycolide) (PLGA) and RADA16-I-BMHP1. The scaffolds were characterized for the presence of peptides both qualitatively and quantitatively using several techniques like SEM, EDX, FTIR, CHN analysis, Circular Dichroism analysis, Confocal and thermal analysis. Peptide self-assembly was retained post-electrospinning and formed rod-like nanostructures on PLGA nanofibers. In vitro cell compatibility was studied using rat Schwann cells and their adhesion, proliferation and gene expression levels on the designed scaffolds were evaluated. Our results have revealed the significant effects of the peptide blended scaffolds on promoting Schwann cell adhesion, extension and phenotypic expression. Neural development markers (SEM3F, NRP2 & PLX1) gene expression levels were significantly upregulated in peptide blended scaffolds compared to the PLGA scaffolds. Thus the hybrid blended novel designer scaffolds seem to be promising candidates for successful and functional regeneration of the peripheral nerve. - Highlights: • A novel blended scaffold of polymer PLGA and designer self-assembling peptide RADA16-I-BMPH1 was designed • The peptide retained the self-assembling features and formed rod like nanostructures on top of PLGA nanofibers • PLGA-peptide scaffolds have promoted the Schwann cell bipolar extension and

  13. Preface: Special Topic on Supramolecular Self-Assembly at Surfaces (United States)

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


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

  14. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers


    Bin Guan; Hamidreza Siampour; Zhao Fan; Shun Wang; Xiang Yang Kong; Abdelmadjid Mesli; Jian Zhang; Yaping Dan


    International audience; This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10−15 cm2 s−1, 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen d...

  15. Exploring the properties and possibilities of self-assembling

    DEFF Research Database (Denmark)

    Andersen, Karsten Brandt; Castillo, Jaime


    The study (and potential application) of diphenylalanine peptide nanotubes is a popular topic that in recent years has experienced a boost in activity. This activity has been propelled forward by new articles continuously being published presenting even more spectacular properties of the nanotube...... and exciting possibilities. The major driving forces supporting the interest in the peptide nanotubes is the fast and simple assembly process combined with their remarkable stability towards alcohols, organic solvents, and biological analytes that was presented shortly after the self-assembling properties...

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

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


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

  17. Photobleaching-activated micropatterning on self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

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


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

  18. Exploiting non-equilibrium phase separation for self-assembly. (United States)

    Grünwald, Michael; Tricard, Simon; Whitesides, George M; Geissler, Phillip L


    Demixing can occur in systems of two or more particle species that experience different driving forces, e.g., mixtures of self-propelled active particles or of oppositely charged colloids subject to an electric field. Here we show with macroscopic experiments and computer simulations that the forces underlying such non-equilibrium segregation can be used to control the self-assembly of particles that lack attractive interactions. We demonstrate that, depending on the direction, amplitude and frequency of a periodic external force acting on one particle species, the structures formed by a second, undriven species can range from compact clusters to elongated, string-like patterns.

  19. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao


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

  20. Buckling Instability of Self-Assembled Colloidal Columns (United States)

    Swan, James W.; Vasquez, Paula A.; Furst, Eric M.


    Suspended, slender self-assembled domains of magnetically responsive colloids are observed to buckle in microgravity. Upon cessation of the magnetic field that drives their assembly, these columns expand axially and buckle laterally. This phenomenon resembles the buckling of long beams due to thermal expansion; however, linear stability analysis predicts that the colloidal columns are inherently susceptible to buckling because they are freely suspended in a Newtonian fluid. The dominant buckling wavelength increases linearly with column thickness and is quantitatively described using an elastohydrodynamic model and the suspension thermodynamic equation of state.

