Neutron activation analysis of wheat samples

The deficiency of essential micronutrients and excess of toxic metals in cereals, an important food items for human nutrition, can cause public health risk. Therefore, before their consumption and adoption of soil supplementation, concentrations of essential micronutrients and metals in cereals should be monitored. This study collected soil and two varieties of wheat samples–Triticum aestivum L. (Jordão/bread wheat), and Triticum durum L. (Marialva/durum wheat) from Elvas area, Portugal and analyzed concentrations of As, Cr, Co, Fe, K, Na, Rb and Zn using Instrumental Neutron Activation Analysis (INAA) to focus on the risk of adverse public health issues. The low variability and moderate concentrations of metals in soils indicated a lower significant effect of environmental input on metal concentrations in agricultural soils. The Cr and Fe concentrations in soils that ranged from 93–117 and 26,400–31,300 mg/kg, respectively, were relatively high, but Zn concentration was very low (below detection limit <22 mg/kg) indicating that soils should be supplemented with Zn during cultivation. The concentrations of metals in roots and straw of both varieties of wheat decreased in the order of K>Fe>Na>Zn>Cr>Rb>As>Co. Concentrations of As, Co and Cr in root, straw and spike of both varieties were higher than the permissible limits with exception of a few samples. The concentrations of Zn in root, straw and spike were relatively low (4–30 mg/kg) indicating the deficiency of an essential micronutrient Zn in wheat cultivated in Portugal. The elemental transfer from soil to plant decreases with increasing growth of the plant. The concentrations of various metals in different parts of wheat followed the order: Root>Straw>Spike. A few root, straw and spike samples showed enrichment of metals, but the majority of the samples showed no enrichment. Potassium is enriched in all samples of root, straw and spike for both varieties of wheat. Relatively to the seed used for cultivation, Jordão presented higher transfer coefficients than Marialva, in particular for Co, Fe, and Na. The Jordão and Marialva cultivars accumulated not statistically significant different concentrations of different metals. The advantages of using INAA are the multielementality, low detection limits and use of solid samples (no need of digestion).

Doppler Echocardiographic Assessment of Pregnant Women with Chronic Arterial Hypertension

OBJECTIVE: To assess structural and functional cardiac changes in asymptomatic pregnant women with chronic arterial hypertension (CAH). METHODS: One hundred pregnant women with CAH underwent conventional Doppler echocardiography. The Student t test was used to compare them with 29 normotensive pregnant women (NT) in their third gestational trimester. RESULTS: Systolic (SBP; mmHg) and diastolic (DBP; mmHg) blood pressure values were higher (p<0.001) in the CAH pregnant women (SBP: 139±19 and DBP: 92± 18) as compared with those of the NT group (SBP: 112±10 and DBP: 74±9). A significant enlargement of the left atrium (4.10±0.48 cm vs 3.6±0.3 cm; p<0.001) and of the left ventricular normalized mass (59.6±19.7 g/cm2,7 vs 41.9±3.4 g/cm2,7; p<0.001) was observed. Cardiac output (CO, L/min) and systolic volume (SV, mL) were significantly higher in the CAH group (CO: 6.0±1.54 vs 4.9±2.1, p<0.01; SV: 77.3±19.8 vs 56.5±25.8, p<0.001). CONCLUSION: Chronic hypertensive pregnant women have structural and functional cardiac changes that justify routine cardiologic assessment, even in the absence of cardiopulmonary symptoms.

Degradación de efluentes de las industrias del cuero y textil mediante procesos fotocatalíticos heterogéneos empleando la luz solar. Degradation of effluents from the leather and textile industries through heterogeneous photocatalytic processes using sunlight.

