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No / Transmembrane pore formation is central to many biological processes such as ion transport, cell fusion, and viral infection. Furthermore, pore formation in the ceramide bilayers of the stratum corneum may be an important mechanism by which penetration enhancers such as dimethylsulfoxide (DMSO) weaken the barrier function of the skin. We have used the potential of mean constraint force (PMCF) method to calculate the free energy of pore formation in ceramide bilayers in both the innate gel phase and in the DMSO-induced fluidized state. Our simulations show that the fluid phase bilayers form archetypal water-filled hydrophilic pores similar to those observed in phospholipid bilayers. In contrast, the rigid gel-phase bilayers develop hydrophobic pores. At the relatively small pore diameters studied here, the hydrophobic pores are empty rather than filled with bulk water, suggesting that they do not compromise the barrier function of ceramide membranes. A phenomenological analysis suggests that these vapor pores are stable, below a critical radius, because the penalty of creating water-vapor and tail-vapor interfaces is lower than that of directly exposing the strongly hydrophobic tails to water. The PMCF free energy profile of the vapor pore supports this analysis. The simulations indicate that high DMSO concentrations drastically impair the barrier function of the skin by strongly reducing the free energy required for pore opening. / EPSRC

Corrosion of reinforcing steel in concrete exposed to chloride-laden environments is a well-known and documented phenomenon. The need for cost effective systems for protection against corrosion has become increasingly clear since the first observations of severe corrosion damage to interstate bridges in the 1960's. As one potential solution to the mounting problem of corrosion deterioration of structures, corrosion-inhibiting admixtures have been researched and introduced into service. This report conveys the results of a three-part laboratory study of corrosion inhibiting admixtures in concrete. The commercial corrosion inhibiting admixtures for concrete have been analyzed by three evaluation methods, including: • Conventional concrete corrosion cell prisms under ponding, • Black steel reinforcing bars immersed in simulated concrete pore solutions, • Electrochemical screening tests of special carbon steel specimens in electrochemical corrosion cells containing filtered cement slurry solution. The purposes of the study include: • Determining the influence of a series of commercially available corrosion inhibiting admixtures on general concrete handling, performance and durability properties not related to corrosion. • Determining the effectiveness of corrosion inhibiting admixtures for reduction or prevention of corrosion of reinforcing steel in concrete, relative to untreated systems, under laboratory conditions. • Conducting a short-term pore solution immersion test for inhibitor performance and relating the results to those of the more conventional long-term corrosion monitoring techniques that employ admixtures in reinforced concrete prisms. • Determining whether instantaneous electrochemical techniques can be applied in screening potential inhibitor admixtures. Concrete properties under test included air content, slump, heat of hydration, compressive strength, and electrical indication of chloride permeability. Monitoring of concrete prism specimens included macro-cell corrosion current, mixed-cell corrosion activity as indicated by linear polarization, and ancillary temperature, relative humidity, and chloride concentration documentation. Simulated pore solution specimens were analyzed on the basis of weight loss and surface area corroded as a function of chloride exposure. Electrochemical screening involved polarization resistance of steel in solution. Results include corrosion potential, polarization resistance and corrosion current density. / Master of Science

Yes / The wave–seabed interaction issue is of great importance for the design of foundation around marine infrastructures. Most previous investigations for such a problem have been limited to uncoupled or one-way coupled methods connecting two separated wave and seabed sub models with the continuity of pressures at the seabed surface. In this study, a strongly coupled model was proposed to realize both wave and seabed processes in a same program and to calculate the wave fields and seabed response simultaneously. The information between wave fields and seabed fields were strongly shared and thus results in a more profound investigation of the mechanism of the wave–seabed interaction. In this letter, the wave and seabed models were validated with previous experimental tests. Then, a set of application of present model were discussed in prediction of the wave-induced seabed response. Numerical results show the wave-induced liquefaction area of coupled model is smaller than that of uncoupled model. / Yes

Yes / The development of ultra-high performance cementitious composite (UHPCC) represents a significant advancement in the field of concrete science and technology, but insufficient hydration and high autogenous shrinkage relatively increase the pores inside UHPCC, in turn, affecting the macro-performance of UHPCC. This paper, initially, optimized the pore structure of UHPCC using different types and dimensions of nanofillers. Subsequently, the pore structure characteristics of nano-modified UHPCC were investigated by the mercury intrusion porosimeter method and fractal theory. Finally, the fluid permeability of nano-modified UHPCC was estimated by applying the Katz-Thompson equation. Experimental results showed that all incorporated nanofillers can refine the pore structure of UHPCC, but nanofillers with different types and dimensions have various effects on the pore structure of UHPCC. Specifically, CNTs, especially the thin-short one, can significantly reduce the porosity of UHPCC, whereas nanoparticles, especially nano-SiO2, are more conducive to refine the pore size. Among all nanofillers, nano-SiO2 has the most obvious effect on pore structure, reducing the porosity, specific pore volume and most probable pore radius of UHPCC by 31.9%, 35.1% and 40.9%, respectively. Additionally, the pore size distribution of nano-modified UHPCC ranges from 10-1nm to 105nm, and the gel pores and fine capillary pores in the range of 3-50nm account for more than 70% of the total pore content, confirming nanofillers incorporation can effectively weaken pore connectivity and induce pore distribution to concentrate at nanoscale. Fractal results indicated the provision of nanofillers reduces the structural heterogeneity of gel pores and fine capillary pores, and induces homogenization and densification of UHPCC matrix, in turn, decreasing the UHPCC fluid permeability by 15.7%-79.2%. / National Science Foundation of China (51978127, 52178188 and 51908103), the China Postdoctoral Science Foundation (2022M720648 and 2022M710973) and the Fundamental Research Funds for the Central Universities (DUT21RC(3)039).

