Synthesis and potency of long end-associative polymers for mist control

Long linear polymers that are end-functionalized with associative groups were studied as additives to hydrocarbon fluids to mitigate the fire hazard associated with the presence of mist in a crash scenario. These polymers were molecularly designed to overcome both the shear-degradation of long polymer chains in turbulent flows, and the chain collapse induced by the random placement of associative groups along polymer backbones. Architectures of associative groups on the polymer chain ends that were tested included clusters of self-associative carboxyl groups and pairs of hetero-complementary associative units.

Linear polymers with clusters of discrete numbers of carboxyl groups on their chain ends were investigated first: an innovative synthetic strategy was devised to achieve unprecedented backbone lengths and precise control of the number of carboxyl groups on chain ends (N). We found that a very narrow range of N allows the co-existence of sufficient end-association strength and polymer solubility in apolar media. Subsequent steady-flow rheological study on solution behavior of such soluble polymers in apolar media revealed that the end-association of very long chains in apolar media leads to the formation of flower-like micelles interconnected by bridging chains, which trap significant fraction of polymer chains into looped structures with low contribution to mist-control. The efficacy of very long 1,4-polybutadiene chains end-functionalized with clusters of four carboxyl groups as mist-control additives for jet fuel was further tested. In addition to being shear-resistant, the polymer was found capable of providing fire-protection to jet fuel at concentrations as low as 0.3wt%. We also found that this polymer has excellent solubility in jet fuel over a wide range of temperature (-30 to +70°C) and negligible interference with dewatering of jet fuel. It does not cause an adverse increase in viscosity at concentrations where mist-control efficacy exists.

Four pairs of hetero-complementary associative end-groups of varying strengths were subsequently investigated, in the hopes of achieving supramolecular aggregates with both mist-control ability and better utilization of polymer building blocks. Rheological study of solutions of the corresponding complementary associative polymer pairs in apolar media revealed the strength of complementary end-association required to achieve supramolecular aggregates capable of modulating rheological properties of the solution.

Both self-associating and complementary associating polymers have therefore been found to resist shear degradation. The successful strategy of building soluble, end-associative polymers with either self-associative or complementary associative groups will guide the next generation of mist-control technology.

The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Extractive institutions in colonial Africa

A common explanation for African current underdevelopment is the extractive character of institutions established during the colonial period. Yet, since colonial extraction is hard to quantify and its exact mechanisms are not well understood, we still do not know precisely how colonial institutions affect economic growth today. In this project, I study this issue by focusing on the peculiar structure of trade and labor policies employed by the French colonizers.

First, I analyze how trade monopsonies and coercive labor institutions reduced African gains from trade during the colonial period. By using new data on prices to agricultural producers and labor institutions in French Africa, I show that (1) the monopsonistic character of colonial trade implied a reduction in prices to producers far below world market prices; (2) coercive labor institutions allowed the colonizers to reduce prices even further; (3) as a consequence, colonial extraction cut African gains from trade by over 60%.

Given the importance of labor institutions, I then focus on their origin by analyzing the colonial governments' incentives to choose between coerced and free labor. I argue that the choice of institutions was affected more by the properties of exported commodities, such as prices and economies of scale, than by the characteristics of colonies, such indigenous population density and ease of settlement for the colonizers.

Finally, I study the long-term effects of colonial trade monopsonies and coercive labor institutions. By combining archival data on prices in the French colonies with maps of crop suitability, I show that the extent to which prices to agricultural producers were reduced with respect to world market prices is strongly negatively correlated with current regional development, as proxied by luminosity data from satellite images. The evidence suggests that colonial extraction affected subsequent growth by reducing development in rural areas in favor of a urban elite. The differential impact in rural and urban areas can be the reason why trade monopsonies and extractive institutions persisted long after independence.