  1. Preface: Special Topic on Supramolecular Self-Assembly at Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bartels, Ludwig [Department of Chemistry and the Materials Science and Engineering Program, University of California - Riverside, Riverside, California 92521 (United States); Ernst, Karl-Heinz [EMPA, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dubendorf (Switzerland); Gao, Hong-Jun [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics,Chinese Academy of Sciences, Beijing 100190 (China); Thiel, Patricia A. [Department of Chemistry, Department of Materials Science and Engineering, Ames Laboratory,Iowa State University, Ames, Iowa 50011 (United States)


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

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

    KAUST Repository

    Vignolini, Silvia


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

  3. Self-assembly of free-standing RNA membranes (United States)

    Han, Daehoon; Park, Yongkuk; Kim, Hyejin; Lee, Jong Bum


    RNA has emerged as a promising material for nanostructure and microstructure engineering. Although rare, some macroscopic RNA structures have also been constructed using lipid or polymer materials. Here, we report the first example of an enzymatically generated RNA membrane. This robust and free-standing RNA membrane has a macroscopic structure and is generated without any polymer support or complexation. Our RNA membrane is fabricated following two sequential processes, complementary rolling circle transcription and evaporation-induced self-assembly, and its structural and functional properties are rationally controlled by adjusting RNA base pairing. In this study, three types of RNA membranes are fabricated and are used to demonstrate potential applications.

  4. Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

    CERN Document Server

    Garti, Nissim


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

  5. Switching properties of self-assembled ferroelectric memory cells (United States)

    Alexe, M.; Gruverman, A.; Harnagea, C.; Zakharov, N. D.; Pignolet, A.; Hesse, D.; Scott, J. F.


    In this letter, we report on the switching properties of an ordered system of Bi4Ti3O12 ferroelectric memory cells of an average lateral size of 0.18 μm formed via a self-assembling process. The ferroelectricity of these cells has been measured microscopically and it has been demonstrated that an individual cell of 0.18 μm size is switching. Switching of single nanoelectrode cells was achieved via scanning force microscopy working in piezoresponse mode.

  6. Equation of State for Phospholipid Self-Assembly

    DEFF Research Database (Denmark)

    Marsh, Derek


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

  7. The self assembly of thymine at Au(110)/liquid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Molina Contreras, J.R. [Departamento de Ingenieria Electrica y Electronica, Instituto Tecnologico de Aguascalientes, Mexico (Mexico); Smith, C.I.; Bowfield, A.; Weightman, P. [Physics Department, University of Liverpool (United Kingdom); Tillner, F. [Fachbereich Physik, Universitaet Konstanz (Germany)


    We show that thymine self-assembles into an ordered structure when adsorbed at a Au(110)/liquid interface. Reflection anisotropy spectroscopy (RAS) shows that as found for cytosine and adenine the adsorbed thymine molecules are oriented essentially vertically on the Au(110) surface with the molecule aligned along one of the principal axes of the Au(110) surface. Simulations of the RA spectra to an empirical model indicates that as found for adsorbed cytosine and adenine, thymine is aligned along the [1 anti 10] direction on the Au(110) surface. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    DEFF Research Database (Denmark)

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


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

  9. Self-assembled organogels formed by monochain derivatives of ethylenediamine. (United States)

    Luo, Xuzhong; Li, Zengfu; Xiao, Wei; Wang, Qiong; Zhong, Jinlian


    A family of low molecular weight organogelators (LMOG) based on monochain derivatives of ethylenediamine were investigated. The monochain derivatives of ethylenediamine show strong gelation ability in a number of organic solvents, including polar solvents and non-polar solvents. In gel state, molecules of monochain ethylenediamine derivatives self-assemble into ordered aggregates, which are juxtaposed and interlocked to form three-dimensional networks of fiber bundles as confirmed by scanning electron microscopy (SEM). The Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) studies demonstrate that intermolecular hydrogen bonds between neighboring molecules are critical factor in the process of organogelation.

