Dissertations / Theses on the topic 'D10 metals'

Computational chemistry has gained interest as a characterization tool to predict photoluminescence, reactivity and structural properties of organic and transition metal complexes. With the rise of methods including relativity, these studies have been expanded to the accurate modeling of luminescence spectra of complexes with considerable spin-orbit splitting due to heavy metal centers as well as the reaction pathways for these complexes to produce natural products such as hydrogen gas. These advances have led to the synthesis and utility of more effective catalysis as well as the development of more effective organic light emitting diodes (OLEDs) through the incorporation of organometallic complexes as emitters instead of typical organic emitters. In terms of significant scientific advancement presented in this work is in relation to the discovery of significant spin-orbit splitting in a gold(I) alkylphosphine complex, where the splitting results in the states that emit in different colors of the visible region of the electromagnetic spectrum. This work also reveals the discovery both computationally and experimentally, of a genuine polar-covalent bond between two-closed shell metals. This work highlights a complex with an incredibly short gold(I) – copper(I) intermetallic distance leading to a vibrational frequency and dissociation energy that is on par with those of other systems with single-bonded metal centers. Lastly, this work outlines a strategy for the production of hydrogen gas through the use of trinuclear cyclic coinage metal complexes as catalysis to split hydrohalic acids.

De nos jours, la chimie est utilisée comme outil général pour accéder (synthèse), contrôler (influence des paramètres) et comprendre (étude des propriétés) le matériau. Ceci est rendu possible grâce à deux approches : l'approche «Top- down» et l'approche « Bottom-up ». La première approche est une des bases de la nanotechnologie. La deuxième approche consiste en l'assemblage de systèmes moléculaires possédant des propriétés intrinsèques pour accéder à des matériaux avec de nouvelles propriétés. Ce concept est généralement appelé: «de la molécule au matériau »; et dans ce contexte, la chimie supramoléculaire occupe une position centrale. Le présent travail porte sur la synthèse et l'étude de propriétés des systèmes de métal-dithiolene comportant des ions métalliques et des lanthanides. Le premier chapitre est une introduction générale sur la chimie du dithiolene et des lanthanides. Le deuxième chapitre décrit la synthèse et la caractérisation de systèmes supramoléculaires basées sur des ligands dithiolene neutres. Dans ce chapitre, l'importance des groupes fonctionnels capables de former des interactions non covalentes sera discutée. Le troisième chapitre est consacré à la réactivité de ces ligands dithiolene neutres avec les métaux de transition (d10) tels que CU1, Hg11, et Au1. Ce chapitre décrira la synthèse de complexes supramoléculaires ainsi que leurs propriétés spectroscopiques. Le quatrième chapitre, s'intéresse à la réactivité de ces ligands vis-à-vis des lanthanides trivalents (Nd, Eu, Gd, Tb, Er), la caractérisation des complexes formés ainsi que les propriétés de luminescence en résultant. Notre discussion sera orientée sur le processus de transfert d'énergie («Effet Antenne»), une fois ces ligands coordonnés à un ion lanthanide
Nowadays, chemistry represents a general tool for accessing (synthesis), controlling (parameters influence) and understanding (study of properties) the material. This is allowed by two possible approaches: the "Top-down" and "Bottom-up". The first approach is a key to nanotechnology. The second approach consists in assembling small systems, with intrinsic properties, to build up macro system with interesting properties. This concept is generally termed as: "from mo/ecu/es to material” and in this context, supramolecular chemistry plays a crucial rote. The present work examines the synthesis and properties of dithiolene systems bearing metal ions and lanthanides. The first chapter is a general introduction on dithiolene chemistry and lanthanides. The second chapter deals with the synthesis and characterisation of supramolecular systems based on neutral dithioiene-like ligands. Ln this chapter importance of non-covalent interactions is discussed. The third chapter concerns the reactivity of these neutral dithiolen like ligands towards d10 transition metals (CU1, Hg11, AU1). This chapter will describe the synthesis of supramolecul complexes and their spectroscopic properties. The fourth chapter deals, with the reactivity of the ligands with lanthanide (Nd, Eu, Gd, Tb, Er) and the characterisation of Ln3+ -dithiolene complexes. The discussion will be oriented on the energy transfer process taking place in these coordination compounds ("Antenna Effect")

This dissertation covers the studies of two major topics: the photochemistry of mononuclear and multinuclear gold(I) complexes and synthetic approaches to tailor photophysical properties of cyclic trinuclear d10 complexes. First a detailed photochemical examination into the photoreactivity of neutral mononuclear and multinuclear gold(I) complexes is discussed, with the aim of gold nanoparticle size and shape control for biomedical and catalysis applications. Next is a comprehensive systematic synthetic approach to tailor the photophysical properties of cyclic trinuclear d10 complexes. This synthetic approach includes an investigation of structure-luminescence relationships between cyclic trinuclear complexes, an examination into their π-acid/π-base reactivity with heavy metal cations and an exploration into the photophysical properties of new heterobimetallic cyclic trinuclear complexes. These photophysical properties inspections are used to screen materials for their employment in molecular electronic devices such as organic light-emitting diodes (OLEDs) and thin film transistors (OTFTs).

