FTIR-ATR studies of diffusion and perturbation of water in polyelectrolyte thin films. Part 4. Diffusion, perturbation and swelling processes for ionic solutions in SPEES/PES membranes

We report diffusion rates and equilibrium concentrations of water in a polyelectrolyte SPEES/PES film using ATR/FTIR spectroscopy. The data for water obtained by fitting spectral intensities to a dual mode diffusion model in the presence of different counter ions (at 0.2 mol dm⁻³) follow the order Li⁺>Cs⁺>Na⁺>Ca²⁺>K⁺. Diffusion is progressively slower for higher concentrations of NaCl (0.2-0.85 mol dm⁻³) and the NO₃⁻ counter anion leads to a faster diffusion rate than for Cl⁻ at the same concentration. Both water uptake and diffusion rates are broadly consistent with expectations based on the differential degrees of swelling, caused by changes in the SO₃⁻/SO₃⁻ interpolymer chain repulsive forces leading to a decrease in volume diffusion compared with the value for pure water. Direct spectral measurements of the degree of swelling confirm that the process does occur, although the order of the swelling amounts does not map directly onto that of the diffusion rates. This is probably because the interfacial dissociation processes are hydration dependent.     

pH and salt responsive poly(N,N-dimethylaminoethyl methacrylate) cylindrical brushes and their quaternized derivatives

We present the synthesis and characterization of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) cylindrical brushes, their pH responsiveness, and the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes. PDMAEMA brushes were prepared by atom transfer radical polymerization (ATRP) using the grafting-from strategy. Initiating efficiencies of the ATRP processes were determined by cleaving the side-chains and gel permeation chromatography (GPC) analysis. Due to the slow initiation and steric hindrance, the initiating efficiency is only around 50%. The PDMAEMA brushes show worm-like structures and pH responsiveness, as proven by dynamic light scattering (DLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Strong cationic polyelectrolyte PMETAI brushes were produced by quaternization of the PDMAEMA brushes. AFM and cryo-TEM images showed similar worm-like morphologies for the PMETAI brushes. The PMETAI brushes collapsed in solution with high concentration of monovalent salt, as proven by DLS and AFM results.     

Flory-Huggins parameter of interaction in polyelectrolyle solutions of chitosan and its alkylated derivative

The enthalpy of dilution of chitosan and alkylchitosan solutions in aqueous 0.3 M acetic acid was experimentally studied over the entire concentration range at 298 K, and the values of Flory-Huggins interaction parameter were determined with the help of a new scaling approach which took into account the electrostatic contribution to the enthalpy of dilution of polyelectrolyte solutions. That made it possible to estimate separately the excluded volume contribution to the enthalpy of dilution and, thus, to calculate the values of χ which appeared to be −0.01 for chitosan and −0.21 for alkylchitosan. It was found out that χ did not depend on the presence of salt in the solution. The hydrophobic modification of chitosan enhanced interaction with water due to the hydrophobic hydration in the aqueous solution.     

Proton conducting composite membranes from crosslinked poly(vinyl alcohol) and poly(styrene sulfonic acid)-functionalized silica nanoparticles

Proton conducting membranes based on crosslinked poly(vinyl alcohol) (PVA) and poly (styrene sulfonic acid)-functionalized silica particles (PSSA-Si) were reported. Two-step crosslinking process involving sulfosuccinic acid (SSA) and glutaraldehyde as crosslinking agents was conducted to provide additional proton source and to enhance hydrolytic and mechanical stabilities. PSSA-Si was synthesized from vinyltrimethoxysilane via Stöber method, followed by radical polymerization of sodium 4-vinylbenzenesulfonate on the silica particle. The obtained PSSA-Si was characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The effects of PSSA-Si loading (0, 2.5, 5, and 10%) and PSSA content in PSSA-Si (2, 5, 8, and 12%) on membrane properties including surface morphology, water vapor absorption, water uptake, ion exchange capacity, mechanical and oxidative stabilities, and proton conductivity were investigated and discussed. Proton conductivities of these composite membranes were found to increase with PSSA-Si loading and PSSA content. Promising proton conductivities of ～0.072 S/cm were obtained from PVA-8%PSSA-Si-10 and PVA-12%PSSA-Si-10 membranes, having PSSA-Si loading of 10%, and PSSA contents of 8%, and 12%, respectively. In addition, these membranes showed good hydrolytic and oxidative stabilities with high storage moduli.     

