Total synthesis of lamellarin D and analogs library

Larnellarins are a group of marine natural products isolated from the prosobranch mollusc Lamellaria sp., the ascidian Didemnum sp., and the sponge Dendrilla Cactos. Several of them exhibit interesting biological activities. Natural as well as synthetic lamellarins should be excellent candidates for the development of new drugs due to their unique skeletal structure and their important biological activities especially as antitumor agents. Lamelarin O has been recently characterized as a topoisomerase 1-targeted anti tumor agent. A variety of synthetic approaches have been developed for this family of alkaloids. Herein we describe a new route to the synthesis of Lamellarin D, from a methyl 2-pyrrolecarboxylate. Transformation of the starting material into the scaffold, a substituted 5,6-dihydropyrrolo (2,l ­a)isoquinoline (5,6-DHPl), was afforded by N-alkylation followed by intramolecular Heck cyclization. From this scaffold the synthetic strategy is based on two sequential regioselective bromination!Suzuki cross-coupling reactions which permitted the introduction of differently substituted aryl groups on positions 1 and 2 followed by oxidation, deprotection, and lactonization.

Decomposing differences in total factor productivity across firm size

This paper investigates the extent to which the gap in total factor productivity between small and large firms is due to differences in the endowment of factors determining productivity and to the returns associated with these factors. We place particular emphasis on the contribution of differences in the propensity to innovate and in the use of skilled labor across firms of different size. Empirical evidence from a representative sample of Spanish manufacturing firms corroborates that both differences in endowments and returns to innovation and skilled labor significantly contribute to the productivity gap between small and large firms. In addition, it is observed that the contribution of innovation to this gap is caused only by differences in quantity, while differences in returns have no effect; in the case of human capital, however, most of the effect can be attributed to increasing differences in returns between small and large firms.

L'educació de qualitat no s'improvisa

El país ha de fer una aposta decidida per l'educació. No és només un problema de currículums; amb el mateix currículum formal tenim molts models escolars, uns de relativament bons i altres de dolents. Cal fer canvis profunds i ser més exigent en les condicions per accedir a la professió de mestre. Aptitud i actitud. S'han fet visites a Finlàndia, model de sistema educatiu i país innovador, per entendre com funciona allà l'educació. No podem pensar que sense canvis en els comportaments socials podem tenir un sistema educatiu similar. Podem tenir un bon sistema, però serà sempre diferent

Implantació d'un Sistema de Gestió Integrada, qualitat i medi ambient, a una empresa constructora.

En aquest treball es defineix la documentació necessària per realitzar la implantació d’un sistema de gestió integrada, basat en la qualitat i en el medi ambient, a una empresa constructora, que permeti desenvolupar les seves activitats d’una forma simplificada i ordenada, i que faciliti la informació necessària per mantenir una millora continuada de les seves activitats.El Sistema de Gestió, integra les normes ISO 9001 i ISO 14001, que són normes de gestió de la Qualitat i el Medi Ambient, respectivament. Durant la implantació del Sistema de Gestió, s’han elaborat els procediments generals que les normes indiquen que s’han d’elaborar per complir amb totes les especificacions definides a elles. També, s’han elaborat els procediments específics, que són aquells propis de les activitats de l’empresa i que defineixen la seva forma de treballar. D’aquesta documentació es deriven els registres, que son els documents del Sistema de Gestió que ens permeten comprovar si s’adequa a la forma de treballar, i que son les evidencies de la posada en marxa del sistema.A la finalització d’aquest projecte, obtindrem un Sistema de Gestió Integrada, amb tots els procediments definits i implantats a l’empresa, que compliran amb les normes ISO 9001 i ISO 14001, dotant a l’organització d’un augment de la seva eficàcia i competitivitat, entrant al procés de millora continuada, i posicionar-se com una empresa socialment responsable, reforçant la seva imatge davant dels seus clients, optimitzant la gestió de residus i reduint els impactes ambientals negatius.

Biomonitoreo de la calidad del agua en los ríos ibéricos: lecciones aprendidas.