Ziel dieser Arbeit war es, das Potenzial von p-tert-Butyltetramercaptotetrathiacalix[4]aren (H4(MTC[4])) zum Aufbau von mehrkernigen Komplexen mit weichen Metallionen mit d10-Elektronenkonfiguration zu untersuchen. H4(MTC[4]) bietet im Vergleich zum bekannteren p-tert-Butylcalix[4]aren erweiterte Bindungsmöglichkeiten für Metallionen an den Thioetherbrücken. Die Funktion der Metallionen Cu(I) und Zn(II) in biologischen Systemen lieferte die anfängliche Inspiration, jedoch erschien auch die Untersuchung anderer Metalle wie Nickel, Silber und Gold in Verbindung mit (MTC[4])4- Liganden lohnenswert, da diese Metalle durch ihre jeweils bevorzugten Koordinationsgeometrien neue Strukturen und Koordinationsmöglichkeiten an H4(MTC[4]) aufzeigen könnten. In Experimenten mit Kupfer(I)-Ionen konnten der Kupferkomplex [(Ph3PCu)4(MTC[4])] sowie das Hexamer [Cu4(MTC[4])]6 hergestellt und charakterisiert werden. [Cu4(MTC[4])]6 weist eine einzigartige, supramolekulare, hohle Cu24S48-Käfigstruktur auf. Die [Cu4(MTC[4])]-Einheiten werden durch Cu2S2-Motive verknüpft, die extrem kurze Cu···Cu-Abstände aufweisen. Durch NMR-Experimente wurde gezeigt, dass die Hohlräume von [Cu4(MTC[4])]6 in Lösung Acetonitril und Methan aufnehmen können. In Experimenten mit Silber(I)-Ionen wurden die Molekülstrukturen der Silberkomplexe [(Ph3PAg)2AgH(MTC[4])], [(Ph3PAg)4AgCl(MTC[4])] und [(Ph3PAg)4(MTC[4])] bestimmt. Diese zeigen, dass H4(MTC[4]) gegenüber Silber- und Kupferionen ein ähnliches Koordinationsverhalten aufweist. In Experimenten mit Gold(I)-vorläufern war es möglich, zu steuern, wie viele Metallionen ein einzelnes Molekül H4(MTC[4]) koordiniert. Die Komplexe [(Ph3PAu)2H2(MTC[4])], [(Me3PAu)3H(MTC[4])] und [(Me3PAu)4TlCl(MTC[4])] wurden synthetisiert. Diese bieten teilweise durch vorhandene freie Thiolfunktionen Potenzial für die Synthese heterometallischer Komplexe.
It was the aim of this work, to assess the potential of p-tert-Butyltetramercaptotetrathiacalix[4]arene (H4(MTC[4])) to create multinuclear complexes with soft metal ions of d10 electron configuration. In contrast to the more known p-tert-Butylcalix[4]aren, H4(MTC[4]) offers extended possibilities for the coordination of metal ions at the thioether groups. While this work was initially inspired by the function of Cu(I) and Zn(II) ions in biological systems, the metal ions, which were incorporated into the Calixarene, were soon expanded by Ni(II), Ag(I) and Au(I) ions. Through their different preferred coordination geometries, these metal ions could yield new information about coordination modes of H4(MTC[4]). In experiments with copper(I) ions the complex [(Ph3PCu)4(MTC[4])] and the hexamer [Cu4(MTC[4])]6 were synthesized and characterized. [Cu4(MTC[4])]6 consists of a unique, supramolecular hollow Cu24S48 cage structure. The [Cu4(MTC[4])] units are connected by Cu2S2 motivs, which display extraordinary short Cu···Cu distances. An investigation by NMR spectroscopy indicated that the cavities of [Cu4(MTC[4])] in solution can hold acetonitrile or methane molecules. In experiments with silver(I) ions, the molecular structures of the compounds [(Ph3PAg)2AgH(MTC[4])], [(Ph3PAg)4AgCl(MTC[4])] and [(Ph3PAg)4(MTC[4])] were determined. In these compounds H4(MTC[4]) exhibits a similar coordination behaviour towards Ag(I) ions as it does towards Cu(I) ions. In experiments with gold(I) precursors it was possible to control how many gold(I) ions were coordinated by H4(MTC[4]). The complexes [(Ph3PAu)2H2(MTC[4])], [(Me3PAu)3H(MTC[4])] and [(Me3PAu)4TlCl(MTC[4])] were synthesized and studied. Due to their free thiol functions, they are potential precursors for the synthesis of heterometallic complexes.

L’objectif de ce travail fut la synthèse de ligands fonctionnels de type N,N'-diphosphanyl-NHC (NHC = carbènes N-hétérocycliques) et l’étude de leur chimie de coordination. La synthèse du nouveau ligand tridentate, stable et rigide, N,N'-diphosphanyl-imidazol-2-ylidene a permis des études expérimentales et théoriques et l’accès à des complexes mono-, di-, tri-, penta-, et hexanucléaires des métaux du groupe 11 (Cu, Ag et Au) originaux et aux propriétés structurales uniques. Les complexes mono- et dinucléaires avec un ou deux atomes de phosphore libres ont permis d’accéder à des complexes hétérotrinucléaires à interactions d10-d10 qui sont luminescents. La transmétallation partielle ou totale des complexes homotrinucléaires de Cu ou d’Ag avec des réactifs contenant du Pd(0) ont conduit à des complexes hétérotrinucléaires à interactions d10-d10. En plus de son comportement pontant, ce ligand peut se agir en chélate dans des complexes du palladium et du chrome. Dans le cas du Cr(III), ils montrent une activité catalytique en oligomérisation de l’éthylène supérieure à celle des complexes du Cr(II) et conduisent principalement à des oligomères
The purpose of this work was the synthesis of N,N'-diphosphanyl-functionalized NHC ligands andtheir coordination chemistry. The novel stable and rigid tridentate N,N'-diphosphanyl-imidazol-2-ylidene was synthesized and experimental and computational information on its stability weregained. It served as a unique platform for the synthesis of novel mono-, di-, tri-, penta-, hexanuclear complexes with the coinage metals (Cu, Ag and Au), exhibiting rare structural features. The mono- and dinuclear complexes with one or two dangling P-donors provided rational access to heterotrinuclear complexes. All these coinage metal complexes have short metal-metalseparations, indicating the presence of d10-d10 interactions, and display excellent luminescentproperties. Partial or complete transmetallation of the homotrinuclear Cu or Ag complexes withPd(0) precursors led to hetero-trinuclear complexes with d10-d10 interactions. In addition to itsbridging behavior, this ligand also showed its chelating behavior in Pd or Cr(III) complexes. Thelatter displayed superior performance in ethylene oligomerization than the Cr(II) complexes andgave mostly oligomers

Thesis (Ph. D.)--Ohio State University, 2003.
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Titanium (Ti) foams of different densities 1622-4100 Kgm-3 made by a powder sintering technique were studied as to their structural and mechanical properties. The foams were tested under static and dynamic loading. The material was tested quasi statically and dynamically under strain rates in the range of 0.001-2500 s-1 and under different loading modes. It was found that strain rate sensitivity is more pronounced in lower density foams. Experiments were complimented by virtual testing. Based on the Voronoi tessellations a computational method was developed to generate stochastic foam geometries. Statistical control was applied to produce geometries with the microstructural characteristics of the tested material. The generated structures were numerically tested under different loading modes and strain rates. Voronoi polyhedrals were used to form the porosity network of the open cell foams. The virtually generated foams replicated the geometrical features of the experimentally tested material. Meshes for finite element simulations were produced. Existing material models were used for the parent material behaviour (sintered Ti) and calibrated to experiments. The virtual foam geometries of different densities were numerically tested quasi statically under uniaxial, biaxial and triaxial loading modes in order to investigate their macroscopic behaviour. Dynamic loading was also applied for compression. Strain rate sensitive and insensitive models were used for the parent material model in order to examine the influence of geometry and material strain rate sensitivity under high rates of deformation. It was found that inertial effects can enhance the strain rate sensitivity for low density foams and numerical predictions for the generated foam geometries were in very good agreement with experimental results. Power laws were established in scaling material properties with density. The study includes: 1. Information on the material behaviour and data for macroscopically modelling this type of foams for a range of densities and under different strain rates. 2. A proposed method for virtually generating foam geometries at a microscopic scale and examine the effect of geometrical characteristics on the macroscopic behaviour of foams.

