Structural analysis of proanthocyanidins from Tetrastigma hemsleyanum Diels et Gilg

Abstract

Abstract: Abstract：The structures of proanthocyanidins from root, stem and leaf of Tetrastigma hemsleyanum Diels et Gilg have been analyzed with 13C nuclear magnetic resonance (13C NMR), reversed-phase high performance liquid chromatography electrospray ionization mass spectrometry (RP-HPLC-ESI-MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The results showed that these proanthocyanidins from T. hemsleyanum were mainly composed of procyanidin (PC) and prodelphinidin (PD), the terminal units were mainly composed with catechin, epicatechin and epigallocatechin were the dominant of the extension units. The mean degree of polymerization (mDP) of proanthocyanidins from root, stem and leaf of T. hemsleyanum were found to be 4.89 ± 0.33, 3.77 ± 0.19 and 4.45 ± 0.48 respectively. Proanthocyanidins from trimers to decamers were detected within proanthocyanidins from root and stem, while proanthocyanidins up to undecamer were detected within proanthocyanidins from from leaf of T. hemsleyanum by MALDI-TOF MS. (Epi)catechin and (epi)gallocatechin monomer units individually and together with galloyl substituents and A type linkages prevalently existed within each single polymeric cluster. Proanthocyanidins from root, stem and leaf of T. hemsleyanum were structurally similar. The results of this study may provide some reference for the fundamental study and further development of T. hemsleyanum.

Key words: Tetrastigma hemsleyanum Diels et Gilg, proanthocyanidins, 13C nuclear magnetic resonance (13C NMR), Revised-phase high performance liquid chromatography electrospray ionization mass spectrometry (RP-HPLC-ESI-MS), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)

CLC Number:

