An RP-LC-UV-TWIMS-HRMS and Chemometric Approach to Differentiate Between Chemotypes from Three Different Geographical Locations in Limpopo Province of South Africa

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2021 Apr 3

PMID 33801575

Authors

Pieter Venter

Kholofelo Malemela

Vusi Mbazima

Leseilane J Mampuru

Christo J F Muller

Sylvia Riedel

Affiliations

Soon will be listed here.

Abstract

leaf extracts originating from three different geographical locations were analyzed using reversed-phase liquid chromatography (RP-LC) coupled to travelling wave ion mobility (TWIMS) and high-resolution mass spectrometry (HRMS) in conjunction with chemometric analysis to differentiate between potential chemotypes. Furthermore, the cytotoxicity of the three individual chemotypes was evaluated using HT-29 colon cancer cells. A total of 11 molecular species including three flavonol glycosides, five cucurbitane-type triterpenoid aglycones and three glycosidic cucurbitane-type triterpenoids were identified. The cucurbitane-type triterpenoid aglycones were detected in the positive ionization mode following dehydration [M + H - HO] of the parent compound, whereas the cucurbitane-type triterpenoid glycosides were primarily identified following adduct formation with ammonia [M + NH]. The principle component analysis (PCA) loadings plot and a variable influence on projection (VIP) analysis revealed that the isomeric pair balsaminol E and/or karavilagen E was the key molecular species contributing to the distinction between geographical samples. Ultimately, based on statistical analysis, it is hypothesized that balsaminol E and/or karavilagen E are likely responsible for the cytotoxic effects in HT-29 cells.

References

Rocha E Silva L, Ramalhete C, Nogueira K, Mulhovo S, Ferreira M, Pohlit A . In vivo evaluation of isolated triterpenes and semi-synthetic derivatives as antimalarial agents. Eur J Med Chem. 2015; 102:398-402. DOI: 10.1016/j.ejmech.2015.08.022. View

Gonzales G, Smagghe G, Coelus S, Adriaenssens D, De Winter K, Desmet T . Collision cross section prediction of deprotonated phenolics in a travelling-wave ion mobility spectrometer using molecular descriptors and chemometrics. Anal Chim Acta. 2016; 924:68-76. DOI: 10.1016/j.aca.2016.04.020. View

Tautenhahn R, Bottcher C, Neumann S . Highly sensitive feature detection for high resolution LC/MS. BMC Bioinformatics. 2008; 9:504. PMC: 2639432. DOI: 10.1186/1471-2105-9-504. View

Lin Y, Low C, Smith L . Sterol metabolism--XLV. Differentiation among monohydroxylated cholesterol derivatives by chromatography and mass spectrometry. J Steroid Biochem. 1981; 14(6):563-8. DOI: 10.1016/0022-4731(81)90031-5. View

Zheng X, Aly N, Zhou Y, Dupuis K, Bilbao A, Paurus V . A structural examination and collision cross section database for over 500 metabolites and xenobiotics using drift tube ion mobility spectrometry. Chem Sci. 2018; 8(11):7724-7736. PMC: 5853271. DOI: 10.1039/c7sc03464d. View

Ramalhete C, da Cruz F, Lopes D, Mulhovo S, Rosario V, Prudencio M . Triterpenoids as inhibitors of erythrocytic and liver stages of Plasmodium infections. Bioorg Med Chem. 2011; 19(24):7474-81. DOI: 10.1016/j.bmc.2011.10.044. View

DAtri V, Causon T, Hernandez-Alba O, Mutabazi A, Veuthey J, Cianferani S . Adding a new separation dimension to MS and LC-MS: What is the utility of ion mobility spectrometry?. J Sep Sci. 2017; 41(1):20-67. DOI: 10.1002/jssc.201700919. View

Venter P, Causon T, Pasch H, de Villiers A . Comprehensive analysis of chestnut tannins by reversed phase and hydrophilic interaction chromatography coupled to ion mobility and high resolution mass spectrometry. Anal Chim Acta. 2019; 1088:150-167. DOI: 10.1016/j.aca.2019.08.037. View

Chong J, Soufan O, Li C, Caraus I, Li S, Bourque G . MetaboAnalyst 4.0: towards more transparent and integrative metabolomics analysis. Nucleic Acids Res. 2018; 46(W1):W486-W494. PMC: 6030889. DOI: 10.1093/nar/gky310. View

10.

