{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,25]],"date-time":"2026-04-25T02:47:49Z","timestamp":1777085269194,"version":"3.51.4"},"reference-count":36,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2005,4,6]],"date-time":"2005-04-06T00:00:00Z","timestamp":1112745600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemBioChem"],"published-print":{"date-parts":[[2005,4,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>The influence of Trp128\u2010substituted mutants of the hydroxynitrile lyase from<\/jats:italic> Manihot esculenta <jats:italic>(MeHNL) on the stereoselectivity of MeHNL\u2010catalyzed HCN additions to aldehydes with stereogenic centers, which yield the corresponding cyanohydrins, is described. In<\/jats:italic> rac<jats:italic>\u20102\u2010phenylpropionaldehyde (<\/jats:italic>rac<jats:italic>\u2010<jats:bold>1<\/jats:bold>) reactions, wild\u2010type (wtMeHNL) and all MeHNL Trp128 mutants are highly (<\/jats:italic>S<jats:italic>)\u2010selective toward the (<\/jats:italic>R<jats:italic>) enantiomer of<\/jats:italic> rac<jats:italic>\u2010<jats:bold>1<\/jats:bold>; this results exclusively in (2<\/jats:italic>S<jats:italic>,3<\/jats:italic>R<jats:italic>)\u2010cyanohydrin ((2<\/jats:italic>S<jats:italic>,3<\/jats:italic>R<jats:italic>)\u2010<jats:bold>2<\/jats:bold>) with \u226596\u2009%<\/jats:italic> de<jats:italic>. The (<\/jats:italic>S<jats:italic>) enantiomer of<\/jats:italic> rac<jats:italic>\u2010<jats:bold>1<\/jats:bold>, however, only reacts (<\/jats:italic>S<jats:italic>)\u2010selectively with wtMeHNL to give (2<\/jats:italic>S<jats:italic>,3<\/jats:italic>S<jats:italic>)\u2010<jats:bold>2<\/jats:bold> with 80\u2009%<\/jats:italic> de<jats:italic>, whereas with Trp128 mutants, (<\/jats:italic>R<jats:italic>) selectivity increases with decreasing size of the amino acids exchanged. The MeHNL W128A mutant is exclusively (<\/jats:italic>R<jats:italic>)\u2010selective, resulting in (2<\/jats:italic>R<jats:italic>,3<\/jats:italic>S<jats:italic>)\u2010<jats:bold>2<\/jats:bold> with 86\u2009%<\/jats:italic> de<jats:italic>. The reaction behavior of<\/jats:italic> rac<jats:italic>\u2010phenylbutyraldehyde (<\/jats:italic>rac<jats:italic>\u2010<jats:bold>5<\/jats:bold>) is comparable with<\/jats:italic> rac<jats:italic>\u2010<jats:bold>1<\/jats:bold>, which also inverts the stereoselectivity from (<\/jats:italic>S<jats:italic>) to (<\/jats:italic>R<jats:italic>) when the enzyme is exchanged from wtMeHNL to the W128A mutant. Stereogenic centers not adjacent to the aldehyde group, as in <jats:bold>7<\/jats:bold> and <jats:bold>9<\/jats:bold>, do not influence the stereoselectivity of MeHNL catalysis, and (<\/jats:italic>S<jats:italic>) selectivity is observed in all cases. Stereoselectivity and inversion of stereoselectivity of MeHNL Trp128 mutant\u2010catalyzed cyanohydrin formation can be explained and rationalized with crystal\u2010structure\u2010based molecular modeling.<\/jats:italic><\/jats:p>","DOI":"10.1002\/cbic.200400302","type":"journal-article","created":{"date-parts":[[2005,4,6]],"date-time":"2005-04-06T10:40:21Z","timestamp":1112784021000},"page":"711-717","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Inversion of Stereoselectivity by Applying Mutants of the Hydroxynitrile Lyase from <i>Manihot esculenta<\/i>"],"prefix":"10.1002","volume":"6","author":[{"given":"Holger","family":"B\u00fchler","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Burkhard","family":"Miehlich","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Franz","family":"Effenberger","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2005,4,6]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0907444998017971"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0907444900015766"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1110\/ps.01301"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1110\/ps.33702"},{"key":"e_1_2_6_6_2","unstructured":"H. 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