硫磺熏蒸知母的化学标志物分析(1)
[摘要]中药知母经硫磺熏蒸制备成含硫知母饮片，利用UPLCQTOFMSE结合UNIFI数据分析平台、主成分分析法(PCA)及正交偏最小二乘判别分析(OPLSDA)，分析并在线鉴定了硫磺熏蒸前后知母饮片中的16个主要的差异性成分，其中9个主要存在于熏蒸后知母饮片中；确定了熏蒸后知母饮片中的化学标志物，为硫熏后新产生的亚硫酸酯化衍生物。同时利用UPLCQTOFMSE寻找主要化学标志物——知母皂苷BⅡ亚硫酸酯(m/z 983)的手段，建立了知母饮片硫磺熏蒸的快速筛查方法，该方法便捷准确，可作为知母质量控制的有效辅助手段。这是首次分析鉴定了甾体皂苷类成分的亚硫酸酯化衍生物，并应用这一方法筛查硫磺熏蒸的知母饮片。
[关键词]知母； 硫磺熏蒸； UPLCQTOFMSE； 化学标志物
Analysis of chemical markers in sulfurfumigated Anemarrhenae Rhizoma
, 百拇医药
ZHENG Wei1，2， WANG Fangxu2， SUN Xinguang2， KANG Liping2，3， ZHAO Yang2， ZHANG Jie2， MA Baiping2*
(1. Tianjin University of Traditional Chinese Medicine， Tianjin 300193， China；
2. Institute of Radiation Medicine， Academy of Military Medical Sciences， Beijing 100850， China；
3. National Resource Center for Chinese Materia Medica， China Academy of Chinese Medical Sciences， Beijing 100700， China)
, http://www.100md.com
[Abstract]Sulfurcontaining Anemarrhenae Rhizoma decoction pieces were prepared by using sulfurfumigating procedure The difference components before and after sulfur fumigation in Anemarrhenae Rhizoma were analyzed and online identified by UPLCQTOFMSE combined with UNIFI informatics platform， principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLSDA) respectively As a result， 16 major differences components were identified， and among them， 9 components were mainly from sulfurfumigated samples The main chemical markers in sulfurfumigated Anemarrhenae Rhizoma were identified as the sulfite derivatives newly produced after sulfurfumigating Meanwhile， UPLCQTOFMSE was used to find the main chemical marker anemarrhena saponin BⅡ sulfite (m/z 983) By using this method， a rapid screening method for sulfurfumigated Anemarrhenae Rhizoma was established This was a convenient and accurate detection method for sulfur dioxide residue， and it can be used as an effective assistant method to control the quality of Anemarrhenae Rhizoma At the same time， it was the first time to identify sulfited derivatives of steroidal saponins， and screen the sulfurfumigated Anemarrhenae Rhizoma
, http://www.100md.com
[Key words]Anemarrhenae Rhizoma； sulfurfumigated； UPLCQTOFMSE； chemical markers
中藥知母为百合科多年生草本植物知母Anemarrhena asphodeloides Bge的干燥根茎，具有清热泻火、滋阴润燥等功效[1]。知母中主要化学成分为甾体皂苷、黄酮、多糖等类型，其中根茎中总多糖含量高达30%[2]。由于其含有较高的多糖成分，新鲜知母药材容易发霉变质，对其药材的储存一直是一个值得关注的问题。
硫熏法是部分中药材传统加工养护方法之一，具有防虫、防霉、杀菌和美化药材外观的作用[3]，因其价格低廉、操作方便仍被应用于知母鲜药材的前期加工中，近年来甚至被滥用[4]。研究表明硫磺熏蒸处理可导致部分药材活性成分发生转化[56]，甚至造成SO2或亚硫酸盐残留量过高，不但影响药材质量，而且存在安全隐患[79]。为了监控药材硫熏情况，2015年版《中国药典》附录收载了中药材及饮片中SO2残留量测定方法[1]。然而有研究显示， 二氧化硫会随着药材贮藏时间的延长不断逸失[10]。因此，寻找并确定硫熏药材的化学标志物变得尤为重要。, http://www.100md.com(郑伟王芳旭孙欣光康利平赵阳张洁马百平)
[关键词]知母； 硫磺熏蒸； UPLCQTOFMSE； 化学标志物
Analysis of chemical markers in sulfurfumigated Anemarrhenae Rhizoma
, 百拇医药
ZHENG Wei1，2， WANG Fangxu2， SUN Xinguang2， KANG Liping2，3， ZHAO Yang2， ZHANG Jie2， MA Baiping2*
(1. Tianjin University of Traditional Chinese Medicine， Tianjin 300193， China；
2. Institute of Radiation Medicine， Academy of Military Medical Sciences， Beijing 100850， China；
3. National Resource Center for Chinese Materia Medica， China Academy of Chinese Medical Sciences， Beijing 100700， China)
, http://www.100md.com
[Abstract]Sulfurcontaining Anemarrhenae Rhizoma decoction pieces were prepared by using sulfurfumigating procedure The difference components before and after sulfur fumigation in Anemarrhenae Rhizoma were analyzed and online identified by UPLCQTOFMSE combined with UNIFI informatics platform， principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLSDA) respectively As a result， 16 major differences components were identified， and among them， 9 components were mainly from sulfurfumigated samples The main chemical markers in sulfurfumigated Anemarrhenae Rhizoma were identified as the sulfite derivatives newly produced after sulfurfumigating Meanwhile， UPLCQTOFMSE was used to find the main chemical marker anemarrhena saponin BⅡ sulfite (m/z 983) By using this method， a rapid screening method for sulfurfumigated Anemarrhenae Rhizoma was established This was a convenient and accurate detection method for sulfur dioxide residue， and it can be used as an effective assistant method to control the quality of Anemarrhenae Rhizoma At the same time， it was the first time to identify sulfited derivatives of steroidal saponins， and screen the sulfurfumigated Anemarrhenae Rhizoma
, http://www.100md.com
[Key words]Anemarrhenae Rhizoma； sulfurfumigated； UPLCQTOFMSE； chemical markers
中藥知母为百合科多年生草本植物知母Anemarrhena asphodeloides Bge的干燥根茎，具有清热泻火、滋阴润燥等功效[1]。知母中主要化学成分为甾体皂苷、黄酮、多糖等类型，其中根茎中总多糖含量高达30%[2]。由于其含有较高的多糖成分，新鲜知母药材容易发霉变质，对其药材的储存一直是一个值得关注的问题。
硫熏法是部分中药材传统加工养护方法之一，具有防虫、防霉、杀菌和美化药材外观的作用[3]，因其价格低廉、操作方便仍被应用于知母鲜药材的前期加工中，近年来甚至被滥用[4]。研究表明硫磺熏蒸处理可导致部分药材活性成分发生转化[56]，甚至造成SO2或亚硫酸盐残留量过高，不但影响药材质量，而且存在安全隐患[79]。为了监控药材硫熏情况，2015年版《中国药典》附录收载了中药材及饮片中SO2残留量测定方法[1]。然而有研究显示， 二氧化硫会随着药材贮藏时间的延长不断逸失[10]。因此，寻找并确定硫熏药材的化学标志物变得尤为重要。, http://www.100md.com(郑伟王芳旭孙欣光康利平赵阳张洁马百平)