Assay of naproxen in rat serum by high-performance thin-layer chromatography/densitometry

A simple, sensitive, and reproducible high-performance thin-layer chromatographic method using densitometry is presented for the determination of naproxen in rat serum. Only 0.1 mL serum was used for extraction. Separations were performed on 10 x 10 cm plates coated with silica gel, with toluene-ethyl acetate-acetic acid (82 + 15 + 3) as the mobile phase. Benzophenone was used as the internal standard. Quantification was performed by densitometry at 260 nm. The response response for naproxen was linear (r = 0.992) over the range 2-100 mg/L. Method validation demonstrated good recoveries (92-96%), sensitivity (limit of quantitation, 1 mg/L), repeatability of sample application (4%), repeatability of the method (8%), and intermediate precision (5%). The procedure was applied to the quantitation of naproxen in rat serum.     

毛细管区带电泳法测定葡萄籽中儿茶素类化合物

 采用毛细管区带电泳法测定了 10种中国产葡萄籽中的 4个主要儿茶素类化合物 :(+)儿茶素、(- )表儿茶素、(± )表没食子儿茶素、(± )表儿茶素没食子酸酯的含量。在 0 0 2mol/L硼砂和 0 0 0 5mol/L磷酸盐的混合缓冲体系 (pH 10 0 )的背景缓冲液中 ,4个化合物在 10min内取得了令人满意的分离。迁移时间的重现性(RSD)小于 2 % ,峰面积的重现性 (RSD)小于 5 %。在质量浓度为 0 0 0 5g/L～ 0 5 g/L时 ,线性相关系数大于0 995。检测限为 3mg/L～ 10mg/L。该方法简单、快速、准确 ,可作为葡萄籽分析和药用开发过程中分析儿茶素类化合物的有效方法推广使用。     

Development of a fully buffered molybdate electrolyte for capillary electrophoresis with indirect detection and its use for analysis of anions in Bayer liquor

A new counterion-buffered molybdate electrolyte was developed and optimized for simultaneous quantitative determination of up to eight anions (chloride, sulphate, oxalate, fluoride, formate, malonate, succinate, and acetate) in Bayer liquor by capillary electrophoresis with indirect detection at 214 nm. The separation parameters were optimized in respect to separation of the critical analyte group fluoride-formate-malonate, with the optimal electrolyte prepared from molybdic trioxide containing 5.0 mmol/L MoO3, 1.3 mmol/L cetyltrimethylammonium bromide (CTAB), and buffered with diethanolamine (DEA) to pH 9.2 (ca. 20 mM DEA). Total length of separation capillary was 80 cm, resulting in run time of under 4 min. The method is suitable for a wide concentration range of the analytes (1-50 mg/L) with linear calibration plots (R2 = 0.9983-0.9999). Relative standard deviations were 0.05%-0.07% for migration times and 0.67%-2.04% for peak areas. The detection limits were in the range of 0.17-0.51 mg/L or 2-10 micromol/L (hydrostatic injection of 30 s of 1000 x diluted sample). Due to its good buffering capacity, the electrolyte exhibited an excellent ruggedness and good tolerance to the alkaline samples. Consequently, Bayer liquor samples could be diluted as little as 100 x which allows more sensitive determination of minor components over previous methods. The method was successfully applied to analysis of Bayer liquor samples with recoveries in the range of 95-105%.     

胶束电动毛细管色谱法测定海洋沉积物中的苯、甲苯和二甲苯

 建立了用胶束电动毛细管色谱法（MECC）对海洋沉积物中的苯、甲苯和二甲苯进行 分析测定的方法 。用45 cm（到检测窗口40 cm）×75　μm i.d.毛细管柱,以75　mmol/L SDS-2　mmol/L 四硼酸钠溶液（外加体积分数为20%的甲醇）为缓冲液（pH 9.16）。当电压为25 kV、检测 波长为200 nm时,苯、甲苯和二甲苯在20 min内得到了良好的分离。用峰面积定量,线性范 围为4～50 mg/L,相对标准偏差在6.2%以内。测得海洋沉积物中的这些苯系物的质量比范围 为3.79～17.36 μg/g。     