L'élaboration de diodes électroluminescentes organiques (OLEDs) est un défi technologique majeur de ce début de siècle. Afin d'optimiser l'efficacité de ces dispositifs, des complexes de métaux de transition luminescents peuvent être incorporés dans la couche émettrice. Dans ce contexte, la chimie de coordination de complexes de métaux d10 a été étudiée pour la préparation de composés phosphorescents homo- et hétéroleptiques à partir de divers ligands diazotés et diphosphorés. Parmi les complexes préparés, plusieurs présentent un excellent potentiel pour l'élaboration de diodes électroluminescentes. La chimie de coordination de métaux d10 permet également de préparer différents types d'édifices supramoléculaires. A partir d'un complexe cuivreux et de différents ligands nitriles, il a été possible d'obtenir des polymères de coordination et des composés macrocycliques. Ces édifices ont été caractérisés par le biais d'une étude systématique à l'état solide par diffraction des rayons X, ainsi qu'en solution par spectroscopies RMN et UV-visible. La préparation de nanostructures riches en fullerène est un autre thème de recherche de notre groupe pour l'élaboration de matériaux intéressants. Dans le cadre de ce travail, des branches dendritiques incorporant le fullerène ont été utilisées pour fonctionnaliser des assemblages supramoléculaires préparés à partir du cuivre(I) ou pour synthétiser des cages d'étain entourées de six branches dendritiques par condensation d'un acide carboxylique avec un acide stannique
The elaboration of organic light emitting diodes (OLEDs) is a technological challenge of this early century. In order to optimize the efficiency of these devices, luminescent transition metal complexes can be incorporated in the emitting layer. In this context, coordination chemistry of d10 metal complexes was studied for the preparation of phosphorescent homo- and heteroleptic compounds starting from N- and P- ligands. Some of these complexes show excellent properties for the elaboration of light emitting diodes. Furthermore, coordination chemistry of d10 metal allows the preparation of different supramolecular structures. Starting from a copper (I) complex and different nitrile ligands, it is possible to obtain coordination polymers and macrocyclic compounds. These structures were characterized systematically in the solid state by X-ray crystallography and solution by NMR and UV-vis spectroscopy. The preparation of fullerene-rich nanostructures is another topic of our research group to elaborate advanced materials. In the context of this work, dendritic branches incorporating fullerene units were used in order to functionalize supramolecular assemblies prepared from copper(I) complexes, or to synthesize organooxotin nanoclusters surrounded by six dendritic branches from condensation of a carboxylic acid and a stannic acid

