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Article: Experimental and Computational Studies of the Macrocyclic Effect of an Auxiliary Ligand on Electron and Proton Transfers Within Ternary Copper(II)-Histidine Complexes

TitleExperimental and Computational Studies of the Macrocyclic Effect of an Auxiliary Ligand on Electron and Proton Transfers Within Ternary Copper(II)-Histidine Complexes
Authors
Issue Date2009
PublisherElsevier Inc. The Journal's web site is located at http://www.elsevier.com/locate/jasms
Citation
Journal Of The American Society For Mass Spectrometry, 2009, v. 20 n. 6, p. 972-984 How to Cite?
AbstractThe dissociation of [Cu II(L)His] •2+ complexes [L = diethylenetriamine (dien) or 1,4,7-triazacyclononane (9-aneN 3)] bears a strong resemblance to the previously reported behavior of [Cu II(L)GGH] •2+ complexes. We have used low-energy collision-induced dissociation experiments and density functional theory (DFT) calculations at the B3LYP/6-31+G(d) level to study the macrocyclic effect of the auxiliary ligands on the formation of His •+ from prototypical [Cu II(L)His] •2+ systems. DFT revealed that the relative energy barriers of the same electron-transfer (ET) dissociation pathways of [Cu II(9-aneN 3)His] •2+ and [Cu II(dien)His] •2+ are very similar, with the ET reactions of [Cu II(9-aneN 3)His] •2+ leading to the generation of two distinct His •+ species; in contrast, the proton transfer (PT) dissociation pathways of [Cu II(9-aneN 3)His] •2+ and [Cu II(dien)His] •2+ differ considerably. The PT reactions of [Cu II(9-aneN 3)His] •2+ are associated with substantially higher barriers (>13 kcal/mol) than those of [Cu II(dien)His] •2+. Thus, the sterically encumbered auxiliary 9-aneN 3 ligand facilitates ET reactions while moderating PT reactions, allowing the formation of hitherto nonobservable histidine radical cations. © 2009.
Persistent Identifierhttp://hdl.handle.net/10722/58466
ISSN
2015 Impact Factor: 3.031
2015 SCImago Journal Rankings: 1.322
ISI Accession Number ID
Funding AgencyGrant Number
University of Hong Kong (UGC)
Hong Kong Research Grants Council
Special Administrative Region, ChinaHKU 7018/06P
HKU 7012/08P
National Natural Science Foundation of China20773016
W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL)
U.S. Department of Energy's Office of Biological and Environmental Research
Pacific Northwest National Laboratory (PNNL)
U.S. Department of Energy
PNNL Interfacial and Condensed Phase summer Research Institute
Natural Sciences and Engineering Research Council of Canada (NSERC)
St. Francis Xavier University Council for Research.
Funding Information:

Most of the research described in this manuscript was supported by the University of Hong Kong (UGC) and the Hong Kong Research Grants Council, Special Administrative Region, China (Project Nos. HKU 7018/06P and HKU 7012/08P). TS, CL, and DCMN thank the Hong Kong RGC for supporting their studentships. DCF thanks the National Natural Science Foundation of China (No. 20773016) for financial support. This study was partially supported by a grant from the W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the U.S. Department of Energy's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy. CL and IKC acknowledge participation in the PNNL Interfacial and Condensed Phase summer Research Institute. GO is grateful for financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC) and the St. Francis Xavier University Council for Research.

References
Grants

 

DC FieldValueLanguage
dc.contributor.authorSong, Ten_HK
dc.contributor.authorLam, CNWen_HK
dc.contributor.authorNg, DCMen_HK
dc.contributor.authorOrlova, Gen_HK
dc.contributor.authorLaskin, Jen_HK
dc.contributor.authorFang, DCen_HK
dc.contributor.authorChu, IKen_HK
dc.date.accessioned2010-05-31T03:30:48Z-
dc.date.available2010-05-31T03:30:48Z-
dc.date.issued2009en_HK
dc.identifier.citationJournal Of The American Society For Mass Spectrometry, 2009, v. 20 n. 6, p. 972-984en_HK
dc.identifier.issn1044-0305en_HK
dc.identifier.urihttp://hdl.handle.net/10722/58466-
dc.description.abstractThe dissociation of [Cu II(L)His] •2+ complexes [L = diethylenetriamine (dien) or 1,4,7-triazacyclononane (9-aneN 3)] bears a strong resemblance to the previously reported behavior of [Cu II(L)GGH] •2+ complexes. We have used low-energy collision-induced dissociation experiments and density functional theory (DFT) calculations at the B3LYP/6-31+G(d) level to study the macrocyclic effect of the auxiliary ligands on the formation of His •+ from prototypical [Cu II(L)His] •2+ systems. DFT revealed that the relative energy barriers of the same electron-transfer (ET) dissociation pathways of [Cu II(9-aneN 3)His] •2+ and [Cu II(dien)His] •2+ are very similar, with the ET reactions of [Cu II(9-aneN 3)His] •2+ leading to the generation of two distinct His •+ species; in contrast, the proton transfer (PT) dissociation pathways of [Cu II(9-aneN 3)His] •2+ and [Cu II(dien)His] •2+ differ considerably. The PT reactions of [Cu II(9-aneN 3)His] •2+ are associated with substantially higher barriers (>13 kcal/mol) than those of [Cu II(dien)His] •2+. Thus, the sterically encumbered auxiliary 9-aneN 3 ligand facilitates ET reactions while moderating PT reactions, allowing the formation of hitherto nonobservable histidine radical cations. © 2009.en_HK
dc.languageengen_HK
dc.publisherElsevier Inc. The Journal's web site is located at http://www.elsevier.com/locate/jasmsen_HK
dc.relation.ispartofJournal of the American Society for Mass Spectrometryen_HK
dc.titleExperimental and Computational Studies of the Macrocyclic Effect of an Auxiliary Ligand on Electron and Proton Transfers Within Ternary Copper(II)-Histidine Complexesen_HK
dc.typeArticleen_HK
dc.identifier.emailChu, IK:ivankchu@hku.hken_HK
dc.identifier.authorityChu, IK=rp00683en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.jasms.2009.01.007en_HK
dc.identifier.pmid19230704-
dc.identifier.scopuseid_2-s2.0-65549124037en_HK
dc.identifier.hkuros155639en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-65549124037&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume20en_HK
dc.identifier.issue6en_HK
dc.identifier.spage972en_HK
dc.identifier.epage984en_HK
dc.identifier.isiWOS:000266466600010-
dc.publisher.placeUnited Statesen_HK
dc.relation.projectFacile generation and characterization of cationic and anionic radical peptides: ligand effects and peptide structures-
dc.identifier.scopusauthoridSong, T=36087959100en_HK
dc.identifier.scopusauthoridLam, CNW=7402990888en_HK
dc.identifier.scopusauthoridNg, DCM=36981534500en_HK
dc.identifier.scopusauthoridOrlova, G=7007153895en_HK
dc.identifier.scopusauthoridLaskin, J=7102409836en_HK
dc.identifier.scopusauthoridFang, DC=14520877500en_HK
dc.identifier.scopusauthoridChu, IK=7103327484en_HK

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