Direct functionalization of heterocyclic and non-heterocyclic arenes

L’application des métaux de transition à la fonctionnalisation directe a ouvert la voie à une nouvelle classe de réactions pour la formation de liens carbone-carbone. De par l'omniprésence des liaisons C–H, l’introduction de nouvelles fonctionnalités chimiques par voie directe et pré-activation minimale s’impose comme une stratégie de synthèse très attrayante. Ainsi, il est envisageable de préparer de manière rapide et efficace des supports complexes menant à des molécules complexes, qui pourraient être utiles dans divers domaines de la chimie. L'objectif principal de la présente thèse vise la fonctionnalisation directe des arènes hétérocycliques et non hétérocycliques et, plus précisément, les techniques d’arylation. Dans un premier temps, nous allons aborder le thème de l’arylation directe tout en mettant l’accent sur les pyridines (Chapitre 1). Ces molécules sont à la base d'une multitude de composés biologiquement actifs et jouent un rôle important dans le domaine des sciences des matériaux, de l’agrochimie et de la synthèse des produits naturels. Dans un deuxième temps, nous discuterons de nos travaux sur l’arylation directe catalysé par un complex de palladium sur des ylures de N-iminopyridinium en soulignant la dérivatisation du sel de pyridinium après une phénylation sp2 (Chapitre 2). L’étude de ce procédé nous a permis de mettre en lumière plusieurs découvertes importantes, que nous expliquerons en détails une à une : l’arylation benzylique directe lorsque des ylures N-iminopyridinium substituées avec un groupement alkyl à la position 2 sont utilisés comme partenaires dans la réaction; les allylations Tsuji-Trost catalysée par un complex de palladium; et l’alkylation directe et sans métal via une catalyse par transfert de phase. Plusieurs défis restent à relever pour le développement de procédés directs utilisant des métaux de transition peu coûteux, d’autant plus que la synthèse par transformation directe des pyridines 2-alcényles, lesquelles sont pertinentes sur le plan pharmacologique, n’a pas encore été rapportée à ce jour. Avec cette problématique en tête, nous avons réussi à mettre au point une alcénylation directe catalysé par un complex de cuivre sur des ylures de N-iminopyridinium. Nous discuterons également d’une nouvelle méthode pour la préparation des iodures de vinyle utilisés dans les couplages. Ces réactions sont non seulement remarquablement chimiosélectives, mais sont aussi applicables à plusieurs substrats (Chapitre 3). En optimisant ce procédé direct, nous avons découvert une façon unique de synthétiser les pyrazolo[1,5-a]pyridines 2-substituées (Chapitre 4). Le mécanisme global met en jeu une séquence tandem de fonctionnalisation-cyclisation directe et un procédé direct en cascade, qui n’avais jamais été rapporté. Cela simplifie ansi la synthèse autrement compliquée de ces substrats en y apportant une solution à un problème de longue date. Dans les deux derniers chapitres, nous examinerons en détail les techniques d’arylation directe qui n'impliquent pas les partenaires de couplage hétérocycliques. Entre autres, au Chapitre 5, nous soulignerons notre découverte d’un umpolung dirigé et catalysé par un complexe de palladium du benzène et de quelques autres dérivés arènes. Il s’agit là du premier cas de fonctionnalisation directe dans laquelle le groupe directeur se trouve sur le partenaire halogène et il s’ajoute à la courte liste d’exemples connus dans la littérature rapportant une arylation directe du benzène. Finalement, au Chapitre 6, nous passerons en revue une nouvelle arylation directe catalysée au fer, qui se veut un procédé peu coûteux, durable et présentant une économie d’atomes. Nous discutons des substrats possibles ainsi des études mécanistiques réalisés.

