Citation: Qing-Lan Guo, Sheng Lin, Ya-Nan Wang, Cheng-Gen Zhu, Cheng-Bo Xu, Jian-Gong Shi. Gastrolatathioneine, an unusual ergothioneine derivative from an aqueous extract of “tian ma”: A natural product co-produced by plant and symbiotic fungus[J]. Chinese Chemical Letters, ;2016, 27(10): 1577-1581. doi: 10.1016/j.cclet.2016.06.040 shu

Gastrolatathioneine, an unusual ergothioneine derivative from an aqueous extract of “tian ma”: A natural product co-produced by plant and symbiotic fungus

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China

Corresponding author: Jian-Gong Shi, shijg@imm.ac.cn
Received Date: 3 June 2016
Revised Date: 14 June 2016
Accepted Date: 23 June 2016
Available Online: 1 October 2016

Figures(5)

Gastrolatathioneine (1), an unusual natural product derived from ergothioneine, a fungal amino acid containing an imidazole-2-thione moiety, was isolated from an aqueous extract of "tian ma" (the Gastrodia elata rhizomes). The structure of 1 including the absolute configuration was determined by extensive spectroscopic data analysis, combined with comparison of an experimental circular dichroism spectrum and calculated electronic circular dichroism spectra of stereoisomers, and confirmed by X-ray crystallography. The natural origin of 1 was proved by HPLC-ESIMS analysis of the crude extract. A biogenetic pathway of 1 is proposed on the basis of metabolic post-modification of ergothioneine that is biosynthesized by a symbiotic fungus. The plant and symbiotic fungus are co-producers of 1.
- Gastrodia elata,
- Orchidaceae,
- Ergothioneine,
- (+)-L-N,N-bis(4-hydroxybenzyl)ergothioneine,
- Gastrolatathioneine
1. [1]
  Jiangsu New Medical College, Dictionary of Traditional Chinese Medicine, Shanghai Science and Technology Publishing House, Shanghai, 1979, pp. 315-317.
2. [2]
  J. Zhou, X.Y. Pu, Y.B. Yang. Nine phenolic compounds of fresh Gastrodia elata Blume[J]. Chin. Sin. Bull., 1982,27:179-181.
3. [3]
  E.J. Shin, W.K. Whang, S. Kim. Parishin C attenuates phencyclidine-induced schizophrenia-like psychosis in mice:involvements of 5-HT1A receptor[J]. J. Pharmacol. Sci., 2010,113:404-408. doi: 10.1254/jphs.10040SC
4. [4]
  N.K. Huang, J.H. Lin, J.T. Lin. A new drug design targeting the adenosinergic system for Huntington's disease[J]. PLoS One, 2011,6e20934. doi: 10.1371/journal.pone.0020934
5. [5]
  K.Y. Kam, S.J. Yu, N. Jeong. p-Hydroxybenzyl alcohol prevents brain injury and behavioral impairment by activating Nrf2, PDI, and neurotrophic factor genes in a rat model of brain ischemia[J]. Mol. Cells, 2011,31:209-215. doi: 10.1007/s10059-011-0028-4
6. [6]
  X.M. Zhao, Y. Zou, H. Xu. Gastrodin protect primary cultured rat hippocampal neurons against amyloid-beta peptide-induced neurotoxicity via ERK1/2-Nrf2 pathway[J]. Brain Res., 2012,1482:13-21. doi: 10.1016/j.brainres.2012.09.010
7. [7]
