817 resultados para Thermo-optic studies in CdSe based quantum dots
Resumo:
The development of load-bearing osseous implant with desired mechanical and surface properties in order to promote incorporation with bone and to eliminate risk of bone resorption and implant failure is a very challenging task. Bone formation and resoption processes depend on the mechanical environment. Certain stress/strain conditions are required to promote new bone growth and to prevent bone mass loss. Conventional metallic implants with high stiffness carry most of the load and the surrounding bone becomes virtually unloaded and inactive. Fibre-reinforced composites offer an interesting alternative to metallic implants, because their mechanical properties can be tailored to be equal to those of bone, by the careful selection of matrix polymer, type of fibres, fibre volume fraction, orientation and length. Successful load transfer at bone-implant interface requires proper fixation between the bone and implant. One promising method to promote fixation is to prepare implants with porous surface. Bone ingrowth into porous surface structure stabilises the system and improves clinical success of the implant. The experimental part of this work was focused on polymethyl methacrylate (PMMA) -based composites with dense load-bearing core and porous surface. Three-dimensionally randomly orientated chopped glass fibres were used to reinforce the composite. A method to fabricate those composites was developed by a solvent treatment technique and some characterisations concerning the functionality of the surface structure were made in vitro and in vivo. Scanning electron microscope observations revealed that the pore size and interconnective porous architecture of the surface layer of the fibre-reinforced composite (FRC) could be optimal for bone ingrowth. Microhardness measurements showed that the solvent treatment did not have an effect on the mechanical properties of the load-bearing core. A push-out test, using dental stone as a bone model material, revealed that short glass fibre-reinforced porous surface layer is strong enough to carry load. Unreacted monomers can cause the chemical necrosis of the tissue, but the levels of leachable resisidual monomers were considerably lower than those found in chemically cured fibre-reinforced dentures and in modified acrylic bone cements. Animal experiments proved that surface porous FRC implant can enhance fixation between bone and FRC. New bone ingrowth into the pores was detected and strong interlocking between bone and the implant was achieved.
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The role of dopamine and serotonin in spinal pain regulation is well established. However, little is known concerning the role of brain dopamine and serotonin in the perception of pain in humans. The aim of this study was to assess the potential role of brain dopamine and serotonin in determining experimental pain sensitivity in humans using positron emission tomography (PET) and psychophysical methods. A total of 39 healthy subjects participated in the study, and PET imaging was performed to assess brain dopamine D2/D3 and serotonin 5-HT1A receptor availability. In a separate session, sensitivity to pain and touch was assessed with traditional psychophysical methods, allowing the evaluation of potential associations between D2/D3 and 5-HT1A binding and psychophysical responses. The subjects’ responses were also analyzed according to Signal Detection Theory, which enables separate assessment of the subject’s discriminative capacity (sensory factor) and response criterion (non-sensory factor). The study found that the D2/D3 receptor binding in the right putamen was inversely correlated with pain threshold and response criterion. 5-HT1A binding in cingulate cortex, inferior temporal gyrus and medial prefrontal cortex was inversely correlated with discriminative capacity for touch. Additionally, the response criterion for pain and intensity rating of suprathreshold pain were inversely correlated with 5-HT1A binding in multiple brain areas. The results suggest that brain D2/D3 receptors and 5-HT1A receptors modulate sensitivity to pain and that the pain modulatory effects may, at least partly, be attributed to influences on the response criterion. 5-HT1A receptors are also involved in the regulation of touch by having an effect on discriminative capacity.
