Study of Gordon (PHAII) and Gitelman (GS) syndromes revealed the importance of the WNK pathway and thiazide-sensitive Na-Cl Cotransporter (NCC) in the renal control of blood pressure. PHAII mutations lead to WNK accumulation resulting in the hyperphosphorylation of the downstream effector, SPAK, which overactivates NCC causing salt retention and hypertension. Mutations causing deletion of exon-9 in Cullin-3, which normally ubiquitylates WNKs for degradation, were recently discovered to cause the severest subtype of PHAII (PHA2E) with early onset salt-sensitive hypertension and hyperkalaemia. The reasons for this severity have remained elusive, however clues came from SPAK knock-out mice which recapitulate GS, the phenotypic mirror image of PHAII, typically caused by activation-inhibiting NCC phosphorylation site mutations resulting in salt-wasting and hypotension. As these mice were also discovered to have reduced vascular tone, it suggests the WNK pathway may have extra-renal roles in vascular smooth muscle function and highlights inhibition of SPAK function as a promising anti-hypertensive strategy with multiple sites of action. To address these possibilities the work aimed to phenotype: (1) heterozygous CUL3$^{WT/\Delta403-459}$ mice to investigate a possible vascular contribution to PHAII pathophysiology, (2) homozygous knock-out mice of MO25, a master regulator known to increase SPAK activity up to 100-fold independent of WNKs, and (3) homozygous SPAK$^{L502A/L502A}$ knock-ins, predicted to have disrupted SPAK binding to WNK/NCC, in order to validate SPAK signalling inhibition as a viable anti-hypertensive strategy. In mice, the CUL3$^{\Delta403-459}$ proteins are hyperflexible, hypermodified and ultimately have reduced WNK ubiquitylation. This lead to hypertension, hyperkalaemia, hyperchloraemia with compensated metabolic acidosis and growth retardation, which closely recapitulates human PHA2E. The discovery of increased vascular tone suggests an explanation for the severity of CUL3$^{\Delta}$$^{ex9}$PHAII. In mice, homozygous MO25$\alpha$ knock-out proved embryonically lethal, while homozygous MO25$\beta$ knock-out did not meaningfully alter blood pressure or electrolyte homeostasis. However, the SPAK$^{L502A}$ protein had a decreased ability to bind WNKs and cation-chloride cotransporters NCC and NKCC1/2, serving to reduce their activation. SPAK$^{L502A/L502A}$ mice showed typical features of GS with mild hypokalaemia, hypomagnesaemia, hypocalciuria and salt-wasting hypotension. The mice also presented with decreased markers of vascular tone potentially due to effects on cardiovascular and neuronal NKCC1. These results show that SPAK binding is crucial for blood pressure control and pharmacological inhibition of this binding is an attractive anti-hypertensive strategy.

Yue Gar-Lee Grace. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 113-120). / Abstracts in English and Chinese. / Abstract (English version) --- p.i / Abstract (Chinese version) --- p.iii / Acknowledgements --- p.v / Table of contents --- p.vi / List of figures --- p.x / List of tables --- p.xiii / List of abbreviations --- p.xiv / Chapter Chapter I: --- Introduction --- p.1 / Chapter 1.1. --- Transepithelial electrolyte transport in colon --- p.1 / Chapter 1.1.1. --- Intestinal fluid secretion --- p.1 / Chapter 1.1.2. --- Cellular mechanism of chloride secretion --- p.3 / Chapter 1.2. --- Biological activities of flavonoids --- p.6 / Chapter 1.2.1. --- Classification and general activities of flavonoids --- p.6 / Chapter 1.2.2. --- Bioavailability and pharmacokinetic properties of flavonoids --- p.8 / Chapter 1.3. --- "What is Scutellariae radix""?" --- p.9 / Chapter 1.3.1. --- Usage in Traditional Chinese Medicine --- p.9 / Chapter 1.3.2. --- Relationship with Coptidis rhizoma --- p.9 / Chapter 1.4. --- Effect of flavonoids on gastrointestinal activities --- p.12 / Chapter 