气相色谱电子捕获检测法测定人尿中α羟基三唑仑及α羟基阿普唑仑

建立了尿中三唑仑的代谢物α羟基三唑仑和阿普唑 仑的代谢物α羟基阿普唑仑的气相色谱电子捕获检测法。代谢物用N,O双三甲基硅烷基三氟乙酰胺（BSTFA）进行三甲基硅烷衍生化后进行检测。尿中代谢物的检出限约为1μg/L（S/N=3）,至少可检出口服治疗量药物人体24h之内排泄尿中的代谢物,满足麻醉后犯罪案件中药物检验的要求。     

气相色谱－电子捕获检测法测定人尿中α－羟基三唑仑及α－羟基阿普唑仑

建立了尿中三唑仑的代谢物α－羟基三唑仑和阿普唑仑的代谢物α－羟基三唑仑的气相色谱－电子捕获检测法。代谢物用N,O－双三甲基硅烷基－三氯乙酰胺（BSTFA）进行三甲基硅烷衍生化后进行检测。尿中代谢物的检出限约为1μg/L（S／N＝3）,至少可检出口服治疗量药物人体24h之内排泄尿中的代谢物,满足麻醉后犯罪案件中药物检验的要求。     

Q Exactive四极杆-静电场轨道阱高分辨质谱系统对丹皮酚经大鼠肝微粒体体外代谢产物的分析

以丹皮酚和2,4-二羟基苯乙酮为研究对象,采用Q Exactive四极杆-静电场轨道阱高分辨质谱系统,及内置有Ⅰ相和Ⅱ相代谢途径分析的MetWorks代谢物鉴定软件,系统分析丹皮酚经肝微粒体代谢的Ⅰ相代谢及其Ⅰ相代谢产物2,4-二羟基苯乙酮经微粒体代谢的Ⅱ相代谢产物。结果表明,丹皮酚在大鼠肝微粒体中经Ⅰ相代谢后产物主要为4位去甲基化的2,4-二羟基苯乙酮和1位相邻羰基的脱甲基化的2-羟基-4-甲氧基苯甲醛以及5位的羟基化代谢产物2,5-二羟基-4-甲氧基苯乙酮,而2,4-二羟基苯乙酮的Ⅱ相代谢产物主要为4位葡萄糖醛酸化的糖苷化代谢产物2-羟基-4’-O-葡萄糖醛酸苯乙酮。     

新型螺双二氢茚二酚衍生物的合成

螺双二氢茚二酚(SPINOL)与N-溴代丁二酰亚胺经溴代反应制得6,6'-二溴-螺双二氢茚二酚(1);1与叔丁基二甲基硅基三氟甲磺酸(TBSOTf)经醚化反应得6,6'-二溴-7-羟基-7'-叔丁基二甲硅氧基-1,1'-螺二氢茚(2);SPINOL经羟基保护后与碘甲烷经双甲基化反应制得6,6'-二甲基-7,7'-双(1-甲氧甲氧基)-1,1'-螺二氢茚(4);4经脱保护后再与TBSOTf经醚化反应合成了6,6'-二甲基-7-羟基-7'-叔丁基二甲硅氧基-1,1'-螺二氢茚(6)。2和6为新化合物,其结构经1H NMR,13C NMR和HR-ESI-MS表征。     

高效液相色谱-电喷雾离子阱质谱法鉴定人尿中奥美拉唑代谢物

应用高效液相色谱－电喷雾离子阱质谱法鉴定了人口服奥美拉唑（OPZ）后0－6h内尿中的代谢物。尿中代谢物经富集后，应用高效液相色谱法分离，然后在线进行选择离子扫描（SIM）、二级碎片离子全扫描（full scan MS^2)和三级碎片离子全扫描（full scan MS^3)，进行对尿中微量的烷烃羟基化、O－脱烷烃化、硫氧化和还原以及葡萄糖醛酸化和硫酸化的9种代谢物进行了质谱解析。     

