µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

MBR activated sludge filterability characterization in cross flow filtration

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia do Ambiente, perfil Sanitária

Is it possible to remove polymeric nanoparticles from aqueous paints during the activated sludge treatment?

The market for emulsion polymers (latexes) is large and growing at the expense of other manufacturing processes that emit higher amounts of volatile organic solvents. The paint industry is not an exception and solvent-borne paints have been gradually substituted by aqueous paints. In their life-cycle, much of the aqueous paint used for architectural or decorative purposes will eventually be discharged into wastewater treatment facilities, where its polymeric nanoparticles (mainly acrylic and styrene-acrylic) can work as xenobiotics to the microbial communities present in activated sludge. It is well established that these materials are biocompatible at macroscopic scale. But is their behaviour the same at nanoscale? What happens to the polymeric nanoparticles during the activated sludge process? Do nanoparticles agregate and are discharged together with the sludge or remain in emulsion? How do microorganisms interact with these nanoparticles? Are nanoparticles degradated by them? Are they adsorbed? Are these nanoparticles toxic to the microbial community? To study the influence of these xenobiotics in the activated sludge process, an emulsion of cross-linked poly(butyl methacrylate) nanoparticles of ca. 50 nm diameter was produced and used as model compound. Activated sludge from a wastewater treatment plant was tested by the OCDE’s respiration inhibition test using several concentrations of PBMA nanoparticles. Particle aggregation was followed by Dynamic Light Scattering and microorganism surfaces were observed by Atomic Force Microscopy. Using sequential batch reactors (SBRs) and continuous reactors, both inoculated with activated sludge, the consumption of carbon, ammonia, nitrite and nitrate was monitored and compared, in the presence and absence of nanoparticles. No particles were detected in all treated waters by Dynamic Light Scattering. This can either mean that microorganisms can efficiently remove all polymer nanoparticles or that nanoparticles tend to aggregate and be naturally removed by precipitation. Nevertheless respiration inhibition tests demonstrated that microorganisms consume more oxygen in the presence of nanoparticles, which suggests a stress situation. It was also observed a slight decrease in the efficiency of nitrification in the presence of nanoparticles. AFM images showed that while the morphology of some organisms remained the same both in the presence and absence of nanoparticles, others assumed a rough surface with hilly like shapes of ca. 50 nm when exposed to nanoparticles. Nanoparticles are thus likely to be either incorporated or adsorbed at the surface of some organisms, increasing the overall respiration rate and decreasing nitrification efficiency. Thus, despite its biocompatibility at macroscopic scale, PBMA is likely to be no longer innocuous at nanoscale.

Hierarchical wrinkling on elastometric Janus spheres

Hierarchical wrinkling on elastomeric Janus spheres is permanently imprinted by swelling, for different lengths of time, followed by drying the particles in an appropriate solvent. First-order buckling with a spatial periodicity (lambda(11)) of the order of a few microns and hierarchical structures comprising of 2nd order buckling with a spatial periodicity (lambda(12)) of the order of hundreds of nanometers have been obtained. The 2nd order buckling features result from a Grinfeld surface instability due to the diffusion of the solvent and the presence of sol molecules.

Catalytic activity of a benzoyl hydrazone based dimeric dicopper(II) complex in catechol and alcohol oxidation reactions

The benzoyl hydrazone based dimeric dicopper(II) complex [Cu2(R)(CH3O)(NO3)]2(CH3O)2 (R-Cu2+), recently reported by us, catalyzes the aerobic oxidation of catechols (catechol (S1), 3,5- itertiarybutylcatechol (S2) and 3-nitrocatechol (S3)) to the corresponding quinones (catecholase like activity), as shown by UV–Vis absorption spectroscopy in methanol/HEPES buffer (pH 8.2) medium at 25 C. The highest activity is observed for the substituted catechol (S2) with the electron donor tertiary butyl group, resulting in a turnover frequency (TOF) value of 1.13 103 h1. The complex R-Cu2+ also exhibits a good catalytic activity in the oxidation (without added solvent) of 1-phenylethanol to acetophenone by But OOH under low power (10 W) microwave (MW) irradiation. 2014 Elsevier B.V. All rights reserved.

Catalytic oxidation of cyclohexane with hydrogen peroxide and a tetracopper(II) complex in an ionic liquid

The catalytic peroxidative oxidation (with H2O2) of cyclohexane in an ionic liquid (IL) using the tetracopper(II) complex [(CuL)2(μ4-O,O′,O′′,O′′′-CDC)]2·2H2O [HL = 2-(2-pyridylmethyleneamino)benzenesulfonic acid, CDC = cyclohexane-1,4-dicarboxylate] as a catalyst is reported. Significant improvements on the catalytic performance, in terms of product yield (up to 36%), TON (up to 529), reaction time, selectivity towards cyclohexanone and easy recycling (negligible loss in activity after three consecutive runs), are observed using 1-butyl-3-methylimidazolium hexafluorophosphate as the chosen IL instead of a molecular organic solvent including the commonly used acetonitrile. The catalytic behaviors in the IL and in different molecular solvents are discussed.

