Synthesis and Transformations of a Few Nitrogen and Oxygen Heterocycles

Department of Applied Chemistry, Cochin University of Science and Technology

Studies on the Synthesis and Transformations of a few Bicyclic and Dispiro Compounds

In this thesis, we report our endeavours in the synthesis of a few polycyclic compounds. We were interested in the synthesis of a few bicyclic compounds designed to undergo interesting photochemical transformations including tripletmediated di-π-methane rearrangement and/or competing singlet-mediated electrocyclic reactions. Our target molecules have "inbuilt" structural features which will potentially alter the photochemistry of the substrate under consideration.The present investigation was undertaken to test our hypothesis on selective intramolecular quenching of singlet or triplet excited states of molecules.We adopted Dies-Alder reaction for the synthesis of several of the bicyclic compounds we were interested in. Some of the precursor dienes synthesised by us are capable of undergoing intramolecular cycloaddition reactions as well. So, it was important to delineate the conditions and structural features that will enable a particular molecule to undergo intermolecular and intramolecular Dies-Alder reaction when treated with a suitable dienophile.Though, the main focus of this thesis is on the synthesis of bicyclic and tricyclic systems capable of undergoing di-π-methane rearrangement, in the last chapter of this thesis, we describe our findings on the synthesis of a few dispirocompounds. These systems were encountered as unexpected products in the attempted synthesis of novel dibenzoylalkene-type systems. Consequently, a brief survey on the synthesis and transformations of dibenzoylalkenes is also included as an integral part of this thesis.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

On the crystallization kinetics and micro-structural transformations of Fe40Ni38B18Mo4 alloys

Activation energy for crystallization (Ec) is a pertinent parameter that decides the application potential of many metallic glasses and is proportional to the crystallization temperature. Higher crystallization temperatures are desirable for soft magnetic applications, while lower values for data storage purposes. In this investigation, from the heating rate dependence of peak crystallization temperature Tp, the Ec values have been evaluated by three different methods for metglas 2826 MB (Fe40Ni38B18Mo4) accurately. The Ec values are correlated with the morphological changes, and the structural evolution associated with annealing temperatures is discussed.

Statistics of avalanches in martensitic transformations, II. Modelling

Using a scaling assumption, we propose a phenomenological model aimed to describe the joint probability distribution of two magnitudes A and T characterizing the spatial and temporal scales of a set of avalanches. The model also describes the correlation function of a sequence of such avalanches. As an example we study the joint distribution of amplitudes and durations of the acoustic emission signals observed in martensitic transformations [Vives et al., preceding paper, Phys. Rev. B 52, 12 644 (1995)].

“Synthesis and Photochemical Transformations of a few Tethered Barrelenes”

the author has designed few barrelene molecules in such a way that the structural features of these compounds will enable them to undergo intriguing triplet state mediated di- -methane rearrangement. The strategy involved the preparation of dibenzobarrelenes appended with a fused ring systems, thereby restricting the rotational freedom of the bridgehead substituent. We describe these systems as ‘tethered barrelenes’. These tethered barrelenes enabled us to examine the effect of orientation and the nature of the bridgehead-substituents in controlling the regioselectivity of di-π-methane rearrangement in a more systematic fashion. In this background, the thesis entitled “SYNTHESIS AND PHOTOCHEMICAL TRANSFORMATIONS OF A FEW TETHERED BARRELENES” reveals our attempts to explore the factors controlling the regioselectivity of di-π-methane rearrangement displayed by dibenzobarrelenes. Moreover, we have observed interesting dark reactions of suitable substituted tethered dibenzosemibullvalenes in a few cases

Effect of dressing on high-order harmonic generation in vibrating H2 molecules

Wir entwickeln die Starkfeldnäherung für die Erzeugung hoher Harmonischer in Wasserstoffmolekülen, wobei die Vibrationsbewegung berücksichtigt wird, sowie die laserinduzierte Kopplung zwischen den beiden untersten Born-Oppenheimer-Zuständen im Molekülion, das durch die anfängliche Ionisation des Moleküls erzeugt wird. Wir zeigen, dass die Kopplung bei längeren Laserwellenlängen (≈ 2 μm) wichtig wird und zu einer Reduzierung der Erzeugung von Harmonischen führt, sowie zu einer Änderung des Verhältnisses von Harmonischen in verschiedenen Isotopen. ----------------------------------------------------------------------- We develop the strong-field approximation for high-order harmonic generation in hydrogen molecules, including the vibrational motion and the laser-induced coupling of the lowest two Born-Oppenheimer states in the molecular ion that is created by the initial ionization of the molecule. We show that the field dressing becomes important at long laser wavelengths (≈ 2 μm), leading to an overall reduction of harmonic generation and modifying the ratio of harmonic signals from different isotopes.