El creciente desarrollo de la industria del cuero y textil en nuestro país, y específicamente en la provincia de Córdoba, ha hecho resurgir en los ultimos años una problemática aún no resuelta que es la elevada contaminación de los recursos hídricos. En ambas industrias, la operación de teñido involucra principalmente colorantes de tipo azoico los cuales son "no biodegradables" y se fragmentan liberando aminas aromáticas cancerígenas. Para abordar esta problemática, la fotocatálisis heterogénea aparece como una nueva tecnología que permitiría la completa mineralización de estos colorantes. A través de radiación y un fotocatalizador sólido adecuado se pueden generan radicales libres eficientes para la oxidación de materia orgánica (colorantes) en medio acuoso. En este sentido, se proponen tamices moleculares mesoporosos modificados con metales de transición (MT) como fotocatalizadores potencialmente aptos para la degradación de estos contaminantes. El propósito principal de este proyecto es el diseño, síntesis, caracterización y evaluación de materiales mesoporosos que presenten actividad fotocatalítica ya sea mediante la modificación de su estructura con diversos metales fotosensibles y/o empleándolos como soporte de óxido de titanio. Se pretende evaluar estos materiales en la degradación de colorantes intentando desplazar su fotosensibilidad hacia la radiación visible para desarrollar nuevas tecnologías con menor impacto ambiental y mayor aprovechamiento de la energía solar. Para ello se sintetizarán materiales del tipo MCM-41 modificados con distintos MT tales como Fe, Cr, Co, Ni y Zn mediante incorporación directa del ión metálico o impregnación. Al mismo tiempo, tanto estos últimos materiales como el MCM-41 silíceo serán empleados como soporte de TiO2. Sus propiedades fisicoquímicas se caracterizarán mediante distintas técnicas instrumentales y su actividad fotocatalítica se evaluará en la degradación de colorantes azoicos bajo radiación visible. Se seleccionará el catalizador más eficiente y se estudiarán los diversos factores que afectan el proceso de fotodegradación. Así mismo, el análisis de la concentración del colorante y los productos presentes en el medio en función del tiempo de reacción permitirá inferir sobre la cinética de la decoloración y postular posibles mecanismos de fotodegradación. Con esta propuesta se espera contribuír al desarrollo de un sector industrial importante en nuestra provincia como es el de las industrias del cuero y textil, mediante la generación de nuevas tecnologías que empleen la energía solar para la degradación de sus efluentes (colorantes). En este sentido, se espera desarrollar nuevos materiales optimizados para lograr la mayor eficiencia fotocatalítica. Esto conduciría entonces hacia la remediación de un problema ambiental de alto impacto tanto para nuestra provincia y nuestro país como para la población mundial, como es la contaminación de los recursos hídricos. Finalmente, con este proyecto se contribuirá a la formación de dos doctorandos y un maestrando, cuyos temas de tesis están vinculados con nuestro objeto de estudio. The increasing development of the textile and leather industries in our country, and specifically in Córdoba, has revived an unresolved problem that is the high contamination of water resources. In both industries, the dyeing involves mainly type azoic dyes which are not biodegradable and break releasing carcinogenic aromatic amines. Heterogeneous photocatalysis appears as a new technology that would allow the complete mineralization of these pollutants. Through radiation and a suitable solid it is possible to generate free radicals for efficient oxidation of organic matter (dyes) in aqueous medium. In this respect, mesoporous molecular sieves modified with transition metals are proposed as potential photocatalysts. The main purpose of this project is the synthesis of mesoporous materials having photocatalytic activity for the degradation of dyes. We will try to move their photosensitivity to visible radiation to develop new technologies with lower environmental impact and greater use of solar energy. Materials MCM-41 modified with metals (Fe, Cr, Co, Ni and Zn) will be synthesized by direct incorporation or impregnation. These materials and the siliceous MCM-41 will be then employed as support of TiO2. The materials will be evaluated in the photocatalytic degradation of azoic dyes under visible radiation. The influence of different factors on the photodegradation proccess will be studied. Kinetic studies will be carried out and a possible reaction way will be proposed. Thus, this work will contribute to the advancement of an important industrial sector and the remediation of an environmental problem with high impact for our province and our country. Moreover, this proyect will contribute to the development of two doctoral tesis and one magister tesis which are vinculated with our study subject.

Criação de flebotomos e transmissão experimental da Leishmaniose visceral americana

Foi conseguida a criação em laboratório do flebotomus intermedius e foram obtidos, de ovos colhidos em natureza, alguns F. longipapis. 231 femeas F. intermedius alimentadas em cães experimentalmente infectados pela Leishmania chagasi não se infectaram, emquanto que de 43 femeas alimentadas em um cão naturalmente infectado, 12 se infectaram; de 8 F. longipalpis que sugaram este cão, 6 se infectaram. O triturado de 3 F. intermedius apresentando flagelados com forma de leptomonas foi inoculado em um hamster, e o de 4 F. intermedius em outro. O segundo hamster, examinado nove meses após a primeira inoculação, mostrou-se infectado.

