微透析-HPLC测定甘草次酸对雄黄染毒小鼠海马细胞外液中Cys和Hcy含量的影响

建立微透析-HPLC测定小鼠海马细胞外液中Cys和Hcy含量的方法 ,探讨甘草次酸对雄黄染毒小鼠海马细胞外液中Cys和Hcy含量的影响.结果表明,所建方法准确、可靠,具有连续活体取样、实时动态检测的优势.此外,甘草次酸对雄黄引起的小鼠海马细胞外液中Cys和Hcy含量的降低有保护作用.     

血红蛋白与葡萄糖氧化酶偶联荧光法测定葡萄糖

利用血红蛋白(Hb)作为辣根过氧化物酶(HRP)的模拟酶,催化H2O2与对甲基酚的荧光反应.并将该反应与葡萄糖氧化酶(GOD)催化氧化葡萄糖的反应偶联,建立了测定葡萄糖的荧光分析法.方法的线性范围为0.0～5.0×10-5mol/L葡萄糖.检测限为6.5×10-8mol/L.用于测定人血清中葡萄糖的含量,获得了满意的结果.     

催化荧光法测定注射用头孢哌酮钠含量

在氢氧化钠介质中,头孢哌酮钠能催化过硫酸钾氧化光泽精褪色,使体系荧光猝灭,据此建立了测定头孢哌酮钠含量的催化荧光分析方法.头孢哌酮钠的质量浓度与荧光强度的变化在7.56～55.44 mg/L范围内呈良好的线性关系,相对标准偏差(RSD)为2.41%,方法的检出限(S/N=3)为6.95 mg/L.该法简便、快速,可靠,并应用于药物粉针制剂中头孢哌酮钠含量的测定,结果令人满意.     

可同时比色检测硫离子和高半胱氨酸/半胱氨酸的化学探针的合成及应用

合成了一个能同时检测硫离子(S2-)和高半胱氨酸/半胱氨酸(Hcy/Cys)的化学探针1,采用核磁共振波谱(NMR)、高分辨质谱(HRMS)、元素分析和傅里叶换红外光谱(FTIR)等表征了其分子结构,并通过高效液相色谱、质谱以及核磁滴定氢谱实验研究了探针1检测S2-和Hcy/Cys的机理.实验结果表明,探针1能同时对S2-和Hcy/Cys进行快速、高敏感性和选择性识别,并且是通过硫醇亲核反应识别的.在Tris-HCl缓冲溶液[10 mmol/L,p H=7.40,50%(体积分数)乙醇]中,探针1对S2-于552 nm处表现了显著的吸收强度增强并伴随溶液颜色由无色变为紫红色;对Hcy/Cys于552 nm处表现了特异的荧光增强,而对Cys的检测还可见溶液颜色由无色变为酒红色,据此制备了负载探针1的滤纸传感器用于比色检测S2-和Cys.此外,将探针1用于人血清的加标回收率测定,获得了较好的结果.     

表面活性剂和染料探针共振光散射法测定蛋白质

在pH为2.1的Britton-Robinson缓冲溶液中,蛋白质与十二烷基磺酸钠和吖啶红作用形成聚集体,导致体系产生较大的共振散射光(RLS)强度,并且RLS的增强程度与蛋白质的浓度呈线性关系,据此建立了测定蛋白质含量的方法.人血清白蛋白(HSA)和牛血清白蛋白(BSA)分别在0.03～3.0μg/mL和0.2～7.0μg/mL的浓度范围内与增强的共振光散射强度有良好的线性关系,相应的检测限分别为0.0119μg/mL和0.026μg/mL.对体系的反应机理进行了讨论.将方法用于人血清中蛋白质含量的测定,并将分析结果与考马斯亮蓝法进行了对照.t-检验证明,两种方法无显著性差异.     

红外光谱对苏云金杆菌制剂中违禁添加溴虫腈的定量检测

建立了利用衰减全反射傅里叶变换红外光谱(ATR-FTIR)结合偏最小二乘法(PLS)对苏云金杆菌制剂中违禁添加的溴虫腈含量进行快速测定的方法.在3种不同来源的苏云金杆菌制剂中加入不同质量的97.00％(m/m)溴虫腈原药,配制成溴虫腈浓度为0.00％ ～5.00％的153个混合样品.选择3种预处理方法:Savitzky...     