气相色谱/质谱联用法鉴定人和大鼠肝微粒体中安定代谢物

采用气相色谱/质谱联用法(GC-MS)鉴定安定在女性混合和Wistar大鼠肝微粒体中的代谢产物,推测安定在女性混合和大鼠肝微粒体中可能的代谢途径。在女性混合和Wistar大鼠肝微粒体中37℃恒温孵育48 h,固相萃取(SPE)净化提取,GC–MS(EI)检测。女性混合和Wistar大鼠肝微粒体中均可代谢生成6-氯-4-苯基喹唑啉、6-氯-2-甲基-4-苯基喹唑啉、2-甲氨基-5-氯-二苯甲酮、6-氯-4-苯基-2(1H)-喹唑啉酮、6-氯-1,4-二氢-1-甲基-4-苯基喹唑啉、去甲安定和6-氯-1,2-二氢-1-甲基-2-氧-4-苯基喹唑啉7种代谢物;此外,女性混合肝微粒体中检出替马西泮,而Wistar大鼠肝微粒体中检出5-羟基苯基安定。推测了安定在女性混合和Wistar大鼠肝微粒体(细胞色素P450酶系或者CYP450)中氧化、去甲基化等主要代谢途径和代谢特点,为进一步研究其代谢和代谢酶奠定基础。     

尿甾类物的气相色谱分析

利用气相色谱研究人尿中甾体激素的代谢产物已有不少报导,一般利用硅烷化试剂与甾体分子中所含羟基反应,制备成三甲基硅醚(TMS)衍生物后再进行气相色谱分析。在室温下,除了17-α的叔羟基和11-β立体位阻较大的羟基外,其余位置的羟基均可顺利反应,重现性好。对于同时含有酮基和羟基的分子可先使酮基反应生成甲肟(MO)衍生物,然后再进行三甲基硅烷化。 Stillwell等曾应用色谱-质谱联用技术研究了甾体避孕药的代谢产物。我们在研究长效口服避孕药-环戊醚乙炔雌二醇(CEE)对尿中中性激素代谢产物影响的工作中,着重试验了雄激素和孕激素代     

高效薄层法检测尿中氟硝西泮的代谢物7-氨基氟硝西泮

 报道了尿中氟硝西泮代谢物 7 氨基氟硝西泮 (7AFLZ)的高效薄层 (HPTLC)定性分析和半定量分析方法 ,分析物斑点用荧光胺进行荧光显现 ,灵敏度高 ,检测限 (LOD)为 5 μg/L ,测量限 (LOQ)为 15 μg/L。该方法可以检测人口服 1mg氟硝西泮后 48h内排泄尿中的 7AFLZ ,适于麻醉抢劫犯罪案件中的药物检测。     

柱前衍生化结合LC-MS~n分析人尿中茶碱及其代谢物

采用固相萃取结合化学衍生化的样品柱前预处理方法,利用液相色谱-电喷雾/多级质谱联用技术(LC-ESI/MSn),对人经口服给药后尿液中的茶碱及其代谢产物进行分析,探讨了茶碱、代谢物及相关衍生物的质谱裂解行为,推测茶碱在人体内的代谢途径。尿样经Bond Elute C18小柱固相萃取,收集甲醇洗脱部分在50℃下氮气吹干,以N,N-二甲氨基氯乙烷为衍生试剂进行衍生化。以Shimpack C18为色谱柱、甲醇-水-甲酸(体积比20∶80∶1)为流动相,在正离子模式下对尿样中茶碱、代谢物及其衍生化产物进行LC-ESI/MSn分析。采用上述方法,共分析鉴定了人尿中的茶碱和4种代谢物(1-甲基尿酸、1,3-二甲基尿酸、1-甲基-N-乙酰化物、3-甲基黄嘌呤),其中1种代谢物未见文献报道。在正离子模式下,茶碱及代谢物的二级质谱大多丢失18 u,28 u或57 u片段生成一系列碎片离子,而衍生化产物的二级质谱均有规律地丢失45 u片段生成一系列碎片离子。通过与未经衍生化的尿样比较发现,衍生化可明显增强茶碱、1-甲基尿酸和3-甲基黄嘌呤的质谱检测灵敏度。本研究补充了茶碱在人体内的代谢轮廓,可为灵敏检测生物样本中茶碱、代谢物及其结构类似物提供借鉴。     

(±)-3,5-二羟基-7,4′-二甲氧基二氢黄酮醇和(±)-3,5,7-三羟基-4′- 甲氧基二氢黄酮醇全合成

二氢黄酮醇是植物界所产生的次生代谢产物[1],除抗菌活性外,它们被广泛应用于医药化工领域[2].3,5-二羟基-7,4′-二甲氧基二氢黄酮醇和3,5,7-三羟基-4′-甲氧基二氢黄酮醇从多种药用植物中分离得到[3,4].本文利用以2,4,6-三羟基苯乙酮和茴草醛为起始原料,经选择性保护、缩合、环氧化、关环首次完成了(±)1和(±)2的全合成.合成路线如图示1所示:     

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。