Kinetic Studies of Bulk Ge22Se78−xBix (x=0, 4 and 8) Semiconducting Glasses

Results of phase transformations, enthalpy released and specific heat of Ge₂₂Se_78–xBi_x(x=0, 4 and 8) chalcogenide glasses, using differential scanning calorimetry (DSC), under non-isothermal condition have been reported and discussed. The glass transition temperature, T _g, is found to increase with an average coordination number and heating rates. Following Gibbs—Dimarzio equation, the calculated values of T _g (i.e. 462.7, 469.7 and 484.4 K) and the experimental values (i.e. 463.1, 467.3 and 484.5 K) increase with Bi concentration. Both values of T _g, at a heating rate of 5 K min^–1, are found to be in good agreement. The glass transition activation energy increases i.e. 102±2, 109±3 and 115±8 kJ mol^–1 with Bi concentration. The demand for thermal stability has been ensured through the temperature difference T _c–T _g and the enthalpy released during the crystallization process. Below T _g, specific heat has been observed to be temperature independent but highly compositional dependent. The growth kinetic has been investigated using the Kissinger, Ozawa, Matusita and modified JMA equations. Results indicate that the crystallization ability is enhanced, the activation energy of crystallization increases with increasing the Bi content and the crystal growth of these glasses occur in 3 dimensions.This revised version was published online in November 2005 with corrections to the Cover Date.     

Gibbs energy of activation for thermal isomerization of (1Z)‐acetaldehyde hydrazone and (1Z)‐acetaldehyde N,N‐dimethylhydrazone by Gaussian‐4 theory and CCSD(T)/CBS computations

In this article, we examined the Gibbs energy of activation for the Z/E thermal isomerization reaction of (1Z)‐acetaldehyde hydrazone and (1Z)‐acetaldehyde N,N‐dimethylhydrazone, at 298.15 K in the solvent of cyclohexane. We carried out computations employing both the Gaussian‐4 (G4) theory and the coupled cluster method using both single and double substitutions and triple excitations noniteratively, CCSD(T). The CCSD(T) energy is extrapolated to the complete basis set (CBS). We compared the calculated results to the available experimental observation. It appeared that both G4 and CCSD(T)/CBS computations overestimated the experimental value by as much as about 6 and 12 kcal/mol in the present two cases. We discussed possible sources of error and proposed the experimental kinetic data could be questionable. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Combined absorption of light in the process of photoactivation of biosystems

The light-oxygen effect consists in a direct excitation of molecular oxygen dissolved in aqueous media of biosystems by the light; it provides the possibility to use lasers for therapeutic purposes. The wavelength of the used light should strictly correspond to the oxygen absorption bands. However, laser therapy also makes use of lasers emitting at 0.89 μm (outside the known oxygen bands), which suggests the action of a new photoreceptor. Here we argue that this mechanism of photoreception is a modification of the light-oxygen effect involving the absorption of photon simultaneously by the oxygen molecule and O-H stretch of the H₂0 molecule of liquid water.     

一步法制备钯纳米粒子修饰的多孔金电极及其对溶解氧的电催化

建立了只需一步操作即可完成在抛光洗净的金微盘阵列电极上进行多孔化处理和钯纳米粒子修饰的方法。通过对金微盘电极连续施加3个电位,分别实现金的氧化、金的还原和电沉积钯纳米粒子。利用扫描电镜和电化学方法监控制备过程,得到的结果证实了本方法的可行性和有效性。考察了溶液pH值与氧化时间对结果的影响,在磷酸盐缓冲溶液(pH7)中氧化90s,得到的修饰电极的电化学活性面积是裸电极的42倍。同时,由于整个过程不需要更换溶液,且只需开启一次仪器,大大简化了实验操作。将制备的修饰电极用于溶解氧的电催化,对溶解氧的灵敏度达到0.1mA·L/(cm2·mg),优于文献报道结果。     

Fast Response Oxygen Micro-Optodes Based on Novel Soluble Ormosil Glasses

 A new type of phenyl substituted ormosils as a matrix for oxygen-sensitive micro-optodes is described. The new ormosils combine features of classical polymers such as solubility in organic solvents and those of sol–gel glasses such as mechanical stability and a porous structure. They make possible a simple and fast fabrication of microsensors with reproducible properties. The influence of the conditions during the polymerisation process (precursor composition and thermal treatment) on the sensing properties has been studied in detail. Oxygen-sensitive films with ruthenium(II)–tris-(4,7-diphenyl-1,10-phenanthroline) and platinum(II)–octaethylporphyrin as indicators were characterised with respect to their mechanical and photophysical properties. Photostability, oxygen sensitivity, response behaviour and signal intensities of the sensing films and the micro-optodes were examined. Micro-optodes based on the new sensing materials are fast responding, photostable and can be produced with a sufficient batch to batch reproducibility. Compared to previously described oxygen micro-optodes, where polystyrene was used as immobilisation matrix, the new sensors can be autoclaved and show favourable properties such as a faster response and a higher sensitivity. They possess many potential applications in medical and biological research. Received June 12, 1998. Revision December 10, 1998.     

Eine einfache Mehrprobenrotationsanordnung zur Aktivierungsanalyse am Neutronengenerator

Es wird eine Anordnung beschrieben, die es gestattet, bis zu 7 Proben unter identischen Bedingungen rotationssymmetrisch zu aktivieren. Die Proben rotieren um zwei parallele Achsen. Es wird über Erprobungsmessungen durch Aktivierung von Cu-und N-haltigen Proben berichtet.