Synthesis and Photochemistry of Diphenylchlorin and Diphenylbacteriochlorin

5, 15-Diphenylporphyrin (DPP), a novel porphyrin model compound, was always inaccessible in quantities suitable for study1 because the difficulty of synthesis. So that the characteristic of this molecule had not been explored until a novel method developed for the preparation of DPP recently2. Therefore it will be possible for the synthesis of DPP-based photosensitizers, and investigation of their photodynamic properties. Here we reported the synthesis of novel photosensitizers 5, 15-diphe…     

The CH_3OH+Cl Hydrogen Abstraction Reactions: An ab initio Study

The hydrogen abstraction from methanol by atomic chlorine can proceed via two possible channels: CH3OH + Cl → CH2OH + HCl (i) → CH3O + HCl (ii)In 2000, Ahmed et al1. reported their investigation for the H abstraction dynamics of the CH3OH+Cl reaction by crossed molecular beams in conjunction with velocity map imaging. Hydroxymethyl (CH2OH) was detected in their experiments. In 1998, Jodkowski et al2. reported their theoretical study on the CH3OH+Cl reactions. They located inte…     

Study of Oxidation of Glutathione Treated with Hypochlorous Acid by Capillary Electrophoresis

Glutathione (GSH) protects human and animal's cells by the exchange with reversible oxidized glutathione (GSSG) when cells meet with oxidants, such as hydrogen peroxide (H2O2) and lipid peroxide. But when GSH meets with hypochlorous acid (HOCl), via the myeloperoxidase-catalysed oxidation of chloride by H2O2, the amount of GSSG formed does not account for all the GSH lost, which is quite different from that we has investigated in the reaction of GSH with H2O21. Prutz proposed the fo…     

Investigations of Thallium(Ⅰ) Underpotential Deposition on the Silver Rotating Disk Electrode and Its Analytical Application

Ｔｈａｌｌｉｕｍｉｓａｔｏｘｉｃｍｅｔａｌ.Ｂｅｃａｕｓｅｉｔｓｃｏｎｃｅｎｔｒａｔｉｏｎｉｎｅｎｖｉｒｏｎｍｅｎｔａｌａｎｄｂｉｏｌｏｇｉｃａｌｓａｍ ｐｌｅｓｉｓｉｎｔｈｅ 1ｎｇ/ｇｒａｎｇｅｏｒｌｅｓｓ[1] ,ｉｔｉｓｄｉｆｆｉｃｕｌｔｔｏｄｅｔｅｒｍｉｎｅｔｈｅｍｅｔａｌｂｙｕｓｉｎｇｃｏｎｖｅｎｔｉｏｎａｌｅｌｅｃｔｒｏａｎａｌｙｓｉｓｍｅｔｈｏｄｓ .Ｄｉｆｆｅｒｅｎｔｉａｌｐｕｌｓｅａｎｏｄｉｃｓｔｒｉｐｐｉｎｇｖｏｌｔａｍｍｅｔｒｙ(ＤＰＡＳＶ )ｉｓａｓｅｎｓｉｔｉｖｅｍｅｔｈｏｄｆｏｒ…     

Synthesis of 5-Substituted-3-[(2’R,4’R)-4’-Hydroxy-2’-hydroxymethyltetrahydrofuran-4’-yl]-1,2,4-oxadiazoles and Their Epimers

The syntheses of 5-substituted-3-[( 2' R, 4' R)-4 ' -hydroxy-2 ' -hydroxymethyltetra-hydrofuran-4' -yl]D-1 ,2, 4-oxadiazoles and their epimers were accomplished with the aid of th construction of 1,2, 4-oxadiazoles by condensation of O-acylated cyanohydrins with hydroxylamine via intramolecular transacylation and subsequent cyclization.     

