Cosolvent Effect on the Tautomerism of Ethyl Acetoacetate in Supercritical CO_2

There are some unique advantages for chemical reactions in SCFs. For example, reaction rates, yields, and selectivity can be tuned by pressure or small amount of cosolvent. SCFs can be used to replace environmentally undesirable solvents. It is not surprised that in recent years the use of SCFs as solvents for chemical reaction media has received much attention. However, mechanism for the effect of pressure and cosolvents on chemical reactions is not very clear. Tautomeric reactions are id…     

Synthesis and Structure of E-2-(2,4,6-tri tert butylphenylphosphinyl)-2-〔N-(tert-butyldimethylsilyl)-N-(p-chrolophenyl)〕amino-1-(2,4,6-tri tert-butyl-phenyl)phosphacthylene

1　INTRODUCTIONItwaswellknown thatelementsofthesecondary and higherrow are in generaldifficulty to form multiplebondsin which apπ hybridized stateisinvolved〔1〕.Thus,simple compounds containing multiple phosphorus carbon bonds,such as methyl dynephosphine( HC≡P) 〔2 - 3〕 and methylenephosphine( H2 C=PH〔4〕,are notstableat room temperature.Three methods to stabilize compounds containing double ormultiple bond involving phosphorusatom in the pπ hybridized state are often used.The f…     

Mono-Allylation of Gem-Diacetates with Allylsamarium Bromide

Our group have explored the reaction of allylsamarium bromide with a variety of substrates, such as N-(2-aminoalkyl)benzotriazoles1, imines2, nitriles3, diorgano diselenides4, disulfides5, isocyanates6 and nitroalkenes7. Here we wish to report the monoallylation of gem-diacetates with allylsamarium bromide. Gem-diacetates are stable in neutral and basic media, thus they are frequently used to protect aldehydes8. However, the presence of two leaving groups at the same carbon may make carbon …     

Site-specifically Hydrolytic Cleavage of Oxidized Insulin B Chain With Cu(II) Ion

Selectively chemical cleavage of peptides and proteins is one of the most important reactions in both chemical and biochemical processes. Over the past decade, the interaction of palladium(II) complexes with methionine, cysteine and histidine-containing peptides and proteins and the hydrolytic cleavage of the corresponding amide bond by Pd(II) complexes have been extensively studied1-13. However, reports concerning the directly selective hydrolysis of peptides and proteins with other simple …     

阴离子表面活性剂在油水界面聚集的分子动力学模拟

用分子动力学方法模拟了油、水和阴离子表面活性剂组成的混合溶液从初始“均相”到“油水两相”分离的动力学过程, 研究了十二烷基苯磺酸钠(SDBS)在界面分离过程中的作用. 模拟发现, 油水两相能够在短时间内分离达到平衡, 形成一个明显的油水界面; 在SDBS存在情况下, 油水界面的分离时间随着SDBS浓度的增加逐渐增加, 达到平衡时SDBS会在界面处形成一个明显的界面膜, 并对油水界面处的水分子有限制作用. 模拟表明, 分子动力学方法可以作为实验的一种补充, 为实验提供必要的微观分子结构信息.     

三角缺口正三角形纳米结构的共振模式

设计了一个三角缺口三角形破缺纳米结构,它是从正三角形底边切掉一个三角切片所构成.应用离散偶极子近似方法研究了其消光光谱及表面电场分布.结果发现,该破缺纳米结构的消光光谱中出现了具有Fano共振的线形.分析表明,这个Fano共振线形是由绑定与反绑定混合表面等离激元模式相互作用所致.研究了三角缺口三角形纳米结构的结构参数对Fano共振的影响.     

染料分子固定基团-CN,-NH2,-OH,-COOH,-SH在ZnO(10-1 0表面吸附

采用基于第一性原理的密度泛函理论系统研究了染料分子中的-CN, -NH2, -OH, -COOH和-SH等5种固定基团在ZnO 表面的吸附, 分析了它们在ZnO 表面上的吸附机制. 结果表明：5种基团在ZnO 表面都发生了化学吸附, 其中-CN、-NH2和-OH发生了非解离吸附, -COOH和-SH则是表面解离吸附. 5种固定基团的吸附能分别是：-0.64 eV, -1.28 eV, -1.03eV, -1.21eV(-1.40 eV)和-1.14 eV. 综上所述, 以-COOH为固定基团的染料分子制备的染料敏化太阳能电池(DSSCs)具有更稳定的性能, 这为ZnO染料敏化太阳能电池的设计和应用提供了理论基础.     

H-Bonding Self-assembled Template-directed Synthesis of a Reactive Amide-bridged Ladder Polyvinylsiloxane

Ladder polysiloxanes (LPS) including both oxygen-bridged ladder polysilsesquioxanes (LPSQ) and organo-bridged ladder polysiloxanes (OLPS) are very important materials because of their excellent properties1. Adrianov et al. in 1960 attempted to prepare 1, …     

Novel preparation of NaA/carbon nanocomposite thin films with high permeance for CO2/CH4 separation

Novel NaA/carbon nanocomposite thin films were successfully prepared on a porous a-Al2O3 substrate by incorporatingnanosized NaA zeolite into novolak-type phenolic resin.The prepared films were characterized by XRD,SEM and single gaspermeation tests.The NaA zeolite/carbon nanocomposite thin films exhibited that the ideal separation factor of CO2/CH4 was 28.4and the carbon dioxide flux was 3.39*10-7mol/(Pa m2s)at room temperature and under a pressure difference of 100 kPa,whichwas two orders of magnitude higher than that of pure carbon membrane prepared at the same procedures and conditions as those ofcomposite films.From the SEM images,the films were continuous and highly intergrown.Compared with carbon membranes,thethickness of nanocomposite films was drastically decreased,which was helpful to reduce the diffusion resistance and increase theflux of gas permeance.     

Capillary electrophoresis with direct chemiluminescence detection for the analysis of catecholamines in human urine

A rapid and sensitive method for the analysis of three catecholamines by capillary electrophoresis(CE)with directchemiluminescence(CL)detection is described.The detection limits(S/N=3)were 1.3*10-8g/mL for isoprenaline,1.0*10-8g/mL for epinephrine and 2.8*10-8g/mL for dopamine.The proposed method was successfully applied to theanalysis of catecholamines in urine samples of cigarette smokers and nonsmokers.The results showed that there is a close relationbetween the release of dopamine in human body fluids and cigarette smoking/nonsmoking.