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Comparative metabolic fingerprinting of Gentiana rhodantha from different geographical origins using LC-UV-MS/MS and multivariate statistical analysis.

Pan Y, Zhang J, Shen T, Zhao YL, Wang YZ, Li WY - BMC Biochem. (2015)

Bottom Line: The most abundant mangiferin (82.21 mg/g) found in sample from Zunyi, Guizhou province.Furthermore, 64 samples according to their geographical origins, could be classified by partial least-squares discriminate analysis (PLS-DA) and nine compounds including two new compounds identified by mass spectrometry could be regarded as characteristic compounds for discriminating samples from different geographical origins.The developed method appears to be a useful tool for analysis of G. rhodantha, which could provide potential indicators for differentiation of different geographical origins.

View Article: PubMed Central - PubMed

Affiliation: Institute of Medicinal Plants, Yunnan Academy of Agricultural Sciences, 2238, Beijing Road, Panlong District, Kunming, 650200, China. panyu412@hotmail.com.

ABSTRACT

Backgrounds: Gentiana rhodantha, a rich source of iridoids and polyphenols, is a traditional ethnomedicine widely used in China. Metabolic fingerprinting based on a LC-UV-MS/MS method was applied to explore the chemical markers for discrimination of G. rhodantha from different geographical origins.

Results: Targeted compounds were separated on a Shim-pack XR-ODS III (150 × 2.0 mm, 2.2 μm), with a mobile phase consisted of acetonitrile and 0.1% formic acid in water, under gradient elution. In quantitative analysis, all of the calibration curves showed good linear regression (R(2) < less than 0.9991) within the tested ranges, and accuracy ranged from 97.8% to 104.2% and the %RSD of precision (less than 3%) were all within the required limits. The most abundant mangiferin (82.21 mg/g) found in sample from Zunyi, Guizhou province. Furthermore, 64 samples according to their geographical origins, could be classified by partial least-squares discriminate analysis (PLS-DA) and nine compounds including two new compounds identified by mass spectrometry could be regarded as characteristic compounds for discriminating samples from different geographical origins.

Conclusions: The developed method appears to be a useful tool for analysis of G. rhodantha, which could provide potential indicators for differentiation of different geographical origins.

No MeSH data available.


Related in: MedlinePlus

The MS2spectra of the [M-H]−ions for (a) rhodenthoside A, (b) secoxyloganin and (c) secologanoside.
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Fig4: The MS2spectra of the [M-H]−ions for (a) rhodenthoside A, (b) secoxyloganin and (c) secologanoside.

Mentions: According to the mass data analysis of peak 27–32, the major product ions and fragmentation pattern of the revealed their derivatives with the same basic skeleton. Among them, peak 29 (m/z 913 [M-H]−), 30 (m/z 1629 [M-H]−) and 32 (m/z 1657 [M-H]−) were tentatively assigned as rhodenthoside A, B and C by matching the fragmentation pattern from published works [17,18]. In negative mode, their fragment ions patterns were highly similar. As shown in Table 6 and Figure 4a, same fragmentation ions (m/z 555, 197, 153 and 109) were detected in their mass spectrum. Using peak 29 as an example, m/z 555 and 197 might be derived from m/z 913 through classical McLafferty-type rearrangement successively losing series of 358 (swerosidic acid moiety) while m/z 153 and 109 were considered as m/z 197 (monoterpene dicarboxylic acid moiety) successively lose series of CO2 (Figure 4a). Moreover, fragment ions of peak 30 (m/z 1271, 913, 555 and 197) were corresponded to losing four 358 moiety in succession. In fragmentation pattern of peak 32, m/z 1285 might be derived from losing a 372 moiety regarded as swerosidic acid methyl ester and m/z 927 were corresponded to [M-H-372-358]−. Interestingly, the same fragment ions (m/z 555, 197, 153) were also found in peak 27 (m/z 1075 [M-H]−), 28 (m/z 1433 [M-H]−) and 31 (m/z 1643 [M-H]−), which implied that the three compounds might be the derivatives of rhodenthosides A-C (Additional file 4: Figure S3). In peak 27, present of ions at m/z at 913 in negative mode (rhodenthoside A) corresponded to loss of a glucose moiety from precursor ions (m/z 1075), which indicated that peak 27 would tentatively assigned as glucosyl rhodenthoside A. The product ions at m/z 1271 and m/z 1075 corresponded to the eliminations of swerosidic acid and glucose moiety respectively, which implied the structure of peak 28 (m/z 1433 [M-H]−) would consider as rhodenthoside A adding a glucose and swerosidic acid. Furthermore, fragment ions of peak 31 at m/z 1285, 1271, 927 and 913 corresponded to the successive loss of 372 and 358 moiety, which implied the structure of peak 31 might be a product of methyl esterification of rhodenthoside B. According to mass data, peak 27, 28 and 31 were three new derivatives of rhodenthoside, whereas their structure should further confirmed by NMR.Table 6


Comparative metabolic fingerprinting of Gentiana rhodantha from different geographical origins using LC-UV-MS/MS and multivariate statistical analysis.

