589 resultados para Friedel-Crafts


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This PhD work deals with problems of synthetic organic chemistry with particular attention to the development of environmentally friendly processes. In particular, new synthetic strategies have been studied based on the use of low cost heterogeneous catalysts, non-toxic reagents and mild operating conditions that do not involve, when possible, the use of solvents. The catalysts examined are both basic and acids, commercial or prepared by hetereogenization of homogeneous catalysts synthesized by tethering or impregnation. In particular it will be discussed the catalytic activity of oxides (Al2O3 and TiO2), supported sulphonic acids and hydrotalcites for the reactions of selective monoesterificazion of dicarboxylic acids, dehydrogenation of butane in gas phase, esterification of levulinic acid, Friedel-Craft acylations, C-C and C-P coupling. The use of these materials has allowed the development of simple processes with low environmental impact. The operating conditions are in fact mild and reaction times short. The selectivity for the desired products is in all reported cases very high and the catalysts can be recycled maintaining their optimum performances.

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Although it may sound reasonable that American education continues to be more effective at sending high school students to college, in a study conducted in 2009, The Council of the Great City Schools states that "slightly more than half of entering ninth grade students arrive performing below grade level in reading and math, while one in five entering ninth grade students is more than two years behind grade level...[and] 25% received support in the form of remedial literacy instruction or interventions" (Council of the Great City Schools, 2009). Students are distracted with technology (Lei & Zhao, 2005), family (Xu & Corno, 2003), medical illnesses (Nielson, 2009), learning disabilities and perhaps the most detrimental to academic success, the very lack of interest in school (Ruch, 1963). In a Johns Hopkins research study, Building a Graduation Nation - Colorado (Balfanz, 2008), warning signs were apparent years before the student dropped out of high school. The ninth grade was often referenced as a critical point that indicated success or failure to graduate high school. The research conducted by Johns Hopkins illustrates the problem: students who become disengaged from school have a much greater chance of dropping out of high school and not graduating. The first purpose of this study was to compare different measurement models of the Student School Engagement (SSE) using Factor Analysis to verify model fit with student engagement. The second purpose was to determine the extent to which the SSE instrument measures student school engagement by investigating convergent validity (via the SSE and Appleton, Christenson, Kim and Reschly's instrument and Fredricks, Blumenfeld, Friedel and Paris's instrument), discriminant validity (via Huebner's Student Life Satisfaction Survey) and criterion-related validity (via the sub-latent variables of Aspirations, Belonging and Productivity and student outcome measures such as achievement, attendance and discipline). Discriminant validity was established between the SSE and the Appleton, Christenson, Kim and Reschly's model and Fredricks, Blumenfeld, Friedel and Paris's (2005) Student Engagement Instruments (SEI). When confirming discriminant validity, the SSE's correlations were weak and statistically not significant, thus establishing discriminant validity with the SLSS. Criterion-related validity was established through structural equation modeling when the SSE was found to be a significant predictor of student outcome measures when both risk score and CSAP scores were used. The third purpose of this study was to assess the factorial invariance of the SSE instrument across gender to ensure the instrument is measuring the intended construct across different groups. Conclusively, configural, weak and metric invariances were established for the SSE as a non-significant change in chi-square indicating that all parameters including the error variances were invariant across groups of gender. Engagement is not a clearly defined psychological construct; it requires more research in order to fully comprehend its complexity. Hopefully, with parental and teacher involvement and a sense of community, student engagement can be nurtured to result in a meaningful attachment to school and academic success.

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Este artigo descreve o uso de artefatos funerários na reconstituição histórica do processo de trabalho em marmorarias instaladas no município de São Carlos (São Paulo, Brasil), no período 1890-1950. Observação direta e registro fotográfico de artefatos funerários, exame de ferramentas de trabalho e utilização de fontes orais permitiram a reconstituição do processo de trabalho. A composição química de fragmentos de artefatos funerários foi determinada por Difração de Raios X e Microscopia Eletrônica de Varredura, evidenciando matérias-primas e sua combinação e uso no processo de trabalho. Considerando-se as etapas produtivas da indústria de rochas ornamentais (extração, serragem e beneficiamento final), os artefatos funerários indicam que as marmorarias inseriam-se na etapa de beneficiamento final. As marmorarias integravam os setores de base técnica artesanal da indústria brasileira, apresentando: baixo grau de concentração de capital e de operários; predomínio da habilidade do ofício especializado; separação pouco nítida entre trabalhadores e instrumentos de trabalho; identificação do trabalhador com o produto. Artefatos de mármore e granito eram destinados a brasileiros de segmentos sociais abastados, durante o início da imigração na cidade de São Carlos (final do século XIX). A partir de 1920, italianos incorporam-se a clientela dos marmoristas, indicando a mobilidade social do imigrante na cidade.

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Senescence-associated coordination in amounts of enzymes localized in different cellular compartments were determined in attached leaves of young wheat (Triticum aestivum L. cv. Arina) plants. Senescence was initiated at the time of full leaf elongation based on declines in total RNA and soluble protein. Removal of N from the growth medium just at the time of full leaf elongation enhanced the rate of senescence. Sustained declines in the amount of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco, EC 4.1.1.39), and a marked decrease in the rbcS transcripts, just after full leaf elongation indicated that Rubisco synthesis/degradation was very sensitive to the onset of senescence. Rubisco activase amount also declined during senescence but the proportion of rca transcript relative to the total poly A RNA pool increased 3-fold during senescence. Thus, continued synthesis of activase may be required to maintain functional Rubisco throughout senescence. N stress led to declines in the amount of proteins located in the chloroplast, the peroxisome and the cytosol. Transcripts of the Clp protease subunits also declined in response to N stress, indicating that Clp is not a senescence-specific protease. In contrast to the other proteins, mitochondrial NADH-glutamate dehydrogenase (EC 1.4.1.2) was relatively stable during senescence and was not affected by N stress. During natural senescence with adequate plant nitrate supply the amount of nitrite reductase (EC 1.7.7.1) increased, and those of glutamine synthetase (EC 1.4.7.1) and glutamate synthase (EC 6.3.1.2) were stable. These results indicated that N assimilatory capacity can continue or even increase during senescence if the substrate supply is maintained. Differential stabilities of proteins, even within the same cellular compartment, indicate that proteolytic activity during senescence must be highly regulated.

