{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,26]],"date-time":"2025-10-26T21:24:34Z","timestamp":1761513874890,"version":"build-2065373602"},"reference-count":60,"publisher":"Wiley","issue":"22","license":[{"start":{"date-parts":[[2016,10,11]],"date-time":"2016-10-11T00:00:00Z","timestamp":1476144000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2016,11,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Absolute rate coefficients for the reaction between the important environmental free radical oxidant NO<jats:sub>3<\/jats:sub><jats:sup>.<\/jats:sup> and a series of <jats:italic>N<\/jats:italic>\u2010 and <jats:italic>C<\/jats:italic>\u2010protected amino acids, di\u2010 and tripeptides were determined using 355\u2005nm laser flash photolysis of cerium(IV) ammonium nitrate in the presence of the respective substrates in acetonitrile at 298\u00b11\u2005K. Through combination with computational studies it was revealed that the reaction with acyclic aliphatic amino acids proceeds through hydrogen abstraction from the \u03b1\u2010carbon, which is associated with a rate coefficient of about 1.8\u00d710<jats:sup>6<\/jats:sup>\u2009<jats:sc>m<\/jats:sc><jats:sup>\u22121<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup> per abstractable hydrogen atom. The considerably faster reaction with phenylalanine [<jats:italic>k<\/jats:italic>=(1.1\u00b10.1)\u00d710<jats:sup>7<\/jats:sup>\u2009<jats:sc>m<\/jats:sc><jats:sup>\u22121<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup>] is indicative for a mechanism involving electron transfer. An unprecedented amplification of the rate coefficient by a factor of 7\u201320 was found with di\u2010 and tripeptides that contain more than one phenylalanine residue. This suggests a synergistic effect between two aromatic rings in close vicinity, which makes such peptide sequences highly vulnerable to oxidative damage by this major environmental pollutant.<\/jats:p>","DOI":"10.1002\/asia.201600994","type":"journal-article","created":{"date-parts":[[2016,9,6]],"date-time":"2016-09-06T13:11:13Z","timestamp":1473167473000},"page":"3188-3195","source":"Crossref","is-referenced-by-count":15,"title":["Reaction of Amino Acids, Di\u2010 and Tripeptides with the Environmental Oxidant NO<sub>3<\/sub><sup>.<\/sup>: A Laser Flash Photolysis and Computational Study"],"prefix":"10.1002","volume":"11","author":[{"given":"Joses G.","family":"Nathanael","sequence":"first","affiliation":[{"name":"School of Chemistry, Bio21 Institute The University of Melbourne  Parkville Victoria 3010 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Amber N.","family":"Hancock","sequence":"additional","affiliation":[{"name":"School of Chemistry, Bio21 Institute The University of Melbourne  Parkville Victoria 3010 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1756-5449","authenticated-orcid":false,"given":"Uta","family":"Wille","sequence":"additional","affiliation":[{"name":"School of Chemistry, Bio21 Institute The University of Melbourne  Parkville Victoria 3010 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2016,10,11]]},"reference":[{"volume-title":"Air Pollution and Health","year":"1999","key":"e_1_2_6_1_1"},{"key":"e_1_2_6_2_1","unstructured":"Selected examples:"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1080\/09603129973344"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00480811"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0013-9351(87)80022-1"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1515\/REVEH.2000.15.1-2.13"},{"key":"e_1_2_6_7_2","first-page":"5","volume":"139","author":"Brunekreef B.","year":"2009","journal-title":"Res. 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Wayne I. Barnes P. Biggs J.\u2005P. Burrows C.\u2005E. Canosa-Mas J. Hjorth G. Le\u2005Bras G.\u2005K. Moortgat D. Perner G. Restelli H. Sidebottom The Nitrate Radical: Physics Chemistry and the Atmosphere(Ed.: R.\u2005P. Wayne) Atmos. Environ. A1991 25 1\u2013206.","DOI":"10.1016\/0960-1686(91)90192-A"},{"key":"e_1_2_6_26_1","doi-asserted-by":"publisher","DOI":"10.1183\/09031936.01.00072501"},{"key":"e_1_2_6_27_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.555808"},{"key":"e_1_2_6_28_1","unstructured":"\u00a0"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0ob01186j"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4OB01577K"},{"key":"e_1_2_6_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201501850"},{"key":"e_1_2_6_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/b803456g"},{"key":"e_1_2_6_33_1","doi-asserted-by":"publisher","DOI":"10.1016\/1010-6030(95)04146-X"},{"key":"e_1_2_6_34_1","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39870001246"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100123a003"},{"key":"e_1_2_6_37_1","unstructured":"10\u2005mJ is the lowest energy possible with our laser flash photolysis system. Higher laser energies (we explored up to 30\u2005mJ) produced a larger NO3.signal but also increased photobleaching as indicated by a higher transmission of the reaction solution after a laser pulse. We also noticed in the reactions of the aromatic amino acids\/peptides that the transmission after the laser flash increased with increasing [substrate] presumably due to oxidation of the benzyl radical of type5by CAN. Both laser power or changes in transmission had no significant effect on the kinetic data."},{"key":"e_1_2_6_38_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC01580D"},{"key":"e_1_2_6_39_1","unstructured":"All experiments were performed without degassing the reaction mixture since purging with argon in an ultrasound bath was detrimental to the signal quality. It was shown previously that the presence of O2has no effect on the rate coefficients for reactions involving NO3.; see ref.\u2005[16]."},{"key":"e_1_2_6_40_1","unstructured":"\u00a0"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2004.06.027"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100117a025"},{"key":"e_1_2_6_43_1","unstructured":"Addition of the electrophilic NO3.to the electron poor \u03c0 system of the nitrile group is considered as an unlikely pathway."},{"key":"e_1_2_6_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b00549"},{"key":"e_1_2_6_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo3021538"},{"key":"e_1_2_6_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo049603"},{"key":"e_1_2_6_47_1","doi-asserted-by":"publisher","DOI":"10.1039\/b507856c"},{"key":"e_1_2_6_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/jms.1543"},{"key":"e_1_2_6_49_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.62.1606"},{"key":"e_1_2_6_50_1","unstructured":"Gaussian\u200509 Revision\u2005C.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery \u2005Jr. J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov T. Keith R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox F.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels O. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT 2010."},{"key":"e_1_2_6_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.6b00007"},{"key":"e_1_2_6_52_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-007-0310-x"},{"key":"e_1_2_6_53_1","doi-asserted-by":"publisher","DOI":"10.1098\/rsta.2012.0476"},{"key":"e_1_2_6_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp3126736"},{"key":"e_1_2_6_55_1","unstructured":"For comparison the computations for the reaction of NO3.with acetonitrile [Eq.\u2005(3)] predict a slightly exothermic process (reaction energy=\u221233.7\u2005kJ\u2009mol\u22121) and a barrier of 285.5\u2005kJ\u2009mol\u22121. This clearly indicates a comparably slow reaction which qualitatively agrees with the experimental findings."},{"key":"e_1_2_6_56_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar50092a002"},{"key":"e_1_2_6_57_1","unstructured":"The alkyl substituent renders the aromatic system electron-rich so that addition of the electrophilic NO3.should preferably occur at the activatedorthoandparapositions and notmeta which was therefore not explored."},{"key":"e_1_2_6_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp011975o"},{"key":"e_1_2_6_59_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbapap.2004.08.007"},{"key":"e_1_2_6_60_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.freeradbiomed.2014.01.014"}],"container-title":["Chemistry \u2013 An Asian Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fasia.201600994","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fasia.201600994","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/asia.201600994","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T17:17:11Z","timestamp":1759943831000},"score":1,"resource":{"primary":{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/10.1002\/asia.201600994"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2016,10,11]]},"references-count":60,"journal-issue":{"issue":"22","published-print":{"date-parts":[[2016,11,22]]}},"alternative-id":["10.1002\/asia.201600994"],"URL":"https:\/\/doi.org\/10.1002\/asia.201600994","archive":["Portico"],"relation":{},"ISSN":["1861-4728","1861-471X"],"issn-type":[{"type":"print","value":"1861-4728"},{"type":"electronic","value":"1861-471X"}],"subject":[],"published":{"date-parts":[[2016,10,11]]}}}