  10. Applications of the theory of computation to nanoscale self-assembly (United States)

    Doty, David Samuel

    This thesis applies the theory of computing to the theory of nanoscale self-assembly, to explore the ability -- and under certain conditions, the inability -- of molecules to automatically arrange themselves in computationally sophisticated ways. In particular, we investigate a model of molecular self-assembly known as the abstract Tile Assembly Model (aTAM), in which different types of square "tiles" represent molecules that, through the interaction of highly specific binding sites on their four sides, can automatically assemble into larger and more elaborate structures. We investigate the possibility of using the inherent randomness of sampling different tiles in a well-mixed solution to drive selection of random numbers from a finite set, and explore the tradeoff between the uniformity of the imposed distribution and the size of structures necessary to process the sampled tiles. We then show that the inherent randomness of the competition of different types of molecules for binding can be exploited in a different way. By adjusting the relative concentrations of tiles, the structure assembled by a tile set is shown to be programmable to a high precision, in the following sense. There is a single tile set that can be made to assemble a square of arbitrary width with high probability, by setting the concentrations of the tiles appropriately, so that all the information about the square's width is "learned" from the concentrations by sampling the tiles. Based on these constructions, and those of other researchers, which have been completely implemented in a simulated environment, we design a high-level domain-specific "visual language" for implementing complex constructions in the aTAM. This language frees the implementer of an aTAM construction from many low-level and tedious details of programming and, together with a visual software tool that directly implements the basic operations of the language, frees the implementer from almost any programming at all

  11. Unzipping the role of chirality in nanoscale self-assembly of tripeptide hydrogels (United States)

    Marchesan, Silvia; Waddington, Lynne; Easton, Christopher D.; Winkler, David A.; Goodall, Liz; Forsythe, John; Hartley, Patrick G.


    Change of chirality is a useful tool to manipulate the aqueous self-assembly behaviour of uncapped, hydrophobic tripeptides. In contrast with other short peptides, these tripeptides form hydrogels at a physiological pH without the aid of organic solvents or end-capping groups (e.g. Fmoc). The novel hydrogel forming peptide DLeu-Phe-Phe (DLFF) and its epimer Leu-Phe-Phe (LFF) exemplify dramatic supramolecular effects induced by subtle changes to stereochemistry. Only the d-amino acid-containing peptide instantly forms a hydrogel in aqueous solution following a pH switch, generating long fibres (>100 μm) that entangle into a 3D network. However, unexpected nanostructures are observed for both peptides and they are particularly heterogeneous for LFF. Structural analyses using CD, FT-IR and fluorescent amyloid staining reveal anti-parallel beta-sheets for both peptides. XRD analysis also identifies key distances consistent with beta-sheet formation in both peptides, but suggests additional high molecular order and extended molecular length for DLFF only. Molecular modelling of the two peptides highlights the key interactions responsible for self-assembly; in particular, rapid self-assembly of DLFF is promoted by a phenylalanine zipper, which is not possible because of steric factors for LFF. In conclusion, this study elucidates for the first time the molecular basis for how chirality can dramatically influence supramolecular organisation in very short peptide sequences.Change of chirality is a useful tool to manipulate the aqueous self-assembly behaviour of uncapped, hydrophobic tripeptides. In contrast with other short peptides, these tripeptides form hydrogels at a physiological pH without the aid of organic solvents or end-capping groups (e.g. Fmoc). The novel hydrogel forming peptide DLeu-Phe-Phe (DLFF) and its epimer Leu-Phe-Phe (LFF) exemplify dramatic supramolecular effects induced by subtle changes to stereochemistry. Only the d-amino acid-containing peptide

  12. Self-assembly of regioregular poly (3,3‴-didodecylquarterthiophene) in chloroform and study of its junction properties

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Manish Kumar; Kumar, Ashish; Prakash, Rajiv, E-mail:


