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International audience; Insisting on the clays properties when in contact with water (and especially the expansion), we describe how archaeological vestiges uncovered in excavations can be impacted by clays reactions. These, good or bad for earthen architecture, take numerous appearances and can provide indications for the needs of its conservation. Examples are taken on archaeological sites (Dura-Europos, Failaka), describing the effects on masonries, that we attempt to explain through the clays reactions. Suggestions are given for the choice of the materials and practices for the conservation (examples in Dura-Europos, Hegra). It is interesting to note that, during ‘Classic’ Antiquity, the ancient builders had a good knowledge of earth and that they could easily use it.

Lithium salts are the main treatment of bipolar disorder, which is characterized by potentially life-threatening maniac and/or depressive episodes. They have proven efficient in the prevention and treatment of acute episodes as well as in the prevention of suicidal risk. However, this efficacy is counterbalanced by a narrow therapeutic range that can lead to potentially harmful overdose, and by adverse long-term events. Nevertheless, they remain first-line treatment, notwithstanding therapeutic alternatives. In this review, we will describe toxic effects of long-term treatment at therapeutic levels of lithium salts. Regarding renal effects, early-impaired urine concentrating ability might lead to polyuria and polydipsia, and even to hypernatremia if free access to water is compromised. Long-term lithium treatment might also lead to chronic kidney disease, characterized by tubulo-interstitial multicystic nephropathy. End-stage renal disease requiring renal replacement therapy is a rare complication. Major extra-renal toxic effects are hypercalcemia and hypothyroidism. Treatment cessation due to these adverse events should be a multidisciplinary and case-by-case decision based on the benefit/risk ratio. Since these toxic effects are mild and display slow progression, treatment cessation is uncommon. However, regular medical and biological check-up is needed in order to prevent these disorders, and patients might be referred to nephrologists and/or endocrinologists once the disorders are established.

Ketoprofen is a non-steroidal anti-inflammatory drug known by its analgesic and antipyretic properties. However, it has a very low water solubility, which limits its bioavailability. To solve this problem, the active pharmaceutical ingredient is administered as a water soluble salt with sodium, lysine, arginine, N-methylglucamine or trometamol. The scope of this thesis is to study, for the first time, the crystal structures of salts of both racemic and S-ketoprofen with L-lysine and trometamol, and to obtain the crystal structure of new ketoprofen co-crystals or salts, in order to analyze the relationship between the structure and the properties of these solid forms. We succeeded to control the crystal growth of the salts of racemic and S-ketoprofen with trometamol and L-lysine, and with 2-amino-2-methyl propanol. The analysis of these salt structures has shown that they are formed by anionic layers of ketoprofenates which are inserted between the cations thanks to strong N-H...O and O-H...O hydrogen bonds. The cations form layers in trometamol and L-lysine salts. However, they are only connected by van der Waals interactions in the salts of 2-amino-2-methylpropanol. The cohesion of the anionic layers is ensured by weak C-H...O, C-H...[pi] or C-H...N interactions. The study of the thickness of anionic layers, as well as that of the surface and the volume occupied by a ketoprofenate anion in each anionic layer, shows significant differences in the salts. These variations may be explained by differences in the conformations of ketoprofenates anions. The study of geometrical parameters of ketoprofenate anions in the salts and those of the ketoprofen molecules in the pure active ingredients shows that the most important changes affect the twisting angles engaging the carboxylate/carboxylic acid that interacts with neighboring molecules/anions by short and highly directional intermolecular hydrogen bonds. The interactions in which the aromatic rings are incurred are rather weak, therefore the twisting angles involving these cycles slightly vary in the different crystal structures. Various techniques have also been used to characterize the salt, such as powder X-ray