Thrusting, extension, and doming during the polyphase tectonometamorphic evolution of the High Himalayan Crystalline Zone in NW India

In the NW Himalaya of India, high-grade metamorphic rocks of the High Himalayan Crystalline Zone (HHCZ) are exposed as a 50 km large dome along the Miyar and Gianbul valleys. This Gianbul dome is cored by migmatitic paragneiss formed at peak conditions around 750 degreesC and 8 kbar, and symmetrically surrounded by sillimanite, kyanite +/- staurolite, garnet, biotite, and chlorite Barrovian mineral zones. Thermobarometric and structural investigations reveal that the Gianbul dome results from a polyphase tectono-metamorphic evolution. The first phase corresponds to the NE-directed thrusting of the Shikar Beh nappe, that is responsible for the Barrovian prograde metamorphic field gradient in the southern limb of the dome. In the northern limb of the dome, the Barrovian prograde metamorphism is the consequence of a second tectonic phase, associated with the SW-directed thrusting of the Nyimaling-Tsarap nappe. Following these crustal thickening events, exhumation and doming of the HHCZ high-grade rocks were controlled by extension along the north-dipping Zanskar Shear Zone, in the frontal part of the Nyimaling-Tsarap nappe, as well as by coeval to late extension along the south-dipping Khanjar Shear Zone, in the southern limb of the Gianbul dome. Rapid syn-convergence extension along both of these detachments induced a nearly isothermal decompression, resulting in a high-temperature/low-pressure metamorphic overprint, as well as enhanced partial melting. Such a rapid exhumation within a compressional orogenic context appears unlikely to be controlled solely by granitic diapirism. Alternatively, large-scale doming in the Himalaya could reflect a sub-vertical ductile extrusion of partially melted rocks.

RMN 2D: Detecção inversa e gradiente de campo na determinação estrutural de compostos orgânicos

A view of the general aspects involving the 2D NMR spectroscopy using inverse detection and field gradient techniques is presented through the analysis of a sesquiterpene.

Aplicação da espectroscopia de ressonância magnética nuclear para estudos de difusão molecular em líquidos: a técnica DOSY

Diffusion coefficients provide uniquely detailed and easily interpreted information on molecular organization and phase structure. They are quite sensitive to structural changes, and to binding and association phenomena, in particular for liquid colloidal or macromolecular systems. This paper describes the principles of diffusion measurements in liquids by pulsed magnetic field gradient spin-echo (PFG-SE) NMR spectroscopy. The important PFG-SE technique known as DOSY is presented and discussed. This is a noninvasive technique that can provide individual multicomponent translational diffusion coefficients with good precision in a few minutes, without the need for radioactive isotopic labelling.

