ESI-Q-TOF-MS直接进样法比较陕西五个不同地区丹参的化学成分差异（英文）
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摘要
该研究采用ESI-Q-TOF-MS直接进样分析法对陕西商州、洛南、大荔、丹凤和铜川等五个地区丹参的化学成分进行了比较分析,通过丹参水溶性和脂溶性成分的质谱丰度差异评价了不同地区丹参化学成分含量的变化,对不同产地丹参的化学成分进行了鉴定,综合分析选出了最优的丹参种植产地。结果表明:五地丹参均含有丹参酮ⅡA、隐丹参酮、丹参酮Ⅰ、二氢丹参酮、丹参酚酮、次丹参醌、丹参醌Ⅱ等9种脂溶性化学成分和丹参素、咖啡酸、阿魏酸、迷迭香酸、原紫草酸、紫草酸、原儿茶醛、丹酚酸A、丹酚酸B等9种水溶性化学成分,其中丹参素钠、紫草酸、丹酚酸B和隐丹参酮的含量普遍较高,质谱丰度均大于30%。但是,随着种植环境不同,不同地区丹参的化学成分含量差异很大,如商州产丹参中含有较多具有生物活性的丹参酮类物质,其中丹参酮Ⅰ含量远远高于其他四个产地,质谱丰度达到72.6%,而其他地区丹参酮Ⅰ的质谱丰度为1.8%～11.3%。这表明丹参质量按照地区排序为商州>铜川>大荔>洛南>丹凤。该方法为中药药材质量评价提供了科学、可靠、便捷的途径,为药材规格等级的制定提供了新途径,为陕西丹参种植区域的选择提供了重要信息。
An direct injection ESI-Q-TOF-MS analysis method was developed to value the chemical constituent in Salvia miltiorrhiza( Danshen) coming from Shangzhou,Luonan,Dali,Danfeng and Tongchuan in Shaanxi Province,through analyzing the MS abundance of water soluble and lipid soluble extracts and obvious variation in chemical constituent. The comparison among different abundances was beneficial to select the optimum planting area of Danshen. The results showed that all Danshen samples from five different regions had nine kinds of lipid soluble chemical constituent( Tanshinone I,TanshinoneⅡA,TanshinoneⅡB,Cryptotanshinone,Dihydrotanshinone,Danshenxinkun A,Danshenxinkun D,2-Isopropyl-8-methylphenanthrene-3,4-dione and 7-beta-hydroxy-8-13-abietadiene-11,12-dione) and nine kinds of water soluble chemical constituent( danshensu,caffeic acid,ferulic acid,rosmarinic acid,prolithospermic acid,lithospermic acid,protocatechuic acid,salvianolic acid A and salvianolic acid B). The contents of danshensu,lithospermic acid,salvianolic acid B and cryptotanshinone were higher than other chemical constituent with a MS abundance of 30% at least. However,with the change of planting environment,the content of the same chemical constituents in Danshen varied greatly in different regions. More tanshinones with important biological activity existed in Danshen coming from Shangzhou,especially the MS abundance of Tanshinone I was as high as 72.6%,which was much higher than that in other four regions ranging from 1.8% to 11.3%. According to the comprehensive comparison,the quality of Danshen was ranged by Shangzhou > Tongchuan > Dali> Luonan> Danfeng. The direct injection ESI-Q-TOF-MS method was not easily affected by the growth environment and extraction conditions of the medicinal materials. It provides a scientific,reliable and convenient way to evaluate the medicine quality and a new way to formulate the specifications and grades of traditional Chinese medicine. The system is suitable for the chemical constituent of Danshen in Shaanxi Province.