diffraction, differential scanning calorimetry (DSC), infrared (IR) spectroscopy, thermogravimetric analysis (TGA) and solid state nuclear magnetic resonance (NMR). The results were correlated with the crystal structures. The solubility measurements of the racemic ketoprofen-trometamol salt and the two polymorphs of S-ketoprofen-trometamol salts confirm that they have greatly improved solubility compared to the pure active ingredients, Le kétoprofène est un anti-inflammatoire non stéroïdien connu par ses propriétés analgésiques et antipyrétiques. Cependant, il présente une très faible solubilité dans l'eau, ce qui limite sa biodisponibilité. Afin de résoudre ce problème, le principe actif est administré sous forme de sels solubles dans l’eau avec le sodium, la lysine, l’arginine, la N-méthylglucamine et le trométamol. L’objectif de cette thèse était d’apporter pour la première fois la caractérisation structurale des sels de kétoprofène racémique et du S-kétoprofène avec la L-lysine et le trométamol, et de chercher à obtenir la structure cristalline de nouveaux co-cristaux ou sels de kétoprofène, pour analyser la relation structure-propriétés de ces formes solides. Nous avons réussi à faire la croissance cristalline des sels de kétoprofène racémique et de S-kétoprofène avec le trométamol et la L-lysine, ainsi qu’avec l’amine 2-amino-2-méthylpropanol. L’analyse des structures de ces sels a montré qu’ils sont tous formés par des couches anioniques de kétoprofènates entre les quelles s’insèrent les cations grâces aux liaisons hydrogène fortes de type N-H…O et O-H…O. Les cations forment des couches dans les sels avec le trométamol et la L-lysine. Cependant, ils ne sont connectés que par des interactions de Van der Waals dans les sels de 2-amino-2-méthylpropanol. La cohésion des couches anioniques est assurée par des interactions faibles de type C-H…O, C-H…[pi] ou C-H…N. L’étude de l’épaisseur des couches anionique, ainsi que la surface et le volume occupé par un anion kétoprofènate dans une couche montre des variations significatives dans les différents sels. Ces variations peuvent être expliquées par des différences des conformations des anions kétoprofènates. L’étude des paramètres géométriques des anions kétoprofènates dans les sels et ceux des molécules de kétoprofène dans les principes actifs montre que les variations les plus importantes touchent les angles de torsions engageant le groupement carboxylate/acide carboxylique qui interagit avec les molécules/anions voisines par des liaisons hydrogène intermoléculaires courtes et fortement directionnelles. Les interactions dans lesquelles les cycles aromatiques sont engagés sont plutôt faibles, par conséquent les angles de torsions mettant en jeu ces cycles varient peu dans les différentes structures cristallines. Différentes techniques ont été également utilisées pour caractériser les sels : diffraction des rayons X sur poudre, calorimétrie différentielle à balayage (DSC), spectroscopie infrarouge (IR), analyse thermogravimétrique (ATG) et résonance magnétique nucléaire à l’état solide (RMN). Les résultats obtenus ont été corrélés aux structures cristallines. Les mesures de solubilité du sel de kétoprofène racémique-trométamol et des deux polymorphes des sels de S-kétoprofène avec le trométamol confirment que ces derniers ont des solubilités très améliorées par rapport aux principes actifs purs

Within the framework of the development of generation IV reactors one of the research tracks is related to the development of fast neutron reactors using fluid sodium heat transfer...; Dans le cadre du développement des réacteurs de génération IV, une des voies de recherche concerne le développement des réacteurs à neutron rapide à caloporteur sodium. Le CEA a pour projet la construction d'un prototype de réacteur de ce type appelé " ASTRID ". En réponse aux besoins de développement de ce prototype, des recherches sont menées sur la disponibilité et, en particulier, sur la réduction des temps de lavage du sodium résiduel des assemblages de combustible, lors de leur déchargement. En effet, le lavage étant réalisé avec de l'eau, qui est très réactive avec le sodium, celle-ci est amenée de façon très progressive pour le traitement. Une solution alternative, actuellement à l'étude au CEA, et qui fait l'objet de ce mémoire de thèse, consiste en l'utilisation de solutions aqueuses salines permettant de ralentir la cinétique de la réaction du sodium avec l'eau. Ce travail de thèse présente les différents sels évalués et tente d'expliquer leur mécanisme d'action.

