Synthèse totale du méthyl ester de la zincophorine et étude DFT du transfert d’hydrogène diastéréosélectif impliquant des intermédiaires radicalaires vicinaux à un ester

Cet ouvrage traite d’une méthodologie pour l’induction de centres stéréogènes au sein des motifs propionates par la chimie des radicaux et de son application à la synthèse totale du méthyl ester de la zincophorine. Cet ionophore, aux propriétés biologiques intéressantes, présente plusieurs défis synthétiques dont une séquence de type polypropionate anti, anti, anti, anti difficilement accessible ainsi qu’un tétrahydropyrane trans trisubstitué. Récemment, l’intérêt renouvelé pour ces composés polyéthers, en tant qu’agents anticancéreux, accentue l’importance de stratégies versatiles permettant l’accès à ces structures ainsi qu’à leurs analogues. Depuis quelques années, notre groupe s’intéresse à la synthèse d’unités propionates acycliques par une séquence réactionnelle contrôlée uniquement par le substrat. La première étape découle d’une aldolisation de Mukaiyama entre un aldéhyde alpha-chiral et un énoxysilane tétrasubstitué portant une liaison carbone-halogène, et où l’issue stéréochimique dépend de la nature monodentate ou bidentate de l’acide de Lewis employé. La seconde réaction-clé implique la formation d’un radical tertiaire, vicinal à un ester, pouvant être réduit diastéréosélectivement en présence d’hydrure d’étain. La première section décrit l’élaboration de motifs tétrahydropyranes trisubstitués et l’induction des centres stéréogènes vicinaux par une réduction radicalaire. Nous avons révélé que l’issue diastéréosélective de la réaction de cyclisation par une iodoéthérification était dictée par le groupement gamma-méthyle des esters alpha,beta-insaturés de départ. Nous avons ensuite démontré que les produits de la réaction radicalaire anti et syn pouvaient être obtenus sélectivement à partir d’un intermédiaire commun, respectivement en prenant appui sur l’effet exocyclique ou endocyclique lors de la réduction. Par une stratégie complémentaire, nous avons révélé que le précurseur radicalaire pouvait également être obtenu par une réaction de cycloéthérification en présence d’un énoxysilane tétrasubstitué. Une étude systématique des substituants du cycle a révélé que certaines relations stéréochimiques conduisaient à une perte de sélectivité au détriment du produit anti. La seconde section concerne l’étude DFT au niveau BHandHLYP/TZVP des intermédiaires radicalaires impliqués lors du transfert d’hydrogène. Par une étude de décomposition de l’énergie d’activation, nous avons été en mesure de rationaliser l’issue diastéréosélective de la réaction sur la base des énergies de distorsion (∆Ed‡) et d’interaction (∆Eint‡) requises pour accéder à la paire d’états de transition pro-anti et pro-syn. De plus, nous avons démontré qu’une analyse NBO permettait de relativiser l’impact des interactions stéréoélectroniques. Par la suite, l’évaluation des intermédiaires radicalaires borinates et aluminates nous a permis de révéler que l’encombrement stérique de la chaîne propionate était la cause principale de la formation sélective des produits anti ou syn lors d’une réduction en présence d’un acide de Lewis. La dernière section décrit l’élaboration de la séquence polypropionate de la zincophorine, et de ses isomères, à partir du fragment tétrahydropyrane substitué. Au cours de notre étude, nous avons identifié que le nombre de sites de chélation potentiels devait être limité à trois lors de l’aldolisation en condition Cram-chélate. De plus, nous avons démontré que les différents motifs acétates sont accessibles sélectivement par l’utilisation d’un énoxysilane encombré. Par ailleurs, nous avons révélé qu’une même séquence réactionnelle pouvait être employée pour la synthèse du fragment C17–C25 de son analogue naturel CP-78,545, et avons complété la plus récente synthèse totale du méthyl ester de la zincophorine.

Assessment of Energy Conservation in Indian Cement Industry and Forecasting of Co2 Emissions

