莨菪烷型生物碱薄层原位表面增强拉曼光谱

１引　言薄层色谱（ＴＬＣ）已广泛用于中药成分的分离与分析，但在薄层原位无法获得分离后各化合物的分子结构信息；表面增强拉曼光谱（ＳＥＲＳ）可高灵敏度获得单一组分的分子振动光谱，将以上技术联用，可在混合物微量分离的原位获得化合物的分子结构信息，本文用ＴＬＣ－ＳＥＲＳ对洋金花注射液中莨菪烷型生物碱进行了探索。２　实验部分２．１　仪器与试剂ＦＴ－Ｒａｍａｎ９１０光谱仪（Ｎｉｃｏｌｌｅｔ公司），Ｎｄ：ＹＶＯ４激光器，激光波长１０６４ｎｍ；三用紫外分析仪（上海分析仪器厂）。硅胶ＣＦ２５４（青岛海洋化工厂）；…     

莨菪类生物碱毛细管电泳分析

采用毛细管区带电泳方法对阿托品（ＤＬ－莨菪碱）、东莨菪碱、山莨菪碱和樟柳碱进 行了系统分离，以 ５０ ｍｍｏｌ／Ｌ磷酸盐缓冲液（ｐＨ ８．０）－四氢呋喃（９：１，Ｖ／Ｖ）作背景电介质， 操作电压为１１ ｋＶ，柱温２４℃，电迁移进样５ ｋＶ×５ｓ，柱上２００ｎｍ检测，４种莨菪类生物碱 可在４０ ｃｍ×５０μｍ的石英毛细管柱上５．５ｍｉｎ之内实现基线分离。     

毛细管区带电泳法测定卷烟中的生物碱

在磷酸缓冲体系中采用毛细管区带电泳法测定卷烟中的生物碱时,检测灵敏度低,分离度差。考察了卷烟中生物碱的 提取条件,分离缓冲溶液的类型、pH值和浓度,卷烟中生物碱测定方法的线性范围、检出限、重现性和回收率。结果发 现,当采用410 mmol/L的酒石酸溶液（pH 2.8）为缓冲体系时,卷烟中生物碱的检测灵敏度和分离度均有明显改善,烟碱 的线性范围为0.06~0.80 mg/L（其他生物碱为0.006~0.10 mg/L）,检出限为0.002~0.01 mg/L,相对标准偏差为2.2%~10%,回收率为87.6%~102%。     

扁形毛细管区带电泳

本文提出用扁形毛细管替代圆形毛细管进行区带电泳,以便解决微孔圆管容量小、光路短,而大孔圆管径向温差大、电泳效率不高的矛盾.从理论和实验两方面对扁、圆两种管的效果进行了比较,证实扁管兼具了微孔圆管和大孔圆管的特长.同时还提出了塑料扁管的制作方法,并研究了此种管的热变形问题.     

离子液体作流动相添加剂高效液相色谱法分离莨菪类生物碱

建立了以离子液体1-辛基-甲基咪唑六氟磷酸盐(Omin PF6)为高效液相色谱流动相添加剂分离莨菪类生物碱的方法,探讨了离子液体的保留模型及机理。采用高效液相色谱法,考察了检测波长、有机相种类和比例、离子液体的种类、p H值和浓度、缓冲盐体系等因素对莨菪类生物碱色谱行为的影响。结果显示,当离子液体作为流动相添加剂时,可明显改善此类生物碱的分离效果,减少色谱峰的拖尾,提高分离效率。研究显示,Omin PF6浓度与容量因子的变化符合溶质计量置换保留模型(SDM-R),且保留过程以竞争吸附为主。     

毛细管电泳安培法检测黄连中的生物碱

本文建立了一种简单快速的毛细管电泳安培检测法分离检测黄连中的黄连碱、盐酸小檗碱、巴马汀、和药根碱.以150 μm的铂电极为工作电极,考察并优化了影响分离和检测的条件.在80 mmol/L磷酸盐缓冲液中添加50%甲醇(pH 6.0),分离电压15 kV,检测电位1.2 V (vs.Ag/AgCl)的条件下,黄连碱、盐酸小檗碱、巴马汀和药根碱在8min内获得良好分离.黄连碱、盐酸小檗碱、巴马汀和药根碱的峰电流面积和浓度分别在1.0×10-5～2.0×10-7,1.0×10-5 ～8.0×10-8 mol/L,1.0×10-5～1.0×10-7 mol/L和1.0×10-5～2.0×10-7mol/L范围内呈良好的线性关系.检出限(S/N=3)低达10-8mmol/L.方法应用于微波辅助溶剂提取黄连中生物碱的测定,回收率在97.0%～104%,RSDs≤3.8%,结果满意.     