1.4.1. --- Genistein and quercetin --- p.12 / Chapter 1.4.2. --- Baicalein --- p.12 / Chapter 1.5. --- Possible intracellular signaling pathway involved in the secretory response by Scutellariae radix (SR) in T84 cells --- p.14 / Chapter 1.5.1. --- Human colonic T84 cell --- p.14 / Chapter 1.5.2. --- Intracellular signaling pathway --- p.14 / Chapter 1.6. --- Aim of study --- p.17 / Chapter Chapter II : --- Methods and Materials --- p.18 / Chapter II.1. --- Culture technique of the T84 cells --- p.18 / Chapter II.2. --- Simultaneous measurement of short-circuit current (Isc) and intracellular calcium ([Ca2+]i) --- p.21 / Chapter II.2.1. --- Experimental setup --- p.21 / Chapter II.2.2. --- Preparation of the permeable supports --- p.23 / Chapter II.2.3. --- Cell seeding --- p.27 / Chapter II.2.4. --- Dye loading --- p.27 / Chapter II.2.5. --- Simultaneous measurement of Isc and [Ca2+]i- --- p.30 / Chapter II.3. --- Conventional short-circuit current (Isc) measurement --- p.34 / Chapter II.3.1. --- Experimental setup --- p.34 / Chapter II.3.2. --- Preparation of the permeable supports --- p.36 / Chapter II.3.3. --- Cell seeding --- p.36 / Chapter II.3.4. --- Measurement --- p.38 / Chapter II.4. --- Measurement of cAMP --- p.39 / Chapter II.5. --- Solutions and chemicals --- p.40 / Chapter II.6. --- Statistical analysis --- p.42 / Chapter Chapter III : --- Results --- p.43 / Chapter III. 1. --- Effects of baicalein and its interaction with calcium and cAMP-dependent secretagogues --- p.43 / Chapter III. 1.1. --- Effects of baicalein on baseline Isc and [Ca2+]i --- p.43 / Chapter III. 1.2. --- Ionic basis of baicalein-evoked Isc --- p.43 / Chapter III. 1.3. --- Effect of baicalein on carbachol-evoked Isc --- p.47 / Chapter III. 1.4. --- "Effect of baicalein on Isc stimulated by another calcium mobilizing agonist, histamine" --- p.58 / Chapter III. 1.5. --- Effect of carbachol on Isc response stimulated by baicalein --- p.61 / Chapter III. 1.6. --- Chronic effect of baicalein on carbachol-evoked increase in Isc --- p.63 / Chapter III.1.7. --- Interaction of baicalein with forskolin --- p.65 / Chapter III.2. --- Effects of baicalein on cAMP generation in T84 cells --- p.69 / Chapter III.2.1. --- Effects of baicalein on cAMP production --- p.69 / Chapter III.2.2 --- Effects of baicalein on forskolin-induced cAMP production --- p.70 / Chapter III.3. --- Effects of Scutellariae radix extract on ion transport activities in T84 cells --- p.73 / Chapter III.3.1. --- Effects of Scutellariae radix extract (SRE) on baseline Isc --- p.73 / Chapter III.3.2. --- Ionic basis of SRE-evoked Isc --- p.77 / Chapter III.3.3. --- Effects of adenylate cyclase inhibitor and PKA inhibitor --- p.77 / Chapter III.3.4. --- PKC modulation --- p.86 / Chapter III.3.5. --- Involvement of intracellular calcium --- p.86 / Chapter III.3.6. --- Involvement of cAMP --- p.94 / Chapter Chapter IV : --- Discussion --- p.98 / Chapter IV. 1. --- Effects of baicalein on ion transport in human colonic T84 cells --- p.98 / Chapter IV. 1.1. --- Roles of baicalein in chloride secretion in intestinal epithelial cells --- p.98 / Chapter IV. 1.2. --- Potentiation effect of baicalein on calcium-mediated chloride secretion --- p.100 / Chapter IV. 1.3. --- Potentiation effect of carbachol on baicalein-stimulated chloride secretion --- p.102 / Chapter IV. 1.4. --- Interaction between baicalein and forskolin --- p.104 / Chapter IV.2. --- Effects of Scutellariae radix extract on ion transport in human colonic T84 cells --- p.107 / Chapter IV.2.1 --- Characteristcs of Isc induced by Scutellariae radix extract --- p.107 / Chapter IV.2.2. --- Possible signaling mechanism involved in Isc induced by Scutellariae radix extract --- p.108 / Chapter IV.3. --- Comparison of the effects on ion transport in human colonic T84 cells produced by baicalein and Scutellariae radix extract --- p.110 / Chapter IV.3.1. --- Properties of baicalein- and Scutellariae radix extract- induced Isc response --- p.110 / Chapter IV.3.2. --- Summary --- p.111 / Chapter Chapter V : --- References --- p.113 / Publications --- p.120

