"Catalysis by pillared montmorillonites exchanged with transition metals"

The present work is oriented to obtain a comparative evaluation of the physicochemical properties and catalytic activities of iron, aluminium and iron aluminium mixed pillared montmorillonites and their transition metal exchanged analogues. Reactions of industrial importance like Friedel Crafts alkylations, catalytic wet peroxide oxidation of phenol and MTBE synthesis have been selected for the present study. The thesis is structured into seven chapters. First chapter deals with a brief introduction and literature survey on pillared clays. Second chapter explains the materials and methods employed in the work. Results and discussions on the characterisation techniques are described in the third chapter. The subsequent three chapters describe the catalytic activities of pillared clays in the industrially important reactions. Last chapter comprises the summary of the investigations and the conclusions drawn from the earlier chapters

Synthesis And Characterization Ofpolystyrene Supportedcatalytically Active Poly(Amidoamine) Dendrimer-Palladium Nanoparticle Conjugates

Poly(amidoamine) dendrimers were synthesized on cross-linked aminomethyl polystyrene. Palladium complexes of supported dendrimers prepared by ligand exchange method were reduced to dendrimernanoparticle conjugates supported on polystyrene resin. The supported nanoparticles were used as heterogeneous catalysts for the Suzuki coupling between aryl boronic acids and aryl halides. Various factors affecting the catalysts performance were studied. Higher generation dendrimers gave well-defined nanoparticles without agglomeration and these particles showed good catalytic performance

Synthesis, Characterization and Catalytic Activity of Nanocrystalline Ceria Modified With Zirconia

The use of catalysts in chemical and refining processes has increased rapidly since 1945, when oil began to replace coal as the most important industrial raw material. Catalysis has a major impact on the quality of human life as well as economic development. The demand for catalysts is still increasing since catalysis is looked up as a solution to eliminate or replace polluting processes. Metal oxides represent one of the most important and widely employed classes of solid catalysts. Much effort has been spent in the preparation, characterization and application of metal oxides. Recently, great interest has been devoted to the cerium dioxide (CeO2) containing materials due to their broad range of applications in various fields, ranging from catalysis to ceramics, fuel cell technologies, gas sensors, solid state electrolytes, ceramic biomaterials, etc., in addition to the classical application of CeO2 as an additive in the so-called three way catalysts (TWC) for automotive exhaust treatment. Moreover, it can promote water gas shift and steam reforming reactions, favours catalytic activity at the interfacial metal-support sites. The solid solutions of ceria with Group IV transitional-metals deserve particular attention for their applicability in various technologically important catalytic processes. Mesoporous CeO2−ZrO2 solid solutions have been reported to be employed in various reactions which include CO oxidation, soot oxidation, water-gas shift reaction, and so on. Inspired by the unique and promising characteristics of ceria based mixed oxides and solid solutions for various applications, we have selected ceria-zirconia oxides for our studies. The focus of the work is the synthesis and investigation of the structural and catalytic properties of modified and pure ceria-zirconia mixed oxide.

An Efficient Multi-component Synthesis of 6-Amino-3-methyl-4-Aryl-2,4- dihydropyrano[2,3-c]Pyrazole-5-carbonitriles