Mecanismes de reacció de sistemes catalítics amb èmfasi en carbens de Fischer i quantificació de l'aromaticitat en petites molècules inorgàniques cícliques i planes.

El tema principal del treball és sobre l'estudi teòric de l'estructura i reactivitat en carbens de Fischer de la forma (CO)5Cr=C(X)R (X= OH, NH2, OMe, NMe2 i R= CHCH2 i Ph). Particularment, el nostre interès va sorgir del tipus de reaccions de cicloadicció que donen lloc a la síntesi de productes naturals i fàrmacs de gran valor afegit. Hem estudiat els mecanismes de reacció dels casos més comuns de cicloanul•lació: la reacció de benzanul•lació de Dötz i ciclopentanulacions que es troben en competència amb el primer cas, derivats de l'inserció de acetilè i fenilacetilè. En l'últim pas de les reaccions que comporten la formació d'un sistema de més d'un anell, hi tenim una migració del complex metàl•lic de crom d'un extrem a un altre anomenat com rearranjament haptotròpic. Aleshores, hem investigat sobre els mecanismes de migració haptotròpica de Cr(CO)3 sobre hidrocarburs aromàtics policíclics analitzant l'efecte de la mida i la curvatura del sistema així com la complexació d'un segon fragment metàl•lic a la manera de coordinació als anells. D'una altre banda, vam estudiar l'aromaticitat en 54 cúmuls cíclics de molecules inorgàniques mitjançant metodologia desenvolupada al nostre grup de recerca i altres. Vam proposar la tècnica del scan-NICS com nova mesura quantitativa d'aromaticitat i reportar l'escassa correlació entre els distints índexs d'aromaticitat a la literatura. Finalment, com resultat de col•laboracions en estades de recerca, he desenvolupat propostes de mecanismes de reacció en sistemes catalítics de isonitrils i fosfinetà-amides i en dímers de gassos nobles.

Trace element differentiation in ferruginous accumulation soil patterns under tropical rainforest of southern Cameroon, the role of climatic change

Regions under tropical rainforest cover, such as central Africa and Brazil are characterised by degradation and dismantling of old ferricrete structures. In southern Cameroon, these processes are relayed by present-day ferruginous accumulation soil facies, situated on the middle and the lower part of hill slopes. These facies become progressively harder towards the surface, containing from bottom to top, mainly kaolinite, kaolinite-goethite and Al-rich goethite-hematite, and are discontinuous to the relictic hematite-dominated ferricrete that exist in the upper part of the hill slope. These features were investigated in terms of geochemical differentiation of trace elements. It appears that, in contrast to the old ferricrete facies, the current ferruginous accumulations are enriched in transitional trace elements (V, Cr, Co, Y, Sc) and Ph, while alkali-earth elements are less differentiated. This recent chemical accumulation is controlled both by intense weathering of the granodiorite bedrock and by mobilisation of elements previously accumulated in the old ferricrete. The observed processes are clearly linked to the present-day humid climate with rising groundwater tables. They slowly replace the old ferricretes formed during Cretaceous time under more seasonal climatic conditions, representing an instructive case of continuos global change. (C) 2002 Elsevier Science B.V. All rights reserved.

Hemilabile phosphine ligands in molybdenum and tungsten octahedral environments

The synthesis of three bidentate, hemilabile phosphine ligands, newly synthesized in the research group (TPOdiphos, DPPrPOdiphos and SODPdiphos), has been up-scaled and optimized. The ligand substitution reaction on Mo(CO)6 and W(CO)6 has been studied and the corresponding complexes fac-[MTPOdiphos(CO)3], fac-[MDPPrPOdiphos(CO)3], and fac-[MSODPdiphos(CO)3], (M= Mo, W) have been isolated in good yields and characterized by NMR, IR and HR MS. In the case of fac- [MoTPOdiphos(CO)3] the XRD crystal structure was resolved. The complexes were found to be octahedral, neutral molecules, with the metal in the zero oxidation state and the ligand adopting a facial P,P,O-coordination. The hard ligand atom (oxygen) is expected to exhibit special features the future applications of these novel ligands.