Oxidative transformation is one of the fundamental reactions occurring in organic chemistry and is the basis of many synthetic processes. This ia an area of an ongoing research work addressed both to the synthetic application and to the understanding of the mechanism involved in these processes, whose interest include reactions occurring in biological system also. In enzymes, as in artificial catalysts, the presence of metals in high oxidation state allow the activation of hydrogen peroxide (H2O2) and alkyl hydroperoxides (RO2H) and the subsequent oxidation of different organic substrates. Both in enzymes and in artificial systems the sourranding environment of the peroxidic reactive species is of great importance. The ligands bounded to a metal center, such as proteins or molecules from synthesis, are able to increase not only the stability and reactivity, but also the stereoselectivity of the metal. However, there are numerous examples in the literature of how the reactivity, stability and stereoselectivity of cataytic synthetic processes catalyzed by polidentate catalysts may be largely influenced by the presence of additives or monodentate ligands able to bind to the metal center. The influence that polidentate ligands or monodentate ligands may exsert on the reactivity of several catalytic systems is part of the topics covered in the first chapter of this thesis. In particular, we have addressed our attention to catalytic oxidative processes which are accelerated after the bind of ligands both poly- and monodentate. Numerous examples from recent literature have been reported. They are divided into two classes of phenomena: the "ligand accelerated catalysis (LAC) and the co-ligand accelerated catalysis (LAC-CO ). In LAC, as defined by Sharpless, the addition of a polydentate chiral ligand induces the genaration, towards ligand exchange, of a new chiral metallic complex characterized by an increased reactivity. In CO-LAC, the addition of a chiral or achiral monodentate ligand allows the modification of the reactivity of the original metal complex without the occurrency of a ligand exchange. In Chapter 2 we have focused our attention on the reactivity of a polyhedral oligomeric silsesquioxane trisilanolate vanadium(V) complex towards oxidation reactions. This catalyst, at room temeperature and in the presence of cumyl hydroperoxide as the terminal oxidant is efficient in oxygen transfer processes towards sulfides, tertiary amine and secondary amine. Sulfoxidations and N-oxidations have been carried out yielding the corrisponding products in good yields. The addition of a Lewis base as a co-ligand can markedly affect reactivity, stability, chemo- and stereo-selectivity. A proposal for the intermolecular activation, using Gutmann analysis supported by MP2/TZVP calculations, has been presented. In Chapter 3 catalytic sulfoxidations, using cumylhydroperoxide as primary oxidant, has been tested in a series of eight aminotriphenolate d0 metals complexes [Sc(III), Ti(IV), Zr(IV), Hf(IV), V(V), Nb(V), Ta(V), Mo(VI)]. The reactivity and selectivity properties ,both in presence and in absence of a strong Lewis Base (dimethylhexyl-N-oxide) as co-ligand, has been determined experimentally. The experimental values have been correlated with the Sanderson value of electronegativity. MP2/LANL2DZ theoretical calculations on model complexes have furnished more insights on the characteristics of the reactive peroxo specie. The experimentals combined with the theoretical calculations have offered the possibility to propose a general mechanism for the peroxide activation and reactivity. The study described in Chapter 4 pertains to V(V)-oxo amine triphenolate complexes as functional and structural model of vanadium haloperoxidases: their trigonal bypiramidal geometry emulates the one found in the enzymes and their ability to catalyse efficiently sulfoxidations as well as chlorination and bromination of trimethoxybenzene reflects the properties of the enzyme. In particular, sulfoxidations using hydrogen peroxide as terminal oxidant are performaed in quantitative yields and high selectivities ( catalyst loading down to 0.01%, TONs up to 9900, TOF up to 8000 h-1), while in the second case TONs up to 1260 and TOF up to 220 h-1 are achieved with a acatlyst loading down to 0.05%. In Chapter 5 some synthtic method for the preparation of a new fluorinated incompletely condensed polyhedral oligomeric silsesquioxane suitable to be immobilized on polymeric fluorous membranes or in addition able to be dissolved in fluorous solvents have been reported.
La trasformazione ossidativa di gruppi funzionali costituisce una delle reazioni fondamentali della chimica organica ed è alla base di moltissimi processi sintetici. Si tratta di un settore che è oggetto di un continuo lavoro di ricerca, indirizzato sia alla risoluzione di problemi sintetico-applicativi che alla comprensione dei meccanismi che operano in tali processi il cui interesse è così vasto da includere reazioni che avvengono anche in sistemi biologici. Negli enzimi, così come nei catalizzatori artificiali, la presenza di metalli in elevato stato di ossidazione permette l'attivazione di acqua ossigenata (H2O2) e di idroperossidi alchilici (RO2H) consentendo l’ossidazione di diversi substrati organici. Sia negli enzimi che nei sistemi artificiali particolare importanza riveste l’intorno chimico della specie reattiva metalloperossidica responsabile del trasferimento di ossigeno. I leganti al centro metallico, siano essi di natura proteica o costituiti da molecole di sintesi, sono in grado di aumentare non solo la stabilità e la reattività ma anche la capacità di stereoselezione del centro reattivo. Tuttavia, si trovano in letteratura numerosi esempi di come la reattività, la stabilità e la stereoselezione di processi sintetici catalizzati da complessi con leganti polidentati vengano ampiamente influenzati anche dalla presenza di additivi, o leganti monodentati per lo più basici, in seguito alla loro interazione con il metallo. L’influenza che leganti polidentati e co-leganti monodentati possono avere sulla reattività di numerosi sistemi catalitici è parte degli argomenti trattati nel primo capitolo di questa tesi di dottorato. In particolare abbiamo voluto indirizzare la nostra attenzione verso processi reattivi, soprattutto di tipo ossidativo, che vengono accelerati in seguito all’azione sia di leganti polidentati che di co-leganti monodentati. I numerosi esempi che sono stati riportati su questo argomento, tratti dalla recente letteratura, sono stati suddivisi all’interno di due classi di fenomeni: la “ligand accelerated catalysis” (LAC) e la “co-ligand accelerated catalysis” (CO-LAC). Nella LAC, secondo la definizione di Sharpless, l’aggiunta di un legante chirale polidentato induce la formazione, tramite scambio di legante, di un nuovo complesso metallico dotato di una aumentata reattività che spesso si accompagna anche ad una aumentata stereoselettività. Nella CO-LAC invece, l’aggiunta di un legante monodentato chirale o achirale, induce una modificazione della reattività del complesso metallico senza che vi sia scambio di legante. Numerosi esempi di CO-LAC prevedono l’utilizzo di leganti monodentati basici. Durante questo dottorato, abbiamo potuto constatare che il processo di trasferimento di ossigeno verso il metil p-tolil solfuro catalizzato da un complesso polisilosanico di V(V) recanti sostituenti iso-butilici in presenza di CHP come ossidante primario viene accelerato, anche di 24 volte, a seguito dell’aggiunta di basi di Lewis in quantità confrontabili con quelle del catalizzatore. Nel Capitolo 2 i dati sperimentali riportati evidenziano l’esistenza di una corrispondenza tra accelerazione osservata del processo e natura elettron donatrice della base di Lewis usata. Più elettron ricca è la base di Lewis maggiore è la reattività del sistema e, probabilmente a causa delle migliori capacità coordinanti del co-legante, minore è la quantità di base di Lewis necessaria per avere l’effetto massimo. Calcoli computazionali condotti hanno dimostrato come la coordinazione di basi di Lewis al vanadio inducano variazioni di distribuzione elettronica con aumento di densità elettronica all’ossigeno della specie reattiva metalloperossidica coinvolto nel trasferimento di ossigeno e contemporanea diminuzione della stessa a livello del centro metallico con conseguente stabilizzazione dell’intermedio reattivo. Lo studio sugli effetti delle basi di Lewis in processi di trasferimento di ossigeno a solfuri organici è stato esteso anche verso un’altra classe di leganti ossia le trifenolammine. Nel Capitolo 3 sono stati investigati processi catalitici di ossidazione del metil p-tolil solfuro per mezzo di cumilidroperossido come ossidante primario in presenza di otto complessi ammino tri-fenolati di metalli d0 [Sc(III), Ti(IV), Zr(IV), Hf(IV), V(V), Nb(V), Ta(V), Mo(VI)]. La reattività e la selettività di questi processi, sia in assenza che in presenza di una base di Lewis forte come il dimetilesil-N-ossido è stata determinata sperimentalmente. I dati sperimentali ottenuti sono stati correlati con i valori di elettronegatività di Sanderson e tramite studi teorici sono state tratte delle delucidazioni sulle caratteristiche della specie reattiva metalloperossidica. I dati sperimentali raccolti e i calcoli teorici ci hanno permesso di proporre un meccanismo generale per spiegare l’attivazione della specie perossidica e la sua reattività. Nel Capitolo 4 sono descritti i complessi ammino tri-fenolati di ossovanadio(V) come modelli funzionali e strutturali di aloperossidasi, grazie alla loro geometria trigonale bipiramidale e alla loro abilità nel catalizzare efficacemente sia le solfossidazioni così come la bromurazione e la clorurazione del trimetossibenzene. In particolare, nell’ossidazione di solfuri, usando perossido d’idrogeno come ossidante primario, sono state ottenute con rese quantitative in prodotto con alta chemoselettività, anche in presenza dello 0.01% di catalizzatore, con TON fino a 9900 e TOF fino a 8000 h-1. Nel caso della bromurazione si sono ottenuti TON pari a 1260 e TOF fino a 220 h-1 usando fino allo 0.05% di catalizzatore. Nel Capitolo 5 viene riportata una serie di strategie di sintesi per la formazione di un nuovo legante trisilanolico polisilossanico recante lunghe catene perfluorurate come sostituenti.

