1－芳氧基乙酰基－4－邻氯苯甲酰基氨基硫脲衍生物的合成及其生物活性研究

于固－液相转移催化条件下，合成了１０个１－芳氧基乙酰基－４－邻氯苯甲酰基氨基硫脲衍生物，用元素分析、ＩＲ和￣１Ｈ－ＮＭＲ光谱确定了它们的结构。该类化合物对小麦幼苗生长具有明显的促进作用。     

全芳香族共聚酯的结构和其液晶行为研究

本文对不同组成的对苯二甲酸(TPA),对羟基苯甲酸(PHBA),联苯二酚(BP),间苯二甲酸(IPA)共聚酯采用热台偏光显微镜、电子显微镜、X-射线衍射、激光小角散射、差热等技术进行了研究.实验结果表明,在一定的组成范围内共聚酯熔体有很好的液晶性.重点讨论了分子组成、转变行为、液晶性的关系,并对液晶相的形态结构进行了表征.     

低共熔混合锂盐相图的绘制及应用

采用热分析法对不同组成的混合锂盐二元体系进行研究, 绘制了混合锂盐体系的步冷曲线和T-x相图, 结果表明体系均为具有最低共熔点的二元体系. LiOH-LiNO3、LiOH-LiCl、LiOH-Li2CO3及LiNO3-LiCl体系的最低共熔点分别为175.7、294.5、418.2及221.6 ℃. 利用低共熔混合物LiNO3-LiOH为锂盐与不同前驱体反应, 制备出了层状结构良好的锂离子电池正极材料LiNiO2、LiNi0.8Co0.2O2及LiNi1/3Co1/3Mn1/3O2. X射线衍射分析表明, 合成的材料具有规整的层状NaFeO2结构, 且XRD衍射峰强度之比I(003)/I(104)>2.0, 电性能测试表明, 在2.7-4.3 V(vs Li/Li+)的电压范围内进行0.1C倍率充放电, LiNiO2、LiNi0.8Co0.2O2、LiNi1/3Co1/3Mn1/3O2首次充电比容量分别达168.0、225.4、194.0 mAh·g-1, 放电比容量分别为138.4、165.8、157.7 mAh·g-1.     

The phase diagram of KNO3-KClO3

The binary phase diagram of KNO₃-KClO₃ is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO₃)_1−x(ClO₃)_x (0<x<0.20) and K(NO₃)_1−x(ClO₃)_x (0.90<x<1.0), were formed in the KNO₃-based solid solutions and KClO₃-based solid solutions phase, respectively. For KNO₃-based solid solutions, KNO₃ ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO₃ by ClO₃-radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO₃-based (α) phase and KClO₃-based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent.     

Ab Initio High Pressure Investigations of InI

The high pressure behaviour of InI is studied by DFT‐calculations and compared with experimental data. The existence of a 5s² electron pair in In⁺ represents an unfavourable bonding situation for high symmetry structures because of effective closed shell repulsion. Since cations with a ns² electron pair are highly polarizable and the electronic situation is more favourable in the low symmetry structure InI prefers a TlI‐type structure at ambient pressure. A pressure induced transition to the more densely packed high symmetry CsCl‐type structure takes place at about 19 GPa according to our calculations. At ambient pressure the interactions are predominantly ionic. However with increasing pressure the distances between In⁺ cations in the TlI‐type structure diminish drastically, mainly due to the changing space requirement of the lone electron pair. Apart from ionic interactions further bonding interactions between the In⁺ cations occur. At elevated pressure the electron localization function (ELF) as well as the band structure diagrams suggest metallic bonding between the In⁺ within the zigzag chain, i. e. increasing bonding interactions between the In⁺ cations due to the electron pair and its s‐p‐mixing. At ambient pressure In‐In interactions are rather weak and the space requirement of the lone electron pair mainly determines the characteristic arrangement of the ions. At elevated pressure the In‐In interactions become stronger and stabilise themselves additionally the specific structural arrangement.     

