中药酸枣仁的真伪鉴别方法研究

目的: 针对酸枣仁的质量问题,研究建立酸枣仁及常见伪品理枣仁的鉴别方法,为酸枣仁的质量控制和市场监管提供依据。方法: 对全国范围内抽取的酸枣仁药材及饮片样品进行检验和研究,分析其总体质量情况和存在的问题,针对理枣仁掺伪情况,建立性状鉴别法、薄层色谱法(TLC法)、超高效液相色谱-飞行时间质谱法(UPLC-QTOF/MS法)等手段鉴别真伪的方法。结果: 抽验结果表明市场上酸枣仁的主要质量问题为以理枣仁冒充或掺伪。研究发现酸枣仁和伪品理枣仁在性状特征、TLC、UPLC-QTOF/MS等方面均存在较为明显的差异。结论: 所建立的方法可针对性应用于酸枣仁药材或饮片的真伪鉴别及掺伪检验,特别是当性状鉴别法和TLC法难以鉴别时,新建的UPLC-QOTF/MS方法对于炒酸枣仁饮片中掺伪理枣仁的鉴别和检验有较大的优势,该法专属性强,灵敏度高,可有效打击掺伪造假的违法行为。建议进一步提高和完善质量标准,加强酸枣仁药材和饮片的质量控制。

Objective: To develop a new method for identification of adulterants according to the quality of crude drug materials and decoction pieces of Ziziphi Spinosae Semen in the market. Methods: Samples from different sources were identified and analyzed according to the standard of Chinese Pharmacopoeia.The total quality status of Ziziphi Spinosae Semen over national wide was evaluated,and the main quality problems were found out.A series of methods for identification of Ziziphi Spinosae Semen and Ziziphi Mauritianae Semen were established based on traditional organoleptic properties,TLC,and modern UPLC-QTOF-MS. Results: Positive results identification of genuine and fake samples were obtained using the new developed methods. Conclusion: The new developed methods can effectively identify different types of samples.UPLC-QTOF-MS method has been validated and verified effective in sensitivity and specificity,especially in identification of adulterant samples of Ziziphi Spinosae Semen and Ziziphi Mauritianae Semen.The further analysis should be performed to improve the standard and strengthen the quality control of Ziziphi Mauritianae Semen.

[1] ChP 2010 Vol Ⅰ(中国药典2010年版.一部)[S].2010:343
[2] WU LF(吴荔芬),Identification of Ziziphi Spinosae Semen and Ziziphi Mauritianae Semen(酸枣仁与理枣仁的鉴别)[J].Strait Pharm J(海峡药学),2013,25(11):69
[3] YAN Y(闫艳),DU CH(杜晨晖),LI XJ(李小菊),et al. HPLC-DAD-ELSD simultaneous determination of spinosin,jujuboside A and jujuboside B inSemen Ziziphi Spinosae(Suanzaoren)(HPLC-DAD-ELSD法同时测定酸枣仁中斯皮诺素、酸枣仁皂苷A和B的含量)[J].Chin J Pharm Anal(药物分析杂志),2011,31(1):30
[4] ZHANG ZF(张志斐),WANG Q(王巧),ZHANG LT(张兰桐),et al. Fingerprints of Semen Ziziphi Spinosae from Hebei province by HPLC-UV(河北道地药材酸枣仁HPLC-UV指纹图谱研究)[J].Chin Tradit Pat Med(中成药),2007,29(8):1097
[5] YANG X(杨昕),YANG G(杨光).HPLC determination of betulinic acid in Semen Ziziphi Spinosae(高效液相色谱法测定酸枣仁中白桦脂酸的含量)[J].Chin J Pharm Anal(药物分析杂志),2006,26(5):683
[6] ZHANG ZF(张志斐),YUAN ZF(袁志芳),ZHANG LT(张兰桐),et al.HPLC-ELSD Fingerprints of genuine Semen Ziziphi Spinosae from Hebei province(河北道地药材酸枣仁HPLC-ELSD指纹图谱研究)[J].Chin Tradit Herb Drugs(中草药),2007,38(8):1247
[7] YAN Y(闫艳),DU CH(杜晨晖),PEI XP(裴香萍),et al.HPLC-DAD-ELSD fingerprint of Semen Ziziphi Spinosae in Shanxi and its hierarchical cluster analysis(山西产酸枣仁药材HPLC-DAD-ELSD指纹图谱及聚类分析)[J].Chin J Inf TCM(中国中医药信息杂志),2011,18(6):49
[8] ZHANG QY(张巧月),YANG HT(杨浩天),SHI H(史贺),et al.Simultaneous quantification of nine constituents in Ziziphi Spinosae Semen by HPLC-MS(HPLC-MS法同时测定酸枣仁中9种成分)[J].Chin Tradit Herb Drugs(中草药),2015,46(1):123
[9] LI HJ(李会军),LI P(李萍).Determination of jujuboside A and jujuboside B in Spine Date Seed by HPLC-ELSD(高效液相色谱法蒸发光散射检测器测定酸枣仁中酸枣仁皂苷A及B的含量)[J].Chin J Pharm Anal(药物分析杂志),2000,20(2):82
[10] ZHANG CY(张翠英),WANG J(王阶),GUO LL(郭丽丽),et al.Species differentiation and quality assessment of Ziziphus jujuba var.spinosa based on the HPLC fingerprint and quantitative analysis(酸枣仁及伪品滇枣仁的质量分析)[J].Chin Med Mat(中药材),2012,35(11):1758
[11] HUANG X(黄星).Compare analysis of effective constituents of Ziziphi Spinosae Semen and Ziziphi Mauritianae Semen(理枣仁与酸枣仁有效成分的分析比较)[J].China Pharm(中国药业),2002,11(9):61