Resumo:
Studies on 68Ga-Based Agents for PET Imaging of Cancer and Inflammation Positron emission tomography (PET) is based on the use of radiolabeled agents and facilitates in vivo imaging of biological processes, such as cancer. Because the detection of cancer is demanding and is often obscured by inflammation, there is a demand for better PET imaging agents. The aim was to preliminarily evaluate new PET agents for imaging cancer and inflammation using experimental models. 68Ga-chloride and peptides, 68Ga-labeled through 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA), targeting matrix metalloproteinase-9 (MMP-9) were tested for tumor imaging. In addition, a 68Ga-DOTA-conjugated peptide targeting vascular adhesion protein-1 (VAP-1), was tested for inflammation imaging. The 68Ga-based imaging agents described here showed potential features by passing the essential in vitro tests, proceeding further to preclinical in vivo evaluation and being able to visualize the target. The target uptake and target-to-background ratios of 68Ga-based agents were, however, not optimal. 68Ga-chloride showed slow clearance caused by its binding to blood transferrin. In the case of 68Ga-DOTA-peptides low in vivo stability and/or low lipophilicity led to too rapid blood clearance and urinary excretion. The properties of 68Ga-labeled peptides are modifiable, as shown with matrix metalloproteinase-9 targeting ligands. In the conclusion of this PhD thesis, 68Ga-based agents for PET imaging of cancer and inflammation could be applied in the development of drugs, earlier diagnostics and following-up of the efficacy of therapies.
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The offset printing process is complex and involves the meeting of two essentially complex materials, printing ink and paper, upon which the final product is formed. It can therefore be expected that a multitude of chemical and physical interactions and mechanisms take place at the ink-paper interface. Interactions between ink and paper are of interest to both the papermakers and ink producers, as they wish to achieve better quality in the final product. The objective of this work is to clarify the combined influence of paper coating structure, printing ink and fountain solution on ink setting and the problems related to ink setting. A further aim is to identify the mechanisms that influence ink setting problems, and to be able to counteract them by changing properties of the coating layer or by changing the properties of the ink. The work carried out for this thesis included use of many techniques ranging from standard paper and printability tests to advanced optical techniques for detection of ink filaments during ink levelling. Modern imaging methods were applied for assessment of ink filament remain sizes and distribution of ink components inside pigment coating layers. Gravimetric filtration method and assessment of print rub using Ink-Surface-Interaction-Tester (ISIT) were utilized to study the influence of ink properties on ink setting. The chemical interactions were observed with the help of modified thin layer chromatography and contact angle measurements using both conventional and high speed imaging. The results of the papers in this thesis link the press operational parameters to filament sizes and show the influence of these parameters to filament size distribution. The relative importance between the press operation parameters was shown to vary. The size distribution of filaments is important in predicting the ink setting behaviour, which was highlighted by the dynamic gloss and ink setting studies. Prediction of ink setting behaviour was also further improved by use of separate permeability factors for different ink types in connection to filtration equations. The roles of ink components were studied in connection to ink absorption and mechanism of print rub. Total solids content and ratio of linseed oil to mineral oil were found to determine the degree of print rub on coated papers. Wax addition improved print rub resistance, but would not decrease print rub as much as lowering the total solids content in the ink. Linseed oil was shown to absorb into pigment coating pores by mechanism of adsorption to pore walls, which highlights the need for sufficient pore surface area for improved chromatographic separation of ink components. These results should help press operators, suppliers of printing presses, papermakers and suppliers to papermakers, to better understand the material and operating conditions of the press as it relates to various print quality issues. Even though paper is in competition with electronic media, high quality printed products are still in demand. The results should provide useful information for this segment of the industry.