α-球蛋白与稀土金属离子钆(Ⅲ)的配位作用

采用固定顺磁金属离子浓度,逐渐改变α-球蛋白浓度,测定溶剂水质子弛豫时间变化的方法,研究了稀土离子钆(Ⅲ)与人血α-球蛋白的配位作用.研究结果表明,α-球蛋白中有3个钆(Ⅲ)离子的结合部位,其配合物的离解常数K_d=2.5×10~(-4)(mol/L)。     

中药多糖及人血清中糖蛋白N-糖链的毛细管电泳指纹图谱研究

该文建立了激光诱导荧光毛细管电泳(CE-LIF)检测中药多糖和人血清糖蛋白中N-糖链的分析方法。利用8-氨基芘-1,3,6-三磺酸钠(APTS)为柱前荧光衍生试剂,结合CE分析,可在15 min内同时测定7种中性单糖。该方法应用于中药制剂和药物植物中单糖组成和含量的测定,加标回收率为88.0%~102%,相对标准偏差(RSD)小于3.0%。该方法灵敏度高、准确性好、实用可靠,适合于监控中药制剂中糖类物质的种类和含量。同时,基于毛细管凝胶电泳方法(CGE)建立了人血清中糖蛋白的N-糖链指纹图谱。利用中性涂层聚乙烯醇(PVA)有效地抑制电渗流,增加分离时间,实现了糖链异构体的有效分离。对5μL人血清进行毛细管电泳分析,共分离得到17个组分。这为进一步研究复杂生物体系血清蛋白的糖基化变化提供了可能性。     

离子液体/表面活性剂协同增敏荧光法测定米力农

基于米力农自身荧光在十六烷基三甲基溴化铵(CTAB)和室温离子液体(RTILs)溴化十二烷基三甲基咪唑混合体系中得到显著增强,提出了测定药物及生物体液中米力农含量的荧光新方法。在优化条件下,线性方程为F=47.32+1378.65ρ(ρ:μg/mL,r=0.998),线性范围为0.02~1.5μg/mL,检出限为6.4 ng/mL。实验中对荧光增敏机理进行了探讨。将方法用于米力农注射液和人血清、尿液中米力农含量的测定,回收率在97.5%~107.4%,米力农注射液测定结果与法定方法一致。     

?OH对肌原纤维蛋白中敏感氨基酸的氧化效应分析

借助Fe3+-H2O2-Vc氧化模型体系,通过测定不同H2O2浓度条件下,氧化对肌原纤维蛋白中的氨基酸及氧化衍生物含量的影响,分析了羟自由基(·OH)对肌原纤维蛋白中敏感氨基酸的氧化效应。结果表明:·OH对构成肌原纤维蛋白氨基酸的氧化具有选择性,门冬氨酸(Asp)、甘氨酸(Gly)及亮氨酸(Leu)等对氧化作用不敏感,其含量变化不显著,而半胱氨酸(Cys)、蛋氨酸(Met)及酪氨酸(Tyr)对氧化敏感,随着H2O2浓度增加,模型体系中·OH的生成量也逐渐增加,导致3种敏感氨基酸含量呈下降趋势;对蛋白的羰基、总巯基及二酪氨酸等氧化衍生物含量的测定结果显示,氧化会导致蛋白的羰基及二酪氨酸含量增加,总巯基含量下降;进一步研究表明,氨基酸氧化存在明显的浓度效应,随着H2O2浓度升高,模型体系中·OH的生成量逐渐增加,氨基酸氧化程度加重,与未氧化的肌原纤维蛋白相比,当H2O2浓度达到20.0 mmol/L时,Cys、Met及Tyr的含量分别下降了13.3%、11.6%、20.5%。综上所述,氧化引起的含有活性基团敏感型氨基酸的结构改变是导致蛋白氧化的主要原因。     

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。