Wettability of zinc oxide surfaces with controllable structures

Zinc oxide (ZnO) surfaces with controllable structures (i.e, microstructure, nanostructure, and micronanobinary structure) have been created by controlling pH at < 4 or > 10.5 in the Zn(gray) + H2O2 reaction. The resulting surface shows superhydrophobicity. It is found that the water contact angle (CA) of the surface with micronanobinary structure is greater than that of nanostructure and that of nanostructure is greater than that of the microstructure. Theoretical analysis is completely in agreement with the experimental results.

Reinforcement of silica with single-walled carbon nanotubes through covalent functionalization

Single-walled carbon nanotubes (SWCNTs) as reinforcing components were extended into silica monoliths and thin films via covalent functionalization for the first time. Silica materials have poor mechanical attributes, which limit their applications. Because of the extreme flexibility of SWCNTs and their large interfacial area, they may be very intriguing as reinforcing fillers for the silica matrix. To get more uniform dispersion and stronger interfacial interaction, SWCNTs were covalently functionalized with silane, and then integrated into silica via a sol - gel process, and their properties were also compared with those of pristine SWCNTs. Results show that the silane-functionalized nanotubes resulted in better mechanical properties ( for example, 33% increase in stress, and 53% increase in toughness), as well as higher electron-transfer kinetics.

Electrogenerated chemiluminescence sensing platform using Ru(bpy)(3)(2+) doped silica nanoparticles and carbon nanotubes

An effective electrogenerated chemiluminescence (ECL) sensor was developed by coimmobilization of the Ru(bpy)(2)(3+)-doped silica (RuDS) nanoparticles and carbon nanotubes (CNTs) on glassy carbon electrode through hydrophobic interaction. The uniform RuDS nanoparticles were prepared by a water-in-oil (W/O) microemulsion method and Ru(bpy)(3)(2+) doped inside could still maintain its high ECL efficiency. With such unique immobilization method, a great deal of Ru(bpy)(3)(2+) was immobilized three-dimensionally on the electrode , which could greatly enhance the ECL response and result in the increased sensitivity. On the other hand, CNTs played dual roles as matrix to immobilize RuDS nanoparticles and promoter to accelerate the electron transfer between Ru(bpy)(3)(2+) and the electrode. The as-prepared ECL sensor displayed good sensitivity and stability.

An effective approach to synthesis of poly(methyl methacrylate)/silica nanocomposites

A novel synthetic route for nearly monodispersed poly(methyl methacrylate)/SiO2 composite particles (PMSCP) is reported. Silica nanoparticles modified with oleic acid were used as 'seeds'. Methyl methacrylate (MMA) monomer was copolymerized with oleic acid via in situ emulsion polymerization, in the presence of an initiator; it resulted finally in the formation of composites with core-shell morphology. The composite particles were examined by transmission electron microscopy (TEM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The number of silica particles inside the composite particles increases with an increase in the silica concentration. The effect of grafted silica concentration on the morphology of PMSCP is also reported in detail. It was found by thermogravimetric analysis that PMSCP show a potential application for fire retardance.

Surface-appropriate lipophobicity - Application in isobutene oligomerization over Teflon-modified silica-supported 12-silicotungstic acid

A series of silica-supported 12-silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by an impregnation method. The surface properties of the catalysts were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), BET, infrared (IR) spectroscopy, NH3-TPD and the Drop Shape Analysis (DSA). SEM results combined with energy-dispersive X-ray (EDX) measurements of HSiW/SiO2-Teflon revealed that F-compound (Teflon) is effectively coated on the catalyst surface. The contact angles for water and oil of 50 wt% HSiW/SiO2 and HSiW/SiO2-Teflon indicate that HSiW/SiO2-Teflon catalyst enhances not only the surface hydrophobicity but also the surface lipophobicity by means of the addition of Teflon. Silica-supported 12-silicotungstic acid modified with Teflon exhibits higher C-8(=) selectivity and longer lifetime than that of silica-supported 12-silicotungstic acid in isobutene oligomerization. Thus, surface-appropriate lipophobicity of catalysts may be effective for decreasing the interaction between coke precursors and the catalyst surface and for removing deposited coke more easily.

