Ionic liquids for the nuclear industry: A radiochemical, structural, and electrochemical investigation

The applicability of ionic liquids within the nuclear industry has been investigated. The radiation stability of ionic liquids containing dialkylimidazolium cations has been tested through with alpha, beta and gamma irradiation. The results of these tests suggest that imidazolium salts have stabilities similar to alkylbenzenes and greater than tetrabutylphosphate / odorless kerosene (TBP/OK) mixtures. The oxidative dissolution of uranium dioxide and the anodic dissolution of uranium metal and plutonium metal have been carried out in various ionic liquid media (C) 2002 American Chemical Society.

Finite element investigation of the structural behaviour of deck slabs in composite bridges

This research studies the structural behaviour of bridge deck slabs under static patch loads in steel–concrete composite bridges and investigates compressive membrane action (CMA) in concrete bridge decks slabs, which governs the structural behaviour. A non-linear 3D finite element analysis models was developed using ABAQUS 6.5 software packages. Experimental data from one-span composite bridge structures are used to validate and calibrate the proposed FEM models. A series of parametric studies is conducted. The analysis results are discussed and conclusions on the behaviour of the bridge decks are presented.

Investigation into mercury bound to biothiols:structural identification using ESI-ion-trap MS and introduction of a method for their HPLC separation with simultaneous detection by ICP-MS and ESI-MS

Mercury in plants or animal tissue is supposed to occur in the form of complexes formed with biologically relevant thiols (biothiols), rather than as free cation. We describe a technique for the separation and molecular identification of mercury and methylmercury complexes derived from their reactions with cysteine (Cys) and glutathione (GS): Hg(Cys)(2), Hg(GS)(2), MeHgCys, MeHgGS. Complexes were characterised by electrospray mass spectrometry (MS) equipped with an ion trap and the fragmentation pattern of MeHgCys was explained by using MP2 and B3LYP calculations, showing the importance of mercury-amine interactions in the gas phase. Chromatographic baseline separation was performed within 10 min with formic acid as the mobile phase on a reversed-phase column. Detection was done by online simultaneous coupling of ES-MS and inductively coupled plasma MS. When the mercury complexes were spiked in real samples (plant extracts), no perturbation of the separation and detection conditions was observed, suggesting that this method is capable of detecting mercury biothiol complexes in plants.

Investigation of structural effects on the reactivity of heterocyclic bioactive compounds

Tese de dout., Química, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2008

STRUCTURAL ANALYSIS, LAYER THICKNESS MEASUREMENTS AND MINERALOGICAL INVESTIGATION OF THE LARGE INTERIOR LAYERED DEPOSIT WITHIN GANGES CHASMA, VALLES MARINERIS, MARS

The interior layered deposit (ILD) in Ganges Chasma, Valles Marineris, is a 4.25 km high mound that extends approximately 110 km from west to east. The deposition, deformation, and erosion history of the Ganges ILD records aids in identifying the processes that formed and shaped the Chasma. To interpret structural and geomorphic processes acting on the ILD, multiple layer attitudes and layer thickness transects were conducted on the Ganges ILD. Mineralogical data was analyzed to determine correlations between materials and landforms. Layer thickness measurements indicate that the majority of layers are between 0.5 m and 4 m throughout the ILD. Three major benches dominate the Ganges ILD. Layer thicknesses increase at the ILD benches, suggesting that the benches are formed from the gradual thickening of layers. This indicates that the benches are depositional features draping over basement topography. Layer attitudes indicate overall shallow dips generally confined to a North-South direction that locally appear to follow bench topography. Layering is disrupted on a scale of 40 m to 150 m in 12 separate locations throughout the ILD. In all locations, underlying layering is disturbed by overlying folded layers in a trough-like geometry. These features are interpreted to have formed as submarine channels in a lacustrine setting, subsequently infilled by sediments. Subsequently, the channels were eroded to the present topography, resulting in the thin, curved layering observed. Data cannot conclusively support one ILD formation hypothesis, but does indicate that the Ganges ILD postdates Chasma formation. The presence of water altered minerals, consistently thin layering, and layer orientations provide strong evidence that the ILD formed in a lacustrine setting.

