Customized morphologies of self-condensed multisegment polymer nanowires

The direct formation of multisegment nanowires consisting of polymer domains by ion beam irradiation is investigated. Cross-linking reactions in the ion tracks result in localized gelation, giving isolated nanowires on substrates. It is demonstrated that the morphology of the final nanostructure is customized by appropriate selection of the ion fluence, combination of polymers, and the solvent employed for development. Octopus-like nanostructures consisting of a tangled hydrophilic polymer core and splayed hydrophobic polymer segments are successfully produced as an example of the process. The present technique provides universal feasibility for the formation of nanostructures based on "any" polymer materials in which radiation induces cross-linking reactions.     

"Lens" effect in directed assembly of nanowires on gradient molecular patterns

We report a new phenomenon, named here as the "lens" effect, in the directed-assembly process of nanowires (NWs) on self-assembled monolayer (SAM) patterns. In this process, the adsorption of NWs is focused in the nanoscale regions at the center of microscale SAM patterns with gradient surface molecular density just like an optical lens focuses light. As a proof of concepts, we successfully demonstrated the massive assembly of V2O5 NWs and single-walled carbon nanotubes (swCNTs) with a nanoscale resolution using only microscale molecular patterning methods. This work provides us with important insights about the directed-assembly process, and from a practical point of view, it allows us to generate nanoscale patterns of NWs over a large area for mass fabrication of NW-based devices.     

Electrochemical template synthesis of multisegment nanowires: fabrication and protein functionalization

Multisegment nanowires represent a unique platform for engineering multifunctional nanoparticles for a wide range of applications. For example, the optical and magnetic properties of nanowires can be tailored by modifying the size, shape, and composition of each segment. Similarly, surface modification can be used to tailor chemical and biological properties. In this article, we report on recent work on electrochemical template synthesis of nanogap electrodes, the fabrication of multisegment nanowires with embedded catalysts, and the selective functionalization of multisegment nanowires with proteins.     

Dielectrophoretic assembly of nanowires

Nanowire (NW) assembly is currently of great interest, partly because NWs are considered as a fundamental component in the fabrication of a variety of devices. A powerful method has been developed to model the assembly of NWs. The three-dimensional dielectrophoretic (DEP) assembly of NWs across opposing electrodes is, for the first time, comprehensively studied using this new method. It is found that the DEP force reaches a maximum when the ratio of gap size to NW length is in the range 0.85-1.0. Both the magnitude and sign of the DEP torque on each NW varies with this ratio, and also with the orientation angle and the geometry and configuration of the electrode. The simulation of the dynamic assembly of individual and bundled NWs agrees with experiment. This method is of sufficient power that it will be of direct use in modeling DEP-based assembly and thus the manufacturing of nanoelectronic devices.     

Protein directed assembly of lipids

Highly ordered ring-like structures are formed via the directed assembly of lipid domains in supported bilayers, using the extracellular matrix protein fibronectin. The ability of biological molecules to guide nanoscale assembly suggests potential biomimetic approaches to nanoscale structures.     

Fluid flow-assisted dielectrophoretic assembly of nanowires

The dielectrophoretic assembly of silicon carbide (SiC) nanowires in a microfluidic flow is shown to enhance the orientation and deposition yield of nanowires. The fluid flow delivers and orients the nanowires in the vicinity of a gap, and they are attracted and deposited by a dielectrophoretic force. Depending upon their lengths, the nanowires are selectively attracted to the gap because the dielectrophoretic force is largest when the lengths are comparable to the gap size. Precise control over the fluid flow and dielectrophoresis shows various interesting phenomena such as landing, shifting, and uniform spacing of nanowires during the assembly process. As a result, the precise control enables the selective positioning of nanowires only at the gap where the fluid direction is consistent with the electric field orientation.     

Halide anion directed assembly of luminescent pseudorotaxanes

A series of new photo-active rhenium(i) bipyridyl based pseudorotaxane complexes is assembled via halide anion templation.     