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The superconducting gap is a basic character of a superconductor. While the cuprates and conventional phonon-mediated superconductors are characterized by distinct d- and s-wave pairing symmetries with nodal and nodeless gap distributions respectively, the superconducting gap distributions in iron-based superconductors are rather diversified. While nodeless gap distributions have been directly observed in Ba1–xKxFe2As2, BaFe2–xCoxAs2, LiFeAs, KxFe2–ySe2, and FeTe1–xSex, the signatures of a nodal superconducting gap have been reported in LaOFeP, LiFeP, FeSe, KFe2As2, BaFe2–xRuxAs2, and BaFe2(As1–xPx)2. Due to the multiplicity of the Fermi surface in these compounds s± and d pairing states can be both nodeless and nodal. A nontrivial orbital structure of the order parameter, in particular the presence of the gap nodes, leads to effects in which the disorder is much richer in dx2–y2-wave superconductors than in conventional materials. In contrast to the s-wave case, the Anderson theorem does not work, and nonmagnetic impurities exhibit a strong pair-breaking influence. In addition, a finite concentration of disorder produces a nonzero density of quasiparticle states at zero energy, which results in a considerable modification of the thermodynamic and transport properties at low temperatures. The influence of order parameter symmetry on the vortex core structure in iron-based pnictide and chalcogenide superconductors has been investigated in the framework of quasiclassical Eilenberger equations. The main results of the thesis are as follows. The vortex core characteristics, such as, cutoff parameter, ξh, and core size, ξ2, determined as the distance at which density of the vortex supercurrent reaches its maximum, are calculated in wide temperature, impurity scattering rate, and magnetic field ranges. The cutoff parameter, ξh(B; T; Г), determines the form factor of the flux-line lattice, which can be obtained in _SR, NMR, and SANS experiments. A comparison among the applied pairing symmetries is done. In contrast to s-wave systems, in dx2–y2-wave superconductors, ξh/ξc2 always increases with the scattering rate Г. Field dependence of the cutoff parameter affects strongly on the second moment of the magnetic field distributions, resulting in a significant difference with nonlocal London theory. It is found that normalized ξ2/ξc2(B/Bc2) dependence is increasing with pair-breaking impurity scattering (interband scattering for s±-wave and intraband impurity scattering for d-wave superconductors). Here, ξc2 is the Ginzburg-Landau coherence length determined from the upper critical field Bc2 = Φ0/2πξ2 c2, where Φ0 is a flux quantum. Two types of ξ2/ξc2 magnetic field dependences are obtained for s± superconductors. It has a minimum at low temperatures and small impurity scattering transforming in monotonously decreasing function at strong scattering and high temperatures. The second kind of this dependence has been also found for d-wave superconductors at intermediate and high temperatures. In contrast, impurity scattering results in decreasing of ξ2/ξc2(B/Bc2) dependence in s++ superconductors. A reasonable agreement between calculated ξh/ξc2 values and those obtained experimentally in nonstoichiometric BaFe2–xCoxAs2 (μSR) and stoichiometric LiFeAs (SANS) was found. The values of ξh/ξc2 are much less than one in case of the first compound and much more than one for the other compound. This is explained by different influence of two factors: the value of impurity scattering rate and pairing symmetry.
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Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.
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Positron emission tomography imaging has both academic and applied uses in revealing the distribution and density of different molecular targets in the central nervous system. Following the significant progress made with the dopamine D2 receptor, advances have been made in developing PET tracers to allow analysis of receptor occupancy of many other receptor types as well as evaluating changes in endogenous synaptic transmitter concentrations of transmitters e.g. serotonin and noradrenaline. Noradrenergic receptors are divided into α1-, α2- and β-adrenoceptor subfamilies, in humans each of which is composed of three receptor subtypes. The α2-adrenoceptors have an important presynaptic auto-inhibitory function on noradrenaline release but they also have postsynaptic roles in modulating the release of other neurotransmitters, such as serotonin and dopamine. One of the subtypes, the α2C-adrenoceptor, has been detected at distinct locations in the central nervous system, most notably the dorsal striatum. Several serious neurological conditions causing dementia, Alzheimer’s disease and Parkinson’s disease have been linked to disturbed noradrenergic signaling. Furthermore, altered noradrenergic signaling has also been implicated in conditions like ADHD, depression, anxiety and schizophrenia. In order to benefit future research into these central nervous system disorders as well as being useful in the clinical development of drugs affecting brain noradrenergic neurotransmission, validation work of a novel tracer for positron emission tomography studies in humans was performed. Altogether 85 PET imaging experiments were performed during four separate clinical trials. The repeatability of [11C]ORM-13070 binding was tested in healthy individuals, followed by a study to evaluate the dose-dependent displacement of [11C]ORM-13070 from α2C-adrenoceptors by a competing ligand, and the final two studies examined the sensitivity of [11C]ORM-13070 binding to reflect changes in endogenous noradrenaline levels. The repeatability of [11C]ORM-13070 binding was very high. The binding properties of the tracer allowed for a reliable estimation of α2C-AR occupancy by using the reference tissue ratio method with low test-retest variability. [11C]ORM-13070 was dose-dependently displaced from its specific binding sites by the subtype-nonselective α2-adrenoceptor antagonist atipamezole, and thus it proved suitable for use in clinical drug development of novel α2C-adrenoceptor ligands e.g. to determine the best doses and dosing intervals for clinical trials. Convincing experimental evidence was gained to support the suitability of [11C]ORM-13070 for detecting an increase in endogenous synaptic noradrenaline in the human brain. Tracer binding in the thalamus tended to increase in accordance with reduced activity of noradrenergic projections from the locus coeruleus, although statistical significance was not reached. Thus, the investigation was unable to fully validate [11C]ORM-13070 for the detection of pharmacologically evoked reductions in noradrenaline levels.