Légaliser la vente de reins : à quel prix… Compte-rendu de The Kidney Sellers: A Journey of Discovery in Iran par Sigrid Fry-Revere

Compte-rendu / Review

Compte-rendu de The Kidney Sellers: A Journey of Discovery in Iran par Sigrid Fry-Revere – Response by the author

Lettre à l'éditeur / Letter to the Editor

Information Discovery in Distributed Systems-A Novel Concept Based on Modelling of Information Elements

Sharing of information with those in need of it has always been an idealistic goal of networked environments. With the proliferation of computer networks, information is so widely distributed among systems, that it is imperative to have well-organized schemes for retrieval and also discovery. This thesis attempts to investigate the problems associated with such schemes and suggests a software architecture, which is aimed towards achieving a meaningful discovery. Usage of information elements as a modelling base for efficient information discovery in distributed systems is demonstrated with the aid of a novel conceptual entity called infotron.The investigations are focused on distributed systems and their associated problems. The study was directed towards identifying suitable software architecture and incorporating the same in an environment where information growth is phenomenal and a proper mechanism for carrying out information discovery becomes feasible. An empirical study undertaken with the aid of an election database of constituencies distributed geographically, provided the insights required. This is manifested in the Election Counting and Reporting Software (ECRS) System. ECRS system is a software system, which is essentially distributed in nature designed to prepare reports to district administrators about the election counting process and to generate other miscellaneous statutory reports.Most of the distributed systems of the nature of ECRS normally will possess a "fragile architecture" which would make them amenable to collapse, with the occurrence of minor faults. This is resolved with the help of the penta-tier architecture proposed, that contained five different technologies at different tiers of the architecture.The results of experiment conducted and its analysis show that such an architecture would help to maintain different components of the software intact in an impermeable manner from any internal or external faults. The architecture thus evolved needed a mechanism to support information processing and discovery. This necessitated the introduction of the noveI concept of infotrons. Further, when a computing machine has to perform any meaningful extraction of information, it is guided by what is termed an infotron dictionary.The other empirical study was to find out which of the two prominent markup languages namely HTML and XML, is best suited for the incorporation of infotrons. A comparative study of 200 documents in HTML and XML was undertaken. The result was in favor ofXML.The concept of infotron and that of infotron dictionary, which were developed, was applied to implement an Information Discovery System (IDS). IDS is essentially, a system, that starts with the infotron(s) supplied as clue(s), and results in brewing the information required to satisfy the need of the information discoverer by utilizing the documents available at its disposal (as information space). The various components of the system and their interaction follows the penta-tier architectural model and therefore can be considered fault-tolerant. IDS is generic in nature and therefore the characteristics and the specifications were drawn up accordingly. Many subsystems interacted with multiple infotron dictionaries that were maintained in the system.In order to demonstrate the working of the IDS and to discover the information without modification of a typical Library Information System (LIS), an Information Discovery in Library Information System (lDLIS) application was developed. IDLIS is essentially a wrapper for the LIS, which maintains all the databases of the library. The purpose was to demonstrate that the functionality of a legacy system could be enhanced with the augmentation of IDS leading to information discovery service. IDLIS demonstrates IDS in action. IDLIS proves that any legacy system could be augmented with IDS effectively to provide the additional functionality of information discovery service.Possible applications of IDS and scope for further research in the field are covered.

Information discovery in distributed systems - A novel concept based on modelling of information elements

This thesis attempts to investigate the problems associated with such schemes and suggests a software architecture, which is aimed towards achieving a meaningful discovery. Usage of information elements as a modelling base for efficient information discovery in distributed systems is demonstrated with the aid of a novel conceptual entity called infotron. The investigations are focused on distributed systems and their associated problems. The study was directed towards identifying suitable software architecture and incorporating the same in an environment where information growth is phenomenal and a proper mechanism for carrying out information discovery becomes feasible. An empirical study undertaken with the aid of an election database of constituencies distributed geographically, provided the insights required. This is manifested in the Election Counting and Reporting Software (ECRS) System. ECRS system is a software system, which is essentially distributed in nature designed to prepare reports to district administrators about the election counting process and to generate other miscellaneous statutory reports.

Energy Efficient Cache Discovery in Wireless Mobile Ad oc Networks

Data caching is an attractive solution for reducing bandwidth demands and network latency in mobile ad hoc networks. Deploying caches in mobile nodes can reduce the overall traf c considerably. Cache hits eliminate the need to contact the data source frequently, which avoids additional network overhead. In this paper we propose a data discovery and cache management policy for cooperative caching, which reduces the power usage, caching overhead and delay by reducing the number of control messages flooded into the network .A cache discovery process based on position cordinates of neighboring nodes is developed for this .The stimulstion results gives a promising result based on the metrics of the studies.

