Solid-state electrolytes based on ionic network polymers

Interpenetrating and semi-interpenetrating polymer networks are synthesized with the use of cationic and anionic ionic monomers: N-[3-(methacryloyloxy)propyl]-N-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide, N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-N-methylpyrrolidinium bis(fluorosulfonyl)imide, and (N-butyl-N-methylpyrrolidinium 1-[3-(methacryloyloxy)propylsulfonyl] (trifluoromethanesulfonyl) imide. Their ionic conductivities, electrochemical stabilities, heat resistances, thermal stabilities, and mechanical properties and the swelling of the films in ionic liquid/lithium salt mixtures were studied. The copolymerization of N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-N-methylpyrrolidinium bis(fluorosulfonyl)imide and poly(ethylene glycol dimethacrylate) and poly(ethylene glycol methacrylate) in the presence of butadiene-acrylonitrile rubber and a solution of Li(CF₃SO₂)₂N in N-(methoxymethyl)-N-methylpyrrolidinium bis(fluorosulfonyl)imide yielded a solid-state electrolyte with a set of properties optimum among the studied films: an ionic conductivity of 1.3 × 10^?4S/cm (25°C), a tensile strength of 80 kPa, and an elongation at break of 60%.     

Preparation of Micron‐Sized Monodisperse Poly(ionic liquid) Particles

Micron‐sized monodisperse poly(ionic liquid) (PIL) particles, poly([2‐(methacryloyloxy)ethyl]trimethylammonium bis(trifluoromethanesulfonyl)amide), were prepared by dispersion polymerization at 70 °C in methanol with poly(vinylpyrrolidone) as a stabilizer. The obtained particle size could be controlled by addition of ethanol to the methanol medium while maintaining narrow monodispersity. The PIL particles exhibit unique properties; they can be observed by scanning electron microscopy without platinum coating, which is generally used to avoid an electron charge. Moreover, the solubility of the PIL particles can be easily changed by changing the counter anion, similar to the process for ionic liquids.     

Biomimetic stimulus-responsive star diblock gelators

Novel biomimetic gelators with star diblock copolymer architectures have been synthesized by atom-transfer radical polymerization (ATRP). Two types of trifunctional ATRP initiator were used to polymerize 2-(methacryloyloxy)ethyl phosphorylcholine [MPC] at 20 degrees C, followed by sequential monomer addition of various tertiary amine methacrylates or mixtures thereof. Poor living character was achieved using an amide-based trifunctional initiator, but the analogous triester initiator gave reasonably well-defined thermo-responsive and pH-responsive star diblock copolymers. The most effective thermo-responsive gelators were obtained by the statistical terpolymerization of 2-(dimethylamino)ethyl methacrylate [DMA], 2-(diethylamino)ethyl methacrylate [DEA], and a monomethoxy-capped poly(propylene oxide) methacrylate [PPOMA], whereas pH-responsive gelators were prepared using 2-(diisopropylamino)ethyl methacrylate [DPA] as the second monomer. Star diblock copolymer gelators that were both thermo-responsive and pH-responsive were obtained by the statistical copolymerization of DMA with DPA. Copolymer compositions were assessed by 1H NMR spectroscopy, and the molecular weight distributions of the three-arm star MPC homopolymer precursors were assessed by aqueous gel permeation chromatography. Static light scattering was used to obtain weight-average molecular weights of selected star diblock copolymers and rheological measurements and variable-temperature 1H NMR were used to probe the onset of gelation.     

Nucleotides. Part XXVII Bis[2-(p-nitrophenyl)ethyl] Phosphorochloridate,a New Versatile Phosphorylating Agent in Nucleotide Chemistry

A new, versatile phosphorylating agent, bis[2-(p-nitrophenyl)ethyl] phosphorochloridate ( 3 ), has been prepared and is used for 3′- and/or 5′-phosphorylations of nucleosides. The resulting bis[2-(p-nitrophenyl)ethyl] phosphotriesters are versatile synthons in oligonucleotide synthesis leading finally to 3′- and/or 5′-terminated monophosphates in excellent yields.     

Preparation of sterol-imprinted polymers with the use of 2-(methacryloyloxy)ethyl phosphate.

