高效液相色谱-程序波长紫外检测法同时测定血浆中的色氨酸及其代谢物

建立了一种高效液相色谱-程序波长紫外检测法同时测定血浆中色氨酸(Trp)及其主要代谢产物犬尿氨酸(Kyn)和5-羟色胺(5-HT)。以茶碱为内标(IS),采用BDS-Hypersil-C8柱(150 mm×4.6 mm, 5 μm)分离。流动相为10 mmol/L醋酸钠缓冲液(pH 4.5)-乙腈(94:6, v/v),流速为0.6 mL/min;柱温为25 ℃;紫外检测波长设定: Kyn和IS为360 nm, 5-HT为220 nm, Trp为302 nm。3种物质的平均回收率为87%～113%;线性范围分别为3.97～400 μmol/L(Trp), 0.421～20.2 μmol/L(Kyn), 4.36～980 nmol/L(5-HT);检出限分别为0.134 μmol/L(Trp), 0.0160 μmol/L(Kyn), 2.03 nmol/L(5-HT)。利用该方法对15例抑郁症患者和15例健康志愿者的血浆进行测定,结果表明两组间Trp的代谢存在显著的差异。     

液相色谱-串联质谱法测定大鼠血浆中福斯克林

建立了测定大鼠血浆中福斯克林的液相色谱-串联质谱法(LC-MS/MS).血浆样品经液-液萃取后,以V(甲醇):V(10 mmol/L 醋酸铵):V(甲酸)=75:25:0.1为流动相,用Hypersil ODS柱分离,流速0.8 mL/min(柱后分流50%),通过电喷雾离子化四极杆串联质谱,以多反应监测方式(MRM)检测.用于定量分析的离子分别为m/z 428/375(福斯克林)和m/z 494/369(格列本脲,内标).福斯克林血浆浓度测定方法的线性范围为0.8～800 μg/L; 日内、日间精密度(RSD)均小于10%;准确度(RE)小于±9%.每个样品测试时间4.5 min.应用此法测试了大鼠口服或静注福斯克林后的血药浓度.     

柱切换-荧光检测反相高效液相色谱法测定血浆中特布他林浓度

采用柱切换技术 荧光检测反相高效液相色谱法测定血浆中特布他林 (TB)浓度。使用LunaC8( 2 )和KromasilC18为分析柱 ( 1 5 0mm× 4.6mm ,5 μm)和预处理柱 ( 2 5mm× 4.6mm ,5 μm) ,流动相分别为pH 3 0 ,0 .0 3 3mol/L磷酸盐缓冲液∶甲醇∶乙腈 ( 92∶7∶1 )和水∶甲醇∶乙腈 ( 97∶2∶1 ) ,流速均为 1 .0ml/L。血浆样品经乙腈沉淀蛋白后进样 ,切换时间为 3 .2～ 4.2min。荧光检测 ,λex为 2 80nm ,λem为 3 0 9nm。以沙丁胺醇作内标 ,按内标法定量。标准曲线线性范围为 0 .8～ 3 2 μg/L ;最低定量限为 0 .8μg/L;TB和内标的保留时间分别为 8.7和 9.3min;日内RSD小于 4% ,日间RSD小于 9% ,方法回收率在 93 %～ 1 1 2 %。     

高效液相色谱-质谱联用技术测定人血浆中的西替利嗪

建立了人血浆中西替利嗪的液相色谱-质谱联用测定方法.血浆样品调至pH 6,经V(乙酸乙酯):V(CH2Cl2)＝4:1液-液提取后,以Agilent Zorbax SB-C18(2.1 mm×150 mm i.d.,3.5 μm)柱为色谱柱,流动相为V(乙腈):V(1%甲酸水)＝55:45溶液,流速为0.5 mL/min,柱温:25 ℃,进样量:5 μL,在Agilent 1100 LC/MSD XCT离子阱质谱仪上,以多重反应离子(MRM)方式进行定量分析,用于监测的离子为m/z 389→201(西替利嗪)和m/z 515→497(替米沙坦,内标物).西替利嗪的检出限为0.50 μg/L(S/N=3),线性范围为2.5～400 μg/L,方法回收率在82.0%～86.7%之间(n=5),精密度与准确度符合生物样品分析要求.该法可用于西替利嗪临床血药浓度和药代动力学研究.     

气相色谱-质谱法测定包装材料中全氟辛酸及其盐类

快速溶剂萃取法萃取包装材料中的全氟辛酸(PFOA)及其盐类, 萃取液与乙酰化试剂反应后, 以全氟癸酸甲酯为内标物, 用内标法进行定量测定. 气相色谱质谱条件为: HP-Innowax毛细柱;柱温: 50 ℃ (5 min)30 ℃/min→240 ℃ (5 min);不分流进样;接口温度: 280 ℃;载气: 氦气, 0.8 mL/min;进样量: 1 μL;负化学源;反应气: 甲烷, 20%;选择离子扫描方式. 方法的线性范围1.0～105 μg/L, 线性相关系数r=0.999, 检出限0.1 μg/L, 不同浓度的PFOA的相对标准偏差分别为4.1%和3.2%, 回收率在87%～109%之间.     