Structural and catalytic investigation of vanadia supported on ceria promoted with high surface area rice husk silica

Rice husk silica was utilized as the promoter of ceria for preparing supported vanadia catalysts. Effect of vanadium content was investigated with 2–10 wt.% V2O5 loading over the support. Structural characterization of the catalysts was done by various techniques like energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area, thermal analysis (TGA/DTA), FT-infrared spectroscopy (FT-IR), UV–vis diffused reflectance spectroscopy (DR UV–vis), electron paramagnetic spectroscopy (EPR) and solid state magnetic resonance spectroscopies (29Si and 51V MASNMR). Catalytic activity was studied towards liquid-phase oxidation of benzene. Surface area of ceria enhanced upon rice husk silica promotion, thus makes dispersion of the active sites of vanadia easier. Highly dispersed vanadia was found for low V2O5 loading and formation of cerium orthovanadate (CeVO4) occurs as the loading increases. Spectroscopic investigation clearly confirms the formation of CeVO4 phase at higher loadings of V2O5. The oxidation activity increases with vanadia loading up to 8 wt.% V2O5, and further increase reduces the conversion rate. Selective formation of phenol can be attributed to the presence of highly dispersed active sites of vanadia over the support.

Investigation of structural, optical and electrical properties and valence band splitting in cu-ln-se compounds

Investigations on thin films that started decades back due to scientific curiosity in the properties of a two-dimensional solid, has developed into a leading research field in recent years due to the ever expanding applications of the thin films in the fann of a variety of active and passive microminiaturized components and devices, solar cells, radiation sowces and detectors, magnetic memory devices, interference filters, refection and antireflection coatings etc. [1]. The recent environment and energy resource concerns have aroused an enonnous interest in the study of materials in thin film form suitable for renewable energy sources such as photovoltaic devices. Recognition of the immense potential applications of the chalcopyrites that can fonn homojunctions or heterojunctions for solar cell fabrication has attracted many researchers to extensive and intense research on them. In this thesis, we have started with studies performed on CuInSe, thin films, a technologically well recognized compound belonging to the l•ill-VI family of semiconductors and have riveted on investigations on the preparation and characterization of compoWlds Culn3Se5. Culn5Seg and CuIn7Se12, an interesting group of compounds related to CuInSe2 called Ordered Vacancy Compounds, having promising applications in photovoltaic devices. A pioneering work attempted on preparing and characterizing the compound Culn7Sel2 is detailed in the chapters on OVC's. Investigation on valence band splitting in avc's have also been attempted for the first time and included as the last chapter in the thesis. Some of the salient features of the chalcopyrite c.ompounds are given in the next section .of this introductory chapter.

Structural And Surface Morphological Investigation Of Formation Stages Of Highly (002) Oriented Zno Films On Glass Substrates By Spray Pyrolysis Method

ZnO thin films were coated on amorphous glass substrate at various temperatures in the range 160-500 0C by spray pyrolysis method. The as deposited films were characterised by using XRD and SEM. Wurtzite phase of ZnO was formed at a substrate temperature of 400 0C, highly oriented (002) phase was developed with respect to increase of substrate temperature from 450 to 500 0C. Morphological and growth mode of these films were analyzed with respect to structural orientation of films from wurtzite to highly (002) oriented phase. Present study reveals that substrate temperature was one of the important parameters which determine the crystalline quality, population of defects, grain size, orientation and morphology of the films

Trinuclear and tetranuclear adduct formation between sodium perchlorate and copper(II) complexes of salicylaldimine type ligands: structural characterization and theoretical investigation