毛细管电泳法测定注射用头孢哌酮钠他唑巴坦钠中目标成分

建立了毛细管区带电泳法同时测定注射用头孢哌酮钠他唑巴坦钠中目标成分含量的方法。采用石英毛细管(75 cm×75 μm i.d.,有效长度63 cm),以40 mmol/L硼砂溶液为背景电解质(BGE),以氢氯噻嗪为内标,分离电压12.0 kV,检测波长220 nm,重力进样10 s(高度10 cm)。实验结果表明,头孢哌酮钠与他唑巴坦钠分别在0.25～3.96 g/L和0.062～0.99 g/L范围内呈良好的线性关系,相关系数(r)分别为0.9995和0.9996。精密度和重复性均良好,相对峰面积的相对标准偏差(RSD)均小于3%,制剂在208 min内稳定,回收试验结果符合方法学要求。该方法简单、准确、耗费少、污染小,可用于注射用粉针剂头孢哌酮钠他唑巴坦钠中头孢哌酮钠和他唑巴坦钠的定量分析。     

胶束电动毛细管色谱-电喷雾质谱联用法同时测定妇宁栓中的5种有效成分

应用胶束电动毛细管色谱-电喷雾电离质谱联用法同时测定了妇宁栓中的小檗碱、巴马汀、苦参碱、儿茶素和黄芩苷5种主要有效成分的含量。在未涂层石英毛细管柱(80 cm×50 μm)中,以40 mmol/L月桂酸-100 mmol/L氨水溶液(含25%的乙腈,pH 9.5)为缓冲液,分离电压为25.0 kV,各组分在16 min内得到完全分离。电喷雾质谱检测时采用50%异丙醇水溶液(含3 mmol/L乙酸)为鞘液。结果表明,小檗碱、巴马汀、苦参碱、儿茶素、黄芩苷的线性范围分别为0.03～15、0.05～15、0.2～250、1.5～300和2.0～500 mg/L,检出限分别为0.01、0.02、0.05、0.5、0.6 mg/L。5种组分的加标回收率为94.0%～104.0%,相对标准偏差(RSD)在0.3%～3.2%之间。该法简便、快速、准确,重现性好,可用于妇宁栓中小檗碱、巴马汀、苦参碱、儿茶素、黄芩苷含量的同时测定。     

毛细管电泳法同时测定血清中的左旋多巴和甲基多巴

建立了毛细管电泳-紫外检测同时测定血清中左旋多巴和甲基多巴的方法。以40 mmol/L硼砂（pH 9.5）为分离缓 冲溶液,在3.45 kPa（0.5 psi）压力下进样7 s、分离电压22 kV、检测波长200 nm、温度25 ℃的条件下进行测定,两 种物质获得了较好的分离。甲基多巴和左旋多巴分别为1.0~64.0 mg/L和1.0~71.0 mg/L时与峰面积呈良好的线性关系, 线性相关系数分别为0.9998和0.9994,检出限分别为0.6和0.8 mg/L(以信噪比为3计)。将该法用于血清中甲基多巴和左 旋多巴的测定,回收率为82.8%~88.8%,相对标准偏差为2.10%~2.63%。     

Enzymatic activity measurement of phospholipid hydroperoxide glutathione peroxidase by capillary electrophoresis

Based on the separation of 1-palmitoyl-2-(13-hydroperoxy-cis-9,trans-11-octadecadienoyl)-L-3- phosphatidylcholine (PC-OOH) and 1-palmitoyl-2-(13-hydroxy-cis-9,trans-11-octadecadienoyl)-L-3- phosphatidylcholine (PC-OH) and the quantitative determination of PC-OH, the enzymatic activity of phospholipid hydroperoxide glutathione peroxidase (PHGPx) can be measured by capillary electrophoresis. The separation was carried out in a fused-silica capillary (30 cm x 100 microns id) at 15 kV positive voltage. Sodium borate (100 mM; pH = 8.4) was used as the running buffer, and the photodiode array detector wavelength was 232 nm. The determination can be completed in 5 min. The detection limit was 5 pmol; and the relative standard deviation (RSD) of the peak area was less than 1% with an average recovery of 98.6%. Compared with traditional methods such as HPLC and spectrophotometry, it is faster and more convenient. Using capillary electrophoresis, the enzymatic activities of PHGPx expressed by the rice PHGPx gene in E. coli. M15 was determined as 1.25 x 10(-5) mumol min-1, and the specific activity of partially purified trans-gene PHGPx was 3.1 x 10(-2) mumol min-1 per mg. The stability of the trans-gene PHGPx was also studied.     