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / IntroduÃÃo: Guanilinas, peptÃdeos natriurÃticos (ANP e urodilatina) e bradicinina estÃo implicados na fisiopatologia, com potencial terapÃutico, do metabolismo do sal e da hipertensÃo. Objetivo: Estudar o mecanismo de aÃÃo e possÃveis interaÃÃes destes peptÃdeos, pelo emprego de inibidores da guanilato ciclase isatina e ODQ. MÃtodo: Foram realizadas experiÃncias no rim isolado e perfundido de rato com ferramentas farmacolÃgicas, isatina (IS; 0,3 ou 10&#956;M) ou com ODQ (37&#956;M), nos estudos com uroguanilina (UGN; 0,3 ou 0,6&#956;M), bradicinina (BK; 0,3 ou 0,9 ou 1,8nM) ou urodilatina (UD; 0,03nM). Investigaram-se ainda possÃveis interaÃÃes entre os referidos petÃdeos. Resultados: Isoladamente, IS (0,3&#956;M), ODQ, UGN (0,3&#956;M), BK (0,9 ou 0,3nM) nÃo interferiram signficativamente na presssÃo de perfusÃo, na diurese ou na reabsorÃÃo tubular fracionada renal de eletrÃlitos (sÃdio - %TNa+; potÃssio - %TK+; cloreto - %TCl- ). Nas condiÃÃes experimentais, ODQ mostrou-se eficaz (p<0,05) em inibir os efeitos de BK (1,8nM) sobre a pressÃo de perfusÃo (ODQ+BK120min: 111+3mmHg; BK120min: 139+5mmHg) e %TNa+ (ODQ+BK120min: 80+1%; BK120min: 76+2%). IS (3&#956;M) mostrou-se parcialmente eficaz em inibir efeitos de UGN (0,6&#956;M; IS+UGN90min: 76+2%; UGN90min: 72+2%) e de BK (1,8nM; IS+BK90min: 81+2%; BK60min: 0,76+2%) sobre %TNa+. UD (0,03nM90min: 86+2%; UGN+UD90min: 73+4%; p<0,05) potencializou a natriurese produzida por UGN (0,3&#956;M90min: 83+2%), cujos efeitos vasculares foram inibidos com BK (0,3nM90min: 104+5mmHg; UGN0,6&#956;M; 90min: 135+4mmHg; UGN+BK90min: 110+2mmHg). ConclusÃes: IS e ODQ comprovaram a participaÃÃo da via de sinalizaÃÃo NO-GMP no mecanismo de aÃÃo dos peptÃdeos estudados. A perfusÃo simultÃnea com mais de um peptÃdio, comprovou que hà interaÃÃes em suas diferentes vias de sinalizaÃÃo. / Introduction: Guanylins, natriuretic peptides (ANP and urodilatina) and bradykinin are involved in the pathophysiology, with therapeutic potential, of salt metabolism and hypertension. Objective: To study the mechanism of action and possible interactions of these peptides, with the employment of guanylate cyclase inhibitors isatina and ODQ. Method: Experiments were performed on isolated perfused rat kidney with pharmacological tools, isatin (IS; 0.3 or 10&#956;M) or with ODQ (37&#956;M), in studies with uroguanylin (UGN, 0.3 or 0.6&#956;M), bradykinin (BK , 0.3 or 0.9 or 1.8nM) or urodilatin (UD, 0.03nM). It was also investigated possible interactions between those peptides. Results: Alone, IS (0.3&#956;M), ODQ, UGN (0.3&#956;M), BK (0.9 or 0.3nM) did not interfere significantly in perfusion perfusion (PP), in diuresis or in fractional renal tubular reabsorption of electrolytes (sodium - %TNa+; potassium - %TK+; chloride - %TCl-). In experimental conditions, ODQ proved to be effective (p<0.05) in inhibiting the effects of BK (1.8nM) on the PP (ODQ+BK120min: 111+3mmHg; BK120min: 139+5mm Hg) and %TNa+ (ODQ+BK120min: 80+1%; BK120min: 76+2%). IS (3&#956;M) proved to be partially effective in inhibiting effects of UGN (0.6&#956;M; IS+UGN90min: 76+2%; UGN90min: 72+2%) and BK (1.8nM; IS+BK90min: 81+2%; BK60min: 0.76+2%) on %TNa+. UD (0.03nM90min: 86+2%; UGN+UD90min: 73+4%, p<0.05) increased the natriuresis produced by UGN (0.3&#956;M90min: 83+2%), whose vascular effects were inhibited with BK (0.3nM90min: 104+5mmHg; UGN0, 6&#956;M; 90min: 135+4mmHg; UGN+BK90min: 110+2mmHg). Conclusions: IS and ODQ confirmed the participation of the NO-GMP signalling pathway in the mechanism of action of peptides studied. The infusion simultaneously over a peptide, proved that there are interactions in their different signalling pathway.