    Graphical abstract: rr-PQT-12 films formed by spin coating before and after ageing (at 25 °C) showing the effect of fiber growth and significant change in charge transfer property. - Highlights: • Self-assembly of rr-PQT-12 into fiber form in chloroform marginal solvent at RT. • As assembled dispersion is processed for the fabrication of organic devices. • Processed fiber shows improvement in charge transport over its pristine one. - Abstract: This article deals with the study of self-assembly of regioregular poly (3,3‴-didodecylquarterthiophene), rr-PQT-12 into fiber form in chloroform by ageing process. Time dependent fiber growth mechanism is monitored by UV–vis absorption and confirmed by atomic force microscopy technique. It is observed that isolated rr-PQT-12 undergoes self-assembled fibril growth along π-π interaction direction and 45 min is sufficient for such assemblies in case of 0.125% w/v of rr-PQT-12 polymer in chloroform. Further the self-assembled fibril polymer is used in fabrication of Schottky diode. It exhibits ten times enhancement in forward current density (with one-fold higher mobility) and high rectification ratio compared to the isolated rr-PQT-12 due to the segmental electronic traps filling within stacking region. Our study provides a facile method of ordering of PQT-12 isolated chains in chloroform solvent and an effective way for improvement of performance of organic polymers based devices through such self-assembly.

  13. Substituent Effects on the Self-Assembly/Coassembly and Hydrogelation of Phenylalanine Derivatives. (United States)

    Liyanage, Wathsala; Nilsson, Bradley L


    Supramolecular hydrogels derived from the self-assembly of organic molecules have been exploited for applications ranging from drug delivery to tissue engineering. The relationship between the structure of the assembly motif and the emergent properties of the resulting materials is often poorly understood, impeding rational approaches for the creation of next-generation materials. Aromatic π-π interactions play a significant role in the self-assembly of many supramolecular hydrogelators, but the exact nature of these interactions lacks definition. Conventional models that describe π-π interactions rely on quadrupolar electrostatic interactions between neighboring aryl groups in the π-system. However, recent experimental and computational studies reveal the potential importance of local dipolar interactions between elements of neighboring aromatic rings in stabilizing π-π interactions. Herein, we examine the nature of π-π interactions in the self- and coassembly of Fmoc-Phe-derived hydrogelators by systematically varying the electron-donating or electron-withdrawing nature of the side chain benzyl substituents and correlating these effects to the emergent assembly and gelation properties of the systems. These studies indicate a significant role for stabilizing dipolar interactions between neighboring benzyl groups in the assembled materials. Additional evidence for specific dipolar interactions is provided by high-resolution crystal structures obtained from dynamic transition of gel fibrils to crystals for several of the self-assembled/coassembled Fmoc-Phe derivatives. In addition to electronic effects, steric properties also have a significant effect on the interaction between neighboring benzyl groups in these assembled systems. These findings provide significant insight into the structure-function relationship for Fmoc-Phe-derived hydrogelators and give cues for the design of next-generation materials with desired emergent properties.

  14. From Cooperative Self-Assembly to Water-Soluble Supramolecular Polymers Using Coarse-Grained Simulations. (United States)

    Bochicchio, Davide; Pavan, Giovanni M


    Supramolecular polymers, formed via noncovalent self-assembly of elementary monomers, are extremely interesting for their dynamic bioinspired properties. In order to understand their behavior, it is necessary to access their dynamics while maintaining high resolution in the treatment of the monomer structure and monomer-monomer interactions, which is typically a difficult task, especially in aqueous solution. Focusing on 1,3,5-benzenetricarboxamide (BTA) water-soluble supramolecular polymers, we have developed a transferable coarse-grained model that allows studying BTA supramolecular polymerization in water, while preserving remarkable consistency with the atomistic models in the description of the key interactions between the monomers (hydrophobic, H-bonding, etc.), self-assembly cooperativity, and amplification of order into the growing fibers. This permitted us to monitor the amplification of the key interactions between the monomers (including H-bonding) in the BTA fibers during the dynamic polymerization process. Our molecular dynamics simulations provide a picture of a stepwise cooperative polymerization mechanism, where initial fast hydrophobic aggregation of the BTA monomers in water is followed by the slower reorganization of these disordered aggregates into ordered directional oligomers. Supramolecular polymer growth then proceeds on a slower time scale. We challenged our models via comparison with the experimental evidence, capturing the effect of temperature variations and subtle changes in the monomer structure on the polymerization and on the properties of the fibers seen in the real systems. This work provides a multiscale spatiotemporal characterization of BTA self-assembly in water and a useful platform to study a variety of BTA-based supramolecular polymers toward structure-property relationships.