Isp Knowledge Portal : A Resource Discovery Tool In Optics

The need to structure knowledge is as important now as it ever has been. This paper has tried to study the ISP knowledge portal to explore how knowledge on various resources and topics in photonics and related areas are organized in the knowledge portal of International School of Photonics, CUSAT. The study revealed that ISP knowledge portal is one of the best portals in the filed. It provides a model for building an effective knowledge portal in other fields

Conceptual knowledge discovery with frequent concept lattices

Knowledge discovery support environments include beside classical data analysis tools also data mining tools. For supporting both kinds of tools, a unified knowledge representation is needed. We show that concept lattices which are used as knowledge representation in Conceptual Information Systems can also be used for structuring the results of mining association rules. Vice versa, we use ideas of association rules for reducing the complexity of the visualization of Conceptual Information Systems.

CEM - visualization and discovery in Email

This paper presents a lattice-based visual metaphor for knowledge discovery in electronic mail. It allows a user to navigate email using a visual lattice metaphor rather than a tree structure. By using such a conceptual multi-hierarchy, the content and shape of the lattice can be varied to accommodate any number of queries against the email collection. The system provides more flexibility in retrieving stored emails and can be generalised to any electronic documents. The paper presents the underlying mathematical structures, and a number of examples of the lattice and multi-hierarchy working with a prototypical email collection.

Conceptual knowledge discovery and data analysis

In this paper, we discuss Conceptual Knowledge Discovery in Databases (CKDD) in its connection with Data Analysis. Our approach is based on Formal Concept Analysis, a mathematical theory which has been developed and proven useful during the last 20 years. Formal Concept Analysis has led to a theory of conceptual information systems which has been applied by using the management system TOSCANA in a wide range of domains. In this paper, we use such an application in database marketing to demonstrate how methods and procedures of CKDD can be applied in Data Analysis. In particular, we show the interplay and integration of data mining and data analysis techniques based on Formal Concept Analysis. The main concern of this paper is to explain how the transition from data to knowledge can be supported by a TOSCANA system. To clarify the transition steps we discuss their correspondence to the five levels of knowledge representation established by R. Brachman and to the steps of empirically grounded theory building proposed by A. Strauss and J. Corbin.

A DHT-Based Grid Resource Indexing and Discovery Scheme

This paper presents a DHT-based grid resource indexing and discovery (DGRID) approach. With DGRID, resource-information data is stored on its own administrative domain and each domain, represented by an index server, is virtualized to several nodes (virtual servers) subjected to the number of resource types it has. Then, all nodes are arranged as a structured overlay network or distributed hash table (DHT). Comparing to existing grid resource indexing and discovery schemes, the benefits of DGRID include improving the security of domains, increasing the availability of data, and eliminating stale data.

Emprendimiento y cultura para la perdurabilidad empresarial

Este documento es un trabajo de grado que aborda temas de emprendimiento en su concepto y proceso, la cultura desde un punto de vista antropológico, indagando sobre conceptos teóricos, luego analizando el estado actual de la actividad empresarial en Colombia, para proponer dos soluciones a la problemática de la perdurabilidad empresarial. Para ello es necesario entender el concepto de emprendimiento, cómo es su proceso, y cómo se relaciona la antropología cultural con éstos y el entorno de negocios. No se pretende plantear un modelo de investigación, se quiere proponer un tema que sirva de base para una futura indagación más profunda que posiblemente aportará el descubrimiento de nuevas oportunidades de creación de empresas innovadoras y perdurables.

Professional, Legal and ethical issues - indicative topic list

indicative list of topic areas for professional, legal and ethical issues modules clustered into broad themes. Document is to be consulted in conjunction with other slides and notes for the module.

e-Research Methods Theme 4 Choosing Your Research Topic

In this theme you will work through a series of texts and activities designed to develop the essential personal, organisational, management, theoretical and research skills you need to select an appropriate topic for a Masters/PhD research project.