Studies in Fuzzy Commutative Algebra

The main objective of this thesis was to extend some basic concepts and results in module theory in algebra to the fuzzy setting.The concepts like simple module, semisimple module and exact sequences of R-modules form an important area of study in crisp module theory. In this thesis generalising these concepts to the fuzzy setting we have introduced concepts of ‘simple and semisimple L-modules’ and proved some results which include results analogous to those in crisp case. Also we have defined and studied the concept of ‘exact sequences of L-modules’.Further extending the concepts in crisp theory, we have introduced the fuzzy analogues ‘projective and injective L-modules’. We have proved many results in this context. Further we have defined and explored notion of ‘essential L-submodules of an L-module’. Still there are results in crisp theory related to the topics covered in this thesis which are to be investigated in the fuzzy setting. There are a lot of ideas still left in algebra, related to the theory of modules, such as the ‘injective hull of a module’, ‘tensor product of modules’ etc. for which the fuzzy analogues are not defined and explored.

Studies on the catalysis by sulfated mixed oxides of tin with some rare earth elements

A comparative study of acid-base properties and catalytic activity of Sn-La and Sn-Sm mixed oxides and their corresponding sulfate modified analogues are reported in this thesis. The catalytic activity and product selectivity in the decomposition of alcohols are correlated with the acid-base and redox properties of the catalyst systems under study The effect of catalyst preparation, pretreatment and various reaction parameters on the catalytic activity of sulfate modified oxides is investigated in the oxidative dehydrogenation reactions The experimental conditions are optimised to synthesise industrially important organic chemicals viz. 2,6 xylenol, o-cresol, N-methylanilne and N,N-dimethylaniline employing the mixed oxide systems. The effect of sulfate treatment on the catalytic activity of these systems in the alkylation reactions of phenol, anisole and aniline is also investigated and the merits and demerits of sulfate treatment are highlighted.

"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

Temperature dependent polarized Raman spectra of nonaaqualanthanoid (Pr) single crystal

Polarized Raman spectral changes with respect to temperature were investigated for Pr(BrO3)3·9H2O single crystals. FTIR spectra of hydrated and deuterated analogues were also recorded and analysed. Temperature dependent Raman spectral variation have been explained with the help of the thermograms recorded for the crystal. Factor group analysis could propose the appearance ofBrO3 ions at sites corresponding to C3v (4) and D3h (2). Analysis of the vibrational bands at room temperature confirms a distorted C3v symmetry for the BrO3 ion in the crystal. From the vibrations of water molecules, hydrogen bonds of varying strengths have also been identified in the crystal. The appearance υ1 mode of BrO3− anion at lower wavenumber region is attributed to the attachment of hydrogen atoms to the BrO3− anion. At high temperatures, structural rearrangement is taking place for bothH2Omolecule and BrO3 ions leading to the loss ofwater molecules and structural reorientation of bromate ions causing phase transition of the crystal at the temperature of 447 K.

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.

Synthesis and characterisation of novel nitrogen and fluorine containing spirobifluorene derivatives for electronic applications and crystal engineering

Among organic materials, spirobifluorene derivatives represent a very attractive class of materials for electronic devices. These compounds have high melting points, glass transitions temperatures and morphological stability, which makes these materials suitable for organic electronic applications. In addition, some of spirobifluorenes can form porous supramolecular associations with significant volumes available for the inclusion of guests. These molecular associations based on the spirobifluorenes are noteworthy because they are purely molecular analogues of zeolites and other microporous solids, with potential applications in separation, catalysis, sensing and other areas.

CODAMAT: a modern analogue techinque for compositional data

The quantitative estimation of Sea Surface Temperatures from fossils assemblages is a fundamental issue in palaeoclimatic and paleooceanographic investigations. The Modern Analogue Technique, a widely adopted method based on direct comparison of fossil assemblages with modern coretop samples, was revised with the aim of conforming it to compositional data analysis. The new CODAMAT method was developed by adopting the Aitchison metric as distance measure. Modern coretop datasets are characterised by a large amount of zeros. The zero replacement was carried out by adopting a Bayesian approach to the zero replacement, based on a posterior estimation of the parameter of the multinomial distribution. The number of modern analogues from which reconstructing the SST was determined by means of a multiple approach by considering the Proxies correlation matrix, Standardized Residual Sum of Squares and Mean Squared Distance. This new CODAMAT method was applied to the planktonic foraminiferal assemblages of a core recovered in the Tyrrhenian Sea. Kew words: Modern analogues, Aitchison distance, Proxies correlation matrix, Standardized Residual Sum of Squares

Uso de Dienogest para el tratamiento de la endometriosis: revision sistematica de la literatura.

