A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Role of FTFSI Anion Asymmetry on Physical Properties of AFTFSI (A=Li,Na and K) Based Electrolytes and Consequences on Supercapacitor Application

This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li⁺, Na⁺ or K⁺) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte.     

Studies on basicity of alkali metal catron exchanged β and X zeolites by pyrrole-IR spectroscopy

The strength of basic sites has been measured by pyrrole-IR on alkali metal cation exchanged β and X zeolites, as well as NaOH loaded Naβ. The influence of cation type and the structure of zeolites on their basicity has been studied. The acidic and basic properties of the samples were investigated by NH3-TPD and isopropanol reaction. It was shown that the strength of basic sites on samples could be characterized by the shift of vNH band in the pyrrole-IR spectra. The framework oxygen charges were calculated from the Sanderson electronegativity. The changes in basic properties with various alkali metal cation are consistent with the changes of local oxygen charges of the zeolite framework.     

山西省农民家庭消费水平和结构分析

本文利用统计计量学方法对山西省农民家庭消费水平和消费结构的变化及原因进行了实证分析。建立了山西省农民人均消费的消费函数和山西省农民总消费支出与食品、衣着、住房、日用品、燃料及文化生活服务支出的关系模型，并通过模型分析解释了农民的消费结构，也为决策者提供一些有效的参考资料。     

系统聚类分析在农村消费水平划分中的应用

中国的经济发展主要存在着“东部”与“西部”的差距，文章利用聚类分析对我国部分省、市、自治区共28个样本进行分类，并加以分析．     

Dislocation unpinning model of acoustic emission from alkali halide crystals

The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations. Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate, the time constantτ _s for surface annihilation of dislocations and the pinning timeτ _p of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related to the AE from alkali halide crystals.     

居民收入和消费预测的灰理论方法

阐述灰色模型GM(1,1)建立及检验的基本理论和方法.并依据2000年—2005年浙江农村居民人均纯收入和人均生活消费数据,利用GM(1,1)模型建模方法,对“十一五”期间浙江农民的纯收入和生活消费进行了预测.     

不确定性因素对我国农村居民现金消费支出的影响分析

本文根据1978—2003年中国农村居民现金消费支出数据,综合考虑影响消费的主要因素来研究中国农村居民的现金消费行为。与以往研究不同的是,对于影响消费支出的不确定性因素,本文不是采用某个具体变量进行近似替代,而是采用刻画不确定性的条件异方差来描述。文章的结论是农村居民现金消费支出的主要影响因素并非收入,而是利率和不确定性因素,不确定性因素在1996年后表现得尤为突出。     

Voltage ‐ Current Study of an Atmospheric Dielectric Barrier Discharge

The discharge behaviour of an atmospheric dielectric barrier parallel plate discharge, used for surface treatment, is studied. Since an uniform plasma is preferable for surface treatment, filaments must be avoided in the discharge. The occurrence of filaments can be detected by measuring the current flowing through the discharge. Current and voltage measurements give an indication of the power consumption by the plasma. The power consumption of the plasma as function of the applied frequency is examined. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)