The synthesis of two new sodium perchlorate adducts (1:2 and 1:3) with copper(II) "ligand-complexes'' is reported. One adduct is trinuclear [(CuL(1))(2)NaClO(4)] (1) and the other is tetranuclear [(CuL(2))(3)Na]ClO(4)center dot EtOH (2). The ligands are the tetradentate di-Schiff base of 1,3-propanediamines and salicylaldehyde (H(2)L(1)) or 2-hydroxyacetophenone (H(2)L(2)). Both complexes have been characterized by X-ray single crystal structure analyses. In both structures, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes in addition to a chelated perchlorate anion in 1 and to six oxygen atoms from three Schiff-base complexes in 2. We have carried out a DFT theoretical study (RI-B97-D/def2-SVP level of theory) to compute and compare the formation energies of 1:2 and 1:3 adducts. The DFT study reveals that the latter is more stabilized than the former. The X-ray crystal structure of 1 shows that the packing of the trinuclear unit is controlled by unconventional C-H center dot center dot center dot O H-bonds and Cu(2+)-pi non-covalent interactions. These interactions explain the formation of 1 which is a priori disfavored with respect to 2.

The processing of number and gender agreement in Spanish: an event related potential investigation of the effects of structural distance

Previous research suggests that the processing of agreement is affected by the distance between the agreeing elements. However, the unique contribution of structural distance (number of intervening syntactic phrases) to the processing of agreement remains an open question, since previous investigations do not tease apart structural and linear distance (number of intervening words). We used event related potentials (ERPs) to examine the extent to which structural distance impacts the processing of Spanish number and gender agreement. Violations were realized both within the phrase and across the phrase. Across both levels of structural distance, linear distance was kept constant, as was the syntactic category of the agreeing elements. Number and gender agreement violations elicited a robust P600 between 400 and 900ms, a component associated with morphosyntactic processing. No amplitude differences were observed between number and gender violations, suggesting that the two features are processed similarly at the brain level. Within-phrase agreement yielded more positive waveforms than across-phrase agreement, both for agreement violations and for grammatical sentences (no agreement by distance interaction). These effects can be interpreted as evidence that structural distance impacts the establishment of agreement overall, consistent with sentence processing models which predict that hierarchical structure impacts the processing of syntactic dependencies. However, due to the lack of an agreement by distance interaction, the possibility cannot be ruled out that these effects are driven by differences in syntactic predictability between the within-phrase and across-phrase configurations, notably the fact that the syntactic category of the critical word was more predictable in the within-phrase conditions.

Morphosyntactic processing in advanced second language (L2) learners: An event-related potential investigation of the effects of L1-L2 similarity and structural distance

Different theoretical accounts of second language (L2) acquisition differ with respect to whether or not advanced learners are predicted to show native like processing for features not instantiated in the native language (L1). We examined how native speakers of English, a language with number but not gender agreement, process number and gender agreement in Spanish. We compare agreement within a determiner phrase (órgano muy complejo “[DP organ-MASC-SG very complex-MASC-SG]”) and across a verb phrase (cuadro es auténtico “painting-MASC-SG [VP is authentic-MASC-SG]”) in order to investigate whether native like processing is limited to local domains (e.g. within the phrase), in line with Clahsen and Felser (2006). We also examine whether morphological differences in how the L1 and L2 realize a shared feature impact processing by comparing number agreement between nouns and adjectives, where only Spanish instantiates agreement, and between demonstratives and nouns, where English also instantiates agreement. Similar to Spanish natives, advanced learners showed a P600 for both number and gender violations overall, in line with the Full Transfer/Full Access Hypothesis (Schwartz and Sprouse, 1996), which predicts that learners can show native-like processing for novel features. Results also show that learners can establish syntactic dependencies outside of local domains, as suggested by the presence of a P600 for both within and across phrase violations. Moreover, similar to native speakers, learners were impacted by the structural distance (number of intervening phrases) between the agreeing elements, as suggested by the more positive waveforms for within than across-phrase agreement overall. These results are consistent with the proposal that learners are sensitive to hierarchical structure.