Silica sol-gel composite film as an encapsulation matrix for the construction of an amperometric tyrosinase-based biosensor

An amperometric tyrosinase enzyme electrode for the determination of phenols was developed by a simple and effective immobilization method using sol-gel techniques. A grafting copolymer was introduced into sol-gel solution and the composition of the resultant organic-inorganic composite material was optimized, the tyrosinase retained its activity in the sol-gel thin film and its response to several phenol compounds was determined at 0 mV vs. Ag/AgCl (sat. KCI). The dependences of the current response on pH, oxygen level and temperature were studied, and the stability of the biosensor was also evaluated. The sensitivity of the biosensor for catechol, phenol and p-cresol was 59.6, 23.1 and 39.4 muA/mM, respectively. The enzyme electrode maintained 73% of its original activity after intermittent use for three weeks when storing in a dry state at 4 degreesC. (C) 2000 Elsevier Science S.A. All rights reserved.

Amperometric enzyme electrode for the determination of hydrogen peroxide based on sol-gel/hydrogel composite film

A new type of organic-inorganic composite material was prepared by sol-gel method, and a peroxidase biosensor was fabricated by simply dropping sor-gel-peroxidase mixture onto glassy carbon electrode surface. The sol-gel composite film and enzyme membrane were characterized by Fourier-transform infrared (FT-IR) spectroscopy and EQCM, the electrochemical behavior of the biosensor was studied with potassium hexacyanoferrate(II) as a mediator, and the effects of pH and operating potential were explored for optimum analytical performance by using amperometric method. The response time of the biosensor was about 10 s; the linear range was up to 3.4 mM with a detection limit of 5 x 10(-7) M. The sensor also exhibited high sensitivity (15 mu A mM(-1)) and good long-term stability. In addition, the performance of the biosensor was investigated using flow injection analysis (FIA), and the determination of hydrogen peroxide in real samples was discussed. (C)2000 Elsevier Science B.V. All rights reserved.

The separation of beta-BBO phase in alpha-BBO crystal by the irradiation of femtosecond laser

We observed and described some phenomena, which were that when a alpha-BBO crystal was irradiated by a focused femtosecond laser beam, the temperature effect happened in a minute area of focus, then the induced beta-BBO phase was separated within the minute area in the alpha-BBO crystal. (C) 2007 Elsevier B.V. All rights reserved.

