Poly(ethylene Glycol) Monomethyl Ether Methacrylate Research Articles

Synthesis internal-plasticized PVC copolymer resin from industrial application view: Copolymerization of vinyl chloride with poly(ethylene glycol) monomethyl ether methacrylate via suspension polymerization

Developing internal-plasticized poly(vinyl chloride) (PVC) resin has been recognized as an effective way to deal with the issues of conventional PVC products such as toxicity and deterioration in properties caused by the migration of plasticizer. Herein, the copolymerization of vinyl chloride with commercial available poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) is firstly conducted via suspension polymerization and internally plasticized random copolymers (PVEGA) are synthesized successfully. These PVEGA copolymers were intensively characterized by FTIR, 1H NMR, GPC, DSC, DMTA, and SEM to determine the composition, number-average molecular weight (Mn), dispersity, glass transition temperature (Tg), and the micromorphology. As a result, the high transparency and the fracture images demonstrated the good compatability between PVC chains with long-chain polyether. The Tg of PVEGA decreased gradually from 80 to 0 °C with the fraction of PEGMA in the copolymer increased from 7 to 37 %. Furthermore, the PVEGA copolymer exhibits outstanding processibility and mechanical performance. Under optimal composition, the tensile strength and the elongation at break can reach to 8 MPa and 525 %, respectively. Meanwhile, the PVEGA copolymers exhibit much lower migration either in water or in orgnic solvent and excellent performance in hemolysis and cytotoxicity, showing great application potential in medical devices.

Promising Gene Delivery Properties of Polycations Based on 2-(N,N-dimethylamino)ethyl Methacrylate and Polyethylene Glycol Monomethyl Ether Methacrylate Copolymers.

Cationic copolymers based on 2-(N,N-dimethylamino)ethyl methacrylate and polyethylene glycol monomethyl ether (pDMAEMA-co-PEO) with different molecular weights have been synthesized. Their physicochemical properties were studied by NMR spectroscopy, sedimentation, and potentiometric titration. According to the data of potentiometric titration for the synthesized pegylated cationic copolymers, the apparent dissociation constants were determined in the pH range from 4.5 to 8.5. The physicochemical properties of interpolyelectrolyte complexes of these polycations with circular DNA (IPEC DNA) were also studied by dynamic light scattering, electrophoretic mobility, and TEM methods. It has been established that the diameter and electrokinetic potential (ζ-potential) of interpolyelectrolyte complexes can be varied over a wide range (from 200 nm to 1.5 μm and from -25 mV to +30 mV) by changing the ratio of oppositely charged ionizable groups in pegylated cationic copolymers and DNA, as well as by regulating medium pH. The resistance of the IPEC DNA/polycation complex to the action of nucleases was studied by electrophoresis in agarose gel; the cytotoxic effect of the polymers in vitro, and the efficiency of penetration (transfection) of IPEC DNA with PDMAEMA-co-PEO-polycations into eukaryotic cells of a cell line derived from human embryonic kidneys HEK 293 in vitro.

Composite Electrolytes Prepared by Improving the Interfacial Compatibility of Organic-Inorganic Electrolytes for Dendrite-Free, Long-Life All-Solid Lithium Metal Batteries.

Compared with simplex ceramic or polymer solid electrolytes, composite solid electrolyte (CSE) is more promising for its better interfacial compatibility to electrode and high ionic conductivity simultaneously. Further, the interfacial compatibility within ceramic and polymer is considered to be more and more critical to the overall performance of solid-state batteries. Avoiding the agglomeration of ceramic particles at high loadings can improve the whole intrinsic characteristic and electrochemical performance of CSEs. Herein, we designed a CSE (EO@LLZTO-PEO), which consists of composite particles (EO@LLZTO) as a filler and polyethylene oxide (PEO) as polymer matrix. EO@LLZTO was prepared by chemically grafting polyethylene glycol monomethyl ether methacrylate (MPEG-MAA) on the micro-sized Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles. By introducing of polymer containing EO segments onto LLZTO, the interfacial compatibility between LLZTO and PEO matrix is highly enhanced, and the intrinsic Li+ complexation capability of MPEG-MAA is improved, even at the high loading of garnet. EO@LLZTO-PEO shows a high ionic conductivity (1.91 mS cm-1), a broad electrochemical window (∼5.2 V vs Li/Li+), and a high lithium ion transference number (0.72). The Li/EO@LLZTO-PEO/Li battery also exhibits a long cycle stability (over 1200 h of cycling). Moreover, all-solid-state batteries with LiFePO4 and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes exhibit excellent cycling stability and rate performance. Consequently, enhancing the interfacial compatibility between organic and inorganic electrolytes is identified to be one of the crucial strategies for commercial solid-state lithium batteries.

