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dc.contributor.authorSnellenburg, Joris J.
dc.contributor.authorLaptenok, Siarhei
dc.contributor.authorDeSa, Richard J.
dc.contributor.authorNaumov, Pance
dc.contributor.authorSolntsev, Kyril M.
dc.date.accessioned2017-01-29T13:51:37Z
dc.date.available2017-01-29T13:51:37Z
dc.date.issued2016-12-08
dc.identifier.citationSnellenburg JJ, Laptenok SP, DeSa RJ, Naumov P, Solntsev KM (2016) Excited-State Dynamics of Oxyluciferin in Firefly Luciferase. Journal of the American Chemical Society 138: 16252–16258. Available: http://dx.doi.org/10.1021/jacs.6b05078.
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.doi10.1021/jacs.6b05078
dc.identifier.urihttp://hdl.handle.net/10754/622762
dc.description.abstractThe color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.
dc.description.sponsorshipThis work was supported by the U.S. National Science Foundation (CHE-1213047, K.M.S.), the Human Frontier Science Project grant (RGY0081/2011, P.N.), and New York University Abu Dhabi.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.6b05078
dc.titleExcited-State Dynamics of Oxyluciferin in Firefly Luciferase
dc.typeArticle
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Division
dc.identifier.journalJournal of the American Chemical Society
dc.contributor.institutionFaculty of Sciences, Department of Physics and Astronomy, VU University Amsterdam, 1081 HV Amsterdam, The Netherlands
dc.contributor.institutionSchool of Chemistry, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ, United Kingdom
dc.contributor.institutionOlis, Inc., 130 Conway Drive, Bogart, Georgia 30622, United States
dc.contributor.institutionNew York University Abu Dhabi, P.O. Box 129188, Abu Dhabi, United Arab Emirates
dc.contributor.institutionSchool of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Drive, Atlanta, Georgia 30332-0400, United States
kaust.personLaptenok, Siarhei
dc.date.published-online2016-12-08
dc.date.published-print2016-12-21


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