Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides

The reaction kinetics of the alcoholysis of substituted benzoyl chlorides was studied. The mechanism of the alcoholysis reaction, which is most generally accepted (1), shows that the overall reaction should be second-order and that the reaction should be first-order with respect to the acid chloride and first-order with respect to the alcohol. This rate study was carried out using a large excess of alcohol as the solvent, thus obtaining pseudo-first order rate constants, first-order with respect to the acid chloride only

A comparative study of the antioxidant profiles of olive fruit and leaf extracts against five reactive oxygen species as measured with a multiple free‐radical scavenging method

Olive fruits and leaves are recognized to have great potential as natural sources of antioxidants. The major phenolic antioxidant component in these plant tissues is oleuropein. The antioxidant activity of olive fruits and leaves was evaluated in this study using multiple free‐radical scavenging (MULTIS) methods, wherein we determined the scavenging abilities of different extracts against five reactive oxygen species (ROS; HO·, O2−·, RO·, t‐BuOO·, and 1O2). Raw olive fruits taste bitter and are inedible without undergoing a debittering treatment. Following the NaOH‐debittering process, the radical scavenging activity of olives decreased by 90%. The MULTIS measurements indicated that oleuropein and hydroxytyrosol are responsible for the radical scavenging activity of olive fruits. Furthermore, we evaluated the radical scavenging profiles of olive leaf extracts against five ROS and found significant seasonal variations in their antioxidant activities. Leaves picked in August possessed greater radical scavenging abilities (180% to 410% for different ROS) than those picked in the cold season (December and February). In roasted olive leaves, we found marked increases (230% to 300% and 180% to 220%) in the antioxidant activities of Maillard reaction products against RO· and t‐BuOO·, respectively. This study presented a useful comparative analysis of the antioxidant capacities of food against various types of ROS

(Im)possibilities of implementing an unified health services management in the Brazilian National Health System (SUS) in a large municipality: the case of São Paulo city, Brazil

A construção da direção única na saúde constitui-se um desafio para a gestão local do SUS, particularmente para municípios de grande porte. Este artigo analisou o processo de implementação do SUS no município de São Paulo, visando identificar estratégias para viabilizar uma direção única, no período de 2001 a 2008. Com base em um estudo de caso, foram utilizados dados obtidos de informantes privilegiados da gestão e de documentos de gestão. O conceito de integração sanitária foi utilizado como categoria analítica. Foram analisados movimentos e estratégias dos atores institucionais envolvidos diretamente na gestão do SUS, os gestores municipal e estadual. Observaram-se avanços institucionais como a municipalização das unidades básicas de saúde estaduais e a habilitação do município na gestão plena do sistema municipal. Apesar dessa condição de gestão e da identidade político-partidária entre os governos municipal e estadual desde 2005, constatou-se a coexistência de dois subsistemas públicos de saúde pouco integrados. Um municipal, que concentrava os serviços de atenção básica; outro estadual, que concentrava parte considerável dos serviços de média e alta complexidades. Instrumentos de gestão adotados, como o sistema de regulação, mostraram-se frágeis para superar a falta de integração entre os referidos subsistemas. Como implementar a direção única no SUS implica uma (re)divisão de recursos e poder, discute-se que não bastam normas nem instrumentos de gestão para viabilizá-la. É um desafio estratégico para o SUS implementar processo de negociação, envolvendo os atores institucionais e políticos, visando a pactuação de um projeto político na saúde.The construction of a unified health management is a challenge to the local Brazilian National Health System (SUS) management, especially in large cities. This article analyzed the implementation process of the SUS in the city of São Paulo. Its objective was to identify strategies to implement the unified health management, in the period from 2001 to 2008. The method used was a case study and data collection was based on management documents and interviews. The concept of health services integration was used as analytical category. Movements and strategies of the SUS institutional actors in the city of São Paulo were analyzed. Institutional improvements were observed, like the municipalization of the state healthcare centers and the qualification of São Paulo in the full management of the municipal health system. Despite this SUS management status and the political party identity that has been occurring between state and city governments since 2005, there were two separate public health subsystems with litle integration between them: the municipal one, which concentrated the primary healthcare services, and the state one, concentrating most of the secondary and tertiary health services. The management tools used, such as the regulation system, proved to be fragile to overcome the lack of integration between those health subsystems. As the implementation of a unified health management in SUS implies a (re)division of resources and power, rules and management tools are not enough to make it feasible. Implementing a negotiation process between the institutional and political actors involved in a common political project in health is a strategic challenge

VLA Observations of H2O Masers in the Class 0 Protostar S106 FIR: Evidence for a 10 AU-Scale Accelerating Jet-like Flow

We conducted VLA observations at 0".06 resolution of the 22 GHz water masers toward the Class 0 source S106 FIR (d=600 pc; 15" west of S106-IRS4) on two epochs separated by ~3 months. Two compact clusters of the maser spots were found in the center of the submillimeter core of S106 FIR. The separation of the clusters was ~80 mas (48 AU) along P. A. = 70 degrees and the size of each cluster was ~20 mas x 10 mas. The western cluster, which had three maser components, was 7.0 km/s redshifted with respect to the ambient cloud velocity. Each component was composed of a few spatially localized maser spots and was aligned on a line connecting the clusters. We found relative proper motions of the components with ~30 mas/yr (18 AU/yr) along the line. In addition, a series of single-dish observations show that the maser components drifted with a radial acceleration of ~1 km/s/yr. These facts indicate that the masers could be excited by a 10 AU-scale jet-like accelerating flow ejected from an assumed protostar located between the two clusters. The outflow size traced by the masers was 50 AU x 5 AU after correction for an inclination angle of 10 degrees which was derived from the relative proper motions and radial velocities of the maser components. The three-dimensional outflow velocity ranged from 40 to 70 km/s assuming symmetric motions for the blue and red components. Since no distinct CO molecular outflows have been detected so far, we suggest that S106 FIR is an extremely young protostar observed just after the onset of outflowing activity.Comment: 24 pages, 6 figures, No. 5 color. Accepted, Astrophysical Journa

Detection of skewed X-chromosome inactivation in Fragile X syndrome and X chromosome aneuploidy using quantitative melt analysis.

Methylation of the fragile X mental retardation 1 (FMR1) exon 1/intron 1 boundary positioned fragile X related epigenetic element 2 (FREE2), reveals skewed X-chromosome inactivation (XCI) in fragile X syndrome full mutation (FM: CGG > 200) females. XCI skewing has been also linked to abnormal X-linked gene expression with the broader clinical impact for sex chromosome aneuploidies (SCAs). In this study, 10 FREE2 CpG sites were targeted using methylation specific quantitative melt analysis (MS-QMA), including 3 sites that could not be analysed with previously used EpiTYPER system. The method was applied for detection of skewed XCI in FM females and in different types of SCA. We tested venous blood and saliva DNA collected from 107 controls (CGG < 40), and 148 FM and 90 SCA individuals. MS-QMA identified: (i) most SCAs if combined with a Y chromosome test; (ii) locus-specific XCI skewing towards the hypomethylated state in FM females; and (iii) skewed XCI towards the hypermethylated state in SCA with 3 or more X chromosomes, and in 5% of the 47,XXY individuals. MS-QMA output also showed significant correlation with the EpiTYPER reference method in FM males and females (P < 0.0001) and SCAs (P < 0.05). In conclusion, we demonstrate use of MS-QMA to quantify skewed XCI in two applications with diagnostic utility