Síntesi i optimització de la DPTMephos. Complexos de Mo i W

La ruta sintètica del bis(2-((difenilfosfino)metil)fenil)sulfà, Ph2PCH2-(C6H4)S(C6H4)-CH2PPh2 , DPTMephos, involucra 5 reaccions en 4 etapes ben diferenciades. Es per aquest motiu que es fa necessària una optimització de la ruta sintètica per assolir rendiments més elevats. La primera reacció parteix del sulfur de difenil i involucra la formació d’un complex litiat per acabar realitzant una carbonilació amb N,N-DMF per obtindre un dialdehid. El següent pas de la ruta passa per la reducció del producte al diol corresponent. Tot seguit ja es por preparar el substrat mitjanjant una bromació per a que en l’última etapa, s’acobli a l’estructura el grup difenilfosfino. Tant mateix s’han sintetitzat els isòmers de la DPTMephos amb [W(CO)6] i [Mo(CO)6], observant-se la formació tant dels complexos meridionals com facials i la seva interconversió. Tot seguit s’ha desenvolupat la sulfuració de la DPTMephos per obtindre els lligands tant mono com di sulfurats. També s’ha realitzat un estudi de l’espectre de RMN 31P{1H} del complex fac-[Mo(CO)3(DPTMephos)] a temperatura variable per determinar el senyal de cada fòsfor no equivalent a 200K. S’ha realitzat un estudi de forma qualitativa de les conformacions que adopta l’anell quelat de 6 baules en les conformacions tant meridional com facial d’un complex.

Acúmulo de metais pesados em solos cultivados com cana-de-açúcar pelo uso contínuo de adubação fosfatada e água de irrigação

Com vistas em verificar se a utilização de fertilizantes fosfatados e irrigação com água poluída trazem elevação dos teores de metais pesados no solo, amostras de um Podzólico Amarelo e de dois Latossolos Amarelos, que receberam fertilizante fosfatado, desde 1968, e de um Cambissolo irrigado com água do rio Paraíba do Sul, desde 1978, cultivados com cana-de-açúcar (Saccharum spp.) em Campos dos Goytacazes, RJ, foram analisadas quanto aos teores totais de Cd, Co, Cr, Cu, Mn, Ni, Pb e Zn. Os resultados mostraram que os solos que receberam fertilizantes fosfatados durante 25 anos apresentaram aumento significativo de Cd quando comparados com áreas-controle, sem, contudo, elevá-los a níveis críticos. O Cambissolo irrigado durante 15 anos apresentou aumentos significativos de Cd, Cr, Co, Cu, Ni e Pb, tendo os resultados da extração seqüencial mostrado que a maior percentagem desses elementos encontra-se na fração residual, de baixa biodisponibilidade e mobilidade.

Aeration condition of a clayey oxisol under long-term no-tillage

The hypothesis of this study was that the absence of soil tillage in long-term no-tillage (NT) systems can be detrimental to soil aeration. The objective was to assess the aeration condition of an Oxisol (Rhodic Ferrasol), very clayey texture (750 g kg-1 of clay; 200 g kg-1 of sand), after 30 years of cultivation under NT. The physical property soil air permeability (Ka) is sensitive to changes in the soil pore system. Aside from Ka, the air-filled porosity (ε a) and indices of pore continuity (K1 and N), derived from the relationship between Ka and εa, were used as indices of soil aeration. From the soil layers 0.0-0.1 and 0.1-0.2 m, 240 undisturbed samples were collected along a transect perpendicular to the crop rows, at three sampling positions: corn plant row (CR); center of the interrow (INT); and the equidistant point between CR and INT (PE). The properties Ka and εa were determined at soil matric potentials (Ψm) of -2, -4, -6, -10, -30, and -50 kPa. Soil bulk density (BD) was also determined. The results confirmed the hypothesis. In the 0.0-0.1 m layer, Ka, K1, N and Ψa were significantly greater and BD significantly lower in CR than at the other sampling positions. At a Ψm of -10 kPa, the Ka of CR was 6.9 and 8.4 times higher than in PE and INT, respectively, in the 0.0-0.1 m layer. The properties Ka, K1 and N were sensitive enough to detect changes in the pore system and their differences between the sampling positions demonstrated the importance of the spatial location for soil sampling. Tilling the crop rows provides better soil aeration under NT.