Choosing amine-based absorbents for CO2 capture

CO2 capture from gaseous effluents is one of the great challenges faced by chemical and environmental engineers, as the increase in CO2 levels in the Earth atmosphere might be responsible for dramatic climate changes. From the existing capture technologies, the only proven and mature technology is chemical absorption using aqueous amine solutions. However, bearing in mind that this process is somewhat expensive, it is important to choose the most efficient and, at the same time, the least expensive solvents. For this purpose, a pilot test facility was assembled and includes an absorption column, as well as a stripping column, a heat exchanger between the two columns, a reboiler for the stripping column, pumping systems, surge tanks and all necessary instrumentation and control systems. Some different aquous amine solutions were tested on this facility and it was found that, from a set of six tested amines, diethanol amine is the one that turned out to be the most economical choice, as it showed a higher CO2 loading capacity (0.982 mol of CO2 per mol of amine) and the lowest price per litre (25.70 ¤/L), even when compared with monoethanolamine, the benchmark solvent, exhibiting a price per litre of 30.50 ¤/L.

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks

Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2]n∙(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h−1), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 1–3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

Development of polymeric membranes for forward osmosis

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Química e Bioquímica

Optimization of antioxidants extraction from coffee silverskin, aroasting by-product, having in view a sustainable process

Coffee silverskin is a major roasting by-product that could be valued as a source of antioxidant compounds. The effect of the major variables (solvent polarity, temperature and extraction time) affecting the extraction yields of bioactive compounds and antioxidant activity of silverskin extracts was evaluated. The extracts composition varied significantly with the extraction conditions used. A factorial experimental design showed that the use of a hydroalcoholic solvent (50%:50%) at 40 °C for 60 min is a sustainable option to maximize the extraction yield of bioactive compounds and the antioxidant capacity of extracts. Using this set of conditions it was possible to obtain extracts containing total phenolics (302.5 ± 7.1 mg GAE/L), tannins (0.43 ± 0.06 mg TAE/L), and flavonoids (83.0 ± 1.4 mg ECE/L), exhibiting DPPHradical dot scavenging activity (326.0 ± 5.7 mg TE/L) and ferric reducing antioxidant power (1791.9 ± 126.3 mg SFE/L). These conditions allowed, in comparison with other “more effective” for some individual parameters, a cost reduction, saving time and energy.

Rheo-NMR study of water-based cellulose liquid crystal system at high shear rates

Since long ago cellulosic lyotropic liquid crystals were thought as potential materials to produce fibers competitive with spidersilk or Kevlar, yet the processing of high modulus materials from cellulose-based precursors was hampered by their complex rheological behavior. In this work, by using the Rheo-NMR technique, which combines deuterium NMR with rheology, we investigate the high shear rate regimes that may be of interest to the industrial processing of these materials. Whereas the low shear rate regimes were already investigated by this technique in different works [1-4], the high shear rates range is still lacking a detailed study. This work focuses on the orientational order in the system both under shear and subsequent relaxation process arising after shear cessation through the analysis of deuterium spectra from the deuterated solvent water. At the analyzed shear rates the cholesteric order is suppressed and a flow-aligned nematic is observed which for the higher shear rates develops after certain time periodic perturbations that transiently annihilate the order in the system. During relaxation the flow aligned nematic starts losing order due to the onset of the cholesteric helices leading to a period of very low order where cholesteric helices with different orientations are forming from the aligned nematic, followed in the final stage by an increase in order at long relaxation times corresponding to the development of aligned cholesteric domains. This study sheds light on the complex rheological behavior of chiral nematic cellulose-based systems and opens ways to improve its processing. (C) 2015 Elsevier Ltd. All rights reserved.

Sulfonated Schiff base copper(ii) complexes as efficient and selective catalysts in alcohol oxidation: syntheses and crystal structures

The reaction between 2-aminobenzenesulfonic acid and 2-hydroxy-3-methoxybenzaldehyde produces the acyclic Schiff base 2-[(2-hydroxy-3-methoxyphenyl) methylideneamino] benzenesulfonic acid (H2L center dot 3H(2)O) (1). In situ reactions of this compound with Cu(II) salts and, eventually, in the presence of pyridine (py) or 2,2'-bipyridine (2,2'-bipy) lead to the formation of the mononuclear complexes [CuL(H2O)(2)] (2) and [CuL(2,2'-bipy)]center dot DMF center dot H2O (3) and the diphenoxo-bridged dicopper compounds [CuL(py)](2) (4) and [CuL(EtOH)](2)center dot 2H(2)O (5). In 2-5 the L-2-ligand acts as a tridentate chelating species by means of one of the O-sulfonate atoms, the O-phenoxo and the N-atoms. The remaining coordination sites are then occupied by H2O (in 2), 2,2'-bipyridine (in 3), pyridine (in 4) or EtOH (in 5). Hydrogen bond interactions resulted in R-2(2) (14) and in R-4(4)(12) graph sets leading to dimeric species (in 2 and 3, respectively), 1D chain associations (in 2 and 5) or a 2D network (1). Complexes 2-5 are applied as selective catalysts for the homogeneous peroxidative (with tert-butylhydroperoxide, TBHP) oxidation of primary and secondary alcohols, under solvent-and additive-free conditions and under low power microwave (MW) irradiation. A quantitative yield of acetophenone was obtained by oxidation of 1-phenylethanol with compound 4 [TOFs up to 7.6 x 10(3) h(-1)] after 20 min of MW irradiation, whereas the oxidation of benzyl alcohol to benzaldehyde is less effective (TOF 992 h(-1)). The selectivity of 4 to oxidize the alcohol relative to the ene function is demonstrated when using cinnamyl alcohol as substrate.

