{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T16:12:03Z","timestamp":1790093523537,"version":"4.0.1"},"reference-count":33,"publisher":"American Chemical Society (ACS)","issue":"37","license":[{"start":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T00:00:00Z","timestamp":1788998400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"name":"China National Tobacco Company Yunnan Branch","award":["2023530000241023"],"award-info":[{"award-number":["2023530000241023"]}]},{"name":"China National Tobacco Company Yunnan Branch","award":["2023530000241028"],"award-info":[{"award-number":["2023530000241028"]}]},{"name":"China National Tobacco Company Yunnan Branch","award":["2025530000241023"],"award-info":[{"award-number":["2025530000241023"]}]},{"name":"Yunnan Daguan Laboratory","award":["YNDG202302ZY03"],"award-info":[{"award-number":["YNDG202302ZY03"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,22]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>A nornicotine glycoside\u2500previously reported with an incorrect structure\u2500was isolated from cherry-red tobacco and structurally re-elucidated. Its molecular formula (C15H22N2O5) was determined by high-resolution electrospray ionization mass spectrometry. Acid hydrolysis combined with gas chromatography\u2013mass spectrometry (GC-MS) preliminarily identified the aglycone as nornicotine. Comprehensive analysis of one-dimensional (1H, 13C, DEPT) and two-dimensional (COSY, HSQC, HMBC) nuclear magnetic resonance (NMR) data unambiguously established the planar structure, confirming the sugar moiety is a six-membered pyranose linked to the pyrrolidine nitrogen of nornicotine via an N\u2013CH2\u2013C bond. Density functional theory (DFT)-based NMR chemical shift calculations were performed for four possible stereoisomers (\u03b2-D, \u03b2-L, \u03b1-D, \u03b1-L). Linear regression analysis showed the \u03b2-D stereoisomer had the highest fitting correlation coefficient (R2 = 0.9952 for 13C and R2 = 0.9801 for 1H), significantly outperforming the others. The mean absolute error (MAE) was 2.41 ppm for 13C NMR chemical shifts and 0.28 ppm for 1H NMR chemical shifts, indicating excellent agreement between theoretical and experimental data. Combined with the prevalent distribution of \u03b2-D configuration in natural glycosides, the sugar moiety\u2019s stereo configuration was determined as \u03b2-D, confirming it as \u03b2-D-xylopyranose. This work corrects the long-standing misassignment of the nornicotine glycoside\u2019s sugar moiety.<\/jats:p>","DOI":"10.1021\/acsomega.6c05861","type":"journal-article","created":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T21:01:35Z","timestamp":1789074095000},"page":"55994-56000","source":"Crossref","is-referenced-by-count":0,"title":["Structural Revision\nof a Nornicotine Glycoside: Identification\nof N-[(\u03b2-D-xylopyranosyl)methyl]nornicotine from Cherry-Red\nTobacco"],"prefix":"10.1021","volume":"11","author":[{"given":"Yong","family":"Li","sequence":"first","affiliation":[{"name":"Yunnan Academy of Tobacco Agricultural Sciences , ,","place":["Kunming, China, 650021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5605-250X","authenticated-orcid":true,"given":"Tao","family":"Pang","sequence":"additional","affiliation":[{"name":"Yunnan Academy of Tobacco Agricultural Sciences , ,","place":["Kunming, China, 650021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junli","family":"Shi","sequence":"additional","affiliation":[{"name":"Yunnan Academy of Tobacco Agricultural Sciences , ,","place":["Kunming, China, 650021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhongbang","family":"Song","sequence":"additional","affiliation":[{"name":"Yunnan Academy of Tobacco Agricultural Sciences , ,","place":["Kunming, China, 650021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"He","family":"Xie","sequence":"additional","affiliation":[{"name":"Yunnan Academy of Tobacco Agricultural Sciences , ,","place":["Kunming, China, 650021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ge","family":"Bai","sequence":"additional","affiliation":[{"name":"Yunnan Academy of Tobacco Agricultural Sciences , ,","place":["Kunming, China, 650021"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,10]]},"reference":[{"issue":"6","key":"2026092211031225300_cit1","doi-asserted-by":"publisher","first-page":"1741","DOI":"10.1093\/jxb\/erad341","article-title":"Genetic regulation\nand manipulation of nicotine biosynthesis in tobacco: strategies to\neliminate addictive alkaloids","volume":"75","author":"Shoji","year":"2024","journal-title":"J. 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A gauge-invariant LCAO method\nfor N.M.R. chemical shifts","volume":"27","author":"Ditchfield","year":"1974","journal-title":"Mol. Phys."},{"issue":"23","key":"2026092211031225300_cit29","doi-asserted-by":"publisher","first-page":"8251","DOI":"10.1021\/ja00179a005","article-title":"Efficient implementation of the gauge-independent\natomic orbital method for NMR chemical shift calculations","volume":"112","author":"Wolinski","year":"1990","journal-title":"J. Am. Chem. Soc."},{"issue":"2","key":"2026092211031225300_cit30","doi-asserted-by":"publisher","first-page":"664","DOI":"10.1063\/1.475428","article-title":"Exchange functionals\nwith improved long-range behavior\nand adiabatic connection methods without adjustable parameters: The\nmPW and mPW1PW models","volume":"108","author":"Adamo","year":"1998","journal-title":"J. Chem. 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Plant\nBiol."}],"container-title":["ACS Omega"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acsomega.6c05861","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/37\/55994\/68478021\/acsomega.6c05861.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/37\/55994\/68478021\/acsomega.6c05861.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T15:49:13Z","timestamp":1790092153000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/acsodf\/article\/11\/37\/55994\/5428010\/Structural-Revision-of-a-Nornicotine-Glycoside"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,10]]},"references-count":33,"journal-issue":{"issue":"37","published-online":{"date-parts":[[2026,9,10]]},"published-print":{"date-parts":[[2026,9,22]]}},"URL":"https:\/\/doi.org\/10.1021\/acsomega.6c05861","relation":{},"ISSN":["2470-1343"],"issn-type":[{"value":"2470-1343","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,10]]}}}