Los autores resumen en un decálogo la experiencia de más de 30 años de estudio de los ríos españoles con dos focos principales: el uso de macroinvertebrados para la obtención de la calidad biológica y el diseño de sistemas de evaluación del estado ecológico de los ríos. Después de una introducción general y de un resumen de cómo se gestaron los estudios de biomonitoreo en España, los autores analizan los trabajos que se han publicado en la revista Limnetica sobre este tema. Se usan estos datos para ilustrar los puntos relevantes en el diseño y aplicación del biomonitoreo, que es posteriormente resumido en un decálogo. Este está pensado para contener todos los puntos necesarios para que el diseño de un sistema de biomonitoreo cumpla las especificaciones de la Directiva Marco del Agua (DMA). Los diez puntos analizados son: 1) establecimiento de la zona de estudio; 2) recursos humanos y materiales disponibles; 3) tipología de ríos; 4) establecimiento de las condiciones de referencia; 5) protocolos de muestreo; 6) métricas a utilizar; 7) establecimiento de los cortes de calidad y relación de las métricas con las presiones; 8) mapas de estado ecológico usando el valor relativo respecto a los valores de referencia (el EQR: Ecological Quality Ratio); 9) control de calidad; 10) uso de los datos para establecer los objetivos de calidad y el programa de medidas. En la revista Limnetica se han publicado desde su inicio en el año 1981 un total de 641 trabajos, de los cuales un 42% trataban de ríos y un 18% se centraban exclusivamente en el biomonitoreo. La mayor parte de los trabajos de biomonitoreo publicados utilizaron a los macroinvertebrados como elemento de calidad (88%), pero relativamente pocos (menos del 20%) usaron la tipología y las condiciones de referencia para establecer correctamente las clases de calidad. Se analiza por separado el período anterior al año 2002, y con un número similar de trabajos se advierte un mayor porcentaje de trabajos de biomonitoreo después de 2002. Sin embargo, y a pesar de la existencia de la DMA desde el año 2000, muchos trabajos publicados en Limnetica a partir de 2002 (cuando se hizo un número especial sobre biomonitoreo en ríos mediterráneos) no cumplen los requisitos que demanda esta Directiva. En este momento, después de la experiencia que se tiene por la implementación de la DMA, cualquier sistema de biomonitoreo desarrollado en Europa debe ser comparable a los que existen actualmente, especialmente a la métrica común de intercalibración (ICM).Este decálogo presenta los pasos necesarios para que cuando se diseñe un sistema de muestreo este cumpla los requisitos que demanda la DMA.

Distribuição de mercúrio total como indicador de poluição urbana e industrial na costa brasileira

The monitoring of the pollution status of the Brazilian coast is hampered by the lack of a consistent environmental indicator. We propose Hg as an environmental proxy to anthropogenic pollution of coastal regions due to its absence in the Brazilian geology, its ubiquity in anthropogenic effluents, and its toxicity. Available data suggest Hg "backgrounds" in coastal sediments of 1-10 ng g-1, in the East and 15-30 ng g-1 in the South. We suggest short sediment cores to establish these values estimating a geo-accumulation index to compare all areas. The distribution of index values showed the majority of southern coast at least moderately contaminated whereas many eastern areas are still pristine.

Espectrofotometría de absorción atómica con tubo en la llama: aplicación en la determinación total de cadmio, plomo y zinc en aguas frescas, agua de mar y sedimentos marinos

Thermospray flame furnace Atomic Absorption Spectrometry (TS-FF-AAS) was used for the total determination of Cd, Pb and Zn in fresh water and seawater samples at µg L-1 levels, and in marine sediment samples at µg g-1 levels. Using a sample loop of 50 µL and a peristaltic pump the samples were transported into the metallic tube placed over an air/acetylene flame, through a ceramic capillary (o.d. = 3.2 mm) containing two parallel internal orifices (i.d = 0.5 mm). The detection limits determined for Cd, Pb and Zn using a synthetic water matrix (2.5% m/v NaCl, 0.5% m/v MgCl2 and 0.8% m/v CaCl2) were 0.32 µg L-1; 2.6 µg L-1 and 0.21 µg L-1 respectively. The methodology by TS-FF-AAS was validated by determination of Cd, Pb and Zn in certified reference materials of water and marine sediment, and the t-test for differences between means was applied. No statistically significant differences were established in fresh water and seawater (p>0.05), whereas differences became apparent in marine sediment (p<0.03).

Determinação das formas de nitrogênio e nitrogênio total em rochas-reservatório de petróleo por destilação com arraste de vapor e método do indofenol

Several extraction procedures are described for the determination of exchangeable and fixed ammonium, nitrate + nitrite, total exchangeable nitrogen and total nitrogen in certified reference soils and petroleum reservoir rock samples by steam distillation and indophenol method. After improvement of the original distillation system, an increase in worker safety, a reduction in time consumption, a decrease of 73% in blank value and an analysis without ammonia loss, which could possibly occur, were achieved. The precision (RSD < 8%, n = 3) and the detection limit (9 mg kg-1 NH4+-N) are better than those of published procedures.

