Understanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Study

The natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.

Origin of Symphyotrichum anticostense (Asteraceae: Astereae) : an endemic species of the Gulf of St.Lawrence

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Microscopic origin of exchange bias in core/shell nanoparticles

We report the results of Monte Carlo simulations with the aim to clarify the microscopic origin of exchange bias in the magnetization hysteresis loops of a model of individual core/shell nanoparticles. Increase of the exchange coupling across the core/shell interface leads to an enhancement of exchange bias and to an increasing asymmetry between the two branches of the loops which is due to different reversal mechanisms. A detailed study of the magnetic order of the interfacial spins shows compelling evidence that the existence of a net magnetization due to uncompensated spins at the shell interface is responsible for both phenomena and allows to quantify the loop shifts directly in terms of microscopic parameters with striking agreement with the macroscopic observed values.

Studies on the mineralogy, geochemistry and origin of the modern sediments of the ashtamudy lake, Kerala

This study enfolds the environment of deposition and the lateral variation in texture, mineralogy and geochemistry of the Ashtamudy lake sediments. While the heavy mineral and clay mineral investigations enable us to decipher the nature, texture and source of sediments; organic matter and carbonate contents and the geochemical analysis of major and minor elements help establish the distribution and concentration of the same in regard to the various physico-chemical processes operating in the lake. Study of trace elements holds prime importance in this work, since their concentrations can be used to outline the extent of contaminated bottom area, as well as the source and dispersal paths of discharged_pollutants. In short, this study brings out a vivid picture of the mineralogy and geochemistry of the lake sediments in different environments, viz., the freshwater, brackish water and marine environments that are confined to the eastern, central and western parts of the lake respectively. For the better understanding and expression of the results of the analysis, the lake has been divided into 3 zones namely: eastern part, central part and western part.

Electronic origin of bond softening and hardening in femtosecond-laser-excited magnesium

Many ultrafast structural phenomena in solids at high fluences are related to the hardening or softening of particular lattice vibrations at lower fluences. In this paper we relate femtosecond-laser-induced phonon frequency changes to changes in the electronic density of states, which need to be evaluated only in the electronic ground state, following phonon displacement patterns. We illustrate this relationship for a particular lattice vibration of magnesium, for which we—surprisingly—find that there is both softening and hardening as a function of the femtosecond-laser fluence. Using our theory, we explain these behaviours as arising from Van Hove singularities: We show that at low excitation densities Van Hove singularities near the Fermi level dominate the change of the phonon frequency while at higher excitations Van Hove singularities that are further away in energy also become important. We expect that our theory can as well shed light on the effects of laser excitation of other materials.

Forms of ethnic prejudice : Assessing the dimensionality of a Spanish-language version of the Blatant and Subtle Prejudice Scale

Resumen tomado de la publicaci??n

Invariance levels across language versions of the PISA 2009 reading comprehension tests in Spain

Resumen tomado de la publicaci??n

Oral and manual language skills of hearing children of deaf parents

This paper reviews a study of the language skills of normal hearing children whose parents are deaf and use manual communication.

An analysis of vocabulary and language constructions of six series of primary readers from the standpoint of teaching the deaf

This paper discusses a study to determnine the vocabulary and language construction of primary readers and suitability for use in teaching of hearing impaired children.