Estudo semi-empírico de ácidos hidroxâmicos: ácido formoidroxâmico e derivados do aleloquímico dimboa

Open chain hydroxamic acid (Hx) can exist as Z and E diastereomers of two tautomers, hydroxamic acid and hydroximic acid. The conformational stability of the formohydroxamic acid isomers evaluated by PM3 compared better to ab initio results from the literature than AM1 results. Structural data of the cyclic Hx 2,4-dihydroxy-7-metoxy-2H-1,4-benzoxazin-3(4 H)-one (DIMBOA) obtained by both semiempirical methods compared well to ab initio results. pKa data from the literature for derivatives of the aldolic isomer of DIMBOA were compared to the stability of the anions resulting from the loss of protons of their phenol and hydroxamic acid groups, determined as the difference in heat of formation between anionic and neutral forms, calculated by AM1 and PM3 methods. Good correlations between theoretical and experimental data were obtained for both semiempirical methods.

Estabilidade relativa de alcenos: análise dos critérios encontrados nos livros textos de graduação e uma proposta de explicação operacional para alcenos dissubstituídos

Despite of being used as thermodynamic criterion to rank alkene stability in a number of undergraduate textbooks, the heat of hydrogenation does not describe adequately the relative stability of disubstituted alkenes. In this work, both the heat of formation and the heat of combustion were used as thermodynamic criteria to rank correctly the stability of alkenes according to the degree of alkyl substitution and also in the disubstituted series (geminal > trans > cis). An operational model based on molecular orbital and valence bond representations of hyperconjugation is proposed to show how this effect can explain the order of stability of this class of compounds.

Remoção de metais pesados de efluentes aquosos pela zeólita natural escolecita - influência da temperatura e do pH na adsorção em sistemas monoelementares

Cation exchange capabilities of a Brazilian natural zeolite, identified as scolecite, were evaluated for application in wastewater control. We investigated the process of sorption of chromium(III), nickel(II), cadmium(II) and manganese(II) in synthetic aqueous effluents, including adsorption isotherms of single-metal solutions. The natural zeolite showed the ability to take up the tested heavy metals in the order Cr(III) > Cd(II) > Ni(II) > Mn(II), and this could be related to the valence and the hydration radius of the metal cations. The influence of temperature (25, 40 and 60 ºC) and initial pH value (from 4 to 6) was also evaluated. It was found that the adsorption increased substantially when the temperature was raised to 60 ºC and that maximum adsorption capacity was observed at pH 6. These results demonstrate that scolecite can be used for removal of heavy metals from aqueous effluents, under optimized conditions.

Sorção e persistência da sorgoleona em um Latossolo Vermelho-Amarelo

The root exudates produced by sorghum contain a biologically active constituent known as sorgoleone. The behavior of sorgoleone in a Red-Yellow Latosol was studied. The sorption model of sorgoleone in soil was better adjusted to the Freundlich equation, through the coefficients Kf (capacity of sorption) and 1/n (linearity of the isotherm). The persistence of sorgoleone in soil and its possible degradation were also evaluated by monitoring their residues in the soil along the time. Recovery rate of sorgoleone from the soil reached 93% after 24h. It was verified that sorgoleone is strongly sorbed in the soil and its half-life is 10 days, under the experimental conditions. The presence of sorgoleone or its metabolites was not detected in the soil after 60 days.

Caracterização de 2,2',4,4',6,6'-hexanitroestilbeno via análises instrumentais

2,2',4,4',6,6'-hexanitrostilbene (HNS) is a very important high explosive that is used in a range of military, aerospace and industrial formulations owing to its suitable properties. It is an insensitive and thermaly stable explosive that can be produced from 2,4,6-trinitrotoluene (TNT). This paper shows the characterization of synthesized HNS by different techniques, such as elementary analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FT-IR) and through the determination of the heat of combustion in a calorimeter.

Estudo teórico da interação existente entre a artemisinina e o heme

The purpose of this work is to study theoretically stereoelectronic aspects of the interaction between heme and artemisinin in the transitional heme-artemisinin complex. Through semi-empirical calculations using the PM3 method, the potential energy barrier of artemisinin rotation relative to heme in the heme-artemisinin complex was studied in vacuum and in the partially solvated state. The minimum heat of formation obtained for the complex with and without water molecules is -702.39 and -100.86 kcal mol-1, respectively, which corresponds to the dihedral angle C-Fe-O1-O2 of 43.93º and 51.90º around the iron-oxygen O1 bond, respectively. The water molecules bind to heme via 13 hydrogen bonds and O-H•••O and 6 C-H•••O interactions, which accounts for -67.23 kcal mol-1. It is observed that the inclusion of water molecules does not affect significantly the stability of the heme-artemisinin complex.

