Polymerization-induced thermal self-assembly (PITSA) was conducted using thermoresponsive poly(N-isopropylacrylamide) to result in micelle, worm, and vesicle polymeric morphologies.
We report mechanistic investigations into aqueous visible-light reversible addition−fragmentation chain transfer (RAFT) polymerizations of acrylamides using eosin Y as a photoinduced electron-transfer (PET) catalyst. The photoinduced polymerization was found to be dependent upon the irradiation wavelength and reagents, where either reduction or oxidation of the PET catalyst leads to inherently different initiation and reversible-termination steps. Using blue light, multiple mechanisms of initiation are observed, depending on the presence or absence of a sacrificial reducing agent. Using green light, both an oxidative and a reductive PET initiation mechanism can be pursued. Investigations into the role of PET catalyst, wavelength, and reducing agent demonstrated that precise polymers with predictable molecular weights are best realized under an oxidative PET-RAFT mechanism. Therefore, this study provides fundamental insight into visible-light RAFT photopolymerizations and the role of eosin Y as a photoredox catalyst.
We
report a new strategy toward polymer–protein conjugates
using a grafting-from method that employs photoinduced electron/energy
transfer–reversible addition–fragmentation chain transfer
(PET–RAFT) polymerization. Initial screening of reaction conditions
showed rapid polymerization of acrylamides under high dilution in
water using eosin Y as a photocatalyst in the presence of a tertiary
amine. A lysozyme-modified chain transfer agent allowed the same conditions
to be utilized for grafting-from polymerizations, and we further demonstrated
the broad scope of this technique by polymerizing acrylic and styrenic
monomers. Finally, retention of the RAFT end group was suggested by
successful chain extension with N-isopropylacrylamide
from the polymer–protein conjugates to form block copolymer–protein
conjugates. This strategy should expand the capabilities of grafting-from
proteins with RAFT polymerization under mild conditions to afford
diverse functional materials.
This mini-review provides a brief overview of recent advances in the area of biologically-relevant nanomaterials composed of poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA). Polymer diversity within the field of nanomedicine has grown considerably in recent years, yet the overwhelming majority of soft nanomaterials intended for medical applications are composed of poly(ethylene glycol) (PEG) and its derivatives. However, it is well known that PHPMA offers several advantages over PEG in some applications, including its ability to be functionalized via its side-chain hydroxyl group to incorporate drugs, imaging agents, targeting ligands, etc. This mini-review focuses on select recent advances in PHPMA-based nanostructures. Particular attention is placed on polymer-drug conjugates, selfassembled nanoparticles, and other recent examples of PHPMA-based nanotherapeutics.
Poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA), a biocompatible and non-immunogenic polymer, was used to form core-crosslinked star polymers for potential drug delivery applications.
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