Unprecedented Chain-Length-Dependent Conformational Conversion Between 11/9 and 18/16 Helix in α/β-Hybrid Peptides†
Dr. Baptiste Legrand
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
These authors contributed equally to this work.
Search for more papers by this authorDr. Christophe André
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
These authors contributed equally to this work.
Search for more papers by this authorLaure Moulat
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
Search for more papers by this authorEmmanuel Wenger
CRM2, UMR 7036 CNRS Université de Lorraine, Boulevard des Aiguilletes, 54506 Vandoeuvre-lès-Nancy Cedex (France)
Search for more papers by this authorDr. Claude Didierjean
CRM2, UMR 7036 CNRS Université de Lorraine, Boulevard des Aiguilletes, 54506 Vandoeuvre-lès-Nancy Cedex (France)
Search for more papers by this authorDr. Emmanuel Aubert
CRM2, UMR 7036 CNRS Université de Lorraine, Boulevard des Aiguilletes, 54506 Vandoeuvre-lès-Nancy Cedex (France)
Search for more papers by this authorDr. Marie Christine Averlant-Petit
LCPM—UMR 7568 CNRS Université de Lorraine, 1 rue Grandville, 54001 Nancy Cedex 1 (France)
Search for more papers by this authorProf. Jean Martinez
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
Search for more papers by this authorCorresponding Author
Dr. Monique Calmes
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.frSearch for more papers by this authorCorresponding Author
Dr. Muriel Amblard
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.frSearch for more papers by this authorDr. Baptiste Legrand
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
These authors contributed equally to this work.
Search for more papers by this authorDr. Christophe André
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
These authors contributed equally to this work.
Search for more papers by this authorLaure Moulat
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
Search for more papers by this authorEmmanuel Wenger
CRM2, UMR 7036 CNRS Université de Lorraine, Boulevard des Aiguilletes, 54506 Vandoeuvre-lès-Nancy Cedex (France)
Search for more papers by this authorDr. Claude Didierjean
CRM2, UMR 7036 CNRS Université de Lorraine, Boulevard des Aiguilletes, 54506 Vandoeuvre-lès-Nancy Cedex (France)
Search for more papers by this authorDr. Emmanuel Aubert
CRM2, UMR 7036 CNRS Université de Lorraine, Boulevard des Aiguilletes, 54506 Vandoeuvre-lès-Nancy Cedex (France)
Search for more papers by this authorDr. Marie Christine Averlant-Petit
LCPM—UMR 7568 CNRS Université de Lorraine, 1 rue Grandville, 54001 Nancy Cedex 1 (France)
Search for more papers by this authorProf. Jean Martinez
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
Search for more papers by this authorCorresponding Author
Dr. Monique Calmes
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.frSearch for more papers by this authorCorresponding Author
Dr. Muriel Amblard
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.fr
IBMM, UMR 5247 CNRS, Universités Montpellier 1 et 2, 15 avenue Charles Flahault, 34000 Montpellier (France) http://www.ibmm.univ-montp1.frSearch for more papers by this authorWe thank the CNRS, MESR, ANR (ANR-08-BLAN-0066-01), and the LabEx CheMISyst for financial support, the SCBIM and Université de Lorraine for NMR and XRD facilities. GENCI-CINES is also thanked for providing access to computing facilities.
Graphical Abstract
The chain length of α,β-hybrid oligomers containing the highly constrained (S)-1-aminobicyclo[2.2.2]octane-2-carboxylic acid residue determines if either the 11/9 or the 18/16 helix is favored. The transition between these two helices involves a single ϕ angle rotation of the α residues.
Abstract
α,β-Hybrid oligomers of varying lengths with alternating proteogenic α-amino acid and the rigid β2,3,3-trisubstituted bicyclic amino acid ABOC residues were studied using both X-ray crystal and NMR solution structures. While only an 11/9 helix was obtained in the solid state regardless of the length of the oligomers, conformational polymorphism as a chain-length-dependent phenomenon was observed in solution. Consistent with DFT calculations, we established that short oligomers adopted an 11/9 helix, whereas an 18/16 helix was favored for longer oligomers in solution. A rapid interconversion between the 11/9 helix and the 18/16 helix occurred for oligomers of intermediate length.
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