Wet-chemical templateless assembly of metal nanowires from nanoparticles

We describe a new, simple, room-temperature wet-chemical approach for assembling Au and Ag nanoparticles into nanowire networks, without the use of lithographic templates. Five to 35 nm-diameter nanowires passivated with a thin organic layer were synthesized by mechanically agitating a biphasic liquid mixture of an aqueous hydrosol containing the nanoparticles, and toluene. Nanowire structure and surface chemistry are discussed based on electron microscopy, UV-visible spectroscopy and thermogravimetric analyses.     

Anion directed assembly of a dinuclear double helicate

The synthesis and structural characterisation of the diamino-bis-pyridine ligand L2 and its diammonium-bispyridinium salt [(H4L2Cl)2].6Cl.H2O 1, are reported; X-ray diffraction studies reveal that chloride coordination causes the latter to adopt a double-helicate structure in the solid-state.     

Switchable assembly of ultra narrow CdS nanowires and nanorods

We report on a simple route for the production of uniform and ultra narrow wurtzite CdS nanowires and nanorods. The nanorods are medium friendly (can exist in organic and aqueous phase) thus making them flexibly suitable for various applications. The centimeter range switchable ordering of the nanowires/rods into 3D microstrings by application of low magnitude DC electric field simply via two graphite electrodes is demonstrated. More sophisticated electrodes can be used for the same system to achieve more complex and fine patterns that can find potential use in nanoelectronics. The aligned microstrings (also wires/rods) show strong polarization dependence along their long axes. The polarized emission with respect to the unique c-axis makes the system suitable for orientation sensitive devices.     

Multimode assembly of phenanthroline nanowires decorated with gold nanoparticles

Self-assembled nanohybrids of a 1,10-phenanthroline derivative and Au nanoparticles exhibit different optoelectronic properties, as a consequence of the different arrangements of the nanoparticles on the surface of the different-sized phenanthroline scaffolds.     

Controllable assembly of aligned ZnO nanowires/belts arrays

We describe a simple method to assemble ZnO nanowires/belts into highly ordered arrays. ZnCu(2) alloy was used as the Zn source, which reacted with water vapor to generate ZnO nanocrystals. The reaction was performed in a mild way, which facilitated the easy control of the reaction conditions. By simply controlling the water bath temperature and carrier gas flux in our experiments, we obtained ZnO nanowires/belts aligned to form ordered arrays. The highly ordered nature of the ZnO arrays is suggested to be related both with the polarities of the H(2)O molecule and the ZnO (0001) surface. Photoluminescence (PL) microscopy revealed that the comblike structures had waveguide properties, where green light enhancement was observed at the tips of the branches. The light enhancement property reveals their promising applications as light source arrays.     

Protein assembly directed by synthetic molecular recognition motifs

Tris-functionalized cyanuric acid (TCA) and melamine (TM) selectively recognize each other in aqueous solution with 1 : 1 stoichiometry. We have coupled biotin to TCA and TM to allow pseudo-tetrahedral display of TCA and TM on streptavidin through biotin-ligand binding. Synthetic cyanuric acid/melamine recognition is found to drive selective protein-protein assembly.     

Simultaneous directed assembly of three distinct heterodimeric coiled coils

We describe simultaneous formation of three distinct heterodimeric coiled coils from a mixture of six different peptides. The choice among electrostatically viable complexes is governed by alignment of buried core residues, including a fundamentally new interaction that exploits urea-terminated side chains. Buried urea/urea contacts lead to extremely stable dimeric coiled coils, with T(m) values between 63 and 79 degrees C. Core ureas can also form stable complexes with a variety of other polar groups, including guanidines, acids, and amides.     