毛细管凝胶电泳法测定硫代寡核苷酸药物癌泰得的含量

癌泰得为20碱基的抑制端粒酶催化亚基hTERT的硫代反义寡核苷酸,体内、体外抗肿瘤活性评价显示其有较好的抗肿瘤活性。采用固相合成仪分别制备了癌泰得及与其碱基百分组成基本相同的硫代寡核苷酸内标,并使用制备型阴离子交换色谱和反相高效液相色谱进行纯化。采用毛细管凝胶电泳仪和单链DNA分离试剂盒测定了癌泰得的含量。所用毛细管规格为内径100 μm,总长31 cm,有效长度20 cm;电动进样,进样电压-10 kV,进样时间1 s;分离电压-12.4 kV;柱体温度40 ℃;样品储存温度为30 ℃;缓冲溶液为pH     

Determination of agmatine in biological samples by capillary electrophoresis with optical fiber light-emitting-diode-induced fluorescence detection

A capillary electrophoresis (CE)/optical fiber light-emitting diode (LED)-induced fluorescence detection method is developed for the determination of agmatine in biological samples. The agmatine was precolumn-derivatized with fluorescence tagging reagent, fluorescein isothiocyanate (FITC). Optimal separation and determination for agmatine were obtained with an electrophoretic buffer of 20 mM sodium borate (pH 9.2). Under the optimal conditions, the determination of agmatine was achieved in less than 4 min, and the detection limit was 4.1x10(-9) M (S/N = 3). The relative standard deviation (RSD) for 11 parallel determination of agmatine was less than 3.0%. The present CE-LED induced fluorescence detection method has been applied to detect agmatine in rat brain tissue, rat stomach tissue, human serum, and human urine. The level of agmatine in human urine was quantified by CE for the first time and found to be in the range 2.5-4.1x10(-7) M.     

Capillary electrophoresis coupled with electrochemical detection using porous etched joint for determination of antioxidants

Capillary electrophoresis coupled with electrochemical detection (CE-EC) for determination of antioxidants, propyl gallate (PG) and tert-butylhydroquinone (TBHQ), in cosmetic samples was proposed in this work. A porous etched joint was used to isolate the electrochemical detection from the electrophoretic high voltage. Compared with the 25 microm i.d. capillary without a decoupler in a CE-EC system, a 75 microm i.d. capillary applied in the present system gave an improvement in both sample injection and sensitivity. Moreover, the carbon fiber working electrode could be directly in touch with the end of separation capillary due to the elimination of the effect of separation voltage on the EC detection, so the alignment of working electrode and capillary became easy and the dead volume was also decreased. Baseline separation of the two antioxidants was achieved by CE in a 50 cm long x 75 microm i.d. capillary at 20 kV using 5.0 mmol L(-1) phosphate buffer (pH 8.00). 0.7 V (versus Ag/AgCl) was applied to the carbon fiber electrode for electrochemical detection. Under the optimal condition, the precisions (RSD, n=4) of peak height and migration time of PG and TBHQ were 2.39-3.59% and 0.34-0.44%, respectively. The detection limits of PG and TBHQ were 2.51x10(-6) and 4.88 x 10(-6) mol L(-1) for standard solution and 0.0751 and 0.0328 mg g(-1) for the real cosmetic samples with consumption of 0.3g sample. Analysis of TBHQ and PG in cosmetics samples was also achieved with the present system and the spiked recoveries of two analytes in cosmetics samples were in the range of 93.6-98.8%.     

毛细管电泳法快速检测消毒剂中的醋酸氯己定

建立了消毒剂中活性成分醋酸氯己定(又名:醋酸洗必泰)的毛细管电泳快速检测法。采用15 mmol/L磷酸盐-乙腈( 体积比为60∶40)缓冲体系,将醋酸氯己定在50 cm×75 μm i.d.的石英毛细管柱中进行电泳分离,电泳电压为15 kV,检 测波长为254 nm。同时,对毛细管电泳分析醋酸氯己定的条件(如缓冲液的种类、pH值、浓度及电泳电压等)进行了优化 。用该方法对消毒剂样品进行测定,在4 min内可完成分析。醋酸氯己定在质量浓度为0.01～0.10 g/L时线性良好,检测 限为0.004 mg/L,吸光度值的相对标准偏差为3.97%,迁移时间的相对标准偏差为2.99%,样品加标回收率为91.4%～116.6%。将该方法 与高效液相色谱法进行比较,两种方法测定结果的相对误差≤4%。所建立的检测醋酸氯己定含量的毛细管区带电泳法简单 、快速,适用于消毒剂样品的测定。     