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

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.

Auditoria à gestão de resíduos industriais

A presente dissertação foi realizada em colaboração com o grupo empresarial Monteiro, Ribas, tendo como principal objectivo a realização de uma auditoria à gestão dos resíduos industriais produzidos pelas suas fábricas localizadas na Estrada da Circunvalação, no Porto. Para cumprir este objectivo, inicialmente foi efectuado um levantamento das obrigações legais relativas aos resíduos e foram procuradas práticas aconselhadas para a gestão interna. Para cada uma das fábricas, verificaram-se, quais os resíduos produzidos e analisaram-se os seus percursos, considerando as suas origens, os locais e modos de acondicionamento na origem, os modos de transporte interno, os locais e modos de armazenagem preliminar, e ainda, as quantidades produzidas, os transportadores, os operadores finais e as operações finais de gestão, sendo que estas quatro últimas informações são relativas ao ano 2013. De seguida procedeu-se à realização da auditoria nas diferentes unidades, verificando o cumprimento dos requisitos legais e das boas práticas em matéria de gestão de resíduos. As principais não conformidades detectadas, comuns às várias unidades fabris foram a inexistência de local/recipiente definido para acondicionamento de alguns resíduos, a falta ou insuficiente identificação de recipientes/zonas de acondicionamento, a inexistência de bacias de retenção para resíduos líquidos perigosos, o facto de no transporte interno apenas os resíduos perigosos serem cobertos e, os resíduos líquidos perigosos não serem transportados sobre bacias de retenção móveis nem com o material necessário para absorver derrames. Para cada resíduo e para cada unidade industrial foram propostas medidas correctivas e/ou de melhoria, quando aplicável. Relativamente à armazenagem preliminar, a principal inconformidade detectada foi o facto de todos os parques (quatro) possuírem resíduos perigosos no momento das auditorias, o que não é adequado. Foram propostas medidas correctivas e/ou de melhoria para cada parque. Como proposta global, tendo em conta factores económicos e de segurança, sugeriu-se que apenas o parque de resíduos perigosos possa armazenar este tipo de resíduos, pelo que os procedimentos de transporte interno devem ser melhorados, fazendo com que estes resíduos sejam transportados directamente para o parque de resíduos perigosos. Desta forma dois dos parques devem sofrer algumas remodelações, nomeadamente serem cobertos e fechados, ainda que não totalmente, e o parque de resíduos perigosos deve ser fechado, mantendo aberturas para ventilação, deve ser equipado com kit´s de contenção de derrames, fichas de segurança, procedimentos a realizar em caso de emergência, e ainda, devido ao facto do sistema de contenção de derrames ser pequeno face ao total de armazenamento, aconselha-se o uso de bacias de retenção para alguns dos recipientes de resíduos líquidos perigosos. Ao longo deste processo e em consequência da realização da auditoria, algumas situações consideradas não conformes foram sendo corrigidas. Também foram preparadas instruções de trabalho adequadas que serão posteriormente disponibilizadas. Foi ainda elaborada uma metodologia de avaliação de processos como base de trabalho para redução dos resíduos gerados. A etapa escolhida para a aplicação da mesma foi uma etapa auxiliar do processo produtivo da Monteiro, Ribas - Revestimentos, S.A - a limpeza de cubas com solventes, por forma a tentar minimizar os resíduos de solventes produzidos nesta operação. Uma vez que a fábrica já realiza a operação tendo em consideração medidas de prevenção e reutilização, a reciclagem é neste momento a única forma de tentar minimizar os resíduos de solventes. Foram então estudadas duas opções, nomeadamente a aquisição de um equipamento de regeneração de solventes e a contratação de uma operadora que proceda à regeneração dos resíduos de solventes e faça o retorno do solvente regenerado. A primeira opção poderá permitir uma redução de cerca de 95% na produção de resíduos de solventes e na aquisição de solvente puro, estimando-se uma poupança anual de cerca de **** €, com um período de recuperação do capital de cerca de 16 meses e a segunda pode conduzir a uma redução significativa na aquisição de solvente puro, cerca de 65%, e a uma poupança anual de cerca de **** €.