Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer

Abstract

A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

Semi‐Fluorinated Methacrylates: A Class of Versatile Monomers for Polymerization‐Induced Self‐Assembly

“…Semi‐fluorinated methacrylates are a class of fluorine‐containing monomers that have many superior properties, such as strong hydrophobicity, and low refractive index . Besides, their corresponding polymers have tunable lipophobicity depending on the side‐chain length of the monomers.…”

Boron Neutron Capture Therapy Enhanced by Boronate Ester Polymer Micelles: Synthesis, Stability, and Tumor Inhibition Studies

“…The process yielded a bromide-end-functionalized PEG macroinitiator, denoted as mPEG-Br. 74 The successful synthesis of mPEG-Br was confirmed through proton nuclear magnetic resonance ( 1 H NMR) spectroscopy. As shown in Figure 1, a broad peak corresponding to the PEG backbone emerged within the range of 3. where I a and I c represents the integrated area values of the peaks at 3.46−3.8 ppm (H a , −OCH 2 CH 2 −) and 1.9 ppm (H c , −CBr(CH 3 ) 2 ), respectively.…”

Polymeric Bowl‐Shaped Nanoparticles: Hollow Structures with a Large Opening on the Surface

“…Amphiphilic block copolymers have been widely used to prepare BNPs. [72][73][74][75][76][77] For instance, Sleiman and coworkers [78] prepared BNPs in the mixed solvent of toluene and acetonitrile based on ruthenium-bipyridine block copolymers synthesized by ring-opening metathesis polymerization. Hawker et al [38] fabricated biodegradable BNPs using poly(allyl glycidyl ether)-bpolylactide (PAGE-b-PLA) as the building block.…”

“…Amphiphilic block copolymers have been widely used to prepare BNPs. [ 72–77 ] For instance, Sleiman and coworkers [ 78 ] prepared BNPs in the mixed solvent of toluene and acetonitrile based on ruthenium‐bipyridine block copolymers synthesized by ring‐opening metathesis polymerization. Hawker et al.…”