The complexity of transport mechanisms in nanofiltration (NF) requires the developmentof reliable modelling tools for understanding and optimizing the separation process.This study is composed of two parts. The first one focuses on the retention of a neutralsolute – poly(ethylene glycol) 600 g mol-1 (PEG) – in single solute solutions and in thepresence of mineral salts by an organic NF membrane (polyamide). Results show that PEGrejection is significantly lower in mixed-solute solutions and that rejection rate drop increaseswith salt concentration. This phenomenon cannot be imputed to only the partial dehydrationof PEG molecules by surrounding ions (salting-out effect). The additional hypothesis whichwas considered in the present work is an increase in the effective pore size (pore swelling).This hypothesis was supported by electrokinetics charge density data. The contribution ofpore swelling and salting-out to the overall decrease in the rejection rate of PEG wasevaluated for different salts at various concentrations.The second part of this study deals with (i) the determination of the dielectric constantinside pores (ep) of an NF organic membrane from membrane potential measurements and (ii)the validation of this technique. Membrane potential data were analyzed by means of theSEDE (steric, electric and dielectric exclusion) transport model. ep values were found to besmaller than the bulk value and to decrease when sodium ions were replaced by calcium ions.The agreement between ep values obtained from membrane potential measurements and thosecalculated from ion rejection rate data (ternary mixtures) highlights the global coherence ofthe transport model used and shows that membrane potential measured with electrolytemixtures can be used to determine the dielectric constant inside pores with no requirement ofadditional rejection rate measurements.; La complexité des mécanismes de transport en nanofiltration (NF) nécessite ledéveloppement d’outils de modélisation fiables permettant de comprendre et d’optimiser lesopérations de séparation en NF.La présente étude comprend deux volets. Le premier porte sur la rétention d’un soluténeutre – le poly(éthylène glycol) à 600 g mol-1 (PEG) – seul et en présence d’ions, par unemembrane organique de NF (polyamide). Les résultats obtenus montrent que la rétention dusoluté neutre chute en présence d’ions et ce, d’autant plus que la concentration du sel estélevée. Ce phénomène ne peut être expliqué par le seul phénomène de déshydratation dusoluté neutre par les ions environnants. Un phénomène supplémentaire de gonflement de porea été mis en évidence et corrélé à la densité de charge membranaire. La contribution des deuxphénomènes à la chute du taux de rejet du PEG a été évaluée pour différents sels à plusieursconcentrations.Le deuxième volet du travail est consacré à (i) l’évaluation de la constante diélectrique desolutions à l’intérieur de nanopores (ep) d’une membrane organique de NF (polyamide) àpartir de mesures de potentiel de membrane et (ii) la validation de cette méthode. Les valeursobtenues s’avèrent être inférieures à celle de la solution externe (effet du confinement) etdiminuer avec l’augmentation de la proportion en ions calcium du mélange (effet structurantdes ions). L’accord entre les constantes diélectriques ep déterminées à partir de mesures depotentiel de membrane et de taux de rejet ionique (mélanges ternaires) valide la cohérence dumodèle de transport utilisé (exclusion stérique, électrique et diélectrique aux interfaces) etmontre que les mesures de potentiel de membrane peuvent être envisagées pour l’évaluationcorrecte de la constante diélectrique à l’intérieur de nanopores

The complexity of transport mechanisms in nanofiltration (NF) requires the developmentof reliable modelling tools for understanding and optimizing the separation process.This study is composed of two parts. The first one focuses on the retention of a neutralsolute – poly(ethylene glycol) 600 g mol-1 (PEG) – in single solute solutions and in thepresence of mineral salts by an organic NF membrane (polyamide). Results show that PEGrejection is significantly lower in mixed-solute solutions and that rejection rate drop increaseswith salt concentration. This phenomenon cannot be imputed to only the partial dehydrationof PEG molecules by surrounding ions (salting-out effect). The additional hypothesis whichwas considered in the present work is an increase in the effective pore size (pore swelling).This hypothesis was supported by electrokinetics charge density data. The contribution ofpore swelling and salting-out to the overall decrease in the rejection rate of PEG wasevaluated for different salts at various concentrations.The second part of this study deals with (i) the determination of the dielectric constantinside pores (ep) of an NF organic membrane from membrane potential measurements and (ii)the validation of this technique. Membrane potential data were analyzed by means of theSEDE (steric, electric and dielectric exclusion) transport model. ep values were found to