Constructing eigenmode excitation spectrum in synthetic photonic lattices using optical heterodyning

A method based on optical heterodyning is proposed for measuring relative optical phases of pulses circulating in a synthetic photonic lattices. The knowledge of the phases can be further used for qualitative reconstruction of an eigenmode excitation spectrum in the synthetic photonic lattice.

Développement et caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque

Ce projet de recherche mené en collaboration industrielle avec St-Jean Photochimie Inc. / PCAS Canada vise le développement et la caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque. La quête du récoltage des photons se situant dans le proche-infrarouge a été au centre des modifications structurales explorées afin d’augmenter l’efficacité de conversion des cellules solaires de type organique et à pigments photosensibles. Trois familles de composés intégrant le motif dipyrrométhène ont été synthétisées et caractérisées du point de vue spectroscopique, électrochimique, structural ainsi que par modélisation moléculaire afin d’établir des relations structures-propriétés. La première famille comporte six azadipyrrométhènes au potentiel de coordination tétradentate sur des centres métalliques. Le développement d’une nouvelle voie synthétique asymétrique combinée à l’utilisation d’une voie symétrique classique ont permis d’obtenir l’ensemble des combinaisons de substituants possibles sur les aryles proximaux incluant les noyaux 2-hydroxyphényle, 2-méthoxyphényle et 2- pyridyle. La modulation du maximum d’absorption dans le rouge a pu être faite entre 598 et 619 nm. De même, la présence de groupements méthoxyle ou hydroxyle augmente l’absorption dans le violet (~410 nm) tel que démontré par modélisation. La caractérisation électrochimique a montré que les dérivés tétradentates étaient en général moins stables aux processus redox que leur contre-parti bidentate. La deuxième famille comporte dix dérivés BODIPY fusionnés de façon asymétrique en position [b]. L’aryle proximal a été modifié de façon systématique afin de mieux comprendre l’impact des substituents riches en électron et de la fusion de cycles aromatiques. De plus, ces dérivés ont été mis en relation avec une vaste série de composés analogues. Les résultats empiriques ont montré que les propriétés optoélectroniques de la plateforme sont régies par le degré de communication électronique entre l’aryle proximal, le pyrrole sur lequel il est attaché et le noyau indolique adjacent à ce dernier. Les maximums d’absorption dans le rouge sont modulables entre 547 et 628 nm et la fluorescence des composés se situe dans le proche- infrarouge. L’un des composé s’est révélé souhaitable pour une utilisation en photovoltaïque ainsi qu’à titre de sonde à pH. La troisième famille comporte cinq complexes neutres de RuII basés sur des polypyridines et portant un ligand azadipyrrométhène cyclométalé. Les composés ont montré une forte absorption de photons dans la région de 600 à 800 nm (rouge à proche- infrarouge) et qui a pu être étendue au-delà de 1100 nm dans le cas des dérivés portant un ligand terpyridine. L’analyse des propriétés optoélectroniques de façon empirique et théorique a montré un impact significatif de la cyclométalation et ouvert la voie pour leur étude en tant que photosensibilisateurs en OPV et en DSSC. La capacité d’un des complexes à photo-injecter un électron dans la bande de conduction du semi-conducteur TiO2 a été démontré en collaboration avec le groupe du Pr Gerald J. Meyer à University of North Carolina at Chapel Hill, premier pas vers une utilisation dans les cellules solaires à pigments photosensibles. La stabilité des complexes en solution s’est toutefois avérée problématique et des pistes de solutions sont suggérées basées sur les connaissances acquises dans le cadre de cette thèse.

