Vinylbenzyltrimethylammonium Chloride Research Articles

Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 8. Selectivity at Poly(vinyl alcohol)-Polyelectrolyte Blend Modified Optically Transparent Electrodes

Poly(vinyl alcohol) (PVA)-based polymer blends show potential utility as polymer films for a newly designed spectroelectrochemical sensor to achieve three modes of selectivity: charge-selective partitioning, electrolysis potential, and spectral absorption wavelength. The polymer blends were formulated by entrapping two polyelectrolytes, poly(vinylbenzyltrimethylammonium chloride) (PVTAC) and poly(acrylic acid) (PAA) into a cross-linked PVA matrix, which was covalently coated onto the surface of ITO glass. Sensing of the analyte is based on the change in attenuation of the light guiding through an optical substrate resulting from an electrochemical reaction of the analyte induced by electromodulation. The signal of the analyte in a competitive binary system is isolated by careful choice of polymer modifying film, potential window and monitoring wavelength. A 10−4 M equimolar binary solution of Ru(BiPy)32+ and Fe(CN)63– was used to study the selectivity of charge-selective partitioning. Cyclic voltammograms clearly demonstrated the exclusion of same charged ions from the selective layer with polymer blend modified sensors. 10−4 M equimolar Ru(CN)64– and Fe(CN)64– was chosen to demonstrate the selectivities of electrolysis potential and spectral absorbance wavelength. The detailed kinetics and associated electrochemical and optical waveforms from the spectroelectrochemical sensors in competitive binary mixtures of analytes are presented.

Preparation of core-shell polystyrene-polyimide particles by dispersion polymerization of styrene using poly(amic acid) as a stabilizer

Dispersion polymerization of styrene (S) and vinylbenzyltrimethylammonium chloride (VBA) was conducted in an ethanol-water medium using an aromatic poly(amic acid) (PAA) as the stabilizer. When equimolar amounts of VBA and the carboxylic acid of PAA were used, monodisperse particles with high PAA content were obtained quantitatively. The imidization of PAA on the particles proceeded with acetic anhydride and N,N-dimethylaminopyridine to form core-shell PS-polyimide particles.

Preparation of microcapsules of strong polyelectrolyte couples by one-step complex surface precipitation

Polyelectrolyte microcapsules are fabricated by a one-step surface precipitation and by a layer-by-layer technique on decomposable colloids. The ternary solvent water/acetone/sodium bromide is adjusted properly keeping dissolved simultaneously the strong polyelectrolytes sodium poly(styrene sulfonate) and poly(vinyl benzyl trimethylammonium chloride). Microcapsules are characterized by confocal laser scanning microscopy and scanning force microscopy. The capsules are dissolvable in the ternary solvent. Other dissolved strong polyelectrolyte couples and template-free preparation pathways are suggested.

Structural stabilities of sulfonated manganese tetramesitylporphyrin and its β-brominated analogue toward NaOCl, H 2O 2 and (CH 3) 3COOH

This article gives the degradation rate constants of meso-tetrakis(3,5-disulfonatomesityl)porphinatomanganese(III) X (where X=H 2O and/or OH − depending on pH) (MnTMSP) and its β-brominated analogue (MnTMSPBr 8) toward the oxidants NaOCl, H 2O 2, and (CH 3) 3COOH at various pHs, I=0.2 M and 30°C. In addition, the degradation rate constants of MnTMSP was determined when it was bound to cationic supports — namely, CTAB, a poly(vinylbenzyltrimethylammonium chloride) latex, 2,6-ionene and 2,10-ionene. MnTMSP showed high structural stability toward the peroxides in strong acidic medium and the degradation rate constants were found as low as 10 −4 min −1 at pH<1.50. When NaOCl was employed as the oxidant, the pH dependence of the stability of MnTMSP was vice versa and its degradation rate constant was determined as 1.43×10 −4 min −1 at pH 14.10. In strong acidic solution, the supports CTAB and latex made the stability of MnTMSP toward the peroxides improve significantly. In strong basic solution, only latex-bound MnTMSP showed higher stability toward NaOCl than the homogeneous MnTMSP. Because MnTMSPBr 8 was not stable in solutions having pH higher than 9 and containing no oxidant, its stability was investigated at pH<9 and it showed slightly lower stability toward the peroxides than the non-brominated analogue.