An direct injection ESI-Q-TOF-MS analysis method was developed to value the chemical constituent in Salvia miltiorrhiza( Danshen) coming from Shangzhou,Luonan,Dali,Danfeng and Tongchuan in Shaanxi Province,through analyzing the MS abundance of water soluble and lipid soluble extracts and obvious variation in chemical constituent. The comparison among different abundances was beneficial to select the optimum planting area of Danshen. The results showed that all Danshen samples from five different regions had nine kinds of lipid soluble chemical constituent( Tanshinone I,TanshinoneⅡA,TanshinoneⅡB,Cryptotanshinone,Dihydrotanshinone,Danshenxinkun A,Danshenxinkun D,2-Isopropyl-8-methylphenanthrene-3,4-dione and 7-beta-hydroxy-8-13-abietadiene-11,12-dione) and nine kinds of water soluble chemical constituent( danshensu,caffeic acid,ferulic acid,rosmarinic acid,prolithospermic acid,lithospermic acid,protocatechuic acid,salvianolic acid A and salvianolic acid B). The contents of danshensu,lithospermic acid,salvianolic acid B and cryptotanshinone were higher than other chemical constituent with a MS abundance of 30% at least. However,with the change of planting environment,the content of the same chemical constituents in Danshen varied greatly in different regions. More tanshinones with important biological activity existed in Danshen coming from Shangzhou,especially the MS abundance of Tanshinone I was as high as 72.6%,which was much higher than that in other four regions ranging from 1.8% to 11.3%. According to the comprehensive comparison,the quality of Danshen was ranged by Shangzhou > Tongchuan > Dali> Luonan> Danfeng. The direct injection ESI-Q-TOF-MS method was not easily affected by the growth environment and extraction conditions of the medicinal materials. It provides a scientific,reliable and convenient way to evaluate the medicine quality and a new way to formulate the specifications and grades of traditional Chinese medicine. The system is suitable for the chemical constituent of Danshen in Shaanxi Province.
引文
CHEN Y,ZHANG N,MA J,et al.,2017.A platelet/cmc coupled with offline Uplc-Qtof-Ms/Ms for screening antiplatelet activity constituents from aqueous extract of Danshen[J].JPharmceut Biomed Anal,117:178-183.
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HERMUND DB,PLAZA M,TUMER C,et al.,2018.Structure dependent antioxidant capacity of phlorotannins from Icelandic Fucus vesiculosus by UHPLC-DAD-ECD-QTOFMS[J].Food Chem,240:904-909.
LIANG K,SUN H,AN R,et al.,2018.Simultaneous determination of eleven constituents in Huxin Oral Liquid by LC-MS/MS[J].Chin Trad Patent Med,40(1)105-109.[梁琨,孙辉,安叡,等,2018.LC-MS/MS法同时测定护心口服液中11种成分[J].中成药,40(1):105-109.]
PAN XJ,NIU GG,LIU HZ,2002.Comparison of microwaveassisted extraction and conventional extraction techniques for the extraction of Tanshinones from Salvia miltiorrhiza Bunge[J].Biochem Eng J,12:71-77.
QIN RA,LIN J,LI CY,et al.,2014.Study of the protective mechanisms of Compound Danshen Tablet(Fufang Danshen Pian)against myocardial ischemia/reperfusion injury via the Akt-eNOS signaling pathway in rats[J].J Ethnopharm acol,156:190-198.
ROBERTS AT,MARTIN CK,LIU Z,et al.,2007.The safety and efficacy of a dietary herbal supplement and gallic acid for weight loss[J].J Med Food,10:184-188.
State Pharmacopoeia Commission,2015.Pharmacopoeia of the People’s Republic of China[M].Beijing:Chinese Medical Science and Technology Press.[国家药典委员会,2015.中华人民共和国药典[M].北京:中国医药科技出版社.]
WANG JJ,PEI TX,GUO JY,et al.,2017.The rapeutic effects of Danshen Dropping Pills on hepatic fibrosis in rats induced by dimethylnitrosamine[J].Drug Clin,32(4):572-578.[王晶晶,裴天仙,郭景玥,等,2017.丹参滴丸对二甲基亚硝胺诱导大鼠肝纤维化的治疗作用[J].现代药物与临床,32(4):572-578.]
WANG WM,DUAN Q,2014.Analysis of phenolic acids and their antioxidant activity by capillary electrophoresis-mass spectrometry with field-amplified sample injection[J].Trad Chin Drug Res Clin Pharmcol,25(3):338-342.[王文明,段启,2014.毛细管电泳和质谱联用在线预浓缩酚酸类化合物及其抗氧化活性评价[J].中药新药与临床药理,25(3):338-342.]
ZHANG XC,LUO DD,TAO AE,et al.,2017.Species differentiation and quality assessment of Salvia miltiorrhiza and Salvia trijuga by HPLC fingerprint[J].J Chin Med Mat,40(5):1061-1065.[张晓灿,罗丹丹,陶爱恩,等,2017.基于指纹图谱和化学计量学的丹参及紫丹参质量评价研究[J].中药材,40(5):1061-1065.]
ZHANG Y,ZHU HL,SUN LR,2017.Phenolic acids from the roots of Salvia miltiorrhiza var.alba[J].J Chin Med Mat,40(4):854-857.[张愉,朱海林,孙隆儒,2017.白花丹参根的酚酸类成分研究[J].中药材,40(4):854-857.]
