Literatura académica sobre el tema "Second coordination sphere"

MhuD is a heme degrading enzyme from Mycobacterium tuberculosis that catalyzes both monooxygenation and dioxygenation leading to novel chromophores, mycobilins. The X-ray crystal structure of heme-bound, cyanide-inhibited MhuD displays a ruffled heme substrate where pyrrole rings are rotated around the Fe-N bonds, distorting the heme. The electronic structure of the heme in heme-bound, cyanide-inhibited MhuD (MhuD-heme-CN) is characterized here to provide insight into the mechanism of heme degradation by MhuD. Analysis of nuclear magnetic resonance (NMR) and magnetic circular dichroism (MCD) data for MhuD-heme-CN leads to the conclusion that the ground, (dxz,yz)4(dxy)1 electron configuration (2B2g state) and excited (dxy)2(dxz,yz)3 electron configuration (2Eg state) are close in energy allowing thermal population of the excited state at cryogenic and physiologically-relevant temperatures. The accessibility of two electronic states is studied with a combination of microbiology, spectroscopy, and computational analysis. The computational model developed describes a ground state that is close in energy to the excited state at ruffled geometries. Additionally, the heme is shown to be dynamic in the MhuD active site as the ground state hosts a double well potential in the ruffling coordinate allowing interconversion between a planar and a ruffled heme. To investigate the role of a ruffled, 2B2g heme and a planar, 2Eg heme in the MhuD reaction, substitutions are made to alter the active site residues Trp66 and Phe23. The Trp66 variants reduce heme ruffling resulting in decreased activity and a more planar heme as determined by optical spectroscopy and density functional theory calculations. F23W MhuD is shown to increase heme ruffling stabilizing the 2B2g state as determined by MCD. The F23W mutation stabilizes the meso hydroxyheme intermediate suggesting the more planar heme substrate conformation is needed to convert meso hydroxyheme into mycobilins. In summary, the data presented here strongly suggests that MhuD promotes formation of meso hydroxyheme with a ruffled substrate conformation and the formation of mycobilins with a more planar substrate conformation.

La transformation du CO₂ en formes réduites valorisables du carbone constitue une approche vers le recyclage de ce gaz à effet de serre, en réintroduisant dans le cycle du carbone des synthons C1 qui ne sont pas issus de ressources fossiles. Les tétraphénylporphyrines de fer et leurs dérivés se sont révélés être des catalyseurs moléculaires efficaces et sélectifs pour la réduction du CO₂ en CO. L'introduction de différentes fonctions dans la seconde sphère de coordination des porphyrines a aussi permis d'améliorer la surtension et les taux catalytiques.Inspirés par la poche distale des centres actifs des enzymes, une porphyrine de fer avec une anse portant une fonction carboxylate est étudiée. Les investigations électrochimiques, cinétiques, et de chimie computationnelle montrent que ce catalyseur permet de réduire fortement la surtension nécessaire à la catalyse tout en conservant des taux catalytiques très élevés. Il est proposé que la fonction carboxylate, initialement ligand axial du métal, joue en conditions catalytiques le rôle important dans l'insertion et la transformation du CO₂.Ensuite, deux porphyrines de fer ont été synthétisées avec un imidazolium à différentes positions par rapport au centre métallique. L'objectif premier était d'établir une corrélation entre la distance de la fonction cationique et les propriétés du catalyseur, afin de guider la conception de nouveaux catalyseurs plus performants.Cependant, l'étude électrochimique de ces composés révèle que ces groupements imidazolium peuvent être électroactifs. La résonance paramagnétique électronique a été utilisée afin de décrire leurs différentes formes réduites. Ces travaux ont amené à dévoiler la nature électroactive de ces groupements imidazolium portés par ces nouvelles porphyrines de fer
Transforming CO₂ into valuable reduced forms of carbon is an interesting approach towards the recycling of this greenhouse gas, by introducing non-fossil fuel based C1 building blocks back into the carbon cycle. Tetraphenyl iron porphyrins and derivatives have been shown to be efficient and selective molecular catalysts for CO₂ reduction to CO. The introduction of various functions in the second coordination sphere of porphyrins showed great improvements of both the overpotential and the catalytic rates.Inspired by the distal pocket of enzymatic active centers, an iron porphyrin with a carboxylate strap is investigated. Electrochemical, kinetic and computational chemistry studies show that this catalyst operates at a low overpotential, while maintaining high catalytic rates. It is proposed that the carboxylate function, initially acting as an axial ligand of the metal, plays an important role in the insertion and transformation of CO₂, in synergy with a water molecule trapped in the superstructure.Furthermore, two iron porphyrins were synthetized bearing an imidazolium group at various positions with respect to the metal center. The original goal of this study was to establish a correlation between the distance of the cationic group from the metal center and the catalytic performances of the catalyst, which can guide the design of new catalysts for CO₂ reduction.The electrochemical study of these catalysts revealed that these imidazolium functions can be electroactive. Electron paramagnetic resonance was used to describe their various reduced forms. These studies revealed and describe the potential electroactive behavior of the imidazolium groups on these novel iron porphyrins catalysts

