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Volumn 42, Issue 16, 2003, Pages 4849-4856

A compelling experimental test of the hypothesis that enzymes have evolved to enhance quantum mechanical tunneling in hydrogen transfer reactions: The β-neopentylcobalamin system combined with prior adocobalamin data

Author keywords

[No Author keywords available]

Indexed keywords

ADOCOBALAMIN; BETA NEOPENTYLCOBALAMIN; COBALAMIN DERIVATIVE; COBAMAMIDE; ETHYLENE GLYCOL; HYDROGEN; METHYLMALONYL COENZYME A MUTASE; PROTEIN; UNCLASSIFIED DRUG;

EID: 0042905762     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic0300722     Document Type: Article
Times cited : (58)

References (100)
  • 55
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    • note
    • 28group finds that there is no significant tunneling enhancement in the triosephosphate isomerase system when gas, solution, or enzyme systems are simulated. This is one reason an experimental test such as the present work was needed and, hence, undertaken.
  • 57
    • 0042257789 scopus 로고    scopus 로고
    • note
    • 5960Convincing experimental support for the validity of comparing these H· abstractions is found in the fact that all three enzyme-free systems studied, NpCbl, AdoCbl, and 8-MeOCbl, give results identical within experimental error to the AdoCbl-dependent methylmalonyl-CoA mutase system; that is, the results themselves strongly support, ex post facto, the comparison of the slightly different enzyme-based and enzyme-free solution systems.
  • 64
    • 85087536209 scopus 로고
    • Ph.D. Thesis, University of Oregon, Chemistry
    • 12. Ph.D. Thesis, University of Oregon, Chemistry, 1986.
    • (1986) 12
    • Hay, B.P.1
  • 68
    • 0001360629 scopus 로고
    • King, R. B.; Eisch, J. J., Ed.; Elsevier: New York
    • Brown, K. L., Peck, S. In Organometallic Synthesis; King, R. B.; Eisch, J. J., Ed.; Elsevier: New York, 1988; Vol. 4, p 304-315.
    • (1988) Organometallic Synthesis , vol.4 , pp. 304-315
    • Brown, K.L.1    Peck, S.2
  • 72
    • 85087536667 scopus 로고    scopus 로고
    • note
    • 5 times more reactive than Np-I in nucleophilic displacement reactions.
  • 81
    • 0042257782 scopus 로고    scopus 로고
    • note
    • We attempted to measure the molecular ions directly by lowering the energy of the electron impact filament, but were not successful as expected since ionized, unfragmented neopentane+ is notoriously difficult to detect.
  • 84
    • 0043260166 scopus 로고    scopus 로고
    • note
    • The H· (or D·) abstraction from the C-H and not the O-H(D) is as expected from Ingold and co-worker's literature: they demonstrated that the abstraction reaction of hydrogen from MeOH and MeOD by methyl radical proceeds at the same rate at 77 K, that is, that C-H abstraction is occurring.
  • 90
    • 0037425523 scopus 로고    scopus 로고
    • (a) Smedarchina, Z.; Siebrand, W.; Fernández-Ramos, A.; Cui, Q. J. Am. Chem. Soc. 2003, 125, 243. This valuable paper also makes it rather clear that only the proper quantum mechanical treatment of KIEs, and not GS-ZPE corrected transition-state theory, can yield reliable KIEs for comparison to experiment. (b) Siebrand, W., Doll, K. M., Finke, R. G. manuscript in preparation.
    • (2003) J. Am. Chem. Soc , vol.125 , pp. 243
    • Smedarchina, Z.1    Siebrand, W.2    Fernández-Ramos, A.3    Cui, Q.4
  • 91
    • 0037425523 scopus 로고    scopus 로고
    • manuscript in preparation
    • (a) Smedarchina, Z.; Siebrand, W.; Fernández-Ramos, A.; Cui, Q. J. Am. Chem. Soc. 2003, 125, 243. This valuable paper also makes it rather clear that only the proper quantum mechanical treatment of KIEs, and not GS-ZPE corrected transition-state theory, can yield reliable KIEs for comparison to experiment. (b) Siebrand, W., Doll, K. M., Finke, R. G. manuscript in preparation.
    • Siebrand, W.1    Doll, K.M.2    Finke, R.G.3
  • 95
    • 0043260168 scopus 로고    scopus 로고
    • Private communication from Dr. Siebrand
    • (b) Private communication from Dr. Siebrand.
  • 96
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    • Knapp, M. J.; Rickert, K. W.; Klinman, J. P. J. Am. Chem. Soc. 2002, 124, 3865. Siebrand and Smedarchina show that there is no statistically valid difference in the data in this paper for mutant vs wild-type enzyme (due to the too narrow temperature range over which the data could be obtained), thereby negating the claimed support in this paper for the putative protein-squeezing mechanism.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 3865
    • Knapp, M.J.1    Rickert, K.W.2    Klinman, J.P.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.