Achieving energy neutrality has shifted focus towards aeration systems optimization, due to the high energy consumption of aeration processes in modern advanced wastewater treatment plants. The activated sludge wastewater treatment process is dependent on aeration efficiency which supplies the oxygen needed in the treatment process. The process is a complex heterogeneous mixture of microorganisms, bacteria, particles, colloids, natural organic matter, polymers and cations with varying densities, shapes and sizes. These activated sludge parameters have different impacts on aeration efficiency defined by the OTE, % and alpha. Oxygen transfer efficiency (OTE) is the mass of oxygen transferred into the liquid from the mass of air or oxygen supplied, and is expressed as a percentage (%). OTE is the actual operating efficiency of an aeration system. The alpha Factor (α) is the ratio of standard oxygen transfer efficiency at process conditions (αSOTE) to standard oxygen transfer efficiency of clean water (SOTE). It is also referred to as the ratio of process water volumetric mass transfer coefficient to clean water volumetric mass transfer coefficient. The alpha factor accounts for wastewater contaminants (i.e. soap and detergent) which have an adverse effect on oxygen transfer efficiency. Understanding their different impacts and how different treatment technologies affect aeration efficiency will help to optimize and improve aeration efficiency so as to reduce plant operating costs. A pilot scale study of fine pore diffuser fouling and mitigation, quantified by dynamic wet pressure (DWP), oxygen transfer efficiency and alpha measurement were performed at Blue Plains, Washington DC. In the study a mechanical cleaning method, reverse flexing (RF), was used to treat two diffusers (RF1, RF2) to mitigate fouling, while two diffusers were kept as a control with no reverse flexing. A 45 % increase in DWP of the control diffuser after 17 month of operation was observed, an indication of fouling. RF treated diffusers (RF1 and RF2) did not show any significant increase in DWP, and in comparison to the control diffuser prevented a 35 % increase in DWP. Hence, the RF fouling mitigation technique potentially saved blower energy consumption by reducing the pressure burden on the air blower and the blower energy requirement. However, no significant impact of the RF fouling mitigation treatment technique in preventing a decrease in alpha-fouling (𝝰F) of the fine pore diffusers over time of operation was observed. This was because either the RF treatment method maintained wide pore openings after cleaning over time, or a dominant effect of other wastewater characteristics such as the surfactant concentration or particulate COD could have interfered with OTE. Further studies on the impact of wastewater characteristics (i.e., surfactants and particulate COD) and operating conditions on OTE and alpha were carried out in another series of pilot and batch scale tests. In this study, the influence of different wastewater matrices (treatment phases) on oxygen transfer efficiency (OTE) and alpha using full-scale studies at the Blue Plains Treatment Plant was investigated. A strong relationship between the wastewater matrices with oxygen transfer characteristics was established, and as expected increased alphas were observed for the cleanest wastewater matrices (i.e., with highest effluent quality). There was a 46 % increase in alpha as the total COD and surfactant concentrations decreased from 303 to 24 mgCOD/L and 12 to 0.3 mg/L measured as sodium dodecyl sulphate (SDS) in the nitrification/denitrification effluent with respect to the raw influent. The alpha improvement with respect to the decrease in COD and surfactant concentration suggested the impact of one or more of the wastewater characteristics on OTE and alpha. Batch testing conducted to characterize the mechanistic impact of the wastewater contaminants present in the different wastewater matrices found that the major contaminants influencing OTE and alpha were surfactants and particulate/colloidal material. The volumetric mass transfer coefficient (kLa) measurements from the test also identified surfactant and colloidal COD as the major wastewater contaminants present in the influent and chemically enhanced primary treatment (CEPT) effluent wastewaters impacting OTE and alpha. Soluble COD was observed to potentially improve OTE and alpha due to its contribution in enhancing the oxygen uptake rate (OUR). Although the