Lactide polymerization with iron alkoxide complexes

Les essais préliminaires pour préparer des alcoolates de fer à partir du bichlorure ou bibromure de fer (II), en les combinant avec des ligands de type diimino pyridine, ont engendré la formation de complexes homoleptiques et hétéroleptiques, dépendant des substituants sur les branches imines du ligand. Ces complexes homoleptiques octaédriques et paramagnétiques ont été étudiés par rapport à leurs propriétés spectroscopiques et cristallographiques. De plus, la synthèse des complexes de fer hétéroleptique a engendré de bons précurseurs penta-coordonnés pour les réactions de substitution de ligands avec des alcoolates de métaux alcalins, de manière à produire les dialcoolates de fer (II) désirés. Des techniques d’analyse telles que la spectroscopie UV-vis, l’analyse élémentaire, la spectrométrie de masse à haute résolution et la cristallographie aux rayons X ont été utilisées pour caractériser ces complexes de fer. L’activité catalytique de ces complexes de fer (II) a aussi été étudiée par rapport à la polymérisation du lactide; les dialcoolates convoités ont été générés in-situ en raison de la difficulté à produire et à isoler les dérivés alcoolates des complexes diimino pyridine de fer. Une étude approfondie a aussi été faite sur les réactions de polymérisation, surtout par rapport aux valeurs de conversion à l’échelle du temps, ainsi qu’à la tacticité des chaines de polymères obtenues. Ces analyses ont été effectuées par l’entremise de la spectroscopie de résonance magnétique nucléaire, de la chromatographie d’exclusion stérique, et de la spectrométrie de masse MALDI (désorption-ionisation laser assistée par matrice).

Rôle de l'isoforme p35 de la chaîne invariante humaine dans la formation et le transport de complexes de CMH II

La présentation antigénique par les molécules de classe II du complexe majeur d’histocompatibilité (CMH II) est un mécanisme essentiel au contrôle des pathogènes par le système immunitaire. Le CMH II humain existe en trois isotypes, HLA-DP, DQ et DR, tous des hétérodimères composés d’une chaîne α et d’une chaîne β. Le CMH II est entre autres exprimé à la surface des cellules présentatrices d’antigènes (APCs) et des cellules épithéliales activées et a pour fonction de présenter des peptides d’origine exogène aux lymphocytes T CD4+. L’oligomérisation et le trafic intracellulaire du CMH II sont largement facilités par une chaperone, la chaîne invariante (Ii). Il s’agit d’une protéine non-polymorphique de type II. Après sa biosynthèse dans le réticulum endoplasmique (ER), Ii hétéro- ou homotrimérise, puis interagit via sa région CLIP avec le CMH II pour former un complexe αβIi. Le complexe sort du ER pour entamer son chemin vers différents compartiments et la surface cellulaire. Chez l’homme, quatre isoformes d’Ii sont répertoriées : p33, p35, p41 et p43. Les deux isoformes exprimées de manière prédominante, Iip33 et p35, diffèrent par une extension N-terminale de 16 acides aminés portée par Iip35. Cette extension présente un motif de rétention au réticulum endoplasmique (ERM) composé des résidus RXR. Ce motif doit être masqué par la chaîne β du CMH II pour permettre au complexe de quitter le ER. Notre groupe s’est intéressé au mécanisme du masquage et au mode de sortie du ER des complexes αβIi. Nous montrons ici que l’interaction directe, ou en cis, entre la chaîne β du CMH II et Iip35 dans une structure αβIi est essentielle pour sa sortie du ER, promouvant la formation de structures de haut niveau de complexité. Par ailleurs, nous démontrons que NleA, un facteur de virulence bactérien, permet d’altérer le trafic de complexes αβIi comportant Iip35. Ce phénotype est médié par l’interaction entre p35 et les sous-unités de COPII. Bref, Iip35 joue un rôle central dans la formation des complexes αβIi et leur transport hors du ER. Ceci fait d’Iip35 un régulateur clef de la présentation antigénique par le CMH II.

