Beta-alanine-based dendritic beta-peptides: dendrimers possessing unusually strong binding ability towards protic solvents and their self-assembly into nanoscale aggregates through hydrogen-bond interactions.
A series of poly(beta-alanine) dendrimers 1-4 with Boc-carbamate as the surface functionality, beta-alanine as the dendritic branch, 3,5-diaminobenzoic acid as the branching agent, and 1,2diaminoethane as the interior core has been synthesized by a solution-phase peptide-coupling method. The structural identities and purities of the products have been fully characterized by spectroscopic and chromatographic methods. 1H NMR studies on the dendrimers indicated that the Boc-carbamate surface groups exist as a mixture of syn and anti rotamers in solution, and that the dendrimers adopt an open structure in polar solvents; this allows the free interaction of the interior core functionality with solvent molecules. Due to the cooperative effect of a large number of carbamate and amide groups, the dendrimers exhibit an unusually strong binding ability towards protic solvents and behave as H-bond sponges. As a result, the H/D exchange rates of the N-H protons are significantly enhanced in such dendritic structures, as compared to those of nondendritic carbamates and amides. These dendritic peptide dendrimers also exhibit a strong tendency to form nanoscopic aggregates in nonpolar or polar aprotic solvents through intermolecular H-bond interactions.
Department of Chemistry, The Chinese University of Hong Kong, Shatin, NT, PR China.
T K
TK
Mong
A
A
Niu
H F
HF
Chow
C
C
Wu
L
L
Li
R
R
Chen
D006860:Hydrogen Bonding; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry*; D012997:Solvents; D015091:beta-Alanine / Q000737:chemistry*
D007202:Indicators and Reagents; D010455:Peptides; D012997:Solvents; D015091:beta-Alanine; C019529:polyalanine