Self-assembly of a water chain with tetrameric and decameric clusters in the channel of a mixed-valence (CuCuII)-Cu-I complex

The reaction of Cu(BF4)(2) with pyridine-2,6-dicarboxylic acid (H(2)pydc) and trans-1,2-bis(4-pyridyl)ethylene (bpe) under hydrothermal conditions afforded a porous mixed-valence (CuCuII)-Cu-I coordination polymer. Coexistence of tetrameric and decameric water clusters within the channels of the complex leads to a novel water chain. The metal-organic framework provides both hydrophilic and hydrophobic environments for stabilizing the clusters and retains its integrity upon dehydration and rehydration.

Self-assembly of crystalline-coil diblock copolymer in solvents with varying selectivity: From spinodal-like aggregates to spheres, cylinders, and lamellae

We have investigated systematically the morphology of thin films spin-coated from solutions of a semicrystalline diblock copolymer, poly(L-lactic acid)-block-polystyrene (PLLA-b-PS), in solvents with varying selectivity. In neutral solvents (chloroform and tetrahydrofuran (THF)), a spinodal-like pattern was obtained and the pattern boundary was sharpened by diluting the solution. Meanwhile, loose spherical associates, together with larger aggregates composed of these associates by unimer bridges, formed partly due to crystallization of the PLLA blocks in relatively concentrated solutions. In slightly PS-selective solvent (e.g., benzene), both loose and compact spherical micelles were obtained, depending on the polymer concentration, coexisting with unimers. When enhancing the selectivity with mixed solvents, for example, mixing the neutral solvent and the slightly selective solvent with a highly PS-selective solvent, CS2, loose assemblies (nanorods in CS2/THF mixtures and polydisperse aggregates in CS2/benzene mixtures) and well-developed lamellar micelles were obtained.

Ordered macroporous films from self-assembly of two-armed polymer with a crown ether core

Highly ordered honeycomb-like macroporous films were obtained via self-assembly of a two-armed polymer with a crown ether core under controlled conditions. A possible mechanism is speculated, primarily based on the strong affinity between the crown ether cores. The pore size and arrangement are sensitive to the solvent evaporation rate and the solution concentration. Upon spontaneous drying, the pore diameter (D) depends on the concentration (c) by a relation of D=518c(-0.610).

Fabrication of magnetic luminescent nanocomposites by a layer-by-layer self-assembly approach

Magnetic luminescent nanocomposites were prepared via a layer-by-layer (LbL) assembly approach. The Fe3O4 magnetic nanoparticles of 8.5 nm were used as a template for the deposition of the CdTe quantum dots (QDs)/polyelectrolyte (PE) multilayers. The number of polyelectrolyte multilayers separating the nanoparticle layers and the number of QDs/ polyelectrolyte deposition cycles were varied to obtain two kinds of magnetic luminescent nanocomposites, Fe3O4/PEn/CdTe and Fe3O4/(PE3/CdTe)(n), respectively. The assembly processes were monitored through microelectrophoresis and UV-vis spectra. The topography and the size of the nanocomposites were studied by transmission electron microscopy. The LbL technique for fabricating magnetic luminescent nanocomposites has some advantages to tune their properties. It was found that the selection of a certain number of the inserted polyelectrolyte interlayers and the CdTe QDs loading on the nanocomposites could optimize the photoluminescence properties of the nanocomposites. Furthermore, the nanocomposites could be easily separated and collected in an external magnetic field.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Synthesis and characterization of functionalized mesoporous silica by aerosol-assisted self-assembly

An efficient, productive, and low-cost aerosol-assisted self-assembly process has been developed to produce organically modified mesoporous silica particles via a direct co-condensation of silicate species and organosilicates that contain nonhydrolyzable functional groups in the presence of templating surfactant molecules. Different surfactants including cetyltrimethylammonium bromide, nonionic surfactant Brij-56, and triblock copolymer P123 have been used as the structure-directing agents. The organosilanes used in this study include tridecafluoro-1, 1,2,2-tetrahydrooctyltriethoxysilane, methytriethoxysilane, vinyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate. X-ray diffraction and transmission electron microscopy studies indicate the formation of particles with various mesostructures. Fourier transform infrared and solid-state nuclear magnetic resonance spectra confirm the organic ligands are covalently bound to the surface of the silica framework. The porosity, pore size, and surface area of the particles were characterized using nitrogen adsorption and desorption measurements.