Self‐Healing Ability of Poly(PEGMA‐5‐UPy) Evaluated by Thermomechanical Analysis

AbstractThe synthesis and characterization of polyethylene glycol monomethyl ether methacrylate (PEGMA) based copolymers incorporating three different percentages (2.5 wt%, 5.0 wt%, and 7.8 wt%) of urea‐N‐2‐amino‐4‐hydroxy‐6‐methylpyrimidine‐N’‐(hexametylen‐n‐carboxyethyl methacrylate) (HEMA‐UPy) are reported. Nuclear magnetic resonance (NMR) and infrared spectroscopy (IR) confirm the synthesis procedure. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are employed to evaluate the thermal properties of the samples. DSC measurements evidence a slight increase in glass transition temperature (Tg), a consistent increase in crystallization and melting temperatures (Tc and Tm), and a reduction in the crystallization degree (Xc) with increasing the amount of HEMA‐UPy moiety. Dynamic mechanical analysis (DMA) is carried out at different values of temperature and oscillation frequency. It highlights the ability of the healed copolymer to recover the pristine values of storage modulus. The healing efficiency depends on the temperature history of the sample. For the sample healed at room temperature, the value of healing efficiency is 64%. DMA tests performed at higher temperatures, after some permanence at room temperature, evidence higher values in the healing efficiency. This demonstrates that the higher value of the temperature employed during DMA tests determines greater mobility of the chains causing an enhancement in the healing efficiency.

Theranostic Copolymers Neutralize Reactive Oxygen Species and Lipid Peroxidation Products for the Combined Treatment of Traumatic Brain Injury.

Traumatic brain injury (TBI) results in the generation of reactive oxygen species (ROS) and lipid peroxidation product (LPOx), including acrolein and 4-hydroxynonenal (4HNE). The presence of these biochemical derangements results in neurodegeneration during the secondary phase of the injury. The ability to rapidly neutralize multiple species could significantly improve outcomes for TBI patients. However, the difficulty in creating therapies that target multiple biochemical derangements simultaneously has greatly limited therapeutic efficacy. Therefore, our goal was to design a material that could rapidly bind and neutralize both ROS and LPOx following TBI. To do this, a series of thiol-functionalized biocompatible copolymers based on lipoic acid methacrylate and polyethylene glycol monomethyl ether methacrylate (FW ∼ 950 Da) (O950) were prepared. A polymerizable gadolinium-DOTA methacrylate monomer (Gd-MA) was also synthesized starting from cyclen to facilitate direct magnetic resonance imaging and in vivo tracking of accumulation. These neuroprotective copolymers (NPCs) were shown to rapidly and effectively neutralize both ROS and LPOx. Horseradish peroxidase absorbance assays showed that the NPCs efficiently neutralized H2O2, while R-phycoerythrin protection assays demonstrated their ability to protect the fluorescent protein from oxidative damage. 1H NMR studies indicated that the thiol-functional NPCs rapidly form covalent bonds with acrolein, efficiently removing it from solution. In vitro cell studies with SH-SY5Y-differentiated neurons showed that NPCs provide unique protection against toxic concentrations of both H2O2 and acrolein. NPCs rapidly accumulate and are retained in the injured brain in controlled cortical impact mice and reduce post-traumatic oxidative stress. Therefore, these materials show promise for improved target engagement of multiple biochemical derangements in hopes of improving TBI therapeutic outcomes.