Silica supported submicron SiO2@Y2SiO5 : Eu3+ and SiO2@Y2SiO5 : Ce3+/Tb3+ spherical particles with a core-shell structure: Sol-gel synthesis and characterization

X-1-y(2)SiO(5):Eu3+ and X-1-Y2SiO5:Ce3+ and/or Tb3+ phosphor layers have been coated on nonaggregated, monodisperse, submicron spherical SiO2 particles by a sol-gel process, followed by surface reaction at high temperature (1000 degrees C), to give core/shell structured SiO2@Y2SiO5:Eu3+ and SiO2@Y2SiO5:Ce3+/Tb3+ particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), TEM, photoluminescence (PL), low voltage cathodoluminescence (CL), and time-resolved PL spectra and lifetimes are used to characterize these materials. The XRD results indicate that X-1-Y2SiO5 layers have been successfully coated on the sur- face Of SiO2 particles, as further verified by the FESEM and TEM images. The PL and CL studies suggest that SiO2@Y2SiO5:Eu3+, SiO2@Y2SiO5:Tb3+ (or Ce3+/Tb3+), and SiO2@Y2SiO5:Ce3+ core/shell particles exhibit red (Eu3+, 613 rim: D-5(0)-F-7(2)), green (Tb3+, 542nm: D-5(4)-F-7(5)), or blue (Ce3+, 450nm: 5d-4f) luminescence, respectively. Pl, excitation, emission, and time-resolved spectra demonstrate that there is an energy transfer from Ce3+ to Tb3+ in the SiO2@Y2SiO5:Ce3+,Tb3+ core/shell particles.

Catalytic properties of silica/silver nanocomposites

The catalytic properties of silver nanoparticles supported on silica and the relation between catalytic activity of silver particles and the support (silica) size are investigated in the present article. The silver nanoparticles with 4 nm diameters were synthesized and were attached to silica spheres with sizes of 40, 78, 105 nm, respectively. The reduction of Rhodamine 6G (R6G) by NaBH4 was designed by using the SiO2/Ag core-shell nanocomposites as catalysts. The experimental results demonstrated that the catalytic activity of silica/silver nanoparticles depends on not only the concentration of catalysts (silver) but also the support silica size. Silver particles supported on small SiO2 spheres (similar to 40 nm) show high catalytic activity. Moreover, by making a comparison between the UV-vis spectra of the catalyst before and after the catalytic reaction, we found that the position of surface plasma resonance (SPR) peak of Ag nanoparticles changes little. The above results suggested that the size and morphology of silver particles were probably kept unchanged after the reduction of R6G and also implied that the catalytic activity of silver particles was hardly lost during the catalytic reaction.

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.

Complex aggregates of spherical colloids via modified micromolding in capillaries

This paper describes a simple approach to fabricate aggregates composed of monodispersed silica microspheres by modified micromolding in capillaries (MIMIC). Two different kinds of contact modes, namely, conformal contact and non-conformal contact, between the poly(dimethylsiloxane) (PDMS) mold and the underlying prepatterned substrate, can be controlled during the micromolding, which result in the formation of different aggregates under the influence of template confinement and capillary forces. These aggregates, including woodpile structure, discoid, conoid and rectangular clusters, possess well-controlled sizes and orientation. The possible mechanisms for the formation of different aggregates are discussed in detail.

