基于特征图谱和UPLC-Q-TOF/MS技术的北柴胡及其常见混淆品的化学鉴别研究

目的基于特征图谱和UPLC-Q-TOF/MS技术对北柴胡及其常见混淆品进行化学鉴别。方法对收集的不同基原、不同产地北柴胡及其常见混淆品进行薄层色谱鉴别,然后依据建立的HPLC特征图谱对北柴胡及其混淆品进行化学成分比较,进一步结合UPLC-Q-TOF/MS技术找出柴胡属混淆品代表性差异标志物。结果薄层色谱显示,不同基原柴胡饮片均具有柴胡皂苷A和柴胡皂苷D,根据荧光斑点强度和位置可将其进行区分。北柴胡及其醋炙品特征图谱分别标定了14、16个共有峰,并指认其中6个成分。不同产地北柴胡饮片所含化学组分类似,建立的方法可以较好地体现柴胡特征。进一步通过特征图谱比较发现,竹叶柴胡在成分类群组成上与正品北柴胡接近,锥叶柴胡和大叶柴胡具有各自响应值较高的特征峰,藏柴胡皂苷含量明显高于北柴胡。利用UPLC-Q-TOF/MS共鉴定出69种柴胡化合物,主要为三萜皂苷类成分,其次是黄酮类,少数色酮、苯丙素类和炔类成分。聚类分析结果显示柴胡种间差异较为明显,不同柴胡混淆品具有代表性差异标志物。结论建立的特征图谱和UPLC-Q-TOF/MS分析方法可用于北柴胡及其常见混淆品的化学鉴别研究,为全面合理开发利用柴胡资源提供依据。

基于标准汤剂的石榴皮配方颗粒质量评价研究

基于标准汤剂建立石榴皮配方颗粒的质量评价方法。制备15批石榴皮标准汤剂和3批配方颗粒,测定出膏率,基于高效液相色谱法(HPLC)建立特征图谱,并进行相似度评价,采用化学计量学方法包括无监督的聚类分析(HCA)、主成分分析(PCA)和有监督的偏最小二乘判别分析(PLS-DA)对特征图谱数据进行分析,针对指标成分进行HPLC含量测定,计算石榴皮标准汤剂和配方颗粒中指标成分的转移率。结果表明:石榴皮配方颗粒与标准汤剂特征图谱的相似度均大于0.9。15批石榴皮标准汤剂出膏率为27.95%~41.32%,标准汤剂中石榴皮鞣素、安石榴苷、鞣花酸的转移率分别为21.49%~39.00%、18.99%~33.62%、53.37%~95.45%。按照标准汤剂数据制定石榴皮配方颗粒中上述指标成分的含量限度应为10.58~19.64 mg/g、29.91~55.55 mg/g、10.51~19.52 mg/g。石榴皮配方颗粒出膏率为41.9%~43.1%,配方颗粒中指标成分的转移率与标准汤剂接近,指标成分的含量在根据标准汤剂所制定含量限度范围内。本研究基于标准汤剂建立了石榴皮配方颗粒的质量控制标准,为石榴皮配方颗粒的质量控制以及后续的工艺研究提供参考。

一起110kV主变铁心多点特殊接地故障诊断消缺的典型案例分析

在例行带电检测过程中,发现某110kV主变本体油色谱分析存在轻微异常,通过长时间采样跟踪发现氢气和总烃含量呈持续增长态势,并在近期采样结果中远超规定值;在完成各项常规及特殊试验诊断后,并未发现明显异常项;经抽油吊检处理,发现内部铁心引线存在明显烧蚀痕迹,系铁心引线与硅钢片短路造成变压器内部铁心多点接地形成的环流放电所致,并直接导致油色谱数据异常。确定故障原因和缺陷位置后,对故障部件进行了更换处理,保证了运行设备的安全稳定。

