La situation et la prise en charge des adolescents suivis parallèlement en vertu de la LPJ et la LSJPA.

Rapport de stage présenté à la Faculté des études supérieures en vue de l’obtention du grade de Maître ès sciences (M. Sc.) en criminologie

La danse des fantômes à la cour Suprême du Canada: les droits autochtones pendant le premier quart de siècle de l'article 35 de la loi constitutionnelle, 1982

Titre de la page de titre additionnel: Ghost dancing at the Supreme Court of Canada : indigenous rights during the First quarter century of s.35.of Canada's Constitution Act, 1982.

L’indignation citoyenne contre la loi hypothécaire en Espagne : complémentarités entre éthiques de la justice et de la sollicitude

Consumers are legitimate stakeholders but are unevenly active and powerful in the dynamics that can lead companies to a more socially responsible behaviour. This article proposes to test the relevance, across the struggles of consumers, of the well-known opposition in business ethics between ethics of justice and ethics of care. Relying on a semi-participant direct and webnographic observation of a wide citizen movement that arose in Spain, questioning banks and mortgage regulation, after the explosion of the housing bubble in 2008, this article strives to highlight the permanent dual approach to ethics at all levels of the movement, from spokespersons to supporters, in speech and in actions. One approach is more focused on laws and principles, whereas the other is more focused on direct support to people affected by foreclosures. This article demonstrates the continuities between these two registers of justice and care and their functional complementarities in the dynamics of mobilization. A discussion will then follow on the substance of the opposition between the ethics of justice and the ethics of care as well as on the possible representativeness of this case: behind the singularities of the mortgage issue or of Spanish political culture, one cannot but observe the challenging mobilizing process that comprises a human rightist activism combined with a feminist approach to social issues.

The Double Pareto-Lognormal Distribution and its applications in actuarial science and finance

Le but de ce mémoire de maîtrise est de décrire les propriétés de la loi double Pareto-lognormale, de montrer comment on peut introduire des variables explicatives dans le modèle et de présenter son large potentiel d'applications dans le domaine de la science actuarielle et de la finance. Tout d'abord, nous donnons la définition de la loi double Pareto-lognormale et présentons certaines de ses propriétés basées sur les travaux de Reed et Jorgensen (2004). Les paramètres peuvent être estimés en utilisant la méthode des moments ou le maximum de vraisemblance. Ensuite, nous ajoutons une variable explicative à notre modèle. La procédure d'estimation des paramètres de ce mo-\\dèle est également discutée. Troisièmement, des applications numériques de notre modèle sont illustrées et quelques tests statistiques utiles sont effectués.

Le processus d’élaboration des politiques publiques comme espace d’autodétermination : les cas de l’Accord de Kelowna et de la Loi sur le contrôle par les Premières Nations de leur système d’éducation

L’objectif du présent mémoire est double. D’une part, il cherche à identifier les facteurs qui permettent au gouvernement canadien et aux peuples autochtones de s’entendre sur des politiques publiques, malgré la persistance d’une logique coloniale. Nous verrons que l’atteinte d’une entente est conditionnelle à la légitimité du processus d’élaboration de la politique publique d’un point de vue autochtone. D’autre part, ce travail invite à penser le processus d’élaboration des politiques publiques comme espace potentiel d’autodétermination. Étant donné la malléabilité des règles qui encadrent l’élaboration des politiques publiques en contexte canadien, le gouvernement – s’il en a la volonté - peut modeler le processus d’élaboration de façon à le rendre plus égalitaire et donc plus légitime d’un point de vue autochtone. Il sera démontré que, dans une optique de changements progressifs, un tel processus d’élaboration peut permettre aux peuples autochtones de regagner une certaine autonomie décisionnelle et ainsi atténuer les rapports de pouvoir inégalitaires. Notre cadre théorique a été construit à l’aide de différents courants analytiques, issus notamment des littératures sur le colonialisme, sur les politiques publiques et sur la légitimité. La comparaison de deux études de cas, soit les processus d’élaboration de l’Accord de Kelowna et du projet de loi C-33, Loi sur le contrôle par les Premières Nations de leur système d’éducation, permettra d’illustrer nos arguments et d’en démontrer l’applicabilité pratique. En somme, nous verrons comment la première étude de cas permet de concevoir l’élaboration des politiques publiques comme espace potentiel d’autodétermination, et comment la deuxième, au contraire, démontre que cette sphère peut encore en être une d’oppression.