高效毛细管区带电泳法分离人血清蛋白质的研究

 研究了高效毛细管区带电泳分离人血清蛋白质的电泳行为及实验条件 ,建立了分离血清蛋白质的高效毛细管区带电泳法。血清样品经硼酸缓冲液 (5 0 mmol/L,p H8.80 )稀释后 ,以 0 .1 mol/L硼酸缓冲液 (p H9.3 5 ,含4g/L PEG80 0 0 )为电泳介质 ,在 5 0 μm i.d.× 3 7cm弹性石英毛细管柱 (有效柱长为 3 2 cm)中进行电泳分离 ,以2 0 0 nm紫外波长检测。方法简便、快速、重复性好 ,1 2 min内便可完成对血清中蛋白质的电泳分离。     

毛细管电泳-电致化学发光检测法分离测定中药马尿泡中的托烷类生物碱成分

以铕离子掺杂类普鲁士蓝(Eu-PB)化学修饰铂电极为工作电极,采用毛细管电泳-电致化学发光检测法对4种托烷类生物碱成分（如山莨菪碱、东莨菪碱、阿托品和樟柳碱）进行了分离检测。考察了氧化电位值、运行缓冲液酸度、盐浓度和甲醇含量等实验条件对电泳分离效果及检测灵敏度的影响。在优化的实验条件下,以20 mmol/L的磷酸盐(pH 8.0)-7%(体积分数）甲醇为运行液,各组分在6 min内可达到基线分离,其峰面积的相对标准偏差小于5.0%,迁移时间的相对标准偏差小于1.1% (n=12)。并将该法成功地应用于测定中药马尿泡根茎中的山莨菪碱和东莨菪碱的含量,其含量平均值分别为27.8 g/kg和4.43 g/kg。样品的加标回收率为97.8%～102%。     

毛细管区带电泳测定食品中甲醛次硫酸氢钠

建立了毛细管区带电泳(CZE)-紫外检测法测定粉丝、挂面、冰糖及腐竹中的甲醛次硫酸氢钠含量的新方法.以Φ75!m"70 cm(有效长度:60 cm)未涂层熔融石英毛细管为分离柱,50 mmol/L磷酸钠+10 mmol/L NaOH+0.5 mmol/L十六烷基三甲基溴化铵(CTAB)+1 g/L聚乙二醇(PEG)35 000为分离缓冲溶液.详细研究了分离缓冲溶液浓度及pH、PEG 35 000浓度及样品提取溶液对甲醛次硫酸氢钠分离及定量的影响.样品粉碎后,用5mmol/L乙酸溶液提取后离心,上清液经滤膜过滤后直接进样.分离电压为-12 k V,检测波长为214 nm.检出限和定量限分别为4 mg/kg和12 mg/kg,线性范围为15~400 mg/kg,线性相关系数(r)为0.999 1,加标回收率在90.0%~95.6%之间.方法测定了从北京当地超市及农贸市场上采集的4种共计12份食品样品,未发现阳性样品.     

测定酚醛树脂中水杨酸的高效毛细管区带电泳法

介绍了应用高效毛细管区带电泳技术测定酚醛树脂中水杨酸含量的新方法。缓冲液采用 75％ (φ )乙醇为溶剂,水杨酸不需提取,直接测定。该法的线性范围为 5.8× 10－ 6～ 1.0× 10－ 4 mol/L,检出限为 8.0× 10－ 7 mol/L（ S/N=3）, RSD为 2.7％（ n=5）,实验操作简便、迅速、准确。     

毛细管电泳法测定密蒙花中的橙皮素、木犀草素和芹菜素

建立了毛细管电泳法分析密蒙花中橙皮素、木犀草素和芹菜素的方法,研究了缓冲溶液pH和浓度、工作电压和进样时间以及β CD的影响。在优化的条件下,3种物质在15min内得到良好分离。橙皮素、木犀草素和芹菜素的质量浓度分别在0.01～0.50mg mL、0.02～0.70mg mL、0.04～0.80mg mL范围内与峰高成良好线性,线性相关系数分别为0.9992、0.9994和0.9984。3种物质基于迁移时间和峰高的相对标准偏差分别为1 3%、2 2%、2 6%和4 2%、3 7%、4 6%。检出限分别为3 5、4 5和5 0μg mL。     

Separation and simultaneous determination of quinolone antibiotics by capillary zone electrophoresis

Summary The potential of capillary zone electrophoresis has been investigated for the separation and quantitative determination of some quinolone antibiotics. The influence of different conditions, such as the nature and concentration of the electrophoretic electrolyte, on migration time, peak symmetry, efficiency and resolution was studied. A buffer consisting of 100mm HEPES adjusted to pH 8.5 containing 10% (v/v) acetonitrile was found to furnish a very efficient and stable electrophoretic system for the separation of exoxacin, ciprofloxacin, ofloxacin, oxolinic acid, nalidixic acid and pipemedic acid. A linear relationship between concentration and peak area for each compound was obtained in the concentration range 0.25–40 μg mL⁻¹; detection limits were approximately 0.25 ng mL⁻¹. It was demonstrated that the method can be used for the simultaneous determination of these six antibiotics in serum and urine samples.     

