硝西泮、氯硝西泮甲基衍生物的气相色谱-质谱分析

对硝西泮和氯硝西泮的衍生化条件、色谱及质谱行为进行了研究,确立了猪肉中硝西泮、氯硝西泮残留的GC-MS检测方法.应用5因素4水平的正交试验,最终确定衍生化条件为反应温度60℃、反应时间30 min、丙酮用量0.5 mL、衍生化试剂20μL、催化剂无水碳酸钾20mg,在此条件下可生成较完全的甲基衍生物.衍生物具有较好的气相色谱和电子轰击质谱行为.硝西泮衍生物的分子离子峰为m/z 295,基峰离子为m/z 267,主要碎片离子分别为m/z 206、220、248、294;氯硝西泮衍生物的分子离子峰为m/z 329,基峰离子为m/z 328,主要碎片离子分别为m/z205、220、248、266、294、331,并对这些离子的产生进行了解析.这些离子均具有较强的相对丰度,可作为其微量检测的多离子选择定性和确证,而基峰离子可用于单离子选择定量.用乙腈提取药物,C18固相萃取柱净化,GC-MS分析.本方法采用外标法定量,两种药物的标准曲线线性回归系数均在0.99以上,线性范围20～500 μg/L,回收率80%左右,相对标准偏差6.9%～14.9%,检出限16.7 μg/kg.     

尿中氯硝西泮代谢物7-氨基氯硝西泮的薄层色谱检测法

采用高效薄层色谱法检测尿中氯硝西泮代谢物7－氨基氯硝西泮（7ACLZ），分析物斑点用弗路兰进行荧光显现，灵敏度高，检出限5μg/L，定量下限15μg/L，可以检测人口服2mg氯硝西泮后48h内排泄尿的7ACLZ,适用于麻醉抢劫犯罪案件中药物检测。     

自动固相萃取-液相色谱-串联质谱法同时测定血液中5种抗抑郁类药物

建立了血液中5种抗抑郁类药物的自动固相萃取-液相色谱-串联质谱(ASPE-LC-MS/MS)分析方法。样品经HLB固相萃取柱提取后,采用LC-MS/MS进行测定,外标法定量。在Waters AtlantisTM dC18反相柱上分离,梯度洗脱,流动相为甲醇-0.1%甲酸(1∶4,V/V)溶液,质谱采集为电喷雾正离子多反应监测模式。采用基质匹配标准溶液校正,5种目标物在1~500μg/L范围内具有良好的线性关系,相关系数(R)大于0.9975,检出限在0.1~0.6μg/L之间;添加浓度水平为10,100和500μg/L时,方法回收率为70.6%~93.8%,相对标准偏差在3.9%~9.2%之间。本方法可用于血液中5种抗抑郁类药物的法庭与临床毒物分析。     

固相萃取/~(18)O标记高氯酸根稀释高效液相色谱-串联质谱法测定水果中的高氯酸盐

建立了水果中高氯酸盐的高效液相色谱-串联质谱分析检测方法。样品采用1%乙酸提取,C18固相萃取柱净化,Waters IC-Pak Anion HR(4.6 mm×75 mm)色谱柱洗脱,流动相为乙腈-100 mmol/L乙酸铵溶液(体积比60∶40),流速0.7 m L/min;液相色谱-三重四极杆质谱联用技术-电喷雾负离子监测模式检测,采用18O标记高氯酸根离子作为内标进行基质校正,内标法定量。结果表明:高氯酸盐在0.1~10.0μg/L范围内线性关系良好,定量下限为1.0μg/kg;在1.0,2.0,10μg/kg 3个加标水平下的回收率为92.5%~110%,相对标准偏差(RSD)为1.4%~5.4%。实际样品检测表明该方法准确可靠,适合于水果中高氯酸盐的测定。     