纳米功能界面的电化学和扫描探针显微镜（SPM）研究

本文简要评述了扫描探针显微学研究的发展过程、目前状况及发展方向，着重介绍了扫描探针显微学(SPM)在分子组装体研究中的一些应用。采用扫描探针显微学结合电化学的方法对自组装膜(SAMs)、纳米颗粒(nanoparticles)、有机无机纳米复合材料(composite material)体系进行了研究，并结合XPS、SEC等多种手段对分子组装体在电极表面的形态和结构进行了探讨。主要结果如下：1．STM研究金属纳米颗粒的隧道成像机理利用柠檬酸三钠还原高氯酸金的反应制备了金的溶胶纳米粒子。将对氨基硫酚自组于金单晶面(Au(111))上形成致密有序的单层；并以此为基底进一步将金溶胶纳米粒子组装于自组膜表面，得到固定化纳米粒子的次单层。用扫描隧道显微镜进行了表征，对金溶胶纳米粒子隧道成像的微观机理作了探讨，提出双势垒隧穿的电子传输界面模型。对扫描隧道显微镜下金溶胶纳米粒子的图像失真作解释。2．共轭有机小分子的导电性的研究利用保护和去保护的方法对带巯基的共轭有机小分子进行了合理地操纵，使其稳定性在我们构筑电化学界面的过程中得到了保证。我们用自组装(SAM)技术将这种共轭有机小分子首先吸附于金电表面，然后用稀氨水将其水解得到致密的共轭有机小分子的单层。在金/SAM二次基底的基础上利用巯基于金的强烈的化学键合力用电化学沉积的方法和湿化学还原的方法得到的金纳米粒子组装于电极表面，得到了金/有机分子层/金的夹心结构，并对构筑这种夹心结构的每一步骤用扫描探针显微镜(SPM)和电化学循环伏安法(CV)进行了表征，实验结果表明，此种共轭有机小分子利用巯基化学键合金属金时，电子能够快速通过这种夹心结构，为分子电子学中之基本问题“分子导线”连接纳米级的分子器件时电子能否在其间传导给出了直接的电化学证明。3．纳米复合材料的合成与表征我们用相转移方法合成了表面功能化的纳米粒子。首先，根据将HAuCl_4溶解于水相中，将Bu_4NClO_4作为相转移试剂、带巯基的有机小分子作为表面修饰剂，NaBH_4和柠檬蒜三钠作为还原剂溶解于硝基苯有机相中。将两相剧烈混合，在混合过程中HAuCl_4在水/硝基苯界面处被有机相中的还原剂还原成金属纳米粒子，刚生成的纳米粒子由于强烈的金硫键合作用而被带巯基的有机小分子表面功能化，而且能在有机溶剂中稳定存在。于是得到的表面功能化的纳米粒子在有机溶剂中的稳定胶体溶液。我们合成了表面被12烷基硫醇和巯基噻酚修饰的金纳米粒子。基于这些表面功能化且带有电化学反应性功能基团的纳米粒子，我们在电化学合成聚噻酚的系统中加入这种具有表面反应性的纳米粒子得到了有机/无机纳米复合材料。对这种复合材料我们用扫描探针显微镜(SPM)、电化学交流阻抗谱(ElS)、X-射线光电子能谱(XPS)进行了表征，结果表面纳米粒子能稳定存在于聚合物基体中，而且这种复合材料的电子传输性能远远大于同等条件下的聚合物膜。

Direct Electrochemistry and Electrocatalysis of Hemoglobin in Lipid Film Incorporated with Room-Temperature Ionic Liquid

A facile phospholipid/room-temperature ionic liquid (RTIL) composite material based on dimyristoylphosphatidylcholine (DMPC) and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6) was exploited as a new matrix for immobilizing protein. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were adopted to characterize this composite film. Hemoglobin (Hb) was chosen as a model protein to investigate the composite system. UV-vis absorbance spectra showed that Hb still maintained its heme crevice integrity in this composite film.

Luminescence functionalization of SBA-15 by YVO4 : Eu3+ as a novel drug delivery system

Luminescence functionalization of the ordered mesoporous SBA-15 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process, resulting in the formation of the YVO4:Eu3+@SBA-15 composite material. This material, which combines the mesoporous structure of SBA-15 and the strong red luminescence property of YVO4:Eu3+, can be used as a novel functional drug delivery system. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, N-2 adsorption, and photoluminescence spectra. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the YVO4:Eu3+ layer and the adsorption of ibuprofen (IBU, drug). The IBU-loaded YVO4:Eu3+@SBA-15 system still shows the red emission of Eu3+ (617 nm, D-5(0)-F-7(2)) under UV irradiation and the controlled drug release property. Additionally, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU in the system, making the extent of drug release easily identifiable, trackable, and monitorable by the change of luminescence. The system has great potential in the drug delivery and disease therapy fields.

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 x 10(-6) to 0.80 X 10(-6) cm(2)/s at room temperature, which was much lower than that of Nafion (2 x 10-6 CM2/s). The copolymers were thermally stable up to 340 degrees C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.

Polyaniline-coated carbon particles and their electrode behavior in organic carbonate electrolyte

In an attempt to increase the interface stability of carbon used in Li-ion batteries, a thin conducting polyaniline (PANI) film was fabricated on the surface of carbon by in situ chemical polymerization. The chemical and electrochemical properties of the composite material were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscope, cyclic voltammetry, and electrochemical impedance spectroscopy. It was confirmed that the PANI film has an obvious effect on the morphology and the electrochemical performance of carbon. The results could be attributed to the electronic and electrochemical activity of the conducting PANI films.

