Alternate assemblies of polyelectrolyte functionalized carbon nanotubes and platinum nanoparticles as tunable electrocatalysts for dioxygen reduction

A novel method based on electrostatic layer-by-layer self-assembly (LBL) technique for alternate assemblies of polyelectrolyte functionalized multi-walled carbon nanotubes (MWNTs) and platinum nanoparticles (PtNPs) is proposed. The shortened MWNTs can be functionalized with positively charged poly(diallyldimethylammonium chloride) (PDDA) based on electrostatic interaction. Through electrostatic layer-by-layer assembly, the positively charged PDDA functionalized MWNTs (PDWNTs) and negatively charged citrate-stabilized PtNPs were alternately assembled on a 3-mercaptopropanesulfonic sodium (NIPS) modified gold electrode and also on other negatively charged surface, e.g. quartz slide and indium-tin-oxide (ITO) plate, directly forming the three-dimensional (3D) nanostructured materials. This is a very general and powerful technique for the assembling three-dimensional nanostructured materials containing carbon nanotubes (CNTs) and nanoparticles. Thus prepared multilayer films were characterized by ultraviolet-visiblenear-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV). Regular growth of the mutilayer films is monitored by UV-vis-NIR.

Photochromic inorganic-organic multilayer films based on polyoxometalates and poly(ethylenimine)

Novel photochromic inorganic-organic multilayers composed of polyoxometalates and poly(ethylenimine) have been prepared by the layer-by-layer (LbL) self-assembly method. The growth process, composition, surface topography, and photochromic properties of the multilayer films were investigated by UV-visible and Fourier transform infrared spectroscopy, atomic force microscopy, electrospin resonance (ESR), and X-ray photoelectron spectroscopy (XPS). Irradiated with ultraviolet light, the transparent films changed from colorless to blue. Moreover, the blue films showed good reversibility of photochromism, and could recover the colorless state gradually in air, where oxygen plays an important role in the bleaching process. On account of the ESR and XPS results, parts of W6+ in multilayers were reduced to W5+, which exhibited a characteristic blue; a possible photochromic mechanism can be speculated. This work provides basic guideline for the assembly of multilayers with photochromic properties.

One-step polyelectrolyte-based route to well-dispersed gold nanoparticles: Synthesis and insight

Polyelectrolytes have been widely used as building blocks for the creation of thickness-controllable multilayer thin films in a layer-by-layer fashion, and also been used as flocculants or stabilizer of colloids. This paper reports novel finding that a kind of polyelectrolyte, polyamines, can facilely induce HAuCl4 to spontaneously form well-stabilized gold nanoparticles without the additional step of introducing a reducing reagent during the elevation of temperature, even at room temperature in some cases. The polymer chain-confined microenvironment and the acid-induced evolution of amide of such kind of polyelectrolyte solution play an important role in the nucleation and growth of gold nanoparticles. This method would not only be helpful to gain an insight into the formation of gold nanoparticles in polyelectrolyte systems, but also provide a novel and facile one-step polyelectrolyte-based synthetic route to polyelectrolyte protected gold nanoparticles in aqueous media for potential applications. More importantly, this strategy will be general to the preparation of other nanoparticles.

Layer-by-layer assembly of multilayer films composed of avidin and biotin-labeled antibody for immunosensing

Protein multilayers composed of avidin and biotin-labeled antibody (bio-Ab) were prepared on gold surface by layer-by-layer assembly technology using the high specific binding constant (K-a: approximate to 10(15) M-1) between avidin and biotin. The assembly process of the multilayer films was monitored by using real-time BIA technique based on surface plasmon resonance (SPR). The multilayer films were also characterized by electrochemical impedance spectroscopy (EIS) and reflection absorption Fourier transform infrared spectroscopy (FTIR). The results indicate that the growth of the multilayer is uniform. From response of SPR for each layer, the stoichiometry S for the interaction between avidin and bio-Ab is calculated to be 0.37 in the multilayer whereas 0.82 in the first layer. The protein mass concentration for each layer was also obtained. The schematic figure for the multilayer assembly was proposed according to the layer mass, concentration and S value. The utility of the mutilayer films for immunosensing has been investigated via their subsequent interaction with hIgG. The binding ability of the multilayer increased for one to three layers of antibody, and then reach saturation after the fourth layer. These layer-by-layer constructed antibody multilayers enhance the binding ability than covalently immobilized monolayer antibody. This technology can be also used for construction of other thin films for immunosensing and biosensor.

