One-pot Atom Transfer Radical Polymerization Research Articles

Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer as Proton Exchange Membrane for Fuel Cells.

This study proposes a hydrophobic and hydrophilic aliphatic diblock copolymer wherein the hydrophobic block contains glycidyl methacrylate (GMA) units that are distanced by poly(acrylonitrile) (PAN) segments to fabricate a proton exchange membrane (PEM). This diblock copolymer also known as ionomer due to the hydrophilic block comprising 3-sulfopropyl methacrylate potassium salt (SPM) block. The diblock copolymer was synthesized in the one-pot atom transfer radical polymerization (ATRP) synthesis. Subsequently, the membrane was fabricated by means of solution casting in which an organic diamine, e.g., ethylene diamine (EDA), was introduced to crosslink the diblock copolymer chains via the addition of amine to the epoxide group of GMA. As a result, the PEM attained possesses dual continuous phases, in which the hydrophobic domains are either agglomerated or bridged by the EDA-derived crosslinks, whereas the hydrophilic domains constitute the primary proton conducting channels. The in-situ crosslinking hydrophobic block by using a hydrophilic cross-linker represents the merit aspect since it leads to both improved proton conductivity and dimensional stability in alcohol fuel. To characterize the above properties, Nafion® 117 and random copolymer of P(AN-co-GMA-co-SPM) were used as control samples. The PEM with the optimized composition demonstrates slightly better fuel cell performance than Nafion 117. Lastly, this diblock ionomer is nonfluorinated and hence favors lowering down both material and environmental costs.

Surface modification of polysulfones via one-pot ATRP and click chemistry: Zwitterionic graft complex and their hemocompatibility

Zwitterionic sulfobetaine groups were grafted onto polysulfone (PSU) membrane surface with 2-azidoethyl methacrylate and N,N-diethyl-N-propargyl-N-(3-sulfopropyl) ammonium (DEPAS) via surface-initiated Atom Transfer Radical Polymerization (ATRP) and “click” chemistry in a two-step process. The PSU membranes were fully characterized by attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and static water contact angle (WCA) measurement. Results showed that zwitterionic monomers were efficiently grafted onto PSU surfaces. The water contact angle, bovine serum albumin (BSA) protein adsorption and platelet adhesion were obviously decreased after grafting zwitterionic sulfobetaine groups onto the membrane surface. These indicated that the zwitterionic sulfobetaine modified PSU membranes presented good biocompatibility. This study provides a new approach for surface modification of polysulfone with different functionalities.

PEGylated Fluorescent Nanoparticles from One-Pot Atom Transfer Radical Polymerization and “Click Chemistry”

The preparation of PEGylated fluorescent nanoparticles (NPs) based on atom transfer radical polymerization (ATRP) and “click chemistry” in one-pot synthesis is presented. First, poly(p-chloromethyl styrene-alt-N-propargylmaleimide) (P(CMS-alt-NPM)) copolymer was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, the azido-containing fluorene-based polymer, poly[(9,9-dihexylfluorene)-alt-(9,9-bis-(6-azidohexyl)fluorene)] (PFC6N3), was synthesized via Suzuki coupling polymerization, followed by azidation. Finally, the PEGylated fluorescent NPs were prepared via simultaneous intermolecular “click” cross-linking between P(CMS-alt-NPM) and PFC6N3 and the ATRP of poly(ethylene glycol) methyl ether methacrylate (PEGMMA) using P(CMS-alt-NPM) as the macroinitiator. The low cytotoxicity of the PEGylated fluorescent NPs was revealed by incubation with KB cells, a cell line derived from carcinoma of the nasopharynx, in an in vitro experiment. The biocompatible PEGylated fluorescent NPs were further used as a labeling agent for KB cells.

Synthesis of star-shaped PCL-based copolymers via one-pot ATRP and their self-assembly behavior in aqueous solution

A series of star-shaped poly(ɛ-caprolactone) (PCL)-based diblock and triblock copolymers containing 2-(dimethylamino)ethyl methacrylate (DMAEMA or DMA) and oligo(ethylene glycol)monomethyl ether methacrylate (OEGMA or OEG) were synthesized by one-pot atom transfer radical polymerization (ATRP) using a sixarm PCL-based macroinitiator. The precursor and the resultant copolymers were analyzed via proton nuclear magnetic resonance spectra (1H NMR) and size exclusion chromatography (SEC). The monomer reactivity ratios for DMAEMA (r1) and OEGMA (r2) were estimated to be near unity and r1×r2=1, which indicates the random distribution of the monomers in the final copolymers. Self-assembly behavior of these copolymers was investigated by fluorimetry, 1H NMR, dynamic light scattering (DLS), transmission electronic microscopy (TEM), potentiometric titrations, and zeta potential measurements. The results suggested that the star copolymers were responsive to salinity depending on their composition and structure.