Electrochemical biosensors based on advanced bioimmobilization matrices

Biosensors have experienced rapid, extensive development. To maintain the bioactivity of biomolecules and to give the electrochemical output signal required, appropriate bioimmobilization matrices for biomolecules are critical.In this review, we describe some advanced membrane materials (including hydrogels, sol-gel-derived organic-inorganic composites and lipid membranes), introduce electrochemical biosensors based on bioimmobilization materials and describe their performance.Biosensors operating in extreme conditions and displaying direct electron transfer with electrodes based on these advanced membrane materials are attractive. Recent developments in nanomaterials include biosensors, so we emphasize the intersection of nanomaterials with advanced membrane materials in biosensors.

Bioorganic/inorganic hybrid composition of sponge spicules: Matrix of the giant spicules and of the comitalia of the deep sea hexactinellid Monorhaphis

The giant basal spicules of the siliceous sponges Monorhaphis chuni and Monorhaphis intermedia (Hexactinellida) represent the largest biosilica structures on earth (up to 3 m long). Here we describe the construction (lamellar organization) of these spicules and of the comitalia and highlight their organic matrix in order to understand their mechanical properties. The spicules display three distinct regions built of biosilica: (i) the outer lamellar zone (radius: >300 mu m), (ii) the bulky axial cylinder (radius: <75 mu m), and (iii) the central axial canal (diameter: <2 mu m) with its organic axial filament. The spicules are loosely covered with a collagen net which is regularly perforated by 7-10 mu m large holes; the net can be silicified. The silica layers forming the lamellar zone are approximate to 5 mu m thick; the central axial cylinder appears to be composed of almost solid silica which becomes porous after etching with hydrofluoric acid (HF). Dissolution of a complete spicule discloses its complex structure with distinct lamellae in the outer zone (lamellar coating) and a more resistant central part (axial barrel). Rapidly after the release of the organic coating from the lamellar zone the protein layers disintegrate to form irregular clumps/aggregates. In contrast, the proteinaceous axial barrel, hidden in the siliceous axial cylinder, is set up by rope-like filaments. Biochemical analysis revealed that the (dominant) molecule of the lamellar coating is a 27-kDa protein which displays catalytic, proteolytic activity. High resolution electron microscopic analysis showed that this protein is arranged within the lamellae and stabilizes these surfaces by palisade-like pillars. The mechanical behavior of the spicules was analyzed by a 3-point bending assay, coupled with scanning electron microscopy. The load-extension curve of the spicule shows a biphasic breakage/cracking pattern. The outer lamellar zone cracks in several distinct steps showing high resistance in concert with comparably low elasticity, while the axial cylinder breaks with high elasticity and lower stiffness. The complex bioorganic/inorganic hybrid composition and structure of the Monorhaphis spicules might provide the blueprint for the synthesis of bio-inspired material, with unusual mechanical properties (strength, stiffness) without losing the exceptional properties of optical transmission. (C) 2007 Elsevier Inc. All rights reserved.

Sol-gel-derived alpha(2)-K7P2W17VO62/graphite/organoceramic composite as the electrode material for a renewable amperometric hydrogen peroxide sensor

The conductive alpha (2)-K7P2W17VO62/graphite/organoceramic composite was prepared by dispersing alpha (2)-K7P2W17VO62 and graphite powder in a propyltrimethoxysilane-based sol-gel solution; it was used as the electrode material for an amperometric hydrogen peroxide sensor. The modified electrode had a homogeneous mirror-like surface and showed well defined cyclic voltammograms. Square-wave voltammetry was employed to study the pH-dependent electrochemical behavior of c alpha (2)-K7P2W17VO62 doped in the graphite organoceramic matrix, and the experiment showed that both protons and sodium cations participated in the odor process. A hydrodynamic voltammetric experiment was performed to characterize the electrode as an amperometric sensor for the determination of hydrogen peroxide. The sensor can be renewed easily in a repeatable manner by a mechanical polishing step and has a long operational lifetime. (C) 2000 Elsevier Science B.V. All rights reserved.