Energian käyttö sahatavaran kuivauksessa

Sahatavaran tuotannossa käytetään runsaasti lämpöä ja sähköä. Sähköä käytetään pääasiassa sahausvaiheessa ja lämpöä kuivausvaiheessa. Sahatavarakuutiosta haihdutetaan vettä kuivaamoissa noin 230-600 kiloa. Sahatavara kuivataan, koska kuivattu sahatavara säilyy paremmin ja on lisäksi kevyempää, kestävämpää ja sen muodonmuutokset ovat pienempiä. Työssä käsiteltävällä sahalla on erääseen kanavakuivaamoon tehty koerakennelma, jonka avulla kuivaamosta poistettavan ilman sisältämää lämpöä hyödynnetään sahatavaran lämmittämisessä kuivauslämpötilaan kuormanvaihdon jälkeen. Energiansäästön lisäksi rakennelman toivotaan ehkäisevän kuormanvaihdosta aiheutuvia olosuhdemuutoksia kuivausprosessin muissa vaiheissa. Poistoilman sisältämä höyry lauhtuu lämmittäessään kylmää sahatavaraa. Lauhtumisen yhteydessä vapautuu runsaasti energiaa. Tehtyjen kokeiden perusteella koerakennelma vähensi lämmönkulutusta selvästi. Lämmönkulutuksen alenema oli jopa teorialaskelmaa suurempi, mistä syystä kokeellisessa osassa tehtyihin mittaustuloksiin on syytä suhtautua varauksella. Perinteisessä kuivaamossa kosteus poistuu pääasiassa vesihöyrynä, mutta koerakennelman avulla saadaan noin puolet puusta haihdutetusta vedestä lauhtumaan takaisin vedeksi.

Calorímetro de gelo: uma abordagem histórica e experimental para o ensino de química na graduação

In addition to the usual advantage of an ice calorimeter of being able to measure slow heat changes, the instrument described here is extremely simple to construct and operate. Specific heat of aluminum, copper, lead and tin metals were determined using the ice calorimeter made with easily accessible materials. The values obtained from specific heat are near to those found in the literature and were 0.204; 0.030; 0.086; 0.046 cal/g °C with an error of theoretical values of 6.84; 1,64; 5.49 and 8.00% for aluminum, copper, lead and tin, respectively.

Caracterización de la biomasa inactiva de Aspergillus niger O-5 como sorbente de Pb (II)

The inactive biomass of fungus Aspergillus niger O-5 obtained in Cuba was characterized as sorbent of Pb2+ by several structural analysis and others techniques. In addition, the biomass was studied for the separation / preconcentration of Pb2+ from aqueous solution. The maximum biosorption capacity was obtained for the contact time of 30 min and pH 5. The kinetic of sorption process occurred according to the model of Ho. The Freundlich or Langmuir models suitably described the experimental adsorption isotherms. The biomass can be used as sorbent for Pb2+ with a maximum capacity of 4.7 - 6.2 mg g-1. The pretreatment with NaOH solution improved its sorption capacity.

DISPOSITIVOS DGT MODIFICADOS COM MATERIAIS ALTERNATIVOS PARA USO NA ESPECIAÇÃO DE ELEMENTOS TRAÇO

The use of MT-K10 Montmorillonite immobilized onto agarose was investigated in this work as an alternative binding phase in Diffusive Gradient in Thin Film (DGT) devices for the determination of metallic labile species. In addition, agarose itself was also used as the diffusive phase. The percentage of sorption of Zn2+, Cu2+, Cr3+, Mn2+, Cd2+, Pb2+, and Ni2+ onto the binding phase was higher than 80% and the desorption process for all elements was also greater than 75%. Elution factors were determined experimentally, ranging from 0.74 for Zn2+ and 0.90 for Cr3+ and Pb2+. The accumulation of all species was linear with time, in agreement with the Fick's 1st law of diffusion. The deployment of the alternative devices in natural waters was compared to commercial devices. Labile concentrations determined by the alternative devices were slightly superior compared to results obtained with the deployment of original DGT devices due to the less restrictive pores of agarose.