O629.9

References

[1]张慧文, 张玉, 马超美.原花青素的研究进展[J].食品科学, 2015, 36(5):296-304 [2]李彦, 李鑫, 刘景玲, 等.鸡血藤原花青素的纯化及活性评价[J].食品科学, 2016, 37(17):45-51 [3]QUIDEAU S, DEFFIEU X, DOUAT-CASASSUS C, et al.Plant polyphenols: chemical properties,biological activities,and synthesis[J].Angewandte Chemie International Edition, 2011, 50(3):586-621 [4]DIXON R A, XIE D Y, Sharma S B.Proanthocyanidins-a final frontier in flavonoid research?[J].New Phytologist, 2005, 165(1):9-28 [5]LI W T, LIU J, GUAN R G, et al.Chemical characterization of procyanidins from Spatholobus suberectus and their antioxidative and anticancer activities[J].Journal of Functional Foods, 2015, 12(null):468-477 [6]ZHOU H C, Tam N F, Lin Y M, et al.Relationships between degree of polymerization and antioxidant activities: a study on proanthocyanidins from the leaves of a medicinal mangrove plant Ceriops tagal[J].PLoS One, 2014, 9(10):e107606-1 [7]FU C L, LOO A E K, CHIA F P P, et al.Oligomeric proanthocyanidins from mangosteen pericarps[J].Journal of Agricultural and Food Chemistry, 2007, 55(19):7689-7694 [8]FU C L, YANG X N, LAI S J, et al.Structure,antioxidant and α-amylase inhibitory activities of longan pericarp proanthocyanidins[J].Journal of Functional Foods, 2015, 14(null):23-32 [9]ZHANG L L, LIN Y M.HPLC,NMR and MALDI-TOF MS analysis of condensed tannins from Lithocarpus glaber leaves with potent free radical scavenging activity[J].Molecules, 2008, 13(12):2986-2897 [10]CHAI W M, SHI Y, FENG H L, et al.NMR,HPLC-ESI-MS,and MALDI-TOF MS analysis of condensed tannins from Delonix regia (Bojer ex Hook) Rafand their bioactivities[J].Journal of Agricultural and Food Chemistry, 2012, 60(19):5013-5022 [11]CZOCHANSKA Z, FOO L Y, NEWMAN R H, et al.Polymeric proanthocyanidinsStereochemistry,structural units,and molecular weight[J].Journal of the Chemical Society, Perkin Transactions, 1980, 38(10):2278-2286 [12]PORTER L J, NEWMAN R H, FOO L Y, et al.Polymeric proanthocyanidins13C N.M.R. studies of procyanidins[J].Journal of the Chemical Society, Perkin Transactions, 1982, null(0):1217-1221 [13]KRAUS T E C, YU Z, PRESTON C M, et al.Linking Chemical Reactivity and Protein Precipitation to Structural Characteristics of Foliar Tannins[J].Journal of Chemical Ecology, 2003, 29(3):703-730 [14]GU L, KELM M A, HAMMERSTONE J F, et al.Screening of Foods Containing Proanthocyanidins and Their Structural Characterization Using LC-MSMS and Thiolytic Degradation[J].Journal of Agricultural and Food Chemistry, 2003, 51(25):7513-21 [15]周海超, 魏淑东, 李敏, 等.基质辅助激光解吸附飞行时间质谱方法分析山竹果皮缩合单宁[J].分析化学, 2010, 38(10):1492-1496 [16]MONAGAS M, QUINTANILLA-LOPEZ J E, GOMEZ-CORDOVES C, et al.MALDI-TOF MS analysis of plant proanthocyanidins[J].Journal of pharmaceutical and biomedical analysis, 2010, 51(2):358-372 [17]范世明, 徐惠龙, 谢心月, 等.三叶青叶指纹图谱研究及种酚类成分含量测定[J].中国中药杂志, 2016, 41(21):3975-3981 [18]XIONG Y, WU X W, RAO L Q.Tetrastigma hemsleyanum (Sanyeqing) root tuber extracts induces apoptosis in human cervical carcinoma HeLa cells[J].Journal of Ethnopharmacology, 2015, 165(null):45-53 [19]PENG X, ZHANG Y Y, WANG J, et al.Ethylacetate extract from Tetrastigma hemsleyanum induces apoptosis via the mitochondrial caspase-dependent intrinsic pathway in HepG2 cells[J].Tumor Biology, 2016, 37(1):865-876 [20]FENG Z, HAO W, LIN X, et al.Antitumor activity of total flavonoids from Tetrastigma hemsleyanum Diels et Gilg is associated with the inhibition of regulatory T cells in mice[J].OncoTargets and Terapy, 2014, 7(null):947-956 [21]YE C L, LIU X G.Extraction of Flavonoids from Tetrastigma hemsleyanum Diels et Gilg and Their Antioxidant Activity[J].Journal of Food Processing and Preservation, 2015, 39(6):2197-2205 [22]LIU D D, CAO G, HAN L K, et al.Flavonoids from Radix Tetrastigmae inhibit TLR4MD-2 mediated JNK and NF-kappaB pathway with anti-inflammatory properties[J].Cytokine, 2016, 84(null):29-35 [23]SUN Y, LI H Y, HU J, LI J N, et al.Qualitative and quantitative analysis of phenolics in Tetrastigma hemsleyanum and their antioxidant and antiproliferative activities[J].Journal of Agricultural and Food Chemistry, 2013, 61(44):10507-10515 [24]SHAO Q S, DENG Y M, SHEN H J, et al.Optimization of polysaccharides extraction from Tetrastigma hemsleyanum Diels et Gilg using response surface methodology[J].International Journal of Biological Macromolecules, 2011, 49(5):958-962 [25]许文, 傅志勤, 林婧, 等.和--的三叶青主要成分定性与定量研究[J].中国中药杂志, 2014, 39(22):4365-4372 [26]于虹敏, 贺文达, 刘巧, 等.法同时测定三叶青中原花青素和儿茶素含量[J].辽宁中医药大学学报, 2016, 18(01):71-73 [27]SUN Y, TSAO R, CHEN F, et al.The phytochemical composition,metabolites,bioavailability and in vivo antioxidant activity of Tetrastigma hemsleyanum leaves in rats[J].Journal of Functional Foods, 2017, 30(null):179-193 [28]SUN Y, QIN Y, LI H Y, et al.Rapid characterization of chemical constituents in Radix Tetrastigma,a functional herbal mixture,before and after metabolism and their antioxidantantiproliferative activities[J].Journal of Functional Foods, 2015, 18(null):300-318 [29]许文, 傅志勤, 林婧, 等.法同时测定三叶青中种黄酮类成分[J].药学学报, 2014, 49(12):1711-1717 [30]曾美玲, 沈耐涛, 吴赛伟, 等.基于----方法的三叶青化学成分分析[J].中草药, 2017, 48(05):874-883 [31]STRINGANO E, CRAMER R, HAYES W, et al.Deciphering the Complexity of Sainfoin (Onobrychis viciifolia) Proanthocyanidins by MALDI-TOF Mass Spectrometry with a Judicious Choice of Isotope Patterns and Matrixes[J].Analytical Chemistry, 2011, 83(11):4147-4153 [32]XIANG P, LIN Y M, LIN P, et al.Effects of Adduct Ions on Matrix-assisted Laser DesorptionIonization Time of Flight Mass Spectrometry of Condensed Tannins: A Prerequisite Knowledge[J].Chinese Journal of Analytical Chemistry, 2006, 34(7):1019-1022