A goal of the Swedish government is to increase the usage of renewable fuels and biomass-based fuels. Fuel cells, and especially the MCFC, are useful for these types of fuels. The Swedish market may benefit from the MCFC in two ways: increased efficiency of the biofuels and also utilisation of produced heat in district heating. Most of the commercial MCFC systems today are optimised for use with methane. The possibility to utilise biomass in Sweden makes it important to study how the MCFC may be adapted or optimised for good performance and low degradation with gas produced from biomass or other renewable fuels. This thesis is focused on methods that may be used to investigate and evaluate MCFC electrodes and electrolytes with renewable fuels i.e. CO2-containing gases. The methods and results are both experimental and mathematically modelled. The objectives of this thesis are to better understand how the performance of the anode is dependent on different fuels. Anode kinetics and the water-gas shift reaction have been investigated as well as the possibility to increase cell lifetime by increasing the initial electrolyte amount by having the anode as a reservoir. The effect of segregation of cations in the electrolyte during operation has also been studied. It was found that if the gas composition at the current collector inlet is in equilibrium according to the water gas-shift reaction the gas composition inside the electrode is almost uniform. However, if the gas is not in equilibrium then the concentration gradients inside the current collector have a large effect on the gas composition inside the electrode. The conversion of the gas in the gas flow channels according to the water-gas shift reaction depends on the gas flow rate. For an anode used in a gas mixture of humidified hydrogen and carbon dioxide that are not in equilibrium some solubility of Ni in a (Li/Na)2CO3 mixture was found. To have the anode act as an electrolyte reservoir to prolong cell lifetime the anode pore size should be carefully matched with that of the cathode and a bimodal pore-size distribution for the anode is preferable to have as good performance as possible for as large electrolyte filling degree interval as possible. Modelling results of segregation of cations in the electrolyte during operation indicate that the electrolyte composition changes during operation and that the lithium ions are enriched at the anode for both types of electrolyte used for the MCFC. The electrolyte composition changes are small but might have to be considered in long-time operation. The results from this thesis may be used to better understand how the MCFC may be used for operation with renewable fuels and how electrodes may be designed to prolong cell lifetime. / Ett av den svenska regeringens mål är att öka användandet av förnyelsebara bränslen och bränslen från biomassa. Bränsleceller och framförallt MCFC är användbara för dessa typer av bränslen. Den svenska marknaden kan dra fördelar av MCFC på två sätt; ökad bränsleutnyttjandegrad och utnyttjande av producerad värme för fjärrvärme. De flesta kommersiella MCFC-systemen idag är optimerade för användning av metan. Möjligheten att använda biomassa på den svenska marknaden gör det viktigt att studera hur MCFC kan anpassas eller optimeras för bra prestanda och låg degradering för användning med gas från biomassa eller andra förnyelsebara bränslen. Fokus i denna avhandling är på metoder som kan användas för att undersöka och utvärdera MCFC-elektroder och -elektrolyter med förnyelsebara bränslen, dvs. gaser innehållande CO2. Metoderna och resultaten är både experimentella och matematiskt modellerade. Målet med denna avhandling är att bättre förstå hur anodens prestanda beror på användningen av olika bränslen. Anodens kinetik och vattengasskiftreaktionen har studerats liksom möjligheten att förlänga cellens livstid genom att öka den initiala mängden elektrolyt medelst användning av anoden som reservoar. Effekten av segregation av katjoner i elektrolyten under last har också undersökts. Om gassammansättningen är i jämvikt enligt vattengasskiftreaktionen vid inloppet till strömtilledaren kommer gassammansättningen att vara nära uniform inuti elektroden. Om ingående gas inte är i jämvikt kommer stora koncentrationsgradienter uppkomma i strömtilledaren och påverka gassammansättningen i elektroden. Omsättningen med avseende på vattenskiftreaktionen av gasen i flödeskanalen verkar vara beroende av gasens flödeshastighet. För en anod som används i en uppfuktad blandning av vätgas och koldioxid som inte är i jämvikt befanns det att Ni har en viss löslighet i (Li/Na)2CO3. För att kunna använda anoden som reservoar för elektrolyt för att förlänga livstiden för MCFC skall anodens porstorleksfördelning överensstämma med katodens och ha en bimodal porstorleksfördelning för att ge en tillräckligt god prestanda i ett så stort elektrolytfyllnadsgradsintervall som möjligt. Modelleringsresultat för segregering av katjoner i elektrolyten under drift visar att litiumjoner anrikas i anoden för båda typerna av elektrolyt som används i MCFC. Elektrolytkoncentrationsförändringarna är små men kan behövas tas i beaktande vid långa driftstider. Denna avhandlings resultat kan användas för att bättre förstå hur MCFC skall anpassas för drift med förnyelsebara bränslen och hur elektroder kan utformas för att förlänga livstiden. / QC 20100630