Rapid self-assembly of oligo(o-phenylenediamine) into one-dimensional structures through a facile reprecipitation route

The self-assembly of oligo(o-phenylenediamine) (OPD) into 1-D nanostructures on a macroscopic length scale was found when they were transferred from N-methyl pyrrolidone to deionized water. Field emission scanning electron microscopy and confocal fluorescence microscopy were used to investigate the morphology of the precipitates. Results showed that large amounts of OPD 1-D supertructures could be obtained through the simple reprecipitation route, and the length of the fibers could be tuned from microscale to macroscale by adjusting the ratio of two solvents. X-ray diffraction patterns and UV-vis spectra revealed that pi-pi interactions between OPD molecules that facilitated the formation of 1-D structures became predominant when they were transferred from a good solvent to a bad one. Accordingly, a possible formation mechanism was proposed.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

One-step synthesis of 3D dendritic gold/polypyrrole nanocomposites via a self-assembly method

Novel spherical three-dimensional (3D) dendritic gold-polypyrrole nanocomposites were successfully prepared in the presence of an amphiphilic p-toluene sulfonic acid (TSA) as dopant and surfactant via a self-assembly process which is based on the oxidation of pyrrole (Py) and the reduction of the chloroaurate ions, yielding PPy and Au(0) simultaneously. It was found that the probability of obtaining dendritic Au@PPy/TSA nanostructures depended on the concentration of TSA and the rate of addition of the oxidant (HAuCl4), It was also proposed that the supramolecular micelles formed by Py and TSA play the role of a 'soft template' to produce the dendritic Au@PPy/TSA nanocomposites.

Preparation and layer-by-layer self-assembly of positively charged multiwall carbon nanotubes

The report described a method of more stably dispersing oxidized carbon nanotubes (CNTs) by forming complex with polycation and the layer-by-layer self-assembly behavior of the complex with polyanion was studied. The properties of the self-assembled multilayer film containing carbon nanotubes were studied. Cyclic voltammetry, UV-vis-NIR spectroscopy, electrochemical impedance spectroscopy and scanning electron microscopy were used for characterization of film assembly. UV-vis-NIR spectroscopy and cyclic voltammetry study indicated the uniform growth of the film. Electrochemical impedance spectroscopy results showed that incorporating of carbon nanotubes in the polyelectrolyte multilayers; decreased in the electron-transfer resistance R, indicating more favorable electrochemical reaction interface. The electrocatalytic property of the multilayer modified electrode to NADH was investigated mainly with different numbers of the bilayers; and the results showed that along with the increase of the assembled bilayers the overpotential of NADH oxidation decreased. The detection lit-nit Could reach 6 mu M at a detection potential of 0.4 V.

Syntheses of Ag, PbSe, and PbTe nanocrystals and their binary self-assembly exploration at low size-ratio

Nanocrystals of Ag, PbSe, and PbTe were prepared via a high-temperature organic solution approach, respectively. Using a size-selection technique, the size-distribution of each set of nanocrystals could be fine-tuned and finally monodisperse products were achieved. Superlattice structure of binary self-assemblies in low size-ratio were also explored and characterized by transmission electron microscopy. It is realized that a success of achieving binary self-assembly pattern is greatly dependent on several key factors including particle size-distributions, relative concentrations of both components, as well as the size-ratios between Ag and PbSe (or PbTe) nanocrystals.

Different colloids self-assembly in micromolding

Micromolding in capillaries (MIMIC) and non-conformal contact micromolding (NCCM) were employed to pattern the silica microspheres by the use of capillary forces. Three types of silica microspheres aggregations, small dot, ring and grid patterns, from the same prepatterned poly(dimethylsiloxane) (PDMS) stamps, were created by tuning the contact mode between the PDMS mold and the substrate and the concentration of silica microspheres suspension during the micromolding. The formation mechanisms of different patterns were discussed.

Self-assembly of 4-ferrocene thiophenol capped electroactive gold nanoparticles onto gold electrode

Gold nanoparticles capped by 4-ferrocene thiophenol with an average core size of 2.5 nm and surface plasmon absorbance at 522 nm were place-exchanged with 1,8-octanedithiol, and then self-assembled onto the gold electrode via tail SH group. The self-assembly was characterized by X-ray photoelectron spectroscopy. Cyclic voltammograms examined the coverage fraction of the self-assembled monolayers of the electroactive gold nanoparticles and the formal potential of the indicated SAMs. Further experiments exhibited that the electrode process was controlled by surface confined faradic reactions.

Synthesis and self-assembly of cetyltrimethylammonium bromide-capped gold nanoparticles

In this article, cetyltrimethylammonium bromide (CTAB)-capped gold nanoparticles were synthesized successfully by using CTAB as a phase-transfer catalyst and stabilizer simultaneously in a two-phase toluene/water system. The as-prepared gold nanoparticles were characterized and analyzed by virtue of X-ray photoelectron spectroscopy, UV-visible absorbance spectroscopy, and infrared spectroscopy. The particle size information and collective self-assembling properties of the CTAB-capped gold nanoparticles on carbon-coated copper grid and mica were evaluated by transmission electron microscopy and atomic force microscopy, respectively. As a result it is demonstrated that the 3-D CTAB monolayers on a gold cluster are in the disordered liquid state. The interparticle spacing can be controlled either physically by the inherent particle-to-particle interactions or chemically by molecular linker. The assembly of both nanoparticles and linker-bridged nanonetworks on mica follows a hydrophobic interaction mechanism.