Antimicrobial surface coatings for polypropylene nonwoven fabrics

Anionic and cationic N-halamine polyelectrolytes were synthesized, characterized and then immobilized onto melt-blown polypropylene fabrics having two different basis-weights. The coatings were rendered biocidal upon exposure to dilute sodium hypochlorite solution. The effect of single and multilayer deposition of the polyelectrolytes on the surfaces was investigated in terms of chlorine loadings, rechargeabilities, antimicrobial efficacies, and air permeabilities. It was found that all of the coatings provided remarkable biocidal efficacies with about six log reductions of bacteria within two min of contact time on filters having higher basis-weight, whereas slower inactivation was observed for lower-basis weight filters due to diminished surface areas and numbers of active halogen atoms. The antimicrobial coatings reduced the air permeabilities of the filters somewhat; however, the air permeabilities of the coated swatches were comparable to those of most protective textiles.     

How the interactions with humic acids affect the mobility of ionic dyes in hydrogels – Results from diffusion cells

The complexation of charged compounds by humic acids represents the process of exceptional environmental importance. Nevertheless, traditional methods utilized in the complexation studies do not address the way, how these interactions affect the transport of ions in humic-rich environments. To overcome this dilemma, the diffusion cells technique is proposed as an innovative reactivity mapping technique. Using this method, the diffusion of methylene blue was studied in aqueous solutions and in agarose gels with and without the addition of humic acids. Experimental results clearly illustrate the immobilizing effects of humic acids on the transport of methylene blue in gels. The partitioning of methylene blue at the solution-gel interface and the specific interactions between methylene blue and humic acids is discussed on the basis of experimental data. Effective structural parameters of hydrogels (effective porosity, tortuosity factor) were calculated, as well as some standard diffusion and interaction parameters (diffusion and partition coefficients and apparent equilibrium constants).     

Cationic Conjugated Polyelectrolytes with Molecular Spacers for Efficient Fluorescence Energy Transfer to Dye‐Labeled DNA

Two water‐soluble conjugated polyelectrolytes, poly(9,9′‐bis(6‐N,N,N‐trimethylammoniumhexyl)fluorene‐alt‐1,4‐(2,5‐bis(6‐N,N,N‐trimethylammoniumhexyloxy))phenylene) tetrabromide ( P1i ) and poly((10,10′‐bis(6‐N,N,N‐trimethylammoniumhexyl)‐10H‐spiro(anthracene‐9,9′‐fluorene))‐alt‐1,4‐(2,5‐bis(6‐N,N,N‐trimethylammoniumhexyloxy))phenylene) tetrabromide ( P2i ) are synthesized, characterized, and used in fluorescence resonance energy transfer (FRET) experiments with fluorescein‐labeled single‐stranded DNA (ssDNA‐Fl). P1i and P2i have nearly identical π‐conjugated backbones, as determined by cyclic voltammetry and UV‐vis spectroscopy. The main structural difference is the presence of an anthracenyl substituent, orthogonal to the main chain in each of the P2i repeat units, which increases the average interchain separation in aggregated phases. It is possible to observe emission from ssDNA‐Fl via FRET upon excitation of P2i . Fluorescein is not emissive within the ssDNA‐Fl/ P1i electrostatic complex, suggesting Fl emission quenching through photoinduced charge transfer (PCT). We propose that the presence of the anthracenyl “molecular bumper” in P2i increases the distance between optical partners, which decreases PCT more acutely relative to FRET.     

In vivo Cellular Uptake,Degradation, and Biocompatibility of Polyelectrolyte Microcapsules

Polyelectrolyte microcapsules are made by layer‐by‐layer (LbL) coating of a sacrificial template, followed by decomposition of the template, to produce hollow microcapsules. In this paper, we report on the in vivo cellular uptake, degradation and biocompatibility of polyelectrolyte microcapsules produced from alternating dextran sulphate and poly‐L‐arginine layers on a template of calcium carbonate microparticles. We show that a moderate tissue reaction is observed after subcutaneous injection of polyelectrolyte microcapsules in mice. Within sixteen days after subcutaneous injection, most of the microcapsules are internalized by the cells and start to get degraded. The number of polyelectrolyte layers determines the stability of the microcapsules after cellular uptake.