超高效液相色谱-串联质谱法测定食品包装纸中的酚类化合物

建立了食品包装纸中2,4,6-三氯酚、五氯酚、4-氯-3,5-二甲基-苯酚和4-叔-辛基酚的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法。样品经丙酮超声萃取,Oasis HLB固相柱净化后,用Waters AC-QUITY UPLC C18柱以乙腈和0.05%氨水为流动相进行分离,以负离子模式离子化,在多离子反应监测(MRM)模式下定量检测。在优化实验条件下,2,4,6-三氯酚的线性范围为20~1 000μg.L-1,五氯酚、4-氯-3,5-二甲基-苯酚和4-叔-辛基酚的线性范围为5~1 000μg.L-1,相关系数均大于0.997。4种酚类化合物的检出限为1~10μg.kg-1,定量下限为5~20μg.kg-1,加标回收率为75%~109%,相对标准偏差均不高于12.5%。该方法灵敏度高、操作简单,可用于食品包装纸中酚类化合物含量的快速检测。     

离子色谱-质谱联用法同时测定饮用水中3种痕量一氯酚

建立了一种新型、灵敏、准确的同时测定饮用水中2-氯酚、3-氯酚和4-氯酚的离子色谱-质谱联用检测方法。饮用水样经固相萃取小柱富集、净化后,在IonPac(AS18阴离子交换色谱柱(250 mm×4.0 mm)及IonPac(AG18预柱(50 mm×4.0 mm)上,以含有10%乙腈的15 mmol/L KOH溶液为淋洗液,采用大气压化学电离源(APC I)在选择离子监测(SIM)模式下进行检测,定量检测离子为m/z127[M-H]-,其日内与日间精密度分别小于8.6%和10.5%;2-氯酚、3-氯酚和4-氯酚在0.02~5.0μg/L范围均具有良好的线性;水样中2-氯酚、3-氯酚和4-氯酚的最低定量检出限分别为0.02μg/L、0.01μg/L和0.01μg/L。用于饮用水中一氯酚的测定,结果满意。     

血、尿中氯硝西泮及其代谢物7-氨基氯硝西泮的GC-ECD法检测

报道了血、尿中氯硝西泮及其代谢物7－氨基氯硝西泮的GC－ECD检测方法。苯－异戊醇碱性条件下（pH10.8）液－液萃取，灵敏度较高，氯硝西泮和7－氨基氯硝西泮的检测限（LOD）分别为3．2ng/mL及1．7ng/mL。线性范围5－300ng/mL，RSD5．3％。     

固相萃取-超高压液相色谱-串联质谱测定水中19种抗生素

应用固相萃取(SPE)及液相色谱-串联质谱(LC-MS/MS)技术,建立了水中痕量(ng/L)四环素类、磺胺类、大环内酯类、喹诺酮类和β-内酰胺类5类共19种抗生素的同时定量检测方法。水样通过HLB萃取小柱富集后,以C18反相色谱柱为分析柱,乙腈-0.1%甲酸溶液为流动相,采用LC-MS/MS进行定量分析。选择电喷雾正电离源(ESI+),多反应监测模式(MRM),内标法定量。19种抗生素在0.5~1 000μg/L范围内均具有良好的线性关系,方法的定量下限(S/N=10,1 000倍浓缩)为0.1~0.5 ng/L。以纯水和河水(黄浦江水)作为基底,13C-咖啡因为内标物,加标质量浓度为20、100 ng/L时,抗生素的平均加标回收率分别为75%~125%和77%~132%,相对标准偏差(RSD)分别为1.7%~6.9%和0.9%~6.5%,表明所建立的测试方法准确可靠。研究结果表明,黄浦江水受到了抗生素污染,共检出15种抗生素,检出的四环素类、磺胺类、大环内酯类、喹诺酮类及β-内酰胺类抗生素污染质量浓度分别为13.0~56.9、12.2~103.4、53.8~84.8、3.1~26.2、16.5~181.6 ng/L。     

