The geometric characteristics of nanogel particles in aqueous solutions were studied by determining their ratios of radius of gyration (mean-square radius; Rg) to hydrodynamic radius (Rh), Rg/Rh, derived from static light scattering and dynamic light scattering experiments, respectively. The various nanogel samples studied included ones composed of lightly cross-linked N-isopropylacrylamide (NIPA) polymer, NIPA-based anionic or cationic copolymers, and amphoteric terpolymers. Polyelectrolyte complexes between anionic or cationic nanogels and oppositely charged polyions or nanogels having opposite charges were also studied. Most NIPA and NIPA-based polyelectrolyte nanogels in a swollen state had Rg/Rh values >0.775, which is the theoretically predicted value for a solid sphere. In a collapsed state, one may expect nanogel particles to be spherical in shape; however, this was not the case for a variety of nanogel samples, either with or without charges. These data were consistent with the idea that the surfaces of these nanogel particles were decorated with attached dangling chains. The Rg/Rh data from polyelectrolyte-nanogel complexes, however, indicated different structures from this. It was found that most of the polyelectrolyte-nanogel complex particles had Rg/Rh approximately 0.775. This suggested that the complexed nanogel particles were spherical in shape and that there were no dangling surface chains.
This work aimed to obtain information on the water dispersibility of a 1:1 stoichiometric polyelectrolyte nanogel complex (SPENC). We synthesized a cationic polyelectrolyte nanogel (CPENG) composed of a cross-linked copolymer of 1-vinylimidazole and N-isopropylacrylamide. SPENC was then prepared at 25 degrees C from the mixing of equimolar amounts (based on fixed charges) of CPENG and potassium poly(vinyl alcohol) sulfate, which were dissolved in an aqueous solution without adding salt and at pH 3.0. We carefully observed at 25 degrees C the reduction of the imidazole-based cationic charge in the CPENG component of SPENC as a function of pH. Dynamic and static light scattering techniques were employed in combination with electrophoretic light scattering experiments. The amount of cationic charge in the SPENC was estimated from the potentiometric titration data of CPENG. It was found that, during the charge reduction process, the complex underwent aggregation, followed by a phase separation. The aggregation started at about 25% of the charge reduction (i.e., at pH approximately = 4.9), and the phase separation took place when almost half of the charge was eliminated (at pH approximately = 5.5). However, the phase-separated complexes became water-soluble again when about 90% of the charge was eliminated (pH approximately = 6.6). By colloid titration, the dissociated free polyanions were not detected in the aqueous SPENC solution before the phase separation but were detected in the complex-redispersed solution. When the pH (9.0) of the redispersion was slowly decreased to the original level (pH 3.0) by the gradual addition of HCl so as to cause again the phase separation, an intraparticle complex was reformed, the physical quantities of which were close to those of the initial SPENC. These findings clearly indicate that the whole and a part (segment) of the complexed polyanions undergoes dissociation-association reactions on the surface of a SPENC particle, depending on the ionization state of the cationic gel component. As a result, these reactions seem to be a key factor for the water dispersibility of the SPENC.
This work aims to provide a basic understanding of the water dispersibility of a 1:1 stoichiometric polyelectrolyte complex (SPEC) in water in the absence of low-molecular-weight salts. We studied the complexation of a linear polyanion, potassium poly(vinyl alcohol sulfate) (KPVS), with a cationic polyelectrolyte nanogel (CPENG) composed of a lightly cross-linked copolymer of N-isopropylacrylamide and 1-vinylimidazole, in an aqueous salt-free solution (pH 3 and 25 °C), as a function of the molar mixing ratio (Mmr) of anionic to cationic groups. Also studied for comparison was the complexation of KPVS with poly(diallyldimethylammonium chloride) (PDDA), which is a standard reaction in colloid titration. Turbidimetric and conductometric measurements were used in combination of dynamic light scattering (DLS). An abrupt increase of turbidity curve and a break of conductivity curve were observed at Mmr =1 when KPVS was added to the CPENG or PDDA solution, indicating the formation of SPEC. All the complexes formed at Mmr ≤ 1 were water-dispersible and hence characterized by DLS. The CONTIN analysis of DLS data showed that (i) an increase of Mmr causes a decrease of the hydrodynamic radius (R(h)) of the nanogel complex particle but (ii) the R(h) of the PDDA complex remains unchanged at Mmr < 0.8. Taking these into account, we discussed the conductometric results in terms of the random model (RM) and all-or-none model (AONM) in polyelectrolyte complex formations. It was found that KPVS and PDDA yield a water-dispersible SPEC particle at each Mmr, accompanying the uptake of counterions (K(+) and Cl(-)) by the complex. This uptake amount was about 7% of the stoichiometric release of the counterions. In the nanogel system, a complete release of the counterions was observed at Mmr < 0.2 at which one or two KPVS chains were bound to a CPENG particle, but further KPVS binding led to about 20% of the counterion uptake to maintain electroneutrality. Thus, we suggest that the counterion uptake becomes a key factor to understand the water dispersibility of SPEC particles.
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