A supramolecular structured complex of poly(acrylic acid) and polystyrene‐block‐poly(vinylbenzyltrimethylammonium chloride)

A supramolecular structured complex of poly(acrylic acid) and polystyrene‐block‐poly(vinylbenzyltrimethylammonium chloride)

Emulsifier-free emulsion copolymerization of styrene with quaternary ammonium cationic monomers

Emulsifier-free emulsion binary copolymerizations of styrene with four types of quaternary ammonium cationic monomers, diallyldimethylammonium chloride (DADMAC), (3-(methacryloylamino) propyl) trimethyl ammonium chloride (MAPTAC), (2-methacryloyloxy) ethyl) trimethyl ammonium chloride (MATMAC), and vinylbenzyl trimethyl ammonium chloride (VBTMAC), were conducted at 70°C. 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (V50) and potassium persulphate (KPS) were used as cationic and anionic initiator, respectively. Ternary copolymerizations were also carried out in the presence of acrylamide as a second comonomer. Monomer conversions were followed by ultraviolet spectroscopy and the polymer microparticles were characterized using photon correlation spectroscopy, electrophoresis, colloid titration, and scanning electron microscopy. The results indicated that VBTMAC and MATMAC were highly reactive in the copolymerization with styrene whereas the incorporation of DADMAC was slow. MAPTAC had an intermediate reactivity. Binary copolymerization with VBTMAC, MATMAC, and MAPTAC produced particles smaller in size, but higher in surface-charge density, than styrene homopolymer particles. However, significant agglomerates were detected in the VBTMAC and MATMAC-containing latexes. In contrast, DADMAC-containing polymer particles were almost identical to styrene particles. Continuous nucleation took place in the binary copolymerizations with VBTMAC and with MATMAC when using V50 initiator. In the case of using KPS, VBTMAC-containing particles grew continuously to a mean size much larger than the corresponding particles initiated by V50. The presence of acrylamide reduced DADMAC-containing particle size and diminished the agglomeration in the VBTMAC- and MATMAC-containing latexes. The results were interpreted via particle formation mechanism. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1129–1140, 2000

A supramolecular structured complex of poly(acrylic acid) and polystyrene-block-poly(vinylbenzyltrimethylammonium chloride)

Complexation of poly(acrylic acid) (PAA) by polystyrene-block-poly(vinylbenzyltrimethyl- ammonium chloride) (PS-b-VB) results in a mesomorphously ordered material with a glass transition temperature of 71 °C. The complex is assumed to consist of hexagonally-ordered ion-rich cylindrical rods containing the PAA embedded in a polystyrene matrix. It has been shown by small-angle X-ray scattering (SAXS) analysis that the mesophase is characterized by sharp phase boundaries between ionic and non-ionic regions. The structure parameters are evaluated by using a two-dimensional interface distribution function resulting in an average cylinder radius in the range 3.0-3.5 nm and a lattice constant of 14nm. The radius distribution is calculated to be relatively broad, which is found to be consistant with sharp phase boundaries. PS-b-VB-PAA represents an example of a new type of polymeric hybrid material with a supramolecular ordered ionic-non-ionic nanostructure. # 2000 Society of Chemical Industry

Structural stabilities of water‐soluble MnTDCSPP, MnTSPP, and supported analogues toward hydrogen peroxide and sodium hypochlorite

This article describes the structural stabilities of 5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphinatomanganese(III) X (X: OH−, H2O) (MnTDCSPP), 5,10,15,20-tetra(4-sulfonatophenyl)porphinatomanganese(III) X (X: OH−, H2O) (MnTSPP) and their supported analogues toward H2O2 and NaOCl or HOCl depending on pH. The supports employed were hexadecyltrimethylammonium bromide (CTAB), 2,6-ionene, 2,10-ionene and a poly(vinylbenzyltrimethylammonium chloride) latex, which all contain quaternary ammonium groups. In the strong basic medium, both manganese porphyrins showed high stabilities toward NaOCl but relatively lower stabilities toward H2O2, and the resistance of MnTDCSPP to degradation was higher than that of MnTSPP. In the acidic solution, both porphyrins showed increasing stabilities toward H2O2 as the pH went down. Toward HOCl, MnTSPP did not show any stability in the neutral and acidic solutions, whereas MnTDCSPP showed some. The supports made some influence on their stabilities. In general, the ionenes affected their stabilities adversely, and the latex and CTAB did positively. Especially when they were bound to CTAB, they were not degraded by H2O2 at pH < 2. The pseudo-first-order degradation rate constants of MnTDCSPP, MnTSPP, and their supported analogues at different pHs at 30°C were determined. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 271–278, 2000