  15. Single-Molecule Transistor from Graphene Nanoelectrodes and Novel Functional Materials From Self-assembly (United States)

    Xu, Qizhi

    This thesis introduces a new strategy to fabricate single molecular transistor by utilizing the covalent chemistry to reconnect the molecule with the electroburnt graphene nanogap. We studied the effect of coupling chemistry and molecular length on the efficiency of reconnection between the molecule and the graphene. With this technique, we are also able to observe the Coulomb Blockade phenomenon, which is a characteristics of single-electron transistors. The high yield and versatility of this approach augur well for creating a new generation of sensors, switches, and other functional devices using graphene contacts. This thesis also introduces a new type of organic single-crystal p-n heterojunction inspired from the ball-and-socket shape-complementarity between fullerene and contorted dibenzotetrathienocoronene (c-DBTTC). We studied the influence of temperature, pressure, and time on the self-assembly process of contorted dibenzotetrathienocoronene on the as-grown fullerene crystals. We also utilized fluorescence microscopy to investigate the charge transfer in this type of p-n heterojunction. Finally, this thesis introduces one-dimensional and two-dimensional programming in solid-state materials from superatom macrocycles. We find that the linkers that bridges the two superatoms determine the distance and electronic coupling between the two superatoms in the macrocycle, which in turn determines the way they self-assembled in the solid-state materials. The thesis is composed of four chapters. The first chapter introduces why we are in terested in molecular transistors and new functional materials, and what has been done so far. The second chapter described the approach we developed to assemble single molecule into circuits with graphene electrodes. The third chapter details the method to fabricate the organic single-crystal C60-DBTTC p-n heterojunction, which is of great importance to understand their charge transfer process. The last chapter introduced a new

  16. Conducting nanowires built by controlled self-assembly of amyloid fibers and selective metal deposition (United States)

    Scheibel, Thomas; Parthasarathy, Raghuveer; Sawicki, George; Lin, Xiao-Min; Jaeger, Heinrich; Lindquist, Susan L.


    Recent research in the field of nanometer-scale electronics has focused on the operating principles of small-scale devices and schemes to realize useful circuits. In contrast to established "top-down" fabrication techniques, molecular self-assembly is emerging as a "bottom-up" approach for fabricating nanostructured materials. Biological macromolecules, especially proteins, provide many valuable properties, but poor physical stability and poor electrical characteristics have prevented their direct use in electrical circuits. Here we describe the use of self-assembling amyloid protein fibers to construct nanowire elements. Self-assembly of a prion determinant from Saccharomyces cerevisiae, the N-terminal and middle region (NM) of Sup35p, produced 10-nm-wide protein fibers that were stable under a wide variety of harsh physical conditions. Their lengths could be roughly controlled by assembly conditions in the range of 60 nm to several hundred micrometers. A genetically modified NM variant that presents reactive, surface-accessible cysteine residues was used to covalently link NM fibers to colloidal gold particles. These fibers were placed across gold electrodes, and additional metal was deposited by highly specific chemical enhancement of the colloidal gold by reductive deposition of metallic silver and gold from salts. The resulting silver and gold wires were 100 nm wide. These biotemplated metal wires demonstrated the conductive properties of a solid metal wire, such as low resistance and ohmic behavior. With such materials it should be possible to harness the extraordinary diversity and specificity of protein functions to nanoscale electrical circuitry.