Material response and failure mechanism of unidirectional metal matrix composites under impulsive shear loading

The material response and failure mechanism of unidirectional metal matrix composite under impulsive shear loading are investigated in this paper. Both experimental and analytical studies were performed. The shear strength of unidirectional C-f/A356.0 composite and A356.0 aluminum alloy at high strain rate were measured with a modified split Hopkinson torsional bar technique. The results indicated that the carbon fibers did not improve the shear strength of aluminum matrix if the fiber orientation aligned with the shear loading axis. The microscopic inspection of the fractured surface showed a multi-scale zigzag feature which implied a complicated shear failure mechanism in the composite. In addition to testing, the micromechanical stress field in the composite was analyzed by the generalized Eshelby equivalent method (GEEM). The influence of cracking in matrix on the micromechanical stress field was investigated as well. The results showed that the stress distribution in the composite is quite nonhomogeneous and very high shear stress concentrations are found in some regions in the matrix. The high shear stress concentration in the matrix induces tensile cracking at 45 degrees to the shear direction. This in turn aggravates the stress concentration at the fiber/matrix interface and finally leads to a catastrophic failure in the composite. From the correlation between the analysis and experimental results, the shear failure mechanism of unidirectional C-f/A356.0 composite can be elucidated qualitatively.

Effects of La2O3 on Microstructure and Wear Properties of Laser Clad gamma/Cr7C3/TiC Composite Coatings on TiAl Intermatallic Alloy

The effects of La2O3 addition on the microstructure and wear properties of laser clad gamma/C(r)7C(3)/TiC composite coatings on gamma-TiAl intermetallic alloy substrates with NiCr-Cr3C2 precursor mixed powders have been investigated by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive spectrometer (EDS) and block-on-ring wear tests. The responding wear mechanisms are discussed in detail. The results are compared with that for composite coating without La2O3. The comparison indicates that no evident new crystallographic phases are formed except a rapidly solidified microstructure consisting of the primary hard Cr7C3 and TiC carbides and the gamma/Cr7C3 eutectics distributed in the tough gamma nickel solid solution matrix. Good finishing coatings can be achieved under a proper amount of La2O3-addition and a suitable laser processing parameters. The additions of rare-earth oxide La,03 can refine and purify the microstructure of coatings, relatively decrease the volume fraction of primary blocky Cr7C3 to Cr7C3/gamma eutectics, reduce the dilution of clad material from base alloy and increase the microhardness of the coatings. When the addition of La2O3 is approximately 4 wt.%, the laser clad composite coating possesses the highest hardness and toughness. The composite coating with 4 wt.%La2O3 addition can result the best enhancement of wear resistance of about 30%. However, too less or excessive addition amount of La2O3 have no better influence on wear resistance of the composite coating.

Experimental investigation of the shear strength of a unidirectional carbon/aluminum composite under dynamic torsional loading

In this paper, the dynamic shear strength of a unidirectional C/A356.0 composite and A356.0 alloy, respectively, are measured with a split Hopkinson torsional bar (SHTB) technique. The results indicate that the carbon fibers make very little contribution to the enhancement of the shear strength of the matrix material. The microscopic inspections on the fracture surface of the composite show a multi-scale zigzag feature. This implies that there is a complicated shear failure mechanism in the unidirectional carbon/aluminum composite.

Wear Studies of Hydroxyapatite Composite Coating Reinforced by Carbon Nanotubes

Multi-walled carbon nanotubes (CNTs) have been successfully introduced into hydroxyapatite (HA) coatings using laser surface alloying. It is evident from transmission electron microscopy (TEM) observations that the CNTs present in the matrix still keep their multi-walled cylinder graphic structure, although they undergo the laser irradiation. Scratching test results indicated that the as-alloyed HA composite coatings exhibit improved wear resistance and lower friction coefficient with increasing the amount of CNTs in the precursor material powders. These composites have potential applications in the field of coating materials for metal implants under high-load-bearing conditions. (c) 2006 Elsevier Ltd. All rights reserved.