Transition metal complexes of some N4-phenylsemicarbazones: crystal structures and spectral studies

The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2009-2012. The thesis is an introduction to our attempts to evaluate the coordination behavior of some compounds of our interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are wellauthenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of new N4- phenylsemicarbazones derived from 2-formylpyridine and 3-ethoxysalicylaldehyde and their transition metal complexes and new transition metal complexes of 2- benzoylpyridine-N4-phenylsemicarbazone. In addition to various physicochemical methods of analysis, single crystal X-ray diffraction studies were also used for the characterization of the complexes.

New meshing capabilities for efficient and quality navigation on a virtual globe

[EN]Polygonal meshes are powerful structures to represent geometric information of the Earth’s surface. In particular, triangle meshes have been massively used as a reliable way to efficiently represent the land surface with real time responses in virtual navigation. In this work we present new ideas for the underlying treatment of a mesh that improve efficiency and quality in the navigation.

La persévérance scolaire des immigrants haïtiens de première génération au Québec et à New York

Le but de cette thèse a consisté à comprendre les facteurs de la persévérance et de l’abandon scolaire des nouveaux arrivants haïtiens au Québec et à New York. La recension d’écrits a révélé une sous-documentation de la thématique en question. Toutefois, l’élaboration du cadre conceptuel nous a permis de mieux cerner la problématique, d’analyser et de synthétiser plusieurs approches théoriques dont les théories du rendement scolaire des immigrants (Rong et Brown, 2001 ; Warikoo et Carter, 2009 ; Xie et Greenman, 2011), l’approche bourdieusienne des capitaux (1979a, 1979b, 1980), le structuro-fonctionnalisme de Merton (1965) et le courant effets-écoles/ effets-enseignants (Crahay, 2000 ; Bressoux, 1994a). Nous avons également mis en évidence deux approches compréhensives à savoir l’interactionnisme (Weber, 1959 ; Boudon, 1979, 1994 ; Goffman, 1998 ; Garfinkel, 1967) et l’approche du rapport au savoir de l’équipe ESCOL (Rochex, 2002 ; Charlot, 2003) dans l’objectif de faire valoir le caractère relatif des conclusions d’une recherche qualitative qui priorise la subjectivité des participants dans l’analyse des faits sociaux. Dans cette recherche, nous avons interviewé onze participants à Montréal et à Brooklyn, parmi lesquels sept hommes et quatre femmes. Ils ont tous une expérience d’abandon scolaire au secondaire ou au secteur des adultes. Nous avons utilisé l’entretien semi-dirigé comme méthode de collecte d’information et l’analyse thématique est celle de l’analyse des données. L’analyse des données nous a permis de classer les informations fournies par les participants en cinq rubriques : capital économique, capital culturel, capital social, encadrement institutionnel et facteurs spécifiques. Ces cinq rubriques regroupent les facteurs de la persévérance et du décrochage scolaire évoqués par les participants de la recherche. La réalisation de cette thèse nous apporte un bon éclairage quant à notre tentative de comprendre la dynamique de l’abandon scolaire des jeunes et des jeunes adultes immigrants haïtiens de première génération au Québec et à New York, au secondaire et au secteur de l’éducation des adultes. Nous avons mis en relation les résultats de la recherche avec ceux des travaux que nous avons recensés dans la problématique et dans le cadre conceptuel de cette thèse. La synthèse de ces résultats nous a amené à faire une proposition d’éléments d’un modèle d’analyse que nous qualifions de « relance scolaire des nouveaux arrivants haïtiens au Québec et à New York ». L’analyse et la synthèse des facteurs émergents de la recherche, plus précisément des six thèmes qui composent la rubrique des facteurs spécifiques : facteurs démographiques, motivation personnelle, lacunes de base, facteurs affectifs, traits de personnalité et problèmes de comportement, nous ont permis d’élaborer un autre concept qui peut représenter une grande contribution à la persévérance scolaire des nouveaux arrivants haïtiens. Il s’agit de l’encadrement psycho-intégrationnel qui est une forme d’accompagnement dont les jeunes et les jeunes adultes nouveaux arrivants haïtiens pourront être bénéficiaires au début en vue d’un bon démarrage sur le plan socioéducatif et de leur persévérance scolaire au pays d’accueil. L’encadrement psycho-intégrationnel, consistera à mettre en relation certains faits psychologiques qui ont marqué la vie pré-migratoire des élèves jeunes et jeunes adultes d’origine haïtienne avec les faits sociaux qui peuvent influencer leur vie au pays d’accueil. C’est une forme d’assistance individuelle dont l’État, les institutions sociales d’intégration et l’école constitueront les principales structures de matérialisation. Les principaux intervenants, notamment les psychologues, les travailleurs sociaux et les anthropo-sociologues se chargeront de comprendre et d’orienter les nouveaux arrivants quant au nouveau comportement à adopter pour une meilleure évolution sur les plans socio-culturel, professionnel et économique. Mots clés : Persévérance scolaire, relance scolaire, immigrants haïtiens, première génération, nouveaux arrivants.