Multi-component reactions are effective in building complex molecules in a single step in a minimum amount of time and with facile isolation procedures; they have high economy1–7 and thus have become a powerful synthetic strategy in recent years.8–10 The multicomponent protocols are even more attractive when carried out in aqueous medium. Water offers several benefits, including control over exothermicity, and the isolation of products can be carried out by single phase separation technique. Pyranopyrazoles are a biologically important class of heterocyclic compounds and in particular dihydropyrano[2,3-c]pyrazoles play an essential role in promoting biological activity and represent an interesting template in medicinal chemistry. Heterocyclic compounds bearing the 4-H pyran unit have received much attention in recent years as they constitute important precursors for promising drugs.11–13 Pyrano[2,3-c]pyrazoles exhibit analgesic,14 anti-cancer,15 anti-microbial and anti-inflammatory16 activity. Furthermore dihydropyrano[2,3-c]pyrazoles show molluscidal activity17,18 and are used in a screening kit for Chk 1 kinase inhibitor activity.19,20 They also find applications as pharmaceutical ingredients and bio-degradable agrochemicals.21–29 Junek and Aigner30 first reported the synthesis of pyrano[2,3-c]pyrazole derivatives from 3-methyl-1-phenylpyrazolin-5-one and tetracyanoethylene in the presence of triethylamine. Subsequently, a number of synthetic approaches such as the use of triethylamine,31 piperazine,32 piperidine,33 N-methylmorpholine in ethanol,34 microwave irradiation,35,36 solvent-free conditions,37–39 cyclodextrins (CDs),40 different bases in water,41 γ -alumina,42 and l-proline43 have been reported for the synthesis of 6-amino-4-alkyl/aryl-3-methyl- 2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles. Recently, tetraethylammonium bromide (TEABr) has emerged as mild, water-tolerant, eco-friendly and inexpensive catalyst. To the best of our knowledge, quaternary ammonium salts, more specifically TEABr, have notbeen used as catalysts for the synthesis of pyrano[2,3-c]pyrazoles, and we decided to investigate the application of TEABr as a catalyst for the synthesis of a series of pyrazole-fused pyran derivatives via multi-component reactions

Immobilization of Diastase α-amylase on to synthetic and natural polymers

Several natural and synthetic supports have been assessed for their efficiency for enzyme immobilization. Synthetic polymer materials are prepared by chemical polymerization using various monomers. As a kind of important carrier, synthetic polymer materials exhibit the advantages of good mechanical rigidity, high specific surface area, inertness to microbial attack, easy to change their surface characteristics, and their potential for bringing specific functional group according to actual needs. Hence, they have been widely investigated and used for enzyme immobilization. When it comes to the natural polymer materials, much attention has been paid to cellulose and other natural polymer materials owing to their wide range of sources, easy modification, nontoxic, and pollution-free, with a possibility of introducing wide variety of functional groups and good biocompatible properties. In this work report the use of synthetic polymer, polypyrrole and its derivatives and natural polymers coconut fiber and sugarcane bagasse as supports for Diastase α- amylase immobilization. An attempt was also made to functionalize both synthetic and natural polymers using Amino-propyl triethoxysilane. Supports and their immobilized forms were characterized via FT-IR, TG, SEM, XRD, BET and EDS techniques. Immobilization parameters were also optimized so as to prepare stable immobilized biocatalyst for starch hydrolysis.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Catalysis by Modified Pillared Clays and Porous Clay Heterostructures

In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are  Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method.  Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications.  The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process.  Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process.  Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays.  The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification.  The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers.  Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs.  In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260  Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions.  For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia.  Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction.  SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials  In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis.  In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR.  In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis.  In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS.  Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261  Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties.  Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol.  Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol.  DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method.  DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.

Studies on Advanced Oxidation Processes for the Removal of Acetamiprid from Wastewater