Qualidade da semente e senescência de genótipos de soja sob dois níveis de infestação de percevejos (Pentatomidae)

Este trabalho objetivou estudar a resistência de duas linhagens de soja, do programa de melhoramento do sabor da Universidade Federal de Viçosa, MG, cultivadas sob dois níveis de infestação de percevejos, em comparação com três cultivares de soja. Os genótipos estudados foram: CR-1, CR-3, Cristalina (linhagem paterna), Davis (padrão de suscetibilidade) e IAC-100 (padrão de resistência). CR-1, CR-3, Davis e Cristalina, sob baixa infestação, produziram porcentagens de sementes normais semelhantes entre si (57%), e inferiores às de IAC-100 (77%). Sob alta infestação, CR-1, CR-3 e Cristalina produziram percentagens de sementes normais semelhantes entre si (22%) e inferiores às de Davis (43%) e IAC-100 (59%). Todos os genótipos apresentaram baixo grau de retenção foliar (menos que 6%) quando cultivados sob baixa infestação, mas sob alta infestação, a CR-1 e IAC-100 apresentaram menores porcentagens de retenção foliar (menos que 5%), seguida por Davis e CR-3 (6-20%) e Cristalina (21-40%). CR-1, IAC-100 e Davis não apresentaram plantas com caule verde sob baixa infestação, ao contrário do que foi registrado com CR-3 (3,6%) e Cristalina (11%). IAC-100, CR-1 e Davis apresentaram menores porcentagens de plantas com caule verde (6,4, 10,3 e 18,3%, respectivamente) que CR-3 (64,8%) e Cristalina (77,3%).

La protection de la personnalité du travailleur : sauvegarde de sa santé et sécurité au travail

Le scandale de l'amiante, l'épidémie de suicides au travail ou bien encore le "karôshi" sont autant de faits qui invitent à une réflexion renouvelée sur les conditions de travail. Cette thèse part d'une volonté de revisiter, dans un monde professionnel bouleversé par les progrès constants de la technique et les pressions économiques, les liens entre santé et sécurité, telles que visées aux art. 328 CO, 6 LTr et 82 LAA. Il s'agit d'examiner l'articulation entre ces dispositions, sur la base d'une analyse historique et de l'apport actuel du système légal, et la pertinence de repenser celui-ci. En effet, le pluralisme des sources en la matière, hétérogènes de par leur nature (de droit public ou privé) et/ou de par leur objet (la santé ou la sécurité), et le manque d'harmonie entre elles ne sont pas sans créer difficultés d'application et doubles emplois. La présente thèse commence par quelques repères chronologiques sur la mise en place progressive et pragmatique de la législation sociale suisse. Suit un survol des lois protectrices et autres normativités extra-juridiques, qui laisse conclure à un foisonnement et à une hétérogénéité des sources applicables. Puis, les trois dispositions générales topiques, à savoir les articles 328 CO, 6 LTr et 82 LAA, font successivement l'objet d'un examen détaillé, en vue d'évaluer leur bien-fondé respectif et la pertinence d'une approche compartimentée de la santé et sécurité au travail. Et donc de conclure par une réflexion sur l'intérêt d'un changement, notamment par la suppression du dualisme LTr / LAA.

