17 research outputs found

    The social mandate of international organisations : what perspective for coherence ?

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    La structure du multilatéralisme onusien l’avait rendu problématique dès ses premiers pas. Mais son éclatement progressif en un Janus bipolaire, couplé à l’évolution du credo économique général, elle-même contemporaine de la globalisation politique et économique, s’est constitué de plus en plus visiblement tel une menace pour la poursuite de l’agenda social dans ses incarnations domestiques et internationales. D’un avis général, la panoplie des réponses inclut l’accélération d’efforts demeurés trop longtemps rhétoriques, en vue d’instaurer les conditions d’une cohérence effective des solutions promues par les composantes institutionnelles du prétendu « système » onusien. Les droits humains, le droit international du travail, la protection sociale et les chantiers de la gouvernance sont autant de champs où cherchent à surgir des options nées d’authentiques démarches intégratives.UN multilateralism was evidently born with a structural problem. However, its gradual splitting into a bipolar institutional setting, together with the transformation of the general economic credo while political and economic globalization was itself evolving, has more and more visibly taken a menacing aspect, imperiling the pursuit of social agendas whether domestic or international. In the opinion of many, responses include an acceleration of the – so far too tepid - efforts to bring about the conditions of an effective coherence among the solutions promoted by the entities of the so-called “UN system”. Human rights, international labour law, social protection and the field of governance are all areas where the genuine integration of agendas helps formulate the required options

    Synthesis and characterization of poly(methyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(methyl methacrylate) copolymers by two-step controlled radical polymerization (ATRP) catalyzed by NiBr2(PPh3)2, 1+

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    Poly(methyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(methyl methacrylate) triblock copolymers (MnBM) have been synthesized by the sequential controlled radical polymerization (atom transfer radical polymerization, ATRP) of n-butyl acrylate (n-BuA) followed by methyl methacrylate (MMA). The polymerization of n-BuA has been first initiated by the difunctional (diethyl meso-2,5-dibromoadipate) initiator in the presence of the NiBr2(PPh3)2 catalyst. After isolation, the α,ω-dibromo poly(n-butyl acrylate) chains have been used as macroinitiators for the polymerization of either n-BuA or MMA leading to chain extension or to the desired triblock copolymers, respectively. The kinetic study of the two-step process has shown that the initiation of the MMA polymerization by the poly(n-BuA) macroinitiator is slow and leads to PMMA outer blocks of broad polydispersity. Differential scanning calorimetry (DSC) and dynamical mechanical analysis (DMA) have confirmed the two-phase morphology of the triblocks. Finally, DMA and tensile testing of these copolymers have emphasized poor mechanical properties in possible relation to the broad polydispersity of the PMMA outer blocks

    Synthesis of fully acrylic thermoplastic elastomers by atom transfer radical polymerization (ATRP), 2a effect of the catalyst on the molecular control and the rheological properties of the triblock copolymers

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    The ATRP of MMA was initiated by α,ω-dibromo poly(n-butyl acrylate) in the presence of NiBr2(PPh3)2 leading to poly(MMA)-b-poly(nBuA)-b-poly(MMA) triblock copolymers (MnBM). The initiation of the MMA polymerization is slow compared to the chain propagation, which results in PMMA blocks of broad molecular weight distribution (MWD). In order to improve this situation, several experimental parameters were varied. CuBr/dNBipy was first substituted for NiBr2(PPh3)2, the results being, however, even worse. Then, the halide exchange was considered by substituting CuCl for CuBr. The CuCl/dNBipy catalyst proved superiority over the originally used NiBr2(PPh3)2 system. Finally, the addition of an excess of CuCl2 (deactivator) to the CuCl/dNBipy catalyst was very beneficial in decreasing the MWD of the PMMA blocks. Indeed, the SEC chromatograms are monomodal and narrow from the very beginning of the polymerization. The rheological analysis of the MnBM triblocks synthesized in the presence of each of the aforementioned catalytic systems confirmed differences in the molecular control of the copolymeriza-tion reaction

    Use of the CO2-laser micropoint micromanipulator for the treatment of laryngomalacia.

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    Between September 1989 and June 1994, 21 children (17 boys, 4 girls) with moderate to severe symptoms due to laryngomalacia underwent endoscopic surgery using the CO2-laser micropoint manipulator (shot-by-shot, 0.1 s, super-pulse, 2-3 W power; 280 microns beam; 400 mm working distance). Mean age of the children was 5 months (range, 1-11 months). The procedure was performed under high-frequency jet ventilation and consisted in the resection and/or vaporization of the aryepiglottic folds. This tissue removal could be extended to the laryngeal mucosa of the arytenoids and the lateral edge of the epiglottis. Results of surgery were excellent with normalization (8 patients) or, at worst, a very definite improvement of symptoms (4 patients). Furthermore, no complications occurred due to the technique used. These results have convinced us that the CO2-laser micropoint manipulator technique, with the "super-pulse" shooting mode and high-frequency jet ventilation, is by far superior to microsurgery with cold instruments when endoscopic treatment of laryngomalacia is indicated

    Controlled radical polymerization of (meth)acrylates by ATRP with NiBr2(PPh3)2 as catalyst

