The rapid and accurate authentication of traditional Chinese medicines(TCMs)has always been a key scientific and technical problem in the field of pharmaceutical analysis.Herein,a novel heating online extraction elect...The rapid and accurate authentication of traditional Chinese medicines(TCMs)has always been a key scientific and technical problem in the field of pharmaceutical analysis.Herein,a novel heating online extraction electrospray ionization mass spectrometry(H-oEESI-MS)was developed for the rapid and direct analysis of extremely complex substances without the requirement for any sample pretreatment or pre-separation steps.The overall molecular profile and fragment structure features of various herbal medicines could be completely captured within 10–15 s,with minimal sample(<0.5 mg)and solvent consumption(<20μL for one sample).Furthermore,a rapid differentiation and authentication strategy for TCMs based on H-oEESI-MS was proposed,including metabolic profile characterization,characteristic marker screening and identification,and multivariate statistical analysis model validation.In an analysis of 52 batches of seven types of Aconitum medicinal materials,20 and 21 key compounds were screened out as the characteristic markers of raw and processed Aconitum herbal medicines,respectively,and the possible structures of all the characteristic markers were comprehensively identified based on Compound Discoverer databases.Finally,multivariate statistical analysis showed that all the different types of herbal medicines were well differentiated and identified(R^(2)X>0.87,R^(2)Y>0.91,and Q^(2)>0.72),which further verified the feasibility and reliability of this comprehensive strategy for the rapid authentication of different TCMs based on H-oEESI-MS.In summary,this rapid authentication strategy realized the ultra-high-throughput,low-cost,and standardized detection of various complex TCMs for the first time,thereby demonstrating wide applicability and value for the development of quality standards for TCMs.展开更多
The automation of traditional Chinese medicine(TCM)pharmaceuticals has driven the development of process analysis from offline to online.Most of common online process analytical technologies are based on spectroscopy,...The automation of traditional Chinese medicine(TCM)pharmaceuticals has driven the development of process analysis from offline to online.Most of common online process analytical technologies are based on spectroscopy,making the identification and quantification of specific ingredients still a challenge.Herein,we developed a quality control(QC)system for monitoring TCM pharmaceuticals based on paper spray ionization miniature mass spectrometry(mini-MS).It enabled real-time online qualitative and quantitative detection of target ingredients in herbal extracts using mini-MS without chromatographic separation for the first time.Dynamic changes of alkaloids in Aconiti Lateralis Radix Praeparata(Fuzi)during decoction were used as examples,and the scientific principle of Fuzi compatibility was also investigated.Finally,the system was verified to work stably at the hourly level for pilot-scale extraction.This mini-MS based online analytical system is expected to be further developed for QC applications in a wider range of pharmaceutical processes.展开更多