颠茄流浸膏膜过滤纯化工艺研究

目的 建立适合于生产的超滤与纳滤结合的纯化精制工艺,制备高品质颠茄流浸膏。方法 采用超滤、纳滤技术,以膜过滤温度、膜通量、操作压力为考察因素,优选颠茄流浸膏膜过滤纯化工艺参数,并对过滤纯化后的颠茄流浸膏进行特征图谱考察。结果 颠茄流浸膏最佳膜过滤工艺为:颠茄草粉碎,用乙醇浸泡渗漉得渗漉液,渗漉液浓缩后经孔径为200 nm的氧化铝陶瓷膜在30℃、0.4 MPa压力条件下超滤可去除色素杂质;超滤后的滤液经截留分子质量为200 u的聚酰胺纳滤膜在30℃、1.0 MPa条件下纳滤浓缩,可去除无机盐。超滤液、纳滤液特征图谱中的相对保留时间、相对峰面积符合规定,表明与提取液化学成分的一致性较好。结论 建立的纯化精制工艺稳定,简便可行,利于工业化生产,对颠茄流浸膏品质提升具备良好的应用价值。

经典名方保元汤UPLC特征图谱研究

目的 建立经典名方保元汤的UPLC特征图谱,为其质量标准的建立提供参考。方法 色谱柱为Agilent ZORBAX SB C18(2.1 mm×150 mm,1.8μm);流动相为乙腈-水(梯度洗脱),流速为0.20 mL/min,柱温为35℃,进样量为1μL,检测波长为203 nm。以峰5芒柄花苷为参照峰,绘制21批保元汤基准样品的UPLC特征图谱,采用《中药色谱指纹图谱相似度评价系统(2012版)》进行相似度评价。结果 21批保元汤基准样品共有12个特征峰,分别为毛蕊异黄酮葡萄糖苷(峰1)、新甘草苷(峰2)、甘草苷(峰3)、芹糖异甘草苷(峰4)、芒柄花苷(峰5)、异甘草苷(峰6)、甘草素(峰7)、人参皂苷Re(峰8)、人参皂苷Rg1(峰9)、毛蕊异黄酮(峰10)、芒柄花素(峰11)、人参皂苷Rd(峰12),相似度大于0.70。结论 所建立的UPLC特征图谱和特征峰的分析结果可为经典名方保元汤的质量控制提供参考。

基于特征图谱和多成分含量测定的维吾尔药材铁力木及其代用品质量评价

目的建立铁力木及长叶格脉树的高效液相色谱(HPLC)特征图谱及多成分定量分析方法,以分析铁力木和长叶格脉树的质量差异,并对铁力木的质量进行评价。方法采用HPLC法,建立铁力木和长叶格脉树的对照特征图谱,进行相似度评价,并指认共有峰;通过聚类分析(HCA)、主成分分析(PCA)及偏最小二乘判别分析(PLS-DA)等化学计量学方法,区分铁力木和长叶格脉树;并对5种指标成分进行质量分数测定。结果建立了铁力木和长叶格脉树特征图谱的分析方法,各标记8个色谱峰,包括长叶格脉树特有的5号峰和铁力木特有的7号峰;同时指认7个共有峰。相似度评价、HCA和PCA均能将样品聚为铁力木和长叶格脉树2类;PLS-DA筛选出3个标志性差异成分。质量分数测定结果显示,铁力木和长叶格脉树中5种成分的质量分数存在显著差异。结论铁力木和长叶格脉树化学成分存在显著差异,不建议二者混用或相互代替。本方法稳定可靠,可快速区分铁力木和长叶格脉树,为铁力木的质量评价提供科学依据。

Bohai crude oil identification by gas chromatogram fingerprinting quantitative analysis coupled with cluster analysis

By gas chromatogram, six crude oils fingerprinting distributed in four oilfields and four oil platforms were analyzed and the corre- sponding normal paraffin hydrocarbon （ including pristane and phytane） concentration was obtained by the internal standard methed. The normal paraffin hydrocarbon distribution patterns of six crude oils were built and compared. The cluster analysis on the normal paraffin hydrocarbon concentration was conducted for classification and some ratios of oils were used for oils comparison. The results indicated： there was a clear difference within different crude oils in different oil fields and a small difference between the crude oils in the same oil platform. The normal paraffin hydrocarbon distribution pattern and ratios, as well as the cluster analysis on the nomad paraffin hydrocarbon concentration can have a better differentiation result for the crude oils with small difference than the original gas chromatogram.

