Sinterabilidade de pós de precursor vitrocerâmico do sistema LZSA tratados por troca iônica

Ion exchange method was employed by means of surface modification of the glass powders of LZSA (Li2O-ZrO2-SiO2-Al2O3) system submitted to a 70wt% NaNO3/30wt% NaSO4 bath salt followed by a heat treatment. Chemical analysis by X-ray fluorescence was used to evaluate the efficiency of ion exchange, while optical dilatometry was employed to evaluate sintering of compacts. Evaluation of the structure of sintered bodies was made by scanning electron microscopy. Substitution of Li+ ions by Na+ ions on the surface of powders during heat treatments of 450 and 600 ºC for 2-10 h promoted an increase in densification of the sintered bodies.

SYNGAS PRODUCTION FROM CO2-REFORMING OF CH4 OVER SOL-GEL SYNTHESIZED Ni-Co/Al2O3-MgO-ZrO2 NANOCATALYST: EFFECT OF ZrO2 PRECURSOR ON CATALYST PROPERTIES AND PERFORMANCE

Ni-Co/Al2O3-MgO-ZrO2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO2-reforming of CH4. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH4 and CO2 conversions were 97.2 and 99% at 850 ºC, respectively. Furthermore, NCAMZ-ZNS demonstrated a stable yield with H2/CO close to unit value during the 1440 min stability test.

Estudo da decomposição térmica de oxalato de estrôncio dopado com cério(III) como precursor de materiais luminescentes

Este trabalho trata da obtenção de SrC2O4, Ce2(C2O4)3, e SrC2O4 dopado com diferentes porcentagens de Ce3+ como precursores do luminóforo azul Sr2CeO4. Os precursores preparados foram estudados por TG e DTA. Uma mistura contendo SrC2O4 e Ce2(C2O4)3 na relação 4:1 respectivamente e SrC2O4 dopado com diferentes porcentagens de Ce3+, foram tratadas termicamente à 1100ºC, 12 horas. Os produtos foram analisados por XRD e espectroscopia de luminescência e apresentam mistura das fases SrCeO3, Sr2CeO4 e SrCO3. Os produtos contendo a fase Sr2CeO4 apresentam luminescência azul de banda larga, com exceção daquele obtido a partir de SrC2O4 dopado com 50% de Ce3+. Neste caso a fase predominante é SrCeO3. Pela curva DTA observa-se um pico endotérmico em torno de 1000ºC para todas as amostras, com exceção da amostra dopada em 50%, evidenciando a temperatura de formação da fase Sr2CeO4. A fase luminescente Sr2CeO4 é preferencialmente obtida partindo-se de SrC2O4:Ce3+ 25% e de misturas mecânicas na proporção de 4:1 de oxalatos de estrôncio e de oxalato de cério.

p16INK4 expression in precursor lesions of squamous cell cervical cancer related to the presence of HPV-DNA

The purpose of the present study was to identify the expression of p16INK4 in cervical cancer precursor lesions by immunohistochemistry and to correlate it with lesion grade and presence of human papillomavirus (HPV) infection. Cervical specimens from 144 women seen consecutively at the gynecology outpatient clinic of our institution from December 2003 to May 2005 were analyzed by cytopathology, histopathology, polymerase chain reaction for HPV-DNA, and p16INK4 immunostaining. Histologically normal biopsies, HPV-DNA negative by polymerase chain reaction, were used as control. HPV-DNA prevalence, including the control group, was 68.1% and the prevalence of p16INK4 expression was 55.0%. The percentage of cells stained by p16INK4 ranged from 10 to 100%, both in the group consisting of cervical intraepithelial neoplasia (CIN)1/HPV specimens and in the group of CIN2/CIN3 specimens with P value of 0.0001. p16INK4 expression was 48.3% in the CIN1/HPV group, as opposed to 94.3% in the CIN2/CIN3 group (P = 0.001), showing a statistically significant difference between the two groups. The quantitative method used here is simple and less subjective than the different semiquantitative methods described in the literature. In view of the different definitions of a p16INK4-positive case, it is almost impossible to compare the findings reported by different investigators. This study confirms the association between p16INK4 and CIN2 and CIN3 lesions. Moreover, it shows that some low grade lesions expressed high levels of this protein. This may indicate that such low grade lesions may be predisposed to progress to high grade lesions. This means that p16INK4 may be a strong marker for "neoplastic lesions" induced by HPV and not just an infection marker.

