{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T06:14:39Z","timestamp":1790144079753,"version":"4.0.1"},"reference-count":32,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2020,7,28]],"date-time":"2020-07-28T00:00:00Z","timestamp":1595894400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["18-13-00047, 18-13-00246"],"award-info":[{"award-number":["18-13-00047, 18-13-00246"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Photoinduced elementary processes in chiral linked systems, consisting of drugs and tryptophan (Trp) residues, attract considerable attention due to several aspects. First of all, these are models that allow one to trace the full and partial charge transfer underlying the binding of drugs to enzymes and receptors. On the other hand, Trp fluorescence is widely used to establish the structure and conformational mobility of proteins due to its high sensitivity to the microenvironment. Therefore, the study of mechanisms of Trp fluorescence quenching in various systems has both fundamental and practical interest. An analysis of the photo-chemically induced dynamic nuclear polarization (CIDNP) and Trp fluorescence quenching in (R\/S)-ketoprofen-(S)-tryptophan ((S\/R)-KP-(S)-Trp) dyad carried out in this work allowed us to trace the intramolecular reversible electron transfer (ET) and obtain evidence in favor of the resonance energy transfer (RET). The fraction of dyad\u2019s singlet excited state, quenched via ET, was shown to be 7.5 times greater for the (S,S)-diastereomer than for the (R,S) analog. At the same time, the ratio of the fluorescence quantum yields shows that quenching effectiveness of (S,S)-diastereomer to be 5.4 times lower than for the (R,S) analog. It means that the main mechanism of Trp fluorescence quenching in (S\/R)-KP-(S)-Trp dyad is RET.<\/jats:p>","DOI":"10.3390\/ijms21155370","type":"journal-article","created":{"date-parts":[[2020,7,29]],"date-time":"2020-07-29T07:31:45Z","timestamp":1596007905000},"page":"5370","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Stereoselectivity of Electron and Energy Transfer in the Quenching of (S\/R)-Ketoprofen-(S)-Tryptophan Dyad Excited State"],"prefix":"10.3390","volume":"21","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8670-0352","authenticated-orcid":false,"given":"Aleksandra A.","family":"Ageeva","sequence":"first","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Simon V.","family":"Babenko","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ilya M.","family":"Magin","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Victor F.","family":"Plyusnin","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"},{"name":"Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Polina S.","family":"Kuznetsova","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"},{"name":"Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander A.","family":"Stepanov","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sergey F.","family":"Vasilevsky","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3666-7750","authenticated-orcid":false,"given":"Nikolay E.","family":"Polyakov","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7572-1476","authenticated-orcid":false,"given":"Alexander B.","family":"Doktorov","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tatyana V.","family":"Leshina","sequence":"additional","affiliation":[{"name":"Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,7,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"18446","DOI":"10.1038\/srep18446","article-title":"Quantifying electron transfer reactions in biological systems: What interactions play the major role","volume":"5","author":"Sjulstok","year":"2016","journal-title":"Sci. Rep."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1080\/00268978900101931","article-title":"Electron transfer in biology","volume":"68","author":"Williams","year":"1989","journal-title":"Mol. Phys."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"7407","DOI":"10.1021\/ja0712827","article-title":"Triplet Reactivity and Regio-\/Stereoselectivity in the Macrocyclization of Diastereomeric Ketoprofen-Quencher Conjugates via Remote Hydrogen Abstractions","volume":"129","author":"Abad","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"128","DOI":"10.1016\/j.jphotochemrev.2007.10.001","article-title":"Photoinduced processes in naproxen-based chiral dyads","volume":"8","author":"Pischel","year":"2007","journal-title":"J. Photochem. Photobiol. C"},{"key":"ref_5","first-page":"1","article-title":"Peculiarities of Electron Transfer in Chiral Linked Systems","volume":"Volume 5","author":"Akitsu","year":"2019","journal-title":"Chirality from Molecular Electronic States"},{"key":"ref_6","first-page":"35","article-title":"Physico\u0441hemical Approach to the Study of Naproxen Enantiomers Activity Difference","volume":"Volume 2","author":"Corner","year":"2018","journal-title":"Naproxen Chemistry, Clinical Aspects and Effects"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"12733","DOI":"10.1039\/C5CP07305G","article-title":"Impact of chirality on the photoinduced charge transfer in linked systems containing naproxen enantiomers","volume":"18","author":"Khramtsova","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Lin, G.-Q., You, Q.-D., and Cheng, J.F. (2011). Chiral Drugs: Chemistry and Biological Action, Wiley.","DOI":"10.1002\/9781118075647"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"315","DOI":"10.3109\/00498254.2015.1076086","article-title":"Enantiospecific effects of chiral drugs on cytochrome P450 inhibition in vitro","volume":"46","author":"Krasulova","year":"2016","journal-title":"Xenobiotica"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"7332","DOI":"10.1039\/c1cc10763a","article-title":"Chiral inversion of 2-arylpropionyl-CoA esters by human \u03b1-methylacyl-CoA racemase 1A (P504S)\u2014A potential mechanism for the anti-cancer effects of ibuprofen","volume":"47","author":"Woodman","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1485","DOI":"10.1007\/s00228-015-1934-8","article-title":"Stereoselective handling of perhexiline: Implications regarding accumulation within the human myocardium","volume":"71","author":"Chong","year":"2015","journal-title":"Eur. J. Clin. Pharm."