Fixação de nitrogênio: estrutura, função e modelagem bioinorgânica das nitrogenases

Biological nitrogen fixation, catalyzed by nitrogenases, contributes about half of the nitrogen needed to global agriculture. For forty years synthetic chemists and theoreticians have tried to understand and model the structure and function of this important metalloenzyme. Ten years after the first report on the crystal structure of the MoFe protein, scientists still have not been able to synthesize a chemical equivalent of the FeMo cofactor nor the structure knowledge revealed the key to its catalytic activity. This paper with 104 references presents a review of the most relevant advances in chemical nitrogen fixation and their relation with the nitrogenases.

Caracterização por XPS de filmes passivos formados sobre aços de baixa liga em meio de bicarbonato

Passive films formed in bicarbonate solutions on carbon steel, chromium steel and high speed steel have been characterized by XPS. The passive films formed on chromium and high speed steels showed superior protective properties than those formed on carbon steel. It was confirmed by XPS that the steel composition influences the passive film composition. Chromium oxide and hydroxide, as well as molybdenum and tungsten oxides and hydroxides are present in the passive film of chromium steel and high speed steel, respectively, besides iron oxide and hydroxide. The more complex composition of the oxide film on high speed steel explains its electrochemical behaviour and highest corrosion resistance.

Determinação direta de molibdênio em comprimidos polivitamínicos por voltametria em meio não aquoso

Adsorptive stripping voltammetry carried out in a homogeneous ternary solvent composed of N,N-dimethylformamide, water and ethanol, with alpha-benzoinoxime (alphaBO) as the complexing agent for Mo(VI) and a 0.5 mol L-1 acetic acid - sodium acetate buffer as supporting electrolyte was successfully used for the determination of molybdenum in polyvitamin-polymineral tablets. Tablet samples were analyzed and the results were compared with those obtained both by graphite furnace atomic absorption and by recovery tests, with good correlations, indicating that this may be considered as an alternative procedure for routine determination of Mo(VI) in pharmaceutical samples.

Commodity Price Driven Risk Management from Viewpoint of High Grade Steel Alloys

The study of price risk management concerning high grade steel alloys and their components was conducted. This study was focused in metal commodities, of which nickel, chrome and molybdenum were in a central role. Also possible hedging instruments and strategies for referred metals were studied. In the literature part main themes are price formation of Ni, Cr and Mo, the functioning of metal exchanges and main hedging instruments for metal commodities. This section also covers how micro and macro variables may affect metal prices from the viewpoint of short as well as longer time period. The experimental part consists of three sections. In the first part, multiple regression model with seven explanatory variables was constructed to describe price behavior of nickel. Results were compared after this with information created with comparable simple regression model. Additionally, long time mean price reversion of nickel was studied. In the second part, theoretical price of CF8M alloy was studied by using nickel, ferro-chrome and ferro-molybdenum as explanatory variables. In the last section, cross hedging possibilities for illiquid FeCr -metal was studied with five LME futures. Also this section covers new information concerning possible forthcoming molybdenum future contracts as well. The results of this study confirm, that linear regression models which are based on the assumption of market rationality, are not able to reliably describe price development of metals at issue. Models fulfilling assumptions for linear regression may though include useful information of statistical significant variables which have effect on metal prices. According to the experimental part, short futures were found to incorporate the most accurate information concerning the price movements in the future. However, not even 3M futures were able to predict turning point in the market before the faced slump. Cross hedging seemed to be very doubtful risk management strategy for illiquid metals, because correlations coefficients were found to be very sensitive for the chosen time span.

Recuperação de metais de catalisadores de hidrorrefino usados via fusão com KHSO4

This work describes a process for metal recovery from spent NiMo and CoMo/Al2O3 commercial hydrorefining catalysts. The samples were treated by fusion with potassium hydrogen sulfate (5 h, 600 ºC) with a KHSO4/catalyst mass ratio of 10:1. After fusion the solid was solubilized in water (100 ºC), leaving silicon compounds as residue. Losses of nickel and cobalt may reach 16 wt% of the amount present in the sample, depending on the silicon content. Soluble metals were isolated by selective precipitation techniques (nickel, cobalt, aluminum) or by solvent extraction with methyl-isobutyl ketone (molybdenum) in a hydrochloric acid medium. All metals were recovered in very good yields except for nickel and cobalt in the presence of considerable amounts of silicon. Soluble wastes consist of potassium/sodium sulfates/chlorides. Solid wastes correspond to about 4 wt% of the catalyst and can be discarded in industrial dumps.