  B.W. Kim, S. Koppula, J.W. Kim. Modulation of LPS-stimulated neuroinflammation in BV-2 microglia by Gastrodia elata:4-Hydroxybenzyl alcohol is the bioactive candidate[J]. J. Ethnopharmacol., 2012,139:549-557. doi: 10.1016/j.jep.2011.11.048
8. [8]
  W.D. Xu, Y. Tian, Q.L. Guo, Y.C. Yang, J.G. Shi. Secoeuphoractin, a minor diterpenoid with a new skeleton from Euphorbia micractina[J]. Chin. Chem. Lett., 2014,25:1531-1534. doi: 10.1016/j.cclet.2014.09.012
9. [9]
  Y. Tian, Q.L. Guo, W.D. Xu. A minor diterpenoid with a new 6/5/7/3 fusedring skeleton from Euphorbia micractina[J]. Org Lett, 2014,16:3950-3953. doi: 10.1021/ol501760h
10. [10]
  F. Wang, Y.P. Jiang, X.L. Wang. Aromatic glycosides from the flower buds of Lonicera japonica[J]. J. Asian Nat. Prod. Res., 2013,15:492-501. doi: 10.1080/10286020.2013.785531
11. [11]
  W.X. Song, Y.C. Yang, J.G. Shi. Two new β-hydroxy amino acid-coupled secoiridoids from the flower buds of Lonicera japonica:isolation, structure elucidation, semisynthesis, and biological activities[J]. Chin. Chem. Lett., 2014,25:1215-1219. doi: 10.1016/j.cclet.2014.05.037
12. [12]
  Z.B. Jiang, W.X. Song, J.G. Shi. Two new 1-(60-O-acyl-b-D-glucopyranosyl) pyridinium-3-carboxylates from the flower buds of Lonicera japonica[J]. Chin. Chem. Lett., 2015,26:69-72. doi: 10.1016/j.cclet.2014.10.011
13. [13]
  Y. Yu, Z.B. Jiang, W.X. Song. Glucosylated caffeoylquinic acid derivatives from the flower buds of Lonicera japonica[J]. Acta Pharm. Sinica B, 2015,5:210-214. doi: 10.1016/j.apsb.2015.01.012
14. [14]
  Y.F. Liu, M.H. Chen, X.L. Wang. Antiviral enantiomers of a bisindole alkaloid with a new carbon skeleton from the roots of Isatis indigotica[J]. Chin. Chem. Lett., 2015,26:931-936. doi: 10.1016/j.cclet.2015.05.052
15. [15]
  Y.F. Liu, M.H. Chen, Q.L. Guo. Antiviral glycosidic bisindole alkaloids from the roots of Isatis indigotica[J]. J. Asian Nat. Prod. Res., 2015,17:689-704. doi: 10.1080/10286020.2015.1055729
16. [16]
  Y.F. Liu, M.H. Chen, S. Lin. Indole alkaloid glucosides from the roots of Isatis indigotica[J]. J. Asian Nat. Prod. Res., 2016,18:1-12. doi: 10.1080/10286020.2015.1117452
17. [17]
  Y.F. Liu, X.L. Wang, M.H. Chen. Three pairs of alkaloid enantiomers from the root of Isatis indigotica[J]. Acta Pharm. Sinica B, 2016,6:141-147. doi: 10.1016/j.apsb.2016.01.003
18. [18]
  M.H. Chen, S. Lin, Y.N. Wang. Antiviral stereoisomers of 3,5-bis(2-hydroxybut-3-en-1-yl)-1,2,4-thiadiazole from the roots Isatis indigotica[J]. Chin. Chem. Lett., 2016,27:643-648. doi: 10.1016/j.cclet.2016.01.042
19. [19]
  Y.P. Jiang, Y.F. Liu, Q.L. Guo. Acetylenes and fatty acids from Codonopsis pilosula[J]. Acta Pharm. Sinica B, 2015,5:215-222. doi: 10.1016/j.apsb.2015.03.005
20. [20]
  Y.P. Jiang, Y.F. Liu, Q.L. Guo. C₁₄-Polyacetylene glucosides from Codonopsis pilosula, J. Asian Nat[J]. Prod. Res, 2015,17:601-614.
21. [21]
  Y.P. Jiang, Q.L. Guo, Y.F. Liu, J.G. Shi. Codonopiloneolignanin A, a polycyclic neolignan with a new carbon skeleton from the roots of Codonopsis pilosula, Chin[J]. Chem. Lett., 2016,27:55-58.