Pollution of water with pesticides has become a threat to the man, material and environment. The pesticides released to the environment reach the water bodies through run off. Industrial wastewater from pesticide manufacturing industries contains pesticides at higher concentration and hence a major source of water pollution. Pesticides create a lot of health and environmental hazards which include diseases like cancer, liver and kidney disorders, reproductive disorders, fatal death, birth defects etc. Conventional wastewater treatment plants based on biological treatment are not efficient to remove these compounds to the desired level. Most of the pesticides are phyto-toxic i.e., they kill the microorganism responsible for the degradation and are recalcitrant in nature. Advanced oxidation process (AOP) is a class of oxidation techniques where hydroxyl radicals are employed for oxidation of pollutants. AOPs have the ability to totally mineralise the organic pollutants to CO2 and water. Different methods are employed for the generation of hydroxyl radicals in AOP systems. Acetamiprid is a neonicotinoid insecticide widely used to control sucking type insects on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, ornamental flowers. It is now recommended as a substitute for organophosphorous pesticides. Since its use is increasing, its presence is increasingly found in the environment. It has high water solubility and is not easily biodegradable. It has the potential to pollute surface and ground waters. Here, the use of AOPs for the removal of acetamiprid from wastewater has been investigated. Five methods were selected for the study based on literature survey and preliminary experiments conducted. Fenton process, UV treatment, UV/ H2O2 process, photo-Fenton and photocatalysis using TiO2 were selected for study. Undoped TiO2 and TiO2 doped with Cu and Fe were prepared by sol-gel method. Characterisation of the prepared catalysts was done by X-ray diffraction, scanning electron microscope, differential thermal analysis and thermogravimetric analysis. Influence of major operating parameters on the removal of acetamiprid has been investigated. All the experiments were designed using central compoiste design (CCD) of response surface methodology (RSM). Model equations were developed for Fenton, UV/ H2O2, photo-Fenton and photocatalysis for predicting acetamiprid removal and total organic carbon (TOC) removal for different operating conditions. Quality of the models were analysed by statistical methods. Experimental validations were also done to confirm the quality of the models. Optimum conditions obtained by experiment were verified with that obtained using response optimiser. Fenton Process is the simplest and oldest AOP where hydrogen peroxide and iron are employed for the generation of hydroxyl radicals. Influence of H2O2 and Fe2+ on the acetamiprid removal and TOC removal by Fenton process were investigated and it was found that removal increases with increase in H2O2 and Fe2+ concentration. At an initial concentration of 50 mg/L acetamiprid, 200 mg/L H2O2 and 20 mg/L Fe2+ at pH 3 was found to be optimum for acetamiprid removal. For UV treatment effect of pH was studied and it was found that pH has not much effect on the removal rate. Addition of H2O2 to UV process increased the removal rate because of the hydroxyl radical formation due to photolyis of H2O2. An H2O2 concentration of 110 mg/L at pH 6 was found to be optimum for acetamiprid removal. With photo-Fenton drastic reduction in the treatment time was observed with 10 times reduction in the amount of reagents required. H2O2 concentration of 20 mg/L and Fe2+ concentration of 2 mg/L was found to be optimum at pH 3. With TiO2 photocatalysis improvement in the removal rate was noticed compared to UV treatment. Effect of Cu and Fe doping on the photocatalytic activity under UV light was studied and it was observed that Cu doping enhanced the removal rate slightly while Fe doping has decreased the removal rate. Maximum acetamiprid removal was observed for an optimum catalyst loading of 1000 mg/L and Cu concentration of 1 wt%. It was noticed that mineralisation efficiency of the processes is low compared to acetamiprid removal efficiency. This may be due to the presence of stable intermediate compounds formed during degradation Kinetic studies were conducted for all the treatment processes and it was found that all processes follow pseudo-first order kinetics. Kinetic constants were found out from the experimental data for all the processes and half lives were calculated. The rate of reaction was in the order, photo- Fenton>UV/ H2O2>Fenton> TiO2 photocatalysis>UV. Operating cost was calculated for the processes and it was found that photo-Fenton removes the acetamiprid at lowest operating cost in lesser time. A kinetic model was developed for photo-Fenton process using the elementary reaction data and mass balance equations for the species involved in the process. Variation of acetamiprid concentration with time for different H2O2 and Fe2+ concentration at pH 3 can be found out using this model. The model was validated by comparing the simulated concentration profiles with that obtained from experiments. This study established the viability of the selected AOPs for the removal of acetamiprid from wastewater. Of the studied AOPs photo- Fenton gives the highest removal efficiency with lowest operating cost within shortest time.

Zur Synthese von alpha-Aminoaldehyden und Aminosäuren mit alpha-quartären Zentren durch Aziridinierung funktionalisierter Olefine