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People with intellectual disability who sexually offend commonly live in community-based settings since the closing of all institutions across the province of Ontario. Nine (n=9) front line staff who provide support to these individuals in three different settings (treatment setting, transitional setting, residential setting) were interviewed. Participants responded to 47 questions to explore how sex offenders with intellectual disability can be supported in the community to prevent re-offenses. Questions encompassed variables that included staff attitudes, various factors impacting support, structural components of the setting, quality of life and the good life, staff training, staff perspectives on treatment, and understanding of risk management. Three overlapping models that have been supported in the literature were used collectively for the basis of this research: The Good Lives Model (Ward & Gannon, 2006; Ward et al., 2007), the quality of life model (Felce & Perry, 1995), and variables associated with risk management. Results of this research showed how this population is being supported in the community with an emphasis on the following elements: positive and objective staff attitude, teamwork, clear rules and protocols, ongoing supervision, consistency, highly trained staff, and environments that promote quality of life. New concepts arose which suggested that all settings display an unequal balance of upholding human rights and managing risks when supporting this high-risk population. This highlights the need for comprehensive assessments in order to match the offender to the proper setting and supports, using an integration of a Risk, Need, Responsivity model and the Good Lives model for offender rehabilitation and to reduce the likelihood of re-offenses.
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La leucémie lymphoblastique aiguë des cellules Pré-B (B-ALL) reste le type de cancer le plus souvent diagnostiqué chez les enfants. Des études ont montré que des déterminants génétiques jouent un rôle important dans la susceptibilité/résistance au développement de ce cancer. À cet égard, les gènes Killer-cell Immunoglobulin-like Receptor (KIR) sont d'une importance particulière. Ces gènes sont fortement polymorphiques et codent pour des récepteurs qui contrôlent l’activité fonctionnelle des cellules Natural Killer (NK). Notre hypothèse est que les gènes activateurs des KIR s’associent avec la résistance innée pour développer la B-ALL. Afin d'évaluer cette hypothèse, nous avons entrepris une étude de cas-contrôles chez des enfants canadiens-français dans laquelle nous avons utilisé l'ADN génomique de 100 patients atteints de B-ALL ainsi que l’ADN de 245 individus sains. La présence ou l'absence de chaque gène KIR a été détectée par PCR en utilisant des amorces de séquences spécifiques. Nous avons trouvé que la présence des gènes KIR activateurs est significativement diminuée chez les enfants leucémiques par rapport aux témoins. En outre, le nombre de ces gènes a aussi montré une association significative linéaire avec la résistance au développement d’une B-ALL. Cela suggère des effets additifs de ces gènes permettant de conférer une protection contre ce cancer. Ces résultats pourraient être utiles afin de déceler de façon précoce les enfants ayant un risque de développer cette leucémie. Enfin, des stratégies thérapeutiques basées sur les récepteurs KIR pourraient être envisagées et s'avérer utiles concernant le traitement de ce cancer chez les enfants.
