Dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of a non-ionic polymer

The dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of increasing amount of the non-ionic polymer polypropylene glycol with molecular weight 425 g mol(-1) (PPG-425) was investigated in a stirred-batch reactor by monitoring the Ce(IV) absorbance changes. The oscillatory parameters are significantly altered by the presence of the polymer. The findings obtained in the present work revealed that the PPG-425 is not only more effective, than other polymer previously [R. Lombardo, C. Sbriziolo, M.L. Turco Liveri, K. Pelle, M. Wittmann, Z. Noszticzius, in: J.A. Pojman, Q. Tran-Cong-Miyata (Eds.), Nonlinear Dynamics in Polymeric Systems, American Chemical Society, Washington, DC, 869 (2004) 292] studied, in perturbing the BZ systems but also more capable of producing key radical species, which in turn can be exploited for the preparation of new polymeric materials

Deconvolution procedure of the UV-vis spectra. A powerful tool for the estimation of the binding of a model drug to specific solubilisation loci of bio-compatible aqueous surfactant-forming micelle

UV-vis-spectra evolution of Nile Red loaded into Tween 20 micelles with pH and [Tween 20] have been analysed in a non-conventional manner by exploiting the deconvolution method. The number of buried sub-bands has been found to depend on both pH and bio-surfactant concentration, whose positions have been associated to Nile Red confined in aqueous solution and in the three micellar solubilisation sites. For the first time, by using an extended classical two-pseudo-phases-model, the robust treatment of the spectrophotometric data allows the estimation of Nile Red binding constant to the available loci. Hosting capability towards Nile Red is exalted by the pH enhancement. Comparison between binding constant values classically evaluated and those estimated by the deconvolution protocol unveiled that overall binding values perfectly match with the mean values of the local binding sites. This result suggests that deconvolution procedure provides more precise and reliable values, which are more representative of drug confinement

Nonlinear Response of a Batch BZ Oscillator to the Addition of the Anionic Surfactant Sodium Dodecyl Sulfate

The response of the Belousov-Zhabotinsy (BZ) system to the addition of increasing amounts of the anionic surfactant sodium dodecyl sulfate (SDS) was monitored at 25.0 °C in stirred batch conditions. The presence of SDS in the reaction mixture influences the oscillatory parameters, i.e., induction period and oscillation period, to an extent that depends on the surfactant concentration. The experimental results have shown that the induction period increases slightly on increasing surfactant concentration and, then, a further increase in the [SDS] leads to an enhancement while the oscillation period increases monotonously on increasing SDS concentration. It has been proposed that the response of the oscillatory BZ system to the addition of SDS is due to the peculiar capability of the organized surfactant assemblies to affect the reactivity by selectively sequestering some key reacting species. Indeed, explanations of the experimental results have been given on the basis of the role played by the micellar shape, which in turn dictates the hydrophobic nature. The suggested perturbation effects have been supported by performing viscosity measurements on the aqueous SDS solutions and by the spectrophotometric estimation of the binding constant of the bromine species to the micellar aggregates. This study has indirectly corroborated the existence of two kind of micelles and unambiguously revealed that the bromine species show a different affinity toward the spherical and rod-like micelles

Thermal Frontal Polymerization with a Thermally Released Redox Catalyst

We studied thermal frontal polymerization using a redox systemin an attempt to lower the temperature of the frontally polymerizable system while increasing the front velocity so as to obtain a self-sustaining front in a thinner layer than without the redox components. A cobalt-containing polymer with a melting point of 63 C (Intelimer 6050X11) and cumene hydroperoxide were used with a triacrylate. The use of the Intelimer decreased the front velocity but allowed fronts to propagate in thinner layers and withmore filler while still having a pot life of days. Nonplanar modes of propagation occurred. Fronts propagated faster when 6-O-palmitoyl-L-ascorbic acid was used as a reductant. Interestingly, fronts were also faster with the reductant even without the Intelimer if kaolin clay was the filler; however, the pot life was significantly reduce

Kinetic studies of the interaction between DNA and polycations based on polyasparthylhydrazide

In the present paper, a systematic kinetic study on the interaction between interpolyelectrolytes such as positive-charged polymers and DNA was carried out. In particular, a qualitative-quantitative kinetic investigation on the interaction between copolymers of the α,β-poly(aspartylhydrazide) and DNA calf thymus filaments was performed. This study gives a new model starting from a well known "pseudo-phase model", and permits to give a qualitative explanation about the trends of experimentally observed kinetic constants by varying the concentration of one of the two poly-electrolytes. Moreover, this study permits to verify the dependence of the binding constants KPAHy-CPTA and KDNA from the cationic copolymer (PAHy-CPTA) concentration and from the DNA concentration, respectively, during the formation process of polyplexes, by the kinetic analysis. It was also possible to know the kinetic constants of the complex formation by the proposed kinetic model, both in the aqueous pseudo-phase than in the non-aqueous pseudo-phase formed by the component in excess. From the parameters (a) and (b), information on the kinetic nature of the interaction between these electrolytes were obtained (cooperative and anti-cooperative bond)

Thermal frontal polymerization with a thermally released redox catalyst

We studied thermal frontal polymerization using a redox system in an attempt to lower the temperature of the frontally polymerizable system while increasing the front velocity so as to obtain a self-sustaining front in a thinner layer than without the redox components. A cobalt-containing polymer with a melting point of 63 °C (Intelimer 6050X11) and cumene hydroperoxide were used with a triacrylate. The use of the Intelimer decreased the front velocity but allowed fronts to propagate in thinner layers and with more filler while still having a pot life of days. Nonplanar modes of propagation occurred. Fronts propagated faster when 6-O-palmitoyl-L-ascorbic acid was used as a reductant. Interestingly, fronts were also faster with the reductant even without the Intelimer if kaolin clay was the filler; however, the pot life was significantly reduced. © 2012 Wiley Periodicals, Inc

Adsorption of triblock copolymers and their homopolymers at laponite clay/solution interface. Role played by the copolymer nature

The adsorption thermodynamics of copolymers, based on ethylene oxide (EO) and propylene oxide ( PO) units, at the laponite (RD) clay/liquid interface was determined at 298 K. The copolymer nature was tuned at molecular level by changing the hydrophilicity, the architecture and the molecular weight (Mw) keeping constant the EO/PO ratio. Polyethylene (PEGs) and polypropylene (PPGs) glycols with varying Mw and their mixture were also investigated to discriminate the role of the EO and the PO segments in the adsorption process. Enthalpies of transfer of RD, at fixed concentration, from water to the aqueous macromolecule solutions as functions of the macromolecule molality were determined. They were treated quantitatively by means of a model based on two equilibria: ( 1) one-to-one binding between the macromolecule and the site on the solid and ( 2) two-to-one binding following which one macromolecule interacts with another one adsorbed onto the solid. The good agreement between the equilibrium constants obtained from calorimetry and those determined from kinetic experiments conformed the reliability of the experimental and theoretical approaches. Almost all of the systems investigated are highlighted by the one-to-one binding; the L35 and 10R5 systems present both equilibria. The insights provided by the thermodynamics of adsorption of their homopolymers onto RD were fruitful in obtaining detailed information on the nature of the forces involved between RD and the copolymers. The data obtained in the present work clearly evidenced that for comparable polymer Mw, PPG is more suitable in building up a steric barrier around the RD particles and, indeed, exhibits several advantages and no drawbacks. Moreover, the parent copolymers may properly functionalize the RD surface by exploiting both their high affinity to the solid surface and the ability to self-assemble onto it as L35 and 10R5 clearly showed