Steroid-selective polymers were prepared by the molecular imprinting technique, using 2-(methacryloyloxy)ethyl phosphate as functional monomer. The retentivity and selectivity of the obtained imprinted polymers were evaluated by liquid chromatography. The cholesterol-imprinted polymer showed higher affinity for cholesterol than that for cholesterol derivatives. The selectivity of the imprinted polymer was superior to the imprinted polymer prepared with the conventional functional monomer, 2-(trifluoromethyl)acrylic acid. Estradiol was also imprinted and gave similar results, demonstrating that 2-(methacryloyloxy)ethyl phosphate would be suitable for imprinted polymers of cholesterol and related compounds.     

Synthesis of cationic polyacrylamide via inverse emulsion polymerization method for the application in water treatment

In order to improve the flocculent efficiency of wastewater treatment, a cationic flocculant poly (acrylamide-[2-(methacryloyloxy) ethyl] trimethyl ammonium chloride) (P (AM-DMC)) (CPAM) has been synthesized successfully via an inverse emulsion polymerization. Acrylamide (AM) and [2-(methacryloyloxy) ethyl] trimethyl ammonium chloride (DMC) were served as monomers. The molecular structure of CPAM was characterized by Fourier transform infrared spectra (FT-IR) and ¹H nuclear magnetic resonance spectrum (¹H-NMR). The morphology of CPAM particles has been investigated by transmission electron microscope (TEM). Results showed that CPAM was the copolymer of AM and DMC and the particles of CPAM were uniform spheres (the size was about 200?nm). The synthetic conditions of CPAM have been studied and optimized by single-factor experiments. An optimized product was obtained at an intrinsic viscosity of 560?mL/g with a total monomer concentration of 25% and initiator concentration V50 of 0.2% (based on the total monomer mass). The amount of emulsion was 6% and the HLB (Hydrophile-Lipophile-Balance) of emulsion was 7.3. In addition, the flocculation property of CPAM was evaluated with kaolin suspension using jar test, and the result demonstrated that the flocculation property of CPAM performed better than kaolin flocculation.     

in vitro biological evaluation of folate-functionalized block copolymer micelles for selective anti-cancer drug delivery

The main objective of this study was to evaluate the ability of folic acid-functionalized diblock copolymer micelles to improve the delivery and uptake of two poorly water-soluble anti-tumor drugs, tamoxifen and paclitaxel, to cancer cells through folate receptor targeting. The diblock copolymer used in this study comprised a hydrophilic poly[2-(methacryloyloxy)ethyl phosphorylcholine] (MPC) block, carrying at the chain end the folate targeting moiety, and a pH-sensitive hydrophobic poly[2-(diisopropylamino)ethyl methacrylate] (DPA) block (FA-MPC-DPA). The drug-loading capacities of tamoxifen- and paclitaxel-loaded micelles were determined by high performance liquid chromatography and the micelle dimensions were determined by dynamic light scattering and transmission electron microscopy. Cell viability studies were carried out on human chronic myelogenous leukaemia (K-562) and colon carcinoma cell lines (Caco-2) in order to demonstrate that drug-loaded FA-MPC-DPA micelles exhibited higher cytotoxicities toward cancer cells than unfunctionalized MPC-DPA micelles. Uptake studies confirmed that folate-conjugated micelles led to increased drug uptake within cancer cells, demonstrating the expected selectivity toward these tumor cells.     

pH-responsive Polymersome Based on PMCP-b-PDPA as a Drug Delivery System to Enhance Cellular Internalization and Intracellular Drug Release

