反相液相色谱保留值的预测模式

液相色谱保留值的预测一直是色谱领域里研究最为活跃的领域之一,寻找一种以最少系数求算和预测色谱保留值是色谱工作者的长期研究的目标,但目前,仍没有真正的预测方法。我们在液相色谱保留值基本方程的基础上,曾对不同C_(18)的担体上的保留规律进行过研究,并从中引入了溶质lnk′=A C·C_B BlnC_B (1)作用指数的概念,作用指数即为方程(1)中的参数C(参数B在反相色谱中忽略),CB为二元冲洗剂中强冲洗组分的浓度。本文从溶质的作用指数出发来探讨反相液相色谱保留值的预测模式。     

线性非理想条件下液相色谱柱末端峰形规律

色谱流出曲线的二阶中心矩μ２和三阶中心矩μ３以及描述峰形非对称程度的偏态系数∑ｋ＝μ３／μ１．５２是反映色谱峰形的重要参数。从液相色谱过程动力学方程出发，运用电子计算机证明了在线性非理想条件下高效液相色谱体系中不同保留值组分在柱末端峰形的分布基本一致的结论。     

气相色谱与液相色谱保留值的换算方法

根据色谱热力学理论,在色谱保留值公式统一形式的基础上导出了气相色谱保留系数（I）与反相液相色谱保留公式参数a,c之间的关系式,证明结构类似化合物的a,c值与保留指数呈线性关系,同时存在氢键作用能、偶极矩作用的影响,从而提出了色相色谱与反相液相色谱保留值换算的方法;该理论为氯代芳烃的文献数据所证实。     

线性非理想条件下液相色谱柱末端峰形规律

 色谱流出曲线的二阶中心矩μ２和三阶中心矩μ３以及描述峰形非对称程度的偏态系数∑ｋ＝μ３／μ１．５２是反映色谱峰形的重要参数。从液相色谱过程动力学方程出发，运用电子计算机证明了在线性非理想条件下高效液相色谱体系中不同保留值组分在柱末端峰形的分布基本一致的结论。     

二元流动相保留值关系式中系数a，b，c规律性和柱系统选择的研究

]本文对反相液相色谱二元流动相系统的保留值方程luk'=a+blnCb+Cb中系数a,c的规律性作了理论解释,系统地说明了这些规律的存在条件及其在实际应用中的可能性。从分子作用力角度出发对色谱柱系统的分离模式的选择,对同系物及非极性化合物的键合相碳链长度的选择和冲洗剂中强组分浓度的选择进行了探讨。     

疏水分配常数用于反相液相色谱保留值的预测

在反相液相色谱保留值基本方程log k_′=a+_cC_B的基础上,描述了采用疏水分配常数及氢键作用能来预测a、c参数的方法,并系统讨论了疏水分配常数对参数a、c的影响,借此对反相液相色谱宽浓度范围内的保留值进行了预测。     

反相液相色谱中保留值变化规律的研究——保留值收敛性的理论探讨与实验验证

本文根据反相液相色谱中顶替吸附多种相互作用模型,系统地研究了不同色谱参数(如流动相组成、柱温、溶质、溶剂及键合相配体分子中的碳数)对保留值收敛性的影响,并用热力学方法导出了4个新的保留值收敛方程,已经在各种同系物实验中得到了验证。另外,本文还建立了一种能够采用计算机直接从实验数据计算保留值收敛点坐标的方法,预测值与做图法得到的结果完全一致。     

色谱保留值方程的统一形式

本文采用点阵模型,运用统计热力学方法推导出色谱保留值方程的统一形式。根据不同的条件从此统一形式可获得描述气-固色谱、气-液色谱、液-固色谱、液-液色谱以及超临界流体色谱保留值规律的方程。上述方程均采用实验数据予以验证。     

反相液相色谱的双柱规律

本文在液相色谱保留值方程ln κ′=A B·C_B C·InC_B的基础上,在很宽的浓度范围内考察了反相液相色谱的双柱规律,根据这个方法,在一个柱上只要做一次先行实验,就可在较宽的浓度范围内把一个柱上的k’转移到另一柱上去。     

单酮类有机物气相色谱保留值与结构参数的相关性

应用半经验量子化学AM1方法和分子图形学技术获得了42种单酮类有机物分子的电子结构和几何结构参数，并将这些参数与它们在非极性固定相(SE-30柱)上的气相色谱保留值相关联，采用逐步回归分析方法，成功地建立了拟合度高、物理意义明确、预测能力强的气相色谱保留值一结构参数定量关系方程，找出了影响气相色谱保留值的主要结构因素．     

用液体有机硝酸盐作气相色谱固定相

选用二乙胺、三乙胺、正丙胺、异丙胺、正丁胺和异丁胺的硝酸盐作为气相色谱固定相,测得它们的使用温度范围均超过１００℃。上述液体有机盐对具有大偶极矩分子化合物或具有氢键成键能力的化合物（如醇类）有良好的选择性,特别对醇类异构体的分离效果更佳;对酮类及单官能团取代苯的分离效果更令人满意,但对烃类不适用。     

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.     

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。     

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.

     

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.     

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.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.