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Helically Chiral Peptides That Contain Ferrocene‐1,1′‐diamine Scaffolds as a Turn Inducer
Author(s) -
Kovačević Monika,
Kodrin Ivan,
Roca Sunčica,
Molčanov Krešimir,
Shen Yuning,
Adhikari Bimalendu,
Kraatz HeinzBernhard,
Barišić Lidija
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701602
Subject(s) - conformational isomerism , chemistry , chirality (physics) , hydrogen bond , stereochemistry , peptidomimetic , ferrocene , folding (dsp implementation) , diamine , turn (biochemistry) , crystallography , nuclear magnetic resonance spectroscopy , ligand (biochemistry) , peptide , molecule , polymer chemistry , organic chemistry , receptor , biochemistry , chiral symmetry breaking , physics , electrode , quantum mechanics , engineering , nambu–jona lasinio model , electrical engineering , electrochemistry , quark
A series of peptides that contain homo‐ and heterochiral Ala−Pro sequences attached to the turn‐inducing ferrocene‐1,1′‐diamine scaffold were synthesized. The effects of the backbone chirality and the N‐terminal group (Boc/Ac) on the conformational properties of the novel peptidomimetics were thoroughly explored by IR, NMR, and CD spectroscopy and the experimental observations were corroborated by DFT studies in solution. The most stable conformers of the homochiral peptides adopted the interstrand hydrogen‐bond patterns, realized through ten‐ and thirteen‐membered rings. The common feature of the most stable conformers of the heterochiral peptides was the adoption of the turn‐like structures that feature the simultaneous intra‐ (seven‐membered) and interstrand (sixteen‐membered) hydrogen‐bonded rings. An exchange of two N‐terminal groups had a somewhat larger influence on the distribution of the hydrogen‐bond patterns in homochiral than in heterochiral derivatives. The homochiral peptides that contain pyridine moieties as metal coordination sites formed 1:1 complexes with divalent metal ions, which included Zn 2+ , Cd 2+ , Cu 2+ and Fe 2+ .