Paper sizing agents from micelle-like aggregates of polystyrene-based cationic copolymers

A series of polystyrene-based cationic copolymers (PSCC) were synthesized by copolymerization of styrene and the cationic comonomer vinylbenzyl trimethylammonium chloride. These copolymers can be used as internal paper sizing agents in a broad pH range. The effect of the charge density on the PSCC colloid properties was investigated. It was found that at room temperature the PSCC could change from water insoluble to colloidally dispersible and finally to fully water soluble as the charge density was increased. Based on the understanding of their colloid behavior, PSCCs were applied as internal sizing agents for paper. The results showed that the hydrophobicity of handsheets could be significantly improved by PSCCs and the sizing performance was a function of copolymer addition, charge density, particle size, drying temperature, and pH conditions. The present study indicated some potential advantages of PSCC copolymers as internal sizes. PSCC can be self-retained on the fiber surface, no hydrolysis occurs during the storage and application, and no sizing reversion occurs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2067–2073, 2000

Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 4. Sensing with Poly(vinyl alcohol)−Polyelectrolyte Blend Modified Optically Transparent Electrodes

The feasibility of using polymer blend thin films covalently attached to indium tin oxide-glass, via the silane coupling agent (3-aminopropyl)triethoxysilane, for performing spectroelectrochemical modulation is demonstrated in aqueous solutions. The polymer blends were formulated by entrapping three polyelectrolytes-poly(vinylbenzyltrimethylammonium chloride) (PVTAC), poly(acrylic acid), and Nafion-in cross-linked poly(vinyl alcohol) (PVA) matrix for the purpose of selectively incorporating solution-phase anions and cations. Ru(BiPy) 3 2+ (BiPy = 2,2'-bipyridine), Ru(CN) 6 4- , and Fe(CN) 6 3- were chosen as the analytes for their suitable optical and electrochemical properties. Peak current enhancements, compared with the bare electrode under the same conditions, ranging from 2 to 7 were observed for these systems with the largest being for Fe(CN) 6 3- at an electrode coated with PVA-PVTAC blend. The optical absorbance change under attenuated total reflection during cyclic voltammetry (spectroelectrochemical modulation) was observed for all systems. The effects of potential window, electrochemical reversibility of the analyte, and potential scan rate on the resulting absorbance-time plot for modulation by cyclic voltammetry are reported for the different analyte-polymer blend systems. The modulation transfer ratios of analyte-polymer systems were studied. Modulation at 450 nm resulting from oxidation/reduction of the Ru(BiPy) 3 2+/3+ couple at 1.30 and 0.90 V vs Ag/AgCl with varying concentrations was used to construct analytical working curves for the spectroelectrochemical sensor.

Synthesis of polystyrene-based cationic copolymers and their colloidal properties in water

A series of polystyrene-based cationic copolymers was synthesized by two different methods: (1) solution copolymerization of styrene and vinylbenzyl trimethylammonium chloride (VBTMAC) in ethanol, and (2) surfactant-free emulsion copolymerization of styrene and vinylbenzyl chloride in water followed by reaction with trimethylamine. The results indicated that the different synthesis methods would result in different polymer structures and, therefore, affect the solubility and colloidal properties of the copolymers in water. For the copolymers prepared by method 2, partial crosslinking was observed. The copolymers made by this method are almost water-insoluble. In contrast, the copolymers made from direct copolymerization of styrene and VBTMAC in ethanol are water-soluble or dispersible, but the solubility and the particle size of microaggregates formed by these copolymers in water strongly depend on charge density and temperature. One of the important results from this study is that uniform colloidal particles with a very small particle size (30–50 nm) can be obtained by dispersing polystyrene-based cationic copolymers in water without adding any surfactants.

