离子液体中卤素离子杂质的离子色谱-直接电导检测法分析

研究了离子色谱-直接电导检测法分离测定离子液体中的卤素离子(F~-、Cl~-、Br~-)杂质.采用Shim-pack IC-A3阴离子交换色谱柱,考察了淋洗液种类及浓度、流速和色谱柱温度对分离测定的影响.最佳色谱条件为:以1.25 mmol/L邻苯二甲酸氢钾为淋洗液,流速1.5 mL/min,色谱柱温45 ℃.在此条件下可以基线分离卤素离子,且NO~-_3、BF~-_4、SO~(2-)_4不干扰测定.该法测定卤素离子的检出限(S/N=3)为0.02 ～0.11 mg/L,峰面积的相对标准偏差(n=5)不大于0.7%,F~-、Cl~- 和Br~- 的标准曲线的线性范围分别为0.1 ～50、0.1 ～50、0.5 ～100 mg/L.将方法用于烷基咪唑四氟硼酸盐离子液体中卤素离子杂质的测定,加标回收率为98% ～102%.     

高效液相色谱-脉冲积分安培电化学检测牛奶中的妥布霉素

采用C18键合硅胶柱和脉冲积分安培电化学检测器对妥布霉素样品进行了分离检测。对两种检测电位波形进行了对比，并选取了表现优良的检测电位。方法对妥布霉素的检出限19μg／L，在0．1～25mg／L范围内表现良好线性（r=0．9999）。该方法应用于市售鲜奶的检测，妥布霉素的回收率为98％。     

高效阴离子交换色谱-铜/铂修饰电极安培法测定大观霉素

采用阴离子交换色谱分离,在CuSO4溶液中加入少量镧系化合物,经电沉积制备La3+-Cu/pt/CME工作电极,建立了直流安培电化学法(DC)直接检测硫酸大观霉素的方法。考察了流动相浓度、测定电位等参数对色谱分离和测定的影响。在固定相为CarboPac PA10阴离子交换柱、流动相为26mmol/L NaOH,流速为0.6mL/min的色谱条件下,检测电位为0.68V时,硫酸大观霉素峰面积与其浓度在0.12～12mg/L(r=0.9991)和12～280mg/L(r=0.9995)两个范围内呈线性。本方法不需要柱前和柱后衍生化,能同时测定硫酸大观霉素中的主要组分和杂质。修饰电极制作方法简单,催化稳定性好,可作为电化学传感器测定硫酸大观霉素中的各组分。     

N-溴代琥珀酰亚胺-荧光素体系流动注射能量转移化学发光法测定妥布霉素

在碱性条件下,N-溴代琥珀酰亚胺(NBS)氧化妥布霉素,在荧光素增敏作用下发生化学发光。基于此,结合流动注射技术,建立了测定痕量妥布霉素的流动注射化学发光分析法。在优化的实验条件下,体系对妥布霉素的测定线性范围为0．2—100mg／L;检出限(3σ)为0．07mg／L;对5．0mg／L妥布霉素进行11次平行测定,其相对标准偏差为2．1％。将本法用于制剂和血样中妥布霉素的分析,结果令人满意。     

高效阴离子交换色谱法检测酱油中的单糖及双糖

建立了高效阴离子交换色谱-脉冲安培检测法(HPAEC-PAD)测定酱油中阿拉伯糖、半乳糖、葡萄糖、蔗糖、木糖、甘露糖和果糖的方法.采用70％乙醇作为蛋白沉淀剂处理酱油样品,以Dionex CarboPac PA20阴离子交换柱为色谱柱,0.25 mol/L NaOH-水为流动相进行梯度洗脱,考察了色谱柱温度和NaOH浓度对各种糖分离的影响,确定最佳柱温为20℃,NaOH浓度为5.0 mmol/L,7种糖可在20 min内实现基线分离.7种糖的检出限(25 μL进样,S/N=3)为2.0～8.0 μg/L,线性范围为0.1～80 mg/L,r2大于0.999.酱油样品测定的相对标准偏差为1.4％～4.0％,加标回收率为92％～104％.该方法简便易行,灵敏度高,重现性好,适用于酱油样品中糖组分的分析.     

