Cl/HN3/I2全气相化学激光体系的化学动力学模拟计算

 对Cl/HN₃/I₂产生NCl(a)/I激光的过程进行了化学动力学计算，主要考察了Cl,HN₃和I₂的初始粒子数密度及其配比对小信号增益系数的影响。结果发现,当温度为400K, 初始Cl粒子数密度为1×10¹⁵，1×10¹⁶和1×10¹⁷cm^-3时,小信号增益系数分别达到1.6×10^-4,1.1×10^-3和1.1×10^-2cm^-1，获得最佳小信号增益系数的HN₃和I₂的初始粒子数密度分别为初始Cl粒子数密度的1～2倍和2%～4%。同时，对Cl，HN₃和I₂配比对小信号增益系数和增益持续时间的影响进行了讨论。     

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

1. INTRODUCTION The development of efficient polymer-supported catalysts has attracted much attention [1]. For obtaining polymeric catalysts, catalytically active groups were introduced onto polymers mostly by copolymerization of the appropriate monomers bearing the desired catalyticfunctionalities (e.g. imidazole, OH, and COOH) or by modification of preformed polymers.Another possibility involves the attachment of side chains, containing the desired arrangement of functional groups, o…     

Monoesterification of styrene–maleic anhydride copolymers with alcohols in ethyl benzene: Catalysis and kinetics

A kinetic investigation on the monoesterification reaction of the maleic anhydride residue (MA) in styrene-maleic anhydride copolymers with aliphatic alcohols was carried out in ethyl benzene solution. By comparison to classic catalysts such as tributylamine (TBA) and pyridine, 4-dimethylaminopyridine (4DMAP) is by far the most effective catalyst for this reaction. While both general base and nucleophilic mechanisms contribute to the reaction catalyzed by TBA or pyridine, a nucleophilic mechanism prevails with 4DMAP. This reaction is reversible, and its chemical equilibrium constant decreases significantly with increasing temperature. Both kinetic and thermodynamic results showed that in the presence of 4DMAP, the forward and reverse reactions are second and first order, respectively. The existence of side reactions, reactivity of two styrene-maleic anhydride copolymers of different MA contents as well as two aliphatic alcohols of different lengths are also addressed. © 1993 John Wiley & Sons, Inc.     

Kinetic Studies of Electrochemical Oxidation of 1,3-Benzenedithiol

The electrochemical oxidation of 1, 3-benzenedithiol was investigated in a 0. 100 mol/L tetrabutylammonium perchlorate/acetonitrile electrolyte. The electrochemical techniques used were potential sweep, bulk electrolysis, rotating disc and the potential step method. The combination of the techniques yielded the number of electrons transferred per molecule, the reaction order, the transfer coefficient, the diffusion coefficient and concentration of dithiol anions, the standard heterogeneous rate constant as well as the formal potential and equilibrium constant of the preceeding dissociation reaction. This paper also illustrates the methods for studying the electrode kinetics of reactions which (a) involve a chemical reaction preceeding the electron-transfer process, (b) have insoluble polymer products, and (c) are totally irreversible.     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Glycosyl azide—a novel substrate for enzymatic transglycosylations

Glycosyl azides are new efficient donors for glycosidases. Their high water solubility facilitates transglycosylations with comparable or better yields than common O-glycosides. The azido group totally changes the β-GalNAc-ase/β-GlcNAc-ase ratio in β-N-acetylhexosaminidases (from the usual 0.3-1.0 to <0.01), contrary to all known aglycons.     

Effect of end groups on complexation kinetics between cyclodextrins and guest polymers

α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006     

Isothermal crystallization kinetics of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006