New water-soluble Ruthenium(II) cytotoxic complex: biological activity and celular distribution

A novel water soluble organometallic compound, [RuCp(mTPPMSNa)(2,2'-bipy)][CF3SO3] (TM85, where Cp=eta(5)-cyclopentadienyl, mTPPMS = diphenylphosphane-benzene-3-sulfonate and 2,2'-bipy = 2,2'-bipyridine) is presented herein. Studies of interactions with relevant proteins were performed to understand the behavior and mode of action of this complex in the biological environment. Electrochemical and fluorescence studies showed that TM85 strongly binds to albumin. Studies carried out to study the formation of TM85 which adducts with ubiquitin and cytochrome c were performed by electrospray ionization mass spectrometry (ESI-MS). Antitumor activity was evaluated against a variety of human cancer cell lines, namely A2780, A2780cisR, MCF7, MDAMB231, HT29, PC3 and V79 non-tumorigenic cells and compared with the reference drug cisplatin. TM85 cytotoxic effect was reduced in the presence of endocytosis modulators at low temperatures, suggesting an energy-dependent mechanism consistent with endocytosis. Ultrastructural analysis by transmission electron microscopy (TEM) revealed that TM85 targets the endomembranar system disrupting the Golgi and also affects the mitochondria. Disruption of plasma membrane observed by flow cytometry could lead to cellular damage and cell death. On the whole, the biological activity evaluated herein combined with the water solubility property suggests that complex TM85 could be a promising anticancer agent. (C) 2013 Elsevier Inc. All rights reserved.

An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.

Production, purification and characterisation of polysaccharides from pleurotus ostreatus with antitumor activity

Background: Mushroom polysaccharides play an important role in functional foods because they exhibit biological modulator properties such as antitumour, antiviral and antibacterial activities. The present study involved the production, purification and characterisation of intracellular and extracellular free and protein-bound polysaccharides from Pleurotus ostreatus and the investigation of their growth-inhibitory effect on human carcinoma cell lines. Results: Several fermentation parameters were obtained: batch polysaccharide productivities of 0.013 +/- 8.12 x 10-5 and 0.037 +/- 0.0005 g L-1 day-1 for intracellular and extracellular polysaccharides respectively, a maximum biomass concentration of 9.35 +/- 0.18 g L-1, Pmax = 0.935 +/- 0.018 g L-1 day-1, µmax = 0.218 +/- 0.02 day-1, YEP/X = 0.040 +/- 0.0015 g g-1 and YIP/X = 0.014 +/- 0.0003 g g-1. Some polysaccharides exhibited superoxide dismutase (SOD)-like activity of 50-200 units. Fourier transform infrared analysis of the polysaccharides revealed absorption bands characteristic of such biological macromolecules. Cytotoxicity assays showed that both intracellular and extracellular polysaccharides exhibited antitumour activity towards several tested human carcinoma cell lines in a dose-dependent manner. Conclusion - The polysaccharides of P. ostreatus exhibited high SOD-like activity, which strongly supports their biological effect on tumour cell lines. The extracellular polysaccharides presented the highest antitumour activity towards the RL95 carcinoma cell line and should be further investigated as an antitumour agent.

Synthesis of organometallic Ruthenium(II) complexes with strong activity against several human canceer cell lines

A new family of "RuCp" (Cp=eta(5)-C5H5) derivatives with bidentate N,O and N,N'-heteroaromatic ligands revealed outstanding cytotoxic properties against several human cell lines namely, A2780, A2780CisR, HT29, MCF7, MDAMB231, and PD. IC50 values were much lower than those found for cisplatin. Crystal structure of compound 4 was determined by X-ray diffraction studies. Density functional theory (DFT) calculations performed for compound 1 showed electronic flow from the ruthenium center to the coordinated bidentate ligand, in agreement with the electrochemical studies and the existence of a metal-to-ligand charge-transfer (MLCT) band evidenced by spectroscopic data.

Liquid crystal beads constrained on thin cellulosic fibers: Electric field induced microrotors and N-I transition

We directly visualize the response of nematic liquid crystal drops of toroidal topology threaded in cellulosic fibers, suspended in air, to an AC electric field and at different temperatures over the N-I transition. This new liquid crystal system can exhibit non-trivial point defects, which can be energetically unstable against expanding into ring defects depending on the fiber constraining geometries. The director anchoring tangentially near the fiber surface and homeotropically at the air interface makes a hybrid shell distribution that in turn causes a ring disclination line around the main axis of the fiber at the center of the droplet. Upon application of an electric field, E, the disclination ring first expands and moves along the fiber main axis, followed by the appearance of a stable "spherical particle" object orbiting around the fiber at the center of the liquid crystal drop. The rotation speed of this particle was found to vary linearly with the applied voltage. This constrained liquid crystal geometry seems to meet the essential requirements in which soliton-like deformations can develop and exhibit stable orbiting in three dimensions upon application of an external electric field. On changing the temperature the system remains stable and allows the study of the defect evolution near the nematic-isotropic transition, showing qualitatively different behaviour on cooling and heating processes. The necklaces of such liquid crystal drops constitute excellent systems for the study of topological defects and their evolution and open new perspectives for application in microelectronics and photonics.