In this experiment,a liquid chromatography tandem mass spectrometry method was built to determine 15 pesticide residues in Chinese cabbage and cucumber samples based on online turbulent flow chromatography purificatio...In this experiment,a liquid chromatography tandem mass spectrometry method was built to determine 15 pesticide residues in Chinese cabbage and cucumber samples based on online turbulent flow chromatography purification.After modified quick,easy,cheap,effective,rugged,and safe(QuEChERS)extraction,extracts were directly injected to the TLX(TurboFlow Liquid Xcalibur)system and brought to TurboFlow™columns for on-line purification and then transferred to analytical column for further separation and analysis.TurboFlow™columns types,transfer flow rate,and transfer time were optimized.Limits of detection and limits of quantification of the method obtained for 15 pesticide residues were ranged between 0.2–1.0μg/kg and 0.5–2.0μg/kg in Chinese cabbage and cucumber samples.Recoveries of pesticide residues were in range of 75.3%–103.7%.Matrix effects for 15 pesticides were in range of 5.6%–106.6%.The developed method has been successfully used for the determination of 15 pesticide residues in real samples.展开更多
本研究分析了水产养殖和垂钓中饲料、窝料、饵料、水样及水产品中地西泮(Diazepam,DZP)的存在情况,并建立了在线净化-液相色谱串联质谱定量检测方法。结果表明DZP含量在0.5~20.0μg/L间线性良好,相关系数(r^(2))均大于0.999;饵料、水样...本研究分析了水产养殖和垂钓中饲料、窝料、饵料、水样及水产品中地西泮(Diazepam,DZP)的存在情况,并建立了在线净化-液相色谱串联质谱定量检测方法。结果表明DZP含量在0.5~20.0μg/L间线性良好,相关系数(r^(2))均大于0.999;饵料、水样和水产品中定量限(Limit of quantitation,LOQ)分别为1.0μg/kg、0.5μg/L、1.0μg/kg;3种基质中1.0μg/kg、5.0μg/kg和10.0μg/kg 3个浓度水平的加标回收率分别为85.2%~106.5%、82.3%~108.0%、90.7%~116.0%,相对标准偏差(Relative standard deviation,RSD)分别为3.6%~5.1%、2.7%~4.3%、2.1%~2.6%。通过调查发现,7份养殖用饲料中均未检出DZP;28份垂钓中使用的窝料、饵料检出率达66.7%,浓度为2.2~213090.0μg/kg;10份诱鱼剂中均检出DZP,检出率达100%,浓度为637000.0~3471000.0μg/kg;27份水样中DZP检出率达85.2%,浓度为0.4~9.8μg/L和71份淡水鱼中DZP的检出率为54.9%,浓度为0.5~21.8μg/kg。由此可见窝料、饵料及诱鱼剂的使用可能是水体和水产品中DZP频繁检出的重要原因之一,对消费者食用安全和水产养殖行业的健康发展均具有潜在风险,亟需加强DZP监管和监测。展开更多
基金supported by the CACMS Innovation Fund,China(Grant Nos.:CI2021A04504 and CI2021A05206)the National Natural Science Foundation of China(Grant Nos.:82104380,81891010,81891013,and 82074012)+2 种基金the Fundamental Research Funds for the Central Public Welfare Research Institutes,China(Grant Nos.:ZZ14-YQ-047 and ZZXT202105)the Key Project at Central Government Level(Grant No.:2060302-2201-26)the Beijing Nova Program.
文摘The rapid and accurate authentication of traditional Chinese medicines(TCMs)has always been a key scientific and technical problem in the field of pharmaceutical analysis.Herein,a novel heating online extraction electrospray ionization mass spectrometry(H-oEESI-MS)was developed for the rapid and direct analysis of extremely complex substances without the requirement for any sample pretreatment or pre-separation steps.The overall molecular profile and fragment structure features of various herbal medicines could be completely captured within 10–15 s,with minimal sample(<0.5 mg)and solvent consumption(<20μL for one sample).Furthermore,a rapid differentiation and authentication strategy for TCMs based on H-oEESI-MS was proposed,including metabolic profile characterization,characteristic marker screening and identification,and multivariate statistical analysis model validation.In an analysis of 52 batches of seven types of Aconitum medicinal materials,20 and 21 key compounds were screened out as the characteristic markers of raw and processed Aconitum herbal medicines,respectively,and the possible structures of all the characteristic markers were comprehensively identified based on Compound Discoverer databases.Finally,multivariate statistical analysis showed that all the different types of herbal medicines were well differentiated and identified(R^(2)X>0.87,R^(2)Y>0.91,and Q^(2)>0.72),which further verified the feasibility and reliability of this comprehensive strategy for the rapid authentication of different TCMs based on H-oEESI-MS.In summary,this rapid authentication strategy realized the ultra-high-throughput,low-cost,and standardized detection of various complex TCMs for the first time,thereby demonstrating wide applicability and value for the development of quality standards for TCMs.