22. [22]
  Y.P. Jiang, Y.F. Liu, Q.L. Guo. Sesquiterpene glycosides from the roots of Codonopsis pilosula[J]. Acta Pharm. Sinica B, 2016,6:46-54. doi: 10.1016/j.apsb.2015.09.007
23. [23]
  Z.B. Jiang, B.Y. Jiang, C.G. Zhu. Aromatic acid derivatives from the lateral roots of Aconitum carmichaelii[J]. J. Asian Nat. Prod. Res., 2014,16:891-900. doi: 10.1080/10286020.2014.939585
24. [24]
  Z.B. Jiang, X.H. Meng, B.Y. Jiang. Two 2-(quinonylcarboxamino)benzoates from the lateral roots of Aconitum carmichaelii[J]. Chin. Chem. Lett., 2015,26:653-656. doi: 10.1016/j.cclet.2015.04.011
25. [25]
  Y.N. Wang, S. Lin, M.H. Chen. Chemical constituents from aqueous extract of Gastrodia elata, China[J]. J. Chin. Mater. Med., 2012,37:1775-1781.
26. [26]
  Q.L. Guo, Y.N. Wang, S. Lin. 4-Hydroxybenzyl-substituted amino acid derivatives from Gastrodia elata[J]. Acta Pharm. Sinica B, 2015,5:350-357. doi: 10.1016/j.apsb.2015.02.002
27. [27]
  Q.L. Guo, Y.N. Wang, C.G. Zhu. 4-Hydroxybenzyl-substituted glutathione derivatives from Gastrodia elata[J]. J. Asian Nat. Prod. Res, 2015,17:439-454. doi: 10.1080/10286020.2015.1040000
28. [28]
  Y. Zhang, M. Li, R.X. Kang. NHBA isolated from Gastrodia elata exerts sedative and hypnotic effects in sodium pentobarbital-treated mice[J]. Pharmacol. Biochem. Behav, 2012,102:450-457. doi: 10.1016/j.pbb.2012.06.002
29. [29]
  J.J. He, Z.G. Luo, L. Huang. Ambient mass spectrometry imaging metabolomics method provides novel insights into the action mechanism of drug candidates[J]. Anal. Chem., 2015,87:5372-5379. doi: 10.1021/acs.analchem.5b00680
30. [30]
  Spartan 10; Wavefunction, Inc., Irvine, CA.
31. [31]
  M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 09. Revision C. 01, Gaussian, Inc, Wallingford, CT, 2009.
32. [32]
  Bruker. SHELXTL. Structure Determination Programs, Version 5.10, Bruker AXS Inc., 6300 Enterprise Lane, Madison, WI 53719-1173, USA, 1997.
33. [33]
  C., M., K., Y. Sugawara, b-Hydroxyergothioneine, a new ergothioneine derivative from the mushroom Lyophyllum connatum, and its protective activity against carbon tetrachloride-induced injury in primary culture hepatocytes, Biosci[J]. Biotechnol. Biochem, 2005,69:357-363. doi: 10.1271/bbb.69.357
34. [34]
  X.C. Li, D. Ferreira, Y.Q. Ding. Determination of absolute configuration of natural products:theoretical calculation of electronic circular dichroism as a tool[J]. Curr. Org. Chem., 2010,14:1678-1697. doi: 10.2174/138527210792927717
35. [35]
  P. Fu, J.B. MacMillan. Spithioneines A and B, two new bohemamine derivatives possessing ergothioneine moiety from a marine-derived Streptomyces spinoverrucosus[J]. Org. Lett., 2015,17:3046-3049. doi: 10.1021/acs.orglett.5b01328
36. [36]
  C.E. Hand, J.F. Honek. Biological chemistry of naturally occurring thiols of microbial and marine origin[J]. J. Nat. Prod., 2005,68:293-308. doi: 10.1021/np049685x
37. [37]
  J. Ey, E. Schömig, D. Taubert. Dietary sources and antioxidant effects of ergothioneine[J]. J. Agric. Food Chem., 2007,55:6466-6474. doi: 10.1021/jf071328f
38. [38]
