{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,10]],"date-time":"2026-03-10T13:26:32Z","timestamp":1773149192445,"version":"3.50.1"},"reference-count":8,"publisher":"Wiley","issue":"6","license":[{"start":{"date-parts":[[2010,6,16]],"date-time":"2010-06-16T00:00:00Z","timestamp":1276646400000},"content-version":"vor","delay-in-days":15,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry &amp; Biodiversity"],"published-print":{"date-parts":[[2010,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The rapid racemization of aspartic acid (Asp) residues in peptides and proteins is due mainly to the succinimide intermediate. However, there should be another mechanism for Asp racemization without intermediacy of the succinimide. The direct H\u2010atom abstraction from the C(<jats:italic>\u03b1<\/jats:italic>)\u2010atom that leads to the enol form of the Asp residue is one possibility. In another study, we have computationally predicted that the corresponding enolization in the succinimide intermediate occurs by assistance of two H<jats:sub>2<\/jats:sub>O molecules. In the present study, we, therefore, investigated the similar two\u2010H<jats:sub>2<\/jats:sub>O\u2010assisted enolization for an Asp\u2010containing model compound by the same computational method as before (B3LYP\/6\u201031+G**). Rather surprisingly, the activation barrier for the two\u2010H<jats:sub>2<\/jats:sub>O\u2010assisted enolization of the Asp residue (protonated form) was calculated to be almost equal to that for the corresponding succinimide. Therefore, an Asp residue is expected to be prone to enolization to almost the same degree as the corresponding succinimide form, and the \u2018direct\u2019 (<jats:italic>i.e.<\/jats:italic>, non\u2010succinimide\u2010mediated) mechanism of Asp racemization may compete with the succinimide\u2010mediated mechanism.<\/jats:p>","DOI":"10.1002\/cbdv.200900298","type":"journal-article","created":{"date-parts":[[2010,6,18]],"date-time":"2010-06-18T16:45:53Z","timestamp":1276879553000},"page":"1630-1633","source":"Crossref","is-referenced-by-count":4,"title":["Computational Modeling of the Enolization in a Direct Mechanism of Racemization of the Aspartic Acid Residue"],"prefix":"10.1002","volume":"7","author":[{"given":"Ohgi","family":"Takahashi","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kana","family":"Kobayashi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Akifumi","family":"Oda","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2010,6,16]]},"reference":[{"key":"e_1_2_1_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0047-6374(01)00363-3"},{"key":"e_1_2_1_1_3","doi-asserted-by":"publisher","DOI":"10.1248\/bpb.28.1585"},{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9258(19)75855-4"},{"key":"e_1_2_1_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9258(18)83327-0"},{"key":"e_1_2_1_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja953505b"},{"key":"e_1_2_1_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/cbdv.200900296"},{"key":"e_1_2_1_6_2","unstructured":"Spartan'04 Wavefunction Inc. Irvine CA."},{"key":"e_1_2_1_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/cbdv.200900297"}],"container-title":["Chemistry &amp; Biodiversity"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fcbdv.200900298","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cbdv.200900298","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,13]],"date-time":"2023-09-13T04:09:08Z","timestamp":1694578148000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/cbdv.200900298"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2010,6]]},"references-count":8,"journal-issue":{"issue":"6","published-print":{"date-parts":[[2010,6]]}},"alternative-id":["10.1002\/cbdv.200900298"],"URL":"https:\/\/doi.org\/10.1002\/cbdv.200900298","archive":["Portico"],"relation":{},"ISSN":["1612-1872","1612-1880"],"issn-type":[{"value":"1612-1872","type":"print"},{"value":"1612-1880","type":"electronic"}],"subject":[],"published":{"date-parts":[[2010,6]]}}}