Ziel dieser Arbeit war, durch Aziridinierung homochiraler 5-Methyl-4H-1,3-dioxinen eine neue Methode zur Synthese von alpha-Aminoaldehyden und den ableitbaren Aminosäuren mit alpha-quartären Zentren zu entwickeln. Die chiralen 5-Methyl-4H-1,3-dioxine sind mit hohen Enantiomerenüberschüssen durch asymmetrische Doppelbindungsisomerisierung von 5-Methylen-1,3-dioxanen zugänglich. Die Metall-katalysierte Aziridinierung der 5-Methyl-4H-1,3-dioxine mit der Nitrenquelle (N-Tosylimino)phenyliodinan führte direkt zu N-Tosyl-geschützen 4-Methyl-1,3-oxazolidin-4-carbaldehyden. Vermutlich über ein Aziridin als nicht isolierbare Zwischenstufe werden über eine Ringöffnungs-/Ringverengungsreaktion die Oxazolidinderivate gebildet, vorzugsweise in Gegenwart von Cu(I)-Katalysatoren, während die Rhodium-katalysierte Reaktion ausschließlich zu Insertionsprodukten führt. In der Cu-katalysierten Aziridinierung ist das Verhältnis von Aziridinierung/Insertion abhängig von der Katalysatorkonzentration. Die Aziridinierung mit N-(p-Nitrobenzolsulfonyl)- und N-(Trimethylsilylethylsulfonyl)- substituierten Nitrenquellen führt zu Oxazolidinderivaten mit leichter abspaltbaren Schutzgruppen. Diese Nitrenquellen können in situ aus den korrespondierenden Sulfonamiden mit Iodosobenzol dargestellt werden. Bei dem Einsatz homochiraler 4H-1,3-Dioxine ist Erhalt der Stereoinformation abhängig vom Substituenten in 2-Position der Dioxine sowie von der Polarität des Lösungsmittels. Die höchsten Selektivitäten wurden in tert-Butylmethylether erzielt. In Falle des 2-tert-Butyl-4-methyl-3-(toluol-4-sulfonyl)-1,3-oxazolidin-4-carbaldehyds kristallisiert das Hauptdiastereomer in enantiomerenreiner Form. Die Absolutkonfiguration wurde durch Röntgenkristallstrukturanalyse ermittelt. Das Anwendungspotential dieser neuen Methode konnte durch Überführen der Serinale in Aminoalkohole und alpha-Methylserin-Derivate sowie in der Synthese der unnatürlichen Aminosäure alpha-Vinylalanin gezeigt werden.

Cultivating the City: Infrastructures of abundance in urban Brazil

Urban agriculture, if it is to become integrated into the city, needs landscape architectural thinking in order to be woven into the larger urban fabric. Thinking at the scale of ecosystems running through a city creates a framework for spatial change; thinking in assemblages of stakeholders and actors creates a framework for social investment and development. These overlapping frameworks are informed and perhaps even defined by the emergent field of landscape democracy. Cultivating the City is a prospective design project seeking to embody landscape democratic principles. The intention is to reclaim the meaning of landscape as the relationship between people and place, both shaping each other. The design in question is a proposed network of urban agriculture typologies in Porto Alegre, Brazil. These hypothetical designs, emphasizing agroforestry with native species, serve as a basis for dialogue between potential stakeholders and as catalysts for future projects. This landscape architecture project sets out to be a mediator in processes of spatial evolution in order to envision just and sustainable urban landscapes.

La inclusión de la democracia en la palestra mediática: el caso colombo venezolano

