Photoinduced oxidation of benzhydrol over lanthana modified sol-gel titania

Lanthana modified sol-gel titania is prepared through particulate sol-gel route and the physico-chemical characterizations of the prepared systems were done using X-Ray diffration, EDX, BET surface area-pore volume measurements and TG-DTG analysis. Benzophenone was observed to be the sole product in the TiO2 photocatalyzed oxidation of benzhydrol in oxygen purged acetonitrile. The influence of various parameters, like irradiation time, amount of catalyst, concentration of the catalyst and other factors on the photocatalytic oxidation has been investigated. The proposed mechanism envisages the involvement of a superoxide radical anion.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

A sensitive fibre optic pH sensor using multiple sol-gel coatings

The fabrication and characterization of a fibre optic pH sensor based on evanescent wave absorption is presented. The unclad portion of a multi-mode optical fibre is coated with a pH sensitive dye, which is immobilized by the sol–gel route. The sensitivity of the device has been found to increase when multiple sol–gel coatings are used as the sensing region. The dynamic range and the temporal response of the sensor are investigated for two different dyes, namely bromocresol purple and bromocresol green. The performance of the device is evaluated in terms of the results obtained during actual measurements.

Sol-Gel Alumina Nano Composites for Functional Applications

The thesis entitled "Sol-Gel Alumina Nano Composites for Functional Applications" investigate sol-gel methods of synthesis of alumina nanocomposites special reference to alumina-aluminium titanate and alumina-lanthanum phosphate composites. The functional properties such as thermal expansion coefficient and thermal shock resistance, machinability of composites as well as thermal protection are highlighted in addition to novel approach in synthesis of composites.A general introduction of alumina matrix composites materials, followed by brief coverage of alumina-aluminium titanate and alumina-lanthanum phosphate composites is highlight of the first chapter. The second chapter deals with the sol-gel synthesis of aluminium titanate and alumina-aluminium titanate composite. The synthesis of machinable substrate, based on alumina and lanthanum phosphate forms the basis of the third chapter. The fourth chapter describes the sol-gel coating of mullite on SiC substrate for the possible gas filtration application.

Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

Aqueous Sol-gel Process for Nanocrystalline Photocatalytic Titania, Transparent Functional Coatings and Ceramic Membrane

The present thesis develops from the point of view of titania sol-gel chemistry and an attempt is made to address the modification of the process for better photoactive titania by selective doping and also demonstration of utilization of the process for the preparation of supported membranes and self cleaning films.A general introduction to nanomaterials, nanocrystalline titania and sol-gel chemistry are presented in the first chapter. A brief and updated literature review on sol-gel titania, with special emphasis on catalytic and photocatalytic properties and anatase to rutile transformation are covered. Based on critical assessment of the reported information the present research problem has been defined.The second chapter describes a new aqueous sol-gel method for the preparation of nanocrystalline titania using titanyl sulphate as precursor. This approach is novel since no earlier work has been reported in the same lines proposed here. The sol-gel process has been followed at each step using particle size, zeta potential measurements on the sol and thermal analysis of the resultant gel. The prepared powders were then characterized using X-ray diffraction, FTIR, BET surface area analysis and transmission electron microscopy.The third chapter presents a detailed discussion on the physico-chemical characterization of the aqueous sol-gel derived doped titania. The effect of dopants such as tantalum, gadolinium and ytterbium on the anatase to rutile phase transformation, surface area as well as their influence on photoactivity is also included. The fourth chapter demonstrates application of the aqueous sol-gel method in developing titania coatings on porous alumina substrates for controlling the poresize for use as membrane elements in ultrafiltration. Thin coatings having ~50 nm thickness and transparency of ~90% developed on glass surface were tested successfully for self cleaning applications.

Structural, magnetic and electrical properties of the sol-gel prepared Li0.5Fe2.5O4 fine particles

Fine particles of lithium ferrite were synthesized by the sol-gel method. By subsequent heat treatment at different temperatures, lithium ferrites of different grain sizes were prepared. A structural characterization of all the samples was conducted by the x-ray diffraction technique. A grain size of around 12 nm was observed for Li0.5Fe2.5O4 obtained through the sol-gel method. Magnetic properties of lithium ferrite nanoparticles with grain size ranging from 12 to 32 nm were studied. Magnetization measurements showed that Li0.5Fe2.5O4 fine particles exhibit a deviation from the predicted magnetic behaviour. The as-prepared sample of lithium ferrite showed a maximum saturation magnetization of 75 emu g−1. Variation of coercivity is attributed to the transition from multi-domain to single domain nature. Dielectric permittivity and ac conductivity of all the samples were evaluated as a function of frequency, temperature and grain size. Variation of permittivity and ac conductivity with frequency reveals that the dispersion is due to the Maxwell–Wagner type interfacial polarization

