水凝胶中物质扩散过程研究进展

主要从模型理论和实验研究方法两个方面综述了国内外聚合物水凝胶中物质扩散行为研究进展.水凝胶中扩散理论模型主要有自由体积模型、流体力学模型、位阻效应模型三大类;实验研究方法主要分为间接法和实时法两种.     

X-ray investigation of the role of the mixed emulsifier in the structure formation in o/w creams

The aim of this research work was to clarify the role of the mixed emulsifier in the structure formation and water binding mode in the case of o/w creams prepared with different surfactants. The swelling behavior of mixed emulsifiers was examined by means of direct investigation methods such as transmission electron microscopy (TEM) and X-ray diffraction. The detailed structure image of the creams was created with the help of the latter. The influence of the structure of the hydrophilic gel phase, and the structural changes during storage were studied with rheological methods. On the basis of the results, it can be stated that the investigated creams had different structures from those mentioned in the literature: surfactant did not create a mixed bilayer with the structure to furnish fatty amphiphile; instead, micelles were formed. These results correlated well with the results of the rheological tests.     

自然流产孕妇体内微量元素含量的变化

为了解自然流产孕妇体内微量元素的变化,检测了50例正常妊娠妇女和50例自然流产妇女（其中忆查明流产原因的33例,不明原因流产17例）头发中微量元素。结果显示,查明原因流产组发锌、铜、铁、钙和不明原因流产组发锌、铜、铁含量均明显低于正常妊娠组;而发铅含量则明显高于正常妊娠组,经统计学处理分析,差别有显著性。提示妊娠期微量元素平衡与否,对宫内胎儿的发育乃至安危均有一定的影响。     

Role of the conformation in the reactivity of 1,3-diphosphapropenes

The symmetrical and unsymmetrical 1,3-diphospha-propenes 3 and 4 were obtained from the corresponding diposphiranes 1 and 2 . The chemical behavior of these compounds has been studied. Phosphonium-phosphaalkenes 7a and 10a have been obtained in the reactions with aluminium trichloride. Whereas the symmetrical diphosphaallene 13 can be obtained by reaction of 1 or 3 with lithio compounds, the unsymmetrical diphosphaalene 14 cannot be prepared by a similar route. Reduction of 3a and 4a (obtained with a different conformation) by lithium aluminum hydride afforded phosphino-phosphaalkenes 17a and 18a (with a similar conformation); further dehydrochlorination with amines led to the symmetrical and unsymmetrical diphosphaalenes 13 and 14 , respectively. The formation of allenes strongly depends on the conformation of the starting diphosphapropenes.     

Distribution of phospholipids in the organs of the cotton plant in the period of mass fruit-formation

The distribution of phosphorus in the vegetative and generative organs of the cotton plant of variety 159-F has been studied. It has been established that the various organs of the cotton plant differ with respect to the qualitative and quantitative compositions of their phospholipids.     

Determination of scandium in wolframite and in the residues obtained after the extraction of tungsten

The separation of scandium from iron and manganese by extraction with TBP from hydrochloric acid was studied in detail and this method was applied to the estimation of scandium in wolframite and its residues. The method consists of the extraction of tungsten from the wolframite with sodium carbonate, dissolution of the residue in hydrochloric acid and preferential extraction of iron and scandium from hydrochloric acid, stripping of the scandium with 8 M hydrochloric acid and re-extraction of accompanying iron with fresh TBP, precipitation of scandium with ammonia in presence of ammonium chloride, and final purification of the scandium by TBP extraction.     

Effect of the nature of inert solvent on the decay kinetics of the carbocation generated in the photolysis of 1,2-dihydroquinolines in methanol