Étude des propriétés de transport dans les hydrogels de curdlan

Les hydrogels de polysaccharide sont des biomatériaux utilisés comme matrices à libération contrôlée de médicaments et comme structures modèles pour l’étude de nombreux systèmes biologiques dont les biofilms bactériens et les mucus. Dans tous les cas, le transport de médicaments ou de nutriments à l’intérieur d’une matrice d’hydrogel joue un rôle de premier plan. Ainsi, l’étude des propriétés de transport dans les hydrogels s’avère un enjeu très important au niveau de plusieurs applications. Dans cet ouvrage, le curdlan, un polysaccharide neutre d’origine bactérienne et formé d’unités répétitives β-D-(1→3) glucose, est utilisé comme hydrogel modèle. Le curdlan a la propriété de former des thermogels de différentes conformations selon la température à laquelle une suspension aqueuse est incubée. La caractérisation in situ de la formation des hydrogels de curdlan thermoréversibles et thermo-irréversibles a tout d’abord été réalisée par spectroscopie infrarouge à transformée de Fourier (FT-IR) en mode réflexion totale atténuée à température variable. Les résultats ont permis d’optimiser les conditions de gélation, menant ainsi à la formation reproductible des hydrogels. Les caractérisations structurales des hydrogels hydratés, réalisées par imagerie FT-IR, par microscopie électronique à balayage en mode environnemental (eSEM) et par microscopie à force atomique (AFM), ont permis de visualiser les différentes morphologies susceptibles d’influencer la diffusion d’analytes dans les gels. Nos résultats montrent que les deux types d’hydrogels de curdlan ont des architectures distinctes à l’échelle microscopique. La combinaison de la spectroscopie de résonance magnétique nucléaire (RMN) à gradients pulsés et de l’imagerie RMN a permis d’étudier l’autodiffusion et la diffusion mutuelle sur un même système dans des conditions expérimentales similaires. Nous avons observé que la diffusion des molécules dans les gels est ralentie par rapport à celle mesurée en solution aqueuse. Les mesures d’autodiffusion, effectuées sur une série d’analytes de diverses tailles dans les deux types d’hydrogels de curdlan, montrent que le coefficient d’autodiffusion relatif décroit en fonction de la taille de l’analyte. De plus, nos résultats suggèrent que l’équivalence entre les coefficients d’autodiffusion et de diffusion mutuelle dans les hydrogels de curdlan thermo-irréversibles est principalement due au fait que l’environnement sondé par les analytes durant une expérience d’autodiffusion est représentatif de celui exploré durant une expérience de diffusion mutuelle. Dans de telles conditions, nos résultats montrent que la RMN à gradients pulsés peut s’avérer une approche très avantageuse afin de caractériser des systèmes à libération contrôlée de médicaments. D’autres expériences de diffusion mutuelle, menées sur une macromolécule de dextran, montrent un coefficient de diffusion mutuelle inférieur au coefficient d’autodiffusion sur un même gel de curdlan. L’écart mesuré entre les deux modes de transport est attribué au volume différent de l’environnement sondé durant les deux mesures. Les coefficients d’autodiffusion et de diffusion mutuelle similaires, mesurés dans les deux types de gels de curdlan pour les différents analytes étudiés, suggèrent une influence limitée de l’architecture microscopique de ces gels sur leurs propriétés de transport. Il est conclu que les interactions affectant la diffusion des analytes étudiés dans les hydrogels de curdlan se situent à l’échelle moléculaire.

Diffusion dans un hydrogel : applications aux biocapteurs et optimisation de la technique de spectroscopie par corrélation de fluorescence (FCS)

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Determination of Very Slow Diffusion of Paramagnetic Ions by NMR Spectroscopy

In this paper, we propose a new method of measuring the very slow paramagnetic ion diffusion coefficient using a commercial high-resolution spectrometer. If there are distinct paramagnetic ions influencing the hydrogen nuclear magnetic relaxation time differently, their diffusion coefficients can be measured separately. A cylindrical phantom filled with Fricke xylenol gel solution and irradiated with gamma rays was used to validate the method. The Fricke xylenol gel solution was prepared with 270 Bloom porcine gelatin, the phantom was irradiated with gamma rays originated from a (60)Co source and a high-resolution 200 MHz nuclear magnetic resonance (NMR) spectrometer was used to obtain the phantom (1)H profile in the presence of a linear magnetic field gradient. By observing the temporal evolution of the phantom NMR profile, an apparent ferric ion diffusion coefficient of 0.50 mu m(2)/ms due to ferric ions diffusion was obtained. In any medical process where the ionizing radiation is used, the dose planning and the dose delivery are the key elements for the patient safety and success of treatment. These points become even more important in modern conformal radio therapy techniques, such as stereotactic radiosurgery, where the delivered dose in a single session of treatment can be an order of magnitude higher than the regular doses of radiotherapy. Several methods have been proposed to obtain the three-dimensional (3-D) dose distribution. Recently, we proposed an alternative method for the 3-D radiation dose mapping, where the ionizing radiation modifies the local relative concentration of Fe(2+)/Fe(3+) in a phantom containing Fricke gel and this variation is associated to the MR image intensity. The smearing of the intensity gradient is proportional to the diffusion coefficient of the Fe(3+) and Fe(2+) in the phantom. There are several methods for measurement of the ionic diffusion using NMR, however, they are applicable when the diffusion is not very slow.

