{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T16:52:18Z","timestamp":1781110338168,"version":"3.54.1"},"reference-count":49,"publisher":"National Academy of Sciences","issue":"25","content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[1996,12,10]]},"abstract":"<jats:p>\n                    The equilibrium for formation of the intramolecular hydrogen bond\n (K\n                    <jats:sup>HB<\/jats:sup>\n                    ) in a series of substituted salicylate monoanions was\n investigated as a function of \u0394pK\n                    <jats:sub>a<\/jats:sub>\n                    , the difference\n between the pK\n                    <jats:sub>a<\/jats:sub>\n                    values of the hydrogen bond donor and\n acceptor, in both water and dimethyl sulfoxide. The dependence of log\n K\n                    <jats:sup>HB<\/jats:sup>\n                    upon \u0394pK\n                    <jats:sub>a<\/jats:sub>\n                    is linear in both solvents, but\n is steeper in dimethyl sulfoxide (slope = 0.73) than in water\n (slope = 0.05). Thus, hydrogen bond strength can undergo\n substantially larger increases in nonaqueous media than aqueous\n solutions as the charge density on the donor or acceptor atom\n increases. These results support a general mechanism for enzymatic\n catalysis, in which hydrogen bonding to a substrate is strengthened as\n charge rearranges in going from the ground state to the transition\n state; the strengthening of the hydrogen bond would be greater in a\n nonaqueous enzymatic active site than in water, thus providing a rate\n enhancement for an enzymatic reaction relative to the solution\n reaction. We suggest that binding energy of an enzyme is used to fix\n the substrate in the low-dielectric active site, where the\n strengthening of the hydrogen bond in the course of a reaction is\n increased.\n                  <\/jats:p>","DOI":"10.1073\/pnas.93.25.14474","type":"journal-article","created":{"date-parts":[[2002,7,26]],"date-time":"2002-07-26T10:34:16Z","timestamp":1027679656000},"page":"14474-14479","update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":151,"title":["The change in hydrogen bond strength accompanying charge rearrangement: Implications for enzymatic\u2009catalysis"],"prefix":"10.1073","volume":"93","author":[{"given":"Shu-ou","family":"Shan","sequence":"first","affiliation":[{"name":"Department of Biochemistry, B400 Beckman Center, Stanford\r University, Stanford, CA 94305-5307"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daniel","family":"Herschlag","sequence":"additional","affiliation":[{"name":"Department of Biochemistry, B400 Beckman Center, Stanford\r University, Stanford, CA 94305-5307"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"341","published-online":{"date-parts":[[1996,12,10]]},"reference":[{"key":"e_1_3_2_1_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac199163020213"},{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00156a004"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01304a034"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00182a020"},{"key":"e_1_3_2_5_2","first-page":"352","volume-title":"Dissociation Constants of Organic Acids in Aqueous Solution","author":"Kortum G","year":"1961","unstructured":"G Kortum, W Vogel, K Andrussow Dissociation Constants of Organic Acids in Aqueous Solution (Butterworths, London), pp. 352\u2013464 (1961)."},{"key":"e_1_3_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja954205x"},{"key":"e_1_3_2_7_2","first-page":"439","volume-title":"Correlation Analysis of Chemical Data","author":"Exner O","year":"1988","unstructured":"O Exner Correlation Analysis of Chemical Data (Plenum, New York), pp. 439\u2013540 (1988)."},{"key":"e_1_3_2_8_2","first-page":"12","volume-title":"Linear Free Energy Relationships","author":"Wells P R","year":"1968","unstructured":"P R Wells Linear Free Energy Relationships (Academic, New York), pp. 12\u201313 (1968)."},{"key":"e_1_3_2_9_2","first-page":"426","volume-title":"Steric Effects in Organic Chemistry","author":"Taft R W","year":"1956","unstructured":"R W Taft Steric Effects in Organic Chemistry (Wiley, New York), pp. 426\u2013442 (1956)."},{"key":"e_1_3_2_10_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.272.5258.97"},{"key":"e_1_3_2_11_2","first-page":"323","volume-title":"Catalysis in Chemistry and Enzymology","author":"Jencks W P","year":"1987","unstructured":"W P Jencks Catalysis in Chemistry and Enzymology (Dover, 2nd Ed., New York), pp. 323\u2013350 (1987).","edition":"2"},{"key":"e_1_3_2_12_2","first-page":"81","volume-title":"Physical Organic Chemistry","author":"Hine J","year":"1972","unstructured":"J Hine Physical Organic Chemistry (McGraw\u2013Hill, 2nd Ed., New York), pp. 81\u2013103 (1972).","edition":"2"},{"key":"e_1_3_2_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00771a038"},{"key":"e_1_3_2_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00274a058"},{"key":"e_1_3_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00323a005"},{"key":"e_1_3_2_16_2","first-page":"391","volume":"29","author":"Pawlak Z","year":"1984","unstructured":"Z Pawlak, G Zundel, J Fritsch Z Naturforsch A 29, 391\u2013395 (1984).","journal-title":"Z Naturforsch A"},{"key":"e_1_3_2_17_2","doi-asserted-by":"publisher","DOI":"10.1515\/zna-1984-1013"},{"key":"e_1_3_2_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/f19848000553"},{"key":"e_1_3_2_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/j150656a042"},{"key":"e_1_3_2_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(94)00921-G"},{"key":"e_1_3_2_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29950002069"},{"key":"e_1_3_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00117a013"},{"key":"e_1_3_2_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00348a003"},{"key":"e_1_3_2_24_2","doi-asserted-by":"crossref","unstructured":"Mihalick J.\u2009E. 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