Determination of Ammonia in Water-borne Adhesives by Ion Chromatography

建立了一种离子色谱电导检测法测定水基胶黏剂中氨残留的方法.样品经10 mmol/L盐酸水溶液振荡、离心、过滤提取后,采用阳离子交换色谱柱分离和电导检测.在优化实验条件下,样品中的氨在0.05～2.0 mg/L范围内呈良好的线性关系(r2=0.9998),加标回收率在93％～ 102％之间,相对标准偏差不高于4.3％,检出限(S/N=3)为0.007 mg/L,定量下限(S/N=10)为0.024 mg/L.结果表明该方法能够达到定量检测的目的.将该方法用于实际样品检测,结果可靠.通过对氨的稳定性实验发现,处理好的样品宜在12 h内测定.     

固相萃取–离子色谱法测定人尿液中钙、镁、氟、磷酸根离子

建立固相萃取–离子色谱法测定人尿液中钙、镁两种阳离子和氟、磷酸根两种阴离子。采用C₁₈固相萃取柱去除样品中杂质以消除干扰,以CS12 A型阳离子交换柱为分离柱,以甲基磺酸溶液为淋洗液,等度洗脱,测定钙、镁离子;以AS15型阴离子交换柱为分离柱,以KOH溶液为淋洗液,梯度洗脱,测定氟、磷酸根离子。钙、镁离子的质量浓度在0.25～10 mg/L范围内,氟、磷酸根离子的质量浓度分别在0.002 5～0.05 mg/L、1.25～50 mg/L范围内与色谱峰面积具有良好的线性关系,相关系数均大于0.999 0,方法检出限为0.002～0.2 mg/L。样品加标回收率为86.0%～99.5%,测定结果的相对标准偏差为0.12%～5.50%(n=6)。该方法操作简便,灵敏度高。     

离子色谱-直接电导检测法测定离子液体的阴离子p-甲苯磺酸根

建立了离子液体阴离子p-甲苯磺酸根的离子色谱-直接电导检测分析方法。采用Shim-pack IC-A3季铵型阴离子交换色谱柱,考察了流动相种类和色谱柱温度对分离测定p-甲苯磺酸根的影响。确定最佳色谱条件为:以1.2 mmol/L柠檬酸-15%乙腈混合水溶液(pH 5.0)为流动相,流速1.0 mL/min,柱温45℃。在此条件下,p-甲苯磺酸根与常见无机阴离子(氟离子、氯离子、溴离子和硝酸根)可以获得很好的分离。该方法测定p-甲苯磺酸根的线性范围为4～100 mg/L,检出限(S/N=3)为1.22 mg/L,保留时间和峰面积的相对标准偏差(n=5)分别为0.42%和1.8%。将方法用于离子液体中p-甲苯磺酸根的测定,加标回收率为99.6%。     

六氟磷酸根的离子色谱-直接电导检测法分析

研究了离子色谱-直接电导检测法分离测定六氟磷酸根,采用Shim-pack IC-A3阴离子交换色谱柱,以苯甲酸为淋洗液,考察了淋洗液种类、浓度及pH值、色谱柱温度对分离测定六氟磷酸根的影响.最佳色谱条件为:以pH 7.5的1.0 mmol/L苯甲酸为淋洗液,流速1.0 mL/min,色谱柱温40 ℃.在此条件下,PF-6的保留时间为12 min.该法测定六氟磷酸根的检出限(S/N=2)为9.2 mg/L,标准曲线的线性范围为20.0 ～200.0 mg/L,保留时间和峰面积的相对标准偏差(n=5)分别为0.2%和0.6%.方法用于测定离子液体中的六氟磷酸根,加标回收率为98% ～100%.     

高效液相色谱-串联质谱法检测乳制品中10种氨基糖苷类抗生素残留

建立了乳制品中链霉素、双氢链霉素、新霉素、卡那霉素、妥布霉素、庆大霉素、安普霉素、潮霉素B、巴龙霉素、阿米卡星等10种氨基糖苷类抗生素(aminoglycosides, AGs)残留的高效液相色谱-串联质谱(HPLC-MS/MS)检测方法。乳制品提取液经亲水-亲脂平衡(hydrophilic- lipophilic balance, HLB)柱净化后,采用反相离子对高效液相色谱分离,电喷雾串联四极杆质谱检测。对样品前处理条件、液相色谱流动相以及质谱条件进行了优化。结果表明: 10种AGs在20～1000 μg/L范围内定量离子的峰面积和样品的质量浓度之间有很好的线性关系;在乳制品中的加标回收率为71.2%～101.7%,相对标准偏差为3.4%～13.8%。该方法简便、灵敏、准确,可用于乳制品中多种AGs残留的同时检测。     

