Offline two-dimensional liquid chromatography coupled with ion mobility-quadrupole time-of-flight mass spectrometry enabling fourdimensional separation and characterization of the multicomponents from white ginseng and red ginseng

Inherent complexity of plant metabolites necessitates the use of multi-dimensional information to accomplish comprehensive profiling and confirmative identification.A dimension-enhanced strategy,by offline two-dimensional liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(2 D-LC/IM-QTOF-MS)enabling four-dimensional separations(2 D-LC,IM,and MS),is proposed.In combination with in-house database-driven automated peak annotation,this strategy was utilized to characterize ginsenosides simultaneously from white ginseng(WG)and red ginseng(RG).An offline 2 DLC system configuring an Xbridge Amide column and an HSS T3 column showed orthogonality 0.76 in the resolution of ginsenosides.Ginsenoside analysis was performed by data-independent high-definition MSE(HDMSE)in the negative ESI mode on a Vion?IMS-QTOF hybrid high-resolution mass spectrometer,which could better resolve ginsenosides than MSEand directly give the CCS information.An in-house ginsenoside database recording 504 known ginsenosides and 58 reference compounds,was established to assist the identification of ginsenosides.Streamlined workflows,by applying UNIFI?to automatedly annotate the HDMSEdata,were proposed.We could separate and characterize 323 ginsenosides(including 286 from WG and 306 from RG),and 125 thereof may have not been isolated from the Panax genus.The established 2 D-LC/IM-QTOF-HDMSEapproach could also act as a magnifier to probe differentiated components between WG and RG.Compared with conventional approaches,this dimensionenhanced strategy could better resolve coeluting herbal components and more efficiently,more reliably identify the multicomponents,which,we believe,offers more possibilities for the systematic exposure and confirmative identification of plant metabolites.

Approaches to establish Q-markers for the quality standards of traditional Chinese medicines

Traditional Chinese medicine(TCM) has played a pivotal role in maintaining the health of Chinese people and is now gaining increasing acceptance around the global scope. However, TCM is confronting more and more concerns with respect to its quality. The intrinsic "multicomponent and multitarget" feature of TCM necessitates the establishment of a unique quality and bioactivity evaluation system, which is different from that of the Western medicine. However, TCM is investigated essentially as"herbal medicine" or "natural product", and the pharmacopoeia quality monographs are actually chemicalmarkers-based, which can ensure the consistency only in the assigned chemical markers, but, to some extent, have deviated from the basic TCM theory. A concept of "quality marker"(Q-marker), following the "property-effect-component" theory, is proposed. The establishment of Q-marker integrates multidisciplinary technologies like natural products chemistry, analytical chemistry, bionics, chemometrics,pharmacology, systems biology, and pharmacodynamics, etc. Q-marker-based fingerprint and multicomponent determination conduce to the construction of more scientific quality control system of TCM.This review delineates the background, definition, and properties of Q-marker, and the associated technologies applied for its establishment. Strategies and approaches for establishing Q-marker-based TCM quality control system are presented and highlighted with a few TCM examples.

Novel C-17 spirost protostane-type triterpenoids from Alisma plantago-aquatica with antiinflammatory activity in Caco-2 cells

Twenty-one protostane-type triterpenoids with diverse structures, including nine new compounds(1 e9), were isolated from the of Alisma plantago-aquatica Linn. Structurally, alisolides A-F(1 e6), composed of an oxole group coupled to a five-membered ring, represent unusual C-17 spirost protostane-type triterpenoids. Alisolide H(8) is a novel triterpenoid with an unreported endoperoxide bridge. Alisolide I(9) represents the first example of 23,24-acetal triterpenoid. Their structures were elucidated based on spectroscopic analysis, wherein the absolute configurations of 4-6, 8 were further confirmed by the Mo2(OAc)4-induced ECD method. Furthermore, all isolates were evaluated for their inhibitory effects on LPS-induced NO production in Caco-2 cells, and all the compounds showed remarkable inhibitory activities, with IC50 values in the range of 0.76 e38.20 mmol/L.

SIMULTANEOUS QUANTITATION OF FIVE PANAX NOTOGINSENG SAPONINS IN EIGHT CHINESE PATENT MEDICINES BY MULTI HEART-CUTTING TWODIMENSIONAL LIQUID CHROMATOGRAPHY

Current China Pharmacopoeia(ChP)standards employ diversified and case-dependent assay methods to evaluate the quality of different Chinese patent medicines(CPM)that contain Panax notoginseng as the monarch drug.This study is aimed to develop a two-dimensional liquid chromatography(2D LC)based assay approach to unify and simplify the quality assessment of Notoginseng containing CPMs.Multi heart-cutting 2D LC(MHC-2D LC)was used to separate and quantify five major