Design and synthesis of new monoterpenoid derived ligands for asymmetric catalysis /

The work to be presented herein illustrates several important facts. First, the synthesis of BIBOL (19), a 1,4-diol derived from the monoterpene camphor has allowed us to demonstrate that oxidative dimerizations of enolates can, and do proceed with nearly complete diastereoselectivity under kinetically controlled conditions. The yield of BIBOL is now 50% on average, with a 10% yield of a second diastereomer, which is likely the result of a non-kinetic hydride reduction, thereby affording the epimeric alcohol, 20, coupled on the exo face of camphor. This implies the production of 60% of a single coupling diastereomer. No other diastereomers from the reduction were observed. The utility of BEBOL has been illustrated in early asymmetric additions of diethylzinc to aryl aldehydes, with e.e.'s as high as 25-30%. '^' To further the oxidative coupling work, the same methodology which gave rise to BIBOL was applied to the chiral pool ketone, menthone. Interestingly, this gave an excellent yield of the a-halohydrin (31), which is the result of a chlorination of menthone. This result clearly indicates the high stereoselectivity of the process regardless of the outcome, and has illustrated an interesting dichotomy between camphor and menthone. The utility of the chlorination product as a precursor other chiral ligands is currently being investigated. > ' Finally, a new series of 1,3-diols as well as a new aminoalcohol have successfully been synthesized from highly diastereoselective aldol/mannich reactions. Early studies have indicated their potential in asymmetric catalysis, while employing pi-stack interactions as a means of controlling enantioselective aldol reactions.

Towards the enantioselective synthesis of lycoricidine alkaloids /

Two efficient, regio- and stereo controlled synthetic approaches to the synthesis of racemic analogs of pancratistatin have been accomplished and they serve as the model systems for the total synthesis of optically active 7-deoxy-pancratistatin. In the Diels-Alder approach, an efficient [4+2] cycloaddition of 3,4-methylenedioxyco- nitrostyrene with Danishefsky's diene to selectively form an exo-nitro adduct has been developed as the key step in the construction of the C-ring of the target molecule. In the Michael addition approach, the key step was a conjugate addition of an organic zinc-cuprate to the 3,4-methylenedioxy-(B-nitrostyrene, followed by a diastereocontroUed closure to form the cyclohexane C-ring of the target molecule via an intramolecular nitro-aldol cyclization on a neutral alumina surface. A chair-like transition state for such a cyclization has been established and such a chelation controlled transition state can be useful in the prediction of diastereoselectivity in other related 6-exo-trig nitroaldol reactions. Cyclization of the above products fi^om both approaches by using a Bischler-Napieralski type reaction afforded two lycoricidine derivatives 38 and 50 in good yields. The initial results from the above modeling studies as well as the analysis of the synthetic strategy were directed to a chiral pool approach to the total synthesis of optically active 7-deoxy-pancratistatin. Selective monsilylation and iodination of Ltartaric acid provided a chiral precursor for the proposed key Michael transformation. The outlook for the total synthesis of 7-deoxy-pancratistatin by this approach is very promising.A concise synthesis of novel designed, optically pure, Cz-symmetrical disulfonylamide chiral ligands starting from L-tartaric acid has also been achieved. This sequence employs the metallation of indole followed by Sfj2 replacement of a dimesylate as the key step. The activity for this Cz-symmetric chiral disulfonamide ligand in the catalytic enantioselective reaction has been confirmed by nucleophilic addition to benzaldehyde in the disulfonamide-Ti (0-i-Pr)4-diethylzinc system with a 48% yield and a 33% e.e. value. Such a ligand tethered with a suitable metal complex should be also applicable towards the total synthesis of 7-deoxy-pancratistatin.