Entre el 2 de febrero de 1999 y el 7 de agosto de 2002, es decir, en el momento en el que coinciden Chávez y Pastrana como presidentes, las relaciones colombo-venezolanas atravesaron por momentos casi permanentes de tensión. La naturaleza turbia y confusa en el trato bilateral, propia de este momento, no representa de por sí una rareza, puesto que la constante en las relaciones entre las dos naciones ha sido la conflictividad. Lo verdaderamente interesante de esta coyuntura es que quizá se encuentran pocos parangones en la historia en los que los medios de comunicación hayan tendido una incidencia decisiva en la política exterior. Así las cosas, la tesis de este documento expone que los medios de comunicación colombianos, (por la manera en que manejaron la información concerniente a Venezuela) dotaron de una alta dosis de conflictividad las relaciones bilaterales, al ocasionar la detonación de tres elementos explosivos: divergencias políticas, mutua incomprensión de la realidad de cada país y estilos políticos chocantes. En consecuencia, generaron una reacción en cadena de tres eslabones, cada uno de los cuales muestra una faceta propia de la influencia mediática que recibió la política exterior de Colombia frente al vecino país. El primer eslabón fue el desencuentro político-diplomático entre las dos naciones. En este nivel, las empresas de la comunicación no fueron las únicas responsables, pero sí actuaron como catalizadoras. El que denominamos segundo eslabón, se deriva del alejamiento entre las autoridades gubernamentales y consiste en que los medios pasaron a consolidarse como los canales de comunicación diplomática, lo que, a su vez, les permitió a las empresas de la comunicación imponer, como tercer eslabón, los temas de la agenda diplomática bilateral. Para sustentar estas ideas, se presentan dos análisis, uno cualitativo y otro cuantitativo, de la información noticiosa que apareció en los diarios El Colombiano de Medellín, La Opinión de Cúcuta y El Tiempo de circulación nacional, en el periodo escogido.-----While Chávez and Pastrana coincide as presidents, between February 2, 1999 and August 7, 2002, there are permanent moments of tension in the relationship between Colombia and Venezuela. The turbulence and confusion of this period does not characterize it, for conflict has been a constant factor between these two nations. What is truly interesting about this time is that there are probably few comparable moments in history when the media has had such a decisive incidence on foreign policy. Hence, this document presents the thesis that Colombian means of communication introduced a high dose of conflict in bilateral relations, by making three sensitive elements explode: political differences, mutual lack of knowledge of domestic conditions, and opposite political styles; due to how they managed information related to Venezuela. Consequently, they generated a chain reaction in three phases, which show different aspects of the influence of the media on Colombia’s foreign policy towards its neighboring country. In  the first phase, which brought out the political and diplomatic differences between the two presidents, the information companies where not solely responsible for the situation, but they did act as catalysts. During the second phase, when these differences create distance between the government authorities, the media became the means of diplomatic communication, which permitted these companies to determine the topics on the bilateral diplomatic agenda, and constitute the third phase. In order to support these ideas, two kinds of analysis are presented, a qualitative one and a quantitative one, based on information printed in the following newspapers: El Colombiano from Medellín, La Opinión from Cúcuta and El Tiempo with national coverage, during the chosen period.

New mono- and dinuclear ruthenium complexes containing the 3,5-bis(2-pyridyl)pyrazole ligand. Synthesis, characterization and applications

