{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T21:14:36Z","timestamp":1790111676991,"version":"4.0.1"},"reference-count":78,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2023,1,12]],"date-time":"2023-01-12T00:00:00Z","timestamp":1673481600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Natural Sciences and Engineering Research Council of Canada"},{"name":"Canada Foundation for Innovation"},{"name":"Alberta Enterprise of Advanced Education"},{"name":"University of Alberta"},{"name":"Digital Research Alliance of Canada"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Steroid hormone molecules may exhibit very different functionalities based on the associated functional groups and their 3D arrangements in space, i.e., absolute configurations and conformations. Infrared (IR) and vibrational circular dichroism (VCD) spectra of four different steroid hormones, namely dehydroepiandrosterone (DHEA), 17\u03b1-methyltestosterone (MTTT), (16\u03b1,17)-epoxyprogesterone (Epoxy-P4), and dehydroepiandrosterone acetate (AcO-DHEA), were measured in deuterated dimethyl sulfoxide and some also in carbon tetrachloride. Extensive conformational searches were carried out using the recent developed conformer-rotamer ensemble sampling tool (CREST) which also accounts for solvent effects using an implicit solvation model. All the CREST conformational candidates were then reoptimized at the B3LYP-D3BJ\/def2-TZVPD with the PCM of solvent. The good agreements between the experimental IR and VCD spectra and the theoretical simulations provide a conclusive information about their conformational distribution and absolute configurations. The experimental and theoretical IR and VCD spectra of AcO-DHEA in the carbonyl and alkene stretching region showed some discrepancies, and the possible causes related to solvent effects, large amplitude motions and levels of theory used in the modelling were explored in detail. As part of the investigation, additional calculations at the B3LYP-D3BJ\/6-31++G (2d,p) and B3LYP-D3BJ\/cc-pVTZ levels, as well as some \u2018mixed\u2019 calculations with the double-hybrid functional B2PLYP-D3 were also carried out. The results indicate that the double-hybrid functional is important for predicting the correct IR band pattern in the carbonyl and alkene stretching region.<\/jats:p>","DOI":"10.3390\/molecules28020771","type":"journal-article","created":{"date-parts":[[2023,1,12]],"date-time":"2023-01-12T05:45:33Z","timestamp":1673502333000},"page":"771","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Conformations of Steroid Hormones: Infrared and Vibrational Circular Dichroism Spectroscopy"],"prefix":"10.3390","volume":"28","author":[{"given":"Yanqing","family":"Yang","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anna","family":"Krin","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada"},{"name":"Centre for Science and Peace Research (ZNF), Universit\u00e4t Hamburg, Bogenallee 11, 20144 Hamburg, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoli","family":"Cai","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada"},{"name":"Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430073, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mohammad Reza","family":"Poopari","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuefei","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430073, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7157-703X","authenticated-orcid":false,"given":"James R.","family":"Cheeseman","sequence":"additional","affiliation":[{"name":"Gaussian Inc., 340 Quinnipiac St., Bldg., 40, Wallingford, CT 06492-4050, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3736-3190","authenticated-orcid":false,"given":"Yunjie","family":"Xu","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,1,12]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"47","DOI":"10.1186\/1743-7075-7-47","article-title":"Cellular cholesterol delivery, intracellular processing and utilization for biosynthesis of steroid hormones","volume":"7","author":"Hu","year":"2010","journal-title":"Nutr. 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