Influence of the buffer environment on the Relative Biological Effectiveness of carbon ion radiation, investigated by Scanning Force Microscopy and gel electrophoresis

This work focuses on the analysis of the influence of environment on the relative biological effectiveness (RBE) of carbon ions on molecular level. Due to the high relevance of RBE for medical applications, such as tumor therapy, and radiation protection in space, DNA damages have been investigated in order to understand the biological efficiency of heavy ion radiation. The contribution of this study to the radiobiology research consists in the analysis of plasmid DNA damages induced by carbon ion radiation in biochemical buffer environments, as well as in the calculation of the RBE of carbon ions on DNA level by mean of scanning force microscopy (SFM). In order to study the DNA damages, besides the common electrophoresis method, a new approach has been developed by using SFM. The latter method allows direct visualisation and measurement of individual DNA fragments with an accuracy of several nanometres. In addition, comparison of the results obtained by SFM and agarose gel electrophoresis methods has been performed in the present study. Sparsely ionising radiation, such as X-rays, and densely ionising radiation, such as carbon ions, have been used to irradiate plasmid DNA in trishydroxymethylaminomethane (Tris buffer) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES buffer) environments. These buffer environments exhibit different scavenging capacities for hydroxyl radical (HO0), which is produced by ionisation of water and plays the major role in the indirect DNA damage processes. Fragment distributions have been measured by SFM over a large length range, and as expected, a significantly higher degree of DNA damages was observed for increasing dose. Also a higher amount of double-strand breaks (DSBs) was observed after irradiation with carbon ions compared to X-ray irradiation. The results obtained from SFM measurements show that both types of radiation induce multiple fragmentation of the plasmid DNA in the dose range from D = 250 Gy to D = 1500 Gy. Using Tris environments at two different concentrations, a decrease of the relative biological effectiveness with the rise of Tris concentration was observed. This demonstrates the radioprotective behavior of the Tris buffer solution. In contrast, a lower scavenging capacity for all other free radicals and ions, produced by the ionisation of water, was registered in the case of HEPES buffer compared to Tris solution. This is reflected in the higher RBE values deduced from SFM and gel electrophoresis measurements after irradiation of the plasmid DNA in 20 mM HEPES environment compared to 92 mM Tris solution. These results show that HEPES and Tris environments play a major role on preventing the indirect DNA damages induced by ionising radiation and on the relative biological effectiveness of heavy ion radiation. In general, the RBE calculated from the SFM measurements presents higher values compared to gel electrophoresis data, for plasmids irradiated in all environments. Using a large set of data, obtained from the SFM measurements, it was possible to calculate the survive rate over a larger range, from 88% to 98%, while for gel electrophoresis measurements the survive rates have been calculated only for values between 96% and 99%. While the gel electrophoresis measurements provide information only about the percentage of plasmids DNA that suffered a single DSB, SFM can count the small plasmid fragments produced by multiple DSBs induced in a single plasmid. Consequently, SFM generates more detailed information regarding the amount of the induced DSBs compared to gel electrophoresis, and therefore, RBE can be calculated with more accuracy. Thus, SFM has been proven to be a more precise method to characterize on molecular level the DNA damage induced by ionizing radiations.

Efectividad de morfina intratecal versus endovenosa / histerectomía vaginal en el Hospital Occidente de Kennedy

Introducción: la histerectomía vaginal es una cirugía frecuente, esta investigación comparo dos vías de suministro de opiáceos: intratecal y endovenosa en un estudio realizado en el Hospital Occidente de Kennedy. Método: Estudio prospectivo observacional comparando dolor utilizando la escala de dolor numérica verbal y determinando los requerimientos de morfina de rescate y o Aines, describiendo la presencia de efectos secundarios del uso de opiáceos en dos grupos. Resultados: Participaron 48 mujeres entre 40 y 65 años con ASA I y II. Manejadas con morfina intratecal fueron 28 y 20 con morfina intravenosa, la dosis intratecal fueron de 80 microgramos y las intravenosas de entre 3 y 5 mg en bolo. El dolor se evaluó a las 6, 12 y 24 horas del procedimiento quirúrgico. A las 6, 12 y 24 horas se encontró diferencia significativa p< 0.0001). Se presentaron 28% que usaron el rescate con intratecal, 100% de los casos con morfina endovenosa lo requirió. El uso de AINES se encontró que solo el 3,6% de los casos manejado con morfina intratecal requirieron uso de AINES en cambio las manejadas con endovenosa fue 80%. El tiempo trascurrido entre la dosis de opiáceos y el requerimiento de morfina tuvo una diferencia que fue significativa (p=0,000008). Las nauseas en 14% y el vomito en 7,1% de los manejados con opiáceos intratecales en cambio con endovenosos tuvieron 70% y 35% respectivamente. Se encontró diferencia significativa en estas dos variables pero no en el prurito, a pesar que se encontró más frecuente en los casos manejados con intratecal. Conclusión: pacientes con morfina intratecal tiene más efecto prolongado de analgesia y es probable que necesiten menos dosis de rescate, con igual nausea, vomito y mas prurito.

