The King and His People in the Discourse of the Ancien Capitaine.

The linkage between king and people in the discourse of the ancien capitaine is based on the dual roles of the captain as an intermediary representing the people to the king and as a royal officer commissioned by the king to exercise royal sovereignty. Maritime captains, Indian chiefs, and French missionaries participated in a discourse that advanced and nurtured the village leader and post captains as links between France and New France, between the king in the old world and his people in the new. Tracing the development of the diplomatic language in New France and observing the old Canadian captains as they extended French dominion into the Mississippi Valley, shows that the chain linking the king to his people was strained by the gap that developed between the interests of the king\u27s service and the welfare of the colony itself. The city of Natchitoches planted by Louis Juchereau de Saint Denis on the border between two empires became the nucleus of a viable frontier community. The economic failure of the Company of the West created new opportunities for those who were ready to learn and apply the techniques of the ancien capitaine, and by demonstrating their ability to control a vast territory with a handful of soldiers, the old captains attempted to bridge the gap between the king\u27s interest and the survival of the colony. The use of words and force by the ancien capitaine forged the strong link of the chain that tied the people--families, tribes, and traders--of the captain\u27s post to the kingdom, confederacy, or federal republic which was best able to defend and protect his people and supply their needs. The ancien capitaine presented himself as the royal agent who could bring the benefits of protection and material prosperity to the people who accepted him as their spokesman. The effective frontier commandant was a royal officer who commanded the loyalty of the fictive kinship groups surrounding his post. The key to Spanish control was the enlistment of French captains in the service of the Spanish king

Straining flow of a micellar surfactant solution

We present a mathematical model describing the distribution of monomer and micellar surfactant in a steady straining flow beneath a fixed free surface. The model includes adsorption of monomer surfactant at the surface and a single-step reaction whereby $n$ monomer molecules combine to form each micelle. The equations are analysed asymptotically and numerically and the results are compared with experiments. Previous studies of such systems have often assumed equilibrium between the monomer and micellar phases, i.e. that the reaction rate is effectively infinite. Our analysis shows that such an approach inevitably fails under certain physical conditions and also cannot accurately match some experimental results. Our theory provides an improved fit with experiments and allows the reaction rates to be estimated

Micelle fragmentation and wetting in confined flow

We use coarse-grained molecular-dynamics (MD) simulations to investigate the structural and dynamical properties of micelles under non-equilibrium Poiseuille flow in a nano-confined geometry. The effects of flow, confinement, and the wetting properties of die-channel walls on spherical sodium dodecyl sulfate (SDS) micelles are explored when the micelle is forced through a die-channel slightly smaller than its equilibrium size. Inside the channel, the micelle may fragment into smaller micelles. In addition to the flow rate, the wettability of the channel surfaces dictates whether the micelle fragments and determines the size of the daughter micelles: The overall behavior is determined by the subtle balance between hydrodynamic forces, micelle-wall interactions and self-assembly forces

Micelle Formation and the Hydrophobic Effect

The tendency of amphiphilic molecules to form micelles in aqueous solution is a consequence of the hydrophobic effect. The fundamental difference between micelle assembly and macroscopic phase separation is the stoichiometric constraint that frustrates the demixing of polar and hydrophobic groups. We present a theory for micelle assembly that combines the account of this constraint with a description of the hydrophobic driving force. The latter arises from the length scale dependence of aqueous solvation. The theoretical predictions for temperature dependence and surfactant chain length dependence of critical micelle concentrations for nonionic surfactants agree favorably with experiment.Comment: Accepted for publication in J. Phys. Chem.

Interaction of an Antituberculosis Drug with a Nanoscopic Macromolecular Assembly: Temperature-Dependent Förster Resonance Energy Transfer Studies on Rifampicin in an Anionic Sodium Dodecyl Sulfate Micelle

In this contribution, we report studies on the nature of binding of a potent antituberculosis drug, Rifampicin (RF) with a model drug delivery system, sodium dodecyl sulfate (SDS) micelle. Temperature dependent dynamic light scattering (DLS), conductometry, and circular dichroism (CD) spectroscopy have been employed to study the binding interaction of the drug with the micelle. The absorption spectrum of the drug RF in the visible region has been employed to study Förster resonance energy transfer (FRET) from another fluorescent drug Hoechst 33258 (H33258), bound to the micelle. Picosecond-resolved FRET studies at room temperature confirm the simultaneous binding of the two drugs to the micelle and the distance between the donor−acceptor pair is found to be 34 Å. The temperature dependent FRET study also confirms that the location and efficiency of drug binding to the micelle changes significantly at the elevated temperature. The energy transfer efficiency of the donor H33258, as measured from time-resolved studies, decreases significantly from 76% at 20 °C to 60% at 55 °C. This reveals detachment of some amount of the drug molecules from the micelles and increased donor−acceptor distance at elevated temperatures. The estimated donor−acceptor distance increases from a value of 33 Å at 20 °C to 37 Å at 55 °C. The picosecond resolved FRET studies on a synthesized DNA bound H33258 in RF solution have been performed to explore the interaction between the two. Our studies are expected to find relevance in the exploration of a potential vehicle for the vital drug rifampicin