| Xanthii Herba and Xanthii Fructus,the acrial part and mature fruit with involucres of Xanthium sibiricum Patr.,a traditional Chinese herb is the original different medicinal parts of the same medicinal materials,which was contained in Standard of Chinese medicinal material in Jiangsu Province(1989 edition).Pharmacopeia of China(2015 edition).Xanthii Herba has the effects of clearing heat and removing toxicity while Xanthii Fructus has the effects of dissipating wind,freeing nasal orifices,and rheumatism.However.due to differences in environment.resulted in the accumulation of the active ingredient heterophylla varied greatly varying quality.How medicine production process,quality assurance,and quality of Xanthiuum sibiricum uniform production process had become a key issue.This topic through the systematic analysis of the multi-index constituents in Xanthium sibiricum,compared the differences between index compositions in Xanthii Herba and Xanthii Fructus from different commercial herbs,before and after processing of Xanthii Fructus,original different medicinal parts of the same medicinal material,and different harvest times o fXanthium sibiricu,m.Through multiple index composition analysis of Xantl-hiulrm s'ibiricum,with the help of research ideas and the method of plant metabolomics,the topic studied on research of metabonomics in Xanthium sibiricum by UPLC-Triple TOF-MS/MS and GC-MS.It compared that the chemical compositions of different parts of Xanthium sibiricurm,before and after processing of Xanthii Fructus,and different harvest times of Xanthii Herba,and screened,identified the differences of chemical compositions.This paper provided basic information and scientific basis to explore the formation process of medicinal materials quality and proper harvest time of Xanthium sibiricum.Research mainly included the following aspects:1.Literature Research A literature review study on Xanthium sibiricum and plant metabolomic.2.Studies on the active components of Xanthium sibiricum Optimizing and establishing the Phenolic acids,Anthraquinones,and Flavones by UPLC-QTRAP-MS/MS,Phenolic acids and Anthraquinones by HPLC,Phenolic acids by HPCE-DAD,Carboxyatractylosides and Atractylosides by HPLC,Volatile components by GC-MS,Fatty acid derivatives by GC-MS,Inorganic elements by ICP-MS.Comparing and analyzing the active components in Xanthii Herba and Xanthii Fructus from different commercial herbs,Xanthii Herba and Xanthii Fructus of the same medicinal material,different harvest times of Xanthii Herba of multi index components accumulation dynamics and before and after processing of Xanthii Fructus.The results showed that:(1)Phenolic acids,Anthraquinones,and Flavones:The contents of 3,4-Dicaffeoylquinic acid,Rutin,and Protocatechuic acid in Xanthii Herba showed the marked differences.The contents of 4-Dicaffeoylquinic acid and 3,4-Dicaffeoylquinic acid in Xanthii Fructus showed the marked differences.The contents of Phenolic acids,Anthraquinones,and Flavones in Xanthii Fructus were much higher than in Xanthii Herba.The contents of concocted processing in Xanthii Fructus had differences.The contents of Neochlorogenic acid,Ferulic acid,and Protocatechuic aldehyde in fired Xanthii Fructus were relative higher.In the Xanthii Herba and Xanthii Fructus of the same medicinal material,the contents of Ferulic acid,4,5-Dicaffeoylquinic acid,Rutin,and Astragalin in Xanthii Herba were much higher,and the others were higher in Xanthii Fructus.Phenolic acids,Anthraquinones,and Flavones had the differences in dynamic accumulation.The contents of multiple active ingredients in Xanthii Herba in May were slightly lower while they were much higher in July,and there was a rapid decrease in July.(2)Phenolic acid and Anthraquinone:The contents of Ferulic acid and 1,3-Dicaffeoylquinic acid showed the marked differences.The contents of components in Xanthii Fructus did not have obvious differences.The contents of Phenolic acids and Anthraquinones in Xanthii Fructus were all much higher than in Xanthii Herba.The contents of concocted processing in Xanthii Fructus had differences.The contents of Neochlorogenic acid,Protocatechuic aldehyde,and Ferulic acid in fired Xanthii Fructus were much higher.In the Xanthii Herba and Xanthii Fructus of the same medicinal material,the contents of Protocatechuic aldehyde,Ferulic acid,Caffeic acid,3,4-Dicaffeoylquinic acid,and 3,5-Dicaffeoylquinic acid in Xanthii Herba were much higher than in Xanthii Fructus.The contents of Phenolic acids and Anthraquinones in Xanthii Herba in May were slightly lower while they were much higher in July,and there was a rapid decrease in Autumn.