Mixture design optimization of extraction and mobile phase media for fingerprint analysis of Bauhinia variegata L

Two statistical mixture designs were used to optimize the proportions of solvents used in both the extraction medium and the reversed liquid chromatographic mobile phase to improve the quality of chromatographic fingerprints of Bauhinia variegata L extracts. For modeling, the number of peaks was used as a measure of fingerprint information. Three mobile phases, each with a chromatographic strength of two, gave good results. A methanol/water (77:23 v/v) mixture resulted in 17 peaks in the chromatographic fingerprint whereas acetonitrile/water (64.5:35.5 v/v) and methanol/acetonitrile/water (35:35:30 v/v/v) mixtures resulted in 18 and 20 peaks, respectively. The corresponding optimum solvent compositions to extract chemical substances for these three mobile phases were ethanol/acetone (25:75 v/v/v) and dichloromethane/acetone (70:30 v/v) mixtures, and pure dichloromethane, respectively. The mixture designs are useful for understanding the influence of different solvents on the strengths of the extraction medium and the mobile phase.     

Thin-layer chromatographic fingerprinting of the nonvolatile fraction extracted from the medicinal herb Cistus incanus L.

ABSTRACT

The aim of this study was to provide the first from-start-to-end thin-layer chromatographic method of fingerprinting the Cistus incanus L. raw herbal material, with a purpose to further use it for rapid screening, authentication, and quality control of the traded C. incanus L. herbs. To this effect, 12 different C. incanus L. samples purchased as herbal teas from a local market were extracted by means of the accelerated solvent extraction (ASE) with chemometrically optimized solvent extraction mixture and temperature (methanol–water, 27:73, v/v; 130°C), to derive the polar fraction from the plant samples. Then, the extracts were developed in two thin-layer chromatographic systems, both using the commercially precoated silica gel 60 chromatographic plates, yet two different mobile phases (mobile phase 1, ethyl acetate–formic acid–acetic acid–water, 100:11:11:13, v/v/v/v, and mobile phase 2, ethyl acetate–dichloromethane–formic acid–acetic acid–water, 100:10:10:10:11, v/v/v/v/v). The chromatograms were densitometrically scanned in the reflectance mode at the wavelength λ?=?366?nm to obtain fingerprints of the extracts derived from individual C. incanus L. samples. Mobile phase 2 performed slightly better, because with its use, the maximum number of 11 peaks could be seen in the respective fingerprints, whereas with mobile phase 1, the maximum number of 10 peaks only. Then an antioxidant potential of the investigated herbal extracts was assessed, making use of mobile phase 2 and the 0.20% methanol solution of 2,2-diphenyl picrylhydrazyl as a visualizing reagent. The resulting chromatograms were densitometrically scanned in the extinction mode at the wavelength λ?=?550?nm to obtain biological fingerprints of the extracts. Finally, chromatographic and biological fingerprints underwent a semiquantitative evaluation in terms of the contents of the extracted polar fraction and an overall antioxidant potential of the individual plant species.     

Partial least squares model and design of experiments toward the analysis of the metabolome of Jatropha gossypifolia leaves: Extraction and chromatographic fingerprint optimization

A major challenge in metabolomic studies is how to extract and analyze an entire metabolome. So far, no single method was able to clearly complete this task in an efficient and reproducible way. In this work we proposed a sequential strategy for the extraction and chromatographic separation of metabolites from leaves Jatropha gossypifolia using a design of experiments and partial least square model. The effect of 14 different solvents on extraction process was evaluated and an optimized separation condition on liquid chromatography was estimated considering mobile phase composition and analysis time. The initial conditions of extraction using methanol and separation in 30 min between 5 and 100% water/methanol (1:1 v/v) with 0.1% of acetic acid, 20 μL sample volume, 3.0 mL min^?1 flow rate and 25°C column temperature led to 107 chromatographic peaks. After the optimization strategy using i‐propanol/chloroform (1:1 v/v) for extraction, linear gradient elution of 60 min between 5 and 100% water/(acetonitrile/methanol 68:32 v/v with 0.1% of acetic acid), 30 μL sample volume, 2.0 mL min^?1 flow rate, and 30°C column temperature, we detected 140 chromatographic peaks, 30.84% more peaks compared to initial method. This is a reliable strategy using a limited number of experiments for metabolomics protocols.     