Ab initio study of the EFG at the N sites in imidazole

We study the nuclear quadrupole interaction at the nitrogen sites in the molecular and crystalline phases of the imidazole compound. We use PAW which is a state-of-the-art method to calculate the electronic structure and electric field gradient at the nucleus in the framework of the density functional theory. The quadrupole frequencies at both imino and amino N sites are in excellent agreement with measurements. This is the first time that the electric field gradient at crystalline imidazole is correctly treated by an ab initio theoretical approach.

Hyperfine interaction studies with (181)Ta and (111)Cd probes in the compound Ti(2)Ag

By using the time-differential perturbed angular correlation technique, the electric field gradients (EFG) at (181)Hf/(181)Ta and (111)In/(111)Cd probe sites in the MoSi(2)-type compound Ti(2)Ag have been measured as a function of temperature in the range from 24 to 1073 K. Ab initio EFG calculations have been performed within the framework of density functional theory using the full-potential augmented plane wave + local orbitals method as implemented in the WIEN2k package. These calculations allowed assignments of the probe lattice sites. For Ta, a single well-defined EFG with very weak temperature dependence was established and attributed to the [4(e)4mm] Ti site. For (111)Cd probes, two of the three measured EFGs are well defined and correlated with substitutional lattice sites, i.e. both the [4(e)4mm] Ti site and the [2(a)4/mmm] Ag site.

Desenvolvimento de Sistemas Microparticulados Superparamagnéticos Gastro-resistentes para Diagnóstico e Terapêutica

This work aimed to develop a suitable magnetic system for administration by the oral route. In addition to that, it was intended to review the current uses of magnetic systems and the safety related to magnetic field exposure. Methods: Coprecipitation and emulsification/crosslinking were carried out in order to synthesize magnetite particles and to coat them, respectively. Results: According to literature review, it was found that magnetic particles present several properties such as magnetophoresis in magnetic field gradient, production of a surrounding magnetic field, and heat generation in alternated magnetic field. When the human organism is exposed to magnetic fields, several interaction mechanisms come into play. However, biological tissues present low magnetic susceptibility. As a result, the effects are not so remarkable. Concerning the development of a magnetic system for oral route, uncoated magnetite particles did undergo significant dissolution at gastric pH. On the other hand, such process was inhibited in the xylan-coated particles. Conclusions: Due to their different properties, magnetic systems have been widely used in biosciences. However, the consequent increased human exposure to magnetic fields has been considered relatively safe. Concerning the experimental work, it was developed a polymer-coated magnetic system. It may be very promising for administration by the oral route for therapy and diagnostic applications as dissolution at gastric pH hardly took place

Desenvolvimento de sistemas magnéticos com potencialidades terapêuticas para vetorização de fármacos

Magnetic targeting is being investigated as a means of local delivery of drugs, combining precision, minimal surgical intervention, and satisfactory concentration of the drug in the target region. In view of these advantages, it is a promising strategy for improving the pharmacological response. Magnetic particles are attracted by a magnetic field gradient, and drugs bound to them can be driven to their site of action by means of the selective application of magnetic field on the desired area. Helicobacter pylori is the commonest chronic bacterial infection. The treatment of choice has commonly been based upon a triple therapy combining two antibiotics and an anti-secretory agent. Furthermore, an extended-release profile is of utmost importance for these formulations. The aim of this work was to develop a magnetic system containing the antibiotic amoxicillin for oral magnetic drug targeting. First, magnetic particles were produced by coprecipitation of iron salts in alkaline medium. The second step was coating the particles and amoxicillin with Eudragit® S-100 by spray-drying technique. The system obtained demonstrated through the characterization studies carried out a possible oral drug delivery system, consisting in magnetite microparticles and amoxicillin, coated with a polymer acid resistant. This system can be used to deliver drugs to the stomach for treatment of infections in this organ. Another important finding in this work is that it opens new prospects to coat magnetic microparticles by the technique of spray-drying.