La endometriosis es una entidad frecuente en ginecología para la que desafortunadamente aun no se tiene un tratamiento del todo efectivo. En los últimos años se ha propuesto el uso de Dienogest, una progestina selectiva, con buenos resultados. Objetivo: Realizar una revisión sistemática de la literatura para determinar la efectividad del Dienogest para el tratamiento de la endometriosis. Materiales y métodos: Se realizó una búsqueda sistemática y ampliada de ensayos clínicos acerca de la efectividad del Dienogest en el manejo de la endometriosis. Resultados: La efectividad del dienogest para el tratamiento de la endometriosis es equiparable al de los análogos de GnRH, tiene un perfil de seguridad adecuado y su uso prolongado no está limitado por la presentación de eventos adversos.

[177Lu – DOTA – Tyr3] – OCTREOTATE para el tratamiento de tumores neuroendocrinos gastroenteropancreáticos. Revisión sistemática de la literatura.

Introducción: los tumores neuroendocrinos gastroenteropancreáticos se diagnostican en estadio avanzado en 60 - 80% de los pacientes y las opciones terapéuticas son limitadas. Se realizó una revisión sobre el beneficio clínico del tratamiento con [177Lu - DOTA - Tyr3] - Octreotate en pacientes con enfermedad metastásica o inoperable. Objetivos: evaluar la eficacia, impacto en calidad de vida y toxicidad de la terapia con 177Lu DOTATE en pacientes con tumores neuroendocrinos gastroenteropancreáticos avanzados. Materiales y Métodos: se condujo una revisión sistemática de la literatura mediante la búsqueda de estudios clínicos prospectivos y retrospectivos en bases electrónicas (MEDLINE, EMBASE, LILACS, SCIELO, OVID y la Biblioteca Cochrane) de cualquier idioma, año y estado de publicación. Se incluyeron 5 estudios, por la heterogeneidad existente entre los estudios no se realizó un metaanálisis. Resultados: la respuesta tumoral global fue del 45 - 57%, la enfermedad permaneció estable en 27% - 38% y progresó en 6% - 21% de casos en las series incluidas. El tiempo libre de progresión osciló entre 31 - 40 meses y la sobrevida global de 31– 51 meses. Se observó toxicidad hematológica grado 3-4 hasta en 9.5% de pacientes. Hubo mejoría significativa en la calidad de vida de pacientes tratados con 177LuDOTATATE. Conclusiones: la terapia con 177Lu- DOTATATE ofrece un beneficio clínico a los pacientes con tumores neuroendocrinos bien diferenciados avanzados por su impacto positivo en calidad de vida, control de síntomas, ralentiza la progresión tumoral y su toxicidad es baja.

Design and synthesis of short antimicrobial peptides for plant protection. Study of their mode of action

Aquesta tesi doctoral està basada en el desenvolupament de nous agents antimicrobians derivats del pèptid híbrid cecropina A-melitina WKLFKKILKVL-NH2 (Pep3) que siguin sostenibles i útils per al control de malalties de plantes. Es van dissenyar i sintetitzar més de 133 anàlegs de Pep3 mitjançant química combinatòria. Es van obtenir anàlegs de Pep3 amb una elevada activitat contra fitopatògens i que presentaven baixa toxicitat. Els millors anàlegs van presentar eficàcies comparables amb pesticides de referència en la prevenció d'infeccions causades per fitopatògens. Es va estudiar el mecanisme d'acció de KKLFKKILKYL-NH2 (BP100) investigant la seva interacció amb models de membrana mitjançant tècniques espectroscòpiques. Es va observar la capacitat de BP100 a induir la permeabilització, la neutralització, i l'agregació de vesícules lipídiques aniòniques a una determinada concentració llindar. Es va deduir una equació que relaciona la CMI d'un pèptid antimicrobià amb la constant de partició i la concentració llindar en la membrana.

