Amphiphilic graft copolymeric micelle using dextrin and poly (N-vinyl caprolactam) via RAFT polymerization: Development and application

Copper oxide nanocomposite particles supported on sodium alginate-g-polyallylamine based reduced graphene oxide: An efficient electrochemical sensor for sensitive detection of cadmium ions in water

This investigation reports the preparation and self-assembly behavior of polyhedral oligomeric silsesquioxane (POSS) containing poly(caprolactone)-graft-poly(acrylic acid) (POSS-PCL-graft-PAA) polymer. This article focuses on the self-assembly behavior of POSS tethered amphiphilic graft copolymer. In this investigation, POSS tethered alkyne functionalized polycaprolactone (PCL) was prepared by strategic ring opening polymerization (ROP) of e-caprolactone and α-propargyl-e-caprolactone using hydroxyl-terminated POSS as an initiator. Azide-terminated poly(tert-butyl acrylate) (PtBA) was grafted onto functional PCL via Cu-catalyzed azide-alkyne “click” (CuAAC) reaction. Finally, hydrolysis of the tert-butyl ester group into acid furnished the POSS tethered PCL-graft-PAA polymer. This amphiphilic graft copolymer was characterized by GPC, NMR, and FT-IR analyses and the morphology of the graft copolymer analyzed by HRTEM and FESEM analyses. On changing the graft copolymer concentration (low to high) in water, the morphology of the final graft copolymer changed from micelles to worm-like and core-shell. The structural motif of POSS plays an important role in this morphological transformation. The pH sensitivity was studied using DLS analysis as well as via release profile of rhodamine B as a model compound.

In this study, cellulose was first treated with 4‐cyano‐4‐((phenyl carbonothioyl)solfanyl) pentanoic acid to serve as the reversible addition‐fragmentation chain transfer polymerization (RAFT) agent, then the controlled grafting polymerization of acrylic acid was successfully performed. A well‐defined, cellulose‐graft‐acrylic acid copolymer (Cell‐g‐PAA), has been prepared by RAFT polymerization technique using three different approaches: RAFT agent was prepared by substitution of dithiobenzoate magnesium bromide with 4,4'‐azobis(4‐cyanopentanoic acid) in ethyl acetate as a solvent, mediated cellulose (Cell) block as the macromolecular Cell‐RAFT agent and (cellulose‐co‐acrylic acid) copolymer with alternating sequence. The resulting (Cell‐RAFT) for “living” free radical polymerization was then heated in the adjacent acrylic acid monomer for the development of the controlled graft copolymer onto cellulose. The structures of the intermediate, graft copolymer were investigated by FT‐IR, DSC, 1H NMR, scanning electron microscopy, and thermo gravimetric. The results demonstrate that the preparation of graft copolymers was successfully confirmed. This approach would provide an extensive classification of molecular designs to obtain modern types of tailored hybrid materials derived from natural polysaccharides and synthetic polymers. Also, using a macro‐initiator is an excellent method for synthesizing new materials.

A well‐defined amphiphilic graft copolymer, consisting of hydrophobic poly(tert‐butyl acrylate) (PtBA) backbone and hydrophilic poly(N‐vinylcaprolactam) (PNVCL) side chains, was synthesized by successive reversible addition‐fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). A new acrylate monomer bearing a chlorine‐based initiating group, tert‐butyl 2‐((2‐chloropropanoyloxy)methyl)acrylate, was first RAFT homopolymerized in a controlled way to give a well‐defined homopolymer with a narrow molecular weight distribution (Mw/Mn=1.15). This homopolymer directly initiated ATRP of N‐vinylcaprolactam (NVCL) to afford a well‐defined PtBA‐g‐PNVCL graft copolymer (Mw/Mn=1.22) via the grafting‐from strategy without polymeric functionality transformation. PAA‐g‐PNVCL graft copolymer was prepared by selectively hydrolyzing PtBA‐g‐PNVCL. Ornidazole (ONZ)‐loaded polymeric micelles using PAA‐g‐PNVCL copolymer as carrier were prepared by physical entrapping. Drug release experiment of the nano‐carrier indicated the pH‐dependent drug release characteristics.

Syntheses and morphologies of fluorinated diblock copolymer prepared via RAFT polymerization

Probing Thermoresponsive Polymerization-Induced Self-Assembly with Variable-Temperature Liquid-Cell Transmission Electron Microscopy

A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αCleCL-co-eCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO2MA-co-OEGMA), designated as P(αCleCL-co-eCL)-g-P(MEO2MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by 1H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αCleCL-co-eCL)-g-P(MEO2MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10−3, 9.1 × 10−4 and 1.5 × 10−3 mg·mL−1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.