DESIGN AND TEST OF A 7-T SPLIT-PAIR MAGNET FOR MAGNETIC SEPARATION

A 160 mm bore, 7 T split-pair magnet was constructed and tested aiming to mineral processing through HGMS (high gradient magnetic separation) or HCMS (helical channel magnetic separation.) This work describes the design and test results of the pair of coils operating under current in parallel mode. In the case of antiparallel current mode large repulsive force between coils is generated and a strong magnetic field gradient outside the magnet is created. A continuous magnetic separation system made with a helical channel magnetic separator for application in TiO2 processing is analysed.

Mechanisms of surface-relief gratings formation in layer-by-layer films from azodyes

Surface-relief gratings are photoinscribed on ionically adsorbed layer-by-layer (LBL) films of an azodye, Brilliant Yellow (BY), which was layered alternately with a polyelectrolyte. Photoinscription is performed by impinging an interference pattern of p- or s-polarized laser light with moderate intensity onto the LBL film, which is unlikely to cause thermal effects. Large-scale mass transport occurs due to the force associated with the field gradient of the light pattern. The ionic interactions between adjacent layers appear to provide the means for the chromophores to drag the polymer chains upon photoizomerization. LBL films were produced from two different polyelectrolytes and under two distinct pH values leading to markedly different film properties especially concerning photodegradation. Exposure to the laser light, for instance, leads to higher photodegradation in the poly(dimethyl diallylammonium chloride)/BY system, in comparison to the poly(allylamine hydrochloride)/BY films. Mass transport in the latter case is predominantly light-driven, which is consistent with the higher amplitude of modulation for p-polarized light (70 nm) compared to that caused by s-polarized light (18 nm). © 2003 Elsevier Ltd. All rights reserved.

Theoretical and Experimental Studies in Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. 31P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The computational DMP work indicated a problem with the current standard 31P reference of 85% H3PO4(aq.). Comparison of the calculations and experimental spectra for the phosphate salts indicated ADHP might be a preferable alternative as a solid state NMR reference for 31P. Experimental work included magic angle spinning experiments on powder samples using the UNL chemistry department’s Bruker Avance 600 MHz NMR to collect data to determine chemical shielding anisotropies. For the quadrupolar nuclei of copper and scandium, the electric field gradient was calculated in diatomic univalent metal halides, allowing determination of the minimal level of theory necessary to compute NMR parameters for these nuclei.

Site localization of Cd impurities in sapphire

By combining first-principles electronic structure calculations and existing time-differential gamma-gamma perturbed-angular-correlation experiments we studied the site localization, the local environment, and the electronic structure of Cd impurities in sapphire (alpha-Al2O3) single crystals in different charged states. The ab initio calculations were performed with the full-potential augmented plane wave plus local orbitals method and the projector augmented wave method. Comparing the calculated electric-field-gradient tensor at the Cd nuclei in the alpha-Al2O3 host lattice and the corresponding available experimental values, we have seen that it is equally possible for Cd to replace an Al atom (in a negative charge state) or to be placed in an interstitial site (in a neutral charge state). To finally address the issue of the Cd impurity localization, we performed formation energy calculations. These results have shown that Cd placed in the substitutional Al site, in the negatively charged state, is the most probable configuration.