  D.S.L. Toh, F.S.G. Cheung, M. Murray. Functional analysis of novel variants in the organic cation/ergothioneine transporter 1 identified in Singapore populations[J]. Mol. Pharmaceutics, 2013,10:2509-2516. doi: 10.1021/mp400193r
39. [39]
  F.P. Seebeck. In vitro reconstitution of mycobacterial ergothioneine biosynthesis[J]. J. Am. Chem. Soc., 2010,132:6632-6633. doi: 10.1021/ja101721e
40. [40]
  W. Hu, H. Song, A.S. Her. Bioinformatic and biochemical characterizations of C S bond formation and cleavage enzymes in the Fungus Neurospora crassa ergothioneine biosynthetic pathway[J]. Org. Lett., 2014,16:5382-5385. doi: 10.1021/ol502596z
41. [41]
  D. Ackermann. P.H. List, Ü ber das vorkommen von herzynin, ergothionein, homarin, trigonellin, glykokollbetain, cholin, trimethylamin, adenin und fast sämtlicher aminosa üren des eiweißes in Limulus polyphemus[J]. L, Bio. Chem, 1958,313:30-36.
42. [42]
  H.X. Liu, Y.B. Luo, H. Liu. Studies of mycorrhizal fungi of Chinese orchids and their role in orchid conservation in China-a review[J]. Bot. Rev., 2010,76:241-262. doi: 10.1007/s12229-010-9045-9
1. [1]
  Lijun Li , Chenliang Guo , Yuelin Fang , Zijian Cheng , Yaowei Li , Zhangyu Wang , Dian Cai , Yuqi Xu , Wenqi Liu , Shouwei Ma , Xinxin Zhang . Deformable hyaluronic acid niosomes overcome multi-barriers for improved ergothioneine transdermal delivery against UV-induced skin damage. Chinese Chemical Letters, 2025, 36(11): 110839-. doi: 10.1016/j.cclet.2025.110839
2. [2]
  Qiuyue Lu , Min Shan , Jiaqi Yang , Zhongren Xu , Yueyue Lei , Wukun Liu . A dinuclear gold(I) complex with bis(N-heterocyclic carbene) ligands potentiated immune responses against liver cancer via ROS-driven endoplasmic reticulum stress and ferroptosis. Chinese Chemical Letters, 2025, 36(12): 110940-. doi: 10.1016/j.cclet.2025.110940
3. [3]
  Kai Han , Guohui Dong , Ishaaq Saeed , Tingting Dong , Chenyang Xiao . Morphology and photocatalytic tetracycline degradation of g-C3N4 optimized by the coal gangue. Chinese Journal of Structural Chemistry, 2024, 43(2): 100208-100208. doi: 10.1016/j.cjsc.2023.100208
4. [4]
  Liang Ma , Zhou Li , Zhiqiang Jiang , Xiaofeng Wu , Shixin Chang , Sónia A. C. Carabineiro , Kangle Lv . Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100416-100416. doi: 10.1016/j.cjsc.2024.100416
5. [5]
  Yanghanbin Zhang , Dongxiao Wen , Wei Sun , Jiahe Peng , Dezhong Yu , Xin Li , Yang Qu , Jizhou Jiang . State-of-the-art evolution of g-C3N4-based photocatalytic applications: A critical review. Chinese Journal of Structural Chemistry, 2024, 43(12): 100469-100469. doi: 10.1016/j.cjsc.2024.100469
6. [6]
  Haitao Wang , Lianglang Yu , Jizhou Jiang , Arramel , Jing Zou . S-Doping of the N-Sites of g-C₃N₄ to Enhance Photocatalytic H₂ Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(5): 2305047-0. doi: 10.3866/PKU.WHXB202305047
7. [7]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-0. doi: 10.3866/PKU.WHXB202408005
8. [8]
  Zhili Yang , Liqun Liu , Xuebi Rao , Zeyu Jin , Jialin Sun , Yongkang Zhu , Shiming Zhang . Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis. Chinese Chemical Letters, 2025, 36(11): 111440-. doi: 10.1016/j.cclet.2025.111440