Choline phosphate(CP) as a novel zwitterion possesses specific and excellent properties compared with phosphorylcholine(PC), as well as its polymer, such as poly(2-(methacryloyloxy)ethyl choline phosphate)(PMCP), has been studied extensively due to its unique characteristics of rapid cellular internalization via the special quadrupole interactions with the cell membrane. Recently, we reported a novel PMCP-based drug delivery system to enhance the cellular internalization where the drug was conjugated to the polymer via reversible acylhydrazone bond. Herein, to make full use of this feature of PMCP, we synthesized the diblock copolymer poly(2-(methacryloyloxy)ethyl choline phosphate)-b-poly(2-(diisopropylamino)ethyl methacrylate)(PMCP-b-PDPA), which could self-assemble into polymersomes with hydrophilic PMCP corona and hydrophobic membrane wall in mild conditions when the p H value is ≥ 6.4. It has been found that these polymersomes can be successfully used to load anticancer drug Dox with the loading content of about 11.30 wt%. After the polymersome is rapidly internalized by the cell with the aid of PMCP, the loaded drug can be burst-released in endosomes since PDPA segment is protonated at low p H environment, which renders PDPA to transfer from hydrophobic to hydrophilic,and the subsequent polymersomes collapse thoroughly. Ultimately, the "proton sponge" effect of PDPA chain can further accelerate the Dox to escape from endosome to cytoplasm to exert cytostatic effects. Meanwhile, the cell viability assays showed that the Dox-loaded polymersomes exhibited significant inhibitory effect on tumor cells, indicating its great potential as a targeted intracellular delivery system with high efficiency.     

Thermal stability and fire retardancy of PMMA (nano)composites with layered metal hydroxides containing dodecyl sulfate anions

Layered double hydroxides (LDHs) with Mg/Al, Zn/Al, Ca/Al metal hydroxide layers, and a Zn/Ni hydroxy double salt (HDS) were prepared with a common anion, dodecyl sulfate [CH₃(CH₂)₁₀COO^?, DS]. The LDH and HDS additives were melt blended with poly(methyl methacrylate) (PMMA). The dispersion and morphology were characterized via X‐ray diffraction (XRD) and transmission electron microscopy. Mg/Al‐DS and Zn/Al‐DS LDHs were found to form nanocomposites with PMMA, exhibiting good dispersion and some degree of exfoliated morphology for the Zn/Al‐DS/PMMA combination and mixed intercalation and exfoliation behavior for Mg/Al‐DS in PMMA. The Ca/Al‐DS LDH and Zn/Ni‐DS HDS formed microcomposites with PMMA. Thermal stability was investigated via thermogravimetric analysis; each of the additives increased the thermal stability of PMMA. Cone calorimetry was used to measure the fire properties; the microcomposite of Zn/Ni‐DS HDS at 10% loading provided the best improvement in peak heat release rate, with a 40% reduction over the pure polymer. The residue composition after burning the composites was investigated. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectral and kinetic characteristics of formyl-substituted spiropyran in poly(methyl methacrylate) modified with elastomers

The efficiency of photochemical transformations of 1′,3′,3′-trimethyl-6′-formyl-8′-allylspiro[2H-1-benzopyran-2,2′-indoline] in PMMA modified with small amounts of poly(ethyl acrylates) of different structures is studied. It is shown that, in the presence of these additives, the quantum yield of the coloring reaction of the photochromic compound under UV irradiation and the rates of photochemical reactions (forward and back) increase. The maximum efficiency of photochemical parameters is observed for PMMA containing small amounts of linear poly(ethyl acrylate) occurring as a microphase in a glassy matrix.     

pH-sensitive vesicles based on a biocompatible zwitterionic diblock copolymer

Highly biocompatible pH-sensitive diblock copolymer vesicles were prepared from the self-assembly of a biocompatible zwitterionic copolymer, poly[2-(methacryloyloxy)ethyl phosphorylcholine-block-2-(diisopropylamino)ethyl methacrylate], PMPC-b-PDPA. Vesicle formation occurred spontaneously by adjusting the solution pH from pH 2 to above 6, with the hydrophobic PDPA chains forming the vesicle walls. Transmission electron microscopy (TEM), dynamic laser light scattering (DLS), and UV-visible absorption spectrophotometry were used to characterize these vesicles. Gold nanoparticle-decorated vesicles were also obtained by treating the vesicles with HAuCl4, followed by NaBH4.     