Surface Charge Dependence of Polyelectrolyte-Induced Domain Size and Composition in Lipid Bilayer Membranes

2H NMR spectroscopy was used to investigate the response of specifically choline-deuterated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) to changes in surface electrostatic charge in lipid bilayer membranes consisting of mixtures of POPC with the anionic lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG), plus the cationic polyelectrolyte poly(vinylbenzyltrimethylammonium chloride) (PVTA). The 2H NMR spectra consisted of two overlapping Pake powder patterns, indicating the coexistence of two lipid domains with only slow exchange of lipids between the two. There was no evidence of any nonbilayer lipid arrangements. Analysis of the quadrupolar splittings of the two 2H NMR spectral components for POPC-α-d2 versus POPC-β-d2 demonstrated that the two domains differ with respect to their overall surface charge environments and that the PVTA-bound domain was enriched with respect to anionic lipids while the PVTA-free domain was depleted. When the initial bilayer POPG content was varied, the number of POPG molecules associated with each bound PVTA molecule remained constant at a 1:1 POPG anion: PVTA cation equivalents ratio. However, the number of POPC molecules associated with each bound PVTA molecule increased with decreasing initial POPG content. Thus, the surface area occupied per PVTA domain expanded or contracted as the available oppositely charged POPG decreased or increased. This indicates that the PVTA/POPG complex is behaving at the surface like a two-dimensional random-coil polymer undergoing swelling by a solvent, POPC. Within the PVTA-bound domain, the 2H NMR quadrupolar splittings suggest that the PVTA/POPG complex penetrates more deeply into the lipid bilayer than does POPG alone, as might be expected for a neutralized salt pair.

Formulation, Characterization, and Sensing Applications of Transparent Poly(vinyl alcohol)−Polyelectrolyte Blends

Several new optically clear polymer blends have been formulated for selectively incorporating solution-phase anions and cations. In all of the blends poly(vinyl alcohol) was the host matrix and it was cross-linked with glutaraldehyde to entrap polyelectrolytes including poly(acrylic acid), Nafion, poly(diallyldimethylammonium chloride), poly(vinylbenzyltrimethylammonium chloride), and poly(styrenesulfonic acid). [Ru(BiPy)3]2+ and Fe(CN)63- were used as prototypical analytes to study the ion-exchange properties of the new blends. The thicknesses of spin-coated thin films of the blends were variable over a wide range (0.70 μm being typical), as determined by an optical interference method. Thin film coatings of three of the blends were optimized for single-step covalent coating on activated oxide surfaces. Two silane coupling agents, 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane, were used to covalently attach these three blends to glass and ITO-coated glass surfaces. The potential use of these materials for chemical sensing has been demonstrated by applying them to multiple internal reflection and spectroelectrochemical devices as thin films.

Effects of Mordant Type and Placement on Inkjet Receiver Performance

We have investigated the effect of two common dye mordants, poly(vinylbenzyl trimethyl ammonium chloride) (PVBTMAC) and poly(diallyldimethyl ammonium chloride) (PDADMAC) on the image stability of inkjet prints generated by two Hewlett Packard inksets. The effect of mordant placement in the coated structure (top, bottom, or throughout) was studied using optical cross sectional micrographs and correlated with the stability data.

Characterization of Cationic Polyelectrolyte-Induced Domains in Mixed POPG−POPC Lipid Bilayers via 2H NMR

The interactions of a cationic polyelectrolyte, poly(vinylbenzyltrimethylammonium chloride) (PVTA), with anionic lipid bilayer membranes composed of a mixture of phosphatidylglycerol (POPG) plus phosphatidylcholine (POPC) have been examined using 2H NMR of choline-deuterated POPC to probe membrane surface electrostatics. PVTA produces distinct membrane domains containing a 1:1 PVTA/POPG cation/anion charge ratio. The remaining PVTA-free domains are depleted with respect to POPG.