Translation Invariance in Object Recognition, and Its Relation to Other Visual Transformations

Human object recognition is generally considered to tolerate changes of the stimulus position in the visual field. A number of recent studies, however, have cast doubt on the completeness of translation invariance. In a new series of experiments we tried to investigate whether positional specificity of short-term memory is a general property of visual perception. We tested same/different discrimination of computer graphics models that were displayed at the same or at different locations of the visual field, and found complete translation invariance, regardless of the similarity of the animals and irrespective of direction and size of the displacement (Exp. 1 and 2). Decisions were strongly biased towards same decisions if stimuli appeared at a constant location, while after translation subjects displayed a tendency towards different decisions. Even if the spatial order of animal limbs was randomized ("scrambled animals"), no deteriorating effect of shifts in the field of view could be detected (Exp. 3). However, if the influence of single features was reduced (Exp. 4 and 5) small but significant effects of translation could be obtained. Under conditions that do not reveal an influence of translation, rotation in depth strongly interferes with recognition (Exp. 6). Changes of stimulus size did not reduce performance (Exp. 7). Tolerance to these object transformations seems to rely on different brain mechanisms, with translation and scale invariance being achieved in principle, while rotation invariance is not.

A comparison of the alr and ilr transformations for kernel density estimation of compositional data

In a seminal paper, Aitchison and Lauder (1985) introduced classical kernel density estimation techniques in the context of compositional data analysis. Indeed, they gave two options for the choice of the kernel to be used in the kernel estimator. One of these kernels is based on the use the alr transformation on the simplex SD jointly with the normal distribution on RD-1. However, these authors themselves recognized that this method has some deficiencies. A method for overcoming these dificulties based on recent developments for compositional data analysis and multivariate kernel estimation theory, combining the ilr transformation with the use of the normal density with a full bandwidth matrix, was recently proposed in Martín-Fernández, Chacón and Mateu- Figueras (2006). Here we present an extensive simulation study that compares both methods in practice, thus exploring the finite-sample behaviour of both estimators

Neuromuscular dressing effects: a literature review

The kinesio taping is a technique that was created in 1979 by Doctor Kenzo Kase I’m looking through it that could generate a new therapeutic option to control pain, improve athletic performance and reduce the impact of musculoskeletal disorders. From the Sydney 2000 Olympic Games, this technique as a therapeutic alternative PTO and is composed of health professionals in the field of sport and physical rehabilitation. Objetive: This article aims to identify theoretical approaches on the bandage neuromuscular. Material and methods: held today, for which conducted a literature search of databases such as como Proquest, Ovid, Cochraine, PEDro, Journal ofOrthopedic and Sports Physical, Sciencedirect, Pubmed y Literatura Latinoamericana y del Caribe en Ciencias de la Salud (Lilacs). The paper proposes a scheme of contextualization of the current landscape of the use and effects of kinesio taping in the management of different pathologies of the musculo-skeletal system in sports. Conclusion: it is concluded that currently many health professionals, and take the neuromuscular bandage a good therapeutic option in the management of diseases affecting the human body is investigated and every day more about the subject, which makes these new therapeutic methods to acquire a scientific value and transcends knowledge.

Dressing up with Mr. Bumble.

El señor Bumble invita a sus amigos a una fiesta de disfraces, y el lector debe adivinar de qué se disfraza cada invitado antes de levantar la solapa de la página para encontrar la respuesta.

Numerical model of solid phase transformations governed by nucleation and growth: microstructure development during isothermal crystallization

A simple numerical model which calculates the kinetics of crystallization involving randomly distributed nucleation and isotropic growth is presented. The model can be applied to different thermal histories and no restrictions are imposed on the time and the temperature dependences of the nucleation and growth rates. We also develop an algorithm which evaluates the corresponding emerging grain-size distribution. The algorithm is easy to implement and particularly flexible, making it possible to simulate several experimental conditions. Its simplicity and minimal computer requirements allow high accuracy for two- and three-dimensional growth simulations. The algorithm is applied to explore the grain morphology development during isothermal treatments for several nucleation regimes. In particular, thermal nucleation, preexisting nuclei, and the combination of both nucleation mechanisms are analyzed. For the first two cases, the universal grain-size distribution is obtained. The high accuracy of the model is stated from its comparison to analytical predictions. Finally, the validity of the Kolmogorov-Johnson-Mehl-Avrami model SSSR, is verified for all the cases studied