基金supported by Ministry of Science and Technology of the People's Republic of China(Grant No.:2022YFC3502300)Beijing Natural Science Foundation(Grant No.:L222150)+2 种基金the National Natural Science Foundation of China(Grant No.:82072247)the second batch of“Ten thousand plan”National High Level Talents Special Support Plan(Grant No.:W02020052)Beijing University of Chinese Medicine(Grant Nos.:XJYS21005,JY21024,MSGZF-202001,2022-syjs-05,and 2022-syjs-10).
文摘The automation of traditional Chinese medicine(TCM)pharmaceuticals has driven the development of process analysis from offline to online.Most of common online process analytical technologies are based on spectroscopy,making the identification and quantification of specific ingredients still a challenge.Herein,we developed a quality control(QC)system for monitoring TCM pharmaceuticals based on paper spray ionization miniature mass spectrometry(mini-MS).It enabled real-time online qualitative and quantitative detection of target ingredients in herbal extracts using mini-MS without chromatographic separation for the first time.Dynamic changes of alkaloids in Aconiti Lateralis Radix Praeparata(Fuzi)during decoction were used as examples,and the scientific principle of Fuzi compatibility was also investigated.Finally,the system was verified to work stably at the hourly level for pilot-scale extraction.This mini-MS based online analytical system is expected to be further developed for QC applications in a wider range of pharmaceutical processes.
基金National Key Research and Development Program of China(Project No.2018YFC1603400)Science and Technology Program of Hebei Province(Project No.19225503D)Technical Support Project of State Administration for Market Regulation(Project No.2019YJ009).
文摘In this experiment,a liquid chromatography tandem mass spectrometry method was built to determine 15 pesticide residues in Chinese cabbage and cucumber samples based on online turbulent flow chromatography purification.After modified quick,easy,cheap,effective,rugged,and safe(QuEChERS)extraction,extracts were directly injected to the TLX(TurboFlow Liquid Xcalibur)system and brought to TurboFlow™columns for on-line purification and then transferred to analytical column for further separation and analysis.TurboFlow™columns types,transfer flow rate,and transfer time were optimized.Limits of detection and limits of quantification of the method obtained for 15 pesticide residues were ranged between 0.2–1.0μg/kg and 0.5–2.0μg/kg in Chinese cabbage and cucumber samples.Recoveries of pesticide residues were in range of 75.3%–103.7%.Matrix effects for 15 pesticides were in range of 5.6%–106.6%.The developed method has been successfully used for the determination of 15 pesticide residues in real samples.
文摘本研究分析了水产养殖和垂钓中饲料、窝料、饵料、水样及水产品中地西泮(Diazepam,DZP)的存在情况,并建立了在线净化-液相色谱串联质谱定量检测方法。结果表明DZP含量在0.5~20.0μg/L间线性良好,相关系数(r^(2))均大于0.999;饵料、水样和水产品中定量限(Limit of quantitation,LOQ)分别为1.0μg/kg、0.5μg/L、1.0μg/kg;3种基质中1.0μg/kg、5.0μg/kg和10.0μg/kg 3个浓度水平的加标回收率分别为85.2%~106.5%、82.3%~108.0%、90.7%~116.0%,相对标准偏差(Relative standard deviation,RSD)分别为3.6%~5.1%、2.7%~4.3%、2.1%~2.6%。通过调查发现,7份养殖用饲料中均未检出DZP;28份垂钓中使用的窝料、饵料检出率达66.7%,浓度为2.2~213090.0μg/kg;10份诱鱼剂中均检出DZP,检出率达100%,浓度为637000.0~3471000.0μg/kg;27份水样中DZP检出率达85.2%,浓度为0.4~9.8μg/L和71份淡水鱼中DZP的检出率为54.9%,浓度为0.5~21.8μg/kg。由此可见窝料、饵料及诱鱼剂的使用可能是水体和水产品中DZP频繁检出的重要原因之一,对消费者食用安全和水产养殖行业的健康发展均具有潜在风险,亟需加强DZP监管和监测。