Lithium‐ion batteries are particularly suitable as energy storage solutions in high power applications, such as hybrid electric vehicles. It is generally considered that one of the processes that limit the power density for lithium‐ion batteries is the mass transport in the electrolyte. Yet, it is still difficult to find a set of properties that fully describe the mass transport for the most common electrolytes. In this work, characterization studies of the mass transport were undertaken for two technically important lithium‐ion battery electrolytes: (1) a liquid electrolyte which consist of LiPF6 dissolved in ethyl methyl carbonate (EMC) and ethylene carbonate (EC) and, (2) a gel electrolyte which consists of LiPF6 dissolved in ethylene carbonate, propylene carbonate (PC) and poly(vinylidenefluoride‐hexafluoropropylene) (P(VdFHFP)).The mass transport in the electrolytes was characterized by combining several experiments. The Maxwell‐Stefan equation was used as basis for the characterization. Models of the transport were formulated from the equation and the apparent transport properties were identified. The characterization methods were first analyzed mathematically in order to establish at which conditions the characterization experiments should be performed. The values of the apparent transport properties were then obtained by optimizing the models to the experimental responses. In order to give the characterization results a comprehensible interpretation and to allow benchmarking of electrolytes, the concept of a normalized potential gradient was introduced.The characterization results of the liquid electrolyte were used in a full cell model of a LiNi0.8Co0.15Al0.05O2 | LiPF6 EC:EMC (3:7) | MAG‐10 cell. The model was developed to analyze the mass transport during a hybrid pulse power characterization (HPPC) test. The analysis was made with a method where the polarization was split up into parts each associated with a process within the cell. The optimum composition in terms of mass transport was found to lie between 0.5 and 1.2 mol/dm3 LiPF6 for the liquid electrolyte and between 5 and 7 wt. % LiPF6 for the gel electrolyte. Less amount of polymer in the gel electrolyte gave a faster mass transport. It was also found that the mass transport in the liquid electrolyte contributed to a major part of the polarization during HPPC tests. / Litiumjonbatterier är speciellt lämpliga som ackumulatorer i högeffektsapplikationer som elhybridfordon. Det är idag allmänt accepterat att en av processerna som begränsar effekttätheten för litiumjonbatterier är masstransporten i elektrolyten. Trots detta är det fortfarande svårt att få tag på data som fullständigt beskriver masstransporten i de vanligaste elektrolyterna. I det här arbetet har masstransportkarakteriseringar gjorts för två tekniskt viktiga elektrolyter: (1) en vätskeelektrolyt som består av LiPF6 upplöst i etylenkarbonat (EC) och etylmetylkarbonat (EMC), och (2) en gel elektrolyt som består av LiPF6 upplöst i EC, propylenkarbonat (PC) och poly(vinylidene fluoride‐hexafluoro propylene) (P(VdFHFP)). Masstransporten i elektrolyterna karakteriserades genom att kombinera ett antal karakteriseringsexperiment. Maxwell‐Stefans ekvation användes som utgångspunkt i karakteriseringarna. Modeller av transporten formulerades från ekvationen och de effektiva transportegenskaperna identifierades. En matematisk analys gjordes först av karakteriseringstekniken, så att det kunde fastslås för vilka förhållanden experimenten skulle utföras. Värderna av transportegenskaperna erhölls genom att optimera modellerna till det experimentella beteendet. För att ge karakteriseringsresultaten en begriplig tolkning och för att kunna mäta prestandan av elektrolyter, infördes konceptet normaliserad potentialgradient. Resultatet från karakteriseringen av vätskeelektrolyten användes i en model av en LiNi0.8Co0.15Al0.05O2 | LiPF6 EC:EMC (3:7) | MAG‐10 cell. Modellen utvecklades för att analysera masstransporten i cellen under ett hybridpulstest (HPPC). Analysen gjordes med en metod där polarisationen delades upp i delar som var och en var kopplad till en process i batteriet. Den optimala sammansättningen med avseende på masstransporten låg i regionen 0.5–1.2 mol/dm3 LiPF6 för vätskeelektrolyten och 5‐7 vikt% LiPF6 för gelelektrolyten. Mindre mängd polymer i gelelektrolyten gav en snabbare masstransport. Det konstaterades också att masstransporten i vätskeelektrolyten bidrog med en av de största delarna till polarisationen i HPPC testen. / QC 20110128