Stabilization of Cu/ZnO Based Catalysts by Nickel Additive in Methanol Decomposition

A series of Cu/Zn based catalysts with and without Ni, prepared by the co-precipitation method, has been studied for methanol decomposition. CO and H2 are the major products. The Cu/Zn catalysts show a low initial activity and a poor stability. The formation of the CuZn alloys was observed in the deactivated Cu/Zn catalysts which were used for methanol decomposition at 250 . When small amounts of Ni were added in the catalyst, the Cu/Zn/Ni(molar ratio 5/4/ x) catalysts showed a high activity at a low temperature. The activity and the stability of the catalyst depend on the nickel content. The activity of the Cu/Zn/Ni catalysts was maintained at a. relatively stable value of 78% conversion of methanol with 95% selectivity of H2, 93% selectivity of CO, and a more than 70% yield of hydrogen was obtained at 250 C when x >1. The stability of the Cu/Zn/Ni (molar ratio 5/4/x) catalysts showed the maximum (ca 88%) when x=1. The stabilization effect of nickel on the Cu/Zn based catalysts may lead to the increasin     

A Thermodynamic Model for Square-well Chain Fluid: Theory and Monte Carlo Simulation

A thermodynamic model for the freely jointed square-well chain fluids was developed based on the thermodynamic perturbation theory of Barker-Henderson, Zhang and Wertheim. In this derivation Zhang's expressions for square-well monomers improved from Barker-Henderson compressibility approximation were adopted as the reference fluid, and Wertheim's polymerization method was used to obtain the free energy term due to the bond connectivity. An analytic expression for the Helmholtz free energy of the square-well chain fluids was obtained. The expression without adjustable parameters leads to the thermodynamic consistent predictions of the compressibility factors, residual internal energy and constant-volume heat capacity for dimer, 4-mer, 8-mer and 16-mer square-well fluids. The results are in good agreement with the Monte Carlo simulation. To obtain the MC data of residual internal energy and the constant-volume heat capacity needed, NVT MC simulations were performed for these square-well chain fluids.     

Propylene Polymerization Catalyzed by Bis(R_3-indenyl) Zirconium Dichloride/Aluminoxane──Synthesis of Metallocenes and Influence ofSolvent Polarity on Polymerization

Three unbridged metallocenes, bis(2,4,7-Me3-indenyl)zirconium dichloride(1) , bis(2-Me-4, 7-Et2-indenyl)zirconium dichloride (2) and bis (2, 4, 6-Me3-indenyl) zirconium dichloride (3) were synthesized. The effect of solvent polarity on propylene polymerization catalyzed by the metallocenes in the presence of methylaluminoxane(MAO) and triisobutylaluminum(TIBA) was investigated in the toluene/CH2Cl2 mixed solvent. Changing the solvent polarity was found to influence the catalytic activity, polymer molecular weight and stereospecificity of the catalysts. The changes in the position of the substituents on the ligand caused the different responses of the catalyst to the changes in solvent polarity. The isotactic stereosequence of polypropylene was found to increase with the increase in the polarity of the reaction medium.     

Studies on the Basic Conformation of Lysozyme by Electrospray Ionization-Mass Spectrometry (ESI- MS)

In the present work, 2-mercaptoethanol and dithiothreitol were used to hydrogenise the internal disulfide bond in lysozyme. The experimental results indicate that the charge distribution of the proteins are different in the reaction process. From the calculated molecular weight, the reduction process of the disulfide bond in the molecules can be described, and the number of the disulfide bonds in the molecule can also be determined.     

Fourth-Order Splitting Methods for Time-Dependant Differential Equations

This study was suggested by previous work on the simulation of evolution equations with scale-dependent processes,e.g.,wave-propagation or heat-transfer,that are modeled by wave equations or heat equations.Here,we study both parabolic and hyperbolic equations.We focus on ADI (alternating direction implicit) methods and LOD (locally one-dimensional) methods,which are standard splitting methods of lower order,e.g.second-order.Our aim is to develop higher-order ADI methods,which are performed by Richardson extrapolation,Crank-Nicolson methods and higher-order LOD methods,based on locally higher-order methods.We discuss the new theoretical results of the stability and consistency of the ADI methods.The main idea is to apply a higher- order time discretization and combine it with the ADI methods.We also discuss the dis- cretization and splitting methods for first-order and second-order evolution equations. The stability analysis is given for the ADI method for first-order time derivatives and for the LOD (locally one-dimensional) methods for second-order time derivatives.The higher-order methods are unconditionally stable.Some numerical experiments verify our results.