Se han sintetizado dos nuevos complejos mononucleares de Ru, con formula [RuCl2(Hbpp)(dmso)2], a partir de la reacción entre [RuCl2(dmso)4] y Hbpp (3,5-bis(2-piridil)pirazola). El hecho que sólo tres de los seis posibles estereoisómeros se obtengan a partir de esta reacción, se ha racionalizado en base a factores estructurales y electrónicos. Estos complejos se han caracterizado de forma estructural, espectroscópica y electroquímica. En acetonitrilo en medio básico, el isómero trans,cis-[RuCl2(Hbpp)(dmso)2] da lugar a procesos de isomerización de enlace de un ligando dmso cuando el Ru(II) se oxida a Ru(III). Las constantes termodinámicas y cinéticas para el proceso se han determinado por voltametria cíclica. La irradiación de trans,cis-[RuCl2(Hbpp)(dmso)2] y cis(out),cis-[RuCl2(Hbpp)(dmso)2] con luz UV o solar da lugar a reacciones de fotosustitución de un ligando dmso por una molécula de acetonitrilo para dar un nuevo compuesto el cual ha sido caracterizado en solución por técnicas espectroscópicas y electroquímicas. Ambos complejos resultan catalizadores útiles en la transferencia de hidrógeno de isopropanol a acetofenona, obteniéndose 1-feniletanol como único producto y un 42.1% de conversión (36.1 ciclos metálicos) a 80ºC con el isómero trans,cis-[RuCl2(Hbpp)(dmso)2], que resulta significativamente más eficaz que el complejo cis(out),cis-[RuCl2(Hbpp)(dmso)2]. La reacción de cis(out),cis-[RuCl2(Hbpp)(dmso)2] con trpy (2,2':6',2"-terpiridina) da lugar a los dos isómeros geométricos del complejo [Ru(Hbpp)(trpy)(Cl)]+, el in y el out. Estos complejos se han aislado y caracterizado por técnicas estructurales, espectroscópicas y electroquímicas. Estos cloro complejos han sido utilizados como precursores para la síntesis de los complejos análogos con ligandos aqua (in,out-[Ru(Hbpp)(trpy)(H2O)]2+) y piridina (in,out-[Ru(Hbpp)(trpy)(py)]2+), los cuales también han sido aislados y caracterizados. Las propiedades ácido-base de los aqua complejos, y del complejo out-py se han estudiado detalladamente por voltametria cíclica y mediante valoraciones espectrofotométricas ácido-base. El tratamiento matemático de los datos así obtenidos nos ha permitido determinar los valores de pKa para los distintos equilibrios de protonación de los complejos en los estados de oxidación II y III. El complejo out-aqua ha demostrado ser un buen catalizador para la oxidación electroquímica del alcohol benzílico, presumiblemente a benzaldehido. La constante de velocidad de segundo orden para el proceso ha sido determinada como 17.1 M-1 s-1, por simulación matemática. El dímero con un puente cloro, [Ru2Cl(bpp)(trpy)2]2+ ha sido preparado por dos rutas sintéticas diferentes. El dímero análogo con un puente acetato se ha obtenido por reacción del cloro dímero con un exceso de acetato sódico. El dímero con dos ligandos aqua [Ru2(bpp)(trpy)2(OH2)2]3+ puede obtenerse por hidrólisis ácida del complejo con un acetato puente o por hidrólisis básica del complejo con un puente cloro. Estos complejos han sido caracterizados por técnicas estructurales, espectroscópicas y electroquímicas. Las soluciones del dímero con dos ligandos aqua en medio ácido resultan inestables a la coordinación de aniones de la solución con el tiempo. Las propiedades ácido-base del dímero con dos aguas coordinadas han sido estudiadas por voltametria cíclica y mediante experimentos de electrólisis a potencial controlado. El pKa para la desprotonación de uno de los ligandos aqua ha sido determinado mediante una valoración espectrofotométrica ácido-base como 6.7. Este valor tan bajo de pKa se atribuye a la formación de la entidad {Ru2O2H3}, favorable termodinámicamente. Los espectros UV-vis para los distintos estados de oxidación del aqua dímero, de RuIIRuII a RuIIIRuIV, han sido obtenidos por oxidación química y electroquímica del complejo. Se han llevado a cabo estudios cinéticos de la oxidación, paso a paso, de RuII,II a RuIV,IV , y se han determinado las constantes de oxidación de segundo orden para los distintos procesos de oxidación. La capacidad del aqua dímero en la oxidación del agua a oxígeno molecular ha sido investigada en solución homogénea utilizando CeIV como oxidante. La evolución de oxígeno se ha demostrado por cromatografia de gases. Se ha obtenido una eficiencia del 73% y 18.6 ciclos catalíticos, cuando 1.83 x 10-6 moles de dímero se han mezclado con un exceso de 100 equivalentes de cerio. El dímero con dos aguas cataliza también la oxidación del agua de forma heterogénea, con el complejo adsorbido sobre una membrana de nafion, aunque la eficiencia es menor. Se ha propuesto un mecanismo intramolecular para la reacción de oxidación del agua. Consiste en la oxidación a 4 electrones del dímero, de RuII,II a RuIV,IV, el cual reacciona con el agua para formar oxígeno y revierte nuevamente al estado de oxidación II,II. Este modelo es consistente con estudios catalíticos de la evolución de oxígeno en función de las concentraciones de cerio y catalizador, llevados a cabo en solución ácida homogénea, que demuestran que la oxidación a 4 electrones del agua se encuentra catalizada por una sola molécula de complejo bajo concentraciones elevadas de cerio. La constante de pseudo-primer-orden para la evolución de oxígeno tiene un valor de 1.4 x 10-2 s-1, que es uno de los valores de constante más elevados obtenidos hasta la fecha. Desafortunadamente, el aqua dímero se desactiva durante el proceso de catálisis dando lugar a una especie naranja, la cual estamos actualmente tratando de caracterizar.

