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Volumn 110, Issue 34, 2006, Pages 10316-10323

Effect of side chains on competing pathways for β-scission reactions of peptide-backbone alkoxyl radicals

Author keywords

[No Author keywords available]

Indexed keywords

QUANTUM CHEMISTRY CALCULATIONS; RADICAL STABILIZATION ENERGIES (RSE); SCISSION REACTIONS; SIDE-CHAIN FRAGMENT RADICALS;

EID: 33748774117     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp062916j     Document Type: Article
Times cited : (20)

References (44)
  • 8
  • 14
    • 33748764546 scopus 로고    scopus 로고
    • Mortimer, A.; Easton, C. J. unpublished data
    • Mortimer, A.; Easton, C. J. unpublished data.
  • 17
    • 33748781600 scopus 로고    scopus 로고
    • note
    • -1 with B3-LYP/6-311 +G(3df,2p). See the Supporting Information for full details.
  • 33
    • 2342567190 scopus 로고    scopus 로고
    • For a comparison of Arrhenius parameters obtained using the harmonic approximation with those obtained from a hindered rotor or free rotor treatment, see for example, Gómez-Balderas, R.; Coote, M. L.; Henry, D. J.; Radom, L. J. Phys. Chem. A 2004, 108, 2874-2883.
    • (2004) J. Phys. Chem. A , vol.108 , pp. 2874-2883
    • Gómez-Balderas, R.1    Coote, M.L.2    Henry, D.J.3    Radom, L.4
  • 38
    • 33748792441 scopus 로고    scopus 로고
    • note
    • as to the level of theory used in their calculation. It is therefore the accuracy of the activation energies that is dominant in determining the accuracy of the calculated rates.
  • 39
    • 33748791914 scopus 로고    scopus 로고
    • note
    • The RSE has been determined through G3X(MP2)-RAD calculations, to be consistent with the values of Table 5.
  • 43
    • 33748791338 scopus 로고    scopus 로고
    • note
    • A comparison of our calculated UB3-LYP/6-31G(d) natural bond orbital (NBO) charges for the reactant and transition structure of, for example, reaction A6 supports this picture of a polarized transition structure. We find that the oxygen holding the unpaired electron in the reactant has a charge of -0.3, which becomes more negative (-0.6) in the transition structure. In addition, the carbon atom that holds the unpaired electron after the bond breaks has a charge of +0.2 in the reactant, which changes to +0.7 in the transition structure.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.