Thesis (Ph. D.)--Boston University Graduate School, 1981. / Typescript. Vita. Includes bibliographical references (leaves 393-420). Discography: leaves 420-421.

M.A.

Phosphorus plays a crucial role in modern p-block chemistry.1 One reason for that is the diagonal relationship between phosphorus and carbon.2 Comparable to carbon and its chemistry, phosphorus tends to form homoatomic bonds, which is explainable by the relatively high P–P single bond energy (ca. 200 kJ/mol).3 Thus, a plethora of poly-phosphorus compounds are reported in the last decades comprising of fascinating bonding motifs4 and interesting applications in coordination5-7 and synthetic8-11 chemistry, as well as in ligand design.12,13 A crucial point in the chemistry of polyphosphanes is of course the formation of P–P bonds. Numerous synthetic procedures are established and reviewed including salt metathesis,4a,14 dehalosilylation15 and dehalostannylation16 reactions, base promoted dehydrohalogenation reactions17 and dehydrogenative coupling reactions mediated by main group compounds18 or catalysis by transition metals.5,19 Moreover, dialkylamino-substituted phosphanes are used in condensation reactions to form P–P bonds since the early 1960’s. Yet these reactions need elevated temperatures, somewhat limiting the formation of polyphosphorus compounds as stated by the few examples reported.17d,20 The application of pyrazolyl-substituted phosphanes in P–P bond formation reactions is a relatively young field of research.21 Their synthesis and general chemical behavior as well as advantages in comparison to dialkylamino-substituted phosphanes is discussed in the following chapter.

Non-covalent interactions taking place in solution are essential in chemical and biological systems. The solvent environment plays an important role in determining the geometry and stability of interactions. This thesis examines aromatic stacking interactions, alkyl-alkyl interactions, edge-to-face aromatic interactions, halogen bonds and hydrogen…hydrogen interactions in solution. Chapter 1 briefly introduces the different classes of non-covalent interactions, in addition to the state-of-the-art models and methods for investigating these weak interactions. The chapter finishes with a focus on dispersion interaction in alkanes and arenes. Chapter 2 investigates dispersion interactions between stacked aromatics in solution using a new class of complexes and thermodynamic double mutant cycles (DMCs). In extended aromatics, dispersion was detected as providing a small but significant contribution to the overall stacking free energies. Chapter 3 concerns the experimental measurement of alkyl-alkyl dispersion interactions in a wide range of solvents using Wilcox torsion balances. The contribution of dispersion interactions to alkyl-alkyl association was shown to be very small, with DMC, QSPR method and Hunter's solvation model. Chapter 4 studies edge-to-face aromatic interactions in series of solvents. In the open system, edge-to-face aromatic interactions were found to be sensitive to the solvent environment. The solvent effects were complicated and cannot be rationalised by a single parameter. Further analysis is needed. Chapter 5 describes a preliminary approach to investigate organic halogen…π interactions in solution using supramolecular complexes and torsion balances. Chapter 6 is a preliminary investigation of the ability of hydrogen atoms to act as H bond acceptors in silane compounds. Computations and 1H NMR demonstrated a weak interaction between silane and perfluoro-tert-butanol.