Biovoimalaitoksen energiatehokkuuden parantaminen ja osakuorma-ajon optimointi

Energiatehokkuus on nykyaikana yksi tärkeimmistä energiataloudellisista tekijöistä voimalaitosten sähköntuotannossa. Varsinkin yhteistuotantolaitoksissa joissa sähkö on lämpöenergian lisänä saatava sivutuote, sähkön tuotannon optimointi voi merkitä laitostalouden ja yrityksen kannalta huomattavia lisätuloja tai -säästöjä. Kaukaan Voima Oy:n biovoimalaitos on vuonna 2009 kaupalliseen käyttöön valmistunut moderni yhteistuotantolaitos, joka sijaitsee Lappeenrannassa UPM Kaukas sellutehtaan tehdasalueella. Voimalaitos tuottaa kaukolämpöä ja sähköä Lappeenrannan kaupungille sekä prosessihöyryä ja sähköä UPM Kaukaan tehtaille. Tämän työn tavoitteena on tarkastella biovoimalaitoksen omakäyttösähkön kulutusta kuukausitasolla verrattuna laitoksella tuotettavan höyryn määrään sekä etsiä voimalaitokselta kohteita, joiden omakäyttösähkön kulutusta voidaan vähentää vaikuttamatta höyryntuotantoon ja näin parantaa laitoksen energiatehokkuutta ja hyötysuhdetta. Työ rajataan käsittelemään voimalaitoksen apulaitteiden ja -järjestelmien omakäyttösähkön kulutusta. Työssä tarkastellaan vuodenaikojen vaihtelun ja kaukolämmön sekä prosessihöyryn tarpeen muutoksen vaikutusta voimalaitoksen ajomalliin sekä höyryntuotannon ja omakäyttösähkön kulutuksen suhteisiin. Työssä esiin nousseiden kohteiden potentiaaliset sähköenergian säästöt ovat noin 2500 MWh vuodessa joka tarkoittaa keskimäärin 3,7 % vähennystä voimalaitoksen kuukausittaiseen omakäyttösähkön kulutukseen. Kohteet eivät käytännössä vaadi minkaanlaista investointirahaa, vaan uusia ajojärjestelyitä. Keskeisimmiksi säästökohteiksi valikoitui laitoksen pumppausjärjestelmien paineenalennukset.

Streamside management zone (SMZ) efficiency in herbicide retention from simulated surface flow

Plot-scale overland flow experiments were conducted to evaluate the efficiency of streamside management zones (SMZs) in retaining herbicides in runoff generated from silvicultural activities. Herbicide retention was evaluated for five different slopes (2, 5, 10, 15, and 20%), two cover conditions (undisturbed O horizon and raked surface), and two periods under contrasting soil moisture conditions (summer dry and winter wet season) and correlated to O horizon and site conditions. Picloram (highly soluble in water) and atrazine (moderately sorbed into soil particles) at concentrations in the range of 55 and 35 µg L-1 and kaolin clay (approximately 5 g L-1) were mixed with 13.000 liters of water and dispersed over the top of 5 x 10 m forested plots. Surface flow was collected 2, 4, 6, and 10 m below the disperser to evaluate the changes in concentration as it moved through the O horizon and surface soil horizon-mixing zone. Results showed that, on average, a 10 m long forested SMZ removed around 25% of the initial concentration of atrazine and was generally ineffective in reducing the more soluble picloram. Retention of picloram was only 6% of the applied quantity. Percentages of mass reduction by infiltration were 36% for atrazine and 20% for picloram. Stronger relationships existed between O horizon depth and atrazine retention than in any other measured variable, suggesting that better solid-solution contact associated with flow through deeper O horizons is more important than either velocity or soil moisture as a determinant of sorption.

Étude de la phase isolant topologique chez le composé demi-Heusler GdBiPt.

Il sera question dans ce mémoire de maîtrise de l’étude d’une nouvelle classification des états solides de la matière appelée isolant topologique. Plus précisément, nous étudierons cette classification chez le composé demi-Heusler GdBiPt. Nous avons principalement cherché à savoir si ce composé ternaire est un isolant topologique antiferromagnétique. Une analyse de la susceptibilité magnétique ainsi que de la chaleur spécifique du maté- riau montre la présence d’une transition antiferromagnétique à 8.85(3) K. Une mesure d’anisotropie de cette susceptibilité montre que les plans de spins sont ordonnés sui- vant la direction (1,1,1) et finalement des mesures de résistivité électronique ainsi que de l’effet Hall nous indiquent que nous avons un matériau semimétallique lorsque nous sommes en présence d’antiferromagnétisme. Présentement, les expériences menées ne nous permettent pas d’associer cet état métallique aux états surfaciques issus de l’état d’isolant topologique.