超高效液相色谱-串联质谱法测定环境样品中溴嘧氯草醚残留及其在土壤中降解特性的研究

建立了超高效液相色谱-串联质谱法(UPLC-MS/MS)测定土壤、沉积物和水中溴嘧氯草醚残留量的方法,研究了溴嘧氯草醚在3种不同类型土壤中的降解特性.样品经乙腈提取后,以C18固相萃取柱净化,采用梯度洗脱程序、BEH C18色谱分离柱、应用UPLC-MS/MS多反应监测模式测定溴嘧氯草醚.对0.005、0.05和2.0 mg/kg添加浓度样品进行回收实验,溴嘧氯草醚在土壤、沉积物和水中的平均回收率为87%~106%,变异系数为2.8%~8.0%.溴嘧氯草醚在0.5~20μg/L浓度范围内相关系数R2>0.9999,溴嘧氯草醚在土壤(沉积物)和水中的定量限分别为0.2μg/kg和0.2μg/L.应用建立的溴嘧氯草醚残留分析方法检测了土壤降解样品,结果表明,溴嘧氯草醚在3种不同土壤中好氧降解的半衰期为1.72~28.2 d,厌氧降解的半衰期为2.93~31.4 d;在同一种土壤样品中,好氧条件下溴嘧氯草醚降解快于厌氧条件;土壤中溴嘧氯草醚降解的快慢与土壤的pH值、阳离子交换量和土壤质地有关.     

固相萃取/液相色谱-串联质谱法测定果蔬中草铵膦的残留量

建立了果蔬中草铵膦残留量的液相色谱-串联质谱(LC-MS/MS)分析方法。样品经水提取、二氯甲烷除去脂溶性杂质,强阳离子固相萃取小柱净化,9-芴甲基氯甲酸酯(FMOC-Cl)衍生后,以C18色谱柱(4.6 mm×50 mm,1.8μm)进行分离,5 mmol/L乙酸铵水溶液(含0.1%甲酸)-乙腈(含0.1%甲酸)作为流动相梯度洗脱,电喷雾正离子模式电离(ESI+),多反应监测模式(MRM)检测,内标法定量。方法在0~200μg/L浓度范围内线性关系良好,相关系数(r2)大于0.995。方法检出限为10μg/kg,定量下限为20μg/kg。在不同食品基质中,草铵膦在20,200,500μg/kg加标水平下的平均回收率为80.8%~102.2%,相对标准偏差(RSD)为1.8%~7.9%。该法采用同位素内标定量,有效地消除了样品基质效应,灵敏度高、准确度好,适用于果蔬中草铵膦残留量的监控测定。     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

钒与糖代谢及糖尿病

微量元素钒作为生物体内必需元素，经证实有很重要的生理学功能，与机体糖代谢有十分密切的关系，且能降低糖尿病动物模型的高血糖，极有可能被开发为治疗糖尿病的药物。     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Synthesis of Tyrosol and Hydroxytyrosol Glycofuranosides and Their Biochemical and Biological Activities in Cell-Free and Cellular Assays

Tyrosol (T) and hydroxytyrosol (HOT) and their glycosides are promising candidates for applications in functional food products or in complementary therapy. A series of phenylethanoid glycofuranosides (PEGFs) were synthesized to compare some of their biochemical and biological activities with T and HOT. The optimization of glycosylation promoted by environmentally benign basic zinc carbonate was performed to prepare HOT α-L-arabino-, β-D-apio-, and β-D-ribofuranosides. T and HOT β-D-fructofuranosides, prepared by enzymatic transfructosylation of T and HOT, were also included in the comparative study. The antioxidant capacity and DNA-protective potential of T, HOT, and PEGFs on plasmid DNA were determined using cell-free assays. The DNA-damaging potential of the studied compounds for human hepatoma HepG2 cells and their DNA-protective potential on HepG2 cells against hydrogen peroxide were evaluated using the comet assay. Experiments revealed a spectrum of different activities of the studied compounds. HOT and HOT β-D-fructofuranoside appear to be the best-performing scavengers and protectants of plasmid DNA and HepG2 cells. T and T β-D-fructofuranoside display almost zero or low scavenging/antioxidant activity and protective effects on plasmid DNA or HepG2 cells. The results imply that especially HOT β-D-fructofuranoside and β-D-apiofuranoside could be considered as prospective molecules for the subsequent design of supplements with potential in food and health protection.     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.