Multicentered initiators for the controlled (pseudoliving) radical polymerization are synthesized via polymer analog transformation of hydroxyl-containing polyimides based on o-aminophenols. Conditions providing variations in the degree of functionalization of polyimides by initiating 2-bromoisobutyrate groups are determined, and optimum conditions for the preparation of macroinitators containing the above groups in each repeat polyimide unit are found. Via the method of controlled radical polymerization with the atom transfer on multicentered macroinitiators in the presence of complexes of univalent copper halides, graft copolymers of poly(methylmethacrylate) on polyimide backbone are obtained. Molecular-mass characteristics of graft copolymers are studied via multiple-detection size-exclusion liquid chromatography. Preparation of graft copolymers (polymer brushes) with a homogeneous grafting density and a homogeneous length of side chains necessitates grafting of the side chain on the polyimide initiator, which contains initiating groups in each repeat unit.

Synthesis of poly(vinyl chloride-graft-2-vinylpyridine) graft copolymers was carried out by reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-vinylpyridine using a novel macroinitiator (RAFT macroinitiator). For this purpose, RAFT macroinitiator was obtained from the potassium salt of ethyl xanthogenate and poly(vinyl chloride) (PVC). Then the graft copolymers were synthesized by using RAFT macroinitiator and 2-vinylpyridine. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the polymerization reaction were studied. The effect of the reaction conditions on the heterogeneity index and molecular weight was also investigated. The block lengths of the graft copolymers were calculated by using 1H nuclear magnetic resonance (1H NMR) spectra. The block lengths of the copolymers could be adjusted by varying the monomer and initiator concentrations. The characterizations of the samples were carried out by using 1H NMR, Fourier-transform infrared spectroscopy, gel-permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and fractional precipitation (γ value) techniques. RAFT polymerization is used to control the polymerization of 2-vinylpyridine over a broad range of molecular weights.

Merging New Organoborane Chemistry with Living Radical Polymerization

The synthesis and controlled ring-opening polymerization (ROP) of a six membered cyclic carbonate monomer with pendant reversible addition–fragmentation chain transfer (RAFT) functionality is reported. The growth of fast propagating monomers (methyl acrylate, tetrahydropyran acrylate and N-isopropylacrylamide) from the obtained RAFT-functional poly(carbonate)s resulted in the formation of well-defined graft copolymers with a biodegradable backbone, when grafting was terminated at low monomer conversions (ca. 30%). Direct dissolution of the thermally responsive poly(carbonate)-graft-PNiPAm copolymer yielded spherical micelles as confirmed by DLS and TEM analysis.

ABSTRACTIn this study, synthesis of poly(epichlorohydrin-g-methyl methacrylate) graft copolymers by reversible addition-fragmentation chain transfer (RAFT) polymerization was reported. For this purpose, epichlorohydrin was polymerized by using HNO3 via cationic ring-opening mechanism. A RAFT macroinitiator (macro-RAFT agent) was obtained by the reaction of potassium ethyl xanthogenate and polyepichlorohydrin. The graft copolymers were synthesized using macro-RAFT agent as initiator and methyl methacrylate as monomer. The synthesis of graft copolymers was conducted by changing the time of polymerization and the amount of monomer-initiator concentration that affect the RAFT polymerization. The effects of these parameters on polymerization were evaluated via various analyses. The characterization of the products was determined using 1H-nuclear magnetic resonance (1H-NMR), Fourier-transform infrared spectroscopy, gel-permeation chromatography, thermogravimetric analysis, elemental analysis, and fractional precipitation techniques. The block lengths of the graft copolymers were calculated by using 1H-NMR spectrum. It was observed that the block length could be altered by varying the monomer and initiator concentrations.

Polymer vectors via controlled/living radical polymerization for gene delivery

Cellulose graft copolymers toward strong thermoplastic elastomers via RAFT polymerization

A three‐step process, combining nitroxide‐mediated polymerization (NMP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization techniques, for synthesizing well‐defined amphiphilic and thermosensitive graft copolymers with fluorescence poly(styrene‐co‐(p‐chloromethylstyrene))‐g‐poly(N‐isopropylacrylamide) (P(St‐co‐(p‐CMS))‐g‐PNIPAAM), was conducted. Firstly, the NMP of styrene (St) and p‐chloromethylstyrene (p‐CMS) were carried out using benzoyl peroxide (BPO) as the initiator to obtain the random copolymers of P(St‐co‐(p‐CMS)). Secondly, the random copolymers were converted into macro‐RAFT agents with fluorescent carbazole as Z‐group through a simple method. Then the macro‐RAFT agents were used in the RAFT polymerization of N‐isopropylacrylamide (NIPAAM) to prepare fluorescent amphiphilic graft copolymers P(St‐co‐(p‐CMS))‐g‐PNIPAAM with controlled molecular weights and well‐defined structures. The copolymers obtained were characterized by gel permeation chromatography (GPC), 1H nuclear magnetic resonance (NMR) spectroscopy, and FT‐IR spectroscopy. The size of self‐assembly micelles of the resulting graft copolymers in deionized water was studied by high performance particle sizer (HPPS), the results showed that the Z‐average size of the micelles increased with the increase of molecular weights of PNIPAAM in side chains. The aqueous solution of the micelles prepared from P(St‐co‐(p‐CMS))‐g‐PNIPAAM using a dialysis method showed a lower critical solution temperature (LCST) at ∼ 27.5 °C, which was below the value of NIPAAM homopolymer (32 °C). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5318–5328, 2007