Inserció laboral i qualitat de la ocupació en els ensenayments de pregrau de la Facultat de Farmàcia

L’Agència per a la Qualitat del Sistema Universitari (AQU) i les universitats catalanes, per tal de copsar el grau d’inserció laboral dels titulats, realitzen una enquesta amb una periodicitat triennal. L’enquesta permet conèixer no només la inserció sinó qüestions més especifiques com la temporalitat, la satisfacció respecte de la formació rebuda i el lloc de treball i el nivell de retribució, entre d’altres. L’anàlisi de les dades de les titulacions de la Facultat de Farmàcia, és d’interès per al disseny d’estratègies i d’activitats de orientació professional al centre.

Determinação de açúcar total em café cru por espectroscopia no infravermelho próximo e regressão por mínimos quadrados parciais

In this work a fast method for the determination of the total sugar levels in samples of raw coffee was developed using the near infrared spectroscopy technique and multivariate regression. The sugar levels were initially obtained using gravimety as the reference method. Later on, the regression models were built from the near infrared spectra of the coffee samples. The original spectra were pre-treated according to the Kubelka-Munk transformation and multiplicative signal correction. The proposed analytical method made possible the direct determination of the total sugar levels in the samples with an error lower by 8% with respect to the conventional methodology.

Health-related quality of life in the Cambridge City over-75s Cohort (CC75C): development of a dementia-specific scale and descriptive analyses.

BACKGROUND: The assessment of Health Related Quality of Life (HRQL) is important in people with dementia as it could influence their care and support plan. Many studies on dementia do not specifically set out to measure dementia-specific HRQL but do include related items. The aim of this study is to explore the distribution of HRQL by functional and socio-demographic variables in a population-based setting. METHODS: Domains of DEMQOL's conceptual framework were mapped in the Cambridge City over 75's Cohort (CC75C) Study. HRQL was estimated in 110 participants aged 80+ years with a confirmed diagnosis of dementia with mild/moderate severity. Acceptability (missing values and normality of the total score), internal consistency (Cronbach's alpha), convergent, discriminant and known group differences validity (Spearman correlations, Wilcoxon Mann-Whitney and Kruskal-Wallis tests) were assessed. The distribution of HRQL by socio-demographic and functional descriptors was explored. RESULTS: The HRQL score ranged from 0 to 16 and showed an internal consistency Alpha of 0.74. Validity of the instrument was found to be acceptable. Men had higher HRQL than women. Marital status had a greater effect on HRQL for men than it did for women. The HRQL of those with good self-reported health was higher than those with fair/poor self-reported health. HRQL was not associated with dementia severity. CONCLUSIONS: To our knowledge this is the first study to examine the distribution of dementia-specific HRQL in a population sample of the very old. We have mapped an existing conceptual framework of dementia specific HRQL onto an existing study and demonstrated the feasibility of this approach. Findings in this study suggest that whereas there is big emphasis in dementia severity, characteristics such as gender should be taken into account when assessing and implementing programmes to improve HRQL.

Mercúrio total em solos de manguezais da Baixada Santista e Ilha do Cardoso, estado de São Paulo

Total Hg content in soils of Baixada Santista, affected by different sources of pollution, and Cardoso Island, which is almost free of anthropogenic activities, were determined by CVAAS. To explain the fate of Hg in the ecosystem, pH, Eh, AVS, Stotal and Total Organic Carbon were also obtained throughout the soil profiles. With the exception of two sampling sites the average content of Hg in samples obtained for Baixada Santista was 0.34 ± 0.20 mg kg-1, which was close to the average data at Cardoso Island (0.30 ± 0.21 mg kg-1). Both of them were below the limit established by CETESB - 0.50 mg kg-1.