pH-responsive nanoaggregation of diblock phosphorylcholine copolymers

We have characterized three diblock copolymers bearing zwitterionic phosphorylcholine and weak tertiary amine groups, namely, poly[((2-(methacryloyloxy)ethyl)phosphorylcholine)30- block-(2-(dimethylamino)ethyl methacrylate)60] (denoted as MPC30-DMA60, Mn=18,000), poly[((2-(methacryloyloxy)ethyl)phosphorylcholine)30- block-(2-(diethylamino)ethyl methacrylate)60) (denoted as MPC30-DEA60, Mn=20,000), and poly[((2-(methacryloyloxy)ethyl)phosphorylcholine)30- block-(2-(diisopropylamino)ethyl methacrylate)60) (denoted as MPC30-DPA60, Mn=21,000), by studying their surface tension and solution aggregation through a combined approach of surface tension measurement, dynamic light scattering, and small-angle neutron scattering. Our results show that larger tertiary amine substituents lead to an increasing tendency to form micellar aggregates, which is consistent with the increasing copolymer hydrophobicity. Thus, MPC30-DMA60 did not aggregate under the experimental conditions studied. The free chains exist in the form of thin cylinders, whose length decreases with copolymer concentration and solution temperature but increases with solution pH. The diameters of the MPC30-DMA60 cylinders remained almost constant at around 30 A under all the conditions studied. At the lower copolymer concentration of 0.5 wt %, the cylindrical lengths correspond to the persistence length of the copolymer backbone and are close to its full length, indicating a rather high rigidity. Further data analysis showed that, at the two higher concentrations of 2 and 4 wt %, the phosphorylcholine and amine blocks associate, inducing bending of the copolymer backbone. One backbone kink was required to satisfy all the constraints, including the dry volume of the copolymer. MPC30-DEA60 showed a similar trend of pH- and concentration-dependent conformational responses for the free copolymer, but in addition micellar aggregation occurred at pH 9. In contrast, MPC30-DPA60 exhibited significantly reduced solubility associated with strong aggregation, which is consistent with it being the most hydrophobic copolymer in the series.     

Synthesis and properties of tocopherol-containing polymeric vesicle systems

Two different tocopherol-containing amphiphilic monomers, [ [ (tocopheryloxy)-carbonyl ]-methyl ] [ 2-(methacryloyloxy)ethyl ]dimethyl-ammonium chloride(3a) and [[ (tocopheryloxy)penta(ethoxy)carbonyl ]methyl ]2-(methacryloyloxy)ethyl]dimethylammonium chloride(3b), were synthesized and polymerized. The formation of polymeric closed vesicles having diameters ranging from 200 to 5200 Å was confirmed by electron micrographs, entrapment of [¹⁴C]sucrose, permeability measurements and gel filtration. The polymeric vesicles showed reduced permeability and enhanced thermodynamic stability. Antioxidative activities were determined by the thiocyanate method confirming that polymeric tocopherols also exhibited significant activities.     

Poly[2-(methacryloyloxy)ethylphosphorylcholine]-coated iron oxide nanoparticles: synthesis, colloidal stability and evaluation for stem cell labelling

Poly[2-(methacryloyloxy)ethylphosphorylcholine]-coated SPIONs were prepared through ATRP and amidation coupling reactions. The coated SPIONs exhibited high stability and re-dispersability in phosphate buffered saline and uptake in a stem cell line, with high T(2) relaxivity.     

Bialkyls from dialkylmetals I. Photochemistry and mass spectra of some (2-cyanoethyl)- and [2-(methoxycarbonyl)ethyl]metals

We have studied the photolysis and the fragmentation in the mass spectrometer of bis(2-cyanoethyl)mercury, bis(2-cyanoethyl) selenide, bis(2-cyanoethyl) sulphide, dibutylbis(2-cyanoethyl)stannane, and bis[2-(methoxycarbonyl)ethyl] selenide. The mercury compound gave a high yield of adiponitrile on photolysis and in the mass spectrometer it gave the fragmentation pattern of adiponitrile, including the molecular ion, as part of the total fragmentation pattern. A low yield of bialkyl was also formed on photolysis of the bis[2-(methoxycarbonyl)ethyl] selenide but no peaks corresponding to biakyl were observed in the mass spectrum. None of the other compounds yielded alkyl dimer.

A preliminary discussion of the results in terms of orbital symmetry is presented.     