besmaller than the bulk value and to decrease when sodium ions were replaced by calcium ions.The agreement between ep values obtained from membrane potential measurements and thosecalculated from ion rejection rate data (ternary mixtures) highlights the global coherence ofthe transport model used and shows that membrane potential measured with electrolytemixtures can be used to determine the dielectric constant inside pores with no requirement ofadditional rejection rate measurements.; La complexité des mécanismes de transport en nanofiltration (NF) nécessite ledéveloppement d’outils de modélisation fiables permettant de comprendre et d’optimiser lesopérations de séparation en NF.La présente étude comprend deux volets. Le premier porte sur la rétention d’un soluténeutre – le poly(éthylène glycol) à 600 g mol-1 (PEG) – seul et en présence d’ions, par unemembrane organique de NF (polyamide). Les résultats obtenus montrent que la rétention dusoluté neutre chute en présence d’ions et ce, d’autant plus que la concentration du sel estélevée. Ce phénomène ne peut être expliqué par le seul phénomène de déshydratation dusoluté neutre par les ions environnants. Un phénomène supplémentaire de gonflement de porea été mis en évidence et corrélé à la densité de charge membranaire. La contribution des deuxphénomènes à la chute du taux de rejet du PEG a été évaluée pour différents sels à plusieursconcentrations.Le deuxième volet du travail est consacré à (i) l’évaluation de la constante diélectrique desolutions à l’intérieur de nanopores (ep) d’une membrane organique de NF (polyamide) àpartir de mesures de potentiel de membrane et (ii) la validation de cette méthode. Les valeursobtenues s’avèrent être inférieures à celle de la solution externe (effet du confinement) etdiminuer avec l’augmentation de la proportion en ions calcium du mélange (effet structurantdes ions). L’accord entre les constantes diélectriques ep déterminées à partir de mesures depotentiel de membrane et de taux de rejet ionique (mélanges ternaires) valide la cohérence dumodèle de transport utilisé (exclusion stérique, électrique et diélectrique aux interfaces) etmontre que les mesures de potentiel de membrane peuvent être envisagées pour l’évaluationcorrecte de la constante diélectrique à l’intérieur de nanopores

Intramuscular injection of quinine is a mainstay treatment for malaria in children. However it can lead to severe orthopedic complications including sciatic paralysis after intragluteal injection and quadriceps contracture after intraquadricipital injection. This report based on a 98-case series of complications following intramuscular quinine injection that were treated surgically in 88 cases describes clinical findings with special emphasis on the severity. Therapeutic alternatives for these complications are presented and discussed including the use of medial release or double subtalar and midtarsal arthrodesis for correction of foot deformity in function of age. Correction may be associated with anterolateral transposition of the posterior tibialis tendon that is generally not paralyzed. For correction of complications involving the knee, the authors recommend extended proximal quadriceps release that is more invasive but achieves better results than lengthening plasty of the distal quadriceps.

The first part of this study consists in the investigation of the evaporation and the condensation rate of H2O in the presence of different types of ice in a low pressure flow reactor. The second part of the present work reports the study of chlorine activation on different types of frozen salt substrates in a low pressure flow reactor. The third part concerns the construction and testing of a laminar flow reactor at atmospheric pressure in order to study bromine and chlorine activation reactions on different types of sea salt and model aerosols at different relative humidity. The kinetics of H2O condensation (kc) and the evaporation flux (Jev) of H2O on ice was studied in the range 130 to 210 K using pulsed-valve and steady state admission techniques in a low pressure flow reactor. The uptake coefficient γ was measured for different types of ice, namely, Condensed (C), Bulk (B), Single Crystal (SC), Snow (S) and Cubic ice (K). The negative temperature dependence of γ for C, B, SC and S ice reveals a precursor-mediated adsorption/desorption process. The non-Arrhenius behavior of the rate of condensation kc manifests itself in a discontinuity in the range 170 to 190 K depending on the type of ice and is consistent with a precursor model of H2O condensation/evaporation. The average of the energy of sublimation Δ0S is (12.0 ± 1.4) kcal/mol for C, B, S, SC ice and is identical within experimental uncertainty between 136 and 210 K. The same is true for the entropy of sublimation ΔSS. In contrast, both γ and the evaporative flux Jev are significantly different for different ices. In the range 130 to 210 K, Jev of H2O ice was significantly smaller than the maximum theoretically allowed value. This corroborates γ values significantly smaller than