Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands

Four cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(PPh3)(2)](+), with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b; 4,3-b'] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells).

Low-Carbon Cement with Waste Oil-Cracking Catalyst Incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Fungal and microbial volatile organic compounds exposure assessment in a waste sorting plant

In the management of solid waste, pollutants over a wide range are released with different routes of exposure for workers. The potential for synergism among the pollutants raises concerns about potential adverse health effects, and there are still many uncertainties involved in exposure assessment. In this study, conventional (culture-based) and molecular real-time polymerase chain reaction (RTPCR) methodologies were used to assess fungal air contamination in a waste-sorting plant which focused on the presence of three potential pathogenic/toxigenic fungal species: Aspergillus flavus, A. fumigatus, and Stachybotrys chartarum. In addition, microbial volatile organic compounds (MVOC) were measured by photoionization detection. For all analysis, samplings were performed at five different workstations inside the facilities and also outdoors as a reference. Penicillium sp. were the most common species found at all plant locations. Pathogenic/toxigenic species (A. fumigatus and S. chartarum) were detected at two different workstations by RTPCR but not by culture-based techniques. MVOC concentration indoors ranged between 0 and 8.9 ppm (average 5.3 ± 3.16 ppm). Our results illustrated the advantage of combining both conventional and molecular methodologies in fungal exposure assessment. Together with MVOC analyses in indoor air, data obtained allow for a more precise evaluation of potential health risks associated with bioaerosol exposure. Consequently, with this knowledge, strategies may be developed for effective protection of the workers.

Exposure to microbial volatile organic compounds in a waste-handling unit

The production of MVOC by fungi has been taken into account especially from the viewpoint of indoor pollution with microorganisms but the relevance of fungal metabolites in working environments has not been sufficiently studied. The purpose of this study was to assess exposure to MVOCs in a waste-handling unit. It was used Multirae equipment (RAE Systems) to measured MVOCs concentration with a 10.6 eV lamps. The measurements were done near workers nose and during the normal activities. All measurements were done continuously and had the duration of 5 minutes at least. It was consider the higher value obtained in each measurement. In addition, for knowing fungi contamination, five air samples of 50 litres were collected through impaction method at 140 L/minute, at one meter tall, on to malt extract agar with the antibiotic chloramphenicol (MEA). MVOCs results range between 4.7 ppm and 8.9 ppm in the 6 locations consider. These results are eight times higher than normally obtained in indoor settings. Considering fungi results, two species were identified in air, being the genera Penicillium found in all the samples in uncountable colonies and Rhizopus only in one sample (40 UFC/m3). These fungi are known as MVOCs producers, namely terpenoids, ketones, alcohols and others. Until now, there has been no evidence that MVOCs are toxicologically relevant, but further epidemiological research is necessary to elucidate their role on human’s health, particularly in occupational settings where microbiological contamination is common. Additionally, further research should concentrate on quantitative analyses of specific MVOCs.

A New Modular Marx Derived Multilevel Converter

A new Modular Marx Multilevel Converter, M(3)C, is presented. The M(3)C topology was developed based on the Marx Generator concept and can contribute to technological innovation for sustainability by enabling wind energy off-shore modular multilevel power switching converters with an arbitrary number of levels. This paper solves both the DC capacitor voltage balancing problem and modularity problems of multilevel converters, using a modified cell of a solid-state Marx modulator, previously developed by authors for high voltage pulsed power applications. The paper details the structure and operation of the M(3)C modules, and their assembling to obtain multilevel converters. Sliding mode control is applied to a M(3)C leg and the vector leading to automatic capacitor voltage equalization is chosen. Simulation results are presented to show the effectiveness of the proposed M(3)C topology.