Στην εργασία αυτή πραγματοποιήθηκε μια βιβλιογραφική ανασκόπηση σχετικά με τις ευαισθητοποιημένες ηλεκτροχημικές κυψελίδες, τις αρχές λειτουργίας τους, τα υλικά τους και τους τρόπους παρασκευής τους. Παρασκευάσαμε ηλεκτροχημικές κυψελίδες χρησιμοποιώντας διαφορετικές χρωστικές και ηλεκτρολύτες. Όλες οι κυψελίδες δοκιμάστηκαν κάτω από τις ίδιες συνθήκες για την εύρεση των παραγόντων που επηρεάζουν την απόδοσή τους. Παράγοντες όπως η συγκέντρωση της χρωστικής και ο χρόνος παραμονής του διαλύματος μέχρι την απόθεσή του στο υπόστρωμα, διαφορετικές χρωστικές και ηλεκτρολύτες κτλ δοκιμάστηκαν για την αύξηση της απόδοσης. Τέλος, εξετάστηκε η σταθερότητα των κυψελίδων αυτών με το χρόνο. / In this study we make a comprehensive literature review on dye-sensitized nanostructured solar cells, their operating principles, materials as well as their manufacturing methods. We have fabricated dye – sensitized electrochemical solar cells using different dyes and electrolytes. All solar cells were tested under the same conditions in order to find the factors limiting their efficiency. Factors like the concentration of the dye and the time of paste storage, different dyes and electrolytes etc were tested in order to improve efficiency. Finally, the stability of these solar cells were also evaluated for different time intervals.

La technologie Lithium-air développée par EDF utilise une électrode à air qui fonctionne avec un électrolyte aqueux ce qui empêche l’utilisation de lithium métal non protégé comme électrode négative. Une membrane céramique (LATP:Li1+xAlxTi2-x(PO4)3) conductrice d’ion Li+ est utilisée pour séparer le milieu aqueux de l’électrode négative. Cependant, cette céramique n'est pas stable au contact du lithium, il est donc nécessaire d'intercaler entre le lithium et la céramique un matériau conducteur des ions Li+. Celui-ci devant être stable au contact du lithium et empêcher ou fortement limiter la croissance dendritique. Ainsi, ce projet s'est intéressé à l'étude d'électrolytes copolymères à blocs (BCE).Tout d'abord, l'étude des propriétés physico-chimiques spécifiques de ces BCEs en cellule lithium-lithium symétrique a été réalisée notamment les propriétés de transport (conductivités, nombre de transport), et la résistance à la croissance dendritique du lithium. Puis dans un second temps, l'étude des composites BCE-céramique a été mise en place. Nous nous sommes en particulier focalisés sur l'analyse du transfert ionique polymère-céramique.Plusieurs techniques de caractérisation ont été utilisées telles que la spectroscopie d'impédance électrochimique (transport et interface), le SAXS (morphologies des BCEs), la micro-tomographie par rayons X (morphologies des interfaces et des dendrites).Pour des électrolytes possédant un nombre de transport unitaire (single-ion), nous avons obtenus des résultats remarquables concernant la limitation à la croissance dendritique. La micro-tomographie des rayons X a permis de montrer que le mécanisme de croissance hétérogène dans le cas des single-ion est très différent de celui des BCEs neutres (t+ < 0.2). / The lithium-air (Li-air) technology developed by EDF uses an air electrode which works with an aqueous electrolyte, which prevents the use of unprotected lithium metal electrode as a negative electrode. A Li+ ionic conductor glass ceramic (LATP:Li1+xAlxTi2-x(PO4)3) has been used to separate the aqueous electrolyte compartment from the negative electrode. However, this glass-ceramic is not stable in contact with lithium, it is thus necessary to add between the lithium and the ceramic a buffer layer. In another hand, this protection should ideally resist to lithium dendritic growth. Thus, this project has been focused on the study of block copolymer electrolytes (BCE).In a first part, the study of the physical and chemical properties of these BCEs in lithium symmetric cells has been realized especially transport properties (ionic conductivities, transference number), and resistance to dendritic growth. Then, in a second part, the composites BCE-ceramic have been studied.Several characterization techniques have been employed and especially the electrochemical impedance spectroscopy (for the transport and the interface properties), the small angle X-ray scattering (for the BCE morphologies) and the hard X-ray micro-tomography (for the interfaces and the dendrites morphologies). For single-ion BCE, we have obtained interesting results concerning the mitigation of the dendritic growth. The hard X-ray micro-tomography has permitted to show that the mechanism involved in the heterogeneous lithium growth in the case of the single-ion is very different from the one involved for the neutral BCEs (t+ < 0.2).