漆酚酯键合硅胶液相色谱固定相的制备与应用

以甲基丙烯酸漆酚酯为色谱配体,制备了一种新型色谱固定相。首先以漆酚和甲基丙烯酰氯为原料制备得到甲基丙烯酸漆酚酯,并通过物理吸附涂覆到由3-（甲基丙烯酰氧）丙基三甲氧基硅烷化学修饰的硅胶上,再通过自由基引发与硅烷化硅胶的双键聚合制得漆酚酯键合硅胶固定相（USP）。对固定相进行傅里叶红外光谱（FT-IR）、热重分析（TGA）、扫描电子显微镜（SEM）和元素分析（EA）表征,结果表明通过共聚反应成功地将漆酚酯固定在硅烷化硅胶上,且制备出的固定相具有良好的单分散性。采用匀浆法装柱,以乙腈-0.05%磷酸溶液（3：97,v/v）为流动相,流速为0.4 mL/min,检测波长为220 nm,考察固定相对天麻浸膏的分离性能。以乙腈-水（50：50,v/v）为流动相,流速为0.5 mL/min,检测波长为290 nm,考察固定相对吴茱萸浸膏的分离性能。结果表明该固定相对天麻浸膏和吴茱萸浸膏均具有良好的分离性能,从天麻浸膏中分离出5个色谱峰,从吴茱萸浸膏中分离出2个色谱峰。与商品化C₁₈ 柱相比,USP柱可以从天麻浸膏中分离出更多的有效组分并实现基线分离,分离吴茱萸浸膏的色谱条件更为环保和安全。采用低流速对天麻浸膏和吴茱萸浸膏进行分离,减少了流动相的使用量,分离结果令人满意。以天然产物漆酚制备色谱固定相,既为分离纯化天麻素和吴茱萸碱提供了一种新的方法,又为液相色谱固定相制备提供了新的思路,还拓展了生漆在色谱分离材料方面的应用。     

Speciation of butyl- and phenyltin compounds in sediments using pressurized liquid extraction and liquid chromatography-inductively coupled plasma mass spectrometry

A liquid chromatographic method with inductively coupled plasma mass spectrometry is proposed for the speciation of butyl- (monobutyltin, dibutyltin, tributyltin) and phenyl- (monophenyltin, diphenyltin, triphenyltin) tin compounds in sediments. After evaluation of different additives in the mobile phase, the use of 0.075% (w/v) of tropolone and 0.1% (v/v) of triethylamine in a mobile phase of methanol-acetic acid-water (72.5:6:21.5) allowed the best chromatographic separation of the six compounds. Pressurized liquid extraction (PLE) with a methanolic mixture of 0.5 M acetic acid and 0.2% (w/v) of tropolone was suitable for the quantitative extraction of butyl- and phenyltin compounds with recovery values ranging from 72 to 102%. This analytical approach was compared to conventional solvent extraction methods making use of acids and/or organic solvent of medium polarity. The main advantages of PLE over conventional solvent extraction are: (i) the possibility to extract quantitatively DPhT and MPhT from sediments, which could not be done by a solvent extraction approach; (ii) to preserve the structural integrity of the organotin compounds; (iii) to reduce the extraction time from several hours in case of solvent extraction techniques to just 30 min. For spiked sediments, limits of detection ranged from 0.7 to 2 ng/g of tin according to the compound. The relative standard deviations were found to be between 8 and 15%. The developed analytical procedure was validated using a reference material and was applied to various environmental samples.     

