本文采用紫外可见吸收光谱和核磁共振波谱等方法研究了pH、溶剂及温度对卷柏属植物中selaginellin类化合物互变异构的影响.实验结果表明：酸性、碱性及质子化溶剂可以催化selaginellin类化合物的互变异构；变温核磁共振技术证实温度低于233K时，selaginellin类化合物的互变异构几乎被阻断.
曹园
,
吴永平
,
陈东军
. 卷柏属Selaginellin类化合物互变异构的波谱学研究[J]. 波谱学杂志, 2019
, 36(2)
: 155
-163
.
DOI: 10.11938/cjmr20182683
Ultraviolet-visible and nuclear magnetic resonance (NMR) spectroscopy was used to investigate the effects of pH, solvent and temperature on the tautomeric equilibrium of selaginellins from Selaginella. The results demonstrated that the tautomerism of selaginellins could be catalyzed by acid, base and protic solvent. Variable-temperature 1H NMR experiments demonstrated that the tautomerism was interrupted when the temperature fell below 233 K.
[1] ZHANG L P, LIANG Y M, WEI X C, et al. A new unusual natural pigment from Selaginella sinensis and its noticeable physicochemical properties[J]. J Org Chem, 2007, 72(10):3921-3924.
[2] CHENG X L, MA S C, YU J D, et al. Selaginellin A and B, two novel natural pigments isolated from Selaginella tamariscina[J]. Chem Pharm Bull (Tokyo), 2008, 56(7):982-984.
[3] CAO Y, CHEN J J, TAN N H, et al. Antimicrobial selaginellin derivatives from Selaginella pulvinata[J]. Bioorg Med Chem Lett, 2010, 20(8):2456-2460.
[4] XU K P, ZOU H, LI F S, et al. Two new selaginellin derivatives from Selaginella tamariscina (Beauv.) Spring[J]. J Asian Nat Prod Res, 2011, 13(2):93-96.
[5] YANG C, SHAO Y T, LI K, et al. Bioactive selaginellins from Selaginella tamariscina (Beauv.) Spring[J]. Beilstein J Org Chem, 2012, 8(1):1884-1889.
[6] ZHANG G G, JING Y, ZHANG H M, et al. Isolation and cytotoxic activity of selaginellin derivatives and biflavonoids from Selaginella tamariscina[J]. Planta Med, 2012, 78(4):390-392.
[7] CAO Y, YAO Y, HUANG X J, et al. Four new selaginellin derivatives from Selaginella pulvinata:mechanism of racemization process in selaginellins with quinone methide[J]. Tetrahedron 2015, 71(10):1581-1587.
[8] LIU X, LUO H B, HUANG Y Y, et al. Selaginpulvilins A-D, new phosphodiesterase-4 inhibitors with an unprecedented skeleton from Selaginella pulvinata[J]. Org Lett, 2014, 16(1):282-285.
[9] HUANG Y Y, LIU X, WU D Y, et al. The discovery, complex crystal structure, and recognition mechanism of a novel natural PDE4 inhibitor from Selaginella pulvinata[J]. Biochem Pharmacol, 2017, 130:51-59.
[10] NGUYEN P H, ZHAO B T, ALI M Y, et al. Insulin-mimetic selaginellins from Selaginella tamariscina with protein tyrosine phosphatase 1B (PTP1B) inhibitory activity[J]. J Nat Prod, 2015, 78:34-42.
[11] KIM J H, CHO C W, TAI B H, et al. Soluble epoxide hydrolase inhibitory activity of selaginellin derivatives from Selaginella tamariscina[J]. Molecules, 2015, 20:21405-21414.
[12] LE D D, NGUYEN D H, ZHAO B T, et al. PTP1B inhibitors from Selaginella tamariscina (Beauv.) Spring and their kinetic properties and molecular docking simulation[J]. Bioorg Chem, 2017, 72:273-281.
[13] RAUF M A, HISAINDEE S, SALEH N. Spectroscopic studies of keto-enol tautomeric equilibrium of azo dyes[J]. RSC Adv, 2015, 5:18097-18110.
[14] ZHANG G, WANG M C, LIU H N, et al. NMR studies of lansoprazole and tautomerism in solution[J]. Chinese J Magn Reson, 2008, 25(2):217-227. 张皋, 王民昌, 刘红妮, 等. 兰索拉唑的NMR分析及其在溶液中的互变异构现象[J]. 波谱学杂志, 2008, 25(2):217-227.
[15] YANG X Y, WU X Y, AN Y P, et al. An NMR study on keto-enol tautomerism of indole-3-pyruvic acid[J]. Chinese J Magn Reson, 2014, 31(1):81-91. 杨晓艳, 吴香玉, 安艳捧, 等. 吲哚丙酮酸的酮-烯醇互变异构化的NMR研究[J]. 波谱学杂志, 2014, 31(1):81-91.
[16] WANG L, WANG Y, MENG D, et al. Study on the interactions of two isomer selaginellins as novel small molecule inhibitors targeting PTP1B by docking and molecular dynamics simulations[J]. OALib J, 2018, 5(2):e4277.
