Sustainable production and consumption, as well as decoupling environmental impact from economy growth are one of the main goals for countries with transition economies. Lithuania, as other Central and Eastern Europe (CEE) countries experienced changes in political, social and economic life in relative short time after the collapse of Soviet Union. Because of an essentially reduced production, use of natural resources and environmental pollution decreased respectively. However, present pronounced growth of transition countries and demand for better quality of life could lead to the increase in material and energy consumption. Such increase would have two implications: firstly, increasing pressure on the environment and health in enlarged EU and could outweigh achievements in Western Europe, and secondly, such increase could impede to reach foreseen objectives to decouple resource consumption from economic growth. The aim of the research was to analyze the main trends of production and consumption and their environmental impact in Lithuania and to assess eco-efficiency of production and consumption and its main determinants. Research on eco-efficiency and the course of decoupling of environmental impact from economy growth in Lithuania is relatively rare and is mostly based on energy issues or covers only one sector. In this study, the eco-efficiency of production and consumption in Lithuania is analyzed jointly for the first time. For the better interpretation of ongoing... [to full text] / Darnios gamybos ir vartojimo siekimas, o tuo pačiu ir poveikio aplinkai atsiejimas nuo ekonomikos, yra vienas pagrindinių darnaus vystymosi tikslų pereinamosios ekonomikos šalims. Lietuva, kaip ir kitos posovietinės šalys, po Sovietų Sąjungos griūties paveldėjo imlų ištekliams ir neefektyvų ūkį. Ūkio restruktūrizavimas lėmė transformacinį ūkio nuosmukį ir jį sekusį išteklių naudojimo ir aplinkos teršimo sumažėjimą. Tačiau dabartinis spartus pereinamosios ekonomikos šalių, kurių dauguma jau tapo ES narėmis, augimas ir geresnės gyvenimo kokybės siekimas gali lemti didesnes medžiagų ir energijos sąnaudas, o tai savo ruožtu sąlygotų didėjantį poveikį aplinkai ir žmonių sveikatai išsiplėtusioje Europos Sąjungoje ir atsvertų kai kuriuos ES šalių senbuvių pasiekimus bei trukdytų pasiekti numatytus išteklių naudojimo atsiejimo nuo ekonomikos augimo tikslus. Darbo tikslas - išanalizuoti Lietuvos gamybos, vartojimo ir jų poveikio aplinkai kitimo tendencijas, ekologinio veiksmingumo pokyčius ir nustatyti jį lemiančius veiksnius. Ekologinio veiksmingumo bei poveikio aplinkai atsiejimo nuo ekonomikos augimo tyrimai Lietuvos mastu palyginti mažai vykdyti ir dažnai apsiriboja tik energetinių išteklių naudojimo veiksmingumo analize arba skirti tik atskiriems sektoriams. Darbe pateikiama dvigubo atsiejimo koncepcija, numatanti būtinybę atsieti gamtos išteklių naudojimą nuo ekonomikos augimo ir aplinkos teršimą nuo gamtos išteklių naudojimo bei sudaranti galimybes detaliau įvertinti... [toliau žr. visą tekstą]

Darnios gamybos ir vartojimo siekimas, o tuo pačiu ir poveikio aplinkai atsiejimas nuo ekonomikos, yra vienas pagrindinių darnaus vystymosi tikslų pereinamosios ekonomikos šalims. Lietuva, kaip ir kitos posovietinės šalys, po Sovietų Sąjungos griūties paveldėjo imlų ištekliams ir neefektyvų ūkį. Ūkio restruktūrizavimas lėmė transformacinį ūkio nuosmukį ir jį sekusį išteklių naudojimo ir aplinkos teršimo sumažėjimą. Tačiau dabartinis spartus pereinamosios ekonomikos šalių, kurių dauguma jau tapo ES narėmis, augimas ir geresnės gyvenimo kokybės siekimas gali lemti didesnes medžiagų ir energijos sąnaudas bei poveikį žmonių sveikatai, o tai savo ruožtu sąlygotų didėjantį poveikį aplinkai išsiplėtusioje Europos Sąjungoje ir atsvertų kai kuriuos ES šalių senbuvių pasiekimus bei trukdytų pasiekti numatytus išteklių naudojimo atsiejimo nuo ekonomikos augimo tikslus. Darbo tikslas - išanalizuoti Lietuvos gamybos, vartojimo ir jų poveikio aplinkai kitimo tendencijas, ekologinio veiksmingumo pokyčius ir nustatyti jį lemiančius veiksnius. Ekologinio veiksmingumo bei poveikio aplinkai atsiejimo nuo ekonomikos augimo tyrimai Lietuvos mastu palyginti mažai vykdyti ir dažnai apsiriboja tik energetinių išteklių naudojimo veiksmingumo analize arba skirti tik atskiriems sektoriams. Darbe pateikiama dvigubo atsiejimo koncepcija, numatanti būtinybę atsieti gamtos išteklių naudojimą nuo ekonomikos augimo ir aplinkos teršimą nuo gamtos išteklių naudojimo bei sudaranti galimybes detaliau įvertinti... [toliau žr. visą tekstą] / Sustainable production and consumption, as well as decoupling environmental impact from economy growth are one of the main goals for countries with transition economies. Lithuania, as other Central and Eastern Europe (CEE) countries experienced changes in political, social and economic life in relative short time after the collapse of Soviet Union. Because of an essentially reduced production, use of natural resources and environmental pollution decreased respectively. However, present pronounced growth of transition countries and demand for better quality of life could lead to the increase in material and energy consumption. Such increase would have two implications: firstly, increasing pressure on the environment in enlarged EU and could outweigh achievements in Western Europe, and secondly, such increase could impede to reach foreseen objectives to decouple resource consumption from economic growth. The aim of the research was to analyze the main trends of production and consumption and their environmental impact in Lithuania and to assess eco-efficiency of production and consumption and its main determinants. Research on eco-efficiency and the course of decoupling of environmental impact from economy growth in Lithuania is relatively rare and is mostly based on energy issues or covers only one sector. In this study, the eco-efficiency of production and consumption in Lithuania is analyzed jointly for the first time. For the better interpretation of ongoing... [to full text]