同位素稀释质谱法测定猪肉中克伦特罗含量的国际比对APMP. QM-S6

建立了同位素稀释质谱法（IDMS）测定猪肉中克伦特罗含量的高准确度方法,并应用于亚太计量规划组织（Asia Pacific Metrology Programme,APMP）开展的国际比对“猪肉中克伦特罗含量测定”（APMP. QM-S6）。本研究考察了影响测定结果的喷雾电压值、流动相、色谱柱、提取条件、净化条件等主要因素并进行了优化,并对测定结果的不确定度进行了评定。结果表明:流动相组成以及pH值会影响克伦特罗的质谱响应以及最优的电喷雾电压值;样品溶剂会影响克伦特罗的色谱保留,甲醇溶剂会引起严重的溶剂效应,甚至导致峰分裂;克伦特罗易在固相萃取柱及亲水性滤膜上吸附,且吸附材料和滤膜上吸附的杂质有可能被洗脱,引起基质效应,干扰测定。提取效率最高的方法是采用0.1%（v/v）甲酸乙腈溶液为提取溶剂,通过匀浆进行提取。方法检出限（以信噪比大于3计）为0.2 μg/kg。比对样品中克伦特罗的含量为5.18 μg/kg±0.50 μg/kg（k=2）,比对结果与参考值等效一致,取得国际互认。该方法准确可靠,可为猪肉中克伦特罗的日常检测提供参考。     

Exploratory analysis of chromatographic fingerprints to distinguish rhizoma Chuanxiong and rhizoma Ligustici

Identification and quality control of products of natural origin, used for preventive and therapeutical goals, is required by regulating authorities, as the World Health Organization. This study focuses on the identification and distinction of the rhizomes from two Chinese herbs, rhizoma Chuanxiong (from Ligusticum chuanxiong Hort.) and rhizoma Ligustici (from Ligusticum jeholense Nakai et Kitag), by chromatographic fingerprints. A second goal is using the fingerprints to assay ferulic acid, as its concentration provides an additional differentiation feature. Several extraction methods were tested, to obtain the highest number of peaks in the fingerprints. The best results were found using 76:19:5 (v/v/v) methanol/water/formic acid as solvent and extracting the pulverized material on a shaking bath for 15 min. Then fingerprint optimization was done. Most information about the herbs, i.e. the highest number of peaks, was observed on a Hypersil ODS column (250 mm × 4.6 mm ID, 5 μm), 1.0% acetic acid in the mobile phase and employing within 50 min linear gradient elution from 5:95 (v/v) to 95:5 (v/v) acetonitrile/water. The final fingerprints were able to distinguish rhizoma Chuanxiong and Ligustici, based on correlation coefficients combined with exploratory data analysis. The distinction was visualized using Principal Component Analysis, Projection Pursuit and Hierarchical Clustering Analysis techniques. Quantification of ferulic acid was possible in the fingerprints of both rhizomes. The time-different intermediate precisions of the fingerprints and of the ferulic acid quantification were shown to be acceptable.     

Influence of solvent effects on retention in reversed-phase liquid chromatography and solid-phase extraction using a cyanopropylsiloxane-bonded,silica-based sorbent

Summary The solvation parameter model is used to characterize the retention properties of a cyanopropylsiloxanebonded, silica-based sorbent with methanol, acetonitrile, tetrahydrofuran, and isopropanol in water as mobile phases. The system constants over the composition range 1 to 50 % (v/v) organic solvent indicate that retention occurs because of the relative ease of cavity formation in the solvated stationary phase compared to the same process in the predominantly aqueous mobile phase as well as from more favorable stationary phase interactions with solutes containing π- and n-electrons. The capacity of the solute for dipole-type interactions is not important whereas all hydrogen-bond-type interactions result in reduced retention. Graphing the system constants as a function of mobile phase composition provides a simple mechanism for interpreting the change in capacity of the chromatographic system for retention in terms of changes in the relative weighting of fundamental intermolecular interactions. A comparison is also made with the retention properties of an octadecylsiloxane-bonded, silica-based sorbent with 30 % (v/v) methanol in water as the mobile phase and the extraction characteristics of a porous polymer sorbent with 1 % (v/v) methanol, acetonitrile, tetrahydrofuran, and isopropanol in water as the sample processing solvent. Changes in sorbent selectivity due to selective uptake of the processing solvent are much smaller for the cyanopropylsiloxane-bonded sorbent than the results found for a porous polymer sorbent.     