9. [9]
  Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He . Nd@C₃N₄-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines. Chinese Chemical Letters, 2025, 36(2): 110568-. doi: 10.1016/j.cclet.2024.110568
10. [10]
  Xiaoxu Duan , Junli Xu , Jiwei Li , Congcong Du , Kai Chen , Teng Xu , Yifei Sun , Haifeng Xiong . Enhancing CO₂ reduction efficiency with axial oxygen coordinated Ni-N₄ active sites on hierarchical pore N-doped carbon. Chinese Chemical Letters, 2025, 36(7): 110340-. doi: 10.1016/j.cclet.2024.110340
11. [11]
  Tianjun Ni , Hui Zhang , Liping Zhou , Roujie Ma , Yanyu Wang , Zhijun Yang , Dan Luo , Nithima Khaorapapong , Xingtao Xu , Yusuke Yamauchi , Dong Liu . Atomic cobalt catalysts on 3D interconnected g-C₃N₄ support for activation of peroxymonosulfate: The importance of Co-N coordination effect. Chinese Chemical Letters, 2025, 36(9): 110659-. doi: 10.1016/j.cclet.2024.110659
12. [12]
  Entian Cui , Yulian Lu , Zhaoxia Li , Zhilei Chen , Chengyan Ge , Jizhou Jiang . Interfacial B-O bonding modulated S-scheme B-doped N-deficient C₃N₄/O-doped-C₃N₅ for efficient photocatalytic overall water splitting. Chinese Chemical Letters, 2025, 36(1): 110288-. doi: 10.1016/j.cclet.2024.110288
13. [13]
  Futao Yi , Ying Liu , Yao Chen , Jiahao Zhu , Quanguo He , Chun Yang , Dongge Ma , Jun Liu . Dual S-Scheme g-C₃N₄/Ag₃PO₄/g-C₃N₅ photocatalysts for removal of tetracycline pollutants through enhanced molecular oxygen activation. Chinese Chemical Letters, 2025, 36(8): 110544-. doi: 10.1016/j.cclet.2024.110544
14. [14]
  Zhi Zhu , Xiaohan Xing , Qi Qi , Wenjing Shen , Hongyue Wu , Dongyi Li , Binrong Li , Jialin Liang , Xu Tang , Jun Zhao , Hongping Li , Pengwei Huo . Fabrication of graphene modified CeO2/g-C3N4 heterostructures for photocatalytic degradation of organic pollutants. Chinese Journal of Structural Chemistry, 2023, 42(12): 100194-100194. doi: 10.1016/j.cjsc.2023.100194
15. [15]
  Xiaoming Fu , Haibo Huang , Guogang Tang , Jingmin Zhang , Junyue Sheng , Hua Tang . Recent advances in g-C3N4-based direct Z-scheme photocatalysts for environmental and energy applications. Chinese Journal of Structural Chemistry, 2024, 43(2): 100214-100214. doi: 10.1016/j.cjsc.2024.100214
16. [16]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
17. [17]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
18. [18]
  Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO₂ and selectivity over N₂ and CH₄. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659
19. [19]
  Qingwang LIU . MoS₂/Ag/g-C₃N₄ Z-scheme heterojunction: Preparation and photocatalytic performance. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 821-832. doi: 10.11862/CJIC.20240148
20. [20]
  Jianyu Qin , Yuejiao An , Yanfeng Zhang . In Situ Assembled ZnWO₄/g-C₃N₄ S-Scheme Heterojunction with Nitrogen Defect for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408002-0. doi: 10.3866/PKU.WHXB202408002

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(1378)
HTML views(63)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142