The dependence of the quantum yield and the decay rate constant for the carbocation generated in the photolysis of 6-ethoxy-1,2,2,4-tetramethyl-1,2-dihydroquinoline (6-EtO-DHQ) in methanol on the solvent composition was studied in the mixtures of methanol with isopropanol, acetonitrile, and pentane by pulse photolysis. The addition of these solvents decreases the yield of the carbocation and differently affects the kinetic parameters of its decay. The carbocation decay in the mixtures MeOH-i-PrOH and MeOH-C₅H₁₂ is described by the pseudo-first order equation (k ₁), with the dependence of k ₁ having a maximum at 50 vol % of MeOH in the MeOH-i-PrOH mixtures, and k ₁ increasing with a decrease in the MeOH concentration in the MeOH-C₅H₁₂ mixtures. In the MeOH-MeCN mixtures, the value of k ₁ decreases with a decrease in the MeOH concentration, and, at the concentration of MeOH lower than 50 vol %, the contribution of the second-order reaction (k ₂) is observed. The activation energies and preexponential factors were determined in the MeOH-C₅H₁₂ mixtures of different compositions, and it was shown that E _act practically did not depend on the solvent composition and were close to E _act for other carbocations obtained in MeOH. The increase in k ₁ with a decrease in the MeOH concentration is caused by an increase in the preexponential factor. The results were discussed on the basis of the reaction mechanism involving the competing reactions of the carbocation combination with two nucleophilic particles, the MeOH molecule and the MeO⁻ anion. The composition of the mixture and the nature of the inert solvent affect strongly the course of these reactions. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 3, pp. 411–416. The article was translated by the authors.     

On the different roles of anions and cations in the solvation of enzymes in ionic liquids

The solvation of the enzyme Candida antarctica lipase B (CAL-B) was studied in eight different ionic liquids (ILs). The influence of enzyme-ion interactions on the solvation of CAL-B and the structure of the enzyme-IL interface are analyzed. CAL-B and ILs are described with molecular dynamics (MD) simulations in combination with an atomistic empirical force field. The considered cations are based on imidazolium or guanidinium that are paired with nitrate, tetrafluoroborate or hexafluorophosphate anions. The interactions of CAL-B with ILs are dominated by Coulomb interactions with anions, while the second largest contribution stems from van der Waals interactions with cations. The enzyme-ion interaction strength is determined by the ion size and the magnitude of the ion surface charge. The solvation of CAL-B in ILs is unfavorable compared to water because of large formation energies for the CAL-B solute cages in ILs. The internal energy in the IL and of CAL-B increases linearly with the enzyme-ion interaction strength. The average electrostatic potential on the surface of CAL-B is larger in ILs than in water, due to a weaker screening of charged enzyme residues. Ion densities increased moderately in the vicinity of charged residues and decreased close to non-polar residues. An aggregation of long alkyl chains close to non-polar regions and the active site entrance of CAL-B are observed in one IL that involved long non-polar decyl groups. In ILs that contain 1-butyl-3-methylimidazolium cations, the diffusion of one or two cations into the active site of CAL-B occurs during MD simulations. This suggests a possible obstruction of the active site in these ILs. Overall, the results indicate that small ions lead to a stronger electrostatic screening within the solvent and stronger interactions with the enzyme. Also a large ion surface charge, when more hydrophilic ions are used, increases enzyme-IL interactions. An increase of these interactions destabilizes the enzyme and impedes enzyme solvation due to an increase in solute cage formation energies.     

Plasters in the Cellars of the Visconti Castle in Pavia. Physico-chemical characterization

An archaeometric investigation on plaster samples taken from the cellars of the Visconti Castle in Pavia has brought out the existence of several layers and colour films of various periods. The oldest plaster spread over the masonry is formed with three main layers. Above them, one film of bluish-black colour can be found on the arcs and on the bearing walls. On this black layer, a white film of calcitic composition, containing also apatite fragments, was spread. These ancient materials were subsequently covered in more recent times with plasters having different compositions and textures. In the present paper the properties of the three main plaster layers and those of the black film are reported in detail. The thermal behaviour of these materials was studied by means of differential thermal analysis and thermogravimetric analysis. The study was completed with scanning electron microscopy,microprobe analysis and X-ray diffraction on powders. The results obtained provide interesting clues for advancing reasonable hypotheses both on the methods adopted in ancient building yards, and on the techniques for the production of the pigments employed. This revised version was published online in July 2006 with corrections to the Cover Date.     