Tunable photonic crystals by mixed liquids

Tunable photonic crystals were prepared by infiltrating mixed liquids into the voids of silica opals. The stop bands of the tunable photonic crystals were continuously tuned by changing the relative refraction index contrast n(mix)/ns(pheres) of the spheres and the mixed liquids by varying the volume fraction of the component of the mixed liquids. The peak wavelengths of the stop band have a red shift as the refractive index of the mixed liquids increases. The transmittance at the stop band decreases with the increase of the refractive index contrast n(mix)/n(spheres). The larger the diameter of silica opals is, the wider the tunable range of the stop band is. The position and transmittance of the peak wavelength obtained by the photonic band calculations agreed very well with the experimental data.

Luminescence and energy transfer of organically modified silica xerogels (OMSX) doped and undoped with Eu3+ and Tb3+

Organically modified silica xerogels (OMSX) and Eu3+ (Tb3+)-doped OMSX were prepared by the reaction of (3-aminopropyl) triethoxysilane (APS) with 3-isocyanatepropyltriethoxysilane (ICPTES) followed by the subsequent hydrolysis and condensation in the presence of Eu3+ (Tb3+) via sol-gel method, which were characterized by FT-IR, XRD, fluorescence excitation and emission spectra. The as-formed OMSX shows a strong blue emission with the maximum excitation and emission wavelength at 351 and 420 nm, respectively. Due to the spectral overlap between the emission band of OMSX and f-f absorption lines of Eu3+ and Tb3+ in the UV-blue region, an energy transfer was observed from OMSX host to Eu3+ and Tb3+ in OMSX/Eu3+ and OMSX/Tb3+, respectively. Excitation at 350-360 nm resulted in a very weak emission around 420 nm from OMSX host and strong emission of Eu3+ and Tb3+ in OMSX/Eu3+ and OMSX/Tb3+, respectively. The emission spectra of Eu3+ and Tb3+ consist of D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4) and D-5(4)-F-7(J) (J = 6, 5, 4, 3), respectively. Furthermore, the predicted structure of OMSX/Eu3+ and OMSX/Tb3+ is presented.

Patterning and optical properties rhodamine B-doped organic-inorganic silica films fabricated by sol-gel soft lithography

Rhodamine B (RB)-doped organic-inorganic silica films and their patterning were fabricated by a sol-gel process combined with a soft lithography. The resulted film samples were characterized by atomic force microscope (AFM), optical microscope and UV/Vis absorption and photoluminescence excitation and emission spectra. The effects of the concentration of the RB dye and heat treatment temperature on the optical properties of the hybrid silica films have been studied. Four kinds of patterning structures with film line widths of 5, 10, 20 and 50 mum have been obtained by micromolding in capillaries by a soft lithography technique. The RB-doped hybrid silica films present a red color, with an excitation and emission bands around 564 and 585 mum, respectively. With increasing the RB concentration, the emission intensity of the RB-doped hybrid silica films increases and the emission maximum presents a red shift. The emission intensity of the films decreases with increasing the heat treatment temperatures.

Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

Electrochemiluminescence sensor using tris(2,2 '-bipyridyl)ruthenium(II) immobilized in Eastman-AQ55D-silica composite thin-films

An electrochemiluminescence (ECL) sensor with good long-term stability and fast response time has been developed. The sensor was based on the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) into the Eastman-AQ55D-silica composite thin films on a glassy carbon electrode. The ECL and electrochemistry of Ru(bpy)(3)(2+) immobilized in the composite thin films have been investigated, and the modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and chlorpromazine (CPZ) in a flow injection analysis system and showed high sensitivity. Because of the strong electrostatic interaction and low hydrophobicity of Eastman-AQ55D, the sensor showed no loss of response over 2 months of dry storage. In use, the electrode showed only a 5% decrease in response over 100 potential cycles. The detection limit was 1 mumol l(-1) for oxalate and 0.1 mumol l(-1) for both TPA and CPZ (S/N = 3), respectively. The linear range extended from 50 mumol l(-1) to 5 mmol l(-1) for oxalate, from 20 mumol l(-1) to 1 mmol l(-1) for TPA, and from 1 mumol l(-1) to 200 mumol l(-1) for CPZ.