Determination of tobramycin in human serum by capillary electrophoresis with contactless conductivity detection

A study on the determination of the antibiotic tobramycin by CE with capacitively coupled contactless conductivity detection is presented. This method enabled the direct quantification of the non-UV-absorbing species without incurring the disadvantages of the indirect approaches which would be needed for optical detection. The separation of tobramycin from inorganic cations present in serum samples was achieved by optimizing the composition of the acetic acid buffer. Field-amplified sample stacking was employed to enhance the sensitivity of the method and a detection limit of 50 microg/L (S/N = 3) was reached. The RSDs obtained for migration time and peak area using kanamycin B as internal standard were typically 0.12 and 4%, respectively. The newly developed method was validated by measuring the concentration of tobramycin in serum standards containing typical therapeutic concentrations of 2 and 10 mg/L. The recoveries were 96 and 97% for the two concentrations, respectively.     

Development and validation of capillary electrophoresis method for tobramycin with precapillary derivatization and UV detection

One of the major drawbacks in the analysis of aminoglycoside antibiotics is their lack of UV chromophore and/or fluorophore. Tobramycin, a representative member of this group, was examined in this study. To overcome the detection hurdle, a precapillary derivatization followed by capillary electrophoresis analysis with direct UV detection was investigated. A central composite design was applied to optimize the method and three parameters were selected in this study: buffer pH, temperature and % acetonitrile (ACN). Selectivity between tobramycin main component and its adjacent peaks as well as the peak efficiency and symmetry factors were established as responses. For each response, a model was obtained by a second-order mathematical expression. Successful results were obtained with a simple background electrolyte (BGE) containing 30 mM sodium tetraborate, pH 10.2, and ACN (75:25 v/v). Under these conditions, baseline separation of tobramycin from its adjacent kanamycin B and an unknown peak was achieved. A temperature of 20 degrees C and applied voltage of 28.0 kV were used. The method showed good validation data in terms of precision, limits of quantitation and detection, specificity and linearity and was found to be suitable for analysis of tobramycin bulk pharmaceutical samples.     

Determination of diastereoisomeric alkaloids in urine by capillary electrophoresis with electrochemiluminescence detection

A new and simple capillary electrophoresis with electrochemiluminescence detection was developed for the separation and the quantification of a pair of diastereoisomenc alkaloids（ephedrine and pseudoephedrine）.The limits of detection（S/N = 3） were 4.5×10^-8 mol/L for ephedrine and 5.2×10^-8 mol/L for pseudoephedrine,respectively.The RSDs of migration time and peak area were less than 1.3 and 2.5%（n = 5）,respectively.The applicability of the propose method was illustrated in the determination of ephedrine and pseudoephedrine in human urine,ephedrine in nasal drops,and the monitoring of pharmacokinetics for pseudoephedrine.     

Monitoring human serum transferrin by capillary zone electrophoresis with end-column amperometric detection

Capillary zone electrophoresis was employed for the determination of human serum transferrin using end-column amperometric detection with a carbon fiber microelectrode at a constant potential of 1.9 V vs. saturated calomel electrode (SCE). The optimum conditions of separation and detection are 7.5 x 10(-4) mol/L Tris-3.44 x 10(-4) mol/L HCl for the buffer solution, 20 kV for the separation voltage, 5 kV and 10 s for the injection voltage and the injection time, respectively. The limit of detection is 6.7 x 10(-8) mol/L or 440 amol (S/N = 2). The relative standard deviations are 0.67% for the migration time and 1.5% for the electrophoretic peak current. The method was applied to the determination of transferrin in human serum. The recovery is between 93-104%.     