unity in the specified T range. Based on the present kinetic parameters the time to complete evaporation of a small ice particle of radius 1 µm is approximately a factor of 5 larger than previously thought. The HOCl heterogeneous reactions on frozen solutions of sea salt (SS), frozen KCl or NaCl were studied in a low pressure flow reactor in order to measure the uptake coefficient γ and the reaction products. The HOCl sample always contained up to 25% of Cl2O that was studied apart in order to relate the Cl2 produced to the HOCl taken up. The main product formed on NSS frozen solution is gas-phase Cl2 that is sustained for at least one hour in contrast to KCl or NaCl frozen solution that produced a transient Cl2 flow that decreases after 100s. We found that approximately 30% of the HOCl taken up from the HOCl/Cl2O mixture reacts to produce Cl2 on NSS, RSS and KCl frozen solution at 200 K at a HOCl concentration larger than 1011 molecule cm-3. In contrast, HOCl concentrations of a few 1010 molecule cm-3 at 200 K failed to produce additional Cl2 in contrast to pure Cl2O uptake. A single Br2 burst event was also monitored when Cl2O or a HOCl/Cl2O mixture is taken up on fresh frozen NSS solution during the first uptake run at 200 K. Further Cl2O or HOCl/Cl2O uptake on the same sample will not lead to a Br2 pulse. Annealing of a previously exposed frozen NSS solution to 240 K and subsequently cooling did not lead to a Br2 burst event either. The HOBr and HOCl uptake coefficient γ on acidified submicron salt aerosol was measured in an atmospheric flow tube reactor. The interaction time of the trace gas with the aerosol was in the range 15 to 90 s and led to γ values ranging from 10-4 to 10-2. The acidity of the aerosol is essential in order to enable heterogeneous reactions on NaCl, recrystallized sea salt (RSS) and natural sea salt (NSS) aerosols for both HOCl and HOBr. Specifically, HOCl exclusively reacts on acidified NSS aerosols with a γ ranging from 1.8 × 10-3 to 0.4 × 10-3 at a relative humidity between 40 and 85%, respectively. In addition, γ(HOBr) is approximately 10-2 for relative humidity in the range 77 to 90% on NaCl and RSS acidified aerosol. Uptake experiments of HOBr on aqueous H2SO4 as well as on acidified NaCl, RSS or NSS aerosols were performed for rh ranging from 40 to 93%. γ of HOBr on acidified NSS reaches a maximum at rh = 77% and decreases significantly for higher rh in contrast to acidified NaCl and RSS aerosols. This difference in γ is attributed to the presence of an organic phase in NSS aerosols that forms an organic coating at high rh. In addition, preliminary uptake experiment of HNO3 was performed on NaCl and NSS aerosols using the atmospheric flow tube reactor. We were able to perform experiments only from 2.8 to 25% relative humidity. For a relative humidity larger than 25%, all gas phase HNO3 is taken up on the reactor wall and no experiments could be performed. γ of HNO3 in the range (2-3) × 10-2 for NaCl and NSS aerosol, respectively, at 2.8% relative humidity. At rh = 25%, γ(HNO3) is approximately 10-1 for both NaCl and NSS aerosols.

Arterial hypertension is a complex trait influenced by a variety of environmental and genetic factors. Several approaches can be used to identify its susceptibility genes : one is to study rare monogenic forms of hypertension, like familial hyperkalemic hypertension (FHH). Also known as pseudohypoaldosteronism type 2 or Gordon syndrome, FHH is characterized by hypertension, hyperkalemia despite normal renal glomerular filtration rate, abnormalities which are particularly sensitive to thiazide diuretics. Mild hyperchloremia, metabolic acidosis, and suppressed plasma renin activity are associated findings. Despite its phenotypic and genetic heterogeneity, mutations in two related genes, WNK1 and WNK4, were recently identified. These genes belong to a newly identified family of serine-threonine (with no lysine [K]) kinases. Both are highly expressed in the kidney and in a variety of epithelia involved in chloride transport. It has thus been postulated that these two kinases could be implicated in a new pathway of ionic transport regulation. Several studies have very recently confirmed this hypothesis in vitro, in Xenopus oocytes or kidney cell lines. They have shown that, in the renal distal tubule, WNK4 inhibits sodium reabsorption and potassium secretion, via inhibition of NCC (thiazide-sensitive Na+-Cl- cotransporter) and K+ channel ROMK activity, respectively. Interestingly, FHH mutations have opposite effects : while they lead to loss of NCC inhibition, they increase ROMK inhibition. Moreover, they also increase paracellular permeability to chloride of MDCK cells. WNK4 also inhibits apical and basal chloride transporters present in extra-renal epithelia, such as CFEX and Na+-K+-2 Cl-, respectively. It is also interesting to note that the WNK4-mediated negative regulation of NCC activity is in turn inhibited by WNK1. By its role on several transporters, WNK4 appears as a putative key regulator of ionic transport and blood pressure.