Finite Element Modeling of Spiral Frequency Steerable Acoustic Transducers (FSATs) for guided waves based Structural Health Monitoring of plate-like structures

Structural Health Monitoring (SHM) is an emerging area of research associated to improvement of maintainability and the safety of aerospace, civil and mechanical infrastructures by means of monitoring and damage detection. Guided wave structural testing method is an approach for health monitoring of plate-like structures using smart material piezoelectric transducers. Among many kinds of transducers, the ones that have beam steering feature can perform more accurate surface interrogation. A frequency steerable acoustic transducer (FSATs) is capable of beam steering by varying the input frequency and consequently can detect and localize damage in structures. Guided wave inspection is typically performed through phased arrays which feature a large number of piezoelectric transducers, complexity and limitations. To overcome the weight penalty, the complex circuity and maintenance concern associated with wiring a large number of transducers, new FSATs are proposed that present inherent directional capabilities when generating and sensing elastic waves. The first generation of Spiral FSAT has two main limitations. First, waves are excited or sensed in one direction and in the opposite one (180 ̊ ambiguity) and second, just a relatively rude approximation of the desired directivity has been attained. Second generation of Spiral FSAT is proposed to overcome the first generation limitations. The importance of simulation tools becomes higher when a new idea is proposed and starts to be developed. The shaped transducer concept, especially the second generation of spiral FSAT is a novel idea in guided waves based of Structural Health Monitoring systems, hence finding a simulation tool is a necessity to develop various design aspects of this innovative transducer. In this work, the numerical simulation of the 1st and 2nd generations of Spiral FSAT has been conducted to prove the directional capability of excited guided waves through a plate-like structure.

Towards NIR emission: 2-(1H-tetrazol-1-yl)pyridine as versatile ligand for the synthesis of two new families of cationic and neutral Ir(III) complexes.

In the last decades, cyclometalated Ir(III) complexes have drawn a large interest for their unique properties: they are excellent triplet state emitters, thus the emission is phosphorescent in nature; typically high quantum yields and good stability make them good candidates for luminescent materials. Moreover, through an opportune choice of the ligands, it is possible to tune the emission along the whole visible spectra. Thanks to these interesting features, Ir(III) complexes have found different applications in several areas of applied science, from OLEDs to bioimaging. In particular, regarding the second application, a remarkable red-shift in the emission is required, in order to minimize the problem of the tissue penetration and the possible damages for the organisms. With the aim of synthesizing a new family of NIR emitting Ir(III) complexes, we envisaged the possibility to use for the first time 2-(1H-tetrazol-1-yl)pyridine as bidentate ligand able to provide the required red-shift of the emission of the final complexes. Exploiting the versatility of the ligand, I prepared two different families of heteroleptic Ir(III) complexes. In detail, in the first case the 2-(1H-tetrazol-1-yl)pyridine was used as bis-chelating N^N ligand, leading to cationic complexes, while in the second case it was used as cyclometalating C^N ligand, giving neutral complexes. The structures of the prepared molecules have been characterised by NMR spectroscopy and mass spectrometry. Moreover, the neutral complexes’ emissive properties have been measured: emission spectra have been recorded in solution at both room temperature and 77K, as well as in PMMA matrix. DFT calculation has then been performed and the obtained results have been compared to experimental ones.

