离子色谱法测定皂粒中葡萄糖酸钠含量

建立了离子色谱检测皂粒中葡萄糖酸钠含量的分析方法。样品经METROSEP CARB 1糖分析色谱柱(150 mm×4.0 mm,5μm)分离,以150 mmol·L~(-1) NaOH+20 mmol·L~(-1)NaAc水溶液为流动相进行等度洗脱,流速1.0 mL·min~(-1),采用瑞士万通850型离子色谱仪,选择脉冲安培检测器进行测定,外标法定量。结果显示:葡萄糖酸钠在0.5～200 mg·L~(-1)质量浓度范围内呈良好的线性,相关系数(r~2)为0.999 6,检出限为0.25 mg·L~(-1),定量下限为0.63 mg·L~(-1)。葡萄糖酸钠在1～20 mg/g加标范围内的回收率为80.7%～104%。该方法无需衍生化处理,操作简单方便,灵敏度高,可用于皂粒产线葡萄糖酸钠含量的监控与测定。     

高效液相色谱-质谱法测定尿液中痕量雷公藤春碱

提出了尿液中雷公藤春碱的高效液相色谱-质谱测定方法。尿液样品经Waters Oasis(MCX固相萃取小柱富集、净化后,以Zorbax Eclipse SB C18反相色谱柱(4.6 mm×250 mm,5μm)为分离柱,以乙酸盐缓冲溶液-乙腈(40+60)为流动相,采用正离子模式大气压化学电离源,在选择离子监测模式下进行检测,雷公藤春碱的定量离子质荷比(m/z)为874.4。线性范围为0.2~50.0μg·L-1,检出限(3S/N)为0.07μg·L-1,测定下限(10S/N)为0.2μg·L-1。回收率在86.0%~92.0%之间,日内(n=6)和日间(n=15)相对标准偏差分别小于7.5%和10.5%。     

亲水作用色谱法同时测定食品添加剂中D-异抗坏血酸、L-抗坏血酸和二氧化硫脲

食品添加剂样品用含1%(体积分数,下同)甲酸的100mmol·L~(-1)甲酸铵溶液溶解,经乙腈稀释后,用0.22μm微孔滤膜过滤,采用亲水作用色谱法同时测定滤液中D-异抗坏血酸、L-抗坏血酸和二氧化硫脲的含量。以InfinityLab Poroshell 120HILIC-Z色谱柱(3.0mm×100mm,2.7μm)为固定相,以含1%甲酸的100mmol·L~(-1)甲酸铵溶液和乙腈以体积比15∶85组成的混合液为流动相,用二极管阵列检测器测定。D-异抗坏血酸、L-抗坏血酸和二氧化硫脲的质量浓度均在1.0～100mg·L~(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)均为1.0%。以空白样品为基体进行加标回收试验,所得回收率为94.7%～108%,测定值的相对标准偏差(n=6)小于8.0%。     

超高效液相色谱-串联质谱法快速测定植物油中黄曲霉毒素B1

2.500g植物油样品用10 mL甲醇(7+3)溶液提取,以6 000r·min~(-1)转速离心10min,在-20℃冷冻30min后,上清液经0.22μm有机滤膜过滤,采用超高效液相色谱-串联质谱法快速测定滤液中黄曲霉毒素B_1的含量。以Accucore aQ色谱柱为固定相,以不同体积比的含5mmol·L~(-1)乙酸铵的0.1%(体积分数)甲酸溶液和甲醇的混合液为流动相进行梯度洗脱,串联质谱分析中采用电喷雾正离子源和选择离子监测模式。黄曲霉毒素B_1的质量浓度在0.50～10.00μg·L~(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)为0.02μg·kg~(-1)。以空白样品为基体进行加标回收试验,所得回收率为86.0%～96.6%,回收量的相对标准偏差(n=6)为5.6%～8.4%。     

高效液相色谱法同时测定化工废水中乙醇酸、乙醛酸和草酸的含量

水样经0.22μm亲水针筒式过滤器过滤,根据需要进行稀释后,在Acclaim MixedMode WAX-1色谱柱(4.6mm×150mm,5μm)上进行分离,以90mmol·L~(-1)磷酸盐缓冲溶液[pH 6.0,溶剂为10%(体积分数)乙腈溶液]为流动相进行等度洗脱,在波长210nm处进行紫外检测。结果表明:乙醇酸、乙醛酸和草酸的质量浓度分别在3.51～2 500,4.20～8 000,18.0～800mg·L~(-1)内与对应的峰面积呈现线性关系,检出限(3S/N)分别为1.00,1.24,4.82mg·L~(-1),测定下限(10S/N)分别为3.32,4.15,16.1mg·L~(-1)。对实际样品进行加标回收试验,乙醇酸、乙醛酸和草酸的回收率分别在98.2%～101%,99.6%～103%,99.2%～101%之间,测定值的相对标准偏差(n=6)分别为0.77%,0.65%,1.1%。     