Identification of three kinds of Plumeria flowers by DNA barcoding and HPLC specific chromatogram

DNA barcoding and HPLC specific chromatogram were used to identify three kinds of Plumeria flowers respectively. DNAs extracted from the three Plumeria species were amplified by PCR with universal primers, and the psbA-trnH region was selected. All the amplified products were sequenced and the results were analyzed by MEGA 5.0. Chemometric methods including principal components analysis and hierarchical clustering analysis were conducted on the SAS 9.0 software to demonstrate the variability among samples. In conclusion, the psbA-trnH of all samples were successfully amplified from total DNA and sequenced. These three varieties of Plumeria can be differentiated by the psbA-trnH region and clustered into three groups respectively through building neighbor joining tree, which conformed to their germplasm origins. However, it was hard to distinguish them by HPLC specific chromatograms combined with chemometrics analysis. These indicated that DNA barcoding was a promising and reliable tool for the identification of three kinds of Plumeria flowers compared to HPLC specific chromatogram generally used. It could be treated as a powerful complementary method for traditional authentication, especially for those varieties which are difficult to be identified by conventional chromatography.

HPLC Fingerprint Chromatogram of Tetracera asiatica Produced in Guangxi

[Objectives] To establish fingerprint chromatogram of Tetracera asiatica and provide basis for controlling and assessing the quality of Tetracera asiatica.[Methods] The high-performance liquid chromatography( HPLC) method was used. Phenomenex C18( 5 μm,4. 6 ×250 mm),acetonitrile-0. 1% phosphoric acid water,gradient elution,flow rate 1 m L/min,detection wavelength 214 nm,and column temperature 25 ℃. The fingerprint chromatogram of 10 batches of samples of Tetracera asiatica was determined for similarity comparison. [Results] It established HPLC fingerprint chromatogram of Tetracera asiatica produced in Guangxi,determined a total of 13 common fingerprint peaks. The similarity of 10 batches of Tetracera asiatica was > 0. 9.[Conclusions] The method is rapid and accurate and can provide references for assessing the quality of Tetracera asiatica.

Typical HPLC Chromatogram of Petroleum Ether in Abutilon indicum(L.) Sweet from Different Habitats

[Objectives] To study the typical HPLC chromatogram of petroleum ether in Abutilon indicum (L.) Sweet from different habitats, in order to provide experimental basis for the quality control of A. indicum and the spectrum-efficacy relationship of petroleum ether.[Methods] The HPLC chromatogram of petroleum ether was obtained using Agilent SB-C 18 (4.6 mm×250 mm, 5 μm) and acetine-0.1% phosphoric acid solution for gradient elution at temperature of 30 ℃, flow rate of 1.0 mL/min and detection wavelength of 205 nm.[Results] The typical HPLC chromatogram of petroleum ether in A. indicum was preliminarily established, with 12 characteristic peaks. It was verified by A. indicum from different habitats, characterized by reproducibility and stability.[Conclusions] Typical HPLC chromatogram provides a stable new method for the quality control of petroleum ether in A. indicum . This study provides experimental basis for further study on the medicinal parts of A. indicum .

Establishment of Specific Chromatogram of Spica Prunellae Formula Granules Based on Standard Decoction

[Objectives]This study aimed to establish HPLC chromatograms of decoction pieces,standard decoction and formula granules of Spica Prunellae.[Methods]The chromatographic conditions were as follows:column,SHISEIDO CAPCELL PAK C18 MGII column(4.6 mm×250 mm,5μm);mobile phase,acetonitrile-0.1%phosphoric acid;gradient elution;detection wavelength,280 nm;flow rate,1.0 mL/min;and column temperature,30℃.The correlation between the decoction pieces,standard decoction and formula granules of Spica Prunellae was analyzed by specific chromatograms.[Results]The fingerprint chromatograms of decoction pieces,standard decoction and formula granules of Spica Prunellae showed five common peaks,with good correlation.Among the five common peaks,four of them were tanshinol,protocatechuic acid,caffeic acid and rosmarinic acid.[Conclusions]The main chemical constituents of decoction pieces,standard decoction and formula granules of Spica Prunellae are basically the same.The HPLC specific chromatogram established can be used for the quality control of Spica Prunellae formula granules.

Analysis for the Defect of Chromatogram in 35kv Oil-immersed Electric Reactor

A defect of chromatogram in a 35kV oil-immersed three-phase one-piece electric reactor in a 500kV substation。The initial analysis suggests that the defect is caused by the loose connection of the iron core magnet shield (magnet shield layer of iron core or earthling top). Examination of winding DC resistance, DGA and other relevant examinations were carried out to investigate the defect reasons., which is demonstrated by the dismantlement. In-depth study is taken and corresponding prevention measures are put forward in the paper.