Separation of organic and inorganic arsenic species by capillary zone electrophoresis

Summary Capillary zone electrophoresis has been used to separate arsenite, arsenate, dimethylarsinic acid, and phenyl-,p-aminophenyl-, ando-aminophenylarsinic acids. Identification and quantification of the arsenic species at mg L⁻¹ levels was possible by use of direct UV detection at 200 nm. The relative standard deviation (n=7) ranged from 0.97 to 1.52% for migration times and from 2.08 to 4.31% for peak areas. A method for rapid separation of inorganic arsenic species was also developed; by use of this method arsenite and arsenate could be separated within 2 min. Presented at Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

毛细管电泳分离几种神经递质的研究

研究了不同毛细管预处理方法对组胺、5-羟色胺及儿茶酚胺类神经递质电泳分离的影响，采用优化的毛细管预处理方法及电泳分离条件基线分离了组胺、5-羟色胺、去甲肾上腺素和肾上腺素。利用多巴胺和5-羟色胺在毛细管内壁吸附效应的不同，对电泳淌度极为相近的多巴胺和5-羟色胺进行了分离和鉴定。以PC22细胞为研究对象，证实了该细胞中所含大量神经递质是多巴胺，不是5-羟色胺。     

Separation of human fibrinopeptides by capillary zone electrophoresis

We describe a method for the simultaneous determination of the five fibrinopeptide forms derived from the thrombin-promoted activation of human fibrinogen by capillary zone electrophoresis (CZE). The fibrinopeptide mixture was first desalted by a solid-phase extraction (SPE) step. The analysis was performed in reversed polarity in a highly cross-linked polyethylene glycol (PEG)-coated capillary with UV-light absorption detection at 200 nm. Several parameters including buffer concentration and pH, presence of an organic modifier, temperature, and applied voltage, have been tested. The best separations were obtained within 20 min, utilizing a 20 mM sodium phosphate buffer without organic modifier, in the narrow 6.1-6.2 pH range, at 25 degrees C, with an applied voltage of 20 kV. Quantitative analysis is made possible by the use of sheep fibrinopeptide A as an internal standard to correct for both extraction and injection errors.     

Separation of enantiomers of butorphanol and cycloamine by capillary zone electrophoresis

Butorphanol tartrate is a synthetic opioid agonist-antagonist used as analgesic, possessing three chiral centres in the basic part of the molecule. Its chiral purity is routinely controlled only by optical rotation. A new capillary zone electrophoresis method, capable to separate the enantiomers of butorphanol and intermediate of its synthesis, cycloamine, was developed. Different electrolyte composition (type and concentration of carrier ion, pH, and organic solvent addition), and type and concentration of several chiral selectors (natural and modified cyclodextrins) were tested. Using the optimized conditions (acidic electrolyte with the addition of highly sulphated gamma-cyclodextrin) as low as 0.05% of undesirable enantiomers can be detected. Selected method characteristics, i.e., linearity (0-50 mg/l), precision (2.5% at 20 mg/l), and accuracy (101 +/- 2% at 20 mg/l) were evaluated. The optimized method was applied for the analysis of real batches of butorphanol and cycloamine. It was found that butorphanol tartrate manufactured by IVAX Pharmaceuticals contains less than 0.05% of undesirable enantiomer.     

Separation of tetracycline and its related substances by capillary zone electrophoresis

Tetracycline was separated from its main impurities 4-epitetracycline, anhydrotetracycline, 4-epianhydrotetracycline, chlortetracycline, and demethyltetracycline by capillary electrophoresis. Systematic method development was performed in which following parameters were consecutively optimized: type and pH of the buffer, buffer concentration, type and concentration of organic modifier, voltage and temperature. Qualitative and quantitative aspects of the method are compared with liquid chromatography.     

薄层扫描法测定洋金花中3种莨菪生物碱的研究

在硅胶G薄层板上,以甲苯 丙酮 无水乙醇 氨水=体积比(15∶10∶7∶2)为展开剂,用改良碘化铋钾与KI I2混合液作为显色剂,采用双波长薄层扫描法实现了中药材洋金花中3种莨菪生物碱(山莨菪碱、阿托品、东莨菪碱)的同时分离和测定。平均加标回收率在105%～107%之间。     

Separation and determination of enkephalin-related peptides using capillary electrophoresis

CZE with UV-absorption detection has been used for the separation and determination of enkephalin-related peptides. The experimental conditions, such as pH and concentration of running buffer, applied voltage, injection method, and time, were investigated in detail. Excellent separation efficiency could be obtained for ten enkephalin-related peptides with a 50 microm (ID) x 58 cm capillary using sodium dihydrogen phosphate as the running buffer (pH 3.11) when 20 kV of applied voltage was used. The concentration detection limits were found to be in the range of 0.31-1.94 microg/mL (defined as S/N = 3). The proposed method has been applied to analyze the spiked cerebrospinal fluid (CSF) sample, and the results showed that CZE is a powerful technique for separation and detection of the above biological peptides.