A Theoretical and Synthetic Investigation of New Donors for Organic Electro-Optic Chromophores: Understanding the Effects of Structure and Substituents on Donor Strength

Thesis (Ph.D.)--University of Washington, 2016-08

Applying a synthetic approach to the resilience of Finnish reindeer herding as a changing livelihood

Reindeer herding is an emblematic livelihood for Northern Finland, culturally important for local people and valuable in tourism marketing. We examine the livelihood resilience of Finnish reindeer herding by narrowing the focus of general resilience on social-ecological systems (SESs) to a specific livelihood while also acknowledging wider contexts in which reindeer herding is embedded. The questions for specified resilience can be combined with the applied DPSIR approach (Drivers; Pressures: resilience to what; State: resilience of what; Impacts: resilience for whom; Responses: resilience by whom and how). This paper is based on a synthesis of the authors’ extensive anthropological fieldwork on reindeer herding and other land uses in Northern Finland. Our objective is to synthesize various opportunities and challenges that underpin the resilience of reindeer herding as a viable livelihood. The DPSIR approach, applied here as a three step procedure, helps focus the analysis on different components of SES and their dynamic interactions. First, various land use-related DPSIR factors and their relations (synergies and trade-offs) to reindeer herding are mapped. Second, detailed DPSIR factors underpinning the resilience of reindeer herding are identified. Third, examples of interrelations between DPSIR factors are explored, revealing the key dynamics between Pressures, State, Impacts, and Responses related to the livelihood resilience of reindeer herding. In the Discussion section, we recommend that future applications of the DPSIR approach in examining livelihood resilience should (1) address cumulative pressures, (2) consider the state dimension as more tuned toward the social side of SES, (3) assess both the negative and positive impacts of environmental change on the examined livelihood by a combination of science led top-down and participatory bottom-up approaches, and (4) examine and propose governance solutions as well as local adaptations by reindeer herders as equally relevant responses to enhance livelihood resilience.

Tissue engineering: technological advances to improve its applications in reconstructive surgery

Background. Tremendous advances in biomaterials science and nanotechnologies, together with thorough research on stem cells, have recently promoted an intriguing development of regenerative medicine/tissue engineering. The nanotechnology represents a wide interdisciplinary field that implies the manipulation of different materials at nanometer level to achieve the creation of constructs that mimic the nanoscale-based architecture of native tissues. Aim. The purpose of this article is to highlight the significant new knowledges regarding this matter. Emerging acquisitions. To widen the range of scaffold materials resort has been carried out to either recombinant DNA technology-generated materials, such as a collagen-like protein, or the incorporation of bioactive molecules, such as RDG (arginine-glycine-aspartic acid), into synthetic products. Both the bottom-up and the top-down fabrication approaches may be properly used to respectively obtain sopramolecular architectures or, instead, micro-/nanostructures to incorporate them within a preexisting complex scaffold construct. Computer-aided design/manufacturing (CAD/CAM) scaffold technique allows to achieve patient-tailored organs. Stem cells, because of their peculiar properties - ability to proliferate, self-renew and specific cell-lineage differentiate under appropriate conditions - represent an attractive source for intriguing tissue engineering/regenerative medicine applications. Future research activities. New developments in the realization of different organs tissue engineering will depend on further progress of both the science of nanoscale-based materials and the knowledge of stem cell biology. Moreover the in vivo tissue engineering appears to be the logical step of the current research.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Développement et caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque

Ce projet de recherche mené en collaboration industrielle avec St-Jean Photochimie Inc. / PCAS Canada vise le développement et la caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque. La quête du récoltage des photons se situant dans le proche-infrarouge a été au centre des modifications structurales explorées afin d’augmenter l’efficacité de conversion des cellules solaires de type organique et à pigments photosensibles. Trois familles de composés intégrant le motif dipyrrométhène ont été synthétisées et caractérisées du point de vue spectroscopique, électrochimique, structural ainsi que par modélisation moléculaire afin d’établir des relations structures-propriétés. La première famille comporte six azadipyrrométhènes au potentiel de coordination tétradentate sur des centres métalliques. Le développement d’une nouvelle voie synthétique asymétrique combinée à l’utilisation d’une voie symétrique classique ont permis d’obtenir l’ensemble des combinaisons de substituants possibles sur les aryles proximaux incluant les noyaux 2-hydroxyphényle, 2-méthoxyphényle et 2- pyridyle. La modulation du maximum d’absorption dans le rouge a pu être faite entre 598 et 619 nm. De même, la présence de groupements méthoxyle ou hydroxyle augmente l’absorption dans le violet (~410 nm) tel que démontré par modélisation. La caractérisation électrochimique a montré que les dérivés tétradentates étaient en général moins stables aux processus redox que leur contre-parti bidentate. La deuxième famille comporte dix dérivés BODIPY fusionnés de façon asymétrique en position [b]. L’aryle proximal a été modifié de façon systématique afin de mieux comprendre l’impact des substituents riches en électron et de la fusion de cycles aromatiques. De plus, ces dérivés ont été mis en relation avec une vaste série de composés analogues. Les résultats empiriques ont montré que les propriétés optoélectroniques de la plateforme sont régies par le degré de communication électronique entre l’aryle proximal, le pyrrole sur lequel il est attaché et le noyau indolique adjacent à ce dernier. Les maximums d’absorption dans le rouge sont modulables entre 547 et 628 nm et la fluorescence des composés se situe dans le proche- infrarouge. L’un des composé s’est révélé souhaitable pour une utilisation en photovoltaïque ainsi qu’à titre de sonde à pH. La troisième famille comporte cinq complexes neutres de RuII basés sur des polypyridines et portant un ligand azadipyrrométhène cyclométalé. Les composés ont montré une forte absorption de photons dans la région de 600 à 800 nm (rouge à proche- infrarouge) et qui a pu être étendue au-delà de 1100 nm dans le cas des dérivés portant un ligand terpyridine. L’analyse des propriétés optoélectroniques de façon empirique et théorique a montré un impact significatif de la cyclométalation et ouvert la voie pour leur étude en tant que photosensibilisateurs en OPV et en DSSC. La capacité d’un des complexes à photo-injecter un électron dans la bande de conduction du semi-conducteur TiO2 a été démontré en collaboration avec le groupe du Pr Gerald J. Meyer à University of North Carolina at Chapel Hill, premier pas vers une utilisation dans les cellules solaires à pigments photosensibles. La stabilité des complexes en solution s’est toutefois avérée problématique et des pistes de solutions sont suggérées basées sur les connaissances acquises dans le cadre de cette thèse.

Multi-sensor Cloud and Aerosol Retrieval Simulator and Its Applications

Executing a cloud or aerosol physical properties retrieval algorithm from controlled synthetic data is an important step in retrieval algorithm development. Synthetic data can help answer questions about the sensitivity and performance of the algorithm or aid in determining how an existing retrieval algorithm may perform with a planned sensor. Synthetic data can also help in solving issues that may have surfaced in the retrieval results. Synthetic data become very important when other validation methods, such as field campaigns,are of limited scope. These tend to be of relatively short duration and often are costly. Ground stations have limited spatial coverage whilesynthetic data can cover large spatial and temporal scales and a wide variety of conditions at a low cost. In this work I develop an advanced cloud and aerosol retrieval simulator for the MODIS instrument, also known as Multi-sensor Cloud and Aerosol Retrieval Simulator (MCARS). In a close collaboration with the modeling community I have seamlessly combined the GEOS-5 global climate model with the DISORT radiative transfer code, widely used by the remote sensing community, with the observations from the MODIS instrument to create the simulator. With the MCARS simulator it was then possible to solve the long standing issue with the MODIS aerosol optical depth retrievals that had a low bias for smoke aerosols. MODIS aerosol retrieval did not account for effects of humidity on smoke aerosols. The MCARS simulator also revealed an issue that has not been recognized previously, namely,the value of fine mode fraction could create a linear dependence between retrieved aerosol optical depth and land surface reflectance. MCARS provided the ability to examine aerosol retrievals against “ground truth” for hundreds of thousands of simultaneous samples for an area covered by only three AERONET ground stations. Findings from MCARS are already being used to improve the performance of operational MODIS aerosol properties retrieval algorithms. The modeling community will use the MCARS data to create new parameterizations for aerosol properties as a function of properties of the atmospheric column and gain the ability to correct any assimilated retrieval data that may display similar dependencies in comparisons with ground measurements.