Cement industry ranks 2nd in energy consumption among the industries in India. It is one of the major emitter of CO2, due to combustion of fossil fuel and calcination process. As the huge amount of CO2 emissions cause severe environment problems, the efficient and effective utilization of energy is a major concern in Indian cement industry. The main objective of the research work is to assess the energy cosumption and energy conservation of the Indian cement industry and to predict future trends in cement production and reduction of CO2 emissions. In order to achieve this objective, a detailed energy and exergy analysis of a typical cement plant in Kerala was carried out. The data on fuel usage, electricity consumption, amount of clinker and cement production were also collected from a few selected cement industries in India for the period 2001 - 2010 and the CO2 emissions were estimated. A complete decomposition method was used for the analysis of change in CO2 emissions during the period 2001 - 2010 by categorising the cement industries according to the specific thermal energy consumption. A basic forecasting model for the cement production trend was developed by using the system dynamic approach and the model was validated with the data collected from the selected cement industries. The cement production and CO2 emissions from the industries were also predicted with the base year as 2010. The sensitivity analysis of the forecasting model was conducted and found satisfactory. The model was then modified for the total cement production in India to predict the cement production and CO2 emissions for the next 21 years under three different scenarios. The parmeters that influence CO2 emissions like population and GDP growth rate, demand of cement and its production, clinker consumption and energy utilization are incorporated in these scenarios. The existing growth rate of the population and cement production in the year 2010 were used in the baseline scenario. In the scenario-1 (S1) the growth rate of population was assumed to be gradually decreasing and finally reach zero by the year 2030, while in scenario-2 (S2) a faster decline in the growth rate was assumed such that zero growth rate is achieved in the year 2020. The mitigation strategiesfor the reduction of CO2 emissions from the cement production were identified and analyzed in the energy management scenarioThe energy and exergy analysis of the raw mill of the cement plant revealed that the exergy utilization was worse than energy utilization. The energy analysis of the kiln system showed that around 38% of heat energy is wasted through exhaust gases of the preheater and cooler of the kiln sysetm. This could be recovered by the waste heat recovery system. A secondary insulation shell was also recommended for the kiln in the plant in order to prevent heat loss and enhance the efficiency of the plant. The decomposition analysis of the change in CO2 emissions during 2001- 2010 showed that the activity effect was the main factor for CO2 emissions for the cement industries since it is directly dependent on economic growth of the country. The forecasting model showed that 15.22% and 29.44% of CO2 emissions reduction can be achieved by the year 2030 in scenario- (S1) and scenario-2 (S2) respectively. In analysing the energy management scenario, it was assumed that 25% of electrical energy supply to the cement plants is replaced by renewable energy. The analysis revealed that the recovery of waste heat and the use of renewable energy could lead to decline in CO2 emissions 7.1% for baseline scenario, 10.9 % in scenario-1 (S1) and 11.16% in scenario-2 (S2) in 2030. The combined scenario considering population stabilization by the year 2020, 25% of contribution from renewable energy sources of the cement industry and 38% thermal energy from the waste heat streams shows that CO2 emissions from Indian cement industry could be reduced by nearly 37% in the year 2030. This would reduce a substantial level of greenhouse gas load to the environment. The cement industry will remain one of the critical sectors for India to meet its CO2 emissions reduction target. India’s cement production will continue to grow in the near future due to its GDP growth. The control of population, improvement in plant efficiency and use of renewable energy are the important options for the mitigation of CO2 emissions from Indian cement industries

One- and two-center energy components in the atoms in molecules theory

The energy decomposition scheme proposed in a recent paper has been realized by performing numerical integrations. The sample calculations carried out for some simple molecules show excellent agreement with the chemical picture of molecules, indicating that such an energy decomposition analysis can be useful from the point of view of connecting quantum mechanics with the genuine chemical concepts

Estimating sectoral cycles using cointegration and common features

This paper investigates the degree of short run and long run co-movement in U.S. sectoral output data by estimating sectoraI trends and cycles. A theoretical model based on Long and Plosser (1983) is used to derive a reduced form for sectoral output from first principles. Cointegration and common features (cycles) tests are performed; sectoral output data seem to share a relatively high number of common trends and a relatively low number of common cycles. A special trend-cycle decomposition of the data set is performed and the results indicate a very similar cyclical behavior across sectors and a very different behavior for trends. Indeed. sectors cyclical components appear as one. In a variance decomposition analysis, prominent sectors such as Manufacturing and Wholesale/Retail Trade exhibit relatively important transitory shocks.

Pro-poor growth and social programmes in Brazil

From a methodological point of view, this paper makes two contributions to the literature. One contribution is the proposal of a new measure of pro-poor growth. This new measure provides the linkage between growth rates in mean income and in income inequality. In this context, growth is defined as propoor (or anti-poor) if there is a gain (or loss) in the growth rate due to a decrease (or increase) in inequality. The other contribution is a decomposition methodology that explores linkages between growth patterns and social policies. Through the decomposition analysis, we assess the contribution of different income sources to growth patterns. The proposed methodologies are then applied to the Brazilian National Household Survey (PNAD) covering the period 1995-2004. The paper analyzes the evolution of Brazilian social indicators based on per capita income exploring links with adverse labour market performance and social policy change, with particular emphasis on the expansion of targeted cash transfers and devising more pro-poor social security benefits.