A DFT study of the origins of the stereoselectivity in the aldol reaction of bicyclic amino ketones in the presence of water

Experimental diastereoselectivities of the direct solvent-less (neat) aldol reactions of tropinone (8-methyl-8-azabicyclo[3.2.1]octan-3-one) and granatanone (pseudopelletierine, 9-methyl-9-azabicyclo[3.3.1]nonan-3-one) in the presence of catalytic amounts of water are most accurately reproduced by thermodynamic distributions of isomeric products calculated in the gas phase at the B3LYP/6-31g(d) level of theory. Less than 30% systematic errors, on average, exist in the predicted anti/syn-diastereomeric ratio (dr) for the solvent-less reaction of tropinone with several aromatic aldehydes. The CPCM-B3LYP/6-31g(d) method reproduces the anti/syn-diastereomeric ratio of the aqueous aldol reaction of tropinone with several aromatic aldehydes with reasonable deviation (0-88%), excellent (0-10)% agreement was found for the reactions of tropinone and granatanone with benzaldehyde. Qualitatively satisfactory agreement was also found for dr values in different solvents (DMF, THF, and Et₃N). The density functional theory (DFT) results support the notion of the thermodynamic control of the reaction.     

Kinetics of the polymerization of tetrahydrofuran in the presence of water

The polymerization of tetrahydrofuran was studied with regard to the presence of polar and nonpolar compounds, or well-solvating and poorly solvating compounds, respectively. Tetrahydrofuran is highly nucleophilic, with a high solvation ability. It is capable of activating the native initiator itself and can be polymerized without any added cocatalyst. The addition of water to the tetrahydrofuran–initiator system decreases the polymerization rate. However, the dependence of the polymerization rate on the concentration of water in the dilute tetrahydrofuran runs through a maximum. The reaction rate is a function of the position of an equilibrium established during the solvation of initiator. All components of the system take part in the establishment of equilibrium.     

Study of the electrochemical reduction of dioxygen in acetonitrile in the presence of weak acids

The electrochemical reduction of dioxygen has been studied in acetonitrile at glassy-carbon electrodes. The initial step is the reversible one-electron reduction to form superoxide. In the presence of hydrogen-bond donors (water, methanol, 2-propanol), the superoxide forms a complex with the donor resulting in a positive shift in the potential that can be analyzed to obtain formation constants for these complexes. Stronger acids result in protonation of the superoxide followed by reduction to produce HO2-. In the absence of hydrogen-bond donors, the reduction of superoxide occurs at very negative potentials, and this second reduction peak is very much drawn-out along the potential axis, indicating a small value of the transfer coefficient, alpha. The addition of hydrogen-bond donors, HA, brings about a positive shift in this peak, without a noticeable change in shape. The reaction occurring at the second peak is a concerted proton and electron transfer (CPET) in which the electron is transferred to superoxide and a proton is transferred from HA to the superoxide, forming HO2- and A- in a concerted process. An estimation of the standard potential for this reaction shows that the second reduction always occurs at a high driving force, which explains the small value of alpha that is observed. Consistent with a CPET, a kinetic isotope effect, HA versus DA, was detected for the three hydrogen-bond donors. The increasing positive shift of the second peak with increasing water concentration has been interpreted as being a consequence of the change in the formal potential, as water is both a reactant in the process and a participant through the hydrogen-bond stabilization of the anions.     

Physicochemical modeling of the behavior of impurities in bismuth oxide in the chemical distillation of the sample matrix

The physicochemical modeling of the behavior of impurities in the course of their preconcentration by the chemical distillation of the sample matrix consisting of granules of a solid solution of impurities in bismuth oxide was carried out. It was supposed that the distillation process is conducted in a kinetic mode. The results of calculations by the model are compared with the earlier results of modeling of the behavior of impurities in distilling a heterophase sample consisting of matrix (bismuth oxide) granules and granules of impurity oxides. The experimental data and results of calculations by the model agree well.     

Investigations in the field of the chemistry of heterocycles

The reaction of 3-aryl-2-chloromethylquinazol-4-ones with secondary amines has given a number of previously unreported 2-aminomethyl-3-arylquinazol-4-ones, and their biological activity has been studied.For part XLV, see [1].     