Focused microwave-assisted solvent extraction and HPLC determination of effective constituents in Eucommia ulmodies Oliv. (E. ulmodies)

A new focused microwave-assisted solvent extraction method using water as solvent has been developed for leaching geniposidic and chlorogenic acids from Eucommia ulmodies Oliv. The extraction procedures were optimized using a two indexes orthogonal experimental design and graphical analysis, by varying irradiation time, solvent volume, solvent composition and microwave power. The optimum extraction conditions were obtained: for geniposidic acid, 50% micorwave power, 40 s irradiation, and 80% (v/v) aqueous methanol as extraction solvent (20 ml g⁻¹ sample); and for chlorogenic acid, 50% micorwave power, 30 s irradiation, and 20% aqueous methanol (20 ml g⁻¹ sample). The composition of the extraction solvent was optimized and can be directly used as the mobile phase in the HPLC separation. Quantification of organic acids was done by HPLC at room temperature using Spherigel C₁₈ chromatographic column (, i.d. 5 μm), the methanol:water:acetic acid (20:80:1.0, v/v) mobile phase and UV detection at 240 nm. The R.S.D. of the extraction process for geniposidic and chlorogenic acid were 3.8 and 4.1%, respectively.     

高速逆流色谱法分离制备中药诃子中的没食子酸

利用高速逆流色谱法从100 mg诃子醇提物中一次性分离制备得到8.6 mg没食子酸。通过分析型高速逆流色谱对5种溶剂系统进行筛选,确定以正己烷-乙酸乙酯-甲醇-水(体积比为1:5:1:5)为两相溶剂体系并放大到制备型上,以上相为固定相,下相为流动相,在主机转速850 r/min、流动相流速2 mL/min、检测波长254 nm的条件下进行分离制备,获得4个分离峰(组分Ⅰ、Ⅱ、Ⅲ、Ⅳ)。经高效液相色谱检测,按照面积归一法计算,其中组分Ⅲ的纯度达96.40%。经电喷雾电离质谱分析,并结合与没食子酸标准品的高效液相色谱测定结果的对比,确定组分Ⅲ为没食子酸。该方法简便、快速、重复性好,适合于诃子中没食子酸的分离制备。     

小白菜中残留虫酰肼的超临界流体萃取条件的研究

将超临界流体萃取(supercritical fluid extraction,SFE)技术与高效液相色谱分析相结合,建立了特异性杀虫剂虫酰肼的萃取分离方法。SFE对虫酰肼的萃取条件:压力48.3 MPa(7000 psi),温度60 ℃,静态萃取时间20 min,CO2体积10 mL,改性剂甲醇添加量0.04 mL/g,丙酮为收集溶剂。在此条件下,SFE对虫酰肼的萃取率为100.75%,所得样品可直接用于高效液相色谱分析。色谱条件：紫外-二极管阵列检测器(检测波长为245 nm),C18键合色谱柱,乙腈     

