Chemical analysis and aqueous solution properties of charged amphiphilic block copolymers PBA-b-PAA synthesized by MADIX.

We have linked the structural and dynamic properties in aqueous solution of amphiphilic charged diblock copolymers poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA, synthesized by controlled radical polymerization, with the physico-chemical characteristics of the samples. Despite product imperfections, the samples self-assemble in melt and aqueous solutions as predicted by monodisperse microphase separation theory. However, the PBA core are abnormally large; the swelling of PBA cores is not due to AA (the Flory parameter chi(PBA/PAA), determined at 0.25, means strong segregation), but to h-PBA homopolymers (content determined by liquid chromatography at the point of exclusion and adsorption transition, LC-PEAT). Beside the dominant population of micelles detected by scattering experiments, capillary electrophoresis CE analysis permitted detection of two other populations, one of h-PAA, and the other of free PBA-b-PAA chains, that have very short PBA blocks and never self-assemble. Despite the presence of these free unimers, the self-assembly in solution was found out of equilibrium: the aggregation state is history dependant and no unimer exchange between micelles occurs over months (time-evolution SANS). The high PBA/water interfacial tension, measured at 20 mN/m, prohibits unimer exchange between micelles. PBA-b-PAA solution systems are neither at thermal equilibrium nor completely frozen systems: internal fractionation of individual aggregates can occur.

On attentional control as a source of residual shift costs: evidence from two-component task shifts.

It is widely assumed that supervisory or attentional control plays a role only in the preparatory reconfiguration of the mental system in task shifting. The well-known fact that residual shift costs are still present even after extensive preparation is usually attributed to passive mechanisms such as cross talk. The authors question this view and suggest that attentional control is also responsible for residual shift costs. The authors hypothesize that, under shift conditions, tasks are executed in a controlled mode to guarantee reliable performance. Consequently, the control of 2 task components should require more resources than the control of only 1. A series of 4 experiments with 2-component tasks was conducted to test this hypothesis. As expected, more residual shift costs were observed when 2 components rather than 1 varied across trials. Interference effects and sequential effects could not account for these results.