Adsorção de íons Cu2+ em latossolo vermelho-amarelo húmico

In environmental studies it is necessary to know the adsorption behavior of metals by soils, since the unfavorable effects of heavy metals and even the micronutrients at high concentrations in the environment are related to these adsorbents' ability to immobilize them. A sample of a humic yellow red oxisol from Araponga region in the State of Minas Gerais, Brazil, was used to verify the adsorption behavior of Cu2+ ions in this substrate. The mathematical model described by Langmuir's adsorption equation in its linearized form was applied and the values of the maximum capacity b and those of the constant related to the bonding energy a were obtained. Aliquots of copper nitrate solutions containing several concentrations of this metal were added to soil samples, the pH being predetermined for developing the adsorption experiments. The chemical and physical characterization of soil sample were performed by determining the organic carbon, nitrogen and phosphorus concentrations, cation exchange capacity (CEC), pH, concentration of metals (Al, Fe, K, Mg, Ca, Zn, Cu, Ni, Cr, Co, Pb, and Cd), granulometric analysis and X-ray diffraction. Langmuir isotherms presented two distinct adsorption regions at both pH 4 and pH 5, showing that the adsorptive phenomenon occurs in two distinct stages. The adsorption sites for the lower part presented greater bonding energy and low adsorption capacity compared with the adsorption sites of the part of the curve corresponding to higher Cu concentrations in the equilibrating solution.

Avaliação da resistência de isolinhas de feijoeiro a diferentes patótipos de Colletotrichum lindemuthianum, Uromyces appendiculatus e Phaeoisariopsis griseola

Isolinhas de feijoeiro (Phaseolus vulgaris)derivadas da cultivar Rudá, com grãos do tipo "carioca", contendo os genes de resistência à antracnose (Co-4 do cv. TOou Co-6 do cv. AB 136 ou Co-10 do cv. Ouro Negro), ferrugem (gene do cv. Ouro Negro) e mancha-angular (phg-1 da linhagem AND 277) foram desenvolvidas pelo Programa de Melhoramento do Feijoeiro do BIOAGRO/UFV, para serem utilizadas na piramidação desses genes em uma única cultivar. Este trabalho teve como objetivo determinar o espectro de resistência dessas isolinhas a diferentes patótipos de Colletotrichum lindemuthianum, Uromyces appendiculatus e Phaeoisariopsis griseola, visando selecionar as linhagens mais similares aos progenitores doadores quanto à sua resistência. Para isto, foram conduzidas inoculações artificiais com 18 patótipos de C. lindemuthianum, dez patótipos de U. appendiculatus e quatro patótipos de P. griseola. Para resistência à antracnose, foi selecionada uma linhagem do cruzamento Rudá x TO, homozigota resistente a 17 patótipos, uma linhagem do retrocruzamento Rudá x AB 136, homozigota resistente a 15 patótipos e uma linhagem do cruzamento Rudá x Ouro Negro, homozigota resistente a 15 patótipos de C. lindemuthianum. Para resistência à ferrugem, uma linhagem do cruzamento Rudá x Ouro Negro, apresentou-se homozigota resistente aos dez patótipos de U. appendiculatus testados. Para resistência à mancha-angular, uma linhagem do cruzamento Rudá x AND277 apresentou-se homozigota resistente aos quatro patótipos de P. griseola inoculados. As melhores isolinhas estão sendo intercruzadas visando a piramidação de genes de resistência à ferrugem, à antracnose e à mancha-angular e o desenvolvimento de cultivares essencialmente derivadas da cultivar Rudá.

Sample preparation and heavy metal determination by atomic spectrometry /

Microwave digestions of mercury in Standards Reference Material (SRM) coal samples with nitric acid and hydrogen peroxide in quartz vessels were compared with Teflon® vessel digestion by using flow injection cold vapor atomic absorption spectrometry. Teflon® vessels gave poor reproducibiUty and tended to deliver high values, while the digestion results from quartz vessel show good agreement with certificate values and better standard deviations. Trace level elements (Ag, Ba, Cd, Cr, Co, Cu, Fe, Mg, Mn, Mo, Pb, Sn, Ti, V and Zn) in used oil and residual oil samples were determined by inductively coupled plasma-optical emission spectrometry. Different microwave digestion programs were developed for each sample and most of the results are in good agreement with certified values. The disagreement with values for Ag was due to the precipitation of Ag in sample; while Sn, V and Zn values had good recoveries from the spike test, which suggests that these certified values might need to be reconsidered. Gold, silver, copper, cadmium, cobalt, nickel and zinc were determined by continuous hydride generation inductively coupled plasma-optical emission spectrometry. The performance of two sample introduction systems: MSIS™ and gas-liquid separator were compared. Under the respective optimum conditions, MSIS^"^ showed better sensitivity and lower detection limits for Ag, Cd, Cu, Co and similar values for Au, Ni and Zn to those for the gas-liquid separator.