indirect positive impact of OUR on alpha observed in this study contradicts some other studies, it shows the need for further investigation of OUR impacts on oxygen transfer. Importantly, the mechanistic characterization and quantitative correlation between wastewater contaminants and aeration efficiency found in this study will help to minimize overdesign with respect to aeration system specification, energy wastage, and hence the cost of operation. This study therefore shows new tools as well as the identification of critical factors impacting OTE and alpha in addition to diffuser fouling. Gas transfer depression caused by surfactants when they accumulate at the gas-liquid interface during the activated sludge wastewater treatment process reduces oxygen mass transfer rates, OTE and alpha which increases energy cost. In order to address the adverse effect of surfactants on OTE and alpha, another study was designed to evaluate 4 different wastewater secondary treatment strategies/technologies that enhances surfactant removal through enhanced biosorption and biodegradation, and to also determine their effect on oxygen transfer and alpha. A series of pilot and batch scale tests were conducted to compare and correlate surfactant removal efficiency and alpha for a) conventional high-rate activated sludge (HRAS), b) optimized HRAS with contactor-stabilization technology (HRAS-CS), c) optimized HRAS bioaugmented (Bioaug) with nitrification sludge (Nit S) and d) optimized bioaugmented HRAS with an anaerobic selector phase technology (An-S) reactor system configuration. The treatment technologies showed surfactant percentage removals of 37, 45, 61 and 87 %, and alphas of 0.37 ±0.01, 0.42 ±0.02, 0.44 ±0.01 and 0.60 ±0.02 for conventional HRAS, HRAS-CS, Bioaug and the An-S reactor system configuration, respectively. The optimized bioaugmented anaerobic selector phase technology showed the highest increased surfactant removal (135 %) through enhanced surfactant biosorption and biodegradation under anaerobic conditions, which also complemented the highest increased alpha (62 %) achieved when compared to the conventional HRAS. This study showed that the optimized bioaugmented anaerobic selector phase reactor system configuration is a promising technology or strategy to minimize the surfactant effects on alpha during the secondary aeration treatment stage / Ph. D. / In the activated sludge process, the energy requirement for aeration which also includes nitrogen removal is a major operating expense for utilities, and it has limited the ability of most water and wastewater reclamation facilities to achieve energy neutrality. Aeration has therefore become one of the most energy and capital intensive aspects of wastewater treatment. There are still knowledge gaps and mechanistic understanding of the impact of wastewater characteristics and treatment processes on aeration efficiency, which past and current studies are yet to provide. Aeration efficiency is defined by oxygen transfer efficiency and alpha (an indicator of wastewater contaminant effect on aeration efficiency). This study provided an insight into important wastewater characteristics, treatment processes and operational parameters contributing to aeration cost. An understanding of the impacts of wastewater characteristics and how different treatment technologies affect aeration efficiency as discussed in this study will help design engineers and operators to optimize and improve aeration efficiency, so as to reduce plant operating costs. The first study objective on fine bubble diffuser fouling dynamics and physical treatment method quantified by dynamic wet pressure (DWP), oxygen transfer efficiency and alpha measurement was carried out in a pilot reactor. DWP quantified the fouling dynamics of fine pore diffusers. A diffuser fouling physical treatment (reverse flexing, RF) method was able to mitigate fouling of the fine pore diffusers by preventing an increase in DWP normally observed in fouled fine pore diffusers. The RF treatment method reduced fouling by 35 % as compared to the control diffuser (without reverse flexing). This will reduce the pressure burden and air blower energy requirement. The second study objective evaluated the impact of different wastewater characteristics and removal in different stages on aeration efficiency. Test results in this study showed that surfactant and particulate COD fractions were the major characteristics constituents contained in wastewater that depressed aeration