DESIGN, SYNTHESIS AND APPLICATIONS OF FLUORESCENT AND ELECTROCHEMICAL PROBES

“Seeing is believing” the proverb well suits for fluorescent imaging probes. Since we can selectively and sensitively visualize small biomolecules, organelles such as lysosomes, neutral molecules, metal ions, anions through cellular imaging, fluorescent probes can help shed light on the physiological and pathophysiological path ways. Since these biomolecules are produced in low concentrations in the biochemical pathways, general analytical techniques either fail to detect or are not sensitive enough to differentiate the relative concentrations. During my Ph.D. study, I exploited synthetic organic techniques to design and synthesize fluorescent probes with desirable properties such as high water solubility, high sensitivity and with varying fluorescent quantum yields. I synthesized a highly water soluble BOIDPY-based turn-on fluorescent probe for endogenous nitric oxide. I also synthesized a series of cell membrane permeable near infrared (NIR) pH activatable fluorescent probes for lysosomal pH sensing. Fluorescent dyes are molecular tools for designing fluorescent bio imaging probes. This prompted me to design and synthesize a hybrid fluorescent dye with a functionalizable chlorine atom and tested the chlorine re-activity for fluorescent probe design. Carbohydrate and protein interactions are key for many biological processes, such as viral and bacterial infections, cell recognition and adhesion, and immune response. Among several analytical techniques aimed to study these interactions, electrochemical bio sensing is more efficient due to its low cost, ease of operation, and possibility for miniaturization. During my Ph.D., I synthesized mannose bearing aniline molecule which is successfully tested as electrochemical bio sensor. A Ferrocene-mannose conjugate with an anchoring group is synthesized, which can be used as a potential electrochemical biosensor.

Synthetic approaches to flexible fluorescent conjugated polymers

Conjugated polymers (CPs) are intrinsically fluorescent materials that have been used for various biological applications including imaging, sensing, and delivery of biologically active substances. The synthetic control over flexibility and biodegradability of these materials aids the understanding of the structure-function relationships among the photophysical properties, the self-assembly behaviors of the corresponding conjugated polymer nanoparticles (CPNs), and the cellular behaviors of CPNs, such as toxicity, cellular uptake mechanisms, and sub-cellular localization patterns. ^ Synthetic approaches towards two classes of flexible CPs with well-preserved fluorescent properties are described. The synthesis of flexible poly( p-phenylenebutadiynylene)s (PPBs) uses competing Sonogashira and Glaser coupling reactions and the differences in monomer reactivity to incorporate a small amount (∼10%) of flexible, non-conjugated linkers into the backbone. The reaction conditions provide limited control over the proportion of flexible monomer incorporation. Improved synthetic control was achieved in a series of flexible poly(p-phenyleneethynylene)s (PPEs) using modified Sonogashira conditions. In addition to controlling the degree of flexibility, the linker provides disruption of backbone conjugation that offers control of the length of conjugated segments within the polymer chain. Therefore, such control also results in the modulation of the photophysical properties of the materials. ^ CPNs fabricated from flexible PPBs are non-toxic to cells, and exhibit subcellular localization patterns clearly different from those observed with non-flexible PPE CPNs. The subcellular localization patterns of the flexible PPEs have not yet been determined, due to the toxicity of the materials, most likely related to the side-chain structure used in this series. ^ The study of the effect of CP flexibility on self-assembly reorganization upon polyanion complexation is presented. Owing to its high rigidity and hydrophobicity, the PPB backbone undergoes reorganization more readily than PPE. The effects are enhanced in the presence of the flexible linker, which enables more efficient π-π stacking of the aromatic backbone segments. Flexibility has minimal effects on the self-assembly of PPEs. Understanding the role of flexibility on the biophysical behaviors of CPNs is key to the successful development of novel efficient fluorescent therapeutic delivery vehicles.^