Metales pesados y toxicidad de aguas del Río Aconcagua en Chile

The toxicity of surface waters in a zone with mining activity in the Aconcagua River was determined through growth inhibition bioassays of Pseudokirchneriella subcapitata, and correlated with heavy metal concentrations. Results show that the waters near the discharge of the mining effluent displayed toxicity during all periods of study; the molybdenum and copper concentration exceeded the norms of water quality. The correlations between the concentrations of metals and the growth rate of P. subcapitata varied in the different periods of the study; inverse and significant correlations with copper stand out in some periods.

Construção de uma cela de fluxo de longo caminho óptico para medidas espectrofotométricas

A simple and low-cost flow cell with 30 cm optical path for spectrophotometric measurements is described. It presents desirable characteristics such as low attenuation of the radiation beam and internal volume (75 µL) comparable to that of a 1-cm conventional cell (80 µL). Despite the increase in optical path, the effect on sample dispersion was also similar to that attained in the commercial cell. The performance of the cell was assessed by the determination of phosphate based on the molybdenum blue method, yielding a linear response range between 0.05 and 0.8 mg L-1 phosphorus (r=0.999). The increase in sensitivity (30.4-fold) in comparison with that obtained with a conventional 1-cm flow cell agreed with that estimated by the Lambert-Beer law.

Rota hidrometalúrgica de recuperação de molibdênio, cobalto, níquel e alumínio de catalisadores gastos de hidrotratamento em meio ácido

This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al2O3). Samples were preoxidized (500 ºC, 5 h) in order to eliminate coke and other volatile species present. The calcined solid was dissolved in concentrated H2SO4 and water (1:1 vol/vol) at 90 ºC; the insoluble matter was separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines at pH around 1.8. Cobalt (or nickel) was separated by addition of aqueous ammonium oxalate at the above pH. Phosphorus was removed by passing the liquid through a strong anion exchange column. Aluminum was recovered by neutralizing the solution with NaOH. The route presented in this work generates less final aqueous wastes because it is not necessary to use alkaline medium during the metal recovery steps.

Branqueamento de polpa celulósica kraft de eucalipto com peróxido ácido ativado por molibdênio

Optimum conditions to run the P Mo stage for bleaching eucalyptus kraft pulp were 90 ºC, pH 3.5, 2 h, 0.1 kg/t Mo and 5 kg/t H2O2. The P Mo stage efficiency increased with decreasing pH (1.5-5.5) and increasing temperature (75-90 ºC), time (2-4 h), and hydrogen peroxide (3-10 kg/t) and molybdenum concentration (0.1-0.4 kg/t). The implementation of the P Mo stage, as replacement for the A stage, decreased total active chlorine demand of the OAZDP sequence by 6 kg/t to reach 90% ISO, both in laboratory and mill scale. Such practice resulted in decreased bleaching chemical costs to produce fully bleached pulp of 90% ISO.

Análise por componentes principais de espectros nexafs na especiação do molibdênio em catalisadores de hidrotratamento

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination.

Epoxidação do óleo de soja com o sistema catalítico [MoO2(acac)2]/TBHP EM [bmim][PF6]

Epoxidation of soybean oil was investigated using 1-n-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] ionic liquid as biphasic medium with molybdenum(VI) acetylacetonate complex and tert-butyl hydroperoxide TBHP as oxidizing agent. Reaction conditions were molar ratio TBHP:number of double bonds of oil:catalyst of 100:100:1, reaction temperature of 60 ºC and reaction time between 2 and 24 h. The proposed system showed catalytic activity for epoxidation reactions under tested conditions. Reuse of ionic liquid/catalyst system for epoxidation reactions was also investigated. Evaluation of epoxidation observed in this catalytic system was done by quantitative ¹H NMR data.

