定量体积排除色谱法不溶性高分子的折光指数增量

用定量体积排除色谱法，从示差折光检测器的响应测定了多种水溶性高子分子在纯水溶液中的折光指数增量，与常规静态方法所得结果相同。ＳＥＣ用盐水溶液作为淋洗液时，盐水溶液类同于混合溶剂，溶质与周围溶剂的色谱分离过程与透析过程等同。     

多检测GPC／SEC技术在高分子表征中的应用：Ⅷ.超支化高分子？…

采用体积排斥色谱法／示差折光指数／直角激光光散射／示差粘度三检测联用技术在２５℃的ＴＨＦ中表征了超支化高分子的溶液性质;结果表明超支化高分子符合普适标室规律,体积排斥色谱法／示差折光指数／直角激光光散射／示差粘度三检测联用技术能解释传统的ＳＥＣ／ＲＩ技术不能解释的溶液行为。     

混合溶剂作淋洗剂的体积排除色谱谱图中溶剂化高分子峰和溶剂峰之间内在关系的理论分析

根据体积排除色谱(SEC)研究高分子溶质优先溶剂化的基本原理,证明在SEC色谱图中被束缚溶剂产生的面积与自由溶剂产生的面积大小相等方向相反,在研究优先溶剂化时从高分子峰入手和从自由溶剂峰入手在理论上具有等价性.分析表明,通过对溶剂化高分子峰的研究,还可以得到另一个重要物理参数——恒化学位时高分子溶液的折光指数增量.     

示差折光和光散射双检测体积排除色谱的绝对定量化

讨论了示差折光和光散射联用双检测体积排除色谱的绝对定量化的原理,强调指出了试样注入量在数据处理中的重要作用.测量注入试样的这两种检测器的检测常数,可以同时得到试样的折光指数增量和重均分子量的绝对值.这一方法除了适用于各种均聚物外,还可以应用于高分子混合物的分析.此时,如将混合物看作为单一溶质,从所得折光指数增量和重均分子量,可对它们的组成作出定量分析,还可以判断共混物两个组分之间有无分子缔合等现象的产生.这一方法应用于聚甲基丙烯酸甲酯/聚苯乙烯(PMMA/PS)混合物的溶液,指明在四氢呋喃中两者产生缔合而形成了复合物.     

定量SEC法同时测定短链共聚物的组成和分子量

由于端基对整体高分子链光学性质的贡献，短链高分子的折光指数增量有明显的分子量依赖性．从整体高分子链折光指数增量依从各结构组成单元折光指数增量的重量分数加和律，指示同一高分子链改变端基后，如分别测定它们的折光指数增量。由其差值可以同时获得链干的分子量和折光指数增量，对共聚物言，从链干的折光指数增量又可进而估定共聚物的组成．这一原则特别适用于具有显著端基效应的短链高分子．本工作用定量尺寸排除色谱方法测量具有不同端基的环氧乙烷－环氧丙烷共聚物苯溶液的折光指数增量，以考验此原则，获得了满意结果．     

多检测GPC/SEC技术在高分子表征中的应用 Ⅲ.新型聚炔类梳形液晶高分子

采用体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测联用技术表征聚炔类梳形液晶高分子,阐述了在溶液中分子尺寸与结构的关系,计算了无扰尺寸（ ＜ ｒ２０ ＞ ／ Ｍ）１／２ 和Ｆｌｏｒｙ 特征比Ｃ∞,讨论了侧基的柔性和体积对主链柔性程度的影响。     

多检测GPC／SEC技术在高分子表征中的应用：Ⅲ.新型聚炔类梳形？…

采用体积排斥色谱法／示差折光指数／直角激光光散射／示差粘度三检测联用技术表征聚炔类梳形液晶高分子,阐述了在溶液中分子尺寸与结构的关系,计算了无无扰尺寸（〈ｒ０＾２〉／Ｍ）＾１／２和Ｆｌｏｒｙ特征比Ｃ∞,讨论了侧基的柔性和体积对主链柔性程度的影响。     

甲基丙烯酰氧基乙基三甲基氯化铵-丙烯酰胺-丙烯酸三元共聚物水溶液的盐效应研究

用恒定外加盐浓度稀释法,测定了甲基丙烯酰氧基乙三甲基氯化铵 丙烯酰胺 丙烯酸（ＤＭＣ ＡＭ ＡＡ） 三元共聚物（ＡＰＡＭ） 水溶液在分别添加不同种类外加盐时的特性粘数．实验结果表明,当外加盐浓度在一定范围内变化时,所有共聚物在ＮａＣｌ 溶液和ＮａＮＯ３ 溶液中均表现出典型的普通聚电解质粘性行为,而ＤＭＣ 和ＡＡ 近似等摩尔的共聚物在Ｎａ２ＳＯ４ 溶液中则呈现出典型的两性聚电解质粘性行为,各种外加盐对ＡＰＡＭ 溶液特性粘数影响的程度为：Ｎａ２ＳＯ４ ＞ ＣａＣｌ２ ,ＮａＮＯ３ ＞ ＮａＣｌ．     

多检测GPC/SEC技术在高分子表征中的应用Ⅳ.氘化高分子的溶液性质

采用体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测联用技术表征了氘化聚苯乙烯、聚苯乙烯和氘化聚苯乙烯－ 聚异戊二烯。结果表明,在θ条件下,虽然氘化聚苯乙烯的化学依赖性常数υＴ,ＤＰＳ比聚苯乙烯的化学依赖性常数υＴ,ＰＳ大,但２５ ℃时在四氢呋喃中,氘化聚苯乙烯的分子尺寸仍小于聚苯乙烯的分子尺寸。由于嵌段共聚物的淋洗体积随组成变化,所以用传统的ＳＥＣ／ＲＩ得不到准确的分子量。经比较膜渗透、小角激光光散射和基质辅助激光脱吸与离子化时间飞行质谱等的实验结果,证明体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测技术能准确地得到氘化二嵌段共聚物的分子量以及其它重要信息。     

多检测GPC／SEC技术在高分子表征中的应用：Ⅳ.氘化高分子的溶液 …

采用体积排斥色谱法／示差折光指数／直角激光光散射／示差粘度三检测联用技术表征了氘化聚苯乙烯、聚苯乙烯和氘化聚苯乙烯－聚异戊二烯。结果表明,在 ０条件下,虽然氘化聚苯乙烯的化学依赖性常数ｖＴ,ＤＰＳ比聚苯乙烯的化学依赖性常数ｖＴ,ＰＳ大,但２５℃时在四氢呋喃中,氘化聚苯乙烯的分子尺寸仍小于聚苯乙烯的分子尺寸。由于嵌段共聚物的淋洗体积随组成变化,所以用传统的ＳＥＣ／ＲＩ得不到准确的分子量。经比较膜渗透     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。