Enhancement of cyclosporine aqueous solubility using α- and hydroxypropyl β-cyclodextrin mixtures

Cyclodextrins (CDs) are cyclic oligosaccharides that form inclusion complexes with lipophilic molecules through their hydrophobic central cavity. In this study, the effect of α-CD, hydroxylpropyl-β-CD (HP-β-CD) and mixtures of these two CDs on the aqueous solubility of cyclosporine A (CyA) was investigated. Infrared spectroscopy and thermal analysis were used to confirm CyA-CD complex formation. CyA aqueous solubility was increased by 10 and 80 fold in the presence of α-CD and HP β-CD, respectively. The phase-solubility profile for HP-β-CD was linear while that for α-CD had positive deviation from linearity. In the presence of constant concentration of α-CD (15% w/v), aqueous solubility of CyA was further increased upon addition of HP-β-CD up to a concentration of 20% w/v. At higher HP-β-CD concentrations, aqueous solubility of CyA was observed to decrease. Addition of sodium acetate (up to 5% w/v) to aqueous solutions containing 20% w/v HP-β-CD and increasing concentrations of α-CD resulted in a significant reduction in CyA solubility. Complex formation between CyA and both α-CD and HP-β-CD was confirmed by differential scanning calorimetry (DSC). No significant changes were observed in the IR spectra of either CyA or CD following complex formation suggesting chemical interaction between CyA and the CD was unlikely. Phase-solubility studies showed that α-CD had a much greater effect on the solubility of CyA than HP-β-CD. Addition of HP-β-CD to aqueous solutions of α-CD affected the solubility of CyA in these systems. A mixture of 15% w/v α-CD and 20% w/v HP-β-CD was optimal for increasing aqueous solubility of CyA.     

Drug metabolite cluster centers-based strategy for comprehensive profiling of Neomangiferin metabolites in vivo and in vitro and network pharmacology study on anti-inflammatory mechanism

Neomangiferin (NMF) is an extremely special xanthone that could be simultaneously attributed to C-glycoside and O-glycoside with a variety of biological activities, such as anti-inflammatory, antitumor, antipyretic, and so on. So far as we know, the metabolism profiling has been insufficient until now. Herein, Drug Metabolite Cluster Centers (DMCCs)-based Strategy has been developed to profile the NMF metabolites in vivo and in vitro. Firstly, the DMCCs was proposed depending on literature-related and preliminary analysis results. Secondly, the specific metabolic rule was implemented to screen the metabolites of candidate DMCCs from the acquired Ultra High Performance Liquid Chromatography Quadrupole Exactive Orbitrap Mass Spectrometry (UHPLC-Q-Exactive Orbitrap MS) data by extracted ion chromatography (EIC) method. Thirdly, candidate metabolites were accurately and tentatively identified according to the pyrolysis law of mass spectrometry, literature reports, comparison of reference substances, and especially the diagnostic product ions (DPIs) deduced preliminarily. Finally, network pharmacology was adopted to elucidate the anti-inflammatory action mechanism of NMF on the basis of DMCCs. As a result, 3 critical metabolites including NMF, Mangiferin (MF) and Norathyriol (NA) were proposed as DMCCs, and a total of 61 NMF metabolites (NMF included) were finally screened and characterized coupled with 3 different biological sample preparation methods including solid phase extraction (SPE), acetonitrile precipitation and methanol precipitation. Among them, 32 metabolites were discovered in rat urine, 30 in rat plasma, 12 in rat liver, 9 metabolites in liver microsomes and 8 in rat faeces, respectively. Our results also illustrated that NMF primarily underwent deglucosylation, glucuronidation, methylation, sulfation, dihydroxylation and their composite reactions in vivo and in vitro. Additionally, network pharmacology analysis based on DMCCs revealed 85 common targets of disease-metabolites, and the key targets were TNF, EGFR, ESR1, PTGS2, HIF1A, IL-2, PRKCA and PRKCB. They exerted anti-inflammatory effects mainly through the pathways of inflammatory response, calcium-dependent protein kinase C activity, nitrogen metabolism, pathways in cancer and so on. In general, our study constructed a novel strategy to comprehensive elucidate the biotransformation pathways of NMF in vivo and in vitro, and provided vital reference for further understanding its anti-inflammatory action mechanism. Moreover, the established strategy could be generalized to the metabolism and action mechanism study of other natural products.     