Avaliação da combinação da nebulização discreta e processos de microextração aplicados à determinação de molibdênio por espectrometria de absorção atômica com chama (FAAS)

Simple and sensitive procedures for the extraction/preconcentration of molybdenum based on vortex-assisted solidified floating organic drop microextraction (VA-SFODME) and cloud point combined with flame absorption atomic spectrometry (FAAS) and discrete nebulization were developed. The influence of the discrete nebulization on the sensitivity of the molybdenum preconcentration processes was studied. An injection volume of 200 µL resulted in a lower relative standard deviation with both preconcentration procedures. Enrichment factors of 31 and 67 and limits of detection of 25 and 5 µg L-1 were obtained for cloud point and VA-SFODME, respectively. The developed procedures were applied to the determination of Mo in mineral water and multivitamin samples.

Dissulfeto de molibdênio, um material multifuncional e surpreendente: doze anos depois

In 2002, a review article was published in which molybdenum disulfide properties were discussed. The last sentence of the article read as follows: "Based on that described above, we can conclude that in spite of the vast applications of molybdenum disulfide in several industrial branches, many of the potential applications need to be investigated in the future". Since 2002, novel properties of molybdenum disulfide have been described which promise to revolutionize science. The objective of the present review paper was to provide an overview of the processes of 2H-MoS2 exfoliation and properties of the single layers, reported mainly in the last decade.

The laser weldability of lean duplex stainless steels

Ruostumattomien terästen hinta on kasvanut maailman laajuisen kysynnän kasvun seurauksena. Samoin on käynyt myös ruostumattomien terästen valmistukseen käytettävien seosaineiden hinnalle. Terästen valmistajat ovatkin kehittäneet lean duplex teräksiä vastatakseen hintatietoisten markkinoiden kysyntään. Näissä lean duplex teräksissä kalliita seosaineita kuten nikkeliä ja molybdeenia on korvattu typellä ja mangaanilla. Houkutteleviksi vaihtoehdoiksi perinteisille ruostumattomille teräksille lean duplex laadut tekee myös niiden hyvät lujuus- ja korroosio-ominaisuudet. Kirjallisuus osio esittelee lasereiden toimintaperiaatteen. Myös avaimenreikähitsauksen periaate on esitetty. Ruostumattomien terästen yleisimmät seosaineet ovat esitelty, kuten myös syy niiden seostamiseen. Ruostumattomat duplex-teräkset on esitelty samoin kuin lean duplex teräkset. Kokeellisen osion koehitsit hitsattiin osin samalla tuotantolinjalla lopputuotteen kanssa ja osin laboratoriossa. Koemateriaaleina olivat lean duplex teräkset 1.4162 ja 1.4362 joiden materiaalipaksuudet olivat 1.2 mm ja 1.5 mm. Hitsatuille lamelleille tehtiin painetestaus. Makroskopiaa ja valomikroskopiaa käytettiin koehitsien arvioinnissa kuten myös ristivetokoetta. Kiinnostavimmista hitseistä määritettiin myös faasisuhde. Lean duplex teräs 1.4362 havaittiin sopivammaksi laaduksi tämän kaltaisessa sovelluksessa, mutta myös laatu 1.4162 täyttää sovelluksen hitsille asetetut vaatimukset, tosin huomattavasti pienemmässä parametri ikkunassa. Valittu menetelmä faasisuhteen määrittämiseen osoittautui epätarkaksi, joten faasisuhteen osalta tämän tutkimuksen tulokset ovat vain suuntaa-antavia.

Sweet grape mini tomato grown in culture substrates and effluent with nutrient complementation

The objective of this study was to evaluate production of Sweet Grape mini tomato (Lycopersicum esculentum Mill.) using culture substrates and nutrient solution sewage effluent, applied by drip irrigation (fertigation). The experiment was conducted at the University of Goiás State (UEG-UnUCET), from June to November 2011 in Anápolis-GO, Brazil. The experimental design was a 2 x 3 factorial arrangement in a randomized complete block design with four repetitions. The plots were made by combining two nutrient solutions, effluent supplemented with mineral fertilizers (EcS); conventional nutrient solution (SnC); in addition three cultivation substrates: 60% of fine sand washed + 40% substrate composed by 20% coconut fiber plus 80% pine bark (S1); 20% coconut fiber and 80% pine bark (S2) and natural coconut fiber (S3). Sewage effluent were determined nitrate, calcium, potassium, manganese, total phosphate, total iron, magnesium, chloride, sulphate, boron, zinc and molybdenum. We evaluated average mass and average number of fruits per bunch, total fruit and total yield per plant. Statistical difference absence among tested solutions indicates sewage effluent can be used as an alternative source of nutrients in growing mini tomatoes in hydroponics.