Determination of quinolizidine alkaloids in Sophora flavescens and its preparation using capillary electrophoresis

A simple and accurate capillary electrophoresis method was developed for the determination of four quinolizidine alkaloids in Sophora flavescens and Kuhuang injection. Optimum separation of the analytes was obtained on a 65 cm x 75 microm i.d. uncoated fused-silica capillary using a aqueous buffer system of 60 mmol L(-1) sodium borate at pH 8.5, with applied voltage and capillary temperature of 12 kV and 25 degrees C, respectively. Detection wavelength was set at 204 nm and jatrorrhizine was used as the internal standard. Good linear relationships between peak-area ratios and concentrations of the analytes were observed over the concentration range 0.044-0.792 mg mL(-1) for matrine, 0.142-1.926 mg mL(-1) for oxymatrine, 0.0377-0.3393 mg mL(-1) for sophocarpine and 0.0664-1.062 mg mL(-1) for sophoridine. The recoveries of four alkaloids ranged between 93.08 and 101.4% with relative standard deviations from 0.7 to 9.2% (n = 6) as determined by standard addition. The limits of detection for four alkaloids were determined to be over the range 8.8-48.0 microg mL(-1). Contents of four alkaloids in Sophora flavescens and three alkaloids in Kuhuang injection were successfully determined under the optimum conditions.     

CE Determination of Droperidol in Tablets and Human Serum

A capillary electrophoretic method was described for the determination of droperidol in pharmaceutical tablets and human serum. Droperidol and internal standard, lansoprazole, were separated on an uncoated fused-silica capillary using a run buffer containing borate (10 mM; pH 9.3) and aqueous methanol (20%, υ/υ). The signals were detected at 210 nm. The migration times for droperidol and internal standard were 2.1 and 2.9 min, respectively. The method has been validated in the range of 2.2 × 10^?5 ? 7.8 × 10^?5 M and applied to both tablets and human serum with good repeatability and no interference.     

毛细管气相色谱法测定速效伤风胶囊中对乙酰氨基酚、咖啡因、马来酸氯苯那敏的含量

 用５％Ｐｈ－Ｍｅ－Ｓｉｌｉｃｏｎｅ毛细管色谱柱，ＦＩＤ，二阶程序升温，以正十六烷作为内标物测定速效伤风胶囊中对乙酰氨基酚、咖啡因、马来酸氯苯那敏的含量。浓度线性范围：对乙酰氨基酚４～２０ｇ／Ｌ，咖啡因０．０８４～０．４２ｇ／Ｌ，马来酸氯苯那敏０．１５～０．７５ｇ／Ｌ。平均回收率（ｎ＝５）：对乙酰氨基酚９９．６２％（ＲＳＤ＝０．４４％）咖啡因９６．４６％（ＲＳＤ＝１．３２％），马来酸氯苯那敏９８．５５％（ＲＳＤ＝０．６５％）。     

Micellar electrokinetic chromatography method for the determination of sulfamethoxazole, trimethoprim and their main metabolites in human serum

A complete analytical procedure, including sample clean-up and a micellar electrokinetic chromatographic method, is presented for the determination of sulfamethoxazole, trimethoprim, and their main metabolites by using 20 mmol L(-1) borate buffer (pH 9.3), 25 mmol L(-1) sodium dodecylsulfate, and 5% v/v acetonitrile as electrolyte. The separation was carried out at 30 kV and 20 degrees C in a fused silica capillary (60.2 cm x 75 microm inner diameter) fitted with a window in the capillary cartridge of 100 x 800 microm. The detector response was linear from the limit of quantification to 3 mg L(-1) for the individual components. The limits of quantification ranged from 0.13 up to 0.24 mg L(-1). The method was applied to human serum, previously spiked at different concentrations of all the analytes, and recoveries between 95% and 108% were obtained.     