  17. Stochastic dynamics of virus capsid formation: direct versus hierarchical self-assembly (United States)


    Background In order to replicate within their cellular host, many viruses have developed self-assembly strategies for their capsids which are sufficiently robust as to be reconstituted in vitro. Mathematical models for virus self-assembly usually assume that the bonds leading to cluster formation have constant reactivity over the time course of assembly (direct assembly). In some cases, however, binding sites between the capsomers have been reported to be activated during the self-assembly process (hierarchical assembly). Results In order to study possible advantages of such hierarchical schemes for icosahedral virus capsid assembly, we use Brownian dynamics simulations of a patchy particle model that allows us to switch binding sites on and off during assembly. For T1 viruses, we implement a hierarchical assembly scheme where inter-capsomer bonds become active only if a complete pentamer has been assembled. We find direct assembly to be favorable for reversible bonds allowing for repeated structural reorganizations, while hierarchical assembly is favorable for strong bonds with small dissociation rate, as this situation is less prone to kinetic trapping. However, at the same time it is more vulnerable to monomer starvation during the final phase. Increasing the number of initial monomers does have only a weak effect on these general features. The differences between the two assembly schemes become more pronounced for more complex virus geometries, as shown here for T3 viruses, which assemble through homogeneous pentamers and heterogeneous hexamers in the hierarchical scheme. In order to complement the simulations for this more complicated case, we introduce a master equation approach that agrees well with the simulation results. Conclusions Our analysis shows for which molecular parameters hierarchical assembly schemes can outperform direct ones and suggests that viruses with high bond stability might prefer hierarchical assembly schemes. These insights increase

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  19. Self-assembly and sensing-group graft of pre-modified CNTs on resonant micro-cantilevers for specific detection of volatile organic compound vapors (United States)

    Xu, Pengcheng; Li, Xinxin; Yu, Haitao; Liu, Min; Li, Jungang


    This paper reports MWCNT (multi-wall carbon nano-tube)-modified resonant micro-cantilever chemical sensors for detection of trinitrotoluene (TNT) vapor. The MWCNTs are pre-modified and then area-selectively self-assembled at the free-end gold pad of a micro-cantilever, in which a resonance-exciting heater and a signal-readout piezoresistive Wheatstone bridge are integrated. Featuring a high specific surface area, the MWCNTs are further functionalized with TNT-sensitive groups by grafting onto the sidewalls of the MWCNTs. To lower the non-specific absorption of water and other small organic molecules, the SiO2 surface of the micro-cantilever was also pre-treated for hydrophobicity and oleophobicity by self-assembling a monolayer of heptadecafluorodecyltrimethoxysilane. The results of our sensing experiments have shown a capability to rapidly detect ppb-level TNT vapor, and a high specificity of the functionalized groups to TNT molecules. The experiment has also confirmed a good long-term stability in detecting sensitivity.

  20. Self assembled monolayers on silicon for molecular electronics. (United States)

    Aswal, D K; Lenfant, S; Guerin, D; Yakhmi, J V; Vuillaume, D


    We present an overview of various aspects of the self-assembly of organic monolayers on silicon substrates for molecular electronics applications. Different chemical strategies employed for grafting the self-assembled monolayers (SAMs) of alkanes having different chain lengths on native oxide of Si or on bare Si have been reviewed. The utility of different characterization techniques in determination of the thickness, molecular ordering and orientation, surface coverage, growth kinetics and chemical composition of the SAMs has been discussed by choosing appropriate examples. The metal counterelectrodes are an integral part of SAMs for measuring their electrical properties as well as using them for molecular electronic devices. A brief discussion on the variety of options available for the deposition of metal counterelectrodes, that is, soft metal contacts, vapor deposition and soft lithography, has been presented. Various theoretical models, namely, tunneling (direct and Fowler-Nordheim), thermionic emission, Poole-Frenkel emission and hopping conduction, used for explaining the electronic transport in dielectric SAMs have been outlined and, some experimental data on alkane SAMs have been analyzed using these models. It has been found that short alkyl chains show excellent agreement with tunneling models; while more experimental data on long alkyl chains are required to understand their transport mechanism(s). Finally, the concepts and realization of various molecular electronic components, that is, diodes, resonant tunnel diodes, memories and transistors, based on appropriate architecture of SAMs comprising of alkyl chains (sigma- molecule) and conjugated molecules (pi-molecule) have been presented.