Vaporization of indium nitrate in the graphite tube atomizer in the presence of chemical modifiers

The CCD spectrometer coupled with the graphite tube furnace was employed to investigate the vaporization of micrograms of In (as nitrate). Fifty absorption spectra between 200 and 475 nm were collected during 10 s while the tube temperature increased from 700 to 2600–2700 K. The vaporization was carried out in the pyrocoated, Ir-sputtered and Ta-lined tubes in the presence of Cu, Co, Ni, Pd and Mg nitrates, sodium tungstate, ascorbic acid and ammonium hexachloroiridate monohydrate after thermal pretreatment. In the pyrocoated tube the vaporization of In occurred at 1350–1550 K with fast evolution of molecular vapor. The observed broad bands with maxima at 225, 290 and 275 nm were attributed to In₂O and InO, according to their thermal behavior. Cu, Co, Ni, Pd, Ir modifiers, Ta-lining and Ir sputtered surface suppressed the release of In oxides and induced the delayed appearance of In atomic lines simultaneous with a broad band at 205 nm, tentatively attributed to In dimer. Tungsten caused faster and more complete reduction of In oxide than carbon. Indium oxide bands were substituted between 1100 and 1350 K by a band at 244 nm assigned to gaseous tungsten oxide. Ascorbic acid caused the decrease of indium oxide fraction in gas phase. The presence of MgO in the tube led to the decrease of the band at 205 nm. The vaporization of micrograms of Cu, Co, Ni, Pd and MgO in the pyrocoated tube caused the appearance of absorption and emission continuum, superimposed to In atomic lines at temperatures above 1550 K. This effect had been earlier explained as induced by exothermal interaction of the vaporized substance with carbon. SEM observations of Ir deposits on the graphite surface confirmed the interaction of Pt group metals with carbon at high temperature. A similar effect is advanced for other metal modifiers.     

Computational characterization of the role of the base in the Suzuki-Miyaura cross-coupling reaction

The role of the base in the transmetalation step of the Suzuki-Miyaura cross-coupling reaction is analyzed computationally by means of DFT calculations with the Becke3LYP functional. The model system studied consists of Pd(CH=CH2)(PH3)2Br as the starting catalyst complex, CH2=CHB(OH)2 as the organoboronic acid, and OH- as the base. The two main mechanistic proposals, consisting of the base attacking first either the palladium complex or the organoboronic acid, are evaluated through geometry optimization of the corresponding intermediates and transition states. Supplementary calculations are carried out on the uncatalyzed reaction and on a process where the starting complex is Pd(CH=CH2)(PH3)2(OH). These calculations, considered together with available experimental data, strongly suggest that the main mechanism of transmetalation in the catalytic cycle starts with the reaction of the base and the organoboronic acid.     

丹参酚酸B生产中去除胶体类杂质的工艺方法

胶体类杂质的去除是丹参酚酸B(salvianolic acid B, SB)纯化工艺的难点之一。实验中基于前沿色谱与置换色谱相结合的原则,改良常规大孔吸附树脂柱的操作方法,将树脂按一定的比例装入大小两支柱。小柱与大柱串联,上样至胶体类杂质在小柱上达到吸附饱和,用50%甲醇单独洗脱大柱上的SB部分,利用树脂吸附色谱法实现了SB与胶体类杂质的分离。结果表明,经过去胶体类杂质处理后,SB的加权平均纯度由59.6%提高到64.5%,收率由69.75%提高到80.0%,并且SB的洗脱条件降低。本工艺方法适合于规模化工业生产。     

倍半硅氧烷合成进展

对以苯基三氯硅烷、苯基三烷氧基硅烷、甲基三氯硅烷、甲基三烷氧基硅烷、甲基三乙酸基硅烷分别为原料采用碱催化平衡水解三步法合成可溶性高分子量聚倍半硅氧烷及其共聚物进行了综述,并对以苯基三氯硅烷为原料采取一步法合成热塑性聚苯基倍半硅氧烷予以介绍,总结了以不同有机基为原料采用碱催化平衡法合成不溶性立方体聚倍半硅氧烷的研究结果,最后对卤盐催化非水解sol-gel法制备有机倍半硅氧烷凝胶作了阐述,以期对合成不同结构的聚倍半硅氧烷提供帮助。