Development of functional amino acid-based star polymers

Adrian Sulistio, Anton Blencowe, Adrian Widjaya, Xiaoqing Zhang, Greg Qiao

Research output: Contribution to journalArticleResearchpeer-review

53 Citations (Scopus)

Abstract

Highly functionalized core cross-linked star (CCS) polymers composed entirely of naturally-occurring amino acids were prepared via the sequential ring-opening polymerisation (ROP) of amino acid N-carboxyanhydride (NCA) derivatives in a facile one-pot, arm-first strategy. The formation of the star polymers was investigated using side-chain protected poly(ε-Z-l-lysine) (PZLL) and poly(γ-benzyl-l-glutamic acid) (PBGA) macroinitiators with various molecular weights in combination with a cystine NCA cross-linker to afford poly(ε-Z-l-lysine)armspoly(l-cystine)core (PZLLarmsPLCcore) and poly(γ-benzyl-l-glutamic acid)armspoly(l-cystine)core (PBLGarmsPLC core) stars, respectively. As the cross-linker to macroinitiator ratio or macroinitiator molecular weights were increased the molecular weights, average number of arms and core size of the resulting stars also increased. Core-isolated NCA moieties remaining after star formation provided a facile approach to core-functionalization with primary amines bearing different functionalities, including aminomethyl pyrene, propargylamine and hexylamine. UV-vis spectroscopic analysis of PZLLarmsPLCcore and PBLGarmsPLCcore stars core-functionalised with aminomethyl pyrene provided high loadings of 240 and 128 mol/mol stars, respectively. Furthermore, stars with alkyne functionalized cores were capable of undergoing further click reactions with azido derivatives, demonstrating the accessibility of the core-isolated moieties. Deprotection of the PZLLarmsPLC core and PBLGarmsPLCcore stars yielded water soluble CCS polymers with poly(l-lysine) and poly(l-glutamic acid) arms, respectively, and functionalised cores. In addition, direct hydrazinolysis of the PBLGarmsPLCcore star provided hydrazide functionalities along the arms, which allow for conjugation of drug molecules via pH sensitive hydrazone linkers. These results open up exciting opportunities for the development of star polymer drug delivery systems, whereby a lack of functionality, biocompatibility and biodegradability are often limiting factors.

Original languageEnglish
Pages (from-to)224-234
Number of pages11
JournalPolymer Chemistry
Volume3
Issue number1
DOIs
Publication statusPublished - Jan 2012
Externally publishedYes

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