Comparison between monopolar and bipolar microsecond range pulsed electric fields in enhancement of apple juice extraction

The effect of monopolar and bipolar shaped pulses in additional yield of apple juice extraction is evaluated. The applied electric field strength, pulsewidth, and number of pulses are assessed for both pulse types, and divergences are analyzed. Variation of electric field strength is ranged from 100 to 1300 V/cm, pulsewidth from 20 to 300 mu s, and the number of pulses from 10 to 200, at a frequency of 200 Hz. Two pulse trains separated by 1 s are applied to apple cubes. Results are plotted against reference untreated samples for all assays. Specific energy consumption is calculated for each experiment as well as qualitative indicators for apple juice of total soluble dry matter and absorbance at 390-nm wavelength. Bipolar pulses demonstrated higher efficiency, and specific energetic consumption has a threshold where higher inputs of energy do not result in higher juice extraction when electric field variation is applied. Total soluble dry matter and absorbance results do not illustrate significant differences between application of monopolar and bipolar pulses, but all values are inside the limits proposed for apple juice intended for human consumption.

Electric vehicles as a mean to reduce, energy, emissions and electricity costs

Electric vehicles (EVs) and plug-in hybrid electric vehicles (PHEVs), which obtain their fuel from the grid by charging a battery, are set to be introduced into the mass market and expected to contribute to oil consumption reduction. This research is concerned with studying the potential impacts on the electric utilities of large-scale adoption of plug-in electric vehicles from the perspective of electricity demand, fossil fuels use, CO2 emissions and energy costs. Simulations were applied to the Portuguese case study in order to analyze what would be the optimal recharge profile and EV penetration in an energy-oriented, an emissions-oriented and a cost-oriented objective. The objectives considered were: The leveling of load profiles, minimization of daily emissions and minimization of daily wholesale costs. Almost all solutions point to an off-peak recharge and a 50% reduction in daily wholesale costs can be verified from a peak recharge scenario to an off-peak recharge for a 2 million EVs in 2020. A 15% improvement in the daily total wholesale costs can be verified in the costs minimization objective when compared with the off-peak scenario result.

Is the electric vehicle a solution for the wind power integration in the portuguese power system?

The integration of Plug-in electric vehicles in the transportation sector has a great potential to reduce oil dependency, the GHG emissions and to contribute for the integration of renewable sources into the electricity generation mix. Portugal has a high share of wind energy, and curtailment may occur, especially during the off-peak hours with high levels of hydro generation. In this context, the electric vehicles, seen as a distributed storage system, can help to reduce the potential wind curtailments and, therefore, increase the integration of wind power into the power system. In order to assess the energy and environmental benefits of this integration, a methodology based on a unit commitment and economic dispatch is adapted and implemented. From this methodology, the thermal generation costs, the CO2 emissions and the potential wind generation curtailment are computed. Simulation results show that a 10% penetration of electric vehicles in the Portuguese fleet would increase electrical load by 3% and reduce wind curtailment by only 26%. This results from the fact that the additional generation required to supply the electric vehicles is mostly thermal. The computed CO2 emissions of the EV are 92 g CO2/kWh which become closer to those of some new ICE engines.

Pulsed electric field pre-treatment for apple juice extraction: Evaluation of monopolar and bipolar pulses effects

Additional apple juice extraction with pulsed electric field pretreated apple cubes towards control samples is evaluated. Monopolar and bipolar shaped pulses are compared and their effect is studied with variation of electric field, pulse width and number of pulses. Variation of electric field strength is ranged from 100 V/cm to 1300 V/cm, pulse width from 20 mu s to 300 mu s and number of pulses from 10 to 200, at frequency of 200Hz. Two pulse trains separated by 1 second are applied to all samples. Bipolar pulses showed higher apple juice yields with all studied parameters. Calculation of specific energies consumed was assessed and a threshold where higher energy inputs do not increase juice yield is found for a number of used parameters. Qualitative parameters of total soluble matter (Brix) and absorbance at 390 nm wavelength were determined for each sample and results show that no substantial differences are found for PEF pre-treated and control samples.

The electric vehicles as a mean to reduce Co2 emissions and energy costs in isolated regions: the São Miguel (Azores) case study

Most of small islands around the world today, are dependent on imported fossil fuels for the majority of their energy needs especially for transport activities and electricity production. The use of locally renewable energy resources and the implementation of energy efficiency measures could make a significant contribution to their economic development by reducing fossil fuel imports. An electrification of vehicles has been suggested as a way to both reduce pollutant emissions and increase security of supply of the transportation sector by reducing the dependence on oil products imports and facilitate the accommodation of renewable electricity generation, such as wind and, in the case of volcanic islands like Sao Miguel (Azores) of the geothermal energy whose penetration has been limited by the valley electricity consumption level. In this research, three scenarios of EV penetration were studied and it was verified that, for a 15% LD fleet replacement by EVs with 90% of all energy needs occurring during the night, the accommodation of 10 MW of new geothermal capacity becomes viable. Under this scenario, reductions of 8% in electricity costs, 14% in energy, 23% in fossil fuels use and CO2 emissions for the transportation and electricity production sectors could be expected.