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Chez les plantes à fleurs, l’ovaire est l’organe reproducteur femelle et il interagit de façon importante avec les gamètes mâles durant la croissance, le guidage, la réception et la rupture du tube pollinique ainsi que la fusion des gamètes. Le processus débute lorsque de nombreux gènes de l’ovule sont activés à longue distance lors de la réception du pollen sur le stigmate. Afin d’explorer les signaux provenant de l’ovule ayant un impact important sur les interactions pollen–pistil, particulièrement les molécules sécrétées impliquées dans la signalisation espècespécifique, l’expression génique des ovules sous forme d’ARNm ainsi et la sécrétion protéique ont été étudiées chez Solanum chacoense, une espèce diploïde de pomme de terre sauvage. S. chacoense a subi beaucoup d’hybridation interspécifique avec d’autres espèces sympathiques de solanacées, facilitant ainsi grandement l’étude des interactions pollen–ovule de façon espècespécifique ainsi que leur évolution. Dans ce projet, des ovules provenant de trois conditions différentes ont été comparés: des ovules matures de type sauvage, des ovules légèrement immatures, récoltés deux jours avant l’anthèse et des ovules provenant du mutant frk1 pour lesquels le sac embryonnaire est absent. Un séquençage d’ARN à haut débit a d’abord été effectué sur les ovules de type sauvage de S. chacoense afin de générer un assemblage de référence comprenant 33852 séquences codantes. D’autres séquençages ont été effectués sur les trois conditions d’ovules et sur les feuilles afin de faire une analyse d’expression différentielle des gènes. En comparaison avec les ovules de type sauvage, 818 gènes sont réprimés dans les ovules du mutant frk1. Un sous-groupe de 284 gènes, étaient également sous-exprimés dans les ovules légèrement immatures, suggérant un rôle spécifique dans les stades tardifs de la maturation du sac embryonnaire (stade de développent FG6 à FG7) ainsi que du guidage du tube pollinique, puisque ni les ovules du mutant frk1 ni ceux légèrement immatures ne sont capables d’attirer les tubes polliniques lors d’essais de croissance semi in vivo. De plus, 21% de ces gènes sont des peptides riches en cystéines (CRPs). En utilisant un transcriptome assemblé de novo provenant de deux proches parents de S. chacoense, S. gandarillasii et S. tarijense, une analyse d’orthologie a été effectuée sur ces CRPs, révélant une grande variabilité et une évolution rapide chez les solanacées. De nouveaux motifs de cystéine uniques à cette famille ont également été découverts. En comparant avec des études similaires chez Arabidopsis, le sac embryonnaire de S. chacoense montre un transcriptome fortement divergent, particulièrement en en ce qui a trait à la catégorisation fonctionnelle des gènes et de la similarité entre les gènes orthologues. De plus,même si la glycosylation n’est pas requise lors du guidage mycropylaire du tube pollinique chez Arabidopsis, Torenia ou le maïs, des extraits d’ovules glycosylés de S. chacoense sont capables d’augmenter la capacité de guidage de 18%. Cette étude est donc la première à montrer une corrélation entre glycosylation et le guidage du tube pollinique par l’ovule. En complément à l’approche transcriptomique, une approche protéomique portant sur les protéine sécrétées par l’ovule (le secrétome) a été utilisée afin d’identifier des protéines impliquées dans l’interaction entre ovule et tube pollinique. Des exsudats d’ovules matures (capables d’attirer le tube pollinique) et d’ovules immatures (incapables d’attirer le tube pollinique) ont été récoltés en utilisant une nouvelle méthode d’extraction par gravité permettant de réduire efficacement les contaminants cytosoliques à moins de 1% de l’échantillon. Un total de 305 protéines sécrétées par les ovules (OSPs) ont été identifiées par spectrométrie de masse, parmi lesquelles 58% étaient spécifiques aux ovules lorsque comparées avec des données de protéines sécrétées par des tissus végétatifs. De plus, la sécrétion de 128 OSPs est augmentée dans les ovules matures par rapport aux ovules immatures. Ces 128 protéines sont donc considérées en tant que candidates potentiellement impliquées dans la maturation tardive de l’ovule et dans le guidage du tube pollinique. Cette étude a