A structural and metamorphic study of the southern Menderes Massif (Western Turkey)

P-T conditions, paragenetic studies and the relation between mineral growth, deformation and - when possible- isograd minerals have been used to describe the type of metamorphism involved within lower units of the southern Menderes Massif of the Anatolide Belt in western Turkey. The study areas mainly consist of Proterozoic orthogneiss and surrounding schists of presumed Paleozoic age. Both units are seen as nappes in the southern study area, the Çine and the Selimiye nappe, on the whole corresponding to Proterozoic orthogneiss and surrounding schists, respectively. The Çine and Selimiye nappes are part of a complex geological structure within the core series of the Menderes Massif. Their emplacement under lower greenschist facies conditions, would result from closure of the northern Neo-Thethys branch during the Eocene. These two nappes are separated by a major tectonic structure, the Selimiye shear zone, which records top-to-the-S shearing under greenschist facies conditions. Amphibolite to upper amphibolite facies metamorphism is widely developed within the metasedimentary rocks of the Çine nappe whereas no metamorphism exceeding lower amphibolite facies has been observed in the Selimiye nappe. In the southern margin of the Çine Massif, around Selimiye and Millas villages, detailed sampling has been undertaken in order to map mineral isograds within the Selimiye nappe and to specify P-T conditions in this area. The data collected in this area reveals a global prograde normal erosion field gradient from south to north and toward the orthogneiss. The mineralogical parageneses and P-T estimates are correlated with Barrovian-type metamorphism. A jump of P-T conditions across the Selimiye shear zone has been identified and estimated c. 2 kbar and 100 °C which evidences the presence of amphibolite facies metasedimentary rocks near the orthogneiss. Metasedimentary rocks from the overlying Selimiye nappe have maximum P-T conditions of c. 4-5 kbar and c. 525 °C near the base of the nappe. Metasedimentary rocks from the Çine nappe underneath the Selimiye shear zone record maximum P-T conditions of about 7 kbar and >550 °C. Kinematic indicators in both nappes consistently show a top-S shear sense. Metamorphic grade in the Selimiye nappe decreases structurally upwards as indicated by mineral isograds defining the garnet-chlorite zone at the base, the chloritoid-biotite zone and the biotite-chlorite zone at the top of the nappe. The mineral isograds in the Selimiye nappe run parallel to the regional SR foliation. 40Ar/39Ar mica ages indicate an Eocene age of metamorphism in the Selimiye nappe and underneath the Çine nappe in this area. Metasedimentary rocks of the Çine nappe 20-30 km north of the Selimiye shear zone record maximum P-T conditions of 8-11 kbar and 600-650 °C. Kinematic indicators show mainly top-N shear sense associated with prograde amphibolite facies metamorphism. An age of about 550 Ma could be indicated for amphibolite facies metamorphism and associated top-N shear in the orthogneiss and metasedimentary rocks of the Çine nappe. However, there is no evidence for polymetamorphism in the 6 metasedimentary rocks of the Çine nappe, making tectonic interpretations about late Neoproterozoic to Cambrian and Tertiary metamorphic events speculative. In the western margin of the Çine Massif metamorphic mineral parageneses and pressure– temperature conditions lead to similar conclusion regarding the erosion field gradient, prograde normal toward the orthogneiss. The contact between orthogneiss and surrounding metasedimentary rocks is mylonitic and syn-metamorphism. P-T estimates are those already observed within the Selimiye nappe and correlated with lower amphibolite facies parageneses. Finally additional data in the eastern part and a general paragenetic study within the Menderes Massif lower units, the Çine and the Selimiye nappes, strongly suggest a single Barrovian-type metamorphism predating Eocene emplacement of the high pressure–low temperature Lycean and Cycladic blueschist nappes. Metamorphic mineral parageneses and pressure–temperature conditions do not support the recently proposed model of high pressure–low temperature metamorphic overprinting, which implies burial of the lower units of the Menderes Massif up to depth of 30 km, as a result of closure of the Neo-Tethys. According to the geochronological problem outlined during this thesis, there are two possible schemes: either Barrovian-type metamorphism is Proterozoic in age and part of the sediments from Selimiye nappe (lower amphibolite facies) has to be proterozoic of age too, or Barrovian-type metamorphism in Eocene of age. In the first case the structure observed now in the core series would correspond to simple exhumation of Proterozoic basement. In the latter case a possible correlation with closure of Neo-Tethys (sensu stricto, southern branch) is envisaged.