Identification and Characterization of Key Chemical Constituents in Processed Gastrodia elata Using UHPLC-MS/MS and Chemometric Methods

Abstract

Gastrodia elata Blume belongs to the Orchidaceae family. G. elata is often processed when used in traditional Chinese medicine (TCM). In the current study, a traditional processing method, known as “Jianchang Bang,” was applied. Steamed and dried (S&D) G. elata was processed with ginger juice for up to 5 days (GEP5D). An UHPLC-MS/MS combined with a chemometric method was developed for the analysis of processed G. elata along with the raw material as well as steamed and dried G. elata. As a result, the primary marker compounds were identified with the aid of TOF-MS and MS/MS analyses. Compared with the raw material of G. elata with GEP5D, three new parishin-type compounds were identified according to their retention time, accurate mass, and fragmentation patterns. The chromatographic peak areas for marker compounds, including S-(gastrodin)-glutathione, S-(4-hydroxybenzylamine)-glutathione, and parishin-type compounds, changed significantly. This result indicated that by applying the “Jianchang Bang” method, changes in chemical composition in G. elata contents were observed. The study also demonstrated that chemometric analysis is helpful in understanding the processing mechanism and will provide scientific support for the clinical application of G. elata.

Insight into Medicinal Chemistry Behind Traditional Chinese Medicines: p-Hydroxybenzyl Alcohol-Derived Dimers and Trimers from Gastrodia elata

“…. Because p-hydroxybenzyl alcohol, which abundantly occurs in G. elata [50][51][52][53][54][55][56][57][58], is highly reactive to produce quinone methide and complex derivative via self-condensation or inter-condensation with other reactants under various conditions [86][87][88][89], this suggests that, (a) p-hydroxybenzyl alcohol is an origin of the p-hydroxybenzyl unit in the p-hydroxybenzyl-containing chemical constituents of "tian ma"; (b) alcoholic forms of the p-hydroxybenzyl-derived dimers and trimers are generable from p-hydroxybenzyl alcohol during processing and/or extracting of the drug material; and (c) the ethyl and methyl ethers were formed in the subsequent isolation procedure through contacting to the solvents EtOH and MeOH. To verify the suggestions, following experiments were performed: (a) an aqueous solution of p-hydroxybenzyl alcohol was refluxed, from which the products were isolated and structurally identified; (b) methylation and ethylation of the p-hydroxybenzyl alcohol-generating products were examined by UPLC-HRESIMS after refluxing of their MeOH and EtOH solutions; (c) the refluxed solutions of p-hydroxybenzyl alcohol in H 2 O, MeOH, and EtOH were compared by UPLC-HRESIMS analysis using the identified pure compounds as references.…”

“…The above experiments demonstrated that the composition of the refluxed solutions of p-hydroxybenzyl alcohol are highly dependent upon the solvent and refluxing time. Because of the abundant occurrence of p-hydroxybenzyl alcohol in G. elata [50][51][52][53][54][55][56][57][58] (Fig. S233), the p-hydroxybenzyl-derived dimers and trimers from the "tian ma" extracts must be formed at least partially by refluxing of the drug materials in H 2 O, MeOH, or EtOH.…”

“…This suggests that the aqueous decoction of the processed drug material might contain more benefit components for patients. Thus, there are important secrets of medicinal chemistry hiding behind processing and/or decocting protocols in TCM though these are yet to be confirmed in many cases including "tian ma" [50][51][52][53][54][55][56][57][58]. Because the previous phytochemical studies of "tian ma" were performed mostly by extracting the drug material with ethanol or methanol [2,[5][6][7][8], the extracting protocol completely differed from that of conventional application by decocting with water.…”

“…Because the previous phytochemical studies of "tian ma" were performed mostly by extracting the drug material with ethanol or methanol [2,[5][6][7][8], the extracting protocol completely differed from that of conventional application by decocting with water. Therefore, an aqueous extract of "tian ma" (the steamed and dried G. elata rhizomes [50][51][52][53][54][55][56][57][58]) was investigated as part of our project to investigate chemical diversity and biological activities of several commonly used TCM [59][60][61][62][63][64][65][66][67][68][69][70]. Previously we reported 27 new and 40 known chemical constituents of the aqueous extract, along with their bioassays and pharmacological activities [71][72][73][74][75][76][77][78][79].…”

Rapid Identification and Systematic Mechanism of Flavonoids from Potentilla freyniana Bornm. Based on UHPLC-Q-Exactive Orbitrap Mass Spectrometry and Network Pharmacology

“…During the past decades, HPLC-MS, as a new technique has been used to profile and identify the chemical in TCM due to its validity, sensitivity, and specialness [ 10 , 11 ]. Especially, UHPLC-HRMS such as UHPLC-Q-Exactive Orbitrap MS, UHPLC-Q-TOF MS, and UHPLC–LTQ-Orbitrap-MS, affording a higher and faster separation and higher resolution of mass, was a much more powerful equipment in the identification of TCM compared to traditional HPLC-MS [ 12 – 14 ].…”