Indicadores da individualização de cuidados para o curso de licenciatura em enfermagem

RESUMO: A individualização dos cuidados de enfermagem tem sido associada a uma evolução clínica mais favorável, representando um importante parâmetro de avaliação e de desenvolvimento dos serviços de saúde. A tónica atribuída a esta problemática não só é evidenciada por diversos autores, como se enquadra nas metas de modernização do Sistema Nacional de Saúde e é destaque em vários códigos normativos da profissão nacionais e internacionais, como uma obrigação moral e deontológica. Assim, pretende-se mediante os ganhos em saúde sensíveis às intervenções de enfermagem, identificar quais indicadores do cuidado individualizado, para se efectivar a sua incorporação na formação inicial em enfermagem. Para tal efeito, construiu-se uma bateria de indicadores mediante análise de duas revisões sistemáticas da literatura, que teve por base o Modelo da Eficácia do Papel de Enfermagem, desenvolvido por Irvine et al. (1998). Para à adaptação à realidade portuguesa recorreu-se à técnica de Delphi, com duas rondas, que incluiu respectivamente, 12 e 10 peritos de enfermagem. Na análise de dados utilizou-se o nível de concordância superior ou igual a 90%, na última ronda. Na segunda fase do estudo, aplicou-se um inquérito por questionário (α de Cronbach = 0,919) para testar a sua aplicabilidade dos indicadores, a 156 enfermeiros, do mesmo hospital da área da grande Lisboa, no Serviço de Medicina e Cirurgia. Recorreu-se ao SPSS, versão 19 e realizou-se análise univariada e estatística analítica. Na bateria final de indicadores foram incorporados aqueles com ponderação positiva (≥51%). Os dados qualitativos obtidos foram submetidos a análise de conteúdo. Dos 58 indicadores iniciais, consolidaram-se 8 categorias: cuidado à pessoa em fim de vida e família, toque terapêutico, educação para a auto-gestão da saúde, cuidados de proximidade, gestão de casos, empoderamento/ literacia para a saúde, linha telefónica de apoio permanente/ tele-assistência e apoio psico-emocional, com valorização de 28 indicadores. O tempo de experiência profissional, tipo de serviço e tempo de permanência no mesmo serviço influenciou a percepção dos enfermeiros, confirmando os pressupostos de Irvine et al. (1998) e Benner (2001). A correlação total dos indicadores, no questionário, variou entre 0,248 e 0,650, para p<0,01. O facto de todas as correlações serem positivas significa que provavelmente estão associados à problemática da individualização, pelo que se sugere a sua transposição para o ensino de enfermagem. ABSTRACT: The individualization of nursing care has been associated with a more favorable clinical evolution, an important parameter for the evaluation and development of health services. The emphasis given to this problem is not only evidenced by several authors, as fits the goals of modernizing the National Health System and is featured in several normative codes of the profession nationally and internationally, as a moral and ethical obligation. Thus, it is intended by the gains in health sensitive to nursing interventions, identify indicators of individualized care and give effect to its incorporation into the initial training in nursing. For this purpose, we constructed a series of indicators by analyzing two systematic reviews of literature, which was based on the The Nursing Role Effectiveness Model developed by Irvine et al. (1998). For the adaptation to the Portuguese appealed to the Delphi technique with two rounds, which included, respectively, 10 and 12 nursing experts. In data analysis we used the level of agreement greater than or equal to 90% in the last round. In the second phase of the study, we applied a questionnaire (Cronbach's α = 0.919) to test the applicability of the indicators, the 156 nurses in the same hospital in the Greater Lisbon area, the Department of Medicine and Surgery. Done using the SPSS, version 19 and conducted a univariate analysis and analytical statistics. In the final heat of indicators were incorporated into those with positive weight (≥ 51%). Qualitative data were subjected to content analysis. Of the initial 58 indicators, eight were consolidated categories: care to the person and family life, therapeutic touch education for self-management of health care outreach, case management, empowerment / literacy to health, a telephone line permanent support / tele-assistance and psycho-emotional, with an appreciation of 28 indicators. The length of professional experience, type of service and length of stay in the same service influenced the perception of nurses, confirming the assumptions of Irvine et al. (1998) and Benner (2001). The total correlation of the indicators in the questionnaire ranged between 0.248 and 0.650, p <0.01. The fact that all correlations are positive means that are probably associated with the problem of individuation, which is suggested by its implementation in nursing education.

Understanding African easterly waves: a moist singular vector approach

Moist singular vectors (MSV) have been applied successfully to predicting mid-latitude storms growing in association with latent heat of condensation. Tropical cyclone sensitivity has also been assessed. Extending this approach to more general tropical weather systems here, MSVs are evaluated for understanding and predicting African easterly waves, given the importance of moist processes in their development. First results, without initial moisture perturbations, suggest MSVs may be used advantageously. Perturbations bear similar structural and energy profiles to previous idealised non-linear studies and observations. Strong sensitivities prevail in the metrics and trajectories chosen, and benefits of initial moisture perturbations should be appraised. Copyright © 2009 Royal Meteorological Society