Survival paths for reaction dynamics in fluctuating environments

We study rate processes in general Gaussian fluctuating environments using a path integral formalism. We derive a variational equation for the dominant survival path when the fluctuations relax exponentially or according to a stretched exponential law. In the case of a slowly varying barrier, the equilibrium regression approximation which is used by Frauenfelder and coworkers emerges. In this approximation, the survival path follows the ordinary law of relaxation to equilibrium. If the rate coefficients vary rapidly with environmental variables, however, the dominant survival paths exhibit more complex behaviour. Many phenomena analogous to geometrical optics occur. These include reflection off of rapid variations in rate constant, as well as refraction, giving paths very different from the equilibrium relaxation properties. A model with a piece-wise linear rate exhibits the basic phenomena, and the survival path equation is exactly solved for the general stretched exponential relaxing environment.     

Controlled/“Living “Radical Polymerization of(-)-Menthyl Methacrylate

The atom transfer radical polymerization(ARP)of (-)-menthyl methacrylatc((-)-MnMA) mediated by CuCl/bipyridine and ethy1 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied.The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obatined was investigated.     

A NEW ONE-STEP REDUCTIVE N-ALKYLATION OF AMINO ACIDS AND THEIR ESTERS

The reductive alkylation of amine with carbonyl compounds usingsodium hydrogen telluride has been investigated in recent years.Application of this method to the synthesis of N-alkyl derivativesof biologically important amino acids and their esters is described.     

Stereoselective synthesis of (+)-SCH 351448: a unique ligand system for sodium, calcium, and other cations

(+)-SCH 351448 (Na+ salt A) was synthesized employing ring-closing olefin metathesis reaction of an open diene diester intermediate for construction of the 28-membered macrodiolide structure. The open diene diester was prepared from the monomeric hydroxy carboxylic acid and two different olefin fragments. The monomeric hydroxy acid was synthesized via Julia-Julia coupling reaction of intermediates derived from the same olefinic fragments. Oxane units in these fragments were prepared by radical cyclization reactions of beta-alkoxyacrylates. Analogous SCH 351448 salts incorporating other mono- and divalent cations may be prepared. Under acidic conditions, SCH 351448 (Na+ salt A) was the most stable complex, but SCH 351448 (Ca2+ salt) and (Na+ salt B) appear to be physiologically important species.     

Study of Tea Digitized Chromatographic Fingerprint Spectra Using Micellar Electrokinetic Chromatography

IntroductionTeaisthemostwidelyconsumedbeverageinpeople’slife .Theheightenedpopularityofthisbeveragethroughouttheworldinrecentyearsmaybedueinparttotheevidenceofarelationshipbetweenteaconsumptionandpreventionofcertainformsofhumandisease .Themaincomponentsofteaarepolyphenoliccompounds ,commonlyknownascatechins ,whichrepresentagroupofcom poundsbelongingtotheflavonoidfamily .Thesecom poundsarewidelydistributedinthetealeavesandconsti tuteupto 30 %ofthedryleafweight.1Muchinteresthasbeenfocusedoncat…     

高配位双环氮氧杂有机锡化合物在二甲亚砜溶剂中的酸性解离常数

本文报道了在DMSO溶剂中利用Bordwell指示剂重迭法测定六种高配位双环氮氧杂有机锡化合物的α-CH的酸性离解常数(pKa)的方法, 并对配合物的结构与其α-CH酸性的关系进行了讨论。     

Studies on the Phase Properties of Winsor Ⅰ-Ⅲ Type Microemulsions with Dielectric Relaxation Spectroscopy

The dielectric relaxation spectroscopy （DRS） of Winsor I -Ⅲ microemulsions for nonionic surfactant octyl polyglucoside CsG1.46/1-butanol/cyclohexanedwater system was studied. The experiment shows that the permittivity decreases with the increase in the frequency and clear dielectric relaxation phenomena were observed. Permittivity obviously decreases with the change of the microstructure of the microemulsion, W/O, B.C. and O/W can be distinguished by the permittivity.     

毛细管流动色谱法研究丙烯在HZSM-5上的聚合作用

用毛细管流动色谱法分析丙烯在HZSM-5上聚合反应尾气,将此法与气相色谱-质谱联用技术相结合,对各反应产物分别定性,此法即可一次完成丙烯聚合反应产物的完全分离和定量。随着反应温度升高,尾气中芳构化产物增加,C_(4-6)链烃含量下降;丙烯通过齐聚物环化脱氢进行芳构化。     

Determination of binding sites in carboplatin-bound cytochrome c using electrospray ionization mass spectrometry and tandem mass spectrometry

Interaction of carboplatin with cytochrome c (Cyt. c) has been investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS). ESI-MS studies revealed that the ring-opened adducts of carboplatin with Cyt. c were formed in the stoichiometric ratio of 1:1 and 2:1 at pH 5.0 and 37 degrees C and in the stoichiometric ratio of 1:1 only at pH 7.0 and 37 degrees C. It was also found that Cyt. c could be cleaved by carboplatin at pH 2.5 and 50 degrees C. The cleaved fragments of Cyt. c were determined by ESI-MS and MS/MS analysis to be Glu66 approximately Met80, Ac-Gly01 approximately Met65, Glu66 approximately Glu104, Ac-Gly01 approximately Met80 and Ile81 approximately Glu104. The carboplatin prefers to anchor to Met65 first, then to Met80. To further confirm the binding site of Met, AcMet-Gly was used as the model molecule to investigate its interaction with carboplatin and its hydrolysis reaction. On the basis of species detected during the reaction monitored by ESI-MS, a possible pathway of the cleavage reaction was proposed.