Encapsulation of transition metal catalysts by ligand-template directed assembly

Encapsulated transition metal catalysts are presented that are formed by templated self-assembly processes of simple building blocks such as porphyrins and pyridylphosphine and phosphite ligands, using selective metal-ligand interactions. These ligand assemblies coordinate to transition metals, leading to a new class of transition metal catalysts. The assembled catalyst systems were characterized using NMR and UV-vis spectroscopy and were identified under catalytic conditions using high-pressure infrared spectroscopy. Tris-3-pyridylphosphine binds three mesophenyl zinc(II) porphyrin units and consequently forms an assembly with the phosphorus donor atom completely encapsulated. The encapsulated phosphines lead exclusively to monoligated transition metal complexes, and in the rhodium-catalyzed hydroformylation of 1-octene the encapsulation of the catalysts resulted in a 10-fold increase in activity. In addition, the branched aldehyde was formed preferentially (l/b = 0.6), a selectivity that is highly unusual for this substrate, which is attributed to the encapsulation of the transition metal catalysts. An encapsulated rhodium catalyst based on ruthenium(II) porphyrins and tris-meta-pyridyl phosphine resulted in an even larger selectivity for the branched product (l/b = 0.4). These encapsulated catalysts can be prepared easily, and various template ligands and porphyrins, such as tris-3-pyridyl phosphite and ruthenium(II) porphyrins, have been explored, leading to catalysts with different properties.     

Highly selective directed assembly of functional actomyosin on Au surfaces

The capability of assembling biomotors onto specific locations of solid substrates is a key for development of biomotor-based nanomechanical systems. We developed a method to direct the assembly of the heavy meromyosin fragment from rabbit skeletal muscle myosin onto specific locations of Au substrates utilizing surface molecular patterns. In this strategy, chemically directed patterns of streptavidin were achieved to direct highly specific assembly of biotinylated heavy meromyosin on the substrates--a strategy applicable for patterning a variety of biotinylated molecules--while BSA was utilized to avoid nonspecific adsorption. In vitro motility assays of filament sliding were used to confirm functionality of assembled actomyosin.     

Controlling interfacial interactions for directed self assembly of block copolymers

Over the past 15 years, block copolymer lithography has emerged as its own research field within the broader block copolymer and polymer thin film communities. This distinction is associated with the unique requirements set by the semiconductor device industry, such as low-defect densities, precise feature registration, and complex pattern layouts. To achieve perfection in block copolymer lithography, the surface and substrate interactions must be carefully tuned to control domain ordering in three dimensions. This perspective discusses recent modeling efforts that underline the challenges of predicting interfacial interactions and the resulting block copolymer structures. We emphasize studies that facilitate the design and interpretation of experiments, including materials selection, guiding pattern geometry, and selecting tools for three-dimensional metrology. Finally, we propose that translation of block copolymer lithography to semiconductor manufacturing will require integrated experimental and modeling efforts to interrogate the vast parameter space that controls both lateral and out-of-plane ordering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 96–102     

Branched networks by directed assembly of shape anisotropic magnetic particles

The directed assembly of shape anisotropic magnetic particles into targeted macrostructures requires judicious particle design. We present a framework to understand the self-assembly of magnetic non-Brownian H-shaped particles and the formation of branched networks under an applied magnetic field. A finite element integration (FEI) method is developed to identify the preferred particle orientation (relative to the applied field) at different values of the geometric parameters defining H shapes, and used to construct a phase diagram to generalize the results. Theoretical predictions are validated by comparing with experiments performed using magnetic hydrogels synthesized using stop-flow lithography (SFL). We demonstrate the ability of H-shaped particles to form chains parallel to the field that can thicken in a direction orthogonal to the field, and in some cases with branching. The assembly of a suspension containing H-shaped particles, or rods, or a combination of both, is reported.     

Controllable assembly of WO3 nanorods/nanowires into hierarchical nanostructures

The controlled synthesis of two novel h-WO3 hierarchical structures made of nanorods/nanowires has been successfully realized in a large scale via a simple hydrothermal method. It is demonstrated that the morphology of the final products is significantly influenced by adding different sulfates. The urchinlike and ribbonlike structures of WO3 can be selectively prepared by adding Rb2SO4 and K2SO4, respectively. The morphology evolvement and the growth mechanism were studied carefully. The sulfate-induced oriented attachment growth mechanism has been proposed for the possible formation mechanism of the ribbonlike sample. For urchinlike products, two growing stages are believed to be involved in the growth process. The current understanding of the growth mechanism of these nanostructures may be potentially applied for designing other oriented or hierarchical nanostructures based on 1D nanoscale building blocks through the direct solution-growth.