The Cu (I)-catalyzed “click” reaction of azides and alkynes was selected as the coupling reaction to prepare a novel biocompatible polyrotaxane (PR) conjugate
which was composed of azidofunctionalized PR backbone (Mn=1.35×105) based on α-cyclodextrins (α-CDs)/poly(ethylene glycol) (PEG) inclusion complex and amino acids protected by tert-butyloxycarbonyl (Boc) groups
that is
Boc-Gly-OH
Boc-Lys(Boc)-OH
and Boc-Phe-OH.The alkynyl groups were introduced into the aforementioned amino acids via N
N-dicyclohexylcarbodiimide(DCC)/4-(dimethylamino)pyridine(DMAP) condensation with propargyl alcohol.The click coupling reaction was demonstrated to be extremely efficient
and high conversion of azido groups
approximate 100%
was achieved in a short reaction time (within several minutes) in the cases of Boc-Gly-OH and Boc-Lys(Boc)-OH.As to the bulky Boc-Phe-OH
only part of the azido groups of the backbone was converted though the coupling reaction time was prolonged (3 h).The corresponding amino acids-PR conjugates were soluble in a wide variety of organic solvents
such as N
Ndimethylformamide
acetone
ethanol and so forth.GPC was utilized to measure the molecular weight of Boc-Lys(Boc)-PR conjugates (PR-Lys)
and the result was Mn = 1.66×105 (Mw/Mn = 1.57)
much smaller than the theoretical ones.This might be resulted from the compactly packed conformation of PRLys.The warmlike morphology of PR-Lys was observed via AFM.Other alkyne-functionalized compounds involving 4-(2-azidoethoxy)-4-oxobutanoic acid and propargyl alcohol were also attached to the PR backbone successfully.This click strategy would be a promising general method for the functionalization of PRs.