Au cours de ce travail de thèse, nous nous sommes focalisés sur deux aspects de la RMN du solide: i) la RMN double-résonance de noyaux de fréquences de Larmor proches, ii) la quantitativité des spectres RMN sous polarisation croisée (CPMAS). L’emploi d’une sonde RMN solide prototype multicanaux (1H/19F/X/Y/Z) nous a permis de développer des outils RMN originaux pour la caractérisation de matériaux fluorés et ou hétérogènes (principes actifs, matériaux poreux, polymères), notamment le triple transfert de polarisation (1H, 19F) -13C, le double-transfert en cascade, les découplages multiples, et autres expériences de double-résonance 1H-19F ou 13C-27Al. La séquence multiCP a ensuite été évaluée pour l’obtention de spectre RMN 13C ou 29Si quantitatifs et la caractérisation de matériaux ayant des temps de relaxation contrastés. Nous avons montré que la condition pour obtenir des spectres RMN multiCP quantitatifs est la présence d’un bain de spins 1H dense. Des mesures quantitatives pour des composés purs (acides aminés, principes actifs, excipients, polymères inorganiques) ou en mélanges ont ainsi été obtenues. Le multiCP a ensuite été utilisé pour caractériser la structure locale de polymères siliciés et la nature fine du système de protons dans des membranes de Nafion. Dans la continuité, nous avons étudié une formulation pharmaceutique. Dans ce système hétérogène, nous avons profité des contrastes de temps de relaxation pour distinguer et quantifier les molécules de principe actif à l’intérieur ou en dehors du surfactant. Nous avons également caractérisé les interactions de la molécule avec le surfactant et suivi sa libération dans différents milieux mimant les milieux physiologiques. L’ensemble de ces travaux offre de nouveaux outils RMN pour la caractérisation de la structure locale de matériaux hétérogènes. / During this work, two aspects of solid-state NMR have been investigated: i) double-resonance NMR of nuclei with close Larmor frequencies, ii) quantitative cross-polarization (CPMAS) measurements. The use of a prototype multichannel solid NMR probe (1H/19F/X/Y/Z) has allowed the development of original NMR tools for the structural characterization of fluorinated or heterogeneous materials (active principles, porous solids, polymers), in particular the triple polarization transfer (1H, 19F) -13C, double-transfer ‘en cascade’, multiple decoupling, and other 1H-19F ou 13C-27Al double-resonance experiments. The multiCP experiment has then been evaluated to get quantitative 13C and 29Si NMR spectra and to characterize materials with contrasted relaxation times. We have shown that the presence of dense proton bath was key to get quantitative data. Quantitative measurements were then obtained for pure solids (aminoacids, active principles, excipients, inorganic polymers) and mixtures. The multiCP has then been used to characterize the local structure of siliceous polymers and the nature of the proton spin system in Nafion membranes. Finally, we have studied a pharmaceutical formulation. In this heterogenous system, we have taken benefit from the contrasted relaxation times to distinguish molecules present inside or outside the surfactant. We have also characterized the interactions between the active principle and the surfactant and followed the drug release in various physiological media. The ensemble of this work provides new NMR tools for the characterization of the local structure of heterogeneous materials.

Abstract Spontaneous changes in protein systems, such as the binding of a ligand to an enzyme or receptor, are characterized by a decrease of free energy. Despite the recent developments in computing power and methodology, it remains challenging to accurately estimate free energy changes. Major issues are still concerned with the accuracy of the underlying model to describe the protein system and how well the calculation in fact emulates the behaviour of the system. This thesis is largely concerned with the quality of current free energy calculation methods as applied to protein-ligand systems. Several methodologies were employed to calculate Gibbs standard free energies of binding for a collection of protein-ligand complexes, for which experimental affinities were available. Calculations were performed using system description with different levels of accuracy and included a continuum approach, which considers the protein and the ligand at the atomic level but includes solvent as a polarizable continuum, and an all-atom approach that relies on molecular dynamics simulations. In most such applications, the effects of ionic strength are neglected. However, the severity of this approximation, in particular when calculating free energies of charged ligands, is not very clear. The issue of incorporating ionic strength in free energy calculations by means of explicit ions was investigated in greater detail and considerable attention was given to the affinities of charged peptides in the presence of explicit counter-ions. A second common approximation is concerned with the description of ligands that exhibit multiple protonation states. Because most of current methods do not model changes in the acid dissociation constants of titrating groups upon binding, protonation equilibria of such ligands are not taken into account in free energy calculations. The implications of this approximation when predicting affinities were analysed. Finally, when calculating free energies of binding, a correct description of the interactions between the protein and the ligand is of fundamental importance. However, active sites of enzymes, where strained conformations may hold a functional role, are not always accurately modelled by molecular mechanics force fields. The case of a strained planar proline in the active site of triosephosphate isomerase was investigated using an hybrid quantum mechanics/molecular mechanics method, which implies a higher level of accuracy.