Catalytic oxidation of alcohols: recent advances

This review concerns metal-catalyzed reactions of oxidation of alcohols to the respective products, mainly ketones and aldehydes, mostly within the period of 2010–2014. Both conventional and unconventional systems, not only with usual reagents, but also with uncommon and prospective ones, are overviewed, with recently achieved developments.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Synthesis of biodiesel from wastes of food industry via direct transesterification with methanol/carbon dioxide mixtures

Dissertation presented at Faculdade de Ciências e Tecnologia from Universidade Nova de Lisboa to obtain the degree of Master in Chemical and Biochemical Engineering

The removal of xenobiotic compounds from wastewater through the use of biological processes and advanced oxidation technologies

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química e Bioquímica pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Decavanadate interactions with actin: cysteine oxidation and vanadyl formation

Dalton Trans., 2009, 7985–7994

Competitive paths for methanol decomposition on ruthenium: a DFT study

Methanol decomposition is one of the key reactions in direct methanol fuel cell (DMFC) state-of-the-art technology, research, and development. However, its mechanism still presents many uncertainties, which, if answered, would permit us to refine the manufacture of DMFCs. The mechanism of methanol decomposition on ruthenium surfaces was investigated using density functional theory and a periodic supercell approach. The possible pathways, involving either initial C−H, C−O or O−H scission, were defined from experimental evidence regarding the methanol decomposition on ruthenium and other metallic surfaces. The study yielded the O−H scission pathway as having both the most favorable energetics and kinetics. The computational data, which present a remarkable closeness with the experimental results, also indicate methanol adsorption, the starting point in all possible pathways, to be of weak nature, implying a considerable rate of methanol desorption from the ruthenium, compromising the reaction.

Fsp27/CIDEC is a CREB target gene induced during fasting and regulated by fatty acid oxidation rate

Dissertação para obtenção do Grau de Mestre em Biotecnologia

The mechanism of formate oxidation by metal-dependent formate dehydrogenases

J Biol Inorg Chem (2011) 16:1255–1268 DOI 10.1007/s00775-011-0813-8

Formation of a stable cyano-bridged dinuclear iron cluster following oxidation of the superoxide reductases from Treponema pallidum and Desulfovibrio vulgaris with K(3)Fe(CN)(6)

Inorg. Chem., 2003, 42 (4), pp 938–940 DOI: 10.1021/ic0262886

Structural and functional characterization of the gene products responsible for phototrophic iron oxidation by purple bacteria

Dissertação para a obtenção de grau de doutor em Bioquímica pelo Instituto de Tecnologia Química e Biológica. Universidade Nova de Lisboa

Catalytic hydrogenation of carbon dioxide to form methanol and methane

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

“One-pot” enzymatic conversion of CO2 to methanol

Dissertação para obtenção do Grau de Mestre em Biotecnologia

The thermal effects on the methanol-to-olefins reaction: A modelling and experimental approach

With the projection of an increasing world population, hand-in-hand with a journey towards a bigger number of developed countries, further demand on basic chemical building blocks, as ethylene and propylene, has to be properly addressed in the next decades. The methanol-to-olefins (MTO) is an interesting reaction to produce those alkenes using coal, gas or alternative sources, like biomass, through syngas as a source for the production of methanol. This technology has been widely applied since 1985 and most of the processes are making use of zeolites as catalysts, particularly ZSM-5. Although its selectivity is not especially biased over light olefins, it resists to a quick deactivation by coke deposition, making it quite attractive when it comes to industrial environments; nevertheless, this is a highly exothermic reaction, which is hard to control and to anticipate problems, such as temperature runaways or hot-spots, inside the catalytic bed. The main focus of this project is to study those temperature effects, by addressing both experimental, where the catalytic performance and the temperature profiles are studied, and modelling fronts, which consists in a five step strategy to predict the weight fractions and activity. The mind-set of catalytic testing is present in all the developed assays. It was verified that the selectivity towards light olefins increases with temperature, although this also leads to a much faster catalyst deactivation. To oppose this effect, experiments were carried using a diluted bed, having been able to increase the catalyst lifetime between 32% and 47%. Additionally, experiments with three thermocouples placed inside the catalytic bed were performed, analysing the deactivation wave and the peaks of temperature throughout the bed. Regeneration was done between consecutive runs and it was concluded that this action can be a powerful means to increase the catalyst lifetime, maintaining a constant selectivity towards light olefins, by losing acid strength in a steam stabilised zeolitic structure. On the other hand, developments on the other approach lead to the construction of a raw basic model, able to predict weight fractions, that should be tuned to be a tool for deactivation and temperature profiles prediction.

Larvicidal activity of the methanol extract and fractions of the green fruits of Solanum lycocarpum(Solanaceae) against the vector Culex quinquefasciatus (Diptera: Culicidae)

IntroductionThe larvicidal activity of Solanum lycocarpumagainst Culex quinquefasciatus is unknown.MethodsWe evaluated the larvicidal activity of extracts of the green fruits of Solanum lycocarpum against third and fourth instar larvae of C. quinquefasciatus.ResultsDichloromethane and ethyl acetate fractions showed the greatest larvicidal effect at 200mg/L (83.3% and 86.7%, respectively). The methanol and dichloromethane, ethyl acetate, and hydromethanolic fractions demonstrated larvicidal effects against C. quinquefasciatus, with LC50 values of 126.24, 75.13, 83.15, and 207.05mg/L, respectively.ConclusionsThus, when considering new drugs with larvicidal activity from natural products, S. lycocarpum fruits may be good candidate sources.

Grafting of adipic anhydride to carbon nanotubes through a Diels-Alder cycloaddition/oxidation cascade reaction

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