Razzazi-Fazeli E, Kleineisen S, Luf W . Determination of cholesterol oxides in processed food using high-performance liquid chromatography-mass spectrometry with atmospheric pressure chemical ionisation. J Chromatogr A. 2000; 896(1-2):321-34. DOI: 10.1016/s0021-9673(00)00719-6. View

11.

Chambers M, MacLean B, Burke R, Amodei D, Ruderman D, Neumann S . A cross-platform toolkit for mass spectrometry and proteomics. Nat Biotechnol. 2012; 30(10):918-20. PMC: 3471674. DOI: 10.1038/nbt.2377. View

12.

van de Venter M, Roux S, Bungu L, Louw J, Crouch N, Grace O . Antidiabetic screening and scoring of 11 plants traditionally used in South Africa. J Ethnopharmacol. 2008; 119(1):81-6. DOI: 10.1016/j.jep.2008.05.031. View

13.

Smith C, Want E, OMaille G, Abagyan R, Siuzdak G . XCMS: processing mass spectrometry data for metabolite profiling using nonlinear peak alignment, matching, and identification. Anal Chem. 2006; 78(3):779-87. DOI: 10.1021/ac051437y. View

14.

Ramalhete C, Spengler G, Martins A, Martins M, Viveiros M, Mulhovo S . Inhibition of efflux pumps in methicillin-resistant Staphylococcus aureus and Enterococcus faecalis resistant strains by triterpenoids from Momordica balsamina. Int J Antimicrob Agents. 2010; 37(1):70-4. DOI: 10.1016/j.ijantimicag.2010.09.011. View

15.

Maekawa M, Shimada M, Iida T, Goto J, Mano N . Tandem mass spectrometric characterization of bile acids and steroid conjugates based on low-energy collision-induced dissociation. Steroids. 2013; 80:80-91. DOI: 10.1016/j.steroids.2013.11.016. View

16.

Stander M, Van Wyk B, Taylor M, Long H . Analysis of Phenolic Compounds in Rooibos Tea (Aspalathus linearis) with a Comparison of Flavonoid-Based Compounds in Natural Populations of Plants from Different Regions. J Agric Food Chem. 2017; 65(47):10270-10281. DOI: 10.1021/acs.jafc.7b03942. View

17.

Cuyckens F, Rozenberg R, de Hoffmann E, Claeys M . Structure characterization of flavonoid O-diglycosides by positive and negative nano-electrospray ionization ion trap mass spectrometry. J Mass Spectrom. 2001; 36(11):1203-10. DOI: 10.1002/jms.224. View

18.

Madala N, Tugizimana F, Steenkamp P . Development and Optimization of an UPLC-QTOF-MS/MS Method Based on an In-Source Collision Induced Dissociation Approach for Comprehensive Discrimination of Chlorogenic Acids Isomers from Momordica Plant Species. J Anal Methods Chem. 2014; 2014:650879. PMC: 4177087. DOI: 10.1155/2014/650879. View

19.

Lanucara F, Holman S, Gray C, Eyers C . The power of ion mobility-mass spectrometry for structural characterization and the study of conformational dynamics. Nat Chem. 2014; 6(4):281-94. DOI: 10.1038/nchem.1889. View

20.

Chen C, Zhang H, Xiao W, Yong Z, Bai N . High-performance liquid chromatographic fingerprint analysis for different origins of sea buckthorn berries. J Chromatogr A. 2007; 1154(1-2):250-9. DOI: 10.1016/j.chroma.2007.03.097. View