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Volumn 128, Issue 47, 2006, Pages 15200-15208

15N solid-state NMR provides a sensitive probe of oxidized flavin reactive sites

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL SHIFT CHANGES; ELECTRON TRANSPORT PROTEINS; FLAVINS; SOLID-STATE NUCLEAR MAGNETIC RESONANCE (SS-NMR);

EID: 33845346158     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0648817     Document Type: Article
Times cited : (13)

References (89)
  • 2
    • 33845312859 scopus 로고    scopus 로고
    • note
    • Abbreviations: CP, cross-polarization; dBF, dibenzyl flavin; DFT, density functional theory; FAD, flavin adenine dinucleotide; FMN, flavin mononucleotide; GIAO, gauge-including atomic orbital; HOMO, highest occupied molecular orbital, used somewhat loosely here to include the several such orbitals that define the reactivity; LUMO, lowest unoccupied molecular orbital, used somewhat loosely to include the several lowest-lying orbitals that define the reactivity; MAS, magic angle spinning; NMR, nuclear magnetic resonance: PASS, phase adjusted spinning sideband; rmsd, root-mean-square deviation; SS, solid state; TARF, tetraacetyl riboflavin.
  • 3
    • 0029038909 scopus 로고
    • Massey, V. FASEB J. 1995, 9, 473-475.
    • (1995) FASEB J. , vol.9 , pp. 473-475
    • Massey, V.1
  • 14
    • 8844231392 scopus 로고    scopus 로고
    • Chapman, S., Perham, R., Scrutton, N. S., Eds.; Rudolf Weber: University of Cambridge, UK
    • Yalloway, G. N.; Löhr, F.; Rüterjans, H. In Flavins and Flavoproteins; Chapman, S., Perham, R., Scrutton, N. S., Eds.; Rudolf Weber: University of Cambridge, UK, 2002; pp 679-684.
    • (2002) Flavins and Flavoproteins , pp. 679-684
    • Yalloway, G.N.1    Löhr, F.2    Rüterjans, H.3
  • 39
    • 0043043738 scopus 로고
    • Ramsey, N. F. Phys. Rev. 1950, 78 (6), 699-703.
    • (1950) Phys. Rev. , vol.78 , Issue.6 , pp. 699-703
    • Ramsey, N.F.1
  • 40
    • 33845316293 scopus 로고    scopus 로고
    • note
    • p is called the paramagnetic contribution because it augments the applied field, not because of any relationship with unpaired electrons.
  • 42
    • 0001675197 scopus 로고    scopus 로고
    • Grant, D. M., Harris, R. K., Eds.; Wiley: Sussex UK
    • Mason, J. In Encyclopedia of NMR; Grant, D. M., Harris, R. K., Eds.; Wiley: Sussex UK, 1996; pp 3222-3251.
    • (1996) Encyclopedia of NMR , pp. 3222-3251
    • Mason, J.1
  • 65
    • 33845336056 scopus 로고    scopus 로고
    • note
    • N10 is also interesting but is more expensive to label and so will be addressed in future studies.
  • 66
    • 33845287128 scopus 로고    scopus 로고
    • note
    • Spinning sidebands occur at intervals equal to the spinning speed on each side of the isotropic shift, over the spectral width of the signal.
  • 67
    • 33845313836 scopus 로고    scopus 로고
    • note
    • N3 displays biexponential CP buildup kinetics, consistent with heterogeneity among the sites, or motion affecting N3 and/or its attached H. e.g., see ref
  • 68
    • 33845295668 scopus 로고    scopus 로고
    • note
    • The latter possibility is supported by the large improvement in signal intensity obtained at lower temperatures. Similar biexponential buildup in analogous compounds has been reported by Solum et al., ref 47.
  • 71
    • 84860049690 scopus 로고    scopus 로고
    • Eichele, K.; Wasylishen, R. E. http://casgm3.anorg.chemie.uni-tuebingen. de/klaus/soft/index.html, 2005.
    • (2005)
    • Eichele, K.1    Wasylishen, R.E.2
  • 73
    • 33845319638 scopus 로고    scopus 로고
    • note
    • 1H decoupling.
  • 78
    • 33845286373 scopus 로고    scopus 로고
    • note
    • 11s of both strongly reflect the nonbonded lone pair of the N and ring aromaticity. However, the decreased aromaticity of the reduced flavin system, as well as the different ring sizes, complicates comparison between the pyrrole N and the flavin N3 and N10, see ref 47. The issue of aromaticity has been addressed in detail in ref 81. Specifically, in the oxidized state, all three rings were found to be aromatic by the criteria of nucleus-independent chemical shifts, the anisotropy of the magnetic susceptibility, the unified Bird index, and natural bond orbital arguments (ref 81), supporting the possibility of comparing the oxidized flavin N1 and N5 with the N of pyridine, as a simple reference point.
  • 88
    • 33845331567 scopus 로고    scopus 로고
    • note
    • The important reactivity of the C4a site is manifest in the reduced state, which is not the focus of this work.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.