Cloud Point Driven Dynamics in Aqueous Solutions of Thermoresponsive Copolymers: Are They Akin to Criticality Driven Solution Dynamics?

Cloud point driven interaction and relaxation dynamics of aqueous solutions of amphiphilic thermoresponsive copolymers were explored through picosecond resolved and steady state fluorescence measurements employing hydrophilic (coumarin 343, C343) and hydrophobic (coumarin 153, C153) solute probes of comparable sizes. These thermoresponsive random copolymers, with tunable cloud point temperatures (Tcp's) between 298 and 323 K, were rationally designed first and then synthesized via reversible addition-fragmentation chain transfer (RAFT) copolymerization of methyl methacrylate (MMA) and poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). Subsequently, copolymers were characterized by NMR spectroscopy and size exclusion chromatography (SEC). A balance between the hydrophilic (PEGMA) and the hydrophobic (MMA) content dictates the critical aggregation concentration (CAC), with CAC ∼ 2-14 mg/L for these copolymers in aqueous media. No abrupt changes in the steady state spectral features of both C153 and C343 in the aqueous solutions of these polymers near but below the cloud point temperatures were observed. Interestingly, spectral properties of C153 in these solutions show the impact of hydrophobic/hydrophilic interaction balance but not by those of C343. More specifically, C153 reported a blue shift (relative to that in neat water) and heterogeneity in its local environment. This suggested different locations for the hydrophilic (C343) and the hydrophobic (C153) probes. In addition, the excited state fluorescence lifetime (⟨τlife⟩) of C153 increased with the increase of hydrophobic (MMA) content in these copolymers. However, C343 reported no such variations, although fluorescence anisotropy decays for both solutes were significantly slowed down in these aqueous solutions compared to neat water. Anisotropy decays indicated bimodal time-dependent friction for these solutes in aqueous solutions of these copolymers but monomodal in neat water. A linear dependence of the average rotational relaxation rates (⟨krot⟩ = ⟨τrot⟩-1) of the type ⟨krot⟩ ∝ (|T - Tcp|/Tcp)γ with negative values for the exponent γ was observed for both solutes. No slowing down of the solute rotation with temperature approaching the Tcp was detected; rather, rotation became faster upon increasing the solution temperature, suggesting domination of the local friction.

Exploring Aqueous Solution Dynamics of an Amphiphilic Diblock Copolymer: Dielectric Relaxation and Time-Resolved Fluorescence Measurements.

We explore in this work, after synthesizing and appropriately characterizing an amphiphilic diblock copolymer, its interaction with water molecules and the subsequent aqueous solution dynamics by employing time-resolved fluorescence measurements (TRF) and megahertz-gigahertz dielectric relaxation (DR) experiments. The synthesized amphiphilic diblock copolymer is poly(2-(((tert-butoxycarbonyl)alanyl)oxy)ethyl methacrylate)-b-poly(polyethylene glycol monomethyl ether methacrylate) (P(Boc-l-Ala-HEMA)-b-PPEGMA). Dynamic light scattering measurements of aqueous solutions indicate formation of 14-20 nm particles from a balance between the chain lengths of the hydrophobic (P(Boc-l-Ala-HEMA) and hydrophilic (PPEGMA) segments. Field-emission scanning electron microscopy, on the other hand, suggests a spherical shape for the dried micelles. The critical micelle concentration of the P(Boc-l-Ala-HEMA)-b-PPEGMA block copolymer at different block lengths in aqueous media, determined via steady-state fluorescence measurements, is very low (∼4-8 mg/L), and the resultant micellar size has been found to be insensitive to the polymer concentration. Interfacial and bulk aqueous dynamics have been investigated by tracking the solution frictional resistance on rotational motion of dissolved hydrophobic and hydrophilic dipolar solute probes of comparable sizes. TRF anisotropy measurements reflect the biphasic temporal profile for the frictional resistance. Interestingly, the hydrophobic probe, because of its preferential location at the micellar interface, experiences greater frictional resistance than the hydrophilic counterpart, although the latter reports stronger polymer concentration dependence of the frictional retardation than the former. DR measurements at the highest of the polymer concentrations considered suggest presence of aqueous dynamics slower than that for neat bulk water, although evidence for such "slow" dynamics at lower concentrations has not been detected in the present DR measurements.