Architectures radiales hétéro-poly-métalliques pour la photosynthèse artificielle et le stockage de l'information

Par une approche supramoléculaire, des architectures radiales hétéro-poly-métalliques ont été réalisées pour des applications en photosynthèse artificielle et en magnétisme moléculaire. Dans une première partie, la synthèse et la caractérisation (spectroscopie UV-vis, émission, électrochimique, DRX) de complexes de ruthénium(II), possédant une gamme de ligands polypyridines, ont été réalisées. Les calculs théoriques ont été effectués afin de soutenir l’interprétation des propriétés photophysiques. Ces complexes, présentant un certain nombre de pyridines externes, ont servi de cœur à des architectures à base de rhénium tris-carbonyles (pour les effets d’antenne), et de cobaloximes (pour les propriétés catalytiques). Les nucléarités obtenues varient de 2 à 7 selon le cœur utilisé. Ces systèmes ont été engagés dans des cycles de photo-production de dihydrogène, démontrant une meilleure efficacité que la référence du domaine, le [Ru(bpy)3]2+. La seconde partie concerne l’étude de couples de métaux de transition, construits à partir de briques polycyanométallates, ou de lanthanides pontés par des ligands oxamides. Ces approches « complexes comme ligand » puis « assemblages comme ligand » permettent d’obtenir des systèmes de haute nucléarité, présentant des propriétés de molécule-aimant ou des effets magnéto-caloriques (à base de CrNi, GdCu, DyCu). Des propriétés photomagnétiques ont été observées sur les couples RuCu et MoCu, pouvant servir de commutateurs moléculaires dans des systèmes complexes. Enfin, une structure hétéro-tétra-métallique trifonctionnelle a été obtenue contenant à la fois un commutateur MoCu, une entité molécule-aimant CuTb et un complexe de ruthénium.

Zeolite Encapsulated Complexes Of Fe,Co,Ni,Cu And Pd:Synthesis , Characterization And Catalysis-2003

This thesis deals with the synthesis, characterization and catalysis activity studies of some zeolite encapsulated complexes. Encapsulation inside the zeolite cages makes the catalysts more stable. Further, the framework prevents the complexes from dimerising. Catalysis by metal complexes encapsulated in the cavities of zeolites and other molecular sieves has many features of homogeneous, heterogenous and enzymatic catalysis. Serious attempts has been made to gain product selectivity in catalysis .The catalytic activity shown by the encapsulated complexes can be correlated to the structure of the active site inside the zeolite pore. It deals with the studies on the partial oxidation of benzyl alcohol to benzaldehyde. The oxidatio was carried out using hydrogen peroxide as oxidant in presence of PdYDMG and CuYSPP as catalysts. The product (benzaldehyde) was detected using TLC and confirmed using GC.The catalytic activity of the complexes was tested for oxidation under various conditions. The operating conditions like the amount of the catalyst, reaction time, oxidant to substrate ratio, reaction temprature, and solvents have been optimized. No further oxidation products were obtained on continuing the reaction for four hours beyond the optimum time. Maximum conversion was obtained at room temperature and the percentage conversion decreased with increase in temperature. Activity was found to be dependent on the solvent used. With increasing awareness about the dangers of environmental degradation, research in chemistry is getting increasing geared to the development of “green chemistry,” by designing environmentally friendly products and processes that bring down the generation and use of hazardous substances.

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors.

Synthesis and Characterization Of Some Transition Metal Complexes Of Multidentate Ligands

Coordination chemistry of schiff bases is of considerable interest due to their various magnetic, catalytic and biological applications. Here it describes the spectral characterization of schiff bases and its Mn (II), Cu (II) and Ni (II) complexes. Then synthesis and spectral characterization of Zn (II), Cd (II) and Co (II) complexes of schiff base derived from 3-Formylsalicilic Acid and 1,3-diaminopropane. Then it discusses the synthesis and spectral studies of Copper (II) complexes of 2-Hydroxyacetophenone N-phenyl semicarbazone. Finally it discusses the synthesis and spectral characterization of Co (III) complexes of salicylaldehyde N-phenyl semicarbazone. The preparation and characterization of Cobalt (III) complexes of salicylaldehyde, N-phenylthiosemicarbazone containing hetrocyclic bases phenalthroline and bipyridine. Thiocyanate, azide and perchlorate ions act as coligands. Elemental analysis suggests +3 state for Cobalt. HNMR, IR and UV-visible spectra characterize the complexes.

Synthesis, Spectral Characterization, Structural Studies and Biological Investigations of Transition Metal Complexes of Some Acid Hydrazones

This study concentrates the chemical properties of hydrazones due to its chelating capability and their pharmacological applications. Studies cover the preparation of different acid hydrazones and their structural studies and studies on their antimicrobial activity, synthesis and spectral characterization of different complexes of copper oxovanadium, manganese, nickel etc. Effect of incorporation of heterocyclic bases to the coordination sphere, change in the biological activity of acid hydrazones upon coordination, development of X-ray quality single crystals and its X-ray diffraction studies, studies on the redox behavior of the coordinated metal ions and correlation between the stereochemistry and biological activities.