胶束毛细管电泳法同时测定消栓通络片中5种有效成分

建立了胶束毛细管电泳法同时测定中药复方制剂消栓通络片中芦丁、丹参素、人参皂苷Rg1、人参皂苷Rb1、三七皂苷R1含量的分析方法。研究了缓冲体系的浓度、添加剂种类、分离电压、进样时间对组分分离的影响,以60 mmol/L SDS-30 mmol/L Tris-10 mmol/L硼酸(含15%甲醇)作运行缓冲液,检测波长214 nm,5种组分在26 min内得到基线分离。芦丁、丹参素、人参皂苷Rb1、人参皂苷Rg1、三七皂苷R1的质量浓度分别在2.5～100、2.5～200、10～300、15～400、15～400 mg/L范围内与其峰面积呈良好的线性关系,检出限分别为0.3、0.9、3.0、5.0、6.0 mg/L。样品在低、中、高3个浓度下的加标回收率为93%～108%,相对标准偏差均不大于4.5%。该方法简便、快速,可用于实际样品检测。     

Separation and determination of norepinephrine, epinephrine and isoprinaline enantiomers by capillary electrophoresis in pharmaceutical formulation and human serum

A capillary electrophoresis method with ultraviolet (UV) detection was developed and optimized for the enantiomer separation of norepinephrine (NE), epinephrine (EP) and isoprenaline (IP) using dual cyclodextrins (CDs) of 2-hydroxypropyl-beta-CD (HP-beta-CD) and heptakis (2,6-di-o-methyl)-beta-CD (DM-beta-CD) as chiral selectors. Optimal separation was obtained using a running buffer of 50mM phosphate containing 30mM HP-beta-CD and 5mM DM-beta-CD at pH 2.90 and a field strength of 20kV in 45cmx75mum (40cm effective length) uncoated capillary. The UV absorbance detection was set at 205nm. A 0.1% (w/w) polyethylene glycol or 0.1% (v/v) acetonitrile was used to enhance the detection sensitivity. There was a wide and excellent linear calibration graph for each enantiomer in the range 1.0x10(-3) to 1.0x10(-6)M and the detection limit (S/N=3) was found from 8.5x10(-7) to 9.5x10(-7)M. The method has been applied for the determination of isoprenaline in isoprenaline hydrochloride aerosol and to the analysis of serum samples. The recoveries of NE and EP in serum and IP in drug were ranged from 90 to 110%. The relative standard deviations of all the analyte peaks were less than 2.8% for migration time and less than 4.8% for peak area.     

高效液相色谱法测定吲哚美辛控释胶囊的血药浓度和生物利用度

采用ＯＤＳ柱,甲醇－稀磷酸溶液（７６２４）为流动相,２６０ｎｍ为检测波长,建立了测定血浆中吲哚美辛浓度的高效液相色谱法,并测定了吲哚美辛控释胶囊炎痛康的血药浓度。结果表明,血浆中吲哚美辛浓度在０．１２５～５．０ｍｇ／Ｌ范围内线性关系良好（ｒ＝０．９９９６）,检测限６２．５μｇ／Ｌ（Ｓ／Ｎ＝３１）,平均回收率为１００．４％,日内和日间ＲＳＤ均小于５％。１１位受试者单剂量口服炎痛康后的相对生物利用度为１０２．３８％。     

Determination of trace metals by capillary electrophoresis

A new analytical procedure is developed using a strong complexing agent, 1,10-phenanthroline (Phen), for direct UV detection of Zn, Mn, Cu, Co, Cd, and Fe at microg/L concentrations in environmental water samples. The metal chelates formed showed different electrophoretic mobilities and solved the comigration problem for capillary electrophoresis (CE) separation of free metal ions. To obtain stable metal-Phen chelates during the capillary zone electrophoresis (CZE) run, both pre-column and on-column complexation are required and threefold excess of Phen over metal ions should be added to the sample. The optimized background electrolyte (BGE) consists of 30 mM hydroxylamine hydrochloride and 0.1% methanol at pH 3.6. Under hydrodynamic sampling, CE run at + 20 kV in 65 cm x 0.05 mm ID fused-silica column with detection at 265 nm, baseline separation, satisfactory working ranges (10 microg/L to 5.5 mg/L), sensitive detection limits (1-3 microg/L), good repeatability for migration times (relative standard deviation, RSD 0.36-0.81%, n = 5), peak area (RSD 3.2-4.2%, n = 5) and peak height (RSD 3.2-4.5%, n = 5) were obtained for the metal cations investigated. The reliability of the method was established by parallel determination using the inductively coupled plasma-atomic emission spectrometry (ICP-AES) method giving results within statistical variation. The procedure developed is shown to provide a quick, sensitive, precise, and economic method for simultaneous determination of metal cations that can form stable chelates with Phen.