Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

NiY分子筛表面酸性影响其选择性吸附脱硫性能的机理研究

采用原位红外光谱技术,以噻吩、环己烯和苯为模型探针分子,分别考察单一烃分子在NiY分子筛上的吸附与反应行为以及噻吩与烯烃、芳烃间的竞争吸附和催化反应行为。单一探针分子吸附研究发现,NiY分子筛中与Ni物种相关的Lewis(L)酸位是噻吩的选择性吸附活性位;噻吩和环己烯在NiY分子筛中Brnsted(B)酸位上发生的质子化和低聚反应明显弱于HY分子筛。双探针分子竞争吸附研究发现,环己烯二聚体在NiY中强B酸位上的强化学吸附与噻吩存在显著的竞争吸附行为。另外,苯和噻吩在NiY上的竞争吸附现象在373K时明显减弱。由此,在选择性吸附脱硫过程中,减少吸附剂表面B酸中心可降低烯烃对噻吩的竞争吸附,另外适当提高吸附体系的温度可以有效避免芳烃对噻吩的竞争吸附。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

化学单元教学设计的探索

论述了单元教学是落实化学新课程三维目标的基本教学过程,同时对教学单元的含义、教学单元的选择与建构、化学单元教学设计及其意义进行了阐述。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Characterization of Losses of Chlorinated Pollutants during Lyophilization of Mussels

The influence of the lyophilization process on the recovery of ten organochlorine compounds, (9 polychlorinated biphenyls (PCBs) and pp′-DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene)] during the pretreatment step of mussels was studied at three concentration levels. Losses of more polar and water-soluble compounds were approximately 50% in samples pulverized prior to lyophilization. Two variables, moisture and lipid concentrations, had statistical influences in the losses of the lower chlorinated compounds (CB 31 and CB 28). In some PCB congeners (CB 52, CB 101, and CB 118), the variation of losses with the PCB concentrations was also statistically significant.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of the thermodynamics of adsorption of hydrolyzed modified polyacrylnitrile

The thermodynamics of adsorption has been studied of hydrolyzed modified polyacrylnitrile (HMP) in water solutions with a concentration ranging from 0.25 g/l to 2.00 g/l on bleached sulphate and unbleached and bleached sulphite celluloses at temperatures of 0, 20, 40, and 60 C.It has been established that with the rise in temperature, the amount of adsorbed polymer —(HMP) decreases. The values of the enthalpy change are negative and show a linear decrease with the increase in the amount of adsorbed polymer. The adsorption equilibrium is defined by the logarithmic isotherm of Tjumkin, valid for uniform heterogeneous surfaces.With the increase in the amount of adsorbed HMP the values of the entropy change become negative and linearly decrease. A compensation effect has been noticed which results from the simultaneous action of the entropy and energy factors.The values of the change of the chemical potential for the three types of cellulose are negative and linearly decrease with the increase in the amount of adsorbed HMP and with the rise in temperature.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

不同电解质溶液对脂质体Zeta电势的影响

卵磷脂（PC）在水溶液中形成类似细胞的脂双层闭合体——脂质体．以它为模型研究水溶液中无机离子与磷脂分子极性端基的作用，对解释生理环境中脂质体的物理化学行为有重要的意义．Tatulian[1]用电泳法给出了一系列一价阴离子与PC膜表面亲合强弱的排序，Eisenberg等[2]测定了一     

Modification of electrochemical properties of pore wall of track-etched mica membranes

The electrochemical properties of the pore wall of track-etched mica membranes are modified (a) by covalent binding of positively and negatively charged groups, and (b) by adsorption of cationic and amonic polyelectrolytes. The electrochemical properties of the pore wall are characterized by measurements of membrane potential, electrical conductivity and streaming potential.By these methods it is possible to change the sign of the surface charge density of the pore wall and to increase its absolute value by a factor of about 30 compared with that of the unmodified pore wall. Changes of electrochemical properties of the pore wall are desirable in studies of negative osmosis and incongruent electrolyte transport in membranes with known pore structure.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.     