Nous complexos de pal·ladi amb lligands macrocíclics triolefínics. Estructura i aplicacions

Aquesta Tesi Doctoral està dividida en diferents capítols tots ells basats en aplicacions de macrocicles nitrogenats triolefínics de 15 membres i dels seus complexos amb metalls de transició. En primer lloc es descriu l'aplicació d'un complex macrocíclic ferrocenílic de Pd0 com a catalitzador en reaccions de Mizoroki-Heck i Suzuki emprant sals de diazoni com a agents arilants. Aquest catalitzador va proporcionar bons rendiments de productes i va poder ser recuperat i reutilitzat, essent el primer sistema catalític reciclable descrit en la reacció de Mizoroki-Heck amb sals de diazoni. La metodologia es va estendre de forma efectiva a alcohols al·lílics, però en no ser possible recuperar el catalitzador macrocíclic, es va emprar Pd(dba)2. Posteriorment es van preparar estructures macromoleculars mitjançant la introducció de diferents unitats macrocícliques sobre un espaiador. La complexació d'aquestes estructures va permetre preparar complexos tant homo (Pd0) com heterometàl·lics (Pd0, Pt0) amb bons rendiments. Els complexos homometàl·lics van resultar ser bons catalitzadors en reaccions de Suzuki i fàcilment recuperables per simple filtració. En una última part, es van preparar nous macrocicles triolefínics contenint d'un a tres grups amino lliures en l'estructura mitjançant la utilització del grup protector (2-trimetilsilil)etansulfonil (SES). Aquesta modificació estructural va permetre ampliar la capacitat coordinant dels macrocicles a altres metalls de transició, com el PdII, possibilitant noves aplicacions. Concretament es va aplicar el lligand contenint un sol grup amino lliure al reconeixement, transport i preconcentració de PdII i PtIV continguts en dissolucions aquoses.

Nous complexos mono- i dinuclears de ruteni amb lligands polipiridílics i de tipus fosfina. Síntesi, caracterització i aplicacions catalítiques

La Tesi descriu de manera completa una sèrie de complexos de ruteni amb lligands polipiridílics i lligands auxiliars de tipus fosfina, dmso, nitril o aquo. Es descriuen estudis d'isomerització (cis/trans o coordinació meridional/facial) en complexos mononuclears, a partir de tècniques espectroscòpiques. Els resultats experimentals es corroboren a partir de càlculs DFT. S'han fet també estudis d'activitat catalítica en transferència d'hidrogen per als complexos Ru-fosfina. S'han sintetitzat també complexos dinuclears de ruteni amb el lligand tetradentat Hbpp i s'ha avaluat llur activitat en la catàlisi d'oxidació d'aigua, determinant la importància de la correcta orientació relativa dels centres actius Ru=O. L'heterogeneïtzació dels complexos sobre suports conductors permet avaluar llur activitat en fase heterogènia, millorant respecte el corresponent procés en dissolució. La co-polimerització dels catalitzadors amb espècies de tipus metalocarborà, amb major dilució del catalitzador i minimització de la sobreoxidació, millora notablement els resultats, permetent diverses reutilitzacions.

Noves aproximacions a la síntesi i caracterització de poliglicols al·lílics, polihidrosiloxans i surfactants copolimèrics. Avaluació d'aquests surfactants en formulacions de poliuretà