Identification of HPLC Characteristic Chromatograms of Phenylethanoid Glycosides and Iridoid Glycosides in Herba Cistanche of Different Origins

[Objectives]This study aimed to establish a quality evaluation method for Herba Cistanche based on the HPLC characteristic chromatograms of the phenylethanoid glycosides and iridoid glycosides,and compare the HPLC characteristic chromatograms of different origins of Herba Cistanche.[Methods]The chromatographic conditions used were as follows:column,Agilent ZORBAX Eclipse Plus C18 column(4.6 mm×250 mm,5μm);gradient elution,acetonitrile-0.1%phosphoric acid aqueous solution;flow rate,1.0 mL/min;detection wavelength,240 nm;column temperature,30℃.[Results]Cistanche tubulosa(Schenk)Wight showed 9 characteristic peaks,Cistanche deserticola Y.C.Ma showed 10 characteristic peaks,Cistanche salsa(C.A.Mey.)G.Beck showed 7 characteristic peaks,and Cistanche sinensis G.Beck showed 4 characteristic peaks.Peak 6 was echinacoside,peak 7 was verbascoside,peak 8 was tubuloside A,peak 9 was isoacteoside and peak 10 was cistanoside A.The characteristic chromatograms of the four different origins of Herba Cistanche were significantly different.[Conclusions]This characteristic chromatogram method has good reproducibility and can be used to distinguish 4 different origins of Herba Cistanche,C.deserticola Y.C.Ma,C.tubulosa(Schenk)Wight,C.sinensis G.Beck and C.salsa(C.A.Mey.)G.Beck.

Study on the Specific GC Chromatograms of Volatile Oil from Xinyi Biyan Pills

[Objectives]This study was conducted to establish characteristic chromatograms of of the volatile oil of Xinyi Biyan Pills by gas chromatography,discover possible problems in the production processes of different manufacturers,and further improve the quality control methods.[Methods]The volatile oil in samples was extracted and tested by gas chromatography to collect chromatograms,which were analyze and evaluated by the similarity evaluation software of chromatographic fingerprints of traditional Chinese medicine.[Results]Nineteen common peaks were calibrated in the characteristic chromatograms;and the characteristic chromatograms of samples produced by different manufacturers were obviously different.[Conclusions]Controlling the volatile components in Xinyi Biyan Pills by the established characteristic chromatograms of GC is accurate and feasible,and can be used as a quality control method for Xinyi Biyan Pills.

Establishment of Characteristic Chromatogram of Honeysuckle Stem Formula Granules Based on the Concept of Whole Process Quality Control

[Objectives]To establish a HPLC characteristic spectrum of honeysuckle stem formula granules,and to evaluate the quality consistency based on the standard decoction.[Methods]Using Agilent ZORBAX SB-C_(18)(5μm,250 mm×4.6 mm)chromatographic column;gradient elution with acetonitrile-0.4%phosphoric acid solution(0.2:99.8,V/V),column temperature at 25℃;detection wavelength at 236 nm;flow rate 1.0 mL/min;using"Similarity Evaluation System for Chromatographic Fingerprint of Traditional Chinese Medicine",to evaluate the similarity of the characteristic chromatogram of crude drug,standard decoction and formula granules of honeysuckle stem.[Results]The similarity of characteristic chromatogram was higher than 0.94,and 6 components were identified from 10 characteristic peaks.[Conclusions]The established method can more comprehensively reflect the overall appearance of the chemical substances in the honeysuckle stem and the transmission law,and can provide an experimental basis for the consistency of the quality of the honeysuckle stem formula granules.

Research on Comparison of Gas Chromatography and Liquid Chromatogram Detecting Pesticide Residue

The existing methods of detecting pesticide residue include gas chromatography, high performance liquid chromatography, gas chromatograph-mass, liquid chromatograph-mass, capillary electrophoresis, radioimmunoassay, biosensor and rapid detection on the spot. The paper analyzes the comparison of gas chromatography and liquid chromatogram detecting pesticide residue, for achieving the development tendency and the future goal of analyzing pesticide residue.