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    NiBr2(PPh3)2 has been found to be an efficient catalyst for the ATRP of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) initiated by an alkyl halide in the absence of any activator (e.g., Lewis acid) at 85 °C. The molecular weight distribution of the poly(meth)acrylates is narrow (Mw/Mn = 1.1−1.4). However, some side reactions (more likely coupling reactions) are observed at high monomer conversions in the case of n-BuA. An excess of PPh3 has proved to increase the polymerization rate of MMA while preserving the control of the molecular parameters. When the catalyst/initiator molar ratio is too small (e.g., 0.05), the polymerization rate decreases, the polydispersity increases, and the initiation is less efficient. α-Acid and α-hydroxyl end groups have been successfully attached to the chains by using functional initiators, such as 2-bromo-2-methylpropionic acid and 2,2‘,2‘ ‘-tribromoethanol. Reactivity ratios for the MMA/n-BuA comonomer pair have been measured and found to be close to the values observed for a conventional free-radical polymerization. Diethyl meso-2,5-dibromoadipate has been used as a difunctional initiator for the n-BuA polymerization, leading to α,ω-bromo-poly(n-BuA) of narrow molecular weight distribution. Finally, the thermal stability of PMMA is consistent with the lack of termination reactions, while Tg is as high as 125 °C

    CO2 laser in the diagnosis and treatment of early cancer of the vocal fold

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    A total of 74 patients underwent cordectomy using CO2 laser for either diagnosis or treatment of an early cancer of the vocal fold. Type I cordectomy consisted in the resection of the entire epithelium, while leaving the vocal ligament intact. Type II cordectomy involved removal of the vocal fold from the vocal process to the anterior commissure and passing through the inferior thyroarytenoid muscle. Type IIIA required vocal fold resection along the internal side of the thyroid ala, while type IIIB included removal of the anterior commissure. Type I cordectomies were carried out with an Acuspot micromanipulator, which provided a 250-micron-diameter beam for a working distance of 400 mm, and in the shot-by-shot cutting mode with 3 W power superpulse. This cordectomy was carried out in 39 patients and a dysplasia or an early carcinoma were detected in 45.9% of cases. Type II and type III procedures were performed with the Microslad micromanipulator having a 700-micron-diameter beam in the continuous cutting mode, 7 W power superpulse. Fifteen cases were treated by type II cordectomy, of which 3 T1aN0M0 cases underwent postoperative radiotherapy due to insufficient resections and 2 cases with T1bN0M0 tumors later underwent reconstructive laryngectomy. A type III cordectomy was used for 14 cases of T1aN0M0 carcinomas and 3 cases of severe dysplasia. The margins of resection were found to be positive histologically in 23.5% of these cases, making frozen section examinations mandatory at time of surgery. Results of all procedures showed that voice was best after a type I cordectomy where only the epithelium was resected. In the type II and type III cordectomies, the quality of voice depended on the development of a fibrous fold and the absence of anterior synechia in the healed larynx

    CO2 laser and Gianturco stent for endoscopic treatment of tracheal stenosis.

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    The self-expandable Gianturco stent was used in eleven cases of tracheal stenosis treated from September 92 to July 94. The stent is placed through a 9 mm outside diameter bronchoscope under optical control after cross-section and dilation of the stenosis with the CO2 laser according to the Shapshay technique. The follow-up varies from 3 to 22 months with a mean of 12 +/- 6 months. Pulmonary function tests (PFTs) show a mean improvement of the PEF (peak expiratory flow). Complications have been corrected in three patients with a second endoscopic procedure: the first case for malposition, the second for granuloma at the superior end of the prosthesis, and the third for the development of a mucous membrane webbing between the two loops of the stent. Owing to the lack of long-term follow-up, we reserve this technique for the treatment of severe tracheal stenosis with cartilage impairment in patients contraindicated when external reconstructive surgery is contraindicated

    Endoscopic treatment of tracheal stenosis using the carbon dioxide laser and the Gianturco stent: indications and results.

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    The self-expandable Gianturco stent was used in 11 patients with tracheal stenosis who where treated from September 1992 through July 1994. Under optical control, the stent was placed through a bronchoscope with an outside diameter of 9 mm after cross-section and dilation of the stenosis were performed with the carbon dioxide laser according to the Shapshay technique. The follow-up period varied from 3 to 22 months, with a mean of 12 +/- 6 months. Pulmonary function tests showed a mean improvement of the peak expiratory flow (50%), from 0.95+/-0.45 L/sec before the operation to 2.13+/-0.86 L/sec after the procedure. Radiologic and fibroscopic controls showed prosthesis stability. Three patients needed a second endoscopic procedure because of malposition of the stent, the formation of granuloma at the superior end of the prosthesis, and the development of a mucous membrane webbing between the two loops of a stent. Due to the lack of long-term follow-up, this technique is reserved for the treatment of severe tracheal stenosis with cartilage impairment in patients who have contraindications for external reconstructive surgery

    Direct observation of microdomain morphology in "all-acrylic" thermoplastic elastomers synthesized via living radical polymerization

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    We investigate the microscopic morphology of thin films of symmetric triblock copolymers synthesized via a two-step “living” radical polymerization of n-butylacrylate and methyl methacrylate. These copolymers with low poly(methyl methacrylate) contents constitute a new class of potential thermoplastic elastomers with higher service temperature and oxidation resistance compared to conventional polydiene−polystyrene-based thermoplastic elastomers. The straightforward synthetic pathway allows for strict control of molecular weight, molecular-weight distribution, and composition. The presence in the copolymer of immiscible segments covalently bound to each other leads to phase separation on the nanometer scale. Regular organization of the phase-separated nanodomains is observed in real space by scanning force microscopy. The data point to a strong contrast in the local mechanical properties, corresponding to the microphase morphology. Cylinders of the minority phase are found to orient perpendicular to the surface, because of the surface energy difference between the constituents. Lamellae are also arranged perpendicular to the surface, in contrast to what is usually observed in block copolymers. This particular orientation is thought to result from the symmetric character of these triblock systems, with the outer blocks more polar than the central sequence
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