efficiency defined by OTE and alpha. Soluble COD did not show any inhibiting effect on OTE and alpha. The third study objective evaluated three different optimized wastewater treatment technologies of surfactant removal during aeration treatment process; 1) High rate activated sludge (HRAS) with contactor-stabilization technology (The contactor stabilization process) (HRAS-CS); 2) HRAS bioaugmented (BioAug) with nitrification sludge (Nit S); and 3) Bioaugmented HRAS with an anaerobic selector phase (An-S) configuration. All three technologies increased surfactant removal through enhanced biosorption and biodegradation to various degrees when compared the conventional high rate activated sludge treatment, but the An-S treatment technology achieved the highest surfactant removal and alpha improvement. The study also established the optimum performance process conditions for each optimized treatment technology.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第25123号 / 理博第5030号 / 新制||理||1717(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)教授 王 功輝, 教授 松四 雄騎, 教授 大見 士朗 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Cry6Aa1, une nouvelle toxine produite par Bacillus thuringiensis (Bt), agit comme insecticide sur la chrysomèle du maïs (WCRW). Dans cette étude, on démontre que Cry6Aa1 est une toxine formeuse de pores (TFP) en bicouches lipidiques planes (BLP). Contrairement aux autres toxines de Bt étudiées jusqu’à présent, la formation de pores par Cry6Aa1 ne requiert pas de prétraitement par protéases et se produit à des doses de toxine deux à trois ordres de grandeur plus faibles que celles nécessaires pour les autres toxines de Bt dans les mêmes conditions. La formation de pores par la forme non traitée de Cry6Aa1 dépend du pH; les pores obtenus ont des conductances comprises entre 31 et 689 pS en conditions symétriques de 150 mM de KCl; ils sont cationiques avec un comportement cinétique complexe. Les propriétés biophysiques des pores ne changent pas lorsque la toxine est traitée avec le suc du mésenthéron de l’insecte (Cry6Aa1 WCR1). Par contre, un traitement à la trypsine (Cry6Aa1 TT) modifie la conductance et la sélectivité des pores à pH 5,5 (le pH physiologique de l’intestin de WCRW). La reconstitution en BLP de fraction de membrane native du mésenthéron de WCRW affecte les propriétés des pores formés par Cy6Aa1. Les déterminants moléculaires du mode d’action de cette nouvelle toxine formeuse de pores semblent donc différer de ceux décrits précédemment pour d’autres toxines de Bt. La structure atomique tridimensionnelle de Cry6Aa1 vient tout juste d’être élucidée. Elle montre que la toxine adopte une conformation riche en hélices α qui ressemble fortement à celle de la TFP ClyA produite par E. coli. En se fondant sur les données disponibles pour ClyA, on a étudié l’effet de divers changements dans les régions N et C terminales de Cry6Aa1 sur sa capacité de former des pores en BLP. / Cry6Aa1 is a new toxin produced by Bacillus thuringiensis (Bt), which displays insecticidal activity against the Western corn rootworm (WCRW). The present work demonstrates that Cry6Aa1 is a pore-forming toxin (PFT) in planar lipid bilayers (PLBs). Contrary to other Bt toxins tested so far, pore formation by Cry6Aa1 does not require protease pretreatment and takes place at doses that are two to three orders of magnitude lower than those required for other Bt toxins under similar conditions. Pore formation by Cry6Aa1 is pH-dependent; the conductances of the pores range between 31 and 689 pS under symmetrical 150 mM KCl conditions; they are cationic and display a complex kinetic behaviour. The treatment of the toxin with midgut juice (Cry6Aa1 WCR1) does not change the biophysical properties of the pores. However, the treatment with trypsin (Cry6Aa1 TT) affects their conductance and selectivity at pH 5.5 (the WCRW gut physiological pH). The incorporation in PLBs of native membrane material from WCRW midgut affects the behaviour of the Cry6Aa1 pores. The molecular determinants of the mode of action of this new PFT appear therefore to differ from those reported before for other Bt toxins. The three-dimensional (3-D) atomic structure of Cry6Aa1 has just been elucidated. It shows that the toxin assumes an α-helix-rich configuration, which is quite similar to that of the ClyA PFT produced by E. coli. Based on the data available for ClyA, we have studied how different changes in the N- and C-terminal regions of Cry6Aa1 affect its pore formation ability in PLBs.