Triplet – triplet absorption of d0 metal complexes was for the first time revealed and studied by means of pulse photolysis and electron-exchange (Dexter) resonant energy transfer energy transfer. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35395

博士
淡江大學
化學學系
88
The self-organization of small molecules into helical structures could be found easily in living system. There are several sophisticated inorganic helicates have been developed. We aimed to introduce the hydrazone group to link polypyridyl binding domain, it plays two roles; both binding, and bridging unit, it also could be deprotonated to modulate the electronic coupling in multinuclear system. A family of novel polypyridyl type multi-binding domains ligands containing hydrazone linker were synthesized successfully, after complexed with Ag(l) or Cu(I) respectly, gives double helicates only, including dinuclear helicates, [Ag2(m-Ph-M-(Bpy)2)2](X)2, [Ag2(Bpy-(M-Pz)2)2](Z)2, [Ag2(Bpy-(M-Thio)2)2](Z)2, [Ag2(Bpy-(H-MThio)2)2](Z)2, trinuclear helicates, [Ag3(Py-M-(Bpy)2)2](X)3, [Ag3(Py-M-(Bpy)2)2](Y)3 [Ag3(C2-M-(Bpy)2)2](Z)3, [Ag3(C2-Ph-(Bpy)2)2](Z)3, [Ag3(Bpy-(H-M2Py)2)2](Z)3, [Cu3(Bpy-(H-M2Py)2)2](Z)3, [Ag3(Bpy-(M-Pz)2)2](Z)3, and finally a unique petanuclear helicate [Ag5(Bpy-(HC2H-Bpy)2)2](Z)5, (X=ClO4, Y=PF6, Z= CF3SO3). Solid state structures of complexes list above were confirmed by Xray diffractometry.The composition and Solution structures were also examined by FAB, ESI Mass and NMR method (COSY,NOESY), the results confirmed the double helix structure is maintained in the solution state. The self-recognition process and cooperative phenomena were studied by NMR and spectrophotometric experiments including UV-Vis,NMRand ESI titration, for helicates [Ag2(m-Ph-M-(Bpy)2)2]2+, [Ag3(Py-M-(Bpy)2)2]3+ , they express highly positive cooperation in individual ligand and self-recognition between ligands. The self-assembling process and reaction mechanism were investigated by means of sytematic measurement of step-wise and overall stability constant

博士
國立臺灣大學
化學系研究所
85
This thesis can be divided into two subjects: I. Synthesis and structures of linear metal chain complexes. II. Photoluminescent properties of d10 metal complexes. I. Synthesis and structures of linear metal chain complexes The linear tri- and penta-nuclear metal chain were helically surrounded by four organic ligands(dpa-, tpda2-) to perform a wire-like structure. Trinuclear metal chain NiII and CoII complexes [M3(dpa)4X2] were synthesized by improved method, and axial position(X) was substituted to different axial ligands to research the property changes. Extending to pentanuclear metal chain complexes, the newly developed ligand, H2tpda, was used to form [M5(tpda)4X2] successfully. The axial ligands were also substituted to provide a serial model to research metal-metal interactions by x-ray structure determinations, magnetic properties(by SQUID), and x-ray absorption spectrum(by synchrotron radiation beam line). II. Photoluminescent properties of d10 metal complexes. Both d10 metal clusters using phenylacetylide ligand and d10 dinuclear metal complexes have interesting photo-luminescent properties. The photoinduced electron and energy transfer, possible photocatalyzed reaction and energy exchange of those compounds were characterized and discussed according to their absorption and emission spectra. Host-guest interaction study was approached by attaching luminescent d10 metal clusters to the peripheral appendages of polyazamacrocycles and crown ethers as supramolecular host. The x-ray structures of these d10 metal complexes were also provided.

碩士
國立中正大學
化學研究所
92
The research focus in this thesis is classified into three parts. The first part is to study the structure, spectroscopic and photophysical properties of the trinuclear complex, [(8-QNS)2 Au(AuPPh3)2]BF4 1 (8-QNS = quinoline-8-thiolate). 1 is structurally characterized by the single crystal X-ray diffraction study, showing two intramolecular gold(I)•••gold(I) interactions (3.0952(4) and 3.0526(3) Å), where two molecules of 1 are further aggregated into a novel hexanuclear supermolecule, (1)2, via a close intermolecular gold(I)•••gold(I) contact of 3.1135(3) Å. In addition to the interesting structural property of 1, it also shows a dramatic solvent effect dependent on the solvent polarity. Second part is to utilize the designed pyridyl amides as bridging ligands for the construction of gold(I) supermolecules. When compared with the literature and free ligands, the emissions of these gold(I) supermolecules is tentatively assigned to a π → π* of PPh3 mixing with a Au → PPh3 transition. Third part includes synthesis and characterizations of a series of inorganic- organic Cd(II) coordination polymers 7 - 11. Py2S (4,4’- dipyridyl sulfide), 4-pytaH [(4-Pyridylthio)acetic acid] and PL3 (N1, N3, N5- tri(pyridin-4-yl)-isophthalamide) are chosen as bridging ligands to synthesize coordination polymers with different Cd(II) salts. 7, 8 and 9 form different polymeric structures due to different counteranions and solvent systems. 10 is formed as a 1-D polymer, but is further hydrogen- bonded to lead to the formation of a 2-D structure. 11 is formed as a 3-D coordination polymer with a channel structure. The luminescence properties of these coordination polymers are also investigated.