La possibilité de reproduire une activité enzymatique de manière artificielle est l’un des objectifs de la chimie moderne mais reste un grand défi, même dans le cas de l’activation de petites molécules. Dans le cas du dihydrogène, certaines bactéries s’en servent comme vecteur d’énergie par l’intermédiaire d’enzymes appelées hydrogénases qui peuvent former ou consommer le dihydrogène grâce à des complexes à base de métaux non nobles. Le dihydrogène pouvant être également utilisé comme vecteur d’énergie dans nos sociétés, les hydrogénases font l’objet de nombreuses recherches. Jusqu’à présent, la plupart des complexes modèles d’hydrogénases se sont employés à modifier la première sphère de coordination pour reproduire au mieux ses propriétés électroniques. Néanmoins, l’étude de mutations ciblées des hydrogénases indique que plusieurs résidus d’acides aminés présents dans le site actif sont indispensables à la stabilité du complexe et à son efficacité catalytique, montrant ainsi comment le mime d’une deuxième sphère de coordination pourrait améliorer les propriétés des catalyseurs artificiels. Notre approche a consisté en l’utilisation de foldamères de type oligoamide aromatique, formant un cône autour d’un complexe modèle d’hydrogénase. La synthèse convergente du composé final, son étude structurale à l’état solide (diffraction des rayons X), en solution (RMN, IR) ainsi que sa dynamique ont été étudiées. La modification de la première sphère de coordination du complexe modèle en présence du foldamère est également décrite et montrant notamment leur interaction
The ability to replicate enzymatic activity with a synthetic molecule is a highly sought after goal in modern chemistry. However, it remains a big challenge even in case of activation of small molecules. In the case of hydrogen, some bacteria can use it as energy carrier by means of enzymes called hydrogenases that can reversely make or break the bond of hydrogen molecules and are made of earth abundant metals. As hydrogen could be used for the same purpose of energy storage in our society, hydrogenases caught interest of scientific community. To date, most biomimetic hydrogenase models mainly focus on first coordination sphere modifications to fine-tune structure and physical properties. However, point mutation studies indicate that several of the amino acid residues surrounding the enzyme active site are required for structural stability or high turnover frequencies. It shows how mimicking second coordination sphere could improve the capabilities of synthetic catalysts. Our approach used aromatic oligoamide foldamers as helical scaffolds around an inspired 2Fe2S4cluster. Convergent synthesis of the final molecule and structural studies in the solid state (x-ray) and in solution (NMR, IR) as well as the dynamic behaviour are reported. Modifications of the first coordination sphere of the model complex in presence of the foldamer are also described, showing interactions between them