Linkages between growth, poverty and the labour market

From a methodological point of view, this paper makes two contributions to the literature. One contribution is the proposal of a new measure of pro-poor growth. This new measure provides the linkage between growth rates in mean income and in income inequality. In this context, growth is defined as pro-poor (or anti-poor) if there is a gain (or loss) in the growth rate due to a decrease (or increase) in inequality. The other contribution is a decomposition methodology that explores linkages growth patterns, and labour market performances. Through the decomposition analysis, growth in per capita income is explained in terms of four labour market components: the employment rate, hours of work, the labour force participation rate, and productivity. The proposed methodology are then applied to the Brazilian National Household Survey (PNAD) covering the period 1995-2004. The paper analyzes the evolution of Brazilian social indicators based on per capita income exploring links with adverse labour market performance.

Linkages between pro-poor growth, social programmes and labour market : the recent Brazilian experience

From a methodological point of view, this paper makes two contlibutions to the literature. One contribution is the proposal of a new measure of pro-poor growth. This new measure provides the linkage between growth rates in mean income and in income inequality. In this context, growth is defined as pro-poor (or anti-poor) if there is a gain (or loss) in the growth rate due to a decrease (or increase) in inequality. The other contribution is a decomposition methodology that explores linkages between three dimensions: growth pattems, labour market performances. and social policies. Through the decomposition analysis, growth in per capita income is explained in terms of four labour market components: the employment rate. hours of work, the labour force participation rate. and productivity. We also assess the contribution of different nonlabour income sources to growth patterns. The proposed methodologies are then applied to the Brazilian National Household Survey (PNAD) covering the period 1995-2004. The paper analyzes the evolution of Brazilian social indicators based on per capita income exploring links with adverse labour market performance and social policy change, with particular emphasis on the expansion of targeted cash transfers and devising more propoor social security benefits.

Metal binding selectivity of oxa-aza macrocyclic ligand: a DFT study of first- and second-row transition metal for four coordination systems

A detailed theoretical study of the 1,7,1l,17-tetraoxa-2,6,12,16-tetraaza-cycloeicosane ligand ([20]AneN(4)O(4)) coordinated to Fe2+, Co2+, Ni2+, Ru2+, Rh2+, and Pd2+ transition metal ions was carried out with the B3LYP method. Two different cases were performed: when nitrogen is the donor atom (1a (q) ) and also with the oxygen as the donor atom (1b (q) ). For all the cases performed in this study 1a (q) structures were always more stable than the 1b (q) ones. Considering each row is possible to see that the energy increases with the increase of the atomic number. The M2+ cation binding energies for the 1a (q) complexes increase with the following order: Fe2+ < Ru2+ < Co2+ < Ni2+ < Rh2+ < Pd2+.

First- and second-row transition metal oxa-aza macrocyclic complexes: a DFT study of an octahedral conformation

A theoretical study of structures of the 1,7,1 l,17-tetraoxa-2,6,12,16-tetraaza-cycloeicosane ligand ([20]AneN(4)O(4)) coordinated to Fe2+, Co2+, Ni2+, Ru2+, Rh2+, and Pd2+ transition metals ions was carried out with the DFT/B3LYP method. Complexes were fully optimized in C-s symmetry with the metal ions coordinated either to nitrogen (1a) or oxygen atoms (1b). For all the cases performed in this work, 1a was always more stable than 1b. Considering each row it is possible to see that the binding energy increases with the atomic number. The M2+ cation binding energies increase in the following order: Fe2+ < Ru2+ < Co2+ < Ni2+ < Rh2+ < Pd2+. In addition, it was observed the preference of Pd2+ and Rh2+ complexes for a tetrahedral arrangement, while Fe2+, Ru2+, Co2+, Ni2+ complexes had a preference for the octahedral arrangement. From the orbital representation results, it was seen that 1b unsymmetrical orbitals may influence the susceptibility over metal ions orientation toward heteroatoms orbitals.

The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes-a computational study

Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications.