Zinc is an essential trace element for the human organism. It acts like cofactor for the metalloenzymes involved in many cellular processes. Its anti-inflammatory activity, which is the basis of therapeutic use, other than acrodermatitis enteropathica, is not well known: production of cytokines, antioxidant activity. Its toxicity is very low, but marked at high doses during chronic administration by the risk of hypocupremia. It is not teratogenic and can be given during pregnancy. Its absorption, through the duodenum, is inhibited by excessive phytate intake. Maximum concentration is reached after 2 to 3 hours. It is widely distributed in the organism, mainly in muscles and bone. Excretion is predominantly digestive. Its spectacular effect in acrodermatitis enteropathica, through compensation of genetically determined malabsorption was discovered in 1973. Its usefulness in acne is based on the anti-inflammatory action and was first described with zinc sulfate, then with better tolerated gluconate. Many controlled studies have shown an efficacy on inflammatory lesions. Doses varied from 30 to 150 mg of elemental zinc and studies against cyclines have shown that minocycline has a superior effect; but zinc might be an alternative treatment when cyclines are contraindicated. To date we don't have convincing data for its use in other indications (leishmaniosis, warts, cutaneous ulcers). Tolerance at usual doses (200 mg of zinc gluconate or 30 mg of elemental zinc) is good. Major side effects are abdominal with nausea, vomiting, but are fleeting and dose dependent.

In order to test the fertilization effect on Artemia production, six treatments of a mineral fertilization with di-ammonium phosphate (DAP) and urea (0.25*F; 0.5*F; 0.75*F; 1*F; 1.5*F; 2*F with F = 15 mg/L of DAP and 15 mg/L of urea) were compared to a control unfertilized. After the initial fertilization (day 0), a half a dose was brought once a week. At day 8, Artemia nauplii were inoculated in all tanks at the rate of 50 nauplii per liter. Physico-chemical and biological parameters of the culture were analysed each week, during the 48 days of experiment. The results showed that the optimal dose is 0.75*F; it gaves the maximal phytoplanctonic biomass expressed by chlorophyll-a has and it allowed to obtain a maximal production of Artemia (cysts and biomass). Results of Artemia production were superior to those observed in a preliminary experiment using only the F dose. En vue de tester l’effet de la fertilisation sur la production d’Artemia, six doses d’une fertilisation minérale à base de phosphate d’ammoniaque (DAP) et d’urée ont été étudiées (0,25*F ; 0,5*F ; 0,75*F ; 1*F ; 1,5*F ; 2*F) et comparées à un témoin non fertilisé avec F=0,015g/l de DAP et 0,015g/l d’urée, pour la fertilisation initiale, puis la moitié de la dose de départ a été apportée ensuite une fois par semaine. Huit jours après la première fertilisation (J0), des nauplii d’Artemia ont été inoculés dans tous les bacs à raison de 50 nauplii/litre ; un suivi des paramètres physico-chimiques et biologiques de la culture a été réalisé tout au long des 48 jours d’expérimentation. Les résultats obtenus ont montré que la dose optimale est 0,75*F ; elle donne la meilleure biomasse phytoplanctonique exprimée par la mesure de la chlorophylle-a, et elle permet d’obtenir la meilleure production d’Artemia (cystes et biomasse). Les résultats de production d’Artemia ont été supérieurs à ceux observés dans une expérience préliminaire employant uniquement la dose F. Published Dunaliella salina; Salines;fertilisation minirale