Visible Light–Induced RAFT Polymerization of Methacrylate with 4‐(N,N‐diphenylamino)benzaldehyde as Organophotoredox Catalyst and the Effect of Temperature on the Polymerization

AbstractWith UV–vis absorption in the range of 270–435 nm, 4‐(N,N‐diphenylamino)benzaldehyde (DPAB) takes efficient photoreduction quench with 4‐cynao‐4‐(phenylcarbonothioylthio)pentanoic acid (CTP). The polymerization rates of methyl methacrylate (MMA) are 0.019, 0.056, and 0.102 h−1 at 33, 40, and 50 °C, respectively, in the presence of DPAB and CTP under visible‐light irradiation. Dark reaction produces no PMMA at 50 °C for 120 h. The living feature is demonstrated by linearly increasing Mn with the monomer conversions and narrow polydispersity index (PDI), chain extension, and block polymerizations with benzyl methacrylate (BnMA) and poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). With PMMA‐CTP (Mn = 6800, PDI = 1.17), chain extension gives PMMA with Mn = 15 900 and PDI = 1.15. With PMMA‐CTP (Mn = 6000, PDI = 1.21) as macro‐RAFT, PMMA‐b‐PBnMA of Mn = 12 600 (PDI = 1.44) and Mn = 18 500 (PDI = 1.31) are prepared. These results support that there is a positive synergistic effect between polymerization temperature and visible‐light irradiation on the photo‐RAFT without losing the living features.

Micellization of a di‐block copolymer in ethylene glycol and its utilization for suspension of carbonaceous nanostructures

ABSTRACTSuspensions of carbonaceous nanoparticles (NPs) in ethylene glycol (EG) can be used as colloidal inks for additive manufacturing and nano‐fluids for heat‐transfer applications. While micellar solutions of surfactants are often used for suspension of the NPs in water, micellization of surfactants in EG is suppressed as compared to aqueous solutions and a well‐defined critical micellization concentration (CMC) is often not observed. Unlike the surfactants, a di‐block copolymer comprising a poly(ethylene glycol) monomethylether methacrylate (PEGMA) segment, 2‐(diethylaminoethyl) methacrylate (DEAEMA) and butyl methacrylate (BMA), poly(O950)‐b‐(DEAEMA‐co‐BMA) was found to assemble into spherical micelles in EG. Surface tension measurements show a well‐defined CMC that depends on the volume fraction of EG. Cryogenic transmission electron microscopy and dynamic light scattering show the presence of spherical micelles with a diameter that reduces with the volume fraction of EG. The micellar solutions were further used for suspending carbonaceous NPs of different geometry and characteristic dimensions: C60 fullerenes, multi‐walled carbon nanotubes, and nanodiamonds. The flow behavior of the suspensions exhibits a relatively low viscosity and mostly Newtonian behavior due to strong interaction between the NPs and the micelles. These suspensions may be used as colloidal inks for two‐dimensional and three‐dimensional printing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46518.

Biomimetic PEGylation of carbon nanotubes through surface-initiated RAFT polymerization

Carbon nanotubes (CNTs) are a type of one-dimensional carbon nanomaterials that possess excellent physicochemical properties and have been potentially utilized for a variety of applications. Surface modification of CNTs with polymers is a general route to expand and improve the performance of CNTs and has attracted great research interest over the past few decades. Although many methods have been developed previously, most of these methods still showed some disadvantages, such as low efficiency, complex experimental procedure and harsh reaction conditions etc. In this work, we reported a practical and novel way to fabricate CNTs based polymer composites via the combination of mussel inspired chemistry and reversible addition fragmentation chain transfer (RAFT) polymerization. First, the amino group was introduced onto the surface of CNTs via self-polymerization of dopamine. Then, chain transfer agent can be immobilized on the amino groups functionalized CNTs to obtain CNT-PDA-CTA, which can be utilized for surface-initiated RAFT polymerization. A water soluble and biocompatible monomer poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) was adopted to fabricate pPEGMA functionalized CNTs through RAFT polymerization. The successful preparation of CNTs based polymer composites (CNT-pPEGMA) was confirmed by transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy in details. The CNT-pPEGMA showed good dispersibility and desirable biocompatibility, making them highly potential for biomedical applications. More importantly, a large number of CNTs based polymer composites could also be fabricated through the same strategy when different monomers were used due to the good monomer adaptability of RAFT polymerization. Therefore, this strategy should be a general method for preparation of various multifunctional CNTs based polymer composites.