The gender wage gap in developing and transition countries

The aim of my dissertation is to study the gender wage gap with a specific focus on developing and transition countries. In the first chapter I present the main existing theories proposed to analyse the gender wage gap and I review the empirical literature on the gender wage gap in developing and transition countries and its main findings. Then, I discuss the overall empirical issues related to the estimation of the gender wage gap and the issues specific to developing and transition countries. The second chapter is an empirical analysis of the gender wage gap in a developing countries, the Union of Comoros, using data from the multidimensional household budget survey “Enquete integrale auprès des ménages” (EIM) run in 2004. The interest of my work is to provide a benchmark analysis for further studies on the situation of women in the Comorian labour market and to contribute to the literature on gender wage gap in Africa by making available more information on the dynamics and mechanism of the gender wage gap, given the limited interest on the topic in this area of the world. The third chapter is an applied analysis of the gender wage gap in a transition country, Poland, using data from the Labour Force Survey (LSF) collected for the years 1994 and 2004. I provide a detailed examination of how gender earning differentials have changed over the period starting from 1994 to a more advanced transition phase in 2004, when market elements have become much more important in the functioning of the Polish economy than in the earlier phase. The main contribution of my dissertation is the application of the econometrical methodology that I describe in the beginning of the second chapter. First, I run a preliminary OLS and quantile regression analysis to estimate and describe the raw and conditional wage gaps along the distribution. Second, I estimate quantile regressions separately for males and females, in order to allow for different rewards to characteristics. Third, I proceed to decompose the raw wage gap estimated at the mean through the Oaxaca-Blinder (1973) procedure. In the second chapter I run a two-steps Heckman procedure by estimating a model of participation in the labour market which shows a significant selection bias for females. Forth, I apply the Machado-Mata (2005) techniques to extend the decomposition analysis at all points of the distribution. In Poland I can also implement the Juhn, Murphy and Pierce (1991) decomposition over the period 1994-2004, to account for effects to the pay gap due to changes in overall wage dispersion beyond Oaxaca’s standard decomposition.

Influence of Social Institutions on Inequality in China

This study analyses the impact of changes in social institutions, i.e. in the informal and formal social security system, on income inequality in China. This study uses an inequality decomposition analysis approach comparing household survey data for 1988 with 1995.Three main results emerge from the analysis: first, it findsthat the family based social security is losing its importance mainly through the changes in employment pattern in a household. This change contributes to rising income inequality. Second, thestudy shows that the introduction of new formal social security system helped to equalise the distribution of retired household members' income in urban areas in 1995. Third, however, these changes have only benefited a restricted number of persons. Benefits for rural migrants are low and most of the rural population has still no access to the new system.

Rules of Origin and Local Content in East Asia

Rules of Origin (RoO) are an integral part of all trade rules. In order to be eligible for Common Effective Preferential Tariffs (CEPT) under AFTA and similar arrangements under the ASEAN-China FTA, a product must satisfy the conditions relative to local content. The paper tries to calculate local content as well as cumulative local content in East Asian economies, with use of the Asian International Input-Output Tables; it also investigates factors of change in local content by applying decomposition analysis. The paper finds that the cumulation rule increased local content of the electronics industry more significantly than local content of the automotive industry, and the contribution of the cumulation rule increased in the period 1990-2000, due to rising dependency on neighboring ASEAN countries and China.

Spatial spillover effects in determining China's regional CO2 emission growth : 2007-2010

This paper proposes an alternative input-output based spatial-structural decomposition analysis to elucidate the role of domestic-regional heterogeneity and interregional spillover effects in determining China's regional CO2 emission growth. Our empirical results based on the 2007 and 2010 Chinese interregional input-output tables show that the changes in most regions' final demand scale, final expenditure structure and export scale give positive spatial spillover effects on other regions' CO2 emission growth, the changes in most regions' consumption and export preference help the reduction of other regions' CO2 emissions, the changes in production technology, and investment preference may give positive or negative impacts on other region's CO2 emission growth through domestic supply chains. For some regions, the aggregate spillover effect from other regions may be larger than the intra-regional effect in determining regional emission growth. All these facts can significantly help better and deeper understanding on the driving forces of China's regional CO2 emission growth, thus can enrich the policy implication concerning a narrow definition of "carbon leakage" through domestic-interregional trade, and relevant political consensus about the responsibility sharing between developed and developing regions inside China.

Four Decades of Studying Global Linear Instability: Progress and Challenges

Global linear instability theory is concerned with the temporal or spatial development of small-amplitude perturbations superposed upon laminar steady or time-periodic three-dimensional flows, which are inhomogeneous in two(and periodic in one)or all three spatial directions.After a brief exposition of the theory,some recent advances are reported. First, results are presented on the implementation of a Jacobian-free Newton–Krylov time-stepping method into a standard finite-volume aerodynamic code to obtain global linear instability results in flows of industrial interest. Second, connections are sought between established and more-modern approaches for structure identification in flows, such as proper orthogonal decomposition and Koopman modes analysis (dynamic mode decomposition), and the possibility to connect solutions of the eigenvalue problem obtained by matrix formation or time-stepping with those delivered by dynamic mode decomposition, residual algorithm, and proper orthogonal decomposition analysis is highlighted in the laminar regime; turbulent and three-dimensional flows are identified as open areas for future research. Finally, a new stable very-high-order finite-difference method is implemented for the spatial discretization of the operators describing the spatial biglobal eigenvalue problem, parabolized stability equation three-dimensional analysis, and the triglobal eigenvalue problem; it is shown that, combined with sparse matrix treatment, all these problems may now be solved on standard desktop computers