Synthesis of Poly(N-vinylpyrrolidone)-Based Polymer Bottlebrushes by ATRPA and RAFT Polymerization: Toward Drug Delivery Application

Abstract

Atom transfer radical polyaddition (ATRPA) was utilized herein to synthesize a specific functional polyester. We conducted ATRPA of 4-vinylbenzyl 2-bromo-2-phenylacetate (VBBPA) inimer and successfully obtained a linear type poly(VBBPA) (PVBBPA) polyester with benzylic bromides along the backbone. To obtain a novel amphiphilic polymer bottlebrush, however, the lateral ATRP chain extension of PVBBPA with N-vinyl pyrrolidone (NVP) met the problem of quantitative dimerization. By replacing the bromides to xanthate moieties efficiently, we thus observed a pseudo linear first order reversible addition–fragmentation chain transfer (RAFT) polymerization to obtain novel poly(4-vinylbenzyl-2-phenylacetate)-g-poly(NVP) (PVBPA-g-PNVP) amphiphilic polymer bottlebrushes. The critical micelle concentration (CMC) and particle size of the amphiphilic polymer bottlebrushes were characterized by fluorescence spectroscopy, dynamic light scattering (DLS), and scanning electron microscopy (SEM) (CMCs < 0.5 mg/mL; particle sizes = ca. 100 nm). Toward drug delivery application, we examined release profiles using a model drug of Nile red at different pH environments (3, 5, and 7). Eventually, low cytotoxicity and well cell uptake of the Madin-Darby Canine Kidney Epithelial (MDCK) for the polymer bottlebrush micelles were demonstrated.

A Comprehensive Evaluation of Mechanical, Thermal, and Antibacterial Properties of PLA/ZnO Nanoflower Biocomposite Filaments for 3D Printing Application

“…Filament types are important in fabricating 3D printing products, and commodity filaments have been produced from several materials, such as polylactic acid (PLA), polycaprolactone (PCL), polyurethane (PU), and acrylonitrile butadiene styrene (ABS). Recently, the biodegradable filaments for 3D printing have been of interest to researchers due to their vast variety of applications and advantages [ 5 ]; one advantage is that they contribute to a decrease in environmental pollution when compared with synthetic ones [ 6 , 7 , 8 , 9 ].…”

Synthesis of Hyperbranched Polymers via Metal‐Free ATRP in Solution and Microemulsion

“…Among these highly branched polymers, hyperbranched polymers receive particular interest from both industries and academia because of their one‐pot inexpensive synthesis and retention of arborescent structures. Hyperbranched polymers typically could be produced in one pot via step‐growth polymerization of multifunctional AB m (m ≥ 2) monomers, [ 7–13 ] step‐growth copolymerization of A n and B m monomers (e.g., A 2 + B 3 ), [ 14–16 ] chain‐growth polymerization of AB m (m ≥ 2) monomers, [ 17–19 ] chain‐growth copolymerization of divinyl cross‐linkers, [ 20–26 ] self‐condensing vinyl polymerization (SCVP) of polymerizable initiators (inimers), [ 27–35 ] or polymerizable transfer agents (transmers). [ 36–40 ] It is important to note that any of these methods could produce hyperbranched polymers and randomly branched polymer as their difference lies in the fraction of branching unit incorporated into the polymer backbone.…”

Progress in the Preparation of Functional and (Bio)Degradable Polymers via Living Polymerizations

“…Among RDRPs, the most widely used techniques include atom transfer radical polymerization (ATRP) [ 79 , 80 , 81 , 82 ], nitroxide-mediated radical polymerization (NMRP) [ 83 ], and reversible addition-fragmentation chain transfer (RAFT) polymerization [ 84 , 85 , 86 , 87 ]. Accordingly, the diverse techniques of RDRPs have been introduced to RROP systems to obtain well-defined (co)polymers with ester linkages.…”

“…Recently, Huang et al [ 87 , 111 , 112 ] designed a highly reactive AB type inimer (i.e., 4-vinylbenzyl 2-bromo-2-phenylacetate (VBBPA)), which significantly improved the reactivity for ATRPA (i.e., polymerizations were reduced to a few hours) but kept high selectivity, to obtain linear aliphatic polyesters. Therefore, high molecular weight aliphatic polyesters ( M w = ca.…”