基于UPLC特征图谱和含量测定的蜜远志标准汤剂质量评价研究

目的建立蜜远志标准汤剂特征图谱以及3种成分质量分数同时测定的UPLC方法,对不同来源蜜远志饮片制成的标准汤剂质量进行评价。方法采用UPLC法建立蜜远志标准汤剂的特征图谱以及细叶远志皂苷、远志酮Ⅲ和3,6′-二芥子酰基蔗糖质量分数测定的方法,并对16批标准汤剂进行测定,采用高分辨质谱对共有峰进行了指认,采用聚类分析及偏最小二乘法分析(PLS-DA)对共有峰进行了分析。结果蜜远志标准汤剂特征图谱标定了9个共有峰,通过高分辨质谱分别指认为:西伯利亚远志糖A5、西伯利亚远志糖A6、远志酮Ⅲ、3,6′-二芥子酰基蔗糖、黄花远志素A、细叶远志皂苷A、远志寡精H、远志寡糖A、1,2,3,7-四甲氧基呫吨酮,相似度结果显示16批样品的相似度均大于0.900。聚类分析及PLS-DA显示不同来源之间的样品可能存在质量差异。结论本研究建立的蜜远志标准汤剂特征图谱和质量分数测定方法简便、快速、准确,可为蜜远志相关制剂的质量评价提供参考。

瑶药小钻的特征图谱及其安五脂素含量和抗炎活性研究

目的 建立瑶药小钻特征图谱及其主要成分安五脂素含量测定方法,并评价安五脂素抗炎活性。方法 采用高效液相色谱法,以乙腈-0.5%磷酸溶液为流动相进行梯度洗脱,采用《中药色谱指纹图谱相似度评价系统(2012版)》建立小钻药材的特征图谱和进行相似度评价,并测定小钻中安五脂素含量。以脂多糖诱导的RAW264.7巨噬细胞为炎症细胞模型,考察安五脂素对细胞上清液中肿瘤坏死因子α(TNF-α)、白细胞介素1β(IL-1β)、IL-6水平的影响。结果 10批小钻样品的特征图谱相似度为0.901~0.994;标定了9个共有峰,指认了3个成分,分别为长南五味子素E、南五味子内酯A、安五脂素;安五脂素的含量为(0.72±0.05)~(1.21±0.03)mg/g(n=3)。0.125~0.5μg/mL的安五脂素可显著降低炎症模型细胞上清液中TNF-α、IL-1β、IL-6水平(P<0.05或P<0.01)。结论 建立了小钻药材HPLC特征图谱及其安五脂素含量测定方法;安五脂素可能是小钻药材发挥抗炎作用的有效成分。

清脂化瘀方HPLC-CAD特征图谱建立及6种糖类含量测定

目的建立清脂化瘀方HPLC-CAD特征图谱,并测定鼠李糖、果糖、甘露醇、D-无水葡萄糖、蔗糖、棉子糖的含量。方法分析采用Dikma Polyamino HILIC色谱柱(4.6 mm×250 mm,5μm);流动相乙腈-水,梯度洗脱;体积流量0.8 mL/min;柱温35℃。结果15批样品特征图谱中有14个特征峰相似度大于0.90。6种糖类在各自范围内线性关系良好(r>0.9950),平均加样回收率93.34%~105.64%,RSD 0.5%~2.6%。结论该方法准确可靠,灵敏度高,重复性好,可用于清脂化瘀方糖类的质量控制。

溶剂提取-高效液相色谱法测定大气颗粒物中18种多环芳烃

建立大气颗粒物PM2.5中18种多环芳烃的样品快速溶剂提取结合高效液相色谱的测定方法。将1/2玻璃滤膜剪碎后加入2.0 mL乙腈,于20℃水浴超声提取30 min,提取液经0.22μm有机相滤膜过滤,多环芳烃C18专用柱分离,以乙腈-水作为流动相进行梯度洗脱,采用紫外串联荧光检测器-高效液相色谱仪检测,以色谱峰面积外标法定量。18种PAHs的质量浓度在0.01~0.50μg/mL范围内与色谱峰面积线性关系良好,相关系数不小于0.999,检出限为0.03~0.47 ng/m^(3),样品加标平均回收率为75.6%~114.7%,相对标准偏差为0.09%~3.78%(n=7)。该方法简便、快速、准确、灵敏,可应用于大气颗粒物PM2.5中18种多环芳烃的测定。