聚乙二醇/无机盐双水相萃取-超高效液相色谱-串联质谱法测定环境水体中5种三嗪类除草剂残留量

移取10.0mL环境水体样品,加入0.90g聚乙二醇-2000,超声溶解后,加入3.25g硫酸铵,超声萃取10min,离心后移取上层萃取相50μL,用流动相稀释至200μL,经0.22μm有机滤膜过滤,采用超高效液相色谱-串联质谱法测定滤液中5种三嗪类除草剂的残留量。以Zorbax Eclipse XDB-C_(18)色谱柱为固定相,以乙腈(7+3)溶液为流动相,串联质谱分析中采用电喷雾正离子源和选择离子监测模式。5种三嗪类除草剂的质量浓度均在0.100～10.00μg·L~(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)为3.72～24.3ng·L~(-1)。方法用于环境水体样品的分析,加标回收率为80.8%～115%,测定值的相对标准偏差(n=5)为0.17%～6.4%。     

超高效液相色谱-串联质谱法测定血液中20种常见毒品

血液样品用乙腈提取,再以8 000r·min-1转速离心10min,取上清液,经0.22μm有机滤膜过滤,采用超高效液相色谱-串联质谱法测定滤液中20种常见毒品的含量。以ACQUITY UPLC HSS C18色谱柱为固定相,以不同体积比的乙腈和pH 3.0的5mmol·L~(-1)甲酸铵溶液的混合液为流动相进行梯度洗脱,串联质谱分析中采用电喷雾正离子源和多反应监测模式。20种毒品的质量浓度均在10.0～100μg·L~(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)为0.10～5.00μg·L~(-1)。以空白样品为基体进行加标回收试验,所得回收率为42.3%～113%,测定值的日内相对标准偏差(n=5)为0.050%～15%,日间相对标准偏差(n=3)为2.1%～15%。     

亲水作用色谱-串联质谱法测定茶叶中 γ-氨基丁酸和茶氨酸

粉碎后的茶叶样品用水在90℃水浴中提取10min(重复提取3次),提取液合并后,用水定容至50mL,移取1.00mL过0.22μm滤膜,采用亲水作用色谱-串联质谱法测定滤液中γ-氨基丁酸和茶氨酸的含量。以Waters Atlantis HILIC氨基色谱柱为固定相,以不同体积比的水和乙腈(9+1)溶液(含2mmol·L~(-1)乙酸铵和体积分数为0.1%的甲酸)的混合液为流动相进行梯度洗脱,串联质谱分析中采用电喷雾正离子模式和多反应监测模式。γ-氨基丁酸和茶氨酸的质量浓度均在5.00～500.00μg·L~(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)依次为1.00,0.50μg·L~(-1)。方法用于茶叶样品的分析,加标回收率为97.8%～107%,测定值的相对标准偏差(n=9)为4.9%～7.1%。     

奶粉中高氯酸盐的液相色谱-串联质谱测定

建立了奶粉中高氯酸盐的液相色谱-串联质谱(LC-MS/MS)测定方法.奶粉样品用水-乙腈(体积比1:2)超声波振荡提取2次,于4 000 r/min离心后,上清液经Oasis HLB固相萃取小柱净化;采用离子交换色谱分离,色谱柱为METROSEP A Supp 5(150 mm×4.0 mm)阴离子交换柱,流动相为0.2 mol/L乙酸铵溶液-乙腈(体积比1 : 1),流速0.7 mL/min;电喷雾负离子模式电离,质谱多反应选择离子检测(MRM),检测离子对为 m/z 99→83和m/z 101→85,其中m/z 99→83为定量离子对.方法的相对标准偏差为3.59%,回收率为91% ～106%,检出限为1.0 μg/kg,定量下限为5.0 μg/kg.结果表明,该法简便快速、准确可靠,也适用于鲜牛奶、酸牛奶等其他乳制品中高氯酸盐的测定.     

高效液相亲水作用色谱-串联质谱法同时测定婴幼儿配方乳粉中胆碱和左旋肉碱的含量

称取乳粉样品1.000g,加入1.0mol·L~(-1)的盐酸溶液25mL,涡旋混匀5min,于70℃水浴中水解3h(每隔30min振摇混匀一次),冷却后加入20mL乙醚,涡旋振荡30s,然后于4℃下以6 000r·min~(-1)冷冻离心10min。取上清液0.10mL,加入1mol·L~(-1)的乙酸铵溶液50μL,用水定容至10.0 mL,涡旋混匀,吸取1～2 mL上清液,经0.22μm水系针式滤膜过滤后,采用Hypersil GOLDTMAQ色谱柱(2.1mm×100mm,1.9μm)分离,以乙腈-乙酸铵溶液为流动相进行梯度洗脱。质谱选择电喷雾正离子源和多反应监测模式。胆碱和左旋肉碱的质量浓度分别在0.05～1.0mg·L~(-1),0.01～0.20mg·L~(-1)内与其定量离子峰面积呈线性关系,检出限(3S/N)分别为0.003,0.005mg·kg~(-1)。方法用于测定质控样品中的胆碱和左旋肉碱,测定值与认定值的相对误差在10%以内。采用本方法测定婴幼儿配方乳粉样品中的胆碱和左旋肉碱,测定结果和国家标准方法的测定结果相符,测定值的相对标准偏差(n=6)小于9.0%     

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.     

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。     

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^-。     

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.     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。