Síntesi i Reactivitat de nous Macrocicles Nitrogenats Poliinsaturats

En aquesta tesi s'han sintetitzat macrocicles nitrogenats poliinsaturats de diferents mides i s'ha estudiat la seva reactivitat. S'han preparat macrocicles de quinze i setze baules triacetilènics i de quinze baules contenint dos triples i un doble enllaç a l'estructura. S'ha estudiat la ciclotrimerització [2+2+2] d'aquests macrocicles catalitzada per metalls de transició en dissolvents orgànics convencionals o en sals foses. S'han sintetitzat complexos de rodi contenint un lligand carbènic N-heterocíclic per tal d'utilitzar-los com a catalitzadors alternatius al complex de Wilkinson en les reaccions de ciclotrimerització dels macrocicles poliinsaturats i d'altres anàlegs oberts. Els complexos carbènics sintetitzats han presentat una eficiència lleugerament superior a la del catalitzador de Wilkinson. També s'ha iniciat un estudi mecanístic de la cicloisomerització d'aquests macrocicles induïda tèrmicament. Finalment, s'han preparat macrocicles de catorze i dinou baules contenint un nucli endiínic a més d'altres insaturacions i s'ha estudiat la corresponent ciclació de Bergman en estat sòlid.

Mosteiro de S. Salvador de Paço de Sousa Contributo para a sua reabilitação arquitetónica

Este trabalho pretende contribuir para a reabilitação do Mosteiro de S. Salvador de Paço de Sousa assente na interpretação espacial do complexo monástico desde a fundação à extinção da comunidade religiosa, com particular nota para a intervenção efetuada pela DGEMN - Direção Geral dos Edifícios e Monumentos Nacionais, no segundo quartel do século XX. Procura trazer pela primeira vez à luz uma representação dos seus espaços, usos e funções ao longo do tempo com recurso a desenhos, esquemas e imagens para permitir a apreensão do conjunto em determinadas fases da história e por consequência fundamentar uma eventual intervenção. O estudo fundamenta-se na recolhe de dados escritos que permitam aferir a vivência dos espaços, sua simbologia e utilidade, nomeadamente através de referências históricas e de carater simbólico e documentação gráfica que permita avaliar e comparar o assunto de estudo com outros exemplos e situações análogas. O cruzamento de dados analisados resulta na sua simbolização gráfica, de forma a veicular o entendimento espacial e simbólico, que remete o real conhecimento da arquitetura do Mosteiro de S. Salvador de Paço de Sousa e, por comparação, viabiliza um ponto de partida para futuras intervenções, seja deste mosteiro, seja de edifícios de características semelhantes.

Synteza analogów nukleozydów i pronukleotydów z zastosowaniem reakcji Huisgena katalizowanej jonami miedzi(I) oraz badania ich aktywności biologicznej

Wydział Chemii: Pracownia Chemii Nukleozydów i Nukleotydów

Olfactory attractiveness of mixtures of some host plant and conspecific semiochemicals to the banana weevil Cosmopolites sordidus (Germar, 1824)

A simple "Y" shaped olfactometer was used in laboratory studies on the olfactory attractiveness of mixtures in various proportions of industrial analogues of some host plant and conspecific-based semiochemicals, or their combinations with banana rhizome, to the banana weevil. The aim was to identify factors that influence their attractiveness to the weevil, and consider the possibility for their use as lures for trapping the weevil in the field. Cosmopolites sordidus was attracted to the mixtures at specific concentrations and proportions of constituent chemicals. 6-methylhept-5-en-2-one was only attractive on its own at 1 µl/100 ml and in mixture with 4- mercaptophenol, but not at 10 µl, 0.01 µl, or in combination with banana rhizome. 4-mercaptohpenol and 2-n-butylfuran, which were compatible with most host plant-based chemicals and were attractive as a mixture, were perceived to be key elements in the composition of attractants to the weevil. It was concluded that in addition to the composition, other factors that may determine the attractiveness or otherwise of a mixture to C. sordidus are the proportions and concentrations of the constituent chemicals.

Approaches to the synthesis of 3-fluoroshikimic acids

Exploitation of the dual dehydrating and fluorodeoxygenating properties of the dialkylaminosulfurtrifluorides has allowed access to the C3-fluorinated analogues of (-)-shikimic acid. (C) 2004 Elsevier Ltd. All rights reserved.