Philosophiae Doctor - PhD (Chemistry) / Supercapacitors, also known as ultracapacitors or electrochemical capacitors, are considered one of the most important subjects concerning electricity or energy storage which has proven to be problematic for South Africa. In this work, graphene oxide (GO) was supported with platinum, silver and copper nanoparticles anchored with dodecylbenzenesulphonic acid (DBSA) doped polyaniline (PANI) to form nanocomposites. Their properties were investigated with different characterization techniques. The high resolution transmission electron microscopy (HRTEM) revealed GO's nanosheets to be light, flat, transparent and appeared to be larger than 1.5 ?m in thickness. This was also confirmed by high resolution scanning electron microscopy (HRSEM) with smooth surfaces and wrinkled edges observed with the energy dispersive X-ray analysis (EDX) confirming the presence of the functional groups such as carbon and oxygen. The HRTEM analysis of decorated GO with platinum, silver and copper nanoparticles (NPs) revealed small and uniformly dispersed NPs on the surface of GO with mean particle sizes of 2.3 ± 0.2 nm, 2.6 ± 0.3 nm and 3.5 ± 0.5 nm respectively and the surface of GO showed increasing roughness as observed in HRSEM micrographs. The X-ray fluorescence microscopy (XRF) and EDX confirmed the presence of the nanoparticles on the surface of GO as platinum, silver and copper which appeared in abundance in each spectra. Anchoring the GO with DBSA doped PANI revealed that single GO sheets were embedded into the polymer latex, which caused the DBSA-PANI particles to become adsorbed on their surfaces. This process then appeared as dark regions in the HRTEM images. Morphological studies by HRSEM also supported that single GO sheets were embedded into the polymer latex as composite formation appeared aggregated and as bounded particles with smooth and toothed edges.

The thesis reports on 6 studies (2 of which were part of a multi-centre trial) examining hydration and fluid balance. The first study described in this thesis investigated the impact of hydration status on Dual energy x-ray absorptiometry (DXA) and other methods that are popular tools to determine body composition in athletes. We observed that it is important to ensure a euhydration when assessing body composition, particularly when considering changes associated with nutritional or exercise interventions. The second and third studies reported identified beverages that promote longer term fluid retention and maintenance of fluid balance in adults. We investigated the effects of 13 different commonly consumed drinks on urine output and fluid balance when ingested in a euhydrated state, with a view to establishing a beverage hydration index (BHI), i.e., the volume of urine produced after drinking expressed relative to a standard treatment (still water) for each beverage. The beverages with the highest BHI were oral rehydration solution, full fat milk and skimmed milk. BHI may be a useful measure to identify the short term hydration potential of different beverages when ingested in a euhydrated state. The fourth study aimed to systematically examine the influence of carbohydrate, sodium and caffeine content of beverages on the BHI. The BHI was greater in beverages with higher carbohydrate or higher sodium content, but not influenced by caffeine. The carbohydrate content of beverages has no effect on BHI at concentration up to 10% carbohydrate. Sodium content of beverages in concentrations of 27mmol/L and higher can improve the hydration potential of beverages. Caffeine doses in beverages up to 400mg/L do not have an impact upon diuresis when ingested in a euhydrated state. The fifth study compared net fluid balance (NFB) responses to the ingestion of commonly consumed drinks in young and older men. We observed that in young adults milk helps to maintain positive net fluid balance for longer than other drinks. In older adults this effect of milk is not observed despite similar net electrolyte balance responses. Future work should more fully explore these potential differences in fluid balance responses to drink ingestion between young and older adults. The final study investigated the hydration habits of Scottish young and older adults (+50 years old), identifying their fluid choices, volume, and preferences in relation to time of day. The results showed that 26.1% of the young females, 30.3% of the young males, 25.8% of the older females and 50.4% of the older males did not meet the European (EU) Food Safety Authority (EFSA) fluid intake recommendations. We also observed that the difference between those who met and those who did not meet the EFSA adequate intake could be attributed to differences in water ingestion, mainly during the mid-morning (after breakfast until 11 am) and during the early-afternoon (after lunch time up to 5 pm). It was concluded that these moments might be key when implementing interventions to improve hydration status especially in the older population.