Precursor nanoscale modulations in ferromagnets: Modeling and thermodynamic characterization

Using a Ginzburg-Landau model for the magnetic degrees of freedom with coupling to disorder, we demonstrate through simulations the existence of stripelike magnetic precursors recently observed in Co-Ni-Al alloys above the Curie temperature. We characterize these magnetic modulations by means of the temperature dependence of local magnetization distribution, magnetized volume fraction, and magnetic susceptibility. We also obtain a temperature-disorder strength phase diagram in which a magnetic tweed phase exists in a small region between the paramagnetic and dipolar phases.

CuInS2/In2S3 Cells using a Cost-effective Technique: Significance of Precursor Ratios on Cell Parameters

Thin film solar cells having structure CuInS2/In2S3 were fabricated using chemical spray pyrolysis (CSP) technique over ITO coated glass. Top electrode was silver film (area 0.05 cm2). Cu/In ratio and S/Cu in the precursor solution for CuInS2 were fixed as 1.2 and 5 respectively. In/S ratio in the precursor solution for In2S3 was fixed as 1.2/8. An efficiency of 0.6% (fill factor -37.6%) was obtained. Cu diffusion to the In2S3 layer, which deteriorates junction properties, is inevitable in CuInS2/In2S3 cell. So to decrease this effect and to ensure a Cu-free In2S3 layer at the top of the cell, Cu/In ratio was reduced to 1. Then a remarkable increase in short circuit current density was occurred from 3 mA/cm2 to 14.8 mA/cm2 and an efficiency of 2.13% was achieved. Also when In/S ratio was altered to 1.2/12, the short circuit current density increased to 17.8 mA/cm2 with an improved fill factor of 32% and efficiency remaining as 2%. Thus Cu/In and In/S ratios in the precursor solutions play a crucial role in determining the cell parameters

"Thematically Analysing Social Network Content During Disasters Through the Lens of the Disaster Management Lifecycle" & "Investigating Similarity Between Privacy Policies of Social Networking Sites as a Precursor for Standardization"

Abstract 1: Social Networks such as Twitter are often used for disseminating and collecting information during natural disasters. The potential for its use in Disaster Management has been acknowledged. However, more nuanced understanding of the communications that take place on social networks are required to more effectively integrate this information into the processes within disaster management. The type and value of information shared should be assessed, determining the benefits and issues, with credibility and reliability as known concerns. Mapping the tweets in relation to the modelled stages of a disaster can be a useful evaluation for determining the benefits/drawbacks of using data from social networks, such as Twitter, in disaster management.A thematic analysis of tweets’ content, language and tone during the UK Storms and Floods 2013/14 was conducted. Manual scripting was used to determine the official sequence of events, and classify the stages of the disaster into the phases of the Disaster Management Lifecycle, to produce a timeline. Twenty- five topics discussed on Twitter emerged, and three key types of tweets, based on the language and tone, were identified. The timeline represents the events of the disaster, according to the Met Office reports, classed into B. Faulkner’s Disaster Management Lifecycle framework. Context is provided when observing the analysed tweets against the timeline. This illustrates a potential basis and benefit for mapping tweets into the Disaster Management Lifecycle phases. Comparing the number of tweets submitted in each month with the timeline, suggests users tweet more as an event heightens and persists. Furthermore, users generally express greater emotion and urgency in their tweets.This paper concludes that the thematic analysis of content on social networks, such as Twitter, can be useful in gaining additional perspectives for disaster management. It demonstrates that mapping tweets into the phases of a Disaster Management Lifecycle model can have benefits in the recovery phase, not just in the response phase, to potentially improve future policies and activities. Abstract2: The current execution of privacy policies, as a mode of communicating information to users, is unsatisfactory. Social networking sites (SNS) exemplify this issue, attracting growing concerns regarding their use of personal data and its effect on user privacy. This demonstrates the need for more informative policies. However, SNS lack the incentives required to improve policies, which is exacerbated by the difficulties of creating a policy that is both concise and compliant. Standardization addresses many of these issues, providing benefits for users and SNS, although it is only possible if policies share attributes which can be standardized. This investigation used thematic analysis and cross- document structure theory, to assess the similarity of attributes between the privacy policies (as available in August 2014), of the six most frequently visited SNS globally. Using the Jaccard similarity coefficient, two types of attribute were measured; the clauses used by SNS and the coverage of forty recommendations made by the UK Information Commissioner’s Office. Analysis showed that whilst similarity in the clauses used was low, similarity in the recommendations covered was high, indicating that SNS use different clauses, but to convey similar information. The analysis also showed that low similarity in the clauses was largely due to differences in semantics, elaboration and functionality between SNS. Therefore, this paper proposes that the policies of SNS already share attributes, indicating the feasibility of standardization and five recommendations are made to begin facilitating this, based on the findings of the investigation.

