Nanopartícul·les core-shell estabilitzades en polímer amb propietats calítiques i bactericides medioambientalment segure

Aquest projecte de doctorat és un treball interdisciplinari adreçat a l’obtenció de nous nanocompòsits (NCs) funcionals sintetitzats a partir de materials polimèrics bescanviadors d’ions que són modificats amb nanopartícules metàl•liques (NPMs) de diferent composició. Els materials desenvolupats s’avaluen en funció de dues possibles aplicacions: 1) com a catalitzadors de reaccions orgàniques d’interès actual (NCs basats en pal•ladi) i, 2) la seva dedicació a aplicacions bactericides en el tractament d’aigües domèstiques o industrials (NCs basats en plata). El desenvolupament de nanomaterials és de gran interès a l’actualitat donades les seves especials propietats, l’aprofitament de les quals és la força impulsora per a la fabricació de nous NCs. Les nanopartícules metàl•liques estabilitzades en polímer (Polymer Stabilized Metal Nanoparticles, PSNPM) s’han preparat mitjançant la tècnica in-situ de síntesi intermatricial (Inter-matrix synthesis, IMS) que consisteix en la càrrega seqüencial dels grups funcionals de les matrius polimèriques amb ions metàl•lics, i la seva posterior reducció química dins de la matriu polimèrica de bescanvi iònic. L’estabilització en matrius polimèriques evita l’agregació entre elles (self-aggreagtion), un dels principals problemes coneguts de les NPs. Pel desenvolupament d’aquesta metodologia, s’han emprat diferents tipus de matrius polimèriques de bescanvi iònic: membrana Sulfonated PolyEtherEtherKetone, SPEEK, així com fibres sintètiques basades en polypropilè amb diferents tipus de grups funcionals, que ens permeten el seu ús com a filtres en la desinfecció de solucions aquoses o com a material catalitzador. Durant el projecte s’ha anat avançant en l’optimització del material nanocomposite final per a les aplicacions d’interès, en quant activitat i funcionalitat de les nanopartícules i estabilitat del nanocomposite. Així, s’ha optimitzat la síntesi de NPs estabilitzades en resines de bescanvi iònic, realitzant un screening de diferents tipus de resines i la seva avaluació en aplicacions industrials d’interès.

Prototip culata del vehicle de baix consum (equip EPS-UdG Shell Eco)

Aquest projecte s’ha portat a terme per tal de millorar en diferentsaspectes el motor Honda Gx35 , del vehicle de baix consum de la Universitat deGirona (Udg). Aquest és un motor de combustió interna de gasolina (cicle Otto).L’objectiu és el disseny d’una culata per poder minimitzar el consum de gasolina, la qual s’ha de poder acoblar amb el motor Honda Gx35. Aquest motor,prèviament s’haurà de modificar per poder-hi instal•lari la nova culata

Second-order Møller-Plesset perturbation theory without basis set superposition error : II : open-shell systems

The basis set superposition error-free second-order MØller-Plesset perturbation theory of intermolecular interactions was studied. The difficulties of the counterpoise (CP) correction in open-shell systems were also discussed. The calculations were performed by a program which was used for testing the new variants of the theory. It was shown that the CP correction for the diabatic surfaces should be preferred to the adiabatic ones

Shell structure in mixed 3He-4He droplets

Due to the immiscibility of 3He into 4He at very low temperatures, mixed helium droplets consist of a core of 4He atoms coated by a 3He layer whose thickness depends on the number of atoms of each isotope. When these numbers are such that the centrifugal kinetic energy of the 3He atoms is small and can be considered as a perturbation to the mean-field energy, a novel shell structure arises, with magic numbers different from these of pure 3He droplets. If the outermost shell is not completely filled, the valence atoms align their spins up to the maximum value allowed by the Pauli principle.