PH and Salt Effects on Surface Activity and Self-Assembly of Copolymers Containing a Weak Polybase.

Copolymers with well-defined architectures, controlled molecular weights, and narrow molar mass dispersities (Đ) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The resultant polymers contain different combinations of the pH-responsive monomer 2-(diethylaminoethyl) methacrylate (DEAEMA), the hydrophobic comonomer butyl methacrylate (BMA), and a neutral hydrophilic stabilizing monomer polyethylene glycol monomethyl ether methacrylate (designated O950). Surface tension and cryo-TEM measurements of native and heavy-atom stained samples were used to characterize the pH and salt responsiveness of the different polymers as a function of their composition. These studies indicate that while the polymers predominately self-assemble to form spherical micelles, a narrow size distribution is observed in aqueous solutions of poly(O950)-b-(BMA) and poly(O950)-b-(DEAEMA-co-BMA), whereas a broad size distribution characterizes the assemblies of poly(O950)-b-(DEAEMA) and poly(DEAEMA-co-BMA). In the latter case, micelles having diameters around 15-25 nm are found along with smaller aggregates (about 10 nm) mostly arranged in elongated necklace-like structures. The pH and salt-responsiveness of the DEAEMA residue, as indicated by the surface activity of the copolymers, was found to depend on the nature of the additional components: covalently linked hydrophobic groups (BMA) moderated the pH response of the copolymer as compared to nonionic and hydrophilic groups as in poly(O950)-b-(DEAEMA). These results suggest that mutual interactions among the building blocks of self-assembling copolymers should be taken into account when designing responsive copolymers.

Polymer-Chlorambucil Drug Conjugates: A Dynamic Platform of Anticancer Drug Delivery.

Recently, polymer drug conjugates (PDCs) have attracted considerable attention in the treatment of cancer. In this work, a simple strategy has been developed to make PDCs of an antitumor alkylating agent, chlorambucil, using a biocompatible disulphide linker. Chlorambucil-based chain transfer agent was used to prepare various homopolymers and block copolymers in a controlled fashion via reversible addition-fragmentation chain transfer polymerization. Chlorambucil conjugated block copolymer, poly(polyethylene glycol monomethyl ether methacrylate)-b-poly(methyl methacrylate), formed nanoaggregates in aqueous solutions, which are characterized by dynamic light scattering and field emission-scanning electron microscopy. Finally, the simplicity of the design is exemplified by performing a release study of chlorambucil under reducing condition by using D,L-dithiothreitol.

A Facile Strategy for Catalyst Separation and Recycling Suitable for ATRP of Hydrophilic Monomers Using a Macroligand.

How to simply and efficiently separate and recycle catalyst has still been a constraint for the wide application of atom transfer radical polymerization (ATRP), especially for the polymerization systems with hydrophilic monomers because the polar functional groups may coordinate with transition metal salts, resulting in abundant catalyst residual in the resultant water-soluble polymers. In order to overcome this problem, a latent-biphasic system is developed, which can be successfully used for ATRP catalyst separation and recycling in situ for various kinds of hydrophilic monomers for the first time, such as poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-dimethyl acrylamide (DMA), and N-isopropylacrylamide (NIPAM). Herein, random copolymer of octadecyl acrylate (OA), MA-Ln (2-(bis(pyridin-2-ylmethyl)amino)ethyl acrylate), and POA-ran-P(MA-Ln) is designed as the macroligand, and heptane/ethanol is selected as the biphasic solvent. Copper(II) bromide (CuBr2 ) is employed as the catalyst, PEG-bound 2-bromo-2-methylpropanoate (PEG350 -Br) as the water-soluble ATRP initiator and 2,2'-azobis(isobutyronitrile) (AIBN) as the azo-initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP system. Importantly, well-defined water-soluble polymers are obtained even though the recyclable catalyst is used for sixth times.