O presente trabalho visou preparar e caracterizar eletrólitos poliméricos (EP) à base de poli(vinil butirato) (PVB) com diferentes sais de lítio (LiClO4, LiCF3SO3 e LiI/I2), com ou sem o plastificante g-butirolactona (GBL), além de viabilizar a aplicação dos mesmos em dispositivos eletrocrômicos e células solares. Observou-se, através das análises por espectroscopia de impedância eletroquímica, que o PVB é capaz de solvatar no máximo 40% de sal de lítio em massa. Foi verificado que as condutividades iônicas dessas amostras, em função do aumento da temperatura, podem ser explicadas pelo modelo Vogel-Tammann-Fulcher, e que o eletrólito PF04 (PVB com 40% de LiCF3SO3) possui o maior valor de condutividade (1,5´10-4 S/cm) com relação às outras amostras. Os espectros de infravermelho das amostras estudadas mostraram um deslocamento nos picos correspondentes às carbonilas da matriz polimérica em resposta à coordenação das mesmas com íons Li+. Os resultados da espectroscopia Raman comprovaram a presença do par redox (I3-/I-) no eletrólito com LiI/I2. Os difratogramas de raios-X do PVB evidenciaram um pico largo centrado em 20º (2q) com 800 c.p.s. de intensidade, a adição de LiI/I2 e LiCF3SO3 ao polímero reduziu as intensidades para 750 e 700 c.p.s respectivamente, ao contrário do observado com LiClO4, onde se nota que o sal não foi completamente solvatado pelo polímero. A micrografia obtida por microscopia eletrônica de varredura (SEM) do eletrólito com 23% de LiClO4 (amostra P04) mostraram evidências de aglomerados iônicos na superfície. As análises por calorimetria exploratória diferencial (DSC) mostraram que um aumento na concentração de sal adicionado ao polímero causou uma diminuição na temperatura de transição vítrea (Tg), e que os eletrólitos possuem em torno de 44% de cristalinidade. Os eletrólitos P04 e PF04 foram aplicados em janelas eletrocrômicas, apresentando uma diferença de 10,5 e 9,3% respectivamente entre os estados colorido e descolorido. O eletrólito com LiI/I2 foi aplicado em célula solar gerando uma fotocorrente máxima de 1,09 mA/cm2 e eficiência de 0,41% sob a irradiação de 100 mW/cm2. Eletrólitos géis com adição de 90% &gamma;-butirolactona também foram aplicados em células solares, os valores de fotocorrente e eficiência foram incrementados (5,82 mA/cm2 e 2,1%, respectivamente). / The aim of the present study was to prepare and characterize polymer electrolytes (EP) based on poly(vinyl butyrate) (PVB) with different lithium salts (LiClO4, LiCF3SO3 and LiI/I2) and/or containing g-butyrolactone (GBL), and to apply them in electrochromic devices and solar cells. It was observed through electrochemical impedance spectroscopy that the PVB is able to solvate up to 40% in weight of lithium salt. It was found that the ionic conductivity of these samples, as a function of temperature, can be explained by Vogel-Tammann-Fulcher model, and the electrolyte PF04 (PVB with 40% of LiCF3SO3) had the highest conductivity value of 1,5´10-4 S/cm when compared to other samples. Infrared spectra of the samples showed a shift in the peaks corresponding to the carbonyl groups of the polymer matrix in response to their coordination with Li+ ions. The results of Raman spectroscopy confirmed the presence of the redox couple (I3-/I-) in the electrolyte with LiI/I2 (PVB04). The X-ray diffractograms of the PVB showed a broad peak centered at 20 (2q) com intensity of 800 cps. The addition of LiI/I2 and LiCF3SO3 to the polymer matrix decreased the intensities to 750 and 700 cps respectively, but not after the LiClO4 addition, which was explained by its not complete solvatation by the polymer matrix. The Scanning Electron Microscopy (SEM) pictures of electrolyte with 23% of LiClO4 (P04 sample) showed evidences of ion clusters on the surface. The analyzes via Differential Scanning Calorimetry (DSC) showed that an increase in the concentration of the salt added to the polymer matrix caused a decrease in glass transition temperature (Tg), and that electrolytes are about 44% crystalline. The electrolytes P04 and PF04 were applied to electrochromic windows (ECDs) and showed a transmittance difference of 10.5 and 9.3%, respectively between the colored and discolored states. The electrolyte with LiI/I2 was applied to dye sensitized solar cell (DSSC) generating a maximum photocurrent of 1.09 mA/cm2 and 0.41% of efficiency under irradiation of 100 mW/cm2. Gel electrolytes containing 90% of &gamma;-butyrolactone were applied to DSSC and showed 5.82 mA/cm2 of photocurrent and 2.1% of efficiency.