Studies On Supported Cobalt (Ii), Nickel (Ii) and Copper (Ii) Complexes Of O-Phenylenediamine and Schiff Bases Derived from 3-Hydroxyquinoxaline-2-Carboxaldehyde

The thesis deals with the synthesis, characterization and catalytic activity studies of supported cobalt(ii), nickel(II) and copper(II) complexes of O-phenylenediamine and Schiff bases derived from 3-hydroxyquinoxaline -2-carboxaldehyde. Zeolite encapsulation and polymer anchoring was employed for supporting the complexes. The characterization techniques proved that the encapsulation as well as polymer supporting has been successfully achieved. The catalytic activity studies revealed that the activities of the simple complexes are improved upon encapsulation. Various characterization techniques are used such as, chemical analysis, EPR, magnetic measurements, FTIR studies, thermal analysis, electronic spectra, XRD, SEM, surface area, and GC.The present study indicated that the that the mechanism of oxidation of catechol and DTBC by hydrogen peroxide is not altered by the change in the coordination sphere around the metal ion due to encapsulation. This fact suggests outer sphere mechanism for the reactions. The catalytic activity by zeolite encapsulated complex was found to be slower than that by the neat complex. The slowing down of the reaction in the zeolite case is probably due to the constraint imposed by the zeolite framework. The rate of DTBC ( 3,5-di-tert-butylchatechol)oxidation was found to be greater than the rate of catechol oxidation. This is obviously due to the presence of electron donating tertiary butyl groups.

Studies on Some New Metal-Hydrazone Complexes and Their Zeolite Encapsulated Analogues

The thesis deals with the synthesis, characterization and catalytic activity studies of some new Fe (III), Co (II), Ni (II) and Cu (II) complexes of hydrazones and their zeolite encapsulated analogues. Hydrazones have diverse applications in biological, non-biological and biochemical front. During the present study three hydrazone types of ligands namely, acetylacetone- 2-hydroxyphenylhydrazone (APAcAc), acetoacetanilide- 2-hydroxyphenylhydrazone (APAcAcA) and acetoacetanilide-3,5-dihydro-2,4-dione pyrimidylhydrazone (AUAcAcA) were synthesized by diazotization of primary amine and coupling with compounds containing active methylene group. First part of the thesis deals with the synthesis of Fe, Co, Ni and Cu complexes using three hydrazone types of ligands are given. Details regarding the characterization of these complexes with a view to establishing the molecular structures are presented in this part. The other part contains the method of encapsulation of these complexes in zeolite cavities and their characterizations of the encapsulated metal species are described. A comparitive account of the catalytic activities of the pure and encapsulated complexes for cyclohexanol oxidation was also carried out.

Diversity in Structural and Spectural Characteristics of Some Transition Metal Complexes Derived From Aldehyde Based Thiosemicarbazone Ligands

The study deals with the diversity in structural and spectural characteristics of some transition metal complexes derived from aldehyde based thiosemicarbazone ligands thiosemicarbazones are a family of compounds with beneficial biological activity viz., anticancer,antitumour, antifungal, antibacterial, antimalarial, antifilarial, antiviral and anti-HIV activities. Many thiosemicarbazone ligands and their complexes have been prepared and screened for their antimicrobial activity against various types of fungi and bacteria. The results prove that the compounds exhibit antimicrobial properties and it is important to note that in some cases metal chelates show more inhibitory effects than the parent ligands. The increased lipophilicity of these complexes seems to be responsible for their enhanced biological potency. Adverse biological activities of thiosemicarbazones have been widely studied in rats and in other species. The parameters measured show that copper complexes caused considerable oxidative stress and zinc zinc complexes behaved as antioxidants. It has applications on analytical field also. Some thiosemicarbazones produce highly colored complexes with metal ions. This thesis aims to synthesis some novel thiosemicarbazone ligands and their transition metal complexes together with their physico-chemical characterization.

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors

Studies on Some Simple and Zeolite-Y Encapsulated 3d-Transition Metal Complexes of Schiff Bases Derived From 2-Aminobenzothiazole

In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.