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Our objective was to determine the coordination of transcript and/or protein abundances of stromal enzymes during leaf senescence. First trifolioliate leaves of Phaseolus vulgaris L. plants were sampled beginning at the time of full leaf expansion; at this same time, half of the plants were switched to a nutrient solution lacking N. Total RNA and soluble protein abundances decreased after full leaf expansion whereas chlorophyll abundance remained constant; N stress enhanced the decline in these traits. Abundances of ribulose-1,5-bisposphate carboxylase/oxygenase (Rubisco; EC 4.1.1.39), Rubisco activase and phosphoribulokinase (Ru5P kinase; EC 2.7.1.19) decreased after full leaf expansion in a coordinated manner for both treatments. In contrast, adenosine diphosphate glucose (ADPGlc) pyrophosphorylase (EC 2.7.7.27) abundance was relatively constant during natural senescence but did decline similar to the other enzymes under N stress. Northern analyses indicated that transcript abundances for all enzymes declined markedly on a fresh-weight basis just after full leaf expansion. This rapid decline was particularly strong for the Rubisco small subunit (rbcS) transcript. The decline was enhanced by N stress for rbcS and Rubisco activase (rca), but not for Ru5P kinase (prk) and ADPGlc pyrophosphorylase (agp). Transcripts of the Clp protease subunits clpC and clpP declined in abundance just after full leaf expansion, similar to the other mRNA species. When Northern blots were analyzed using equal RNA loads, rbcS transcripts still declined markedly just after full leaf expansion whereas rca and clpC transcripts increased over time. The results indicated that senescence was initiated near the time of full leaf expansion, was accelerated by N stress, and was characterized by large decline in transcripts of stromal enzymes. The decreased mRNA abundances were in general associated with steadily declining stromal protein abundances, with ADPGlc pyrophosphorylase being the notable exception. Transcript analyses for the Clp subunits supported a recent report (Shanklin et al., 1995, Plant Cell 7: 1713--1722) indicating that the Clp protease subunits were constitutive throughout development and suggested that ClpC and ClpP do not function as a senescence-specific proteolytic system in Phaseolus.

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We tested the hypothesis that light activation of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is inhibited by moderately elevated temperature through an effect on Rubisco activase. When cotton (Gossypium hirsutum L.) or wheat (Triticum aestivum L.) leaf tissue was exposed to increasing temperatures in the light, activation of Rubisco was inhibited above 35 and 30°C, respectively, and the relative inhibition was greater for wheat than for cotton. The temperature-induced inhibition of Rubisco activation was fully reversible at temperatures below 40°C. In contrast to activation state, total Rubisco activity was not affected by temperatures as high as 45°C. Nonphotochemical fluorescence quenching increased at temperatures that inhibited Rubisco activation, consistent with inhibition of Calvin cycle activity. Initial and maximal chlorophyll fluorescence were not significantly altered until temperatures exceeded 40°C. Thus, electron transport, as measured by Chl fluorescence, appeared to be more stable to moderately elevated temperatures than Rubisco activation. Western-blot analysis revealed the formation of high-molecular-weight aggregates of activase at temperatures above 40°C for both wheat and cotton when inhibition of Rubisco activation was irreversible. Physical perturbation of other soluble stromal enzymes, including Rubisco, phosphoribulokinase, and glutamine synthetase, was not detected at the elevated temperatures. Our evidence indicates that moderately elevated temperatures inhibit light activation of Rubisco via a direct effect on Rubisco activase.

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Top Row: Wesley Winkler, Ralph Drake, Charles Rothschild, Norman Sterry, Kenneth Robinson, Alfred Chadwick, Weldon Fix, Ross Kidston, Les Barkenbus, Harrison Weeks, David Dunlap, George Gregory, Harold Baker, Cecil Gooding, George Sadler

Third Row: student mngr. H.C. Crafts, Edward Dickey(?), David Beardsley, William Snushall, ? Smith, George Davison, Kennedy Potter, ? Clark, Charles Van Valkenberg, Neil Snow, Joseph Horgan, James Forrest, William Foote, Webb Sadler, ? Hayes

Second Row: trainer Keene Fitzpatrick, ? Smith, Samuel Sackett, Everett Sweeley, Herbert Graver, Walter Shaw, Hugh White, Albert Herrnstein, Curtis Redden, Dan McGugin, Ebin Wilson, Bruce Shorts, Arthur Redner, Temple Owens

Front Row: Ralph Husson, Albert Preussman, Arthur Urquhart, Willie Heston, Benjamin Southworth, coach Fielding Yost, Charles Crane, Jerome (mascot), John Lewis, Frank Doty, Frank Belknap

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With: "The study and practice of artistic crafts" / by W.R. Lethaby.

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All copies are signed by the editor and initialized by the author.

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National Highway Traffic Safety Administration, Washington, D.C.

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Mode of access: Internet.

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Readers' guide to periodical literature