Abstract
6-Tuliposides A (6-PosA) and B (6-PosB) are major defensive secondary metabolites in tulip cultivars (Tulipa gesneriana), having an acyl group at the C-6 position of d-glucose. Although some wild tulip species produce 1,6-diacyl-glucose type of Pos (PosD and PosF), as well as 6-PosA/B, they have not yet been isolated from tulip cultivars. Here, aiming at verifying the presence of PosD and PosF in tulip cultivars, tissue extracts of 25 cultivars were analyzed by high-performance liquid chromatography (HPLC). Although no HPLC peaks for PosD nor PosF were detected in most cultivars, we found two cultivars giving a minute HPLC peak for PosD and the other two cultivars giving that for PosF. PosD and PosF were then purified from petals of cultivar ‘Orca’ and from pistils of cultivar ‘Murasakizuisho’, respectively, and their identities were verified by spectroscopic analyses. This is the first report that substantiates the presence of 1,6-diacyl-glucose type of Pos in tulip cultivars.
Funding source: JSPS KAKENHI
Award Identifier / Grant number: JP23780120
Award Identifier / Grant number: JP26850072
Award Identifier / Grant number: JP18K05463
Funding statement: We thank Mr. Kohei Yamaguchi (Toyama Prefectural University, Japan) for technical assistance. This work was supported by JSPS KAKENHI grant nos. JP23780120, JP26850072, and JP18K05463 (Funder Id: http://dx.doi.org/10.13039/501100001691) (to TN).
References
1. Tschesche R, Kämmerer F-J, Wulff G, Schönbeck F. Über die antibiotisch wirksamen substanzen der tulpe (Tulipa gesneriana). Tetrahedron Lett 1968;9:701–6.10.1016/S0040-4039(00)75615-2Search in Google Scholar
2. Tschesche R, Kämmerer F-J, Wulff G. Über die struktur der antibiotisch aktiven substanzen der tulpe (Tulipa gesneriana L.). Chem Ber 1969;102:2057–71.10.1002/cber.19691020631Search in Google Scholar
3. Nomura T. Function and application of a non-ester-hydrolyzing carboxylesterase discovered in tulip. Biosci Biotechnol Biochem 2017;81:81–94.10.1080/09168451.2016.1240608Search in Google Scholar PubMed
4. Christensen LP, Kristiansen K. Isolation and quantification of tuliposides and tulipalins in tulips (Tulipa) by high-performance liquid chromatography. Contact Dermat 1999;40:300–9.10.1111/j.1600-0536.1999.tb06080.xSearch in Google Scholar PubMed
5. Kato Y, Shoji K, Ubukata M, Shigetomi K, Sato Y, Nakajima N, et al. Purification and characterization of a tuliposide-converting enzyme from bulbs of Tulipa gesneriana. Biosci Biotechnol Biochem 2009;73:1895–7.10.1271/bbb.90226Search in Google Scholar PubMed
6. Nomura T, Ogita S, Kato Y. A novel lactone-forming carboxylesterase: Molecular identification of a tuliposide A-converting enzyme in tulip. Plant Physiol 2012;159:565–78.10.1104/pp.112.195388Search in Google Scholar PubMed PubMed Central
7. Nomura T, Tsuchigami A, Ogita S, Kato Y. Molecular diversity of tuliposide A-converting enzyme in the tulip. Biosci Biotechnol Biochem 2013;77:1042–8.10.1271/bbb.130021Search in Google Scholar PubMed
8. Nomura T, Murase T, Ogita S, Kato Y. Molecular identification of tuliposide B-converting enzyme: a lactone-forming carboxylesterase from the pollen of tulip. Plant J 2015;83:252–62.10.1111/tpj.12883Search in Google Scholar PubMed
9. Nomura T, Ueno A, Ogita S, Kato Y. Molecular diversity of tuliposide B-converting enzyme in tulip (Tulipa gesneriana): identification of the root-specific isozyme. Biosci Biotechnol Biochem 2017;81:1185–93.10.1080/09168451.2017.1295806Search in Google Scholar PubMed
10. Nomura T, Kuchida R, Kitaoka N, Kato Y. Molecular diversity of tuliposide B-converting enzyme in tulip (Tulipa gesneriana): identification of the third isozyme with a distinct expression profile. Biosci Biotechnol Biochem 2018;82:810–20.10.1080/09168451.2018.1438170Search in Google Scholar PubMed
11. Kato Y, Futanaga T, Nomura T. Substrate specificity of tuliposide-converting enzyme, a unique non-ester-hydrolyzing carboxylesterase in tulip: effects of the alcohol moiety of substrate on the enzyme activity. Bioorg Med Chem Lett 2019;29:664–7.10.1016/j.bmcl.2018.12.010Search in Google Scholar
12. Christensen LP. Tuliposides from Tulipa sylvestris and T. turkestanica. Phytochemistry 1999;51:969–74.10.1016/S0031-9422(98)00716-XSearch in Google Scholar
13. Nomura T, Ogita S, Kato Y. One-step enzymatic synthesis of 1-tuliposide A using tuliposide-converting enzyme. Appl Biochem Biotechnol 2019;188:12–28.10.1007/s12010-018-2903-3Search in Google Scholar PubMed
14. Wilford R. Tulips: species and hybrids for the gardener. Portland, OR: Timber Press, 2006.Search in Google Scholar
15. Nomura T, Hayashi E, Kawakami S, Ogita S, Kato Y. Environmentally benign process for the preparation of antimicrobial α-methylene-β-hydroxy-γ-butyrolactone (tulipalin B) from tulip biomass. Biosci Biotechnol Biochem 2015;79:25–35.10.1080/09168451.2014.946395Search in Google Scholar PubMed
Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/znc-2019-0123).
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