博士
中原大學
化學研究所
103
This thesis includes two parts discussing the synthese, structures and interactions of d10 metal complexes containing polydentate nitrogen ligands. Part I. The reactions of N,N′-di(pyridin-2-yl)oxalamide (L1), N,N′-di(pyridin-2-yl)succinamide (L2), N,N′- di(pyridin-3-yl)oxalamide (L3) and N,N′- di(pyridin-2-yl)adipamide (L4) with Ag(I) , Cd(II) , Hg(II) and Zn(II) metal salts afforded dinuclear and one-dimensional complexes, which have been fully characterized by EA and IR analysis and single-crystal X-ray diffraction. The dinuclear complexes [Ag2(L1)(CH3CN)6](SbF6)2, 1, Ag2(L1)(CH3CN)2(CF3CO2)2, 2, and Ag2(L1)(CH3CN)2(p-TsO)2, 3, (p-TsO- = p-toluenesulfonate), and 1-D polymeric chains [Ag(L1)(CH3CN)(CF3SO3)]n, 4, {[Ag2(L2)2(p-TsO)](p-TsO) • 2CH3CN}n, 5, {[Ag(L2)](SbF6) • CH3CN}n, 6, {[Ag(L3)](SbF6)•DMF}n, 7, {[Ag(L3)](PF6)}n, 8, {[Ag(L4)](BF4) • CH3CN}n, 9, {[Ag(L4)](PF6)}n, 10, and {[Ag(L4)](SbF6) • CH3CN}n, 11 form supermolecular structures through π-π stacking and weak Ag---O or Ag---F interactions. The 1-D helical chains of {[Cd(L1)(H2O)2](ClO2)2 • (CH3)CO}n, 12, are linked through π – π stacking interactions and N-H---O及C-H---O hydrogen bonds to form a 3-D supramolecular framework, and those of [HgCl2(L1)]n, 13, [HgBr2(L1)]n, 14, and the dinuclear Hg2(L1)(NO3)2, 15, are interlinked through π – π stacking interactions and various hydrogen bonds. The 1-D polymeric chains of [ZnBr2(L3) • DMF]n, 16, [ZnI2(L3) • DMF]n, 17 and [HgBr2(L3) • DMF]n, 18, are linked by their DMF molecules through the hydrogen bonds, while the molecules of the dinuclear Hg2I4(L3)2, 19 interact each with other through π – π stacking interactions and hydrogen bonds to form 3-D supramolecular frameworks. Similarily, the 1-D chains [Cd(L4)(ClO4)2]n, 20, and the dinuclear complexes, Hg2Br4(L4), 21 and Hg2I4(L4), 22 form 3-D nets through π – π stacking interactions and various hydrogen bonds. Part II. The amino-pyrimidine ligands, 2,4,6-triaminopyrimidine (L5) and 2-amino-4-methoxy-6-methylpyrimidine (L6) reacted with Ag(I) metal salts to form the complexes {[Ag2(L5)2(ClO4)](ClO4) • CH3OH}n, 23, {[Ag(L5)](p-TsO) • CH3OH}n, 24, [Ag4(L5)4(p-TsO)2](p-TsO)2 • 6DMF, 25, {[Ag2(L6)2(SO4)]•6H2O}n, 26,{[Ag(L6)](BF4)}n, 27, [Ag(L6)2](ClO4), 28, {[Ag(L6)2](PF6)}n, 29, [Ag(L6)(CF3CO2)]n, 30, and {[Ag(L6)](CF3SO3)}n, 31. All compounds have been characterized by spectroscopic methods and their structures determined by X-ray crystallography. The Ag(I) atoms of 23 and 24 are bridged by the L5 ligands to form 1-D polymeric infinite chain structures, and 0-D tetranuclear complex. The molecules of 23 – 25 are interlinked through weak C-H---π, π – π stacking and Ag---O interactions. The 1-D chains 26, 27, 30 and 31, and the molecules of the 0-D of 28 and 2-D grids of 29, are interlink through π – π stacking interactions and hydrogen bonds to form 3-D frameworks.

碩士
國立臺灣大學
化學學系
82
This thesis consists of a number of polynuclear metal cluster complexes of Group 11 ( = Cu ,Ag ,Au ) containing bridging phosphine ligand and plolypyridyl ligand. These complexes which electron configuration are all d10 and are of interest because of the their intriguing structures and photophysical.In this work, we also provide a new entry to polypyridyl (PPy3) ligand that is made use of forming polymatallic complexes. We now describe a new general synthetic method that how to bind metal together. The pentanuclear Ag(I) metal cluster complex involving the tetrapodal PPy3 ligands of the type has been successfully synthesized. The studying of the synthesis and the crystal structure has also been described. Beside of the studying of physical properties, the chemistry of assembled molecules continue to attract much our attention. The designment of synthesis of ligands which have the ability to bond to transition metals, forming a large number of polynuclear complexes has been of much interest, and is important in our work.

博士
國立臺灣大學
化學學系
84
In this thesis,the ligand: 2,6-(diphenylphosphino)pyridine was used to obtain three Cu(I),Ag(I),Au(I) isostructure metal complexes.These complexes form a metallomacrocycle,which has an open cavity and should therfore be capable of binding a second, different ion.The host complex [(PNP)3Au2](ClO4)2 feature a red shift in the emission spectrum when guest ion was added, such as Cu(I),Ag(I) metal ion.And a character of down field shift in 31P NMR spectrum.A series of phenylacetylide-metal complexes contain tridentate ligand were synthesised.The metal-metal distance were short because of the metal-metal interaction. There are a red shift effect in solid state emission spectrum compare to the emission spectrum in solution,which was arise from the metal- metal interaction.We also successful synthesed a new ligand H2tpda(H2tpda=N,N''-bis(pyridine)-2,6- diaminopyridine),and [H2tpdaCoCl2],linear pentnickle complex [Ni5(tpda)4Cl2] were also synthesed.

碩士
東吳大學
化學系
98
Diphenyl(2-pyrrolyl)phosphine, Pyrr2P, which is a bidentate ligand, reacted with the group 11 metal ions to from dimeric compounds of the types [Au2(Pyrr2P)2] (3), [AuAg(Pyrr2P)2] (4) and [AuCu(Pyrr2P)2] (5). Their aurophilicity and metallophilicity with regard to the distances between two metal ions and the influence of luminescent properties were investigative. For compound 3, the Au-Au distance is 2.8865(5)~2.8745(5) ?? while in compounds 4 and 5, the Au-M distances are 2.8353(7) ? (M = Ag) and 2.7890(13) ? (M = Cu) respectively. Structures of 3 and 4 show head-to-tail coordination mode and structure 5 is head-to-head. The NMR spectra have been investigated for all three compounds. The Ag-P chemical shift and coupling constants in compound 4 are δ 0.23 (J1107Ag-31P = 567.0Hz, J1109Ag-31P = 656.1Hz). Their luminescent properties are also dependent on the metal-metal interaction or inter-molecular interaction. Compound 5 absorbs the visible light (424 nm) and emits the light-green color (546 nm). In this thesis, we also used the DFT calculation to describe each energy gap for 3, 4 and 5.