(3)Phenolic acids:The contents of Phenolic acids were much higher in the field samples.This demonstrated that the different fields and harvest processing resulted in the differences in contents of Phenolic acids in Xanthii Herba.The contents of concocted processing in Xanthii Fructus had differences.The contents of Neochlorogenic acid,Ferulic acid,Caffeic acid,and 4,5-Dicaffeoylquinic acid in fired Xanthii Fructus were much higher.In the Xanthii Herba and Xanthii Fructus of the same medicinal material,the contents of Ferulic acid,Caffeic acid,and 3,5-Dicaffeoylquinic acid in Xanthii Herba were higher than in Xanthii Fructus.The contents of Phenolic acids in Xanthii Herba in May were slightly lower while they were much higher in July,and there was a rapid decrease in Autumn.(4)Carboxyatractylosides and Atractylosides:The contents of Carboxyatractylosides and Atractylosides in Xanthii Fructus were higher than in Xanthii Herba.The contents of Carboxyatractylosides and Atractylosides showed differences in concocted processing of Xanthii Fructus,the contents of Xanthii Fructus were higher than in fired Xanthii Fructus and the toxicity decreased after processing.In the Xanthii Herba and Xanthii Fructus of the same medicinal material,the contents of Carboxyatractylosides and Atractylosides in Xanthii Herba were lower in Xanthii Fructus.The Atractylosides has not been detected in Xanthii Herba from different harvest times,the contents of carboxyatractylosides showed a decrease in May to July,and in August the contents of Carboxyatractylosides showed a rising trend.(5)Volatile components:The contents of volatile components had differences in Xanthii Herba and Xanthii Fructus,which contained aldehydes,alkene,alcohol,acids,alkanes,heterocyclic,ketone,esters,and hydrocarbon.The contents of volatile components showed differences in Xanthii Fructus and the contents of Furfural.2-Hexenal.(E)-,Nonanoic acid,Hexanoic acid,methyl ester,Benzaldehyde,2,5-Octanedione,Octanal,1,3-Hexadiene,3-ethy]-2-methyl-,Hexanoic acid,anhy dride.Silane,cyclohexyldime-thoxymethyl-,a-Terpineol,2-Cyclohexen-l-one,2-methyl-5-(1-m ethylethenyl)-,2,4-Decadienal,Benzene,1,2-dimethoxy-4-(2-propenyl)-,Caryophyllene,Nonad ecane,9-methyl-,Tetracosane,Eicosane were much higher.The contents of others were decreased.The contents of volatile components were the highest in Xanthii Herba in July.(6)Fatty acid:The contents of Linoleic acid,Oleic acid,Hexadecanoate and Octadecanoic acid in Xanthii Fructus were higher,the contents of unsaturated fatty acids were the highest,which accounted for 74.76%.(7)Inorganic elements:The contents of inorganic elements in Xanthii Herba and Xanthii Fructus showed the same trends.The contents of inorganic elements in Xanthii Fructus(S18?S19)were higher than in fired Xanthii Fructus,and the contents of the most inorganic elements were decreased.In the different part of the same plants,the variety of inorganic elements in Xanthii Herba and Xanthii Fructus were the same,but the contents of inorganic elements showed the marked differences.3.Studies on the metabolomics of Xanthium sibiricum based on UPLC-Triple TOF-MS/MS UPLC-Triple TOF-MS/MS combined with ultivariate statistical analysis were used to compare the chemical components of ethanol extract in different parts of Xanthium sibiricum,before and after processing of Xanthii Fructus,and different harvest times of Xanthii Herba.Through the multi-stage tandem mass spectrometry,peak matching,peak alignment and noise filtering were used in analyzing mass spectrometry data.Accurated m/z value analysis of MS data based on software of database search and MS/MS fragment analysis were applied to constituents identification.Data processing used PCA and PLS-DA to find out the differences in chemical components and rule of metabolic changes in different parts of Xanthium sibiricum,before and after processing of Xanthii Fructus,and different harvest times of Xanthii Herba.The results showed that:(1)The components of Xanthii Herba and Xanthii Fructus had the marked differences,44 kinds of differential chemical compositions are screened and 41 chemical compositions are identified.12 differential components were found through PLS-DA analysis,th e contents of Liquiritigenin 4'-O-apiosyl-O-glucoside,Quercetin-3-O-(6'-O-malo-nyl)-glucoside,4-Dicaffeoylquinic acid,1,3-Dicaffeoylquinic,Butyl phenylacetate,3,4-Dicaffeoylquinic acid,3,5-Dicaffeoylquinic acid,I sorhamnetin-7-O-glucoside,4,5-Dicaffeoylquinic acid,and Octadecanoic acid in Xanthii Fructus were much higher;the contents of sucrose and 4',5,6,7-Dimethylflavone were much higher in Xanthii Herba.