基于水溶性浸出物及HPLC指纹图谱评价不同贮存年限半夏的品质

研究不同贮存年限半夏药材的浸出物,建立浸出物的HPLC特征指纹图谱,为半夏药材品质评控提供参考。浸出物测定方法采用药典法;HPLC指纹图谱的色谱条件:采用C_(18)色谱柱(150 mm×4.6 mm,5μm),以水–甲醇为流动相,梯度洗脱,流量为0.8 m L/min,检测波长为260 nm,柱温为25℃,进样体积为50μL。采用相似度评价及聚类分析技术揭示14批样品的相似性及差异性。14批半夏浸出物有12批合格,2批不合格。建立14批半夏浸出物样品的高效液相指纹图谱,确定了3个共有峰,共有峰保留时间的相对标准偏差小于2%,峰面积的相对标准偏差差异较大。1~#~7~#半夏样品有12个共有峰,共有峰保留时间的相对标准偏差小于1.5%,峰面积的相对标准偏差差异较大。各批次药材化学成分组成及含量均存在一定差异。以半夏浸出物数据与其高效液相色谱指纹图谱数据为基础,将指纹图谱相似度评价与聚类分析结合起来,用浸出物含量及评价软件测评结果对半夏品质进行综合评估,可以更精确地对半夏药材进行质量控制。     

Influence of solvent effects on retention in reversed-phase liquid chromatography and solid-phase extraction using a cyanopropylsiloxane-bonded,silica-based sorbent

Summary The solvation parameter model is used to characterize the retention properties of a cyanopropylsiloxane-bonded, silica-based sorbent with methanol, acetonitrile, tetrahydrofuran, and isopropanol in water as mobile phases. The system constants over the composition range 1 to 50% (v/v) organic solvent indicate that retention occurs because of the relative ease of cavity formation in the solvated stationary phase compared to the same process in the predominantly aqueous mobile phase as well as from more favorable stationary phase interactions with solutes containing - and n-electrons. The capacity of the solute for dipole-type interactions is not important whereas all hydrogen-bond-type interactions result in reduced retention. Graphing the system constants as a function of mobile phase composition provides a simple mechanism for interpreting the change in capacity of the chromatographic system for retention in terms of changes in the relative weighting of fundamental intermolecular interactions. A comparison is also made with the retention properties of an octadecylsiloxane-bonded, silica-based sorbent with 30% (v/v) methanol in water as the mobile phase and the extraction characteristics of a porous polymer sorbent with 1% (v/v) methanol, acetonitrile, tetrahydrofuran, and isopropanol in water as the sample processing solvent. Changes in sorbent selectivity due to selective uptake of the processing solvent are much smaller for the cyanopropylsiloxane-bonded sorbent than the results found for a porous polymer sorbent.     

Determination of the R-(-) and S-(+) enantiomers of the monohydroxylated metabolite of oxcarbazepine in human plasma by enantioselective high-performance liquid chromatography.

An enantioselective liquid chromatographic assay for the simultaneous determination of the S-(+) and R-(-) enantiomers of the monohydroxylated metabolite of oxcarbazepine in human plasma is described. The metabolite is the active principle. The method is based on the extraction of plasma with diethyl ether-dichloromethane (2:1, v/v), separation of the organic phase, evaporation of the solvent and dissolution of the residue in the mobile phase. The two enantiomers were resolved on a Chiralcel OD (250 mm x 4.6 mm I.D.) high-performance liquid chromatographic column. The separation was achieved by isocratic elution with n-hexane-2-propanol (77:23, v/v). The flow-rate of the mobile phase was 1.0 ml/min and the two enantiomers were detected by ultraviolet absorbance at 210 nm. The analytical method is suitable for the quantitative and simultaneous determination of the two enantiomers in plasma at concentrations down to 0.4 mumol/l after administration of oxcarbazepine.     