More than 30% of all enzymes present a metal ion in their active site. Interesting sub-families present a mononuclear active site where a single metal ion (Zn2+ or Cun+) is coordinated to a polyhistidine core. The elaboration of model compounds is important for understanding the fundamental mechanisms involved in their bio-catalytic cycles. In this context, we have developed calix[6]arene based ligands presenting an aza cap covalently linked to the calixarene moiety. These supramolecular assemblies present several advantages: they offer a coordination site for a metal ion through the nitrogen donor atoms of the cap, the small rim of the calixarene moiety defines the second coordination sphere, and the hydrophobic cavity presents an access channel for exogenous ligands. In these systems the coordinating nitrogen atoms are separated from the oxygen rich small rim by two carbon atoms, which allows the controlled coordination of one single guest inside the cavity. Wanting to modulate the properties of the calix[6]arene tren-based (tris(2-aminoethyl)amine) ligand, we successfully synthetized several new receptors and studied their reactivity.The synthesis of “two-story” receptors, the calix[6]amido-tren and calix[6]amido-tacn, allowed the modification of the first and second coordination sphere of a coordinated metal ion by introducing an additional spacer between the tripodal aza-cap and the calixarene macrocycle. The complexes of CuI, CuII and ZnII of these new ligands were synthesized and their reactivity was studied. The presence of three potentially coordinating carbonyl groups changed the host-guest reactivity of these metal complexes as they are in competition with exogenous ligands. A comparative study of the host-guest properties and of the reactivity of the metal complexes of both ligands, calix[6]amido-tren and calix[6]amido-tacn was realized. The cavity of these “two-story” ligands is larger than the one of the parent calix[6]tren and more flexible, allowing not only the coordination of an anion, but the simultaneous coordination of two Cl ligands. The oxidation of sterically hindered amines into hydroxylamines and oximes in the presence of O2 was electrochemically realized by the reduction of the cupric center forming a CuII-superoxo adduct as the reactive species. Amine oxidation has been shown for the parent complex, however, the scope of this reaction was limited due to the smaller cavity. The formation of a CuII-superoxo adduct of the calix[6]amido-tren complex was qualitatively evidenced at low temperature upon addition of O2 to the isolated cuprous complex. This type of adduct has attracted much attention in recent years since it is considered to be a reactive intermediate in the catalytic cycle of copper monooxygenases, such as PHM and DβM. A supramolecular assisted demethylation methodology was developed for different capped calix[6]azacryptands. This methodology was then successfully applied to the demethylation of calix[6]tren in order to obtain calix[6]trentrisPhOH. This receptor showed a very different behavior in comparison to the parent one. Indeed, the complexation of anions and biologically relevant ammonium ions was evidenced by the monoprotonated receptor. The metal complexes of CuII and ZnII were synthesized. The interaction between the metal center and the phenate groups in presence of base has been evidenced and has conducted to a multi-step molecular switch. The cupric complex showed the presence of a phenoxyl radical resembling the oxidized form of galactose oxidase, catalyzing the oxidation of alcohols into aldehydes. These results open the way to new perspectives in reactivity studies.An analog of calix[6]tren, bearing a functionalized reactive arm on the tren cap, was synthesized and the corresponding CuII complex was immobilized on a gold surface through a monolayer formation. In organic medium, the host-guest properties of the grafted calix[6]tren are unchanged, while in aqueous medium, a reversible redox system was observed allowing the selective detection of linear alkylamines at basic pH. To our knowledge, this is the first copper supramolecular system immobilized on surface which permits that kind of detection in an aqueous environment.
Plus de 30% des enzymes présentent un ion métallique dans leur site actif qui est la clé pour les réactions de catalyse. Une sous-famille d’enzymes comporte un site actif où un seul ion métallique (Zn2+ ou Cun+) est coordiné à un cœur polyhistidine. L’élaboration de composés modèles est important pour la compréhension des mécanismes fondamentaux impliqués dans le cycle biocatalytique de ces enzymes mononucléaires. Dans ce contexte, nous avons développé des ligands basés sur des calix[6]arènes présentant un chapeau polyazoté lié de manière covalente au macrocycle. Ces ligands offrent un site de coordination pour le métal et une cavité hydrophobe bien définie. Cet assemblage permet et contrôle la liaison d’un ligand exogène dans la cavité. Afin de moduler les propriétés des complexes métalliques calixaréniques basés sur une unité coordinante tren (tris(2-aminoéthyl)amine), nous avons synthétisé avec succès et étudié plusieurs nouveaux récepteurs calix[6]aréniques.La synthèse de récepteurs bisétagés, le calix[6]amido-tren et le calix[6]amido-tacn, a permis de modifier la seconde sphère de coordination par incorporation de groupements amide entre la cavité et le site de coordination. Cette stratégie s’est avérée efficace. En effet, la coordination d’anions au centre métallique a été mise en évidence et en particulier celle simultanée de deux Cl pour le Cu-calix[6]amido-tren. Cette coordination d’un ou plusieurs invités anioniques était impossible dans le cas du calix[6]tren parent qui présente une seconde sphère de coordination électroniquement dense et un chapeau trop petit pour y accueillir plusieurs invités. La présence de groupements carbonyle entre la chapeau tren et le calixarène modifie également le comportement des complexes :leur coordination au centre métallique entre en compétition avec celle d’invités exogènes. L’oxydation d’amines encombrées sous O2 en hydroxylamines et oximes a été réalisée par la réduction du complexe cuivrique du calix[6]amido-tren par électrochimie. Ce type d’amines n’est pas oxydable par l’adduit superoxo du complexe parent, dû à la taille de la cavité qui empêche la coordination d’invités encombrés. De plus, la formation d’un adduit superoxo a été mise en évidence qualitativement au départ du complexe cuivreux isolé de ce même composé. Ces résultats permettent d’envisager des études de réactivité mimant le site actif des enzymes PHM et DβM par exemple. Enfin, une comparaison des propriétés hôte-invité et de la réactivité des complexes du calix[6]amido-tren avec celles des complexes du calix[6]amido-tacn a été réalisée afin d’évaluer l’impact de la nature du chapeau polyazoté sur les propriétés hôte-invité et la réactivité de ces complexes.Une méthodologie de déméthylation assistée de manière supramoléculaire a été développée pour différents calix[6]azacryptands chapeautés. Celle-ci a ensuite été appliquée avec succès à la déméthylation du calix[6]tren pour obtenir le calix[6]trentrisPhOH. Ce récepteur a montré un comportement très différent de celui du récepteur parent. En effet, la complexation d’anions et d’ammoniums biologiquement pertinents a été possible par ce récepteur protonné. L’interaction entre le centre métallique et les phénates en présence de base a conduit à la réalisation d’un switch moléculaire multi-étapes entre différents états de protonation du récepteur et du complexe zincique. Son complexe cuivrique a montré la présence d’un radical phénoxyle après oxydation du phénate. Cette espèce CuII-radical phénoxyle mime la forme oxydée du site actif de la galactose oxydase, catalysant l’oxydation d’alcools en aldéhydes. Ces résultats ouvrent donc la voie à de nouvelles perspectives pour les études de réactivité de ce composé.Un analogue du calix[6]tren, porteur d’un bras avec une fonction réactive sur le chapeau, a été synthétisé et complexé au cuivre avant d’être immobilisé sur surface via la formation de monocouches. Les électrodes ainsi modifiées ont été étudiées en milieu organique et aqueux. En milieu organique, les propriétés hôte-invité du calix[6]tren sont conservées après immobilisation. En milieu aqueux, un système redox réversible a été observé. Celui-ci a permis la détection sélective d’alkylamines linéaires par le système à pH basique. A notre connaissance, il s’agit du premier système supramoléculaire à cuivre, immobilisé sur surface, qui permet cette détection en milieu aqueux.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished

