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This article presents the derivation of the thermodynamic expressions for the activation free energy and reaction rate constant for cosolvent reaction systems. These expressions account for the factors that are specific to solution-phase reactions, which include isotropic electrostatic effects and close-range solvent−solute interactions. This article discusses the idea that electrostatic effects can be correlated with the isotropic relative permittivity, and solvent−solute interactions can be correlated with the cosolvent mole fraction. This article also shows that this type of thermodynamic analysis is necessary for understanding certain nuances of solution-phase reaction processes not tractable by other types of analyses.

Cette étude vise à une meilleure compréhension des phénomènes rencontrés en filtration des aérosols nanométriques, c’est-à-dire inférieurs à 100 nm, neutres et/ou chargés. Pour ce faire, trois différents types de média ont été étudiés : des grilles, en acier et matières synthétiques, des filtres non tissés, en fibres de verre ou polymériques, et des lits granulaires, constitués de billes d’acier ou de zéolithe. Il ressort des résultats expérimentaux obtenus que quel que soit le média testé, l’efficacité de collecte des particules augmente lorsque le diamètre de l’aérosol diminue, et ce jusque 4 nm. Ceci entre en contradiction avec l’approche théorique dite du rebond thermique, développée par Wang et Kasper en 1991, selon laquelle l’efficacité de collecte serait susceptible de diminuer en-dessous de 10 nm. La vérification des calculs de Wang et Kasper permet d’expliquer cette incohérence, et montre, à partir de valeurs plus réalistes de l’énergie d’adhésion particule-fibre, que si le rebond thermique existe, celui-ci ne pourra se manifester qu’en-dessous de 1 nm, au mieux. Ainsi, les perméances expérimentales des différents médias testés ont pu être modélisées en tenant compte des mécanismes de collecte par diffusion et/ou par effets électrostatiques. Une étude originale sur les performances, dans le domaine nanométrique, de filtres en fibres de verre intentionnellement percés complète ce travail. Pour un même média fibreux, la perméance augmente avec le diamètre de perforation réalisée. Par ailleurs, pour une taille de perforation donnée, la perméance devient indépendante du diamètre des particules en-dessous d’une taille limite, fonction de la dimension de la perforation. Il a enfin été mis en évidence que la baisse d’efficacité est d’autant plus importante que la résistance à l’écoulement de l’air du filtre est importante. Un modèle semi-empirique, fondé sur la différenciation du flux d’aérosol traversant la fuite du flux traversant le matelas fibreux résiduel du filtre, permet de bien représenter ces états de fait / This study aims to better understand the mechanisms encountered in nanoparticles aerosol filtration, the particles being charged or not. Three different types of media were studied: stainless steel or synthetics wire screens, unwoven filters in glass or polymer fibres, and at last, granular beds made from steel or zeolite balls. Experimental results show that, whatever the media, collection efficiency increases as the particle diameter decreases down to 4 nm. This point conflicts with the so-called thermal rebound effect developed by Wang and Kasper in 1991, according to which collection efficiency could decrease below 10 nm. The checking of Wang and Kasper’s calculations enables to explain this discrepancy and shows from more probable particle-to-fibre adhesion energy values that if thermal rebound phenomenon exists, it would only be measurable below 1 nm. Then, experimental points can be modelled from both diffusion and electrostatic forces collection mechanisms. An investigation on the filtration behaviour of fibreglass filters in the nanometric domain when intentionally-pierced with calibrated needles completes the above-mentioned works. For a same media, penetration increases as the leak diameter does. On the other hand, for a given hole size, penetration becomes independent of the particle diameter below a critical scale, which is a function of the leak diameter. It was lastly shown that the efficiency of a pierced media decreases all the more that its air flow resistance is higher. A semi-empirical model based on the differentiation between the aerosol flow across the leak and the one through the residual fibrous bed of the filter enables to well represent these points

<p>When drug molecules are passively absorbed through the cell membrane in the small intestine, the first key step is partitioning of the drug into the membrane. Partition data can therefore be used to predict drug absorption. The partitioning of a solute can be analyzed by drug partition chromatography on immobilized model membranes, where the chromatographic retention of the solute reflects the partitioning. The aims of this thesis were to develop the model membranes used in drug partition chromatography and to study the effects of different membrane components and membrane structures on drug partitioning, in order to characterize drug–membrane interactions.</p><p>Electrostatic effects were observed on the partitioning of charged drugs into liposomes containing charged detergent, lipid or phospholipid; bilayer disks; proteoliposomes and porcine intestinal brush border membrane vesicles (BBMVs), and on the retention of an oligonucleotide on positive liposomes. Biological membranes are naturally charged, which will affect drug partitioning in the human body.</p><p>Proteoliposomes containing transmembrane proteins and cholesterol, BBMVs and bilayer disks were used as novel model membranes in drug partition chromatography. Partition data obtained on proteoliposomes and BBMVs demonstrated how cholesterol and transmembrane proteins interact with drug molecules. Such interactions will occur between drugs and natural cell membranes. In the use of immobilized BBMVs for drug partition chromatography, yet unsolved problems with the stability of the membrane were encountered. A comparison of partition data obtained on bilayer disks with data on multi- and unilamellar liposomes indicated that the structure of the membrane affect the partitioning. The most accurate partition values might be obtained on bilayer disks.</p><p>Drug partition data obtained on immobilized model membranes include both hydrophobic and electrostatic interactions. Such partition data should preferably be used when deriving algorithms or computer programs for prediction of drug absorption.</p>

When drug molecules are passively absorbed through the cell membrane in the small intestine, the first key step is partitioning of the drug into the membrane. Partition data can therefore be used to predict drug absorption. The partitioning of a solute can be analyzed by drug partition chromatography on immobilized model membranes, where the chromatographic retention of the solute reflects the partitioning. The aims of this thesis were to develop the model membranes used in drug partition chromatography and to study the effects of different membrane components and membrane structures on drug partitioning, in order to characterize drug–membrane interactions. Electrostatic effects were observed on the partitioning of charged drugs into liposomes containing charged detergent, lipid or phospholipid; bilayer disks; proteoliposomes and porcine intestinal brush border membrane vesicles (BBMVs), and on the retention of an oligonucleotide on positive liposomes. Biological membranes are naturally charged, which will affect drug partitioning in the human body. Proteoliposomes containing transmembrane proteins and cholesterol, BBMVs and bilayer disks were used as novel model membranes in drug partition chromatography. Partition data obtained on proteoliposomes and BBMVs demonstrated how cholesterol and transmembrane proteins interact with drug molecules. Such interactions will occur between drugs and natural cell membranes. In the use of immobilized BBMVs for drug partition chromatography, yet unsolved problems with the stability of the membrane were encountered. A comparison of partition data obtained on bilayer disks with data on multi- and unilamellar liposomes indicated that the structure of the membrane affect the partitioning. The most accurate partition values might be obtained on bilayer disks. Drug partition data obtained on immobilized model membranes include both hydrophobic and electrostatic interactions. Such partition data should preferably be used when deriving algorithms or computer programs for prediction of drug absorption.