Two case studies on generating administrative process applications with AdminDSL

Some organizations end up reimplementing the same class of business process over and over: an "administrative process", which consists of managing a form through several states and involving various roles in the organization. This results in wasted time that could be dedicated to better understanding the process or dealing with the fine details that are specific to the process. Existing virtual office solutions require specific training and infrastructure andmay result in vendor lock-in. In this paper, we propose using a high-level domain-specific language (AdminDSL) to describe the administrative process and a separate code generator targeting a standard web framework. We have implemented the approach using Xtext, EGL and the Django web framework, and we illustrate it through two case studies: a synthetic examination process which illustrates the architecture of the generated code, and a real-world workplace survey process that identified several future avenues for improvement.

Production of activated carbons from single and mixtures of synthetic polymers

The production of activated carbons (ACs) involves two main steps: the carbonization of the carbonaceous of raw materials at temperatures below 1073 K in the absence of oxygen and the activation had realized at the temperature up to 1173 but the most useful temperature at 1073 K. In our study we used the most common industrial and consumer solid waste, namely PET, alone or blended with other synthetic polymer PAN. By mixing the two polymers in different ratios, an improvement of the yield of the AC production was found and some textural properties were enhanced by comparison with the AC prepared using each polymer separately. When all the samples were exposed through the carbonization process with a pyrolysis the mixture of PAN-PET (1:1w/w) yield around 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The combine activation, with CO2 at 1073 K, allow ACs with a lower burn-off degree isothermally, when compared with those attained with PET or PAN alone, but with similarly chemicals or textural properties. The resultant ACs are microporous in their nature, as the activation time increase, the PET-PAN mixture AC are characterized by a better developed porous structure, when associated with the AC prepared from PAN. The AC prepared from PET-PAN mixture are characterized by basic surface characteristics, with a pHpzc around 10.5, which is an important characteristic for future applications on acidic pollutants removals from liquid or gaseous phase. In this study we had used the FTIR methods to determine the main functional groups in the surface of the activated carbons. The adsorbents prepared from PAN fibres presents an IR spectrum with similar characteristics to those obtained with PET wastes, but with fewer peaks and bands with less intensity, in particular for the PAN-8240 sample. This can be reflected by the stretching and deformation modes of NH bond in the range 3100 – 3300 cm-1 and 1520 – 1650 cm-1, respectively. Also, stretching mode associated to C–N, C=N, can contributed to the profile of IR spectrum around 1170 cm-1, 1585 – 1770 cm-1. And the TGA methods was used to study the loses of the precursors mass according to the excessive of the temperature. The results showed that, there were different decreasing of the mass of each precursors. PAN degradation started at almost 573 K and at 1073 K, PAN preserve more than 40% of the initial mass. PET degradation started at 650 K, but at 1073 K, it has lost 80% of the initial mass. However, the mixture of PET-PAN (1:1w/w) showed a thermogravimetric profile between the two polymers tested individually, with a final mass slightly less than 30%. From a chemical point of view, the carbonisation of PET mainly occurs in one step between 650 and 775 K.

Experimental and numerical investigation on short and long term performance of macro-synthetic fibre reinforced concrete materials

Fibre Reinforced Concretes are innovative composite materials whose applications are growing considerably nowadays. Being composite materials, their performance depends on the mechanical properties of both components, fibre and matrix and, above all, on the interface. The variables to account for the mechanical characterization of the material, could be proper of the material itself, i.e. fibre and concrete type, or external factors, i.e. environmental conditions. The first part of the research presented is focused on the experimental and numerical characterization of the interface properties and short term response of fibre reinforced concretes with macro-synthetic fibers. The experimental database produced represents the starting point for numerical models calibration and validation with two principal purposes: the calibration of a local constitutive law and calibration and validation of a model predictive of the whole material response. In the perspective of the design of sustainable admixtures, the optimization of the matrix of cement-based fibre reinforced composites is realized with partial substitution of the cement amount. In the second part of the research, the effect of time dependent phenomena on MSFRCs response is studied. An extended experimental campaign of creep tests is performed analysing the effect of time and temperature variations in different loading conditions. On the results achieved, a numerical model able to account for the viscoelastic nature of both concrete and reinforcement, together with the environmental conditions, is calibrated with the LDPM theory. Different type of regression models are also elaborated correlating the mechanical properties investigated, bond strength and residual flexural behaviour, regarding the short term analysis and creep coefficient on time, for the time dependent behaviour, with the variable investigated. The experimental studies carried out emphasize the several aspects influencing the material mechanical performance allowing also the identification of those properties that the numerical approach should consider in order to be reliable.