A new cloning system based on the OprI lipoprotein for the production of recombinant bacterial cell wall-derived immunogenic formulations

The conjugation of antigens with ligands of pattern recognition receptors (PRR) is emerging as a promising strategy for the modulation of specific immunity. Here, we describe a new Escherichia coli system for the cloning and expression of heterologous antigens in fusion with the OprI lipoprotein, a TLR ligand from the Pseudomonas aeruginosa outer membrane (OM). Analysis of the OprI expressed by this system reveals a triacylated lipid moiety mainly composed by palmitic acid residues. By offering a tight regulation of expression and allowing for antigen purification by metal affinity chromatography, the new system circumvents the major drawbacks of former versions. In addition, the anchoring of OprI to the OM of the host cell is further explored for the production of novel recombinant bacterial cell wall-derived formulations (OM fragments and OM vesicles) with distinct potential for PRR activation. As an example, the African swine fever virus ORF A104R was cloned and the recombinant antigen was obtained in the three formulations. Overall, our results validate a new system suitable for the production of immunogenic formulations that can be used for the development of experimental vaccines and for studies on the modulation of acquired immunity.

Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

The influence of curing conditions on the mechanical performance of concrete made with recycled concrete waste

Research on the use of Construction and Demolition Waste (CDW) as recycled aggregate (in particular crushed concrete) for the production of new concrete has by now established the feasibility of this environmentally-friendly use of otherwise harmful waste. However, contrary to conventional concrete (CC), no large applications of concrete made with recycled concrete have been made and there is still a lack of knowledge in some areas of production and performance of recycled aggregate concrete (RAC). One issue concerns curing conditions: these greatly affect the performance of concrete made on site and some potential users of RAC wonder how RAC is affected by far-from-ideal curing conditions. This paper shows the main results of experiments to determine the influence of different curing conditions on the mechanical performance of concrete made with coarse recycled aggregate from crushed concrete. The properties analyzed include compressive strength, splitting tensile strength, modulus of elasticity, and abrasion resistance. The general conclusion in terms of mechanical performance is that RAC is affected by curing conditions roughly in the same way as CC. (C) 2011 Elsevier Ltd. All rights reserved.

Waste Marble Dust Blended Cement

Marble processing activities generates a.significant amount of waste in dust form. This waste, which is nowadays one of the environmental problems worldwide, presents great potential of being used as mineral addition in blended cements production. This paper shows preliminary results of an ongoing project which ultimate goal is to investigate the viability of using waste marble dust (WMD), produced by marble Portuguese industry, as cement replacement material. In order to evaluate the effects of the WMD on mechanical behaviour, different mortar blended cement mixtures were tested. These mixtures were prepared with different partial substitution level of cement with WMD. Strength results of WMD blended cements were compared to control cements with same level of incorporation of natural limestone used to produce commercial Portland-limestone cements. The results obtained show that WMD blended cements perform better than limestone blended cements for same replacement level up to 20% w/w. Therefore, WMD reveals promising attributes for blended cements production.

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.

Biodiesel production from waste frying oils over lime catalysts

Biodiesel production from semi-refined oils (SRO) and waste frying oils (WFO) was studied using commercial CaO as heterogeneous catalyst. The methanolysis tests were carried out in mild reaction conditions (62 A degrees C, atmospheric pressure). With such conditions, SRO (soybean and rapeseed) allowed to produce a biodiesel containing 97-98 % of methyl esters (FAME), whereas WFO only provided 86-87 % of FAME. The lower FAME yield for WFO oil is ascribable to the partial neutralization of the catalyst by free fatty acids. Also, soaps formation from the WFO oil reduced the weight yield of the oil phase (containing FAME) obtained and increased the MONG content of the glycerin phase. The catalysts stability tests showed high stability even when WFO oil was processed. Catalytic tests performed with blends of WFO/semi-refined oils showed blending as a good strategy to process low value raw oils with minor decay of the catalyst performance. Both WFO and semi-refined oils showed S-shape kinetics curves thus discarding significant differences of the reaction mechanisms.