安培检测-离子色谱法测定乳品中的微量碘

 用安培检测 离子色谱法检测了乳品中的微量碘。以NaOH作淋洗液 ,直接进样 ,优化了碘的离子色谱分离和测定条件 ,方法的检测限达 1μg/L(3倍信噪比 )。测定了婴儿奶粉、孕产妇专用奶粉和鲜牛奶中的微量碘 ,加标回收率分别为 89 0 % ,86 0 %和 84 1%。     

高效液相色谱法测定人脑脊液中γ-氨基丁酸和谷氨酸

研究了丹酰氯柱前衍生反相高效液相色谱法测定人脑脊液中γ－氨基丁酸（Ｇａｂａ）和谷氨酸（Ｇｌｕ）的方法。检测波长为ＵＶ２５４ｎｍ;流动相Ａ：甲醇;流动相Ｂ：四氢呋喃－甲醇－０．０５ｍｏｌ／Ｌ醋酸钠（ｐＨ６．２）（５７５４２０,Ｖ／Ｖ）;流速为１ｍＬ／ｍｉｎ;梯度洗脱。讨论了有关测试条件。方法的线性范围分别为５～１０００μｍｏｌ／Ｌ（Ｇｌｕ）和１～６００μｍｏｌ／Ｌ（Ｇａｂａ）;最低检出限（μｍｏｌ／Ｌ）分别为０．００２（Ｇｌｕ）和０．００１（Ｇａｂａ）。     

Determination of clozapine by capillary zone electrophoresis following end-column amperometric detection with simplified capillary/electrode alignment

Capillary zone electrophoresis was employed for the determination of clozapine using an end-column amperometric detection at a carbon fiber array microdisk electrode with simplified capillary/electrode alignment. The optimum conditions of separation and detection are: Britton-Robinson buffer, pH 2.0 (1.3 x 10(-2) mol/L total concentration of acids, 3.2 x 10(-3) mol/L NaOH), 15 kV for separation voltage, 5 kV and 10 s for injection voltage and injection time, respectively. The limit of detection is 4.2 x 10(-7) mol/L or 1.2 fmole (signal to noise, S/N = 2). The relative standard deviation is 1.4% for the migration time and 2.5% for the electrophoretic peak current. The method was applied to the determination of clozapine in human blood. The recovery of the method is between 94-104%.     

Determination of lipoperoxide in animal tissue by ion-pair reversed phase high performance liquid chromatography

An ion-pair reversed phase high performance liquid chromatographic method was developed for the quantitative determination of lipoperoxide (as malondialdehyde, MDA) in animal tissue using a ODS column and a mobile phase of methanol + phosphate buffer (53:47 v/v, pH 6.5). Tetrabutylammonium bromide was used as an ion-pair reagent and the detection wavelength was set at 532 nm. The method was sensitive, accurate and simple. A linear relationship was obtained between the peak height and the amount of MDA from 50 nmol/L to 1200 nmol/L and the lower limit of detection of MDA was 15 nmol/L (signal-to-noise ratio greater than 2), and the coefficient of variation at the 200 nmol/L level was 3.7% (n = 7). The results correlated well with those from the 2-thiobarbituric acid colorimetric method. The method has been used in the pathogenic studies of cerebral ischemia and acute renal failure for the determination of trace lipoperoxide.     

高效液相色谱-共振瑞利散射联用测定大鼠血清中依替米星

应用高效液相色谱-共振瑞利散射联用技术建立了测定依替米星的新方法。采用滂胺天蓝作为分子探针,共振瑞利散射(RRS)检测波长设为λex=λem=361nm,通过优化分子探针浓度、分子探针流速、柱后管长和pH等影响因素,确定了最佳实验条件,在该条件下依替米星的检出限(信噪比为3)为1.0mg/L。以妥布米星为内标物,以内标法定量,依替米星与妥布米星的峰面积比与依替米星的质量浓度之间的线性响应范围为2.5～60mg/L。将该方法应用于大鼠血清中依替米星的药代动力学研究,结果满意。     

Monitoring myoglobin by capillary zone electrophoresis with end-column amperometric detection

Capillary zone electrophoresis was employed for the determination of myoglobin in human urine using end-column amperometric detection with a carbon fiber microelectrode at a constant potential of 1.80 V vs. saturated calomel electrode (SCF). The optimum conditions of separation and detection are: 3.73 x 10-4 mol/L sodium diethyl malonyl urea (barbitone sodium), 1.34 x 10-4 mol/L HCl for the buffer solution, 20 kV for separation voltage, 5 kV and 5 s for injection voltage and injection time, respectively. The limit of detection is 4.4 x 10-8 mol/L or 84 amole signal to noise (S/N = 2). The relative standard deviation is 2.9% for the migration time and 2.5% for the electrophoretic peak current. The method can be used for the determination of myoglobin in human urine. The samples can be directly injected and need no pretreatment. The method is also rapid, less than 2 min, and has a recovery rate of 94-106%.