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.     

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.     

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.     

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.

     

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。     

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。     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

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.     

两种吲唑合成方法的改进

苯乙烯类吲唑衍生物是一类重要的类胰岛素生长因素1受体抑制剂。本文介绍了它的两种合成原料：6-氯-3-甲基吲唑和6-氟-3-羰甲基吲唑的合成方法,并对以邻卤苯羰基类化合物为原料生成苯腙再分子内环化和吲哚的重氮化反应这两种方法进行了改进。改进后的方法产率大大提高,反应时间缩短,后处理简化,更利于吲唑类化合物的大规模生产,对...     

The use of surfactants in the cleaning of works of art

Surfactants have been historically used for cleaning artifacts, but it was only in the last decades that serendipitous approaches were replaced by research in the field of soft matter and colloid science. Surfactants are components of nanostructured fluids, which were assessed for the removal of soil and aged coatings from paintings and are fundamental in processes that range from the inclusion of grime in micelles to the swelling and dewetting of polymer layers. Intriguing aspects involve the synthesis and use of biodegradable and self-cleavable surfactants, and the confinement of nanostructured fluids in gels, which boost the selectiveness of cleaning interventions. The performances of these advanced systems surpass those of traditional cleaning materials such as solvent blends and thickeners. The most important results are here reviewed and future perspectives given. Besides granting the transfer of cultural heritage to future generations, advanced cleaning materials are relevant to transversal fields, such as detergency, cosmetics, and drug delivery.     

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^-。     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

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.     

百部酰胺的全合成研究进展

百部酰胺(Stemoamide)是从百部科植物对叶百部Stemona tuberosa L.根部分离得到的天然产物。百部化合物在中医药应用中具有镇咳和驱虫的功效。其结构是γ-丁内酯并氮杂薁环的三环体系,有四个连续的手性中心。文章综述了目前国内外对百部酰胺Stemoamide的全合成方法,着重从成环顺序的角度进行论述,介绍了(Diels-Alder)-(逆-Diels-Alder)策略、自由基环化、RCM环化、分子内的Barbier反应和仿生亚胺离子环化等方法在百部酰胺全合成中的应用。     

Study of the solid-state hydrolysis of chitosan in presence of HCl

Chemical depolymerization of chitosan was obtained in the solid state by means of gaseous HCl. This new method allowed us to simultaneously form the hydrochloric salt and saturate the hydration water with acid. The depolymerization was carried out by keeping the product at a given temperature for the desired time. The measurements of the molecular weight distributions demonstrated the ability to control the reaction and produce oligomers with chosen dimensions. This solid-state hydrolysis favors the presence of a four-fold distribution that can be related to the original morphology and crystallinity of the initial material. The effects of the hydrolysis on the crystallinity, the crystalline structure, and the supramolecular order of the obtained chitosans were also studied. Finally, the washing of the hydrolyzed products in concentrated alkaline or acidic media allowed us to eliminate the lowest DPs and thus to narrow the molecular weight distribution. In this case, the crystallinity was also increased up to values beyond 70%. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3181–3191, 1997     

Voltammetry of microparticles of lutetium bisphthalocyanine

Oxidation of microparticles of lutetium (bis-tert-butylphthalocyaninato) complex immobilized on the surface of paraffin-impregnated graphite electrode and immersed into an aqueous electrolyte was investigated by cyclic voltammetry and square wave voltammetry. The electrode reaction exhibits the typical features of insertion electrochemistry where the anions of the aqueous electrolyte are transferred into the solid phase upon oxidation of the redox centers there in. The reaction is quasi-reversible and influenced by the ohmic resistance of the compound. The formal potentials of the electrode reaction involving the transfer of perchlorate, nitrate, and chloride ions follow the same order as the Gibbs energies of ion transfer in the systems water–nitrobenzenene and water–octanol. Bromide and thiocyanate ions are not intercalated.     

Pulse polarographic determination of the complexation capacity of various organic phosphonates of heavy metals with the aid of design of experiments

This study presents the determination of the complexation capacity of phosphonates (ATMP, EDTMP, and DTPMP) by differential pulse polarography. All of them are non-volatile, stable in water samples, and resistant to hydrolysis. Therefore, their decomposition rate in natural water is low. The metal complexation capacity of these phosphonates was detected for cobalt, copper, and zinc ions. DTPMP is the best of the investigated chelating agents for these three metal ions.Owing to the environmental fate of aminocarboxylates, these were often replaced by phosphonates. Therefore, we compared NTA and EDTA with ATMP and EDTMP according to their Zn-CC and could find out approximately four times higher complexation of zinc ions by phosphonates than by aminocarboxylates.Furthermore, the interaction between phosphonates and the influence of iron ions on the Zn-CC were investigated by chemometric means. The design of experiments indicated no significant interaction in phosphonate mixtures but significant influence of iron ions. Thus, the complexation capacity of a mixture of ATMP, EDTMP, and DTPMP can be calculated by the addition of several individual Zn-CC of the phosphonates according to their percentage in the mixture. A similar calculation is impossible in the presence of iron ions.     

Thermochemistry of dissolution of sodium alkylsulfonates

The effect of temperature on the solubility of ionic surfactants was interpreted in terms of standard enthalpy and entropy of dissolution at reference temperature by considering the change in the heat capacity. The significant value of the latter quantity causes the curvature of the function logarithm of equilibrium constant (or solubility) vs. the reciprocal thermodynamic temperature. The solubility data for several sodium n-alkylsulfonates, published by Saito, Moroi, and Matuura, were interpreted by nonlinear regression analysis. It was found that both the enthalpy and entropy of dissolution decrease with the chain length. The heat capacity increases in the course of the dissolution process.