Distorted-wave calculation of cross sections for inner-shell ionization by electron and positron impact

The relativistic distorted-wave Born approximation is used to calculate differential and total cross sections for inner shell ionization of neutral atoms by electron and positron impact. The target atom is described within the independent-electron approximation using the self-consistent Dirac-Fock-Slater potential. The distorting potential for the projectile is also set equal to the Dirac-Fock-Slater potential. For electrons, this guarantees orthogonality of all the orbitals involved and simplifies the calculation of exchange T-matrix elements. The interaction between the projectile and the target electrons is assumed to reduce to the instantaneous Coulomb interaction. The adopted numerical algorithm allows the calculation of differential and total cross sections for projectiles with kinetic energies ranging from the ionization threshold up to about ten times this value. Algorithm accuracy and stability are demonstrated by comparing differential cross sections calculated by our code with the distorting potential set to zero with equivalent results generated by a more robust code that uses the conventional plane-wave Born approximation. Sample calculation results are presented for ionization of K- and L-shells of various elements and compared with the available experimental data.

Microscopic origin of exchange bias in core/shell nanoparticles

We report the results of Monte Carlo simulations with the aim to clarify the microscopic origin of exchange bias in the magnetization hysteresis loops of a model of individual core/shell nanoparticles. Increase of the exchange coupling across the core/shell interface leads to an enhancement of exchange bias and to an increasing asymmetry between the two branches of the loops which is due to different reversal mechanisms. A detailed study of the magnetic order of the interfacial spins shows compelling evidence that the existence of a net magnetization due to uncompensated spins at the shell interface is responsible for both phenomena and allows to quantify the loop shifts directly in terms of microscopic parameters with striking agreement with the macroscopic observed values.

Stable C and N isotope concentration in several tissues of the loggerhead sea turtle Caretta caretta from the western Mediterranean and dietary implications

The isotopic concentrations of carapace scutes, skin, muscle and blood of loggerhead sea turtles (Caretta caretta) from the Balearic Archipelago were analysed to investigate the pattern of variation between tissues and to assess the position of this species in the trophic webs of the Algerian Basin. Skin showed higher δ13C values than muscle or carapace scutes and these showed higher values than blood. Conversely, muscle showed higher δ15N values than skin, skin showed higher values than blood and blood showed higher values than carapace scutes. Dead and live sea turtles from the same habitat did not differ in the concentration of stable isotopes. However, some of the tissues of the turtles caught in drifting longlines in the oceanic realm showed higher δ13C values than those from the turtles caught by hand or in trammel nets over the continental shelf, although they did not differ in the δ15N. Comparison of the concentration of stable isotopes in the turtles with that of other species from several areas of the Algerian Basin revealed that they consumed planktonic prey and that the trophic level of the sea turtles was higher than that of carnivorous cnidarians but lower than that of zooplanktophagous fish and crustaceans.

Mortality rates in by-caught loggerhead turtle Caretta caretta in the Mediterranean Sea and implications for the Atlantic populations

Reliable estimates of the post-release mortality probability of marine turtles after incidental by-catch are essential for assessing the impact of longline fishing on these species.Large numbers of loggerhead turtles Caretta caretta from rookeries in the northwestern Atlantic Ocean have been by-caught annually in the southwestern Mediterranean Sea since the 1980s, but nothing is known about their post-release mortality probability under natural conditions. Pop-up archival transmitting tags were attached to 26 loggerhead turtles following incidental capture by Spanish longliners. Hooks were not removed, and 40 cm of line was left in place. The post-release mortality probability during the 90 d following release ranged from 0.308 to 0.365, and was independent of hook location. When the post-release mortality probability was combined with previously reported estimates of the mortality probability before hauling, the aggregated by-catch mortality probability ranged from 0.321 to 0.378. Assuming a total annual by-catch of 10656 loggerhead turtles by the Spanish longline fleet operating in the southwestern Mediterranean, by-catch results in 3421 to 4028 turtle deaths annually. This range is equivalent to 8.5−10.1% of the approximately 40000 turtles inhabiting the fishing grounds used by Spanish longliners, most of them from rookeries in the northwestern Atlantic. As a consequence, the accumulated mortality during the oceanic stage is expected to be larger for those loggerhead turtles of Atlantic origin that spend several years in the Mediterranean Sea than for turtles of the same cohort that remain in the Atlantic. For this reason, the Mediterranean can be considered a dead end for loggerhead turtle populations nesting in the Atlantic, although the actual demographic relevance of by-catch mortality of loggerhead turtles in the Mediterranean remains unknown.