Assembly of alternating polycation and DNA multilayer films by electrostatic layer-by-layer adsorption

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. The real-time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. Electrochemical impedance spectroscopy (EIS) and UV-vis absorbance measurements were also used to study the film assembly, and linear film growth was observed. All the results indicate that the uniform multilayer can be obtained on the poly(ethylenimine)- (PEI-) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by the real-time BIAcore technique; the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1).

Ultrathin multilayer films incorporating Keggin-type heteropolyanion clusters

Two new ultrathin multiplayer films have been successfully prepared fi-om Keggin-type heteropoly acids H-4[SiW12O40] and H-3[PMo12O40] with polyelectrolytes PEI, PSS, and PAH, using the electrostatic layer-by-layer self-assembly, technique. The XR results reveal their film thickness at nanoscale (similar to 20 nm). According to the AFM images, it is believed that the surface roughness (rough degree of film surface) of the polyelectrolyte-polyoxometalate film greatly depends on the kind of polyoxometalates.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

Bragg diffraction of multilayer volume holographic gratings under ultrashort laser pulse readout

The multilayer coupled wave theory is extended to systematically investigate the diffraction properties of multilayer volume holographic gratings (MVHGs) under ultrashort laser pulse readout. Solutions for the diffracted and transmitted intensities, diffraction efficiency, and the grating bandwidth are obtained in transmission MVHGs. It is shown that the diffraction characteristics depend not only on the input pulse duration but also on the number and thickness of grating layers and the gaps between holographic layers. This analysis can be implemented as a useful tool to aid with the design of multilayer volume grating-based devices employed in optical communications, pulse shaping, and processing. (C) 2008 Optical Society of America

Efficient excitations of radially and azimuthally polarized Nd 3+:YAG ceramic microchip laser by use of subwavelength multilayer concentric gratings composed of Nb2O5/SiO2

Cylindrical vector beams were produced from laser diode end-pumped Nd:YAG ceramic microchip laser by use of two types of subwavelength multilayer gratings as the axisymmetric-polarization output couplers respectively. The grating mirrors are composed of high- and low-refractive-index (Nb2O5/SiO2) layers alternately while each layer is shaped into triangle and concentric corrugations. For radially polarized laser output, the beam power reached 610mW with a polarization extinction ratio ( PER) of 61: 1 and a slope efficiency of 68.2%; for azimuthally polarized laser output, the beam power reached 626mW with a PER of 58: 1 and a slope efficiency of 47.6%. In both cases, the laser beams had near-diffraction limited quality. Small differences of beam power, PER and slope efficiency between radially and azimuthally polarized laser outputs were not critical, and could be minimized by further optimized adjustment to laser cavity and the reflectances of respective grating mirrors. The results manifested, by use of the photonic crystal gratings mirrors and end-pumped microchip laser configuration, CVBs can be generated efficiently with high modal symmetry and polarization purity. (C) 2008 Optical Society of America.

Newly designed multilayer thin film mirror for dispersion compensation in Ti:sapphire femtosecond lasers

There are two different effects to generate group delay dispersion by multilayer thin film mirrors: chirper effect and Gires-Tournois effect. Both effects are employed to introduce desired dispersion in the designed mirror. Thus the designed mirror provides large dispersion throughout broad waveband. Such mirror can be used for dispersion compensation in Ti:sapphire femtosecond lasers. Most group delay dispersion of a 5-mm Ti:sapphire crystal can be compensated perfectly with only four bounces of the designed mirror.

Characteristics of high reflection mirror with an SiO2 top layer for multilayer dielectric grating

The high reflection (HR) mirror composed of dielectric stacks with excellent spectrum characteristics and high damage resistant ability is critical for fabricating multilayer dielectric (MLD) grating for pulse compressor. The selection of the SiO2 material as the top layer of the HR mirror for grating fabrication is beneficial for improving the laser-induced damage threshold of MLD grating as well as minimizing the standing-wave effect in the photoresist during the exposure process. Based on an (HLL) H-9 design comprising quarter-waves of HfO2 ( H) and half-waves of SiO2 ( L), we obtain an optimal design of the HR mirror for MLD grating, the SiO2 top layer of which is optimized with a merit function including both the diffraction efficiency of the MLD grating and the electric field enhancement in the grating. Dependence of the performance of the MLD grating on the fabrication error of the dielectric mirror is analysed in detail. The HR mirror is also fabricated by E-beam evaporation, which shows good spectral characteristics at the exposure wavelength of 413 nm and at the operation wavelength of 1053 nm and an average damage threshold of 10 J cm(-2) for a 12 ns pulse.