également montré que la maturation du sac embryonnaire du stade FG6 au stade FG7 influence le niveau de sécrétion de 44% du sécrétome total de l’ovule. De façon surprenante, la grande majorité (83%) de ces protéines n’est pas régulée au niveau de l’ARN, soulignant ainsi l’importance de cette approche dans l’étude du guidage du tube pollinique comme complément essentiel aux études transcriptomiques. Parmi tous les signaux sécrétés par l’ovule et reliés au guidage, obtenus à partir des approches transcriptomiques et protéomiques décrites ci-haut, nous avons spécifiquement évalué l’implication des CRPs dans le guidage du tube pollinique par l’ovule chez S. chacoense, vu l’implication de ce type de protéine dans les interactions pollen-pistil et le guidage du tube pollinique chez d’autres espèces. Au total, 28 CRPs étaient présentes dans les ovules capables d’attirer le tube pollinique tout en étant absentes dans les ovules incapables de l’attirer, et ce, soit au niveau de l’ARNm et/ou au niveau du sécrétome. De celles-ci, 17 CRPs ont été exprimées dans un système bactérien et purifiées en quantité suffisante pour tester le guidage. Alors que des exsudats d’ovules ont été utilisés avec succès pour attirer par chimiotactisme le tube pollinique, les candidats exprimés dans les bactéries n’ont quant à eux pas été capables d’attirer les tubes polliniques. Comme l’utilisation de systèmes d’expression hétérologue eucaryote peut permettre un meilleur repliement et une plus grande activité des protéines, les candidats restants seront de nouveau exprimés, cette fois dans un système de levure ainsi que dans un système végétal pour produire les peptides sécrétés. Ceux-ci seront ensuite utilisés lors d’essais fonctionnels pour évaluer leur capacité à guider les tubes polliniques et ainsi isoler les attractants chimiques responsable du guidage du tube pollinique chez les solanacées comme S. chacoense.
Photoemission optogalvanic effect studies in N2, NO2 and Ar discharges under pulsed laser excitation
Resumo:
A two-photon induced photoemission optogalvanic effect which brings about a change in the discharge voltage when a pulsed dye laser beam is focused on a tungsten electrode has been described. The experiment is performed with N2, NO2 and Ar discharges. The magnitude of the signal voltage is studied as a function of laser energy and discharge current. The effective quantum efficiency in the discharge is found to be larger than that in the vacuum condition.
Photoemission optogalvanic effect studies in N2, NO2 and Ar discharges under pulsed laser excitation
Resumo:
A two-photon induced photoemission optogalvanic effect which brings about a change in the discharge voltage when a pulsed dye laser beam is focused on a tungsten electrode has been described. The experiment is performed with N2, NO2 and Ar discharges. The magnitude of the signal voltage is studied as a function of laser energy and discharge current. The effective quantum efficiency in the discharge is found to be larger than that in the vacuum condition.
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The authors apply the theory of photothermal lens formation and also that of pure optical nonlinearity to account for the phase modulation in a beam as it traverses a nonlinear medium. It is used to simultaneously determine the nonlinear optical refraction and the thermo-optic coefficient. They demonstrate this technique using some metal phthalocyanines dissolved in dimethyl sulfoxide, irradiated by a Q-switched Nd:YAG laser with 10 Hz repetition rate and a pulse width of 8 ns. The mechanism for reverse saturable absorption in these materials is also discussed.
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An efficient method is developed for an iterative solution of the Poisson and Schro¿dinger equations, which allows systematic studies of the properties of the electron gas in linear deep-etched quantum wires. A much simpler two-dimensional (2D) approximation is developed that accurately reproduces the results of the 3D calculations. A 2D Thomas-Fermi approximation is then derived, and shown to give a good account of average properties. Further, we prove that an analytic form due to Shikin et al. is a good approximation to the electron density given by the self-consistent methods.