Electron scattering in isotonic chains as a probe of the proton shell structure of unstable nuclei

Electron scattering on unstable nuclei is planned in future facilities of the GSI and RIKEN upgrades. Motivated by this fact, we study theoretical predictions for elastic electron scattering in the N=82, N=50, and N=14 isotonic chains from very proton-deficient to very proton-rich isotones. We compute the scattering observables by performing Dirac partial-wave calculations. The charge density of the nucleus is obtained with a covariant nuclear mean-field model that accounts for the low-energy electromagnetic structure of the nucleon. For the discussion of the dependence of scattering observables at low-momentum transfer on the gross properties of the charge density, we fit Helm model distributions to the self-consistent mean-field densities. We find that the changes shown by the electric charge form factor along each isotonic chain are strongly correlated with the underlying proton shell structure of the isotones. We conclude that elastic electron scattering experiments on isotones can provide valuable information about the filling order and occupation of the single-particle levels of protons.

Geographic patterns of genetic variation in a broadly distributed marine vertebrate: new insights into loggerhead turtle stock structure from expanded mitochondrial DNA sequences

Previous genetic studies have demonstrated that natal homing shapes the stock structure of marine turtle nesting populations. However, widespread sharing of common haplotypes based on short segments of the mitochondrial control region often limits resolution of the demographic connectivity of populations. Recent studies employing longer control region sequences to resolve haplotype sharing have focused on regional assessments of genetic structure and phylogeography. Here we synthesize available control region sequences for loggerhead turtles from the Mediterranean Sea, Atlantic, and western Indian Ocean basins. These data represent six of the nine globally significant regional management units (RMUs) for the species and include novel sequence data from Brazil, Cape Verde, South Africa and Oman. Genetic tests of differentiation among 42 rookeries represented by short sequences (380 bp haplotypes from 3,486 samples) and 40 rookeries represented by long sequences (~800 bp haplotypes from 3,434 samples) supported the distinction of the six RMUs analyzed as well as recognition of at least 18 demographically independent management units (MUs) with respect to female natal homing. A total of 59 haplotypes were resolved. These haplotypes belonged to two highly divergent global lineages, with haplogroup I represented primarily by CC-A1, CC-A4, and CC-A11 variants and haplogroup II represented by CC-A2 and derived variants. Geographic distribution patterns of haplogroup II haplotypes and the nested position of CC-A11.6 from Oman among the Atlantic haplotypes invoke recent colonization of the Indian Ocean from the Atlantic for both global lineages. The haplotypes we confirmed for western Indian Ocean RMUs allow reinterpretation of previous mixed stock analysis and further suggest that contemporary migratory connectivity between the Indian and Atlantic Oceans occurs on a broader scale than previously hypothesized. This study represents a valuable model for conducting comprehensive international cooperative data management and research in marine ecology.

Crassostrea patagonica (d'Orbigny, 1842) shell concentrations from the late Miocene Rio Negro province, NE Patagonia, Argentina

The Río Negro Formation (late Miocene-early Pliocene) mainly consists of continental deposits, but it contains a middle member of marine origin. It represents a transgressive-regressive sequence that can be seen at several outcrops along the N Patagonian coast. The taphonomical approach to the El Espigón marine deposits permits the identification of four main layers containing different kinds of skeletal accumulation, which mainly consist of oyster shells [Crassostrea patagonica (D'Orbigny, 1842)]. These concentrations display three different morphologies (pouches, pavements and bouquets) with a different taphonomic signature. These deposits were formed in shallow marine environments influenced by wave activity that produced valve concentrations of different entities. They contain several shell beds that represent event, composite, hiatal to lag skeletal concentrations. Traces of bioturbation in the sediment (Thalassinoides, Teichichnus) and bioerosion on the shells (Entobia, Gastrochaeonolites, Caulostrepsis), and encrusters (cirripeds, bryozoans), are also abundant in the outcrop and consititue common components of these Miocene materials. Layers 1 and 2 of the sequence were deposited in shoreface/foreshore environments at the beginning of a highstand systems tract, while layers 3 and 4 were deposited at the end, or at the beginning of a forced regression, in foreshore environments. A final erosional episode cut the top of the layer 4, which truncated the abundant bioturbaation developed there.