Le postconditionnement cardiaque est paradoxal chez le rat. Certains auteurs ont montré que cet animal pouvait être protégé par le postconditionnement alors que d’autres ont montré qu’il était inefficace. L’objectif de notre travail était d’éclaircir cette situation et d’établir un lien entre la régulation des fonctions mitochondriales et la réussite ou l’échec du postconditionnement. Nous avons montré sur un modèle in vivo que le rat est sensible au postconditionnement cardiaque sous certaines conditions. Il semble que la réussite de cette thérapie nécessite à la fois une préservation de la phosphorylation oxydative, une inhibition de l’ouverture du mPTP et une diminution de la production de ROS. Nous avons également montré que le complexe I de la chaîne respiratoire régule l’ouverture du mPTP en liaison avec l’état de la Cyp D. L’ensemble de nos résultats montrent que le rat n’est pas réfractaire au postconditionnement, mais pour que celui-ci soit efficace, il est nécessaire de préserver l’intégrité des différentes fonctions mitochondriales. La cardioprotection et la régulation des fonctions mitochondriales sont donc spécifiquement liées au modèle utilisé / Cardiac postconditioning is paradoxical in rat. Certain authors showed that this animal could be protected by postconditioning whereas others showed that it was ineffective. The objective of our work was to clarify this situation and to establish a link between the regulation of the mitochondrial functions and the success or the failure of postconditioning. We showed on an in vivo model that the rat is sensitive to cardiac postconditioning under certain conditions. It seems that the success of this therapy requires at the same time a safeguarding of oxidative phosphorylation, an inhibition of the mitochondrial permeability transition pore opening and a reduction in the ROS production. We also showed that complex I of the respiratory chain controls the opening of the mPTP in relation with the state of Cyp D. Our results show that the rat is not insensitive to postconditioning, but it is necessary to preserve the integrity of the mitochondrial functions to be effective. The cardioprotection and the regulation of the mitochondrial functions are specifically related to the model used

L’I/R et la cardioprotection par PreC et PostC impactent la fonction mitochondriale et plus précisément le mPTP. Le mPTP est non seulement modulé par des protéines qui participent à sa formation comme la CypD mais aussi par l’environnement cellulaire. Le but de ma thèse a été d’étudier la régulation du mPTP par la CypD, le complexe I et le Ca2+ durant l’I/R et la cardioprotection. Nos conclusions sont : 1. Le complexe I de la chaîne respiratoire mitochondriale régule l’ouverture du mPTP et cela de façon CypD-dépendante. 2. Le PostC est un inhibiteur du complexe I, l’Iso, est le seul PostC efficace chez le rat in vivo. 3. L’inhibition pharmacologique ou génétique de la CypD cardioprotège en modulant l’ouverture du mPTP et l’homéostasie calcique. 4. La CypD a un nouveau rôle dans la cardioprotection, indépendamment de son action sur le mPTP. En effet, elle module le transfert calcique au niveau des MAM et plus précisément le transfert de Ca2+ entre les RS et la mitochondrie. Son inhibition prévient la surcharge calcique mitochondriale intervenant lors de l’I/R. L’ensemble de ces résultats nous permet de conclure que le mPTP est régulé par de nombreux facteurs interconnectés. Le Ca2+ est l’effecteur principal de l’ouverture du mPTP. La CypD a une action Ca2+ dépendante et module l’homéostasie calcique au niveau des MAM. Le complexe I régule l’ouverture du mPTP de façon CypD dépendante. Enfin les fonctions mitochondriales cardioprotecteurs mPTP-dépendants englobe la CypD, le Ca2+, le complexe I et les fonctions mitochondriales. Cette vision plus large et intégrée de la régulation du mPTP pourra donner des pistes plus efficaces dans le développement de traitements pharmacologiques cardioprotecteurs / Reperfusion of the heart after an ischemic event leads to the opening of a nonspecific pore in the inner mitochondrial membrane, the mitochondrial permeability transition pore (mPTP). Inhibition of mPTP opening is an effective strategy to prevent cardiomyocyte death. For example, inhibition of mPTP opening via ischaemic preconditioning (PreC) and post-conditioning (PostC) decreased the myocardial infarct size after ischemia–reperfusion. Although the molecular composition of the mPTP remains unclear, the matrix protein cyclophilin-D (CypD) is the best defined regulatory component of mPTP. In this thesis, we demonstrated that Complex I of the respiratory mitochondrial chain also regulates mPTP in a CypD-dependent manner. We also proved that inhibition of Complex I by isoflurane prevents lethal reperfusion injury in an in vivo rat model of ischemia-reperfusion. Finally, we proved that cardioprotective inhibition of CypD modulates calcium homeostasis and fluxes between mitochondria and sarcoplasmic reticulum. In summary, our results suggest that mPTP is regulated by several interconnected factors like calcium, CypD, complex I and mitochondrial functions