Self-assembly is used to describe the process in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of non-covalent interactions among the components themselves, without external direction. Self-assembly suggests the distinction between ‘‘self’’ and ‘‘non-self,’’ with recognition and selection between the two during assembly. According to Lehn, supramolecular chemistry can be described as an information science in which molecular components that contain the necessary information, self-assemble into large specific structures.Consequently, self-assembly has been recognized as a powerful tool for the construction of supramolecular scaffolds, as established by several excellent contributions.To achieve self-assembled systematized architecture, the necessary instructions must be incorporated into the structures of the building blocks by chemical synthesis. Thus, molecules can be made to self-assemble spontaneously into multi-component complex structures when they are instructed to do so. The instructions exist in the form of the molecule’s shape, its chemical properties, and how well it fit into the space where the assembly takes place etc. Each step in the assembly process is reversible and dynamic, that means the complex product is constantly forming, dissipating and proceeds via an error correcting method. Over the last two decades, the field of metallo-supramolecular selfassembly has emerged as a promising area of research for the development of specific, three-dimensional structures of increasing complexity and functionality.The beginning of this area of research has been benefited from design principles that consist of the ligand geometry and metal coordination geometry, thus opening up routes towards rationally designed classical supramolecular architectures. The success of this melal assisted self-assembled supramolecular architectures lies in its wide range of applications. Metal ion mediated self-assembled helical compounds are one of the most important and remains a crucial area for research over the last two decades.
The research was carried out under the supervision of Prof. Pradyut Ghosh, Inorganic Chemistry division under the SCS [School of Chemical Sciences]
The research was conducted under CSIR fellowship and project

This chapter analyses redox reactions. It explains that the oxidation–reduction reactions of transition metal complexes proceed via two primary mechanistic pathways: outer and inner sphere reactions. An outer sphere mechanism occurs when an electron is transferred between two coordination complexes in solution, both of the coordination spheres remain intact, and no ligand is transferred between them. The chapter notes that it is only possible to establish such a mechanism unambiguously when both of the coordination complexes are substitutionally inert. Finally, the chapter describes the inner sphere mechanism: the electron transfer is mediated by an ambidentate ligand which is capable of bridging the two metal centres in the transition state and is transferred from one complex to the second in the course of the reaction.