The Meanings of New Money: Social Constructions of Value in the Rise of Digital Currencies

Thesis (Ph.D.)--University of Washington, 2016-07

Topology Optimization of continuum structures with epsilon-relaxed stress constraints

Topology optimization of linear elastic continuum structures is a challenging problem when considering local stress constraints. The reasons are the singular behavior of the constraint with the density design variables, combined with the large number of constraints even for small finite element meshes. This work presents an alternative formulation for the s-relaxation technique, which provides an workaround for the singularity of the stress constraint. It also presents a new global stress constraint formulation. Derivation of the sensitivities for the constraint by the adjoint method is shown. Results for single and multiple load cases show the potential of the new formulation.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

New morpho-bathymetric and tectono-stratigraphic data on Naples and Salerno gulfs (southern tyrrhenian sea, Italy) derived from bathymetric and seismic data analysis and integrated geological interpretation

New morpho-bathymetric and tectono-stratigraphic data on Naples and Salerno Gulfs, derived from bathymetric and seismic data analysis and integrated geologic interpretation are here presented. The CUBE(Combined Uncertainty Bathymetric Estimator) method has been applied to complex morphologies, such as the Capri continental slope and the related geological structures occurring in the Salerno Gulf.The bathymetric data analysis has been carried out for marine geological maps of the whole Campania continental margin at scales ranging from 1:25.000 to 1:10.000, including focused examples in Naples and Salerno Gulfs, Naples harbour, Capri and Ischia Islands and Salerno Valley. Seismic data analysis has allowed for the correlation of main morpho-structural lineaments recognized at a regional scale through multichannel profiles with morphological features cropping out at the sea bottom, evident from bathymetry.Main fault systems in the area have been represented on a tectonic sketch map, including the master fault located northwards to the Salerno Valley half graben. Some normal faults parallel to the master fault have been interpreted from the slope map derived from bathymetric data. A complex system of antithetic faults bound two morpho-structural highs located 20km to the south of the Capri Island. Some hints of compressional reactivation of normal faults in an extensional setting involving the whole Campania continental margin have been shown from seismic interpretation.

DESIGN, FABRICATION, AND PERFORMANCE CHARACTERIZATION OF MULTIFUNCTIONAL STRUCTURES TO HARVEST SOLAR ENERGY FOR FLAPPING WING AERIAL VEHICLES

Flapping Wing Aerial Vehicles (FWAVs) have the capability to combine the benefits of both fixed wing vehicles and rotary vehicles. However, flight time is limited due to limited on-board energy storage capacity. For most Unmanned Aerial Vehicle (UAV) operators, frequent recharging of the batteries is not ideal due to lack of nearby electrical outlets. This imposes serious limitations on FWAV flights. The approach taken to extend the flight time of UAVs was to integrate photovoltaic solar cells onto different structures of the vehicle to harvest and use energy from the sun. Integration of the solar cells can greatly improve the energy capacity of an UAV; however, this integration does effect the performance of the UAV and especially FWAVs. The integration of solar cells affects the ability of the vehicle to produce the aerodynamic forces necessary to maintain flight. This PhD dissertation characterizes the effects of solar cell integration on the performance of a FWAV. Robo Raven, a recently developed FWAV, is used as the platform for this work. An additive manufacturing technique was developed to integrate photovoltaic solar cells into the wing and tail structures of the vehicle. An approach to characterizing the effects of solar cell integration to the wings, tail, and body of the UAV is also described. This approach includes measurement of aerodynamic forces generated by the vehicle and measurements of the wing shape during the flapping cycle using Digital Image Correlation. Various changes to wing, body, and tail design are investigated and changes in performance for each design are measured. The electrical performance from the solar cells is also characterized. A new multifunctional performance model was formulated that describes how integration of solar cells influences the flight performance. Aerodynamic models were developed to describe effects of solar cell integration force production and performance of the FWAV. Thus, performance changes can be predicted depending on changes in design. Sensing capabilities of the solar cells were also discovered and correlated to the deformation of the wing. This demonstrated that the solar cells were capable of: (1) Lightweight and flexible structure to generate aerodynamic forces, (2) Energy harvesting to extend operational time and autonomy, (3) Sensing of an aerodynamic force associated with wing deformation. Finally, different flexible photovoltaic materials with higher efficiencies are investigated, which enable the multifunctional wings to provide enough solar power to keep the FWAV aloft without batteries as long as there is enough sunlight to power the vehicle.