Assessment of total cardiovascular risk in hypertensive subjects

Valtimotautiriskin arviointi verenpainepotilailla Valtimotaudit ovat yleisin kuolinsyy koko maailmassa. Väestön elintapojen muuttuminen ja ikääntyminen uhkaavat edelleen lisätä valtimotautien esiintyvyyttä. Kokemäenjokilaakson valtimotautien ehkäisyprojektin tavoitteena oli löytää 45–70-vuotiaasta väestöstä henkilöt, joilla on kohonnut riski sairastua valtimotauteihin. Kaksivaiheisen seulontamenetelmän avulla voitiin terveydenhoitajan antama elintapaneuvonta kohdistaa riskihenkilöihin ja rajoittaa lääkärin vastaanoton tarve niihin potilaisiin, jotka todennäköisesti hyötyvät ennaltaehkäisevästä lääkityksestä. Suomalainen tyypin 2 diabeteksen sairastumisriskin arviointikaavake ja hoitajan toteama kohonnut verenpaine osoittautuivat käytännöllisiksi menetelmiksi seuloa väestöstä riskihenkilöitä. Valtimotautien ehkäisyprojektissa Harjavallassa ja Kokemäellä todettiin verenpainetauti 1 106 henkilöllä, jotka eivät sairastaneet valtimotautia tai aiemmin todettua diabetesta. Heidän tutkimustulostensa avulla voidaan arvioida kohonneen verenpaineen vaikutusta sokeriaineenvaihduntaan ja verenpaineen aiheuttamiin kohde-elinvaurioihin. Sokeriaineenvaihdunnan häiriöt ovat verenpainetautia sairastavilla yleisempiä kuin väestössä muutoin. Käyttämällä metabolisen oireyhtymän kriteerejä sokerirasituskokeen suorittamisen edellytyksenä voidaan tutkimusten määrää vähentää kolmanneksella ja silti löytää lähes kaikki diabetesta tai sen esiastetta sairastavat verenpainepotilaat. Verenpainepotilaista etenkin metabolista oireyhtymää sairastavilla naisilla on suurentunut munuaisten vajaatoiminnan riski. Jos verenpainepotilaan munuaisten toimintaa arvioidaan pelkästään plasman kreatiniini -arvon perusteella, kolme neljästä munuaisten vajaatoimintaa potevasta jää toteamatta verrattuna laskennallisen glomerulusten suodattumisnopeuden määritykseen seulontamenetelmänä. Joka kolmannella verenpainetautia sairastavalla voidaan todeta alaraajavaltimoiden kovettumista; useammin niillä, joiden ylä- ja alaverenpaineen erotus, pulssipaine on yli 65 mmHg. Verenpainetauti on itsenäinen perifeerisen valtimotaudin vaaratekijä. Tutkimuksessa käytetty menetelmä nilkka-olkavarsipainesuhteen määrittämiseksi soveltunee hyvin perusterveydenhuollon käyttöön riskihenkilöiden löytämiseksi. Valtimotautien kokonaisriskin arviointimenetelmät tai uuden riskitekijän, herkän C-reaktiivisen proteiinin määritys eivät voi korvata kohde-elinvaurioiden mittaamista verenpainepotilaan valtimotautiriskin huolellisessa arvioinnissa.

Estudo da oxidação total do etanol usando óxidos tipo perovskita LaBO3 (B= Mn, Ni, Fe)

The present work investigated the effect of coprecipitation-oxidant synthesis on the specific surface area of perovskite-type oxides LaBO3 (B= Mn, Ni, Fe) for total oxidation of ethanol. The perovskite-type oxides were characterized by X-ray diffraction, nitrogen adsorption (BET method), thermogravimetric analysis (TGA-DTA), TPR and X-ray photoelectron spectroscopy (XPS). Through method involving the coprecipitation-oxidant was possible to obtain catalysts with different BET specific surface areas, of 33-51 m²/g. The results of the catalytic test confirmed that all oxides investigated in this work have specific catalytic activity for total oxidation of ethanol, though the temperatures for total conversion change for each transition metal.

Impact of multimorbidity on disability and quality of life in the spanish older population

BACKGROUND: Population aging is closely related to high prevalence of chronic conditions in developed countries. In this context, health care policies aim to increase life span cost-effectively while maintaining quality of life and functional ability. There is still, however, a need for further understanding of how chronic conditions affect these health aspects. The aim of this paper is to assess the individual and combined impact of chronic physical and mental conditions on quality of life and disability in Spain, and secondly to show gender trends. METHODS: Cross-sectional data were collected from the COURAGE study. A total of 3,625 participants over 50 years old from Spain were included. Crude and adjusted multiple linear regressions were conducted to detect associations between individual chronic conditions and disability, and between chronic conditions and quality of life. Separate models were used to assess the influence of the number of diseases on the same variables. Additional analogous regressions were performed for males and females. RESULTS: All chronic conditions except hypertension were statistically associated with poor results in quality of life and disability. Depression, anxiety and stroke were found to have the greatest impact on outcomes. The number of chronic conditions was associated with substantially lower quality of life [β for 4+ diseases: -18.10 (-20.95,-15.25)] and greater disability [β for 4+ diseases: 27.64 (24.99,30.29]. In general, women suffered from higher rates of multimorbidity and poorer results in quality of life and disability. CONCLUSIONS: Chronic conditions impact greatly on quality of life and disability in the older Spanish population, especially when co-occurring diseases are added. Multimorbidity considerations should be a priority in the development of future health policies focused on quality of life and disability. Further studies would benefit from an expanded selection of diseases. Policies should also deal with gender idiosyncrasy in certain cases.