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Volumn 49, Issue 36, 2010, Pages 6324-6327

Tuning the cis/trans conformer ratio of xaa-pro amide bonds by intramolecular hydrogen Bonds: The effect on PPII helix stability

Author keywords

Ab initio calculations; Conformation analysis; Helical structures; Isomerization; Peptides

Indexed keywords

AB INITIO CALCULATIONS; AMIDE BOND; BUILDING BLOCKES; CONFORMATION ANALYSIS; H-BONDING; HELICAL STRUCTURES; HELIX STABILITY; HYDROGEN BONDINGS; INTRAMOLECULAR HYDROGEN BOND; NON-COVALENT INTERACTION; PROLINE DERIVATIVES;

EID: 77956055128     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201001851     Document Type: Article
Times cited : (99)

References (55)
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  • 35
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    • The acetylated methyl esters were chosen as model systems in which H-bonding by a γ turn as observed in Ac-Pro-NHMe cannot occur
    • The acetylated methyl esters were chosen as model systems in which H-bonding by a γ turn as observed in Ac-Pro-NHMe cannot occur, G.-B. Liang, C. J. Rito, S. H. Gellman, Biopolymers 1992, 32, 293 - 301.
    • (1992) Biopolymers , vol.32 , pp. 293-301
    • Liang, G.-B.1    Rito, C.J.2    Gellman, S.H.3
  • 37
    • 0029927552 scopus 로고    scopus 로고
    • For previous discussions on the effect of intramolecular Hbonding on the conformation of proline, see: refs[3c, h, 4e] and
    • For previous discussions on the effect of intramolecular Hbonding on the conformation of proline, see: refs. c, h, 4eand T. P. Curran, N. M. Chandler, R. J. Kennedy, M. T. Keaney, Tetrahedron Lett. 1996, 37, 1933-1936
    • (1996) Tetrahedron Lett. , vol.37 , pp. 1933-1936
    • Curran, T.P.1    Chandler, N.M.2    Kennedy, R.J.3    Keaney, M.T.4
  • 41
    • 77956028347 scopus 로고    scopus 로고
    • 3 (refs. [3-5])
    • 3 (refs. [3-5]).
  • 42
    • 77956013750 scopus 로고    scopus 로고
    • The trans and cis isomers were assigned based on NOEs between the protons of the acetyl group and those at Cδ and Cα, respectively
    • The trans and cis isomers were assigned based on NOEs between the protons of the acetyl group and those at Cδ and Cα, respectively.
  • 43
    • 77956046623 scopus 로고    scopus 로고
    • Conformational searches and ab initio calculations were performed by using the Spartan'02 package (Spartan'02, Wavefunction, Inc., Irvine, CA) and a development version of the QChem program package, respectively
    • Conformational searches and ab initio calculations were performed by using the Spartan'02 package (Spartan'02, Wavefunction, Inc., Irvine, CA) and a development version of the QChem program package (http://www.q-chem.com), respectively.
  • 44
    • 77956051933 scopus 로고    scopus 로고
    • See the Supporting Information for details
    • See the Supporting Information for details.
  • 51
    • 77956043757 scopus 로고    scopus 로고
    • The existence of the hydrogen bond in 2S-4S is further supported by the larger vicinal NH-Hg coupling constants in the trans conformer of 2S-4S (7.9-8.6 Hz) compared to those observed for the cis conformer (5.4-6.5 Hz) as well as those of 2R-4R (6.5-6.8 Hz, both conformers). A large coupling constant is expected for a C4-endo conformation with a fixed dihedral angle Hγ-C-N-H close to 180° (see Scheme 2, right). Crystal structures of 1S and 2S are controlled by intermolecular hydrogen bonds and therefore not representative of their conformations in solution phase
    • The existence of the hydrogen bond in 2S-4S is further supported by the larger vicinal NH-Hg coupling constants in the trans conformer of 2S-4S (7.9-8.6 Hz) compared to those observed for the cis conformer (5.4-6.5 Hz) as well as those of 2R-4R (6.5-6.8 Hz, both conformers). A large coupling constant is expected for a C4-endo conformation with a fixed dihedral angle Hγ-C-N-H close to 180° (see Scheme 2, right). Crystal structures of 1S and 2S are controlled by intermolecular hydrogen bonds and therefore not representative of their conformations in solution phase.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.