4 years ago

Synthesis and Multi-Responsive Self-Assembly of Cationic Poly(caprolactone)–Poly(ethylene glycol) Multiblock Copolymers

Synthesis and Multi-Responsive Self-Assembly of Cationic Poly(caprolactone)–Poly(ethylene glycol) Multiblock Copolymers
Bhingaradiya Nutan, Suresh K. Jewrajka, Arvind K. Singh Chandel
Individual dissimilar blocks were combined to obtain well-defined AnBn and (A–B–A)n types of cationic amphiphilic multiblock copolymers (MBCs) through mild sequential nucleophilic substitution without formation of byproducts. MBCs were synthesized by reacting end-functional polymer blocks of poly(caprolactone) (PCL), poly(ethylene glycol) (PEG), and PCL-b-PEG-b-PCL. For selective degradation, acid- and base-labile ester as well as reducible disulfide groups were introduced as linkers between the blocks. The micellar self-assemblies of these MBCs showed exceptional stability under normal physiological conditions with negligible release of the guest molecules. Selective disassembly under mildly acidic and basic conditions or in the presence of reducing agents caused triggered release of the guest molecules. This strategy is versatile and opens an opportunity to obtain a variety of tailor-made MBCs for selective and triggered release of therapeutics. Around the block: Cationic multi-responsive AnBn and (A–B–A)n types of multiblock copolymers are easily accessible by sequential nucleophilic substitution using the reactive termini of the individual blocks. The strategy provides a great opportunity to manipulate the structure of the termini and, hence, the behavior of the copolymers. Self-assembly and selective as well as triggered release behavior of the degradable multiblock copolymers consisting of well-defined poly(caprolactone) and poly(ethylene glycol) blocks is demonstrated.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701900

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