分子烙印固相萃取-毛细管电泳法分析大米中神经性毒剂降解产物

采用自分子烙印聚合物－固相萃柱来分离净化实际样品大米中的神经性毒剂降解产物,并用毛细管电泳法进行检测,方便简便,准确,灵敏度高。在0．2－5．0μg/g浓度范围内,大米样品中5种神经性毒剂降解产物的标准回归曲线线性关系良好,检出限为0.05μg/g,方法的RSD小于6．20％。     

《分析化学》第34卷总目录

目次研究报告纳升电喷雾串联质谱“序列对接法”确定多肽的加钠位点………………………………………吴胜明王杰刘炳玉王鸿丽魏开华*张学敏杨松成(1)(1)阴离子交换固相萃取-气相色谱/质谱法分析人血浆中6种神经性毒剂降解产物……………………………………………………………………王清清*顾明松冯建林阮金秀(1)(5)电位滴定法研究多胺铕铽络合物稳定性及其对磷酸二酯键水解断裂………………上官国强曲晓刚*(1)(10)高分辨气相色谱/高分辨质谱联用测定大气降尘中的二英………………………………………任曼*彭平安张素坤余莉萍麦碧娴盛国英傅…     

高效液相色谱法同时测定婴幼儿配方乳粉中5种游离核苷酸

建立了婴幼儿配方乳粉中5种游离核苷酸的准确测定方法。采用等电点沉淀蛋白,强阴离子交换固相萃取柱净化,Atlantis T3色谱柱分离,二极管阵列检测器检测,外标法定量。结果表明:5种核苷酸在0.1~100μg/m L范围内线性关系良好(r≥0.999),平均回收率为95.2%~103%,相对标准偏差均小于4.5%。方法可为企业质量控制和政府监管提供有力的技术支撑。     

尿样中神经性毒剂代谢产物的HPLC/Q-TOFMS/MS检测方法研究

建立了尿样中甲基膦酸单乙酯(EMPA)、甲基膦酸单异丙酯(IMPA)、甲基膦酸频哪基酯(PMPA)3种神经性毒剂代谢产物的HPLC/Q-TOFMS/MS检测方法。以StrataSi-1型固相萃取小柱对尿样中的3种神经性毒剂代谢产物进行分离,HPLC/Q-TOFESIMS/MS进行测定,内标法定量。该方法对EMPA、IMPA、PMPA的线性范围均为5～320μg/L,相关系数均不低于0.9974;EMPA、IMPA、PMPA的加标回收率分别为57%、98%、81%;检出限(S/N≥3)均为0.1μg/L,定量下限(S/N≥10)均为1μg/L。并将该方法应用于禁化武组织(OPCW)首次生物医学样品分析演练未知尿样的检测,结果满意。     

液相色谱串联四极杆质谱法同时测定婴幼儿配方食品中甲基香兰素和乙基香兰素

建立了混合阴离子交换固相萃取柱净化,液相色谱串联四极杆质谱法测定婴幼儿配方食品中甲基香兰素和乙基香兰素的方法.样品经水和乙腈提取,CuSO4溶液沉淀蛋白,NaOH调节pH,增加样品溶解性,阴离子交换固相萃取柱净化.目标化合物在梯度洗脱条件下经C18柱分离后采用ESI源负离子多反应监测模式进行检测.分别选取了婴幼儿配方乳...     

液相色谱法分析烟叶酸性洗涤纤维素的碱性氧化铜降解产物

应用石油醚-乙醇(6 : 4, v/v)、30 g/L十二烷基硫酸钠溶液以及含20 g/L十六烷基三甲基溴化铵的0.5 mol/L硫酸溶液依次处理烟叶样品,制备得到烟叶酸性洗涤纤维素(ADF)。采用碱性氧化铜氧化降解方法制备得到ADF降解产物。以Ultimate XB C18色谱柱为固定相,甲醇和水为流动相,梯度洗脱,在柱温35 ℃、流速0.8 mL/min、检测波长280 nm和320 nm条件下,对6种烟叶样品的ADF降解产物进行了液相色谱分离,得到4个特征色谱峰。以这4个特征色谱峰为考察对象,可研究不同烟叶木质素组成的差异及其与烟叶吸味品质的关系。     

沙土中5种神经性毒剂降解产物的实时直接分析-质谱法快速检测

建立了实时直接分析离子源-质谱（DART-MS）快速检测沙土中5种神经性毒剂降解产物的方法。方法在0.03～10 mg/L范围内线性关系良好，检出限为0.03～0.1 mg/kg, 5种神经性毒剂降解产物在沙土中的回收率均不低于71.8%，相对标准偏差（RSD）不超过11%。利用建立的DART-MS定性方法分析了禁止化学武器组织（OPCW）的PT48次环境样品水平考试盲样样品，根据获得的母离子和碎片离子的高分辨质谱（HRMS）数据及MS/HRMS质谱碎裂特征，鉴定出所有适合DART-MS分析的化学毒剂相关化合物，与OPCW发布的配样清单一致。     

液相色谱法分析烟叶酸性洗涤纤维素的碱性氧化铜降解产物北大核心CSCD

应用石油醚-乙醇(6∶4,v/v)、30 g/L十二烷基硫酸钠溶液以及含20 g/L十六烷基三甲基溴化铵的0.5mol/L硫酸溶液依次处理烟叶样品,制备得到烟叶酸性洗涤纤维素(ADF)。采用碱性氧化铜氧化降解方法制备得到ADF降解产物。以Ultimate XB C18色谱柱为固定相,甲醇和水为流动相,梯度洗脱,在柱温35℃、流速0.8mL/min、检测波长280 nm和320 nm条件下,对6种烟叶样品的ADF降解产物进行了液相色谱分离,得到4个特征色谱峰。以这4个特征色谱峰为考察对象,可研究不同烟叶木质素组成的差异及其与烟叶吸味品质的关系。     

固相萃取-液相串联质谱测定人血浆中安妥沙星的药物浓度

建立了专属性更高的固相萃取(SPE)-高效液相三重四级杆质谱(LC-MS/MS)测定人血浆中安妥沙星的方法。血浆样品经弱阴离子固相萃取柱净化后,洗脱吹干,复溶后进行检测。采用Agilent Eclipse plusC8色谱柱,流动相为10mmol/L乙酸铵(pH 3.5)-甲醇(35∶65,V/V),流速为0.35mL/min,选择离子检测,线性范围为7.0～5080μg/L,R>0.996,检出限0.5μg/L,绝对回收率>77.6%,日间相对标准偏差<7.9%。将本方法用于受试者给药后的血药浓度测定,结果满意。     

阴离子交换色谱-积分脉冲安培检测法测定寿胎丸中游离氨基酸

建立了阴离子交换色谱-积分脉冲安培检测法测定寿胎丸煎煮液中游离氨基酸的分析方法。实验考察了18种氨基酸的梯度洗脱条件,优化了固相萃取条件,最终选用SSDBX型固相萃取小柱净化煎煮液。在优化实验条件下,进行了加标回收实验,回收率在71.2%~120.9%之间,相对标准偏差为0.8%~10.4%。18种氨基酸的检测限为0.07~5.00μg/L。方法能满足寿胎丸煎煮液中氨基酸的检测要求。     

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。