仿刺参中皂苷类成分的高效液相色谱指纹图谱

利用高效液相色谱法建立了仿刺参皂苷类成分的指纹图谱,为仿刺参的质量控制提供了新的方法。采用固相萃取制备供试品溶液,选用Zorbox SB-C18色谱柱(250 mm×4.6 mm, 5 μm),以乙腈-0.1%磷酸水溶液为流动相进行梯度洗脱,检测波长为205 nm,柱温30 ℃。分析了不同产地的10批仿刺参样品,采用国家药典委员会推荐的“中药色谱指纹图谱相似度评价系统(2004 A版)”处理谱图,确定了6个共有峰。计算了10个样本间的指纹图谱相似度,所得相似度计算结果均大于0.97。该方法具有良好的稳定性和重现性,可用于仿刺参的质量控制。     

Determination of nizatidine and two of its main metabolites in human serum using high-performance liquid chromatography

A high-performance liquid chromatographic assay has been developed for the determination of nizatidine, a new histamine H2-receptor antagonist, and two of its main metabolites, N-desmethylnizatidine and nizatidine sulphoxide. Drugs were extracted with chloroform-2-propanol (90:10, v/v) from alkalinized samples of serum, using ranitidine as an internal standard. After evaporation of the extraction solvent, the residue was removed and analysed on a LiChrosorb Si60 5-microns column with a mobile phase of acetonitrile-methanol-water-ammonia solution (1000:200:20:5, v/v). The compounds were detected at 320 nm. The lower detection limits were 6-18 ng/ml at a signal-to-noise ratio of 3. This method is simple and specific, and the single-step extraction makes it rapid. It is the first high-performance liquid chromatographic assay to be described for the determination of nizatidine metabolites.     

Isolation and purification of inflacoumarin A and licochalcone A from licorice by high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) technique in semi-preparative scale has been applied to isolate and purify bioactive flavone compounds from the ethanol extract of Glycyrrhiza inflata Bat., a particular plant species of licorice. HSCCC separation was performed with a two-phase solvent system composed of n-hexane-chloroform-methanol-water (5:6:3:2, v/v) by eluting the lower mobile phase at a flow rate of 1.8 ml/min and a revolution speed of 800 rpm. Purification was performed with a two-phase solvent system composed of n-hexane-chloroform-methanol-water (1.5:6:3:2, v/v) by eluting the lower mobile phase at a flow-rate of 1.5 ml/min and a revolution speed of 800 rpm. Two major flavone peaks: inflacoumarin A and licochalcone A were collected and the respective yields of the peaks amount to 6 mg (8.6%, w/w) and 8 mg (11.4%, w/w) from 70 mg of the crude extract sample. The purities of inflacoumarin A and licochalcone A reached 99.6% and 99.1%, respectively, after a sequential purification run. The structures of inflacoumarin A and licochalcone A were positively confirmed by 1H NMR and 13C NMR, 1H-13C-COSY, UV, FT-IR and electron ionization MS analyses.     

三角形法和四面体法优化选择毛细管区带电泳背景电解质

建立了两种高效、快速的毛细管区带电泳背景电解质(BGE)的优化方法三角形优化法和四面体优化法。以色谱指纹图谱指数F和色谱指纹图谱相对指数Fr作为评价毛细管电泳分析系统的目标函数,以雪莲药材水提取液为样品,考察一定浓度的硼砂、硼酸、磷酸氢二钠和磷酸二氢钠溶液按三角形优化法和四面体优化法构成背景电解质时对样品的分离情况,通过添加有机改性剂和调节pH进行再优化。用三角形法优化出以50 mmol/L硼砂-含3%乙腈的150 mmol/L磷酸二氢钠(体积比为1∶1)作为BGE时分离效果最佳,用四面体法优化出以50 mmol/L硼砂-150 mmol/L磷酸二氢钠-200 mmol/L硼酸(体积比为1∶1∶2,用0.1 mol/L氢氧化钠调pH 8.55)作为BGE时分离效果最佳,分别获得28个和25个电泳峰。所建立的方法操作简捷,适用于中药材水提取液或醇提取液的毛细管区带电泳BGE的选择。     

RP-HPTLC fingerprinting of secondary metabolites from Nephrolepis exaltata and Cycas revoluta

