Selective Dynamic Assembly of Disulfide Macrocyclic Helical Foldamers with Remote Communication of Handedness.
Disulfide bridge formation was investigated in helical aromatic oligoamide foldamers. Depending on the position of thiol-bearing side chains, exclusive intramolecular or intermolecular disulfide bridging may occur. The two processes are capable of self-sorting, presumably by dynamic exchange. Quantitative assessment of helix handedness inversion rates showed that bridging stabilizes the folded structures. Intermolecular disulfide bridging serendipitously yielded a well-defined, C2 -symmetrical, two-helix bundle-like macrocyclic structure in which complete control over relative handedness, that is, helix-helix handedness communication, is mediated remotely by the disulfide bridged side chains in the absence of contacts between helices. MM calculations suggest that this phenomenon is specific to a given side chain length and requires disulfide functions.
University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France.|CNRS, CBMN (UMR 5248), France.
Christos
C
Tsiamantas
University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France.|CNRS, CBMN (UMR 5248), France.
Xavier
X
de Hatten
University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France.|CNRS, CBMN (UMR 5248), France.
Céline
0000-0003-2678-1047
C
Douat
University of Bordeaux, Institut Européen de Chimie et Biologie (UMS3033), 2 rue Escarpit, 33600, Pessac, France.|CNRS, IECB (UMS 3033), Pessac, France.|INSERM, IECB (US 001), Pessac, France.
Brice
B
Kauffmann
University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France.|CNRS, CBMN (UMR 5248), France.
Victor
V
Maurizot
Kumamoto University, Department of Applied Chemistry and Biochemistry, 2-39-1 Kurokami, Kumamoto, 860-8555, Japan.
Hirotaka
H
Ihara
Kumamoto University, Department of Applied Chemistry and Biochemistry, 2-39-1 Kurokami, Kumamoto, 860-8555, Japan.
Makoto
M
Takafuji
Ruhr University Bochum, Faculty for Chemistry and Biochemistry, Universitätstrasse 150, 44801, Bochum, Germany.
Nils
0000-0001-8111-9959
N
Metzler-Nolte
University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France. i.huc@iecb.u-bordeaux.fr.|CNRS, CBMN (UMR 5248), France. i.huc@iecb.u-bordeaux.fr.
Ivan
0000-0001-7036-9696
I
Huc
chirality; foldamers; macrocycles; remote conformational communication; thiol-disulfide exchange