Mobile cockpit system for enhanced electric bicycle use

This paper presents the project of a mobile cockpit system (MCS) for smartphones, which provides assistance to electric bicycle (EB) cyclists in smart cities' environment. The presented system introduces a mobile application (MCS App) with the goal to provide useful personalized information to the cyclist related to the EB's use, including EB range prediction considering the intended path, management of the cycling effort performed by the cyclist, handling of the battery charging process, and the provisioning of information regarding available public transport. This work also introduces the EB cyclist profile concept, which is based on historical data analysis previously stored in a database and collected from mobile devices' sensors. From the tests performed, the results show the importance of route guidance, taking into account the energy savings. The results also show significant changes on range prediction based on user and route taken. It is important to say that the proposed system can be used for all bicycles in general.

Biofunctional composite coating architectures based on polycaprolactone and nanohydroxyapatite for controlled corrosion activity and enhanced biocompatibility of magnesium AZ31 alloy

In this work a biofunctional composite coating architecture for controlled corrosion activity and enhanced cellular adhesion of AZ31 Mg alloys is proposed. The composite coating consists of a polycaprolactone (PCL) matrix modified with nanohydroxyapatite (HA) applied over a nanometric layer of polyetherimide (PEI). The protective properties of the coating were studied by electrochemical impedance spectroscopy (EIS), a non-disturbing technique, and the coating morphology was investigated by field emission scanning electron microscopy (FE-SEM). The results show that the composite coating protects the AZ31 substrate. The barrier properties of the coating can be optimized by changing the PCL concentration. The presence of nanohydroxyapatite particles influences the coating morphology and decreases the corrosion resistance. The biocompatibility was assessed by studying the response of osteoblastic cells on coated samples through resazurin assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The results show that the polycaprolactone to hydroxyapatite ratio affects the cell behavior and that the presence of hydroxyapatite induces high osteoblastic differentiation. (C) 2014 Elsevier B.V. All rights reserved.

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.

Hydrogenating activity of Pt/zeolite catalysts focusing acid support and metal dispersion influence

Toluene hydrogenation was studied over catalysts based on Pt supported on large pore zeolites (HUSY and HBEA) with different metal/acid ratios. Acidity of zeolites was assessed by pyridine adsorption followed by FTIR showing only small changes before and after Pt introduction. Metal dispersion was determined by H2–O2 titration and verified by a linear correlation with the intensity of Pt0–CO band obtained by in situ FTIR. It was also observed that the electronic properties of Pt0 clusters were similar for the different catalysts. Catalytic tests showed rapid catalyst deactivation with an activity loss of 80–95% after 60 min of reaction. The turnover frequency of fresh catalysts depended both on metal dispersion and the support. For the same support, it changed by a 1.7-fold (HBEA) and 4.0-fold (HUSY) showing that toluene hydrogenation is structure-sensitive, i.e. hydrogenating activity is not a unique function of accessible metal. This was proposed to be due to the contribution to the overall activity of the hydrogenation of adsorbed toluene on acid sites via hydrogen spillover. Taking into account the role of zeolite acidity, the catalysts series were compared by the activity per total adsorbing sites which was observed to increase steadily with nPt/(nPt + nA). An increase of the accessible Pt atoms leads to an increase on the amount of spilled over hydrogen available in acid sites therefore increasing the overall activity. Pt/HBEA catalysts were found to be more active per total adsorbing site than Pt/HUSY which is proposed to be due to an augmentation in the efficiency of spilled over hydrogen diffusion related to the proximity between Pt clusters and acid sites. The intervention of Lewis acid sites in a greater extent than that measured by pyridine adsorption may also contribute to this higher activity of Pt/HBEA catalysts. These results reinforce the importance of model reactions as a closer perspective to the relevant catalyst properties in reaction conditions.

Y Trinuclear Cu-II structural isomers coordination, magnetism, electrochemistry and catalytic activity towards the oxidation of alkanes

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with copper(II) nitrate, acetate or metaborate has led to the isomeric complexes [Cu-3(L)(2)(MeOH)(4)] (1), [Cu-3(L)(2)(MeOH)(2)]2MeOH (2) and [Cu-3(L)(2)(MeOH)(4)] (3), respectively, in which the ligand L exhibits dianionic (HL2-, in 1) or trianionic (L3-, in 2 and 3) pentadentate 1O,O,N:2N,O chelation modes. Complexes 1-3 were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography, electrochemical methods and variable-temperature magnetic susceptibility measurements, which indicated that the intratrimer antiferromagnetic coupling is strong in the three complexes and that there exists very weak ferromagnetic intermolecular interactions in 1 but weak antiferromagnetic intermolecular interactions in both 2 and 3. Electrochemical experiments showed that in complexes 1-3 the Cu-II ions can be reduced, in distinct steps, to Cu-I and Cu-0. All the complexes act as efficient catalyst precursors under mild conditions for the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, leading to overall yields (based on the alkane) of up to 31% (TON = 1.55x10(3)) after 6 h in the presence of pyrazinecarboxylic acid.