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Helix-Forming Oligoureas: Temperature-Dependent NMR, Structure Determination, and Circular Dichroism of a Nonamer with Functionalized Side Chains

2002; Wiley; Volume: 85; Issue: 11 Linguagem: Inglês

10.1002/1522-2675(200211)85

1522-2675

Christine Hemmerlin, Michel Marraud, Didier Rognan, R. Graff, Vincent Semetey, Jean‐Paul Briand, Gilles Guichard,

Plant Molecular Biology Research

Helvetica Chimica ActaVolume 85, Issue 11 p. 3692-3711 Research Article Helix-Forming Oligoureas: Temperature-Dependent NMR, Structure Determination, and Circular Dichroism of a Nonamer with Functionalized Side Chains Christine Hemmerlin, Christine Hemmerlin LCPM, UMR CNRS-INPL 7568, ENSIC-INPL, B.P. 451, F-54001 NancySearch for more papers by this authorMichel Marraud, Michel Marraud LCPM, UMR CNRS-INPL 7568, ENSIC-INPL, B.P. 451, F-54001 NancySearch for more papers by this authorDidier Rognan, Didier Rognan Laboratoire de Pharmacochimie de la Communication Cellulaire, UMR CNRS, ULP 7081, 74 Route du Rhin, B.P. 24, F-67401 IllkirchSearch for more papers by this authorRoland Graff, Roland Graff Faculté de Chimie, 1 Rue Blaise Pascal, F-67008 StrasbourgSearch for more papers by this authorVincent Semetey, Vincent Semetey Immunologie et Chimie Thérapeutiques, UPR CNRS 9021, Institut de Biologie Moléculaire et Cellulaire, 15 Rue Descartes, F-67084 StrasbourgSearch for more papers by this authorJean-Paul Briand, Jean-Paul Briand Immunologie et Chimie Thérapeutiques, UPR CNRS 9021, Institut de Biologie Moléculaire et Cellulaire, 15 Rue Descartes, F-67084 StrasbourgSearch for more papers by this authorGilles Guichard, Gilles Guichard Immunologie et Chimie Thérapeutiques, UPR CNRS 9021, Institut de Biologie Moléculaire et Cellulaire, 15 Rue Descartes, F-67084 StrasbourgSearch for more papers by this author Christine Hemmerlin, Christine Hemmerlin LCPM, UMR CNRS-INPL 7568, ENSIC-INPL, B.P. 451, F-54001 NancySearch for more papers by this authorMichel Marraud, Michel Marraud LCPM, UMR CNRS-INPL 7568, ENSIC-INPL, B.P. 451, F-54001 NancySearch for more papers by this authorDidier Rognan, Didier Rognan Laboratoire de Pharmacochimie de la Communication Cellulaire, UMR CNRS, ULP 7081, 74 Route du Rhin, B.P. 24, F-67401 IllkirchSearch for more papers by this authorRoland Graff, Roland Graff Faculté de Chimie, 1 Rue Blaise Pascal, F-67008 StrasbourgSearch for more papers by this authorVincent Semetey, Vincent Semetey Immunologie et Chimie Thérapeutiques, UPR CNRS 9021, Institut de Biologie Moléculaire et Cellulaire, 15 Rue Descartes, F-67084 StrasbourgSearch for more papers by this authorJean-Paul Briand, Jean-Paul Briand Immunologie et Chimie Thérapeutiques, UPR CNRS 9021, Institut de Biologie Moléculaire et Cellulaire, 15 Rue Descartes, F-67084 StrasbourgSearch for more papers by this authorGilles Guichard, Gilles Guichard Immunologie et Chimie Thérapeutiques, UPR CNRS 9021, Institut de Biologie Moléculaire et Cellulaire, 15 Rue Descartes, F-67084 StrasbourgSearch for more papers by this author First published: 06 December 2002 https://doi.org/10.1002/1522-2675(200211)85:11 3.0.CO;2-WCitations: 48AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract To further investigate the degree of structural homology between γ-peptides A and N,N′-linked oligoureas B, we prepared oligourea nonamer 2 containing Ala, Val, Leu, Phe, Tyr and Lys side chains. Oligomer 2 was synthesized on solid support from activated monomers, i.e., from enantiomerically pure succinimidyl {2-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}ethyl}carbamates 3a–f that are further substituted at C(2) of the ethyl moiety. These precursors were conveniently prepared from N-Fmoc-protected β3-amino acids with corresponding side chains. Detailed NMR studies (DQF-COSY, TOCSY, and ROESY) in (D5)pyridine revealed that 2 adopts a regular (P)-2.5 helical secondary structure very similar to that previously determined for oligourea heptamer 1 and closely related to the (P)-2.614 helix of γ-peptides. Temperature-dependent NMR further demonstrated the conformational homogeneity and remarkable stability of the structure of 2 in pyridine. The CD spectrum of 2 (0.2 mM) was recorded in MeOH with the aim to gain more information about the conformation of oligoureas. In contrast to 2.6-helical γ-peptides, which display only a weak or no Cotton effect, oligourea 2 exhibits an intense positive Cotton effect at ca. 203 nm ([Θ]=+373000 deg cm2 dmol−1) that decreases only slowly upon increasing the temperature. References 1 D. J. Hill, M. J. Mio, R. B. Prince, T. S. Hughes, J. S. Moore, Chem. Rev. 2001, 101, 3893; M. S. Cubberley, B. L. Iverson, Curr. Opin. Chem. Biol. 2001, 5, 650; K. D. Stigers, J. S. Nowick, Curr. Opin. Chem. Biol. 1999, 3, 714; K. Kirshenbaum, R. N. Zuckermann, K. A. Dill, Curr. Opin. Struct. Biol. 1999, 9, 530; S. H. Gellman, Acc. Chem. Res. 1998, 31, 173. 2a D. Seebach, M. Overhand, F. N. M. Kühnle, B. Martinoni, L. Oberer, U. Hommel, H. Widmer, Helv. Chim. 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