碩士
國立中正大學
化學研究所
91
The research focus in this thesis is classified into three parts. The first part includes synthesis and characterization of a series of inorganic-organic d10 (Zn2+, Cd2+ and Hg2+) coordination polymers (1)—(5) with pyridyl-amide ligands, (L1-L3). Compounds (1)—(5) have been structurally characterized by single crystal X-ray diffraction studies, consisting of the frameworks of one-dimensional chains. The crystal packing of compound (4) is built up by the interwoven chains, where the micropore (8.5Å x 8.5Å) shows selective sensing for volatile organic compounds (VOCs) in size, aromaticity and hydrogen-bonding ability. Second part is to synthesize the luminescent Au(I) compounds (6)—(9) with sodium 1,4,7,10-tetraoxa-13-azacyclopentadecane-13-carbodithioate (NaCS2), and the X-ray crystal structures of compound (6) and (9) have been determined. The interesting structural, spectroscopic and photophysical properties of compound (6)—(9) are compared and discussed in this part. The excited states of these compounds are mostly due to S→Au charge-transfer transition because of the strong σ donor strength of thiolates. The host-guest recognition study has been performed on compound (10) in the third part. The luminescent host has been demonstrated to differentiate among alkali, transition metal, and lanthanide ions, showing interesting molecular-recognition events.

博士
國立臺灣大學
化學學系
84
In this thesis,the three tetradentate ligands : 2-tolylsulfonyl- amido-7-hydroxy-1,8-naphthyridine(I),2,7- tolylsulfonylamido-1,8- naphthyridine(II),2,7-bis( diphphenylphosphino)-1,8-naphthyridine (III) was used to obtain polynuclear metal complexes.The two tri- nuclear metal complexes in which there are long distance between metal ions was obtained by using ligand I to react with Cu(II) and Co(II) respectively.As for ligand II, a trinuclear Cu(I) metal complex with red luminescence and a dinuclear Au(I) metal complex with green luminescence was synthesized. The latter can be regarded as a inorganic host to catch a guest ion such as Cu(I) which will let the color of luminescence change from green to red.The ligand III reacting with Cu(I) and Ag(I) ions gave linear trinuclear metal complexes. The Cu(I) ion was added as a guest ion to the analogous Au(I) dinuclear complex of ligand III for acquiring a host-guest supramolecular.It will induce the bleach of emission origined from host complex by the Cu(I) ion. The three Au(I)-Cu(I) heteronuclear metal complexes was synthesized by using pyrazolate anion as a bridge ligand.The shoter distance between Au(I) and Cu(I) ions than that in similar Pt( II)-Cu(I) heteronuclear complex shows the stronger attractive force existing in heternuclear d10 metal ions than in homonuclear d10 metal ions.In these heteronuclear complexes, the tetranuclear Au(I)-Cu(I) metal complex have a low-lying emissive state which was assigned as a cluster center excited state.

碩士
中原大學
化學研究所
97
Abstract This thesis discusses the chemistry of znic(II) and cadmium(II) complexes containing N,N'-di(4-pyridyl)adipoamide (H2dpya) and 1,4-benzenedicarboxylate (1,4-BDC). Two new coordination polymers, [Zn(1,4-BDC)(H2dpya)] •(H2O) (1) and [Cd(1,4-BDC)(H2dpya)] •2(H2O) (2), have been synthesized by hydrothermal reactions. All the complexes have been characterized by EA, IR, TGA and PL spectroscopic methods and structurally characterized by X-ray crystallography. Complex 1 and complex 2 form the distorted diamondoid net supported by N,N'-di(4-pyridyl)adipoamide and 1,4-benzenedicarboxylate. Complex 1 is a [4+4] mode of interpenetration and complex 2 is a 9-fold interpenetrating mode. The H2dpya ligands in complex 1 adopts the AGA-cis conformation while in complex 2 the AAA-trans onformation.

碩士
國立中正大學
化學暨生物化學研究所
99
The novel metal-organic coordination polymers︰{[Zn2(bpe)2(TDC)2(H2O)]‧H2O}n (1), {[Zn(dpe)(TDC)]}n(2), {[Zn(bpe)0.5(TDC)(DMA)]}n (3), {[Zn2(dpe)2(TDC)2]‧DMSO}n (4), {Zn(bpp)(TDC)}n (5) and {[Cd0.5(TDC)]‧(CH3)2NH2‧H2O‧0.72DMA}n (6) (bpe = 1,2-bis(4-pyridyl)-ethane, dpe = 1,2-bis(4-pyridyl)-ethylene, bpp = 1,3-bis(4-pyridyl)-propane, H2TDC = Thiophene-2,5-dicarboxylic acid). All these compounds were structurally characterized by single-crystal and powder X-ray diffraction technique, in which complexes 3, 5 and 6 are 2D structures, and complexes 1, 2 and 4 are 3D structures. Their thermal stabilities and photoluminescence behaviors have also been investigated, in which complexes 1, 3 and 4 appear phase transformation after heating, and they are irreversible process.