A new construction of Calabi–Yau manifolds: Generalized CICYs

We present a generalization of the complete intersection in products of projective space (CICY) construction of Calabi–Yau manifolds. CICY three-folds and four-folds have been studied extensively in the physics literature. Their utility stems from the fact that they can be simply described in terms of a ‘configuration matrix’, a matrix of integers from which many of the details of the geometries can be easily extracted. The generalization we present is to allow negative integers in the configuration matrices which were previously taken to have positive semi-definite entries. This broadening of the complete intersection construction leads to a larger class of Calabi–Yau manifolds than that considered in previous work, which nevertheless enjoys much of the same degree of calculational control. These new Calabi–Yau manifolds are complete intersections in (not necessarily Fano) ambient spaces with an effective anticanonical class. We find examples with topology distinct from any that has appeared in the literature to date. The new manifolds thus obtained have many interesting features. For example, they can have smaller Hodge numbers than ordinary CICYs and lead to many examples with elliptic and K3-fibration structures relevant to F-theory and string dualities.

Between path dependency and contingency: new challenges for the geography of port system evolution.

Seaports play a critical role as gateways and facilitators of economic interchange and logistics processes and thus have become crucial nodes in globalised production networks andmobility systems. Both the physical port infrastructure and its operational superstructure have undergone intensive evolution processes in an effort to adapt to changing economic environments, technological advances,maritime industry expectations and institutional reforms. The results, in terms of infrastructure, operator models and the role of an individual port within the port system, vary by region, institutional and economic context. While ports have undoubtedly developed in scale to respond to the changing volumes and structures in geographies of trade (Wilmsmeier, 2015), the development of hinterland access infrastructure, regulatory systems and institutional structures have in many instances lagged behind. The resulting bottlenecks reflect deficits in the interplay between the economic system and the factors defining port development (e.g. transport demand, the structure of trade, transport services, institutional capacities, etc. cf. Cullinane and Wilmsmeier, 2011). There is a wide range of case study approaches and analyses of individual ports, but analyses from a port system perspective are less common, and those that exist are seldom critical of the dominant discourse assuming the efficiency of market competition (cf. Debrie et al., 2013). This special section aims to capture the spectrum of approaches in current geography research on port system evolution. Thus, the papers reach from the traditional spatial approach (Rodrigue and Ashar, this volume) to network analysis (Mohamed-Chérif and Ducruet, this volume) to institutional discussions (Vonck and Notteboom, this volume; Wilmsmeier and Monios, this volume). The selection of papers allows an opening of discussion and reflection on current research, necessary critical analysis of the influences on port systemevolution and,most importantly, future directions. The remainder of this editorial aims to reflect on these challenges and identify the potential for future research.

Superlattice structures in twisted bilayers of folded graphene

The electronic properties of bilayer graphene strongly depend on relative orientation of the two atomic lattices. Whereas Bernal-stacked graphene is most commonly studied, a rotational mismatch between layers opens up a whole new field of rich physics, especially at small interlayer twist. Here we report on magnetotransport measurements on twisted graphene bilayers, prepared by folding of single layers. These reveal a strong dependence on the twist angle, which can be estimated by means of sample geometry. At small rotation, superlattices with a wavelength in the order of 10 nm arise and are observed by friction atomic force microscopy. Magnetotransport measurements in this small-angle regime show the formation of satellite Landau fans. These are attributed to additional Dirac singularities in the band structure and discussed with respect to the wide range of interlayer coupling models.

Saranac Lake, New York /

Scale 1:25,000; 1 cm. to 250 m.

Saranac Lake, New York /

Scale 1:25,000; 1 cm. to 250 m.