ZHAO QY,JIA LQ,WANG JY,et al.,2016.The effect of TanshinoneⅡA on macrophages reverse cholesterol transport related genes expression in Apo E-/-Mice[J].Guid J Trad Chin Med Pharm,22(11):15-19.[赵秋宇,贾连群,王俊岩,等,2016.丹参酮ⅡA对Apo E~(-/-)动脉粥样硬化小鼠腹腔巨噬细胞胆固醇流出相关基因表达的影响[J].中医药导报,22(11):15-19.]
FENG Y,2017.Modern pharmacological study and clinical application of radix salviae miltiorrhizae[J].Clin J Chin Med,9(30):46-47.[冯彦,2017.丹参的现代药理研究及临床应用[J].中医临床研究,9(30):46-47.]
HERMUND DB,PLAZA M,TUMER C,et al.,2018.Structure dependent antioxidant capacity of phlorotannins from Icelandic Fucus vesiculosus by UHPLC-DAD-ECD-QTOFMS[J].Food Chem,240:904-909.
LIANG K,SUN H,AN R,et al.,2018.Simultaneous determination of eleven constituents in Huxin Oral Liquid by LC-MS/MS[J].Chin Trad Patent Med,40(1)105-109.[梁琨,孙辉,安叡,等,2018.LC-MS/MS法同时测定护心口服液中11种成分[J].中成药,40(1):105-109.]
PAN XJ,NIU GG,LIU HZ,2002.Comparison of microwaveassisted extraction and conventional extraction techniques for the extraction of Tanshinones from Salvia miltiorrhiza Bunge[J].Biochem Eng J,12:71-77.
QIN RA,LIN J,LI CY,et al.,2014.Study of the protective mechanisms of Compound Danshen Tablet(Fufang Danshen Pian)against myocardial ischemia/reperfusion injury via the Akt-eNOS signaling pathway in rats[J].J Ethnopharm acol,156:190-198.
ROBERTS AT,MARTIN CK,LIU Z,et al.,2007.The safety and efficacy of a dietary herbal supplement and gallic acid for weight loss[J].J Med Food,10:184-188.
State Pharmacopoeia Commission,2015.Pharmacopoeia of the People’s Republic of China[M].Beijing:Chinese Medical Science and Technology Press.[国家药典委员会,2015.中华人民共和国药典[M].北京:中国医药科技出版社.]
WANG JJ,PEI TX,GUO JY,et al.,2017.The rapeutic effects of Danshen Dropping Pills on hepatic fibrosis in rats induced by dimethylnitrosamine[J].Drug Clin,32(4):572-578.[王晶晶,裴天仙,郭景玥,等,2017.丹参滴丸对二甲基亚硝胺诱导大鼠肝纤维化的治疗作用[J].现代药物与临床,32(4):572-578.]
WANG WM,DUAN Q,2014.Analysis of phenolic acids and their antioxidant activity by capillary electrophoresis-mass spectrometry with field-amplified sample injection[J].Trad Chin Drug Res Clin Pharmcol,25(3):338-342.[王文明,段启,2014.毛细管电泳和质谱联用在线预浓缩酚酸类化合物及其抗氧化活性评价[J].中药新药与临床药理,25(3):338-342.]
ZHANG XC,LUO DD,TAO AE,et al.,2017.Species differentiation and quality assessment of Salvia miltiorrhiza and Salvia trijuga by HPLC fingerprint[J].J Chin Med Mat,40(5):1061-1065.[张晓灿,罗丹丹,陶爱恩,等,2017.基于指纹图谱和化学计量学的丹参及紫丹参质量评价研究[J].中药材,40(5):1061-1065.]
ZHANG Y,ZHU HL,SUN LR,2017.Phenolic acids from the roots of Salvia miltiorrhiza var.alba[J].J Chin Med Mat,40(4):854-857.[张愉,朱海林,孙隆儒,2017.白花丹参根的酚酸类成分研究[J].中药材,40(4):854-857.]
ZHAO QY,JIA LQ,WANG JY,et al.,2016.The effect of TanshinoneⅡA on macrophages reverse cholesterol transport related genes expression in Apo E-/-Mice[J].Guid J Trad Chin Med Pharm,22(11):15-19.[赵秋宇,贾连群,王俊岩,等,2016.丹参酮ⅡA对Apo E~(-/-)动脉粥样硬化小鼠腹腔巨噬细胞胆固醇流出相关基因表达的影响[J].中医药导报,22(11):15-19.]