Pan Y, Zhang J, Shen T, Zhao YL, Wang YZ, Li WY - BMC Biochem. (2015)

The MS2spectra of the [M-H]−ions for (a) rhodenthoside A, (b) secoxyloganin and (c) secologanoside.
© Copyright Policy - open-access
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC4390080&req=5

Fig4: The MS2spectra of the [M-H]−ions for (a) rhodenthoside A, (b) secoxyloganin and (c) secologanoside.
Mentions: According to the mass data analysis of peak 27–32, the major product ions and fragmentation pattern of the revealed their derivatives with the same basic skeleton. Among them, peak 29 (m/z 913 [M-H]−), 30 (m/z 1629 [M-H]−) and 32 (m/z 1657 [M-H]−) were tentatively assigned as rhodenthoside A, B and C by matching the fragmentation pattern from published works [17,18]. In negative mode, their fragment ions patterns were highly similar. As shown in Table 6 and Figure 4a, same fragmentation ions (m/z 555, 197, 153 and 109) were detected in their mass spectrum. Using peak 29 as an example, m/z 555 and 197 might be derived from m/z 913 through classical McLafferty-type rearrangement successively losing series of 358 (swerosidic acid moiety) while m/z 153 and 109 were considered as m/z 197 (monoterpene dicarboxylic acid moiety) successively lose series of CO2 (Figure 4a). Moreover, fragment ions of peak 30 (m/z 1271, 913, 555 and 197) were corresponded to losing four 358 moiety in succession. In fragmentation pattern of peak 32, m/z 1285 might be derived from losing a 372 moiety regarded as swerosidic acid methyl ester and m/z 927 were corresponded to [M-H-372-358]−. Interestingly, the same fragment ions (m/z 555, 197, 153) were also found in peak 27 (m/z 1075 [M-H]−), 28 (m/z 1433 [M-H]−) and 31 (m/z 1643 [M-H]−), which implied that the three compounds might be the derivatives of rhodenthosides A-C (Additional file 4: Figure S3). In peak 27, present of ions at m/z at 913 in negative mode (rhodenthoside A) corresponded to loss of a glucose moiety from precursor ions (m/z 1075), which indicated that peak 27 would tentatively assigned as glucosyl rhodenthoside A. The product ions at m/z 1271 and m/z 1075 corresponded to the eliminations of swerosidic acid and glucose moiety respectively, which implied the structure of peak 28 (m/z 1433 [M-H]−) would consider as rhodenthoside A adding a glucose and swerosidic acid. Furthermore, fragment ions of peak 31 at m/z 1285, 1271, 927 and 913 corresponded to the successive loss of 372 and 358 moiety, which implied the structure of peak 31 might be a product of methyl esterification of rhodenthoside B. According to mass data, peak 27, 28 and 31 were three new derivatives of rhodenthoside, whereas their structure should further confirmed by NMR.Table 6

Bottom Line: The most abundant mangiferin (82.21 mg/g) found in sample from Zunyi, Guizhou province.Furthermore, 64 samples according to their geographical origins, could be classified by partial least-squares discriminate analysis (PLS-DA) and nine compounds including two new compounds identified by mass spectrometry could be regarded as characteristic compounds for discriminating samples from different geographical origins.The developed method appears to be a useful tool for analysis of G. rhodantha, which could provide potential indicators for differentiation of different geographical origins.

View Article: PubMed Central - PubMed

Affiliation: Institute of Medicinal Plants, Yunnan Academy of Agricultural Sciences, 2238, Beijing Road, Panlong District, Kunming, 650200, China. panyu412@hotmail.com.

ABSTRACT

Backgrounds: Gentiana rhodantha, a rich source of iridoids and polyphenols, is a traditional ethnomedicine widely used in China. Metabolic fingerprinting based on a LC-UV-MS/MS method was applied to explore the chemical markers for discrimination of G. rhodantha from different geographical origins.

Results: Targeted compounds were separated on a Shim-pack XR-ODS III (150 × 2.0 mm, 2.2 μm), with a mobile phase consisted of acetonitrile and 0.1% formic acid in water, under gradient elution. In quantitative analysis, all of the calibration curves showed good linear regression (R(2) < less than 0.9991) within the tested ranges, and accuracy ranged from 97.8% to 104.2% and the %RSD of precision (less than 3%) were all within the required limits. The most abundant mangiferin (82.21 mg/g) found in sample from Zunyi, Guizhou province. Furthermore, 64 samples according to their geographical origins, could be classified by partial least-squares discriminate analysis (PLS-DA) and nine compounds including two new compounds identified by mass spectrometry could be regarded as characteristic compounds for discriminating samples from different geographical origins.

Conclusions: The developed method appears to be a useful tool for analysis of G. rhodantha, which could provide potential indicators for differentiation of different geographical origins.

No MeSH data available.


Related in: MedlinePlus