{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"institution":[{"name":"bioRxiv"}],"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T13:30:11Z","timestamp":1790861411937,"version":"4.1.0"},"posted":{"date-parts":[[2025,11,16]]},"group-title":"Biophysics","reference-count":0,"publisher":"openRxiv","license":[{"start":{"date-parts":[[2025,11,16]],"date-time":"2025-11-16T00:00:00Z","timestamp":1763251200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"award":["5R01GM127528-04"],"award-info":[{"award-number":["5R01GM127528-04"]}],"id":[{"id":"https:\/\/ror.org\/01cwqze88","id-type":"ROR","asserted-by":"publisher"}]},{"award":["DBI-2210041"],"award-info":[{"award-number":["DBI-2210041"]}],"id":[{"id":"https:\/\/ror.org\/021nxhr62","id-type":"ROR","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"accepted":{"date-parts":[[2025,11,16]]},"abstract":"<jats:p>\n                  The increase in enzyme-catalyzed reaction rates with temperature is typically modeled using Arrhenius or Eyring relations. Interpretation of extracted parameters is subject to multiple caveats. Here we analyze the impact of expected small temperature variations of underlying activation\/Eyring parameters on this modeling. Linear Arrhenius\/Eyring behavior can still be observed when the underlying activation energy E\n                  <jats:sub>a<\/jats:sub>\n                  or enthalpy  \u0394H and entropy \u0394S vary with temperature. Modest variations \u2014 of the order of an H-bond energy over 60 \u00b0C \u2014 lead to large fractional deviations of  E\n                  <jats:sub>a<\/jats:sub>\n                  , \u0394H  and \u0394S  values derived from linear fits from their underlying values and to deviations of Arrhenius prefactors\n                  <jats:italic>A<\/jats:italic>\n                  by orders of magnitude. In a family of related enzymes with similar activation free energies \u0394G , small differences in temperature variation of   \u0394H  and \u0394S  will lead to apparent enthalpy-entropy compensation and may scramble enzyme ordering based on \u0394H  or \u0394S. For enzymes from cold and warm-adapted species having largely similar active sites, small temperature variations of  \u0394H  and \u0394S may explain large differences in apparent  \u0394H  values. Similar considerations apply to interpretation of van \u2032t Hoff plots of equilibrium measurements and related observations of enthalpy-entropy compensation. Complementary methods including simulations and multi-temperature static and time-resolved atomic-resolution structural studies should play a key role in interpreting temperature-dependent kinetic and equilibrium data from enzymatic systems.\n                <\/jats:p>","DOI":"10.1101\/2025.11.16.688712","type":"posted-content","created":{"date-parts":[[2025,11,17]],"date-time":"2025-11-17T03:20:16Z","timestamp":1763349616000},"source":"Crossref","is-referenced-by-count":1,"title":["Activation parameters, enthalpy-entropy compensation and the temperature-dependent activity of enzymes"],"prefix":"10.64898","author":[{"given":"Matthew J","family":"McLeod","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7489-8074","authenticated-orcid":false,"given":"Robert E","family":"Thorne","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"54368","container-title":[],"original-title":[],"link":[{"URL":"https:\/\/syndication.highwire.org\/content\/doi\/10.1101\/2025.11.16.688712","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,1,15]],"date-time":"2026-01-15T10:02:10Z","timestamp":1768471330000},"score":1,"resource":{"primary":{"URL":"http:\/\/biorxiv.org\/lookup\/doi\/10.1101\/2025.11.16.688712"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,11,16]]},"references-count":0,"URL":"https:\/\/doi.org\/10.1101\/2025.11.16.688712","relation":{},"subject":[],"published":{"date-parts":[[2025,11,16]]},"subtype":"preprint"}}