Predicting the outcomes of interpolyelectrolyte neutralization at surfaces on the basis of complexation experiments and vice versa.

This study was carried out with the aim of establishing how the outcomes of polyelectrolyte multilayer formation can be predicted on the basis of the results of complexation studies in solution and vice versa. For this purpose, the correlation between the processes of complex and multilayer formation involving three pairs of vinylic polyions in solutions of binary 1 : 1 sodium salts (NaX; X = F, Cl, Br, I, NO3, ClO4) was explored by means of dynamic and electrophoretic light scattering, potentiometry, microcalorimetry, spectrophotometry and quartz crystal microbalance. The gradual reactant mixing in solution at lower salt concentrations resulted in a Fuoss-Sadek sequence of events (primary complexes → secondary complexes → 1 : 1 flocculate), whereby the obtained nano-complexes could be successively overcharged. At high salt concentration and with excess polycation present, metastable nano-complexes and precipitates containing surplus of positively charged monomers were formed. The amount of extrinsically compensated charge was in accord with the polycation affinities toward counteranions, established by monitoring the electrolyte-induced aggregation of positively charged nano-complexes. Perfect analogy with respect to counteranion influence on the amount of adsorbed polycation was noticed for corresponding multilayers. Aside from providing a deeper understanding of interpolyelectrolyte neutralization, the gained insights can also be used to steer the polyelectrolyte multilayer composition and properties.

Interactions of zein and zein/rosin nanoparticles with natural polyanion gum arabic.

The objective of this study was to investigate interactions of zein (Z) and zein/rosin (Z/R) nanoparticles with gum arabic (GA), at different pH. Nanoparticles were firstly prepared by antisolvent precipitation of biopolymers from aqueous ethanol solutions. Nanoparticles suspensions were then dialyzed against water in order to remove ethanol and other impurities, and water suspensions of zein and zein/rosin nanoparticles were obtained. It was shown that composition of nanoparticles affects their surface charge density. Zeta potential of nanoparticles was positive without GA and changed to negative after addition of GA, at all pH tested. SEM analysis proved both Z and Z/R nanoparticles to be spherical and in size around 200 nm. The effect of addition of GA on particle size was determined using dynamic light scattering method. It was found that addition of GA increases size of nanoparticles at pH = 4 and pH = 5.5, from 150 - 220 nm to 250 - 320 nm. However, at pH = 3 it causes aggregation process, and diameter of particles increases up to few micrometres. Isothermal titration calorimetry was used to measure enthalpy changes in reaction between Z or Z/R nanoparticles and GA. Results showed that reaction between GA and Z or Z/R NPs is exothermic at each pH tested, except for Z NPs at pH = 3, where it was endothermic. At presented pHs, Z/R NPs were less charged compared to Z NPs, and their surface get saturated with GA molecules more rapidly. Z NPs showed greater enthalpy change in reaction with GA, compared to Z/R NPs.

Soft nanotechnology: the potential of polyelectrolyte multilayers against E. coli adhesion to surfaces.

Preventing bacterial attachment to surfaces is the most efficient approach to controlling biofilm proliferation. The aim of this study was to compare anti-adhesion potentials of 5 and 50 mmol/L polyelectrolyte multilayers of poly(allylamine hydrochloride)/poly(sodium 4-styrenesulfonate), poly(4-vinyl-N-ethylpyridinium bromide)/ poly(sodium 4-styrenesulfonate), and poly(4-vinyl-N-isobutylpyridinium bromide)/poly(sodium 4-styrenesulfonate) against Escherichia coli. Glass surface was covered with five polyelectrolyte layers and exposed to bacterial suspensions. Poly(4-vinyl-N-ethylpyridinium bromide)/poly(sodium 4-styrenesulfonate) was the most effective against bacterial adhesion, having reduced it by 60 %, followed by poly(4-vinyl-N-isobutylpyridinium bromide)/poly(sodium 4- styrenesulfonate) (47 %), and poly(allylamine hydrochloride)/poly(sodium 4-styrenesulfonate) (38 %). Polyelectrolyte multilayers with quaternary amine groups have a significant anti-adhesion potential and could find their place in coatings for food, pharmaceutical, and medical industry.