This chapter provides an account of the post-Second World War rebuilding of the war-torn countries and societies. It explores classic Weberian systems in the modern history of management and public administration thinking, which are considered as best arrangement for planning, coordination, and personnel routines focusing on long-term visions, stability, and merit in the public or private sphere. It also describes the globalisation of innovation thinking through the financial and policy influence of the US on European and Asian rebuilding projects. The chapter talks about the different regions and countries that entered the rebuilding stage with varying histories and political and administrative legacies that are considered in the formation of the charismatic networks and new types of public sector organisations charged with dynamic capabilities. It examines the challenge of balancing between globalisation and convergence versus contextualisation that has been an everlasting policy challenge ever since.

This study elucidated the location where Cs atoms resided at the solid–water interface in smectite hydrates that composed bentonite using EXAFS spectroscopy. Samples were prepared by adding 4ml of a 0.1M CsCl solution to 2g dry weight of suspended KunipiaF bentonite at pH 3.9, 7.1, and 9.8. The Cs K-edge absorption was measured in transmission mode at a synchrotron, Spring-8, Japan, using a Si(311) monochromator at room temperature for the wet paste and air-dried compacted samples. Data were analyzed with the program TECHXAS. The structural parameters were determined by a two-oxygen-shell fit using the ab initio program FEFF6 and ATOMS code. EXAFS analyses have suggested that for air-dried samples the first shell consisted of about 5O at a distance of 3.19–3.20 Å, and the second shell consisted of about 7O at a distance of 3.59–3.60 Å. For the wet paste, the first shell was observed at a distance of 3.15–3.16 Å with the coordination number of about 7O. The second shell consisted of about 6O at a distance of 3.59–3.60 Å. Debye-waller factors of the first oxygen shells were 0.021 and 0.04 Å2 for the air-dried and wet paste samples, respectively. For the second oxygen shells they were 0.039 and 0.052 Å2, respectively. Based on coordination numbers and Debye-waller factors, it concluded that the adsorption sites of Cs+ on smectite hydrates were positioned near the edge of the oxygen hexagonal cavity of the siloxane sheets on basal surface, and appeared between two aluminol sheets at fractured sections, assuming that the first shells were formed by oxygen of inter-layer water, and that the second shells consisted of oxygen forming clay minerals. Furthermore, in the wet paste Cs ions were considered to form incomplete inner-sphere-like complexes and to roam freely in inter-layer water in smectite.

European Union principle of Public administration service delivery is a key principle underpinning the efficiency principle and simplification of administrative procedures. Serbian government has done a lot of efforts and made a progress in the last five years in the sphere of public services digitalization, through strategic, institutional, normative changes, but some weaknesses still remain in terms of realizing the full potential of the different strategies and legislation. The purpose of the paper is to elaborate the application of quality and efficient public service delivery through analysis of Serbian strategic and normative framework de lege ferenda, simplification of administration procedures, focusing to main concerns for effective implementation of general procedure legislation and applying consistent practice. In the Introduction authors emphasize the progressing importance of digitalization of public services, from the perspective of European Union principles. This part also addresses conceptual issues of efficiency and effectiveness for ensuring high quality of public service delivery. The second part reveals the analysis of Serbian normative and strategic framework towards reducing bureaucratic burdens, simplification of administrative procedures through one-stop-shops, coordinating and “connecting” procedures from the jurisdiction of one or more administrative organs or organizations in the way the they provide better access to public services across the country. This part contains analysis of general legal framework from the aspect of reducing bureaucratic burdens for citizens and business entities, by imposing the obligation for public authorities to provide the documents ex officio and use them in administrative procedures. The authors analyze the provisions of the General Administrative Procedure Act de lege ferenda and its weaknesses for effective implementation. In Conclusion authors will summarize results of research in the way to point out to contemporary tendencies regarding digitalization of public services and means of application of efficiency, transparency, accessibility, openness and quality of public services in practice. Dominant methods of scientific research are dogmatic, comparative, content analysis, analysis and synthesis.