Cette thèse s'inscrit dans un ensemble de travaux menés au laboratoire de Chimie Thérapeutique de Lyon sur la mise au point d'analogues de di- ou tripeptides hydrophobes appelés réversines susceptibles de moduler la chimiorésistance des cellules tumorales liée à l'expression de protéines de transport appartenant à la famille « ATP-Binding Cassette » (ABC). Des analogues de ces réversines ont été synthétisés afin d'augmenter leur activité et leur biodisponibilité et de préciser les requis structuraux nécessaires à cette activité vis-à-vis de deux protéines de transport, la glycoprotéine P (P-gp) et la « Breast Cancer Resistance Protein » (BCRP). Dans un premier temps, afin d'évaluer l'influence de la liaison peptidique, nous avons synthétisé des analogues aminométhyléniques des réversines les plus actives ainsi que des dérivés cétométhyléniques d'une réversine de référence. Dans un second temps, nous avons entrepris la synthèse d'autres dérivés modifiés au niveau de la chaîne latérale du côté N-terminal d'une réversine de référence ainsi que des dérivés contraints de cette chaîne latérale afin d'explorer l'espace conformationnel dans cette région de liaison aux protéines de type ABC. Les activités biologiques des analogues synthétisés ont été évaluées sur les deux protéines de transport de type ABC, P-gp et BCRP. Les premiers résultats ont montré une sélectivité des produits vis-à-vis de la P-gp par rapport à BCRP ainsi que l'interaction de la chaîne latérale du côté N-terminal avec le site de liaison de la P-gp. Cette démarche a permis d'aboutir à des analogues plus actifs que les réversines de référence sur P-gp notamment ceux des dérivés contraints.

Lepton pairs resulting from the decay of heavy flavor mesons are an important tool to probe the hot and dense matter created in nucleus-nucleus collisions at the Relativistic Heavy Ion Collider. Due to their large mass, heavy quarks are produced in the earliest stages of the collision and will, therefore, experience the full evolution of the system. The yield of heavy flavor mesons can be measured through their semi-leptonic decay channel by constructing like-sign and unlike-sign lepton pairs. Cross section measurements in p + p collisions provide a test of perturbative quantum chromodynamics (pQCD) theory in addition to a crucial baseline measurement to study the hot and cold nuclear matter effects present in heavy ion collisions. For the first time, the b¯b cross section in p+p collisions at √s = 500 GeV is measured. The results are based on the yield of high mass, like-sign dimuons measured in the PHENIX muon arm acceptance (1.2 < |y| < 2.2). The extrapolated total cross section is 25.2 ± 3.2 (stat) +11.4 -9.5 µb (sys). The cross section is comparable to pQCD calculation within uncertainties.

The STAR collaboration recorded s =200 GeV per nucleon d+Au and p+p collision events during the year 2003 RHIC run. In the p+p and the d+Au data samples, it is possible to reconstruct jets and make comparisons between them. This dissertation describes the reconstructed jet sample from the p+p events, the measurements of the jet jT distribution which quantifies the shape of the jet perpendicular to the jet direction, the jet fragmentation function (z), which quantifies the fraction of jet momentum carried by the jet particles, and the width of the parton momentum broadening distribution (kT). This dissertation also describes the comparison of these results to the reconstructed jet sample from d+Au events. Measurements of jet jT and jet fragmentation from p+p, d+Au, and PYTHIA are compared. The z and jT distributions from p+p and also d+Au are found to be consistent with PYTHIA event simulation version 6.205. RMS(jT) equals 612±12±30 MeV/c for p+p, and RMS(jT) equals 630±13±30 MeV/c for d+Au. The p+p kT Gaussian sigma (width) equals 2.08±0.12±0.13 GeV/c. This width is consistent with PYTHIA, kT literature surveys, and other RHIC measurements. A limit on nuclear kT broadening in the Au nucleus is also obtained, showing that nuclear kT is consistent with zero to within 0.5 GeV/c. The present status of the RdAu measurement from jets is also described. The nuclear kT broadening, in particular, is a measurement which has been done at this energy for the first time at RHIC. These measurements, while interesting by themselves, also will contribute ultimately to the understanding of Au+Au collisions at RHIC, and the properties of the high-density matter which results from them.

