Polymerizations and mechanistic studies have been performed to understand the kinetic pathways for polymerization of monomer oligo(ethylene oxide) monomethyl ether acrylate (OEOA) in aqueous media. Typically, medium consisted 18 wt % OEOA water, presence Cu catalysts coordinated by tris[2-(dimethylamino)ethyl]amine (Me6TREN). Well-controlled can be achieved halide anions wire with ≲600 ppm soluble CuII species, rather than previously reported ca. 10 000 Cu0 particles formed...

Abstract This work contributes to the development of integrated lignocellulosic‐based biorefineries by pioneering exploitation hardwood xylans solubilization and extraction in deep eutectic solvents (DES). DES formed choline chloride urea or acetic acid were initially evaluated as for commercial xylan a model compound. The effects temperature, molar ratio, concentration aqueous solutions optimized using response surface methodology. results obtained demonstrated potential these solvents,...

Inorganic sulfites such as sodium dithionite (Na2S2O4), metabisulfite (Na2S2O5), and bisulfite (NaHSO3) have been studied reducing agents for atom transfer radical polymerization (ATRP). They act not only very efficient but also supplemental activators SARA (supplemental activator agent) ATRP of methyl acrylate in DMSO at ambient temperature. In combination with Cu(II)Br2/Me6TREN, they produced poly(methyl acrylate) controlled molecular weight, low dispersity (Mw/Mn = 1.05), well-defined...

Abstract The field of transition‐metal‐mediated controlled/“living” radical polymerization (CLRP) has become the subject intense discussion regarding mechanism this widely‐used and versatile process. Most mechanistic analyses (atom transfer (ATRP) vs. single‐electron living (SET‐LRP)) have been based on model experiments, which cannot correctly mimic true reaction conditions. We present, for first time, a determination [Cu I Br]/[L] (L=nitrogen‐based chelating ligand) ratio extent Cu Br/L...

Controlled/"living" radical polymerization (CLRP) of vinyl chloride (VC) via the reversible addition–fragmentation chain transfer (RAFT) process is reported for first time. The cyanomethyl methyl(phenyl)carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling CLRP VC monomer under certain experimental conditions. Two different initiators, having very distinct half-life times at room temperature, were employed in this study. kinetic studies show a linear increase molecular...

New copolymers based on renewable PBF/PEGF are tailored to show advantageous processing features as compared PBF (enlarged working temperatures and no crystallisation at slow rates).

Successful supplemental activator and reducing agent atom transfer radical polymerization of (3-acrylamidopropyl)trimethylammonium chloride under ecofriendly conditions.

Infections caused by bacteria represent a great motif of concern in the health area. Therefore, there is huge demand for more efficient antimicrobial agents. Antimicrobial polymers have attracted special attention as promising materials to prevent infectious diseases. In this study, new polymeric system exhibiting activity against range Gram-positive and Gram-negative bacterial strains at micromolar concentrations (e.g., 0.8 μM) was developed. Controlled linear star-shaped copolymers,...

The synthesis of poly(vinyl chloride) (PVC) by nitroxide-mediated polymerization (NMP) using the SG1-based BlocBuilder alkoxyamine at low temperature (30 and 42 °C) is reported. reaction system was studied regarding nature solvent, monomer-to-solvent ratio, temperature, target molecular weight. First-order kinetics linear evolutions weight with vinyl chloride (VC) conversion were obtained in dichloromethane (DCM) dimethyl sulfoxide (DMSO) together decreasing dispersities (Đ) down to...

Thiourea dioxide, a green and inexpensive compound used at industrial scale, was employed as reducing agent for the controlled polymerization of wide range monomer families, namely, acrylates (methyl acrylate, 2-hydroxyethyl butyl methacrylates (2-(dimethylamino)ethyl methacrylate, 2-aminoethyl methacrylate hydrochloride, methyl methacrylate), styrene, acrylonitrile, vinyl chloride (nonactivated monomer) by ATRP. Mechanistic studies confirmed that polymerizations are ruled activators...

Abstract Atom transfer radical polymerization (ATRP) is one of the most popular advanced techniques in macromolecular science, allowing synthesis tailor‐made polymers with controlled molecular weight, architecture, composition, and functionality. The combination ATRP ring‐opening (ROP) provides a straightforward route for preparation exhibiting both targeted well‐defined features biodegradability, which very interesting development new materials biomedical applications. Among different types...

A very fast and controlled atom transfer radical (co)polymerization (ATRP) of acrylates, methacrylates, styrene, vinyl chloride is reported in a single dipolar aprotic solvent, sulfolane, with the use ppm amount copper catalyst. The observed rates polymerization (kpapp) monomers studied are similar to those using dimethyl sulfoxide (DMSO) other polar solvents typically employed electron (SET)-mediated processes. As proof-of-concept, ABA type block copolymers polystyrene-b-poly(vinyl...

Activators regeneration by electron transfer atom radical polymerization (ARGET ATRP) of 2-aminoethyl methacrylate hydrochloride (AMA) was successfully performed for the first time. The polymerizations were conducted at 35 °C in isopropanol (IPA)/water mixtures or pure water, using CuBr2/TPMA (TPMA: tris(2-pyridylmethyl)amine) as a metal catalyst complex with slow feeding ascorbic acid (AscA) to allow activator species. reactions showed first-order kinetics monomer conversion and high...

Supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of acrylates, methacrylates, styrene vinyl chloride was successfully performed in sulfolane/water mixtures using ppm amounts soluble copper.

Cationic glycopolymers stand out as gene delivery nanosystems due to their inherent biocompatibility and high binding affinity the asialoglycoprotein receptor (ASGPR), a target overexpressed in hepatocellular carcinoma (HCC) cells. However, synthesis procedure remains laborious complex, with problems of solubilization need for protection/deprotection steps. Here, mini-library well-defined poly(2-aminoethyl methacrylate hydrochloride-co-poly(2-lactobionamidoethyl methacrylate) (PAMA-co-PLAMA)...

Abstract The current trend in developing next‐generation LRP systems and particular ATRP involves reduction, elimination, and/or replacement of toxic highly expensive catalysts solvents with environmently friendly ones. Here, the unexpected, accelerated, ambient‐temperature methyl acrylate catalyzed by a Fe(0)/CuBr 2 /Me 6 TREN system mixture water inexpensive environmentally more alcohols (methanol, ethanol, 1‐propanol) is reported. data presented open up possibility using fast mixed...

Inorganic sulfites as reducing agents were successfully used in combination with typical reversible addition–fragmentation chain transfer (RAFT) for the controlled DET-RAFT (DET: dissociative electron transfer) of methacrylates, methyl acrylate (MA), and styrene (Sty) near room temperature (30 °C). The polymerizations first-order respect to monomer conversion polymers narrow molecular weight distributions (Đ < 1.2), "living" features obtained. MALDI-TOF experiments demonstrated integrity...

This work presents a novel approach for tailoring molecularly imprinted polymers (MIPs) with preliminary stage of atom transfer radical polymerization (ATRP), more precise definition the cavity. A well-defined copolymer acrylamide and N,N′-methylenebisacrylamide (PAAm-co-PMBAm) was synthesized by ATRP applied to gold electrodes template, followed crosslinking reaction. The template removed from polymer matrix enzymatic/chemical action. surface modifications were monitored via electrochemical...