AGET ATRP of Poly[poly(ethylene glycol) methyl ether methacrylate] Catalyzed by Hydrophobic Iron(III)–Porphyrins

Commercially available hydrophobic porphyrins are investigated as an environmentally friendly catalytic system for iron‐mediated atom transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). Polymerizations in organic solvent are optimized using activators generated by electron transfer (AGET ATRP), based on iron(III)–porphyrin complexes, and tin(II) 2‐ethyl hexanoate or ascorbic acid as a reducing agent. Copper‐free PPEGMA macromolecules are obtained with high conversion, controlled molecular weight, and polydispersity index compared with standard copper‐based ATRP. The facile preparation and availability of the catalyst, together with its expected low toxicity, represent clear advantages for the synthesis of PPEGMA‐based materials for biomedical use. image

Hybrid PVDF/PVDF-graft-PEGMA Membranes for Improved Interface Strength and Lifetime of PEDOT:PSS/PVDF/Ionic Liquid Actuators

The exploitation of soft conducting polymer-based actuators suffers from two main shortcomings: their short life cycle and the reproducibility of the fabrication techniques. The short life cycle usually results from the delamination of the components due to stresses at the interface during the actuation. In this work, to achieve strong adhesion to poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) ( PSS) electrodes, the wetting properties of the surface of a polyvinylidene fluoride (PVDF) membrane are improved using argon-plasma-induced surface polymerization of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). Hybrid membranes are created with hydrophilic PVDF-graft-PEGMA outer surfaces and hydrophobic bulk. The width of each layer is controlled by spray coating, as it allows for the deposition of the reaction precursor to a certain depth. Subsequently, a PSS water solution fills the pores of the functionalized part of the membrane and a mixing layer between PSS and PVDF is created. We also show that PVDF-graft-PEGMA copolymers play an important role in binding the membrane to the electrodes and that direct mechanical interlocking in the pores can further improve the adhesion. Finally, PSS/PVDF-graft-PEGMA/PEDOT:PSS actuators are made by simple solution casting. They are capable of producing high strains of 0.6% and show no signs of delamination after more than 150 h or 10(4) actuation cycles. Furthermore, the preservation of the hydrophobic membrane in between two PSS layers increases the resistance between them from 0.36 Ω to 0.16 MΩ, thus drastically modifying the power dissipation of the actuators.

Lithium battery with solid polymer electrolyte based on comb-like copolymers

In this paper we report on the synthesis of comb-like copolymers as solid polymer electrolytes (SPE). The synthesis involved anionic polymerization of styrene (St) and 4-vinylanisole (VA) as the followed by grafting of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization (ATRP). The comb-like copolymer's structure was analyzed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The membranes were made by solvent casting and the morphologies were analyzed by atomic forces microscopy (AFM) and scanning electron microscopy (SEM). We observed that a nano and micro phase separation occurs which improves ionic conductivity. The ionic conductivities were determined by AC Impedance, which showed that the SPEs have good conductivities (10−5 Scm−1) at room temperature owing to the negligible values (<10 kJ mol−1) of the activation energies for conductivity. The batteries with these polymers exhibit a capacity of 146 mAh g−1 at C/24, and no evidence of degradation after intense cycling was observed. However, poor cycle life was observed at C/6 and C/3, which is a consequence of several factors. We partially explain that behavior by arguing that whereas PEO lightly “solvates” Li+ thus slowing Li-ion mobility, and PEGMA chains “solvate” Li ions too strongly, trapping and inhibiting their mobility.