Evangelista Torricelli : un precursor del cálculo.

Breve recorrido por la historia de Evangelista Torricelli, científico renacentista y pionero en el cálculo matemático. Destacan el cálculo integral y el diferencial, dos de los aspectos en los que más énfasis hizo Torricelli, y que se destacan a lo largo del artículo.

Un precursor en la renovación de métodos de enseñanza de la lectura y escritura a finales del Antiguo Régimen.

Resumen en inglés. Texto completo facilitado por la Secretaría de la revista

Tagore, un precursor de la nueva educación.

Se analiza la época de Tagore, el contexto sociocultural y su biografía, su pensamiento antropológico, su modelo educativo y la primera escuela que creó en oriente, la de 'Shantiniketan'. Finalmente se resumen los principios educativo-didácticos y los principios activos y organizativos que configuran esta nueva escuela.

D. Jerónimo Mariano Usera y Alarcón y su obra : un precursor de la pedagogía social.

Estudiar la vida y obra de Jerónimo Mariano Usera y Alarcón, 1810-1891, su dimensión educadora y social. Antes de analizar la vocación y formación de este monje cisterciense, se revisa el marco político, social y cultural del s. XIX. Se estudia su acción personal como pedagogo en la universidad, en la selva africana y en el seminario de Santiago de Cuba. Se constatan sus intuiciones pedagógicas por su trabajo social y educativo con los niños, las mujeres, y emancipador con los esclavos y campesinos, en el marco institucional de asociaciones religiosas o laicas. Y por último, se analiza su lugar en la generación de educadores del siglo XIX, promotores de la Pedagogía Social y la educación popular para el desarrollo comunitario, y la proyección histórica de su obra. Se buscan escritos del propio Usera en archivos civiles o eclesiásticos, públicos o privados, de España, Cuba, Puerto Rico y Vaticano; y bibliografía sobre él. La investigación es hermenéutica-interpretativa, empírico-analítica de hechos y datos. Con los datos, se realiza un análisis teórico sistemático y comparado entre Usera y sus contemporáneos, sus intuiciones y las corrientes pedagógico-sociales de nuestros días. Usera no deja amplios estudios sobre teoría y métodos pedagógicos, sino la realización práctica de su pensamiento en su trabajo como profesor universitario en España, misionero en Africa y con cargos eclesiásticos en las Antillas. Su talento pedagógico queda patente en la rapidez con que pasa del reconocimiento del problema, al diseño racional, operativo, organizativo y ejecutivo de sus planes de ayuda pedagógico-social. Él mismo experimenta su proyecto y lo transmite a la Casa de Caridad y Oficios de S. Ildefonso, fundada en Puerto Rico en 1858, y a la Congregación de Hermanas del Amor de Dios, cuya primera fundación fue en Zamora en 1864, y posteriormente se extiende por Cuba y Africa. Ensaya métodos de Pedagogía Social individual, de grupo y comunitaria. Con su obra educativa-social, suple y soluciona los problemas educativos y humanos que la familia, la sociedad o el Estado no había resuelto. Debe ser considerado como pionero de la Pedagogía Social porque se adelantó a la pedagogía del siglo XX y superó a notables figuras de su tiempo. El sistema pedagógico de Usera conserva su actualidad porque se basa en principios que no envejecen y abre a su educando la socialización y el desarrollo de las relaciones interculturales.