Neurophysiological, molecular and pathophysiological aspects of synthetic torpor

Synthetic torpor is a peculiar physiological condition resembling natural torpor, in which even non-hibernating species can be induced through different pharmacological approaches. The growing interest in the induction of a safe synthetic torpor state in non-hibernating species stems from the possible applications that it may have in a translational perspective. In particular, the deeper understanding of the functional changes occurring during and after synthetic torpor may lead to the standardization of a safe procedure to be used also in humans and to the implementation of new therapeutic strategies. Some of the most interesting and peculiar characteristics of torpor that should be assessed in synthetic torpor and may have a translational relevance are: the reversible hyperphosphorylation of neuronal Tau protein, the strong and extended neural plasticity, which may be related to Tau regulatory processes, and the development of radioresistance. In this respect, in the present thesis, rats were induced into synthetic torpor by the pharmacological inhibition of the raphe pallidus, a key brainstem thermoregulatory area, in order to assess: i) whether a reversible hyperphosphorylation of Tau protein occurs at the spinal cord level, also testing the possible involvement of microglia activation in this phenomenon; ii) sleep quality after synthetic torpor and its possible involvement in the process of Tau dephosphorylation; iii) whether synthetic torpor has radioprotective properties, by assessing histopathological and molecular features in animals exposed to X-rays irradiation. The results showed that: i) a reversible hyper-phosphorylation of Tau protein also occurs in synthetic torpor in the dorsal horns of the spinal cord; ii) sleep regulation after synthetic torpor seems to be physiological, and sleep deprivation speeds up Tau dephosphorylation; iii) synthetic torpor induces a consistent increase in radioresistance, as shown by analyses at both histological and molecular level.

Nanostructured Systems for Electrocatalysis of Reduction Reactions for Energy Conversion Applications

Oxygen Reduction Reaction (ORR) requires a platinum-based catalyst to reduce the activation barrier. One of the most promising materials as alternative catalysts are carbon-based, graphene and carbon nanotubes (CNT) derivatives. ORR on a carbon-based substrate involves the less efficient two electrons process and the optimal four electrons process. New synthetic strategies to produce tunable graphene-based materials utilizing graphene oxide (GO) as a base inspired the first part of this work. Hydrogen Evolution Reaction (HER) is a slow process requiring also platinum or palladium as catalyst. In the second part of this work, we develop and use a technique for Ni nanoparticles electrodeposition using NiCl2 as precursor in the presence of ascorbate ligands. Electrodeposition of nano-nickel onto flat glassy carbon (GC) and onto nitrogen-doped reduced graphene oxide (rGO-N) substrates are studied. State of the art catalysts for CO2RR requires rare metals rhenium or rhodium. In recent years significant research has been done on non-noble metals and molecular systems to use as electro and photo-catalysts (artificial photosynthesis). As Cu-Zn alloys show good CO2RR performance, here we applied the same nanoparticle electrosynthesis technique using as precursors CuCl2 and Cl2Zn and observed successful formation of the nanoparticles and a notable activity in presence of CO2. Using rhenium complexes as catalysts is another popular approach and di-nuclear complexes have a positive cooperative effect. More recently a growing family of pre-catalysts based on the earth-abundant metal manganese, has emerged as a promising, cheaper alternative. Here we study the cooperative effects of di-nuclear manganese complexes derivatives when used as homogeneous electrocatalysts, as well as a rhenium functionalized polymer used as heterogeneous electrocatalyst.