Concordancia entre citologia cervico vaginal anormal, colposcopia y biopsia de cervix de usuarias de la Clinica Colombia

El cáncer de cuello uterino, es una de las principales causas de morbimortalidad por cáncer a nivel mundial, el cual se perfila como un problema de salud pública; que gracias a la introducción de la toma de citología cervico vaginal como prueba de tamizaje, para detección temprana de cáncer de cuello uterino, ha venido en descenso. La sociedad Americana de Cáncer en estado Unidos, estima 11.270 casos nuevos para el 2009 y a nivel mundial, casi 500.000 casos nuevos (1,2). Actualmente, según las últimas estadísticas del Instituto Nacional de Cancerología 2009, comprende un 19,1% de casos nuevos. En el siguiente estudio se realizó un análisis descriptivo de concordancia, entre la citología cervico vaginal anormal, con el reporte de colposcopia y el estudio histológico (biopsia de cérvix); así como las principales alteraciones citológicas, según la clasificación de Bethesda que se presentan en las pacientes que son remitidas a la consulta de Ginecología Oncológica de la clínica Colombia. Los resultados obtenidos del estudio, nos mostró una concordancia kappa pobre a débil entre las variables: citología cervico vaginal anormal, colposcopia y biopsia de cérvix, en la Clínica Universitaria Colombia. Se recomienda realizar nuevos estudios de concordancia, previa modificación del informe de colposcopia de la CUC, para así poder unificar todos los conceptos, con el sistema de Bethesda, y el histológico y obtener un mejor resultado de concordancia.

Longitud cervical como predictor de exito en induccion de trabajo de parto en nuliparas

La inducción del trabajo de parto ha demostrado aumentar simultáneamente las tasas de cesárea, especialmente en nulíparas con cérvix clínicamente desfavorables. Ya que la valoración clínica del cérvix es un método subjetivo, aunque ampliamente utilizado, el objetivo del presente estudio fue determinar la utilidad de la medición ecográfica de la longitud cervical comparándola con el puntaje de Bishop, en la predicción del éxito de la inducción del parto en las pacientes nulíparas en el servicio de Obstetricia del Hospital Universitario Clínica San Rafael, Bogotá. Materiales y métodos: Se realizó un estudio observacional, evaluando una cohorte prospectiva de 80 gestantes a quienes se les realizó valoración ultrasonográfica y clínica del cérvix antes de iniciar la inducción del trabajo de parto. Resultados: El análisis bivariado demostró que las pacientes con longitud cervical >20mm tienen 1.57 veces la probabilidad de tener parto por cesárea (RR 1.57 IC95% 1.03-2.39 p <0.05). De manera similar las pacientes con puntaje de Bishop 0 a 3 tienen 2.33 veces la probabilidad de tener parto por cesárea (RR 2.33 IC95% 1.28-4.23 p <0.05). La regresión logística binaria demostró que la edad materna y la longitud cervical fueron los únicos parámetros independientes con significancia estadística para predecir el éxito de la inducción. Conclusiones: La medición ecográfica de la longitud cervical tiene mayor utilidad que la valoración clínica del cérvix en la predicción del éxito de la inducción del parto en nulíparas.

