双波长动力学光度法测定邻苯二酚的研究

Fe(Ⅲ)能够催化H2O2氧化中性红和灿烂甲酚蓝混合体系并使其褪色,加入邻苯二酚以后,该催化氧化褪色反应的速度明显提高.分别测定540 nm和640 nm处加入邻苯二酚和没有加入邻苯二酚体系的吸光度变化,发现吸光度的变化之和(△A)与邻苯二酚的浓度之间存在线性关系.研究了反应体系的吸收光谱,优化了实验条件,建立了双波长动力学光度法测定邻苯二酚的新方法.该方法测定邻苯二酚的线性范围为0.16～1.44 mg/L,检出限为0.05 mg/L.方法用于废水样品中邻苯二酚的测定,结果满意.     

对乙酰基偶氮羧-铈(Ⅲ)-人血清白蛋白体系的吸收光谱性质及其分析应用

在pH 2.0~3.0的B-R缓冲介质中,对乙酰基偶氮羧(p-ACA)与铈(Ⅲ)生成蓝色配合物,其吸收峰在727nm处,而显色剂本身吸收峰在577nm处,对比度达150mm。在此显色体系中加入人血清白蛋白(HSA)时,发生消光反应,呈现在波长727nm处吸光度的减弱。试验表明:HSA的质量浓度在10~120mg·L-1范围内与相应的吸光度减弱程度(ΔA)之间呈线性关系。显色体系对HSA的表观摩尔吸光率为5.14×105L·mol-1·cm-1。加入TX-100使该体系的灵敏度提高45%。应用上述方法测定了3份人血清样品中HSA的含量,测定值与考马斯亮蓝法的测定结果一致。     

苎麻叶中绿原酸的分光光度法测定

探讨了采用分光光度法测定苎麻叶中绿原酸的含量的方法。12.5%的醋酸用量为0.1mL,7%尿素2.0mL,0.5%亚硝酸钠0.25mL,3min后加入5%氢氧化钠0.5mL,绿原酸与试剂形成鲜红色络合物,通过在510nm处测定溶液的吸光度确定绿原酸的含量。绿原酸浓度在0.01~0.12g/L范围内与吸光度值有良好的线性关系,回收率为95%~107%,相对标准偏差(RSD)为2.4%。该方法简便、快速。     

酸性铬兰K分光光度法测定血红蛋白

在pH 3.2的Clark-Lub’s缓冲溶液中,酸性铬兰K与血红蛋白发生反应,使体系吸光度增大,在375 nm处的吸光度增加值与血红蛋白的加入量成正比,据此建立了测定血红蛋白的分光光度法。探讨了测定血红蛋白的最佳条件和干扰情况,方法的线性范围0～112μg/mL,表观摩尔吸光系数ε375为4.7×105L.mol-.1cm-1,方法已用于动物血液和人尿液中血红蛋白含量的测定。     

甲醛对金属离子-胺络合体系光学性质的影响

对11种金属离子与羟胺、乙二胺混合配体形成络合物的可见光谱特征、摩尔吸光系数、络合比、络合稳定常数以及加入甲醛后的特征吸收峰的吸光度变化进行了测定。为建立新的金属离子-羟胺-乙二胺络合体系分光光度测定痕量甲醛含量方法提供可靠的理论与实验依据。     

纳氏试剂分光光度法测定土壤中全氮含量

提出了纳氏试剂分光光度法测定土壤中全氮含量。以硫酸铜为加速剂,用硫酸对土壤样品进行消解。消解完毕的溶液用400g·L-1氢氧化钠溶液调节其酸度至pH 10左右,溶液与沉淀一起移入容量瓶中,定容至200mL。移取上清液10mL于50mL比色管中,加入酒石酸钾钠溶液作掩蔽剂,加入纳氏试剂显色后,加水定容,于波长420nm处测量其吸光度并计算土壤样品中全氮含量。氮的质量浓度在2mg·L-1以内与吸光度呈线性关系。方法用于土壤样品分析,测定值与滴定法测定值相符,测定值的相对标准偏差(n=10)为0.24%;回收率在92.3%~112%之间。     

应用Fe2+与K3[Fe(CN)6]反应测定还原性物质Vc

在pH 2～3的溶液中,低浓度Fe^2＋与K3[Fe（CN）6]反应产生的蓝色沉淀为近似真溶液,最大吸收波长为710 nm.形成的近似真溶液吸光度随静置时间变化而逐渐变大,30 min后吸光度变化缓慢.K3[Fe（CN）6]过量时,Fe^2＋浓度与吸光度呈很好的线性关系.Fe^2＋浓度较大时,易形成絮状沉淀.在pH 2～3的Fe^3＋-K3[Fe（CN）6]体系中,加入Vc能将Fe^3＋还原成Fe^2＋,进而与K3[Fe（CN）6]反应,30 min后测定蓝色拟真溶液的吸光度,Vc的量与溶液的吸光度同样有很好的线性关系,线性相关系数R〉0.999,检出限为0.94μg.     

乙醇-硫酸铵双水相萃取分光光度法测定粮食中钼含量

试验表明:在乙醇-硫酸铵双水相体系中,所形成的乙醇相对钼与水杨基荧光酮红色络合物具有增敏作用。在pH 3的乙酸-乙酸钠缓冲溶液条件下,钼与水杨基荧光酮形成1∶2的稳定红色络合物,在乙醇-硫酸铵双水相体系的乙醇相中,该络合物的最大吸收波长为516 nm,与单一水溶液中络合物相比,发生了2 nm波长的红移现象。在乙醇相中钼(Ⅵ)-SAF络合物的表观摩尔吸光率为1.12×105L.mol-1.cm-1,钼(Ⅵ)质量浓度在20 mg.L-1以内与其对应的吸光度呈线性关系。方法的检出限(3S/N)为0.06 mg.L-1。该方法应用于粮食作物中微量钼的测定,测得方法的回收率为97.4%～100.1%。     

火焰原子吸收光谱法连续测定高纯铋锭中痕量铜、银、锌

建立了用火焰原子吸收光谱法在同一体系中连续测定铋锭中的铜、银、锌的方法。试样用硝酸溶解,在稀盐酸介质中,分别于原子吸收光谱仪波长324.7,328.1,213.8nm处,使用空气-乙炔火焰连续测定铜、银、锌的含量。在最佳实验条件下,铜的质量浓度在0.20~0.80mg/L范围内与吸光度线性关系良好,加标回收率为94.5%~101.8%。银的质量浓度在0.5~2.0mg/L范围内与吸光度成线性关系,加标回收率为97.3%~102.6%。锌的质量浓度在0.10~0.40mg/L范围内与吸光度成线性关系,加标回收率为96%~106.3%。火焰原子吸收光谱法测定铋锭中的铜、银、锌,相对标准偏差(n=11)均小于8.0%,测定结果与理论值基本一致。     

协同增敏Fe(Ⅱ)-邻二氮杂菲阻抑光度法测定微量过氧化氢

在乙酸介质中,H2O2对Fe(Ⅱ)-邻二氮杂菲体系的显色反应有明显的阻抑作用,表面活性剂协同增敏有效提高体系吸光度,据此建立了测定微量H2O2的新方法。测得最大吸收波长500~510 nm,H2O2质量浓度在0.05~0.3μg/m L范围内与吸光度递减呈良好的线性关系,方法的相对标准偏差为0.24%~0.28%;回收率为98.7%~102.8%。方法已用于测定消毒液中微量H2O2。     

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.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。