Le processus d’élaboration des politiques publiques comme espace d’autodétermination : les cas de l’Accord de Kelowna et de la Loi sur le contrôle par les Premières Nations de leur système d’éducation

L’objectif du présent mémoire est double. D’une part, il cherche à identifier les facteurs qui permettent au gouvernement canadien et aux peuples autochtones de s’entendre sur des politiques publiques, malgré la persistance d’une logique coloniale. Nous verrons que l’atteinte d’une entente est conditionnelle à la légitimité du processus d’élaboration de la politique publique d’un point de vue autochtone. D’autre part, ce travail invite à penser le processus d’élaboration des politiques publiques comme espace potentiel d’autodétermination. Étant donné la malléabilité des règles qui encadrent l’élaboration des politiques publiques en contexte canadien, le gouvernement – s’il en a la volonté - peut modeler le processus d’élaboration de façon à le rendre plus égalitaire et donc plus légitime d’un point de vue autochtone. Il sera démontré que, dans une optique de changements progressifs, un tel processus d’élaboration peut permettre aux peuples autochtones de regagner une certaine autonomie décisionnelle et ainsi atténuer les rapports de pouvoir inégalitaires. Notre cadre théorique a été construit à l’aide de différents courants analytiques, issus notamment des littératures sur le colonialisme, sur les politiques publiques et sur la légitimité. La comparaison de deux études de cas, soit les processus d’élaboration de l’Accord de Kelowna et du projet de loi C-33, Loi sur le contrôle par les Premières Nations de leur système d’éducation, permettra d’illustrer nos arguments et d’en démontrer l’applicabilité pratique. En somme, nous verrons comment la première étude de cas permet de concevoir l’élaboration des politiques publiques comme espace potentiel d’autodétermination, et comment la deuxième, au contraire, démontre que cette sphère peut encore en être une d’oppression.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

Characterization of commercial double-walled carbon nanotube material : composition, structure, and heat capacity

A purified commercial double-walled carbon nanotube (DWCNT) sample was investigated by transmission electron microscopy (TEM), thermogravimetry (TG), and Raman spectroscopy. Moreover, the heat capacity of the DWCNT sample was determined by temperature-modulated differential scanning calorimetry in the range of temperature between -50 and 290 °C. The main thermo-oxidation characterized by TG occurred at 474 °C with the loss of 90 wt% of the sample. Thermo-oxidation of the sample was also investigated by high-resolution TG, which indicated that a fraction rich in carbon nanotube represents more than 80 wt% of the material. Other carbonaceous fractions rich in amorphous coating and graphitic particles were identified by the deconvolution procedure applied to the derivative of TG curve. Complementary structural data were provided by TEM and Raman studies. The information obtained allows the optimization of composites based on this nanomaterial with reliable characteristics.

St. John’s wort and Kava in treating major depressive disorder with comorbid anxiety : a randomised double-blind placebo-controlled pilot trial

Objective - We report the first randomised controlled trial (RCT) using a combination of St. John’s wort (SJW) and Kava for the treatment of major depressive disorder (MDD) with comorbid anxiety. Methods - Twenty-eight adults with MDD and co-occurring anxiety were recruited for a double-blind RCT. After a placebo run-in of 2 weeks, the trial had a crossover design testing SJW and Kava against placebo over two controlled phases, each of 4 weeks. The primary analyses used intention-to-treat and completer analyses. Results - On both intention-to-treat ( p¼0.047) and completer analyses ( p¼0.003), SJW and Kava gave a significantly greater reduction in self-reported depression on the Beck Depression Inventory (BDI-II) over placebo in the first controlled phase. However, in the crossover phase, a replication of those effects in the delayed medication group did not occur. Nor were there significant effects on anxiety or quality of life. Conclusion - There was some evidence of antidepressant effects using SJW and Kava in a small sample with comorbid anxiety. Possible explanations for the absence of anxiolysis may include a potential interaction with SJW, the presence of depression, or an inadequate dose of Kava.

Silylation of layered double hydroxides via a calcination−rehydration route

Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by 29Si cross-polarization magic-angle spinning nuclear magnetic resonance (29Si CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a “rodlike” aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T2 and T3 types of linkage between adjacent silane molecules as indicated in the 29Si NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 °C as observed in IES spectra.