Gel vs aceite mineral en el tratamiento del fotoenvejecimiento de manos con luz pulsada intensa

Introducción: En el tratamiento con Luz Pulsada Intensa (LPI) para el fotoenvejecimiento de las manos no se encuentran estudios que evidencien si existe alguna diferencia estadísticamente significativa en el grado de efectividad y seguridad al utilizar gel o aceite mineral como medios de acople. Objetivo: Determinar la efectividad y seguridad terapéutica en el uso de gel vs aceite mineral. Materiales y Métodos: Estudio observacional analítico de cohorte retrospectivo que involucró 29 pacientes. Realizado en tres fases; selección y recolección de las historias clínicas, evaluación fotográfica de registros pre tratamiento y pos tratamiento con determinación del grado de mejoría global en el fotoenvejecimiento de las manos por parte de tres evaluadores cegados, y análisis estadístico de los datos obtenidos por medio de las pruebas de Mann Whitney y Wilcoxon. Resultados: Se encontró mejoría dada por disminución en un grado del fotoenvejecimiento para los dos medios de acople con la misma significancia estadística. La percepción subjetiva mostró mejoría en todos los pacientes evaluados. La seguridad es similar en los dos grupos pero se evidenció mayor severidad en los efectos secundarios con el uso de aceite, con diferencias estadísticamente significativas en los efectos moderados y severos. Conclusión: La efectividad es la misma independiente del medio de acople que se use. La seguridad a pesar de evidenciar un perfil similar es mayor con el uso de gel en cuanto a la menor severidad de los efectos presentados. Se requieren más estudios de tipo ensayos clínicos controlados que permitan determinar una mayor evidencia.

Four year efficacy of prophylactic human papillomavirus quadrivalent vaccine against low grade cervical, vulvar, and vaginal intraepithelial neoplasia and anogenital warts: randomised controlled trial

Objectives: To evaluate the prophylactic efficacy of the human papillomavirus (HPV) quadrivalent vaccine in preventing low grade cervical, vulvar, and vaginal intraepithelial neoplasias and anogenital warts (condyloma acuminata). Design: Data from two international, double blind, placebo controlled, randomised efficacy trials of quadrivalent HPV vaccine (protocol 013 (FUTURE I) and protocol 015 (FUTURE II)). The trials were to be 4 years in length, and the results reported are from final study data of 42 months' follow-up. Setting: Primary care centres and university or hospital associated health centres in 24 countries and territories around the world. Participants: 17 622 women aged 16-26 years enrolled between December 2001 and May 2003. Major exclusion criteria were lifetime number of sexual partners (>4), history of abnormal cervical smear test results, and pregnancy. Intervention: Three doses of quadrivalent HPV vaccine (for serotypes 6, 11, 16, and 18) or placebo at day 1, month 2, and month 6. Main outcome measures: Vaccine efficacy against cervical, vulvar, and vaginal intraepithelial neoplasia grade I and condyloma in a per protocol susceptible population that included subjects who received all three vaccine doses, tested negative for the relevant vaccine HPV types at day 1 and remained negative through month 7, and had no major protocol violations. Intention to treat, generally HPV naive, and unrestricted susceptible populations were also studied. Results: In the per protocol susceptible population, vaccine efficacy against lesions related to the HPV types in the vaccine was 96% for cervical intraepithelial neoplasia grade I (95% confidence interval 91% to 98%), 100% for both vulvar and vaginal intraepithelial neoplasia grade I (95% CIs 74% to 100%, 64% to 100% respectively), and 99% for condyloma (96% to 100%). Vaccine efficacy against any lesion (regardless of HPV type) in the generally naive population was 30% (17% to 41%), 75% (22% to 94%), and 48% (10% to 71%) for cervical, vulvar, and vaginal intraepithelial neoplasia grade I, respectively, and 83% (74% to 89%) for condyloma. Conclusions: Quadrivalent HPV vaccine provided sustained protection against low grade lesions attributable to vaccine HPV types (6, 11, 16, and 18) and a substantial reduction in the burden of these diseases through 42 months of follow-up. Trial registrations: NCT00092521 and NCT00092534.

Improvement of heat-induced gel properties of porcine plasma

L'objectiu és millorar els gels de plasma porcí induïts per calor a pH àcid utilitzant transglutaminasa microbiana (MTGasa). El tractament millora textura i CRA dels gels a pH 5,5, però les millores no són suficients per recuperar les pèrdues degut a l'acidificació. L'estructura globular de les proteïnes dificulta l'atac enzimàtic. La reactivitat de l'enzim no millora amb l'addició de cisteïna a plasma amb MTGasa. El tractament del plasma amb MTGasa sota alta pressió (HP) millora la duresa dels gels. No obstant, la CRA només millora lleugerament. La duresa es pot incrementar mantenint les solucions de plasma pressuritzat sota refrigeració, encara que no millora la CRA. Es pot concloure que les pèrdues en la textura dels gels de plasma induïts per calor a pH àcid es poden recuperar parcialment tractant amb MTGasa, especialment afegint cisteïna o sota HP. Encara que la CRA només es veu lleugerament millorada en el segon cas.