Physical-chemical and mineralogical characterization of fine aggregates from construction and demolition waste recycling plants

Construction and demolition waste (CDW) represents around 31% of all waste produced in the European Union. It is today acknowledged that the consumption of raw materials in the construction industry is a non-sustainable activity. It is thus necessary to reduce this consumption, and the volume of CDW dumped, by using this waste as a source of raw materials for the production of recycled aggregates. One potential use of these aggregates is their incorporation in reinforced concrete as a replacement of natural aggregates. A concrete that incorporates these aggregates and still performs well requires them to be fully characterized so that their behaviour within the concrete can be predicted. Coarse recycled aggregates have been studied quite thoroughly, because they are simpler to reintroduce in the market as a by-product, and so has the performance of concrete made with them. This paper describes the main results of research designed to characterize the physical and chemical properties of fine recycled aggregates for concrete production and their relationship with mineralogical composition and preprocessing. The constraints of the incorporation of fine aggregates in reinforced concrete are discussed. It is shown that, unless a developed processing diagram is used, this application is not feasible. (C) 2013 Elsevier Ltd. All rights reserved.

Assessment of fungal contamination in waste sorting and incineration: case study in Portugal

Organic waste is a rich substrate for microbial growth, and because of that, workers from waste industry are at higher risk of exposure to bioaerosols. This study aimed to assess fungal contamination in two plants handling solid waste management. Air samples from the two plants were collected through an impaction method. Surface samples were also collected by swabbing surfaces of the same indoor sites. All collected samples were incubated at 27◦C for 5 to 7 d. After lab processing and incubation of collected samples, quantitative and qualitative results were obtained with identification of the isolated fungal species. Air samples were also subjected to molecular methods by real-time polymerase chain reaction (RT PCR) using an impinger method to measure DNA of Aspergillus flavus complex and Stachybotrys chartarum. Assessment of particulate matter (PM) was also conducted with portable direct-reading equipment. Particles concentration measurement was performed at five different sizes (PM0.5; PM1; PM2.5; PM5; PM10). With respect to the waste sorting plant, three species more frequently isolated in air and surfaces were A. niger (73.9%; 66.1%), A. fumigatus (16%; 13.8%), and A. flavus (8.7%; 14.2%). In the incineration plant, the most prevalent species detected in air samples were Penicillium sp. (62.9%), A. fumigatus (18%), and A. flavus (6%), while the most frequently isolated in surface samples were Penicillium sp. (57.5%), A. fumigatus (22.3%) and A. niger (12.8%). Stachybotrys chartarum and other toxinogenic strains from A. flavus complex were not detected. The most common PM sizes obtained were the PM10 and PM5 (inhalable fraction). Since waste is the main internal fungal source in the analyzed settings, preventive and protective measures need to be maintained to avoid worker exposure to fungi and their metabolites.

Utilização de materiais anti-vibráteis e de isolamento acústico na via férrea

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Vias de Comunicação e Transportes

Assessment of workers’ exposure to Aflatoxin B1 in a Portuguese waste industry

Aflatoxin B1 (AFB1) is considered by different International Agencies as a genotoxic and potent hepatocarcinogen. However, despite the fact that the fungi producing this compound are detected in some work environments, AFB1 is rarely monitored in occupational settings. The aim of the present investigation was to assess exposure to AFB1 of workers from one Portuguese waste company located in the outskirt of Lisbon. Occupational exposure assessment to AFB1 was done with a biomarker of internal dose that measures AFB1 in the serum by enzyme-linked immunosorbent assay. Forty-one workers from the waste company were enrolled in this study (26 from sorting; 9 from composting; 6 from incineration). A control group (n = 30) was also considered in order to know the AFB1 background levels for the Portuguese population. All the workers showed detectable levels of AFB1 with values ranging from 2.5ng ml−1 to 25.9ng ml−1 with a median value of 9.9±5.4ng ml−1. All of the controls showed values below the method’s detection limit. Results obtained showed much higher (8-fold higher) values when compared with other Portuguese settings already studied, such as poultry and swine production. Besides this mycotoxin, other mycotoxins are probably present in this occupational setting and this aspect should be taken into consideration for the risk assessment process due to possible synergistic reactions. The data obtained suggests that exposure to AFB1 occurs in a waste management setting and claims attention for the need of appliance of preventive and protective safety measures.