Rui Wang, Ning Xu, Fu-sheng Du, Zi-chen Li. SYNTHESIS AND AGGREGATION BEHAVIOR OF MANNOSE-TERMINATED POLYLYSINE[J]. Acta Polymerica Sinica, 2013,(6):774-780.
Two alkynyl-functionalized mannoses (A-Man and A-DiMan) and 2-(2-(2-azido-ethoxy)-ethoxy)-ethyl amine (N3-TEG-NH2) were synthesized.N3-TEG-NH2 was used to initiate the ring-opening polymerization of N-benzyloxycarbonyl-L-lysine N-carboxyanhydride (Lys(Z)-NCA) to obtain two azido-terminated polylysines with different degree of polymerization
N3-P(Lys(Z))15 and N3-P(Lys(Z))35.Click reactions of these two polymers with A-Man and A-DiMan produced four mannose-terminated polylysines
M-P(Lys(Z))15
M-P(Lys(Z))35
DiM-P(Lys(Z))15 and DiM-P(Lys(Z))35.The structure of these polymers was characterized by a range of means including GPC
NMR and FTIR.These polymers belong to amphiphilic diblock copolymers with P(Lys(Z)) as the hydrophobic chain and the mannose-containing moieties as the hydrophilic part
and their aggregation behavior in water were investigated.The polymers were first dissolved in THF/DMF (4/1
V/V)
and then water was added slowly to induce the self-assembly of polymers.After removing the orgnic solvents by dialysis
the morphologies formed were observed by transmission electron microscopy (TEM).TEM results revealed that vesicles were the main morphologies for the two polymers with shorter P(Lys(Z)) chains (M-P(Lys(Z))15 and DiM-P(Lys(Z))15)
while the two polymers with longer P(Lys(Z)) chains (M-P(Lys(Z))35 and DiM-P(Lys(Z))35) tended to form micelle-like aggregates.This phenomenon was different from the common self-assembly behavior of amphiphilic diblock copolymers in water
which was attributed to the easy -helix formation of polymers containing longer P(Lys(Z)) chains.