Size and pH effect on electrical and conformational behavior of poly(acrylic acid): Simulation and experiment

Analytical and Biophysical Environmental Chemistry (CABE), Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, Sciences II, 30 quai E. Ansermet, CH-1211 Geneva 4, Switzerland
European Polymer Journal 01/2006; DOI: 10.1016/j.eurpolymj.2005.11.023

ABSTRACT Monte Carlo simulations, experimental titrations and fluorescence correlation spectroscopy experiments were used to investigate the conformational and electrical properties of polyacrylic acids (PAA). On the one hand, titration curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of PAA chains. On the other hand, experimental potentiometric titrations of PAA were also achieved for different PAA molecular weights and compared to the calculated titration curves obtained by Monte Carlo coarse grained simulations. It was found that for a large range at intermediate PAA ionizations, a good correlation is obtained between experimental and simulations data thanks to the prominence of electrostatic interactions in this domain. The effect of ionic concentration and PAA molecular weight on the titration curves was also investigated. In order to get a better understanding of PAA conformational behavior, we also investigated PAA diffusion properties in aqueous solutions as a function of pH and ionic strength by fluorescence correlation spectroscopy (FCS), thanks to its high sensitivity to measure diffusion coefficients of tracer solutes. Good qualitative agreements were observed between experimental diffusivities and polymer properties calculated from MC simulations. It was shown that the high molecular weight PAA chains display more significant changes in diffusivity in agreement with the ionization degrees and conformational changes observed in the simulations.

  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The gelation kinetics in the static and dynamic modes was studied for hydrogels of cross-linked polyacrylic acid synthesized using two initiating systems: the widely used system ammonium persulfate-tetramethylethylenediamine and the system ammonium persulfate-sodium sulfite-Mohr’s salt, which has not been used for this synthesis previously. The monomer concentration was varied, with the monomer/cross-linking agent ratio kept constant. The pH dependences of the gel swelling were determined, and the effective degrees of cross-linking were calculated in relation to the monomer concentration. The factors that give rise to defects affecting the regularity of the gel network structure and the degree of gel swelling were analyzed.
    Russian Journal of Applied Chemistry 12/2011; 84(12). · 0.29 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced emission (AIE) characteristics. Free DCTPE molecules are non-emissive in aqueous solution, but they become highly emissive when trapped in polymer coils. The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils. By correlation the change of fluorescence intensity with the variation of pH value (from 1.78 to 12.06), the PAA chain’s dynamics in the relatively concentrated solution have been elucidated into three processes. In the pH range from 12.06 to 6.0, PAA chains take an extended and non-folding conformation. Changing pH from 6.0 to 3.86, PAA chains are partially protonated and loosely packed polymer coils are formed. Further lowering the pH value of the solution (from 3.86 to 1.78), protonated segments dominate the PAA chains, and at the same time, the intermolecular hydrogen bonding takes effect, thus the polymer chains posses in the conformation of more compact coils.
    Science China-Chemistry · 1.52 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The behavior of pH-responsive polymers poly(N-methacryloyl-L-valine)(P1), poly(N-methacryloyl-L-phenylalanine)(P2), and poly(N-methacryloylglycyne-L-leucine)(P3) has been studied in the presence of the non-ionic surfactant Brij98. The pure polymers phase-separate in an acidic medium with critical pHtr values of 3.7, 5.5, and 3.4, respectively. The addition of the surfactant prevents phase separation and promotes reorganization of polymer molecules. The nature of the interaction between polymer and surfactant depends on the amino acid structure in the side chain of the polymer. This effect was investigated by dynamic light scattering, isothermal titration calorimetry, electrophoretic measurements, small-angle neutron scattering, and infrared spectroscopy. Thermodynamic analysis revealed an endothermic association reaction in P1/Brij98 mixture, whereas a strong exothermic effect was observed for P2/Brij98 and P3/Brij98. Application of regular solution theory for the analysis of experimental enthalpograms indicated dominant hydrophobic interactions between P1 and Brij98 and specific interactions for the P2/Brij98 system. Electrophoretic and dynamic light scattering measurements support the applicability of the theory to these cases. The specific interactions can be ascribed to hydrogen bonds formed between the carboxylic groups of the polymer and the oligo(ethylene oxide) head-groups of the surfactant. Thus, differences in polymer-surfactant interactions between P1 and P2 polymers result in different structures of polymer-surfactant complexes. Specifically, small-angle neutron scattering revealed pearl-necklace complexes and "core-shell" structures for P1/Brij98 and P2/Brij98 systems, respectively. These results may help in the design of new pH-responsive site-specific micellar drug-delivery systems or pH-responsive membrane-disrupting agents.
    Langmuir : the ACS journal of surfaces and colloids. 09/2014;