液膜分离富集二甲氧基羟基苯基荧光酮荧光猝灭法测定微量钼的研究

研究了在pH5．0～6．4的HAC-NaAC缓冲介质中和CTMAB存在下,Mo(Ⅳ)对二甲氧基羟基苯基荧光酮(DMH-PF)的荧光猝灭效应,建立了荧光猝灭法测定微量Mo(Ⅳ)的新体系,DMH-PF最大激发波长为λex=514nm、最大发射波长为λem=547nm,DMH-PF与Mo(Ⅵ）形成1：2配合物使荧光猝灭,荧光猝灭量与Mo(Ⅵ)在0～0．072mg／L范围内呈线性关系,方法的检出限为0．0022mg／L,体系稳定,灵敏度高,采用液膜分离富集钼,可应用于合金钢和石墨中微量钼的测定。     

SAF-Tween80-β-CD荧光熄灭法测定微量钼的研究

在HCl介质中,吐温80(Tween80)和β-环糊精(β-CD)存在下,钼与水杨基荧光酮(SAF)形成复杂配合物使荧光熄灭,由此建立了测定微量钼的荧光熄灭新方法。该体系的最大激发波长λex=455 nm,最大发射波长λem=522 nm。Mo(Ⅵ)量在0~0.12μg/mL范围荧光熄灭程度(ΔF)与Mo(Ⅵ)质量浓度呈线性关系,线性回归方程为ΔF=31.839ρ(μg/mL) 29.726,相关系数R2=0.9996,检出限为1.53μg/L。该方法灵敏度高,选择性好,用于测定水样中的微量钼,回收率在99.4%~100.8%之间。     

水中微量磷的磷钼蓝光度法测定 --还原剂的研究

研究和配制了一种作为水中微量磷(磷钼蓝)光度法测定的还原剂,其稳定性、灵敏度、准确性均较好,适用干多种水样中微量磷的测定。     

5-Br-PADAP分光光度法测定微量镓

Гусеъ等曾研究了2-吡啶偶氮氨基苯酚及其卤代物和镓的反应。我们在此基础上作了较系统的研究,拟定了 Br-PADAP 光度测定镓的方法。镓(Ⅲ)与5-Br-PADAP 生成可溶于乙醇的橙红色络合物,最大吸收波长为570纳米,摩尔吸光系数为1.7×10~5。本法应用于铝土矿、铜矿、烟尘、锌及渣中微量镓的测定,结果较为满意。     

磷钼杂多酸-罗丹明B缔合显色反应的研究与应用

磷的测定方法有磷钼杂多酸法、磷钼蓝法、钒一钼酸铵法、磷锑钼蓝法等。本法研究了在硫酸介质中,磷与适量的钼酸根形成磷钼杂多酸络阴离子[P（Mo3O10）4]^3-,再与罗丹明B阳离子（RDB）。形成离子缔合物（RDB）3[P（Mo3O10）4]直接水相光度法测定磷。结果表明,该体系灵敏度较高,稳定性好,且操作简便,重现性好,适用于各种水样中微量磷的测定,结果满意。     

磷钼杂多酸光度法测定水果中的维生素C

在一定条件下,PO43-与Mo(VI)形成的磷钼杂多酸H3[P(Mo3Ol0)4]被维生素C还原成磷钼蓝,其最大吸收波长为710 nm,磷钼蓝的表观摩尔吸光系数为4.8×103L/(mol.cm),维生素C在1.0～80.0μg/mL浓度范围内符合比尔定律,线性回归方程为A=-0.01747+0.02722ρ(μg/mL),相关系数为0.9992,检测限为0.23μg/mL。该方法已用于水果中维生素C含量的测定。     

Triton X-100增敏光度法测定铝土矿中的微量钪

研究了在HCl溶液中微量钪(Ⅲ)-偶氮氯膦Ⅲ(CPAⅢ)之间的配合反应。结果表明,在0.5mol/LHCl溶液中和TritonX 100的存在下,有色溶液的最大吸收波长为680nm,表观摩尔吸光系数为2.62×104L·mol-1·cm-1。钪(Ⅲ)质量浓度在0～0.45mg/L范围内符合比耳定律,钪(Ⅲ)的加标回收率在98.0%～105.1%之间,RSD(n=6)为2.1%～2.6%。可用于铝土矿中的微量钪的测定。     

三波长吸光光度法的算法研究及应用

提出了三波长吸光光度法新的计算方法即线性回归法.方法同时适用于普通三波长法和波长位移三波长法.它是将几个不同组成的已知混合溶液,在三个选定的波长下所测得的吸光度直接进行线性拟合,采用线性回归技术进行处理,建立了三波长法线性回归方程Y=kX B,从而克服了通常三波长法测定实际混合样时,对完全由纯组分所建立的定量公式的偏离而引入的误差,提高了测定结果的精确度和可靠性,操作简便易行.已用于PF-CPC显色体系在适量W(Ⅵ)存在下测定微量Mo(Ⅵ)和THPP-OP显色体系在适量锌存在下测定微量镉.     

Mo(Ⅵ)-邻硝基苯基荧光酮配合物光谱探针测定蛋白质

研究了Mo(Ⅵ)-邻硝基苯基荧光酮(o-NPF)配合物与蛋白质的相互作用及光谱性质. 提出了以Mo(Ⅵ)-邻硝基苯基荧光酮配合物作为光谱探针测定微量蛋白质的方法. 结果表明, 在pH为2.2的 HAc-NaAc缓冲介质中, 乳化剂OP存在下, o-NPF-Mo(Ⅵ)在40 ℃加热10 min后与蛋白质形成稳定的复合物, 最大吸收波长红移至587 nm. 蛋白质质量浓度在0～10 mg/L 范围内符合比尔定律, 复合物的表观摩尔吸光系数为3.53×106 L·mol-1·cm-1. 该方法具有很高的灵敏度和选择性, 可直接用于人尿、新生牛血清中蛋白质的测定, 回收率分别为93%和99%.     

五氧化二钒中微量砷和磷的直接同时测定

提出了以数学校正扣除基体四价钒色泽对砷(磷)铋钼蓝色泽干扰的方法和校正磷对砷测定干扰的方法.应用于五氧化二钒中微量砷和磷的测定,结果准确、可靠.     

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。