碩士
國立中正大學
化學所
97
To take advantage of self-assembly to construct a variety of supramolecular architectures and polymeric networks with potential applications is a challenging in crystal engineering. In this thesis, we designed and synthesized two unsymmetrical pyridyl-amine ligands as bridging-bidentates,N-(4-(4-aminophenoxy)phenyl)isonicotinamide (papoa) and N-(4-(4-aminophenylthio)phenyl)isonicotinamide (papsa), to react with ZnX2 (X = Cl, Br, I, NO3)、CdX2 (X = NO3, ClO4), and CuI to give a series of coordination polymers. We try to investigate the anion and solvent effects on the formation of metal-organic frameworks. The complexes studied in this thesis contain [Zn(papoa)Br2]2 (2), [Zn(papoa)I2]2(3),[Zn(papoi)Cl2]2(1''),[Zn(papoi)Br2]2(2''), [Zn(papoa)(NO3)2]2 (4a), [Zn(papoa)(NO3)2]n (4b), [Zn(papsa)Cl2]2 (5), [Zn(papsa)Br2]2 (6), [Cd(papoa)(NO3)2]n (8), {[Cd(papoa)(MeCN)2]- (ClO4)2}n (9a), [Cd(papoa)(ClO4)2]n (9b) and [Cu2(papoa)2I2]n (10), which are isolated and structurally characterized by the X-ray diffraction study. The X-ray analysis reveals the formation of 0-D macrocyclic structures for 2, 3, 4a, 5, and 6, 1-D double zigzag chains for 4b, 8, and 9a, and a 2-D wave framework for 9b. The 0-D and 1-D complexes can be extended into multidimensional structures by hydrogen bonds. Each macrocycle includes two ZnX2 units, with roughly tetrahedral coordination geometries at Cd(II) centers, and two papoa (or papsa). When Zn(II) nitrate is reacted with papoa in the presence of different solvents, two coordinated patterns for 4a and 4b can be obtained. 4a involves two papoa and two nitrate units, whereas 4b is composed of four papoa and two nitrate. These Zn(II) complexes display blue emission in the solid state, and can be probably assigned to an intraligand transition (IL). When Cd(II) perchlorate is reacted with papoa in the presence of different solvents, two coordinated patterns for 9a and 9b can be also obtained. Both structures of 9a and 9b have roughly octahedral geometries at Cd(II) centers and four ligands(papoa), whereas the axial coordination for 9a is acetonitrile and 9b is perchlorate. Cd(II) complexes also display emissions in the solid state, and they can be probably assigned to a metal-to-ligand charge-transfer (MLCT) transition. Moreover, the reaction of papoa with CuI can form 1D coordination polymer, 10, where the interesting Cu2I2 unit with a short CuI???CuI contact (2.666 Å) was expected to be responsible for the intriguing emission properties. Finally, when zinc halides were reacted with papoa in acetone, ZnX2 (X = Cl,Br) can act as a transition-metal-based catalyst to catalyze a nucleophilic attack on the carbonyl group by the amine led to the formation of Zn(II)-imine complexess, 1’ and 2’, following dehydration.

Shen, Hao.
"July 2007."
n and 0 in "4fn/d0" in title is superscript.
Thesis (Ph.D.)--Chinese University of Hong Kong, 2007.
Includes bibliographical references (p. 207-220).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstracts in English and Chinese.

O presente trabalho teve como objetivo a realização de testes descontínuos de biodegradabilidade anaeróbia de efluentes provenientes da primeira etapa de branqueamento de pasta kraft (D0), ricos em compostos recalcitrantes e potencialmente inibidores (AOX). No presente trabalho foram avaliados os efeitos na remoção de AOX e na produção de metano por aplicação de várias condições no tratamento anaeróbio, a temperatura mesófila, do efluente D0: carga orgânica aplicada; adição de um co-substrato; adição de cinzas como suplemento e aplicação de um pré-tratamento enzimático ao D0. Assim, foi estudada a utilização de duas cargas orgânicas de D0 diferentes (3 e 2 g-CQOs·L-1), verificando-se remoções de AOX de 70,6 e 74,2 %, remoções de CQOs de 47,5 e 26,2 % e produção de CH4 de 121,7 e 193,9 mL-CH4·g-CQOs inicial, respetivamente. A adição acetato e glucose conduziu a remoções de AOX de 52,6 e 70,4 %, respetivamente, remoções de CQOs de 76,2 e 42,9 %, e eficiências de metanização de 335,0 e 124,0 mL-CH4·g-CQOs inicial. Concluiu-se que a remoção de AOX foi maximizada no reator alimentado com 2 g-CQOs·L-1 de D0. Foi estudada a digestão anaeróbia da mistura filtrada e não filtrada de D0 com cinzas volantes da caldeira auxiliar (CA5), cinzas volantes da caldeira de queima de biomassa (CTB) e lamas de cal obtendo-se remoções de AOX entre 62,0 e 74,4 %. Nos reatores alimentados com a mistura não filtrada de D0 neutralizado com cinzas CA5 e cinzas CTB ocorreu a produção de 166,3 e 157,2 mL-CH4·g-CQOs inicial-1, respetivamente. A utilização de cinzas CA5 e CTB parece ter sido vantajosa na remoção de AOX, com remoções de 70,1 e 62,0%, e não ter efeitos significativos na produção de metano (CH4). Estudou-se a adição de enzimas e de cinzas CA5 e CTB. Verificou-se que nas condições aplicadas, a utilização de enzimas e cinzas parece não ter o efeito pretendido. No estudo das comunidades Archaea e Bacteria verificou-se que a aplicação do D0 como substrato parece ter conduzido a mudanças na composição das comunidades presentes nas lamas biológicas. Concluindo, a digestão anaeróbia demonstrou ter potencial para o tratamento do D0, nomeadamente a remoção de AOX, e para a produção de CH4
The present work had as objective the accomplishment of batch tests of anaerobic biodegradability of effluents from the first stage of kraft pulp bleaching (D0), rich in recalcitrant and potentially inhibitory compounds (AOX). The effects on the removal of AOX and on the production of methane were evaluated by applying several conditions in the anaerobic treatment of the effluent D0: applied organic load; addition of a co-substrate; addition of ashes as a supplement and application of an enzymatic pre-treatment to D0. Thus, the use of two different organic loads of D0 (3 and 2 g-CQOs·L-1) was studied, with AOX removals of 70.6 and 74.2 %, removals of CODs of 47.5 and 26.2 % and CH4 production of 121.7 and 193.9 mL-CH4 initial·g-COD-1, respectively. Addition of acetate and glucose led to AOX removals of 52.6 and 70.4 %, respectively, COD removals of 76.2 and 42.9 %, and methanization efficiencies of 335.0 and 124.0 mL- CH4 initial·g-COD-1. It was concluded that the AOX removal was maximized in the reactor fed with 2 g-COD·L-1 of D0. Anaerobic digestion of the filtered and unfiltered D0 mixture with CA5, CTB and lime sludge ash was studied, was obtained AOX removals between 62.0 and 74.4 %. In reactors fed with unfiltered D0 mixture neutralized with CA5 ashes and CTB ashes occurred the production of 166.3 and 157.2 mL-CH4 initial·g-COD-1, respectively. The use of CA5 and CTB ashes appears to have been advantageous in the removal of AOX and have no significant effects on CH4 production. The addition of enzymes, and CA5 and CTB ashes was studied. It has been found that under the conditions applied, the use of enzymes and ashes together does not appear to have the desired effect. In the study of the Archaea and Bacteria communities it was verified that the application of D0 as substrate seems to have led to changes in the composition of the communities present in the biological sludge. In conclusion, anaerobic digestion has been shown to have potential for the treatment of D0, namely the removal of AOX, and to produce CH4
Mestrado em Biotecnologia