Lepton pairs resulting from the decay of heavy flavor mesons are an important tool to probe the hot and dense matter created in nucleus-nucleus collisions at the Relativistic Heavy Ion Collider. Due to their large mass, heavy quarks are produced in the earliest stages of the collision and will, therefore, experience the full evolution of the system. The yield of heavy flavor mesons can be measured through their semi-leptonic decay channel by constructing like-sign and unlike-sign lepton pairs. Cross section measurements in p + p collisions provide a test of perturbative quantum chromodynamics (pQCD) theory in addition to a crucial baseline measurement to study the hot and cold nuclear matter effects present in heavy ion collisions. For the first time, the b¯b cross section in p+p collisions at √s = 500 GeV is measured. The results are based on the yield of high mass, like-sign dimuons measured in the PHENIX muon arm acceptance (1.2 < |y| < 2.2). The extrapolated total cross section is 25.2 ± 3.2 (stat) +11.4 -9.5 µb (sys). The cross section is comparable to pQCD calculation within uncertainties.

Les diodes réalisées avec le diamant comme semi-conducteur comportent de nombreuses potentialités dues à sa bande interdite de 5.45 eV. Parmi les principales, il y a le fonctionnement à des températures très supérieures à celles supportées par les autres semi-conducteurs, ainsi qu'une tension de claquage de plusieurs kV. Le but de ce travail est de réaliser des couches de diamant homoépitaxié faiblement dopées bore et préparées avec ajout d'oxygène, adaptées à ces diodes. Des méthodes de caractérisation telles que la spectroscopie Raman et la cathodoluminescence fournissent des informations sur la qualité cristalline des couches et la nature des défauts présents. Une étude de l'optimisation de la gravure par plasma O2 a permis de réaliser des contacts ohmiques sur la couche p+ et des structures mesa. Les caractéristiques de contacts ohmiques Au/Ti et Si/Al/Si et de contacts Schottky Ag/Ti et Ni/Er sont étudiées. La génération et la passivation des défauts révélés ainsi que leur interaction avec la compensation des accepteurs introduits par le bore sont déterminées par des mesures électriques et transitoires.

I here present a combined AVO analysis of P-P and P-S reflection data whose objective is to improve the identification of lithology by estimating the specific values of Poisson's ratio, [sigma], for each rock formation in a given geological model, rather than a contrast between formations. Limited knowledge on the elastic parameters of a given rock formation and difficulty regarding the availability and processing of P-S data constitute hindrances of lithology identification. Considering that ocean bottom seismology (OBS) has aided in solving the problem of P-S data availability, limited information on elastic parameters is still a challenge, and the focus of this thesis. The present analysis is based on Zoeppritz' solution for the P-P and P-S reflection coefficients, RPP and RPS, with a slight modification. We used the normalized P-S reflection coefficient; i.e., R'PS = RPS / sin [theta] for [theta] > 0, instead of RPS, where [theta] is the incident angle. By normalizing RPS, we avoid dealing with the absence of converted S-waves at small incident angles and enhance the similar linear behavior of the P-P and normalized P-S reflection coefficients at small angles of incidence. We have used the linearity of RPP and R'PS at angles smaller than 35 degrees to simultaneously estimate the average VP/VS ratio, the contrasts of P- and S-wave velocities, and the contrast of density. Using this information, we solve for Poisson's ratio of each formation, which may enable lithology discrimination. The feasibility of this analysis was demonstrated using nonlinear synthetic data (i.e., finite-difference data). The results in estimating Poisson's ratio yielded less than 5 percent error. We generalize this new combined P-P and P-S AVO analysis for dipping interfaces. Similarly to the nondipping interface case, our derivations show that the amplitude variation with offset (AVO) of P-P and P-S for a dipping interface can be cast into intercepts and gradients. However, these intercepts and gradients depend on the angle of the dipping interface. Therefore, we further generalize our analysis by including a migration step that allows us to find the dipping angle. Because seismic data is not available in terms of RPP and R'PS, this process includes recovery of reflection coefficients after migrating the data and correcting for geometrical spreading, as done by Ikelle et al. (1986 and 1988). The combination of all of these steps, namely geometrical-spreading correction, migration, and AVO analysis, is another novelty of this thesis, which leads to finding the specific values of Poisson's ratio of each rock formation directly from the seismic data.