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3882","DOI":"10.1002\/chem.201705863","article-title":"Spin Selectivity in Chiral Linked Systems","volume":"24","author":"Ageeva","year":"2018","journal-title":"Chem. Eur. J."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"18587","DOI":"10.1002\/chem.201801625","article-title":"Role of association in chiral catalysis: From asymmetric synthesis to spin selectivity","volume":"24","author":"Ageeva","year":"2018","journal-title":"Chem. Eur. J."},{"key":"ref_14","unstructured":"Salikhov, K.M., Molin, Y.N., Sagdeev, R.Z., and Buchachenko, A.L. (1984). Spin Polarization and Magnetic Effects in Radical Reactions, Akademiai Kiado."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"599","DOI":"10.1070\/RC2007v076n07ABEH003714","article-title":"Spin chemistry of enzymatic Processes","volume":"76","author":"Afanasyeva","year":"2007","journal-title":"Russ. Chem. Rev."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1394","DOI":"10.1089\/ars.2017.7406","article-title":"Redox active pro-drugs metal chelators: Properties, mechanisms of action, cells delivery and cells toxicity","volume":"28","author":"Polyakov","year":"2018","journal-title":"Antioxid. Redox. Signal."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"245101","DOI":"10.1063\/1.5128043","article-title":"Spin effects as a tool to study photoinduced processes in (S\/R)-ketoprofen-(S)-N -methylpyrrolidine dyads","volume":"151","author":"Polyakov","year":"2019","journal-title":"J. Chem. Phys."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"10705","DOI":"10.1021\/bi800499k","article-title":"Mechanism of the efficient tryptophan fluorescence quenching in human \u03b3D-crystallin studied by time-resolved fluorescence","volume":"47","author":"Chen","year":"2008","journal-title":"Biochemistry"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"3900","DOI":"10.1039\/b704636g","article-title":"Chiral highly luminescent CdS quantum dots","volume":"38","author":"Moloney","year":"2007","journal-title":"Chem. Commun."},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Lazzari, F., Manfredi, A., Alongi, J., Marinotto, D., Ferruti, P., and Ranucci, E. (2019). D-, L-and D, L-Tryptophan-Based Polyamidoamino Acids: pH-Dependent Structuring and Fluorescent Properties. Polymers, 11.","DOI":"10.3390\/polym11030543"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"12433","DOI":"10.1038\/s41598-017-10525-5","article-title":"Using chirality to probe the conformational dynamics and assembly of intrinsically disordered amyloid proteins","volume":"7","author":"Raskatov","year":"2017","journal-title":"Sci. Rep."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"9363","DOI":"10.1021\/jp071301z","article-title":"Excited-state interactions in flurbiprofen-tryptophan dyads","volume":"111","author":"Miranda","year":"2007","journal-title":"J. Phys. Chem. B"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"609","DOI":"10.1515\/zpch-2016-0842","article-title":"Photoinduced electron transfer in dyads with (R)-\/(S)-naproxen and (S)-tryptophan","volume":"231","author":"Khramtsova","year":"2017","journal-title":"Z. Phys. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2918","DOI":"10.1046\/j.1432-1033.2002.02963.x","article-title":"Tryptophan fluorescence study of the interaction of penetratin peptides with model membranes","volume":"269","author":"Christiaens","year":"2002","journal-title":"Eur. J. Biochem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"12774","DOI":"10.1021\/ja053518h","article-title":"Excited state enantiodifferentiating interactions between a chiral benzophenone derivative and nucleosides","volume":"127","author":"Encinas","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"22518","DOI":"10.3390\/ijms151222518","article-title":"Intrinsic tryptophan fluorescence in the detection and analysis of proteins: A focus on F\u00f6rster resonance energy transfer techniques","volume":"15","author":"Ghisaidoobe","year":"2014","journal-title":"Int. J. Mol. Sci."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"93","DOI":"10.1524\/zpch.1982.133.1.093","article-title":"Photoinduced electron transfer in solution: Exciplex and radical ion pair formation free enthalpies and their solvent dependence","volume":"133","author":"Weller","year":"1982","journal-title":"Z. Phys. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"265","DOI":"10.1016\/0304-4173(85)90014-X","article-title":"Electron transfers in chemistry and biology","volume":"811","author":"Marcus","year":"1985","journal-title":"Biochim. Biophys. Acta"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2093","DOI":"10.1016\/S0006-3495(01)76183-8","article-title":"Mechanisms of Tryptophan Fluorescence Shifts in Proteins","volume":"80","author":"Vivian","year":"2001","journal-title":"Biophys. J."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1269","DOI":"10.1134\/S0006297917110049","article-title":"Temperature dependence of tryptophan fluorescence lifetime in aqueous glycerol and trehalose solutions","volume":"82","author":"Gorokhov","year":"2017","journal-title":"Biochem. Mosc."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"56","DOI":"10.1016\/j.ijpharm.2005.09.019","article-title":"Conformational study of ketoprofen by combined DFT calculations and Raman spectroscopy","volume":"307","author":"Vueba","year":"2006","journal-title":"Int. J. Pharm."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2265","DOI":"10.1021\/acs.jpcb.7b00217","article-title":"Can F\u00f6rster Theory Describe Stereoselective Energy Transfer Dynamics in a Protein\u2013Ligand Complex","volume":"121","author":"Pinheiro","year":"2017","journal-title":"J. Phys. Chem. B"}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/21\/15\/5370\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:52:27Z","timestamp":1760176347000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/21\/15\/5370"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,7,28]]},"references-count":32,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2020,8]]}},"alternative-id":["ijms21155370"],"URL":"https:\/\/doi.org\/10.3390\/ijms21155370","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,7,28]]}}}