Temperature‐responsive linear polyelectrolytes and hydrogels based on [2‐(methacryloyloxy)ethyl] trimethylammonium chloride and N‐isopropylacrylamide and their complex formation with potassium hexacyanoferrates (II,III)

Water‐soluble temperature‐responsive polyelectrolytes and hydrogels have been synthesized by γ‐radiation copolymerization of [2‐(methacryloyloxy)‐ethyl]trimethylammonium chloride with N‐isopropylacrylamide. Complex formation of soluble copolymers with potassium hexacyanoferrates (II, III) was studied in aqueous solutions. It was shown that, depending on the concentration and temperature, the formation of soluble or insoluble polycomplexes is observed. The hydrogels show good ability to absorb potassium hexacyanoferrates (II, III) from aqueous solutions. Sorption ability of hydrogels depends on the content of cationic monomer in copolymer and the nature of coordination ion. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 515–522, 2004     

Synthesis of biocompatible poly[2-(methacryloyloxy)ethyl phosphorylcholine]-coated magnetite nanoparticles

A well-defined, double-hydrophilic diblock copolymer comprising poly[2-(methacryloyloxy)ethyl phosphorylcholine]-block-(glycerol monomethacrylate) (PMPC30-PGMA30, where the numbers represent the average degrees of polymerization for each block) was evaluated for the synthesis of colloidally stable ultrafine magnetite sols. Sterically stabilized paramagnetic sols were prepared in aqueous solution by chemical coprecipitation of ferric and ferrous salts in the presence of this block copolymer. The PMPC30-PGMA30-stabilized magnetite sol had a mean transmission electron microscopy (TEM) diameter of 9.4 +/- 1.7 nm and a mean hydrodynamic diameter of 34 nm. This sol exhibited improved colloidal stability with respect to long-term storage and pH variation compared with magnetite sols prepared in the presence of alternative water-soluble homopolymers and diblock copolymers. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetry, electron spectroscopy imaging (ESI), and zeta potential studies indicate that the PMPC30-PGMA30 diblock copolymer was adsorbed onto the surface of the sol via the PGMA30 block, with the PMPC30 chains acting as the stabilizing block. Such sterically stabilized sols are expected to be improved contrast agents for magnetic resonance imaging (MRI) applications.     

Variation of anions in layered double hydroxides: Effects on dispersion and fire properties

Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of the nanocomposites while the thermal stability and fire properties of nanocomposites were studied by thermogravimetric analysis and cone calorimetry; the mechanical properties are also investigated. In general, it is easier to disperse these organo-LDHs in PMMA than in PS, but the sulfate cannot be dispersed at the nanometer level in either material. The addition of these organo-LDHs does not affect the mechanical properties. The best fire properties are obtained with the sulfonate LDH, SDBS; the reduction in the peak heat release rate is almost 50% for both polymers.     

Bis[2-(4-pyridyl)ethyl](2-cyanoethyl)phosphine Oxide: Synthesis and Reactions with 1,4-Dihalobutanes

Russian Journal of General Chemistry - Bis[2-(4-pyridyl)ethyl]phosphine reacts with acrylonitrile under mild conditions to form bis[2-(4- pyridyl)ethyl](2-cyanoethyl)phosphine which is readily...     

Surfactant-free miniemulsion polymerization as a simple synthetic route to a successful encapsulation of magnetite nanoparticles

Due to the existing interest in new hybrid particles in the colloidal range based on both magnetic and polymeric materials for applications in biotechnological fields, this work is focused on the preparation of magnetic polymer nanoparticles (MPNPs) by a single-step miniemulsion process developed to achieve better control of the morphology of the magnetic nanocomposite particles. MPNPs are prepared by surfactant-free miniemulsion polymerization using styrene (St) as a monomer, hexadecane (HD) as a hydrophobe, and potassium persulfate (KPS) as an initiator in the presence of oleic acid (OA)-modified magnetite nanoparticles. The effect of the type of cross-linker used [divinylbenzene (DVB) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP)] together with the effect of the amount of an aid stabilizer (dextran) on size, particle size distribution (PSD), and morphology of the hybrid nanoparticles synthesized is analyzed in detail. The mixture of different surface modifiers produces hybrid nanocolloids with various morphologies: from a typical core-shell composed by a magnetite core surrounded by a polymer shell to a homogeneously distributed morphology where the magnetite is uniformly distributed throughout the entire nanocomposite.