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Investigation on the reactivity of 1,3-bis (chloromethyl) tetramethyl disiloxane: 1-Interaction with Lewis acidic metal salts. 2-Application on Ionic Liquids.Alhaddad, Maha 07 1900 (has links)
This research explored the amination reaction of 1,3-bis-chloromethyl-tetramethyl-disiloxane in two different pathways. First, will discuss the synthesis of a new bipodal amino siloxane ligand which was achieved by the reaction of bis-chloromethyl-tetramethyl-disiloxane with t-BuNH3 in the presence of n-BuLi. The new ligand, of t-Butyl-[3-(t-butylamino-methyl)-1,1,3,3-tetramethyl disiloxanylmethyl]-amine (L1), is a model ligand designed to simulate the SOMC model of silica support and bipodal amido ligand that has been presented by the Basset group. Hence, developing this type of siloxane ligand and their complexes will be valuable in the synthesis of new homogenous catalyst, studying the reactivity and attempt to connect them with the SOMC examples. For this, the reaction of L1 with several Lewis acids and afforded several uncommon dimer and cluster complexes in the solid state.
The second part of this research found that heating of bis-chloromethyl-tetramethyl-disiloxane with a 4-6 equivalent of amine, affording 4-N-Alkyl-tetramethyl- oxazadisilinane as six heterocycle ring by using a new simple and neat method. Using six different amine functional groups afforded six new oxazadisilinane compounds with different alkyls substituted.
Each oxazadisilinane compound was utilized and reacted with four different acids, affording a series of twenty-one examples of new siloxane protic ionic liquids (Si-PILs). Also, the reaction of the cation with methyl iodide provided two examples of siloxane aprotic ionic liquids (Si-AILs). The new family of Si-ILs were well characterized by using NMR, mass, melting point, elemental analysis and thermal gravimetric analyses. Additionally, twelve crystals were suitable for X-ray diffraction as Si-PILs and one for Si-AILs. By studying their chemical and physical properties, a good library of the new Si-ILs has been built. Finally, one group of the new Si-PILs was used for butyl acetate esterification. The 5-X group of new Si-PILs salt was tested for esterification of butanol with acetic acid by thermal heat and under microwave irradiation. The salt 5-BF4- showed a good result in both systems with easy separation from the reaction mixture and recyclability discriminates the 5-BF4- as a good catalyst for the esterification reaction.
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Conséquences de contractions musculaires volontaires et électro-induites exhaustives sur le contrôle postural bipodal et la fatigue centrale / Consequences of voluntary and stimulated fatiguing muscular contractions on bipedal postural control and central fatiqueFelipe Fernandez, Emma 12 December 2011 (has links)
L’objectif général de ce travail doctoral était de comparer les effets de la fatigue musculaire des quadriceps femoris après un exercice musculaire volontaire (VOL) et un exercice musculaire électroinduit (ES) sur le contrôle postural bipodal, ainsi que sur la fatigue centrale. Les résultats montrent qu’à l’issue d’une tâche fatigante unilatérale ou bilatérale, l’exercice ES dégrade davantage la force usculaire que l’exercice VOL. Cependant, le contrôle postural bipodal est indifféremment perturbépar les deux exercices. En outre, les vitesses de récupération des capacités posturales et de force musculaire ne diffèrent pas à l’issue des exercices. Par ailleurs, l'exercice VOL altère davantage la commande centrale que l'exercice ES (immédiatement à l’issue de l’effort), tandis que celui-ci retarde l’apparition de la fatigue centrale et la maintient plus longuement. Etant donné que l'exercice VOL estinduit par la commande centrale et que l'exercice ES est généré par une stimulation artificielle externe, on peut émettre l’hypothèse que l'exercice VOL produit essentiellement une fatigue supraspinale, tandis que l'exercice ES engendre surtout une fatigue spinale. / The overall objective of this thesis was to compare the effect of fatigue of the quadriceps femoris after fatiguing voluntary contractions (VOL) and fatiguing neuromuscular electrical stimulation (ES) on bipedal postural control, and central fatigue. The results show that after unilateral or bilateral muscle fatigue, the ES exercise affected the muscle strength more than the VOL exercise. However, bipedal postural control was similarly deteriorated for both exercises. Moreover, the recovery speeds of postural control and muscle strength abilities did not differ for the both exercises. In addition, the VOL exercise alters central drive quicker than the ES exercise immediately after their completion while the ES exercise delays and prolongs the central fatigue. As the VOL exercise is induced by central command and the ES exercise is generated by artificial external stimulation, one can hypothesize that the VOL exercise especially produces supraspinal fatigue, while the ES exercise especially engenders spinal fatigue.
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