Kinetics of Electrophilic Fluorination of Steroids and Epimerisation of Fluorosteroids

Fluorinated steroids, which are synthesised by electrophilic fluorination, form a significant proportion of marketed pharmaceuticals. To gain quantitative information on fluorination at the 6-position of steroids, kinetics studies were conducted on enol ester derivatives of progesterone, testosterone, cholestenone and hydrocortisone with a series of electrophilic N−F reagents. The stereoselectivities of fluorination reactions of progesterone enol acetate and the kinetic effects of additives, including methanol and water, were investigated. The kinetics of epimerisation of 6β-fluoroprogesterone to the more pharmacologically active 6α-fluoroprogesterone isomer in HCl/acetic acid solutions are detailed.     

On the possibilities of theoretical analysis of kinetics of the thermal decomposition of solids

The main reasons for changes in the environment surrounding us are discussed on the basis of thermodynamics of irreversible processes. Subsequently, relations between thermodynamics of irreversible processes and chemical kinetics are shown, then the possibilities of theoretical determination of rate constants on the framework of the modified RRKM theory are presented. These latter considerations are supplemented by a discussion concerning the possibilities of determining the activation barriers and structural changes (necessary to account for entropy changes upon reaction) in molecules kept on the surface of crystalline phases by combination of quantum chemistry methods for isolated molecules with those reflecting the influence of the environment (i.e. interaction within the lattice). Finally, the future of theoretical methods in examining the reactivity of solid state systems is briefly discussed.     

Application of exploratory data analysis for the characterization of tubular wells of the North of Brazil

Roraima is located in the extreme North of Brazil, in the Western Amazon Region. The groundwater has an important role in the public supply of potable water on the Roraima State. The objective of this work is the application of PCA (Principal Component Analysis) and HCA (Hierarchical Cluster Analysis) for the characterisation of tubular wells of the Roraima State, as regards physical–chemical composition of water. The parameters analyzed in laboratory were the following ones: pH, electric conductivity, Total Hardness, Total Alkalinity, Bicarbonate, Calcium, Potassium, Magnesium, Nitrate, Chloride, Total Iron. The physical–chemical analyses, were carried out during the months of September and October 2000 (winter, period of rains). The laboratory analysis was performed using classical methods (titrimetry and uv–visible spectroscopy), the samples were processed in agreement with the Standard Methods for Examination of Water and Wastewater.The physical–chemical analyses, were accomplished in September and October 2000. In physical–chemical terms, the groundwater samples analyzed do not indicate any restriction to human consumption and the two chemometric methods of exploratory data analysis: PCA and HCA are efficient for the discrimination of bicarbonated (tubular wells locateds in the South of the Roraima State) and not bicarbonated (tubular wells locateds in the North of Roraima) groundwater.     

栽培草莓品种果实香气特性研究

通过对4个不同栽培草莓(Fragaria ananassa Duch．)品种果实糖和氨基酸测定及香气的GC-MS分析,结果表明：不同品种间氨基酸和糖含量不同,氨基酸含量由高到低依次为丰香、瓦尔达、哈达和全明星;哈达、丰香、全明星和瓦尔达4个品种果实分别检测出39、46、37和44种香气成分,各占总峰面积98.52％、99.15％、98.77％和95.4l％,检测成分的多少与氨基酸总量显著正相关,相关系数为0.967;哈达有5种独有的成分,丰香有9种独有的成分,全明星有3种独有的成分,瓦尔达有2种独有的成分,4个品种共有的成分有19种。     

Thermodynamic parameters of solvation of nonelectrolytes in aqueous solutions of amides of carboxylic acids

Interaction and reorganization contributions to solvation enthalpies of nonelectrolytes in aqueous solutions of amides of carboxylic acids with different degree of N-substitution and N-methylpyrrolidone are calculated. The data are discussed using structurally thermodynamic characteristics of water-amide systems obtained by us previously. It is found that the type of concentration dependence of the solvation enthalpy of nonelectrolytes in all solutions investigated is determined by the type of reorganization component. It is shown that the highest solvation exothermicity of nonelectrolytes in water is due to the lowest value of the reorganization contribution in spite of that nonelectrolytes interact weaker with water than with non aqueous components.