Polymer-clay nanocomposites: Free-radical grafting of polystyrene on to organophilic montmorillonite interlayers

Vinyl monomer-montmorillonite intercalates, which are able to swell and disperse in organic solvents, have been prepared by a cation exchange process by the interaction between the Na+ or Ca2+ cations of montmorillonite and vinylbenzyltrimethylammonium chloride. The resulting vinyl monomer-montmorillonite materials have been identified by X-ray diffraction (XRD), elemental analysis and infrared absorption spectra. Free-radical solution polymerizations of the penetrated styrene between the interlayers of 5, 10, 25 and 50 wt% vinyl monomer-montmorillonite have resulted in grafted polystyrenemontmorillonite materials. The effect of montmorillonite amounts on the formed polystyrene was determined by extraction with organic solvents, which showed an increase in the grafted polymer formed (0.84–2.94 g/g MMT), and a decrease in the external polystyrene with increasing amounts of montmorillonite. The molecular weight of the external polystyrenes was found to be in the range of 22000. The vinyl monomer-montmorillonite and polymer-montmorillonite intercalates have been identified by XRD, elemental analysis and infrared spectroscopy. Examination of the polystyrene-montmorillonite materials by SEM, TEM and XRD showed spherical particles of nanosize about 150–400 nm, and basal spacings of 1.72–2.45 nm.

Polymeric molluscicides containing niclosamide moieties

Polymeric molluscicides containing a niclosamide moiety have been prepared by the chemical reactions of the commercial resins: poly(methacrylic acid),poly(styrene sulfonic acid),poly(chloromethylstyrene), poly (vinylbenzyltrimethylammonium chloride) with niclosamide. The resulting polymers contain the niclosamide active group via a covalent or ionic bond. The release rates of niclosamide were determined in different pH media by UV spectrophotometric analyses. The data of the niclosamide release from the different polymeric systems show that the pH of the medium, the type of linkage between the polymer and the active moiety, and the degree of crosslinking present in the polymer are important factors governing the release rates.

Novel Ion‐Exchange Membranes for Electrodialysis Prepared by Radiation‐Induced Graft Polymerization

Novel ion‐exchange membranes containing sulfonic acid and trimethyl ammonium groups were prepared by a simple method of radiation‐induced cografting of sodium styrenesulfonate (SSS) with acrylic acid (AAc) and vinyl benzyl trimethyl ammonium chloride (VBTAC) with 2‐hydroxyethyl methacrylate (HEMA), onto a polyethylene film with a thickness of 50 μm. The high density graft chain was introduced throughout the polyethylene film. The maximum cation‐ and anion‐exchange capacities of the resultant membranes were 2.5 and 1.3 mol/kg, respectively. These membranes exhibited an electrical resistance one order lower than commercially available ion‐exchange membranes; for example, 12 h cografting provided cation‐ and anion‐exchange membranes whose electrical resistances in a solution were 0.25 and 0.85 Ω cm2, respectively. From the evaluation of electrodialytic desalination in a batch mode, using a pair of the graft‐type ion‐exchange membranes, the time required to achieve 99.5% desalination of the initial solution was reduced to 85% comparing with that of the commercial ion‐exchange membranes.

Cationic polymer colloid for promotion of nucleophilic displacements in aqueous medium

A cationic latex I was prepared by emulsion polymerization of styrene, 50 mol.% of chloromethylstyrene, 1 mol.% of divinylbenzene, 2 mol.% of vinylbenzyltrimethylammonium chloride followed by treatment of the obtained polymer with trimethylamine. This colloidal polymer I showed good activity for promotion of the reaction of the sodium salts of carboxylic acids and alkyl halides in an aqueous medium. Good yields of esters were obtained and no coagulation of the latex was observed under the reaction conditions.

Binding of Ionic Pyrene Derivatives to Polyelectrolytes. A Uv Absorption and Fluorescence Study

Abstract The binding of pyrenesulfonic acid and pyrenebutyric acid to poly(vinyl benzyl trimethylammonium) chloride was investigated by UV and fluorescence spectroscopy. It was found that the binding constant was 7.5 × 104 and 3.5 × 104M−1, respectively. The addition of the polyelectrolyte quenches the fluorescence of the pyrene group, and at the same time the typical excimer emission appears. This emission originates in pre-formed ground state aggregates of the pyrene derivatives incorporated into the polyion domain. Similar effects were observed when anionic polyelectrolytes, poly(styrene sulfonic), and poly(vinyl sulfonic) acids were added to cationic pyrene derivatives. The binding constants depend on the length of the aliphatic sidechain of the derivatives.