离子色谱-等离子体质谱联用测定热泉水样的砷形态

利用阴离子色谱与六极碰撞等离子体质谱联用的方法,在线同时测定水样的4种砷形态(As(Ⅴ),As(Ⅲ),MMA,DMA),并用于实际样品-热泉水中砷形态的测定.使用K2HPO4-KH2PO4为淋洗液等度淋洗,用Hamilton PRP-X100阴离子色谱柱分离,4种砷形态在7 min之内完全分离.调节淋洗液中K2HPO4与KH2PO4的比例可以优化峰的分离.地下水(含热泉水)基质、样品及淋洗液中的Cl-对砷形态的分离测定没有影响,淋洗液中的盐份在样品锥和截取锥上的积累对测定的影响很小.检出限分别为As(Ⅴ) 0.23 μg/L,As(Ⅲ) 0.30 μg/L,MMA 0.26 μg/L,DMA 0.54 μg/L.     

分散液液微萃取-柱前衍生-高效液相色谱法测定水样中双酚A

建立了分散液液微萃取-柱前衍生-高效液相色谱法测定水样中双酚A的分析方法.通过交互正交试验和混合型优化实验设计对影响因素(萃取剂体积、分散剂类型及其体积、水样体积、pH值及离子强度)进行了优化.优化后的分散液液微萃取条件为:60 μL萃取剂,0.4 mL分散剂(甲醇),pH 4.0;优化后的柱前衍生化条件:0.1 mL 2.0 g/L衍生剂(对硝基苯甲酰氯)、衍生化时间30 min;方法的线性范围:0.002～0.2 mg/L(r=0.9997),检出限0.007 μg/L(S/N=3);不同浓度双酚A的萃取率为59.0%～63.0%,相对标准偏差(RSD)2.5%～9.2%(n=5);水样中双酚A的加标率为86.5%～107.1%,RSD为4.0%～11.9%(n=5),其它雌激素(雌酮、雌二醇、雌三醇和17α-乙炔基雌二醇)对双酚A的测定无干扰.本方法可以对水环境中的痕量BPA进行检测,具有操作简便、快速等优点.     

高效液相色谱-荧光检测法测定血清中的犬尿氨酸

建立了高效液相色谱-荧光检测(HPLC-FLD)测定血清中犬尿氨酸(kynurenine,Kyn)含量的方法。采用Hypersil C8色谱柱(300 mm×6.0 mm,10 μm), 流动相为0.25 mol/L醋酸锌及50 mmol/L醋酸溶液(含3%乙腈),流速为1.5 mL/min, 荧光检测激发波长和发射波长分别为365 nm和480 nm。血清标本经5%(v/v)高氯酸溶液去除蛋白质后取上层清液直接进样, Kyn经流动相等度洗脱分离后,用FLD进行测定。研究结果表明Kyn保留时间约为8.3 min,线性范围为0.098～19.6 μmol/L,最低检出浓度为0.04 μmol/L,回收率为90.8%～96.2%,日内、日间测定的相对标准偏差均小于5%,苯丙氨酸、酪氨酸、色氨酸、5-羟色胺和犬尿喹啉酸等物质对犬尿氨酸的测定均无干扰。建立的方法简便、快速、灵敏、特异,适用于临床和科研应用。     

离子色谱法同时测定离子液体中六氟磷酸根及痕量杂阴离子

建立了一种同时测定离子液体中六氟磷酸根(PF~6)和痕量杂阴离子氟、氯、溴(F~,Cl~,Br~)的离子色谱方法(IC)。样品经溶解、稀释、过滤后用Dionex IonPac AS22分离柱(250 mm×4 mm)分离,淋洗液为碳酸盐-乙腈体系(体积比为70:30),流速1.0 mL/min,采用Dionex DS6电导检测器检测,外标法定量。F~,Cl~,Br~和PF~6的线性范围分别为0.5～50 μg/L、10～200 μg/L、10～200 μg/L和0.9～45 mg/L,线性相关系数分别为0.9999,0.9998,0.9999和0.9998,加标回收率为94.5%～100.5%,相对标准偏差为0.63%～1.03%,检出限(以信噪比为3计)分别为0.5 μg/L、2.0 μg/L、5.0 μg/L和0.9 mg/L。该方法用于离子液体中六氟磷酸根和痕量杂阴离子的同时测定,结果令人满意。     

毛细管色谱法测定芳香异羟肟酸二丁基锡中有机溶剂残留量

建立了毛细管气相色谱法测定芳香异羟肟酸二丁基锡中的有机溶剂残留量.采用HP-5 (5%苯基甲基聚硅氧烷)毛细管色谱柱,FID检测器.载气为N2,柱温为45 ℃,检测器温度为160 ℃,流速为1.2 mL/min,分流比为20∶1,四氢呋喃为内标进行测定.结果表明: 甲醇、无水乙醇、三氯甲烷、正己烷、苯的线性范围分别为: 7.9～63.2 μg/mL (r=0.9991),8.69～69.52 μg/mL (r=0.9999),19.77～158.16 μg/mL (r=0.9990),295.6～2364.8 μg/mL (r=0.9996),8.74～69.92 μg/mL (r=0.9996),平均回收率分别为104.2%、 98.8%、 97.9%、 103.1%和102.0%,RSD分别为1.6%、 2.3%、 2.1%、 3.8%和1.9% (n=9);检出限分别为3.16、 3.47、 23.90、 1.97和0.87 ng.方法可用于有机溶剂残留量的测定.     

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.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。