Els polímers són una sèrie de compostos que troben un ampli ventall d'aplicacions en la indústria actual. Un exemple són les espumes de poliuretà, estructures de tipus cel·lular obtingudes mitjançant la reacció química entre compostos de tipus isocianat i compostos de tipus poliol (polièters amb diferent nombre de grups hidroxil). És imprescindible l'ús d'additius d'estructura tensioactiva (surfactants de silicona) per estabilitzar el procés d'espumació i per proporcionar una estructura cel·lular ordenada i homogènia en mida i distribució. La síntesis i caracterització de les molècules precursores (polihidrosiloxans i polièters al·lílics), l'estudi de la reacció d'hidrosililació com a via d'obtenció dels diferents surfactants per reacció d'addició entre els polihidrosiloxans i els polièters al·lílics i la caracterització i avaluació en formulacions comercials de poliuretà dels surfactants sintetitzats han constituït els objectius del present treball. MEMÒRIA La Tesi Doctoral ha estat presentada seguint el següent esquema: CAPÍTOL I. INTRODUCCIÓ A LA QUÍMICA DEL POLIURETÀ. Es presenten els principis de la química del poliuretà, fent esment dels recents avenços en la síntesis i caracterització d'aquests compostos polimèrics, així com un apartat concret centrat en els surfactants de silicona. Es presenten les estructures habituals d'aquests compostos comercials i es detallen les reaccions de síntesi i les característiques físiques que aquests compostos proporcionen a les espumes de poliuretà. CAPÍTOL II. OBJECTIUS. 1.- Síntesis y caracterització d'una àmplia gamma de poliglicols al·lílics i de polihidrosiloxans amb grups hidrur reactius, ambdós precursors d'estructures polimèriques de tipus surfactant. 2.- Estudi de la reacció d'hidrosililació com a via de formació d'enllaços Si-C no hidrolitzables, mitjançant la reacció d'addició entre els substrats al·lílics insaturats i els polisiloxans amb grups hidrur reactius. 3.- Caracterització de les estructures polimèriques de tipus surfactant sintetitzades i avaluació d'aquestes en formulacions de poliuretà, a fi de relacionar l'estructura química d'aquests oligómers amb els efectes físics que originen en l'espuma de poliuretà. CAPÍTOL III. SÍNTESI I CARACTERITZACIÓ DE SUBSTRATS AL·LÍLICS INSATURATS DE TIPUS POLIGLICOL. S'han caracteritzat per HPLC-UV una sèrie de polietilenglicols comercials. S'ha estudiat la reacció de derivatització al·lílica sobre els grups hidroxil dels polièters comercials (PEG, PPG i copolímers PEG-PPG) i s'han caracteritzat exhaustivament els productes sintetitzats (1H,13C-RMN, GC, GC-MS, FTIR, ESI-MS, HPLC-UV). S'ha iniciat un estudi de polimerització aniònica sobre nous epòxids amb un punt de diversitat molecular, sintetitzant-se i caracteritzant-se els corresponents nous polièters obtinguts. CAPÍTOL IV. SÍNTESI I CARACTERITZACIÓ DE POLIHIDROSILOXANS REACTIUS. S'estudia la síntesis de polihidrosiloxans amb grups hidrur reactius, mitjançant la reacció de polimerització aniònica d'obertura d'anell ("AROP, anionic ring opening polimerization") i mitjançant la reacció de polimerització per equilibració catiònica. Es presenta una caracterització exhaustiva dels productes sintetitzats i es descriu la naturalesa de la microestructura polimèrica a partir de la distribució bivariant dels copolímers PDMS-co-PHMS (poli(dimetilsiloxà)-co-poli(hidrometilsiloxà)). CAPÍTOL V. ESTUDI SISTEMÀTIC DE LA REACCIÓ D'HIDROSILILACIÓ. S'ha estudiat la reacció d'hidrosililació amb la finalitat de sintetitzar estructures copolimèriques poliglicol-polisiloxà a partir de la reacció de polisiloxans hidrur reactius i polièters al·lílics. S'han provat diferents catalitzadors (Pt/C 5%, cat. de Speier i cat. de Karstedt), s'han sintetitzat diferents estructures tensoactives (lineals i ramificades) i s'ha modelitzat les diferents reaccions secundàries observades, per presentar un estudi mecanístic de la reacció d'hidrosililació aplicada a la síntesis de molècules d'elevat PM a partir de la reacció entre substrats al·lílics insaturats i polihidrosiloxans. CAPÍTOL VI. AVALUACIÓ DELS SURFACTANTS EN FORMULACIONS DE POLIURETÀ. S'ha estudiat la idoneïtat dels surfactants de silicona sintetitzats en diferents formulacions de poliuretà comercials. S'ha relacionat el comportament físic d'aquests surfactants en les espumes de poliuretà amb la seva estructura química a partir de l'anàlisi per microscòpia electrònica de rastreig. CAPÍTOL VII. CONCLUSIONS. S'han esposat les conclusions extretes de cada capítol.