Facile and highly efficient “living” radical polymerization of hydrophilic vinyl monomers in water

In this work, well-defined polymerization of water soluble poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and N,N-dimethyl-acrylamide (DMA) were successfully conducted in water by a facile and efficient polymerization system, only including oxidatively stable copper(II) acetate and 1-cyano-1-methylethyl diethyldithiocarbamate (MANDC). The effects of temperature, copper concentration, and monomer concentration on polymerization of PEGMA were systematically investigated to optimize the polymerization conditions. The polymerization of PEGMA can be conveniently carried out with ppm levels of the copper catalyst at 30–70 °C. The linearity of the kinetic plots, linear increase of molecular weight with conversion, and narrow molecular weight distribution (Mw/Mn < 1.3) of the polymer showed the typical character of “living” radical polymerization (LRP). Chain-extension reactions further verify the “living” features of this polymerization system.

PH-responsive stealth micelles composed of cholesterol-modified PLA as a nano-carrier for controlled drug release.

Present research is a preliminary report on the novel pH-responsive micelles based on an amphiphilic brush copolymer P(PEGMA)-b-P(DMAEMA-co-CPLAMA) used as the promising drug carrier. The copolymer was synthesized using cholesteryl poly(l-lactic acid) methacrylate (CPLAMA), poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) with appropriate hydrophobic/hydrophilic ratios via atom transfer radical polymerization. The copolymer compositions were determined by 1H NMR. The synthesized copolymer self-assembled into nano-scale micelles capable of encapsulating hydrophobic model drug naproxen in their hydrophobic cores in aqueous solutions. pH sensitivity and self-assembly behaviors of copolymer were studied by UV–vis transmittance, fluorescence spectroscopy, transmission electron microscopy (TEM) and dynamic light scattering. The results showed that the copolymer had high pH responsivity with a phase transition pH around pH 6.2. The critical micelle concentrations at pH 6.5 were found about 2.4 mg L−1. The stable and small micelles were obtained at pH 5.5–6.5. Upon increasing pH higher than 7, the single micelles further assembled into the micellar aggregates. TEM images of copolymer micelles showed that the micelles are spherical in shape with the mean diameter of 152 nm at pH 6.2. In vitro release study of naproxen-loaded micelles with about 44 % loading efficiency and 8 % loading capacity was performed using dialysis method in phosphate-buffered solution at 37 °C. Release study implied that the proposed brush copolymer could produce stable nano-carriers with controllable drug release at the target sites (pH 5.5–7).

Bifunctional nanoparticles with magnetism and NIR fluorescence: controlled synthesis from combination of AGET ATRP and ‘click’ reaction

In this work, bifunctional nanoparticles (NPs) capable of emitting near infrared (NIR) fluorescence and generating superparamagnetism under an external magnetic field were prepared by combination of ‘click’ reaction and surface-initiated activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) of water-soluble poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) and glycidyl methacrylate (GMA) using biocompatible iron as the catalyst on the surface of silica-coated iron oxide (Fe3O4@SiO2) NPs. The nanosized Fe3O4@SiO2@PPEGMA-co-PGMA@N3 was prepared through AGET ATRP and alkynyl bearing NIR dye was also prepared; afterwards they were integrated together by ‘click’ reaction. The different stages of surface modification were approved by employing different characterization techniques such as TEM, XRD, XPS, VSM and FT-IR, and the properties of the final NPs were thoroughly studied. Their suitability as dual model imaging agents for magnetic resonance (MR) and fluorescence imaging was investigated, indicating them to be a competitive candidate for imaging contrast agents.

A versatile Fe3O4based platform via iron-catalyzed AGET ATRP: towards various multifunctional nanomaterials

In this work, iron-catalyzed atom transfer radical polymerization with activators generated by electron transfer (AGET ATRP) of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) and 2-((ethoxycarbonothioyl)thio)ethyl methacrylate (ETCEMA) followed by reduction were performed to modify Fe3O4@SiO2 nanoparticles (NPs) for introducing thiol groups on the surface of the NPs. Gold NPs and two near infra-red (NIR) organic dyes with different quantum yields were covalently fixed into the polymer shells independently to afford magnetic NPs with surface-enhanced Raman spectroscopy (SERS), NIR fluorescence imaging and photo-thermal therapy (PTT) functionalities, respectively. In addition, all of these NPs are able to display as contrast agents for magnetic resonance imaging (MRI) because of the existence of the paramagnetic Fe3O4 cores.