This study aims to develop a quantitative fingerprinting between two evolutionary close plant species Nephrolepis exaltata (L.) Schott and Cycas revoluta Thunb. The crude plant extracts were prepared in 1:1:1, v/v/v: Ethyl Acetate: n-Hexane: Methanol (AR) solvent system through cold extraction for 24 Hrs. The plant extracts were diluted (10 mg/mL) with a similar solvent system spotted (10 μL) on silica gel 60 F²⁵⁴ thin-layer chromatography plates. Five mobile phases (i) tetrahydrofuran (THF): toluene: formic acid: water (16:8:2:1) (ii) toluene: ethyl acetate: diethylamine (7:2:1) (iii) toluene: ethyl acetate: formic acid (7:3:0.1) (iv) n-hexane: ethyl acetate (7.2:2.9) (v) toluene: methanol (9:1) were used. The results were scanned at 254 nm, 366 nm, and in visible white light. This study gave minimum compact spots between Rf 0.06 to 0.051 corresponding to terpenoids, simultaneously for flavonoids spots were found between Rf 0.004 to 0.910. Total eight phenolic bands were found in Cycas revoluta among which five was found in leaf extract with Max RF of 0.033, 0.093, 0.273, 0.901 and 0.964 whereas three bands were found in stem extract with Max Rf of 0.007, 0.897 and 0.954. The presence of fifteen different types of flavonoids was determined by the flavonoids profile at Rf 0.004, 0.027, 0.047, 0.073, 0.134, 0.230, 0.303, 0.369, 0.369, 0.427, 0.514, 0.631, 0.703, 0.757, 0.846 and 0.910 for Nephrolepis exaltata. HPTLC fingerprint has shown several peaks with different Rf for different mobile phases. The fingerprinting would be helpful in the identification, and authentication of these species ecologically and therapeutically.     

Comparison of microemulsion electrokinetic chromatography with high-performance liquid chromatography for fingerprint analysis of resina draconis

Microemulsion electrokinetic chromatography (MEEKC) has been developed for fingerprint analysis of resina draconis, a substitute for sanguis draconis in the Chinese market. The microemulsion as the running buffer was made up of 3.3% (w/v) sodium dodecyl sulfate (SDS), 6.6% (w/v) n-butanol, 0.8% (w/v) n-octane, and 10 mmol/L sodium tetraborate buffer (pH 9.2), which was also used as the solvent for ultrasonic extraction of both water- and fat-soluble compounds in the traditional Chinese medicine samples. Four batches of resina draconis obtained from different pharmaceutical factories located in different geographic regions were used to establish the electrophoretic fingerprint. MEEKC was performed using a Beckman PACE/MDQ system equipped with a diode-array detector and with monitoring at 280 nm. The fingerprint of resina draconis comprised 27 common peaks within 100 min. The relative standard deviations of the relative migration time of these common peaks were less than 2.1%. Through repetitive injection of the sample solution six times in 24 h, all relative standard deviations of the migration time and peak area of loureirin A and loureirin B were less than 2.5 and 3.8%, which demonstrated that the method had good stability and reproducibility. The relative peak areas of these common peaks in the electropherograms of four batches of resina draconis were processed with two mathematical methods, the correlation coefficient and the interangle cosine, to valuate the similarity. The values of the similarity degree of all samples were more than 0.91, which showed resina draconis samples from different origins were consistent. On the other hand, high-performance liquid chromatography (HPLC) coupled with photodiode-array detection was also applied to establish the fingerprint of resina draconis. The samples were separated with a LiChrospher C₁₈ column using acetonitrile (solvent A) and water containing 0.1% H₃PO₄ (solvent B) as the mobile phase in linear gradient elution mode at a flow rate of 0.6 mL/min and detection was at 280 nm. There were only 20 common peaks in the HPLC fingerprint, and the values of the similarity degree of all samples were also more than 0.91. Though the similarity results of fingerprint analysis seemed to be the same, MEEKC resulted in more common peaks and higher separation efficiency for a variety of polarities of the components than HPLC. So, MEEKC was more suitable for development of the fingerprint of resina draconis.