Excess heat capacities and orientational order in systems containing hexadecane isomers of different molecular structure

Using the Picker flow microcalorimeter, excess heat capacities have been obtained at 25°C throughout the concentration range for 2,2-dimethylbutane,n-hexane, and cyclohexane each mixed with a series of hexadecane isomers of increasing degrees of orientational order, as determined by depolarized Rayleigh scattering. The isomers are 2,2,4,4,6,8,8-heptamethylnonane, 6-, 4-, and 2-methylpentadecane, andn-hexadecane. Thec _p ^E values are negative, increasing rapidly in magnitude with increase of orientational order, and are not predicted by the Prigogine—Flory theory which neglects order. Values ofc _p ^E are obtained at 10, 25, and 55°C for cyclohexane +6-, 4-, and 2-methylpentadecane which with other literature data lead to the temperature dependence of the thermodynamic excess functions for cyclohexane solutions of the five C₁₆ isomers. The excess enthalpy and entropy vary with the C₁₆ isomer and with temperature, but the corresponding variation of the excess free energy is small, indicating a high degree of enthalpy-entropy compensation. This is consistent with a rapid decrease with temperature of orientational order in the C₁₆ isomers.     

On the ternary B 2-phase in the Al-Co-Ga system

Summary Lattice parameter values were determined for the ternary B 2-phase in the Al-Co-Ga system, and it was found that a continuous solid solution exists between -AlCo and -CoGa. Phase boundaries of the ternary phase at 1 100 K were derived from the variation of the lattice parameter with composition.

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Über die ternäre B 2-Phase im System Al-Co-Ga

Zusammenfassung Im Bereich der ternären B 2-Phase im System Al-Co-Ga wurden die Werte des Gitterparameters bestimmt; es stellte sich heraus, daß eine durchgehende feste Lösung zwischen -AlCo und -CoGa besteht. Die Phasengrenzen der ternären Phase bei 1 100 K wurden aus der Änderung des Gitterparameters mit der Zusammensetzung abgeleitet.

     

Phase separation of poly(γ-benzyl L-glutamate) to liquid crystal and isotropic solution in various helicogenic solvents

Solvent effects on the phase separation of poly(-benzyl L-glutamate) to liquid crystal and isotropic solution have been observed in various helicogenic solvents. The temperature-composition phase diagrams have been determined for each solution. The critical concentrations, ₂ ^* , at which the phase separation occours have been compared in various solvents. In dimethylformamide in which the polymer is molecularly dispersed, the observed ₂ ^* value has agreed with that calculated by Flory's theory. In some solvents in which the polymer aggregates in a head-to-tail mode such as chloroform, the observed ₂ ^* values have been considerably small. It is assumed that the polymer aggregates behave as longer particles than the original particles. In dioxane in which the polymer aggregates highly both in a head-to-tail and a side-by-side modes, the ₂ ^* value has been a little larger than that in chloroform. In this case the relationship between the aggregation and the liquid crystal formation is so complicated that further investigation is necessary. In aromatic solvents such asm-cresol that dissolves the polymer almost molecularly, the ₂ ^* is smaller than that in dimethylformamide. Therefore, the intermolecular interactions between the phenyl groups in the side groups of the polymer and those in solvent molecules must be considered.The author is grateful to Mr. K. Sano and Mr. M. Watanabe for their observation of the liquid crystal formation.