(2)The components of concocted processing in Xanthii Fructus had differences.44 kinds of differential chemical compositions are screened and 41 chemical compositions are identified.In the 10 differential components,the contents of Liquiritigenin 4'-O-apiosyl-O-glucoside,Deoxyadenosine,1.3-Dicaffeoylquinic acid,3,4-Dicaffeoylquinic acid,Astragalin,and ?-carotene were much higher in fired Xanthii Fructus.The contents of 4',5,6,7-Dimethylflavone.Chlorogenic acid,4-Dicaffeoylquinic acid,and 4'-Desulphate-atractylosid were lower in fired Xanthii Fructus.(3)In the different harvest times of Xanthii Herba,the chemical compositions of traditional harvest time and other harvest times were dif-ferent.43 kinds of differential chemical compositions are screened and 40 chemical compositions are identified.In the 8 differential components,the relative amounts of Neochlorogenic acid,1,3-Dicaffeoylquinic acid,3,4-Dicaffeoylquinic acid.3,5-Dicaffeoylquinic acid,Unknownl.and Glucuronolactone have peaked in the traditional harvest time of samples.The relative content of Unknown 2 had high-level after the traditional harvest time.The relative content of Unknown 3 had high-level before the traditional harvest time.4.Studies on the metabolomics of Xanthium sibiricum based on GC-MS GC-MC combined with ultivariate statistical analysis were used to compare the chemical components of volatile oils in different parts of Xanthium sibiricum,before and after processing of Xanthii Fructus,and different harvest times of Xanthii Herba.Through the multi-stage tandem mass spectrometry,peak matching,peak alignment and noise filtering were used in analyzing mass spectrometry data.Accurated m/z value analysis of MS data based on software of database search and MS/MS fragment analysis were applied to constituents identification.Data processing used PCA and PLS-DA to find out the differences in chemical components and rule of metabolic changes different parts of Xanthium.sibiricum.before and after processing of Xanthii Fructus.and different harvest times of Xanthii Herba.The results showed that:(1)The volatile components in Xanthii Herba and Xanthii Fructus showed significantly differences.109 kinds of'differential chemical compositions are identified and 33 chemical compositions are screened.In the 9 differential volatile components,the contents of 2-Hexenal,(E)-,p-Cymene.Decanal.Caryophyllene,and Dibutyl phthalate were higher in Xanthii Herba.The contents of Hexanal,a-pinene,a-Terpineol and(Z)-9,17-Octadecadienal were higher in Xanthii Fructus.(2)The volatile components in Xanthii Fructus and fired Xanthii Fructus were obviously different.109 kinds of differential chemical compositions are identified and 41 chemical compositicons arc screened.In the 14 differential volatile components,the contents of hexanal.2-Heptanone.Heptanal.Furan,2-pentyl-.Hexadecanoic acid,methyl ester.9,12-Octadccadicn-l-of,(9Z,12Z)-?Linoleic acid.and 13-Docosenam ide,(Z)-were loxwer in Xanthii Fructus:and the contents of Octanal,3-Octen-2-one,Decanal,Dibutyl phthalate,10,13-Octadecadienoic acid methyl ester,and Hexadecanoic acid were higher in fired Xanthii Fructus.(3)In the different harvest times of Xanthii Herba,samples of Xanthii Herba have been a clear distinction in traditional harvest time,before traditional harvest time,after traditional harvest time.141 kinds of differential chemical compositions are identified and 53 chemical compositions are screened.There are 11 differences in chemical compositions,which 5 common compounds such as Camphene,Decanal,2-Cyclohe xen-l-one,2-methyl-5-(1-methy-lethenyl)-,(S)-,?-Guaiene and Cyclohexene,6-(2-butenyl)-1,5,5-trimethyl-,(E)-had higher relative content in Xanthii Herba harvested in traditional harvest time.5.Studies on fingerprints of Xanthium sibiricum Establishing the method of HPLC UPLC-MS and GC-MS fingerprints of Xanthium sibiricum,belonging the calibration of the common peak,analyzing the active components and similarity assessments,providing the comprehensive information and assessments of the quality in Xanthium sibiricum.The results showed that the samples of Xanthium sibiricum had good similarity,the PCA and similarity analysis found that there were some differences in different samples of Xanthium sibiricum.Yhe established fingerprints could be provided the basis for the comprehensive evaluation of the intrinsic quality of Xanthium sibiricum. |
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