{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T11:42:09Z","timestamp":1790336529942,"version":"4.1.0"},"reference-count":31,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2024,6,11]],"date-time":"2024-06-11T00:00:00Z","timestamp":1718064000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Intramural Research Program of the NIH, NCI\/CCR"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>An untargeted metabolomic study identified four potential lung cancer diagnostic biomarkers in human urine. One of the potential biomarkers was an unidentified feature possessing a m\/z value of 561+. \u201c561+\u201d was isolated from human urine and tentatively identified as 27-nor-5\u03b2-cholestane-3\u03b1,7\u03b1,12\u03b1,24,25 pentol glucuronide with unknown C24,25 stereochemistry using 1H NMR and mass spectrometry. In a prior report, the C24,25 stereochemistry of the aglycone, 27-nor-5\u03b2-cholestane-3\u03b1,7\u03b1,12\u03b1,24,25 pentol, was found to be 24S,25R through GC analysis of the acetonide-TMS derivative. An authentic sample was prepared and found not to have the same stereochemistry as \u201d561+\u201d. To identify the C24,25 stereochemistry, four C24,C25 diastereoisomeric alcohols of 27-nor-5\u03b2-cholestane-3\u03b1,7\u03b1,12\u03b1,24,25 pentol were prepared from chiral amino acids. Using an LCMS method, the C24,C25 stereochemistry of the \u201c561+\u201d aglycone was determined to be 24R,25S. With the correct aglycone in hand, it was coupled with glucuronic acid to complete the first reported synthesis of 27-nor-5\u03b2-cholestane-3\u03b1,7\u03b1,12\u03b1,24R,25S pentol glucuronide. Deuterium labeled 27-nor-5\u03b2-cholestane-3\u03b1,7\u03b1,12\u03b1,24R,25S pentol was also synthesized for use as an internal standard for MS quantitation.<\/jats:p>","DOI":"10.3390\/molecules29122781","type":"journal-article","created":{"date-parts":[[2024,6,11]],"date-time":"2024-06-11T11:58:58Z","timestamp":1718107138000},"page":"2781","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Isolation and Identification of a Urinary Biomarker for Lung Cancer: 27-Nor-5\u03b2-Cholestane-3\u03b1,7\u03b1,12\u03b1,24R,25S Pentol Glucuronide and Its Deuterated Analog"],"prefix":"10.3390","volume":"29","author":[{"given":"Burchelle","family":"Blackman","sequence":"first","affiliation":[{"name":"Chemistry and Chemical Synthesis Center, National Heart, Lung, and Blood Institute, National Institutes of Health, 9800 Medical Center Drive, Rockville, MD 20850, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natarajan","family":"Raju","sequence":"additional","affiliation":[{"name":"Chemistry and Chemical Synthesis Center, National Heart, Lung, and Blood Institute, National Institutes of Health, 9800 Medical Center Drive, Rockville, MD 20850, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chandrasekhar","family":"Mushti","sequence":"additional","affiliation":[{"name":"Chemistry and Chemical Synthesis Center, National Heart, Lung, and Blood Institute, National Institutes of Health, 9800 Medical Center Drive, Rockville, MD 20850, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kelly","family":"Lane","sequence":"additional","affiliation":[{"name":"Chemistry and Chemical Synthesis Center, National Heart, Lung, and Blood Institute, National Institutes of Health, 9800 Medical Center Drive, Rockville, MD 20850, USA"},{"name":"AstraZeneca, 1 MedImmune Way, Gaithersburg, MD 20878, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9620-8660","authenticated-orcid":false,"given":"Daxeshkumar","family":"Patel","sequence":"additional","affiliation":[{"name":"Laboratory of Human Carcinogenesis, Center for Cancer Research, National Cancer Institute, Bethesda, MD 20892, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5268-0181","authenticated-orcid":false,"given":"Curtis","family":"Harris","sequence":"additional","affiliation":[{"name":"Laboratory of Human Carcinogenesis, Center for Cancer Research, National Cancer Institute, Bethesda, MD 20892, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7804-7202","authenticated-orcid":false,"given":"Rolf E.","family":"Swenson","sequence":"additional","affiliation":[{"name":"Chemistry and Chemical Synthesis Center, National Heart, Lung, and Blood Institute, National Institutes of Health, 9800 Medical Center Drive, Rockville, MD 20850, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2024,6,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"7","DOI":"10.3322\/caac.21654","article-title":"Cancer Statistics, 2021","volume":"71","author":"Siegel","year":"2021","journal-title":"CA A Cancer J. 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