Amine-functionalized nanoporous thin films from a poly(ethylene oxide)-block-polystyrene diblock copolymer bearing a photocleavable o-nitrobenzyl carbamate junction

The synthesis of a poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer bearing an o-nitrobenzyl carbamate junction is reported via a one-pot atom transfer radical polymerization (ATRP)–copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC). The accordingly obtained block copolymer was self-assembled into thin films showing, after solvent annealing, ordered PEO cylinders oriented normal to the film surface and embedded in a PS matrix. In the next step, the easy photocleavage of the o-nitrobenzyl carbamate junction and the subsequent removal of the PEO nanophase were demonstrated. This led to amine-functionalized nanoporous PS thin films as evidenced by the successful coupling of a fluorescent dye bearing a carboxylic acid group. The possibility to obtain fluorescent nanopores was then further exploited to pattern the films using a photolithographic mask.

Direct synthesis of pH-responsive polymer nanoparticles based on living radical polymerization and traditional radical polymerization

Well-defined pH-responsive polymer nanoparticles were prepared in water directly after a simple dialysis procedure without the process of self-assembly from branched copolymers. The branched AB diblock copolymers of poly(ethyleneglycol methacrylate/dimethylamino ethyl methacrylate) (P(PEGMA/DMA)) and poly(ethyleneglycol methacrylate)/diethylamino ethyl methacrylate) (P(PEGMA/DEA)) have been synthesized using a one-pot atom-transfer radical polymerization (ATRP) approach in presence of a bifunctional monomer-ethyleneglycol dimethacrylate (EGDMA). Clear polymer nanoparticle (170 nm–244 nm) suspensions were obtained after a dialysis process. The aqueous solution behavior of the branched and linear copolymers at different pH (pH 3.7–12) was investigated using dynamic light scattering (DLS). pH-responsiveness was observed for both branched copolymer systems. As a comparison, branched copolymers of P(PEGMA/DMA) were also synthesized via traditional radical polymerization (TRP) in the presence of EGDMA, followed by similar dialysis. Most TRP branched copolymers could not afford neat particles and polymers precipitated on increasing the pH above 7.5. The controlled branching structure is suggested as the key point for the direct synthesis of pH-responsive branched copolymer nanoparticles.

Polymeric Phosphorylcholine−Camptothecin Conjugates Prepared by Controlled Free Radical Polymerization and Click Chemistry

Novel polymer-drug conjugates, consisting of zwitterionic poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) as the polymer component, and camptothecin (CPT) as the drug, were prepared by two methods. In one case, CPT was transformed by acylation into a functional initiator for copper catalyzed atom transfer radical polymerization (ATRP), and polyMPC was grown from this therapeutic initiator. In the other case, a one-pot ATRP-"click" conjugation strategy was employed to synthesize novel polyMPC structures containing multiple copies of the drug pendant to the zwitterionic polymer chain. The latter method allows polyMPC-graft-CPT conjugates to be prepared with a high weight percent drug loading (up to 14% CPT) with excellent solubility in pure water (>250 mg/mL). The linkage chemistry chosen between the polyMPC backbone and the pendant drugs proved critically important for assuring drug release within a time frame reasonable to consider these structures as a platform for injectable cancer therapeutics. Liberation of the drug from the polymer backbone was monitored by high-performance liquid chromatography, using size-exclusion and reverse-phase columns, and the toxicity of the polymer-drug conjugates was examined in cell culture against breast (MCF7), ovarian (OVCAR-3), and colorectal (COLO 205) cancer cell lines.

Esterification of hydroxylated polymers with 2-sulfobenzoic acid cyclic anhydride: A facile approach for the synthesis of near-monodisperse strong acid homopolymers and diblock copolymers

A convenient two-step route was developed to prepare a range of low polydispersity strong acid homopolymers and several examples of well-defined diblock copolymers. Atom transfer radical polymerization (ATRP) of either 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate or glycerol monomethacrylate afforded the corresponding near-monodisperse hydroxylated homopolymers, while several diblock copolymer precursors were prepared by either (1) the one-pot ATRP of 2-hydroxypropyl methacrylate and 2-(diethylamino)ethyl methacrylate using sequential monomer addition or (2) the ATRP of either 2-hydroxypropyl methacrylate or glycerol monomethacrylate using a poly(ethylene oxide)-based macro-initiator. Excess 2-sulfobenzoic acid cyclic anhydride was used to fully esterify the hydroxy groups of these homopolymers and diblock copolymers under mild conditions. The resulting zwitterionic diblock copolymers undergo micellar self-assembly on adjusting the pH of the solution, while one of the anionic poly(ethylene oxide)-based diblock copolymers formed colloidal polyelectrolyte complexes in aqueous solution when mixed with a cationic poly(ethylene oxide)-based diblock copolymer.