Influence of the pre-treatments on the properties of biodegradable films from bovine hair

The replacement of conventional synthetic films and coatings by biodegradable alternatives reduces the use of non-renewable resources and waste disposal problems. Considering that Portugal is a major producer of leather, and consequently a large producer of related wastes, in this research, bovine hair was tested for the production of biodegradable films directly by thermo-compression, allowing waste valorisation and reduction of environmental pollution. The aim of this study was to determine the influence of the different pre-treatments performed by two processes (removal by mechanical action and removal by chemical process), applied to bovine hair, in order to obtain a biodegradable film with appropriate properties. Mechanical properties for these films were evaluated, namely strain at break, stress at break and Young modulus. Additionally colour, solubility and swelling in water were also studied. The mechanical removal hair only produced films with Na2S treatment. Chemical removed hair (immunization) depends of the pre-treatment and the degreasing with petroleum ether or sodium sulphide pre-treatment leads better mechanical properties. The results obtained indicated that the pre-treatments have an important role in the final properties of biodegradable films.

Evaluation of solubility and partition properties of ampicillin-based ionic liquids

In order to overcome the problems associated with low water solubility, and consequently low bioavailability of active pharmaceutical ingredients (APIs), herein we explore a modular ionic liquid synthetic strategy for improved APIs. Ionic liquids containing l-ampicillin as active pharmaceutical ingredient anion were prepared using the methodology developed in our previous work, using organic cations selected from substituted ammonium, phosphonium, pyridinium and methylimidazolium salts, with the intent of enhancing the solubility and bioavailability of l-ampicillin forms. In order to evaluate important properties of the synthesized API-ILs, the water solubility at 25 °C and 37 °C (body temperature) as well as octanol–water partition coefficients (Kow's) and HDPC micelles partition at 25 °C were measured. Critical micelle concentrations (CMC's) in water at 25 °C and 37 °C of the pharmaceutical ionic liquids bearing cations with surfactant properties were also determined from ionic conductivity measurements.

Exploring bioactive properties of marine cyanobacteria Isolated from the Portuguese coast: high potential as a source of anticancer compounds

The oceans remain a major source of natural compounds with potential in pharmacology. In particular, during the last few decades, marine cyanobacteria have been in focus as producers of interesting bioactive compounds, especially for the treatment of cancer. In this study, the anticancer potential of extracts from twenty eight marine cyanobacteria strains, belonging to the underexplored picoplanktonic genera, Cyanobium, Synechocystis and Synechococcus, and the filamentous genera, Nodosilinea, Leptolyngbya, Pseudanabaena and Romeria, were assessed in eight human tumor cell lines. First, a crude extract was obtained by dichloromethane:methanol extraction, and from it, three fractions were separated in a Si column chromatography. The crude extract and fractions were tested in eight human cancer cell lines for cell viability/toxicity, accessed with the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) and lactic dehydrogenase release (LDH) assays. Eight point nine percent of the strains revealed strong cytotoxicity; 17.8% showed moderate cytotoxicity, and 14.3% assays showed low toxicity. The results obtained revealed that the studied genera of marine cyanobacteria are a promising source of novel compounds with potential anticancer activity and highlight the interest in also exploring the smaller filamentous and picoplanktonic genera of cyanobacteria.

Accounting for the dissociating properties of organic chemicals in LCIA: an uncertainty analysis applied to micropollutants in the assessment of freshwater ecotoxicity

In life cycle impact assessment (LCIA) models, the sorption of the ionic fraction of dissociating organic chemicals is not adequately modeled because conventional non-polar partitioning models are applied. Therefore, high uncertainties are expected when modeling the mobility, as well as the bioavailability for uptake by exposed biota and degradation, of dissociating organic chemicals. Alternative regressions that account for the ionized fraction of a molecule to estimate fate parameters were applied to the USEtox model. The most sensitive model parameters in the estimation of ecotoxicological characterization factors (CFs) of micropollutants were evaluated by Monte Carlo analysis in both the default USEtox model and the alternative approach. Negligible differences of CFs values and 95% confidence limits between the two approaches were estimated for direct emissions to the freshwater compartment; however the default USEtox model overestimates CFs and the 95% confidence limits of basic compounds up to three orders and four orders of magnitude, respectively, relatively to the alternative approach for emissions to the agricultural soil compartment. For three emission scenarios, LCIA results show that the default USEtox model overestimates freshwater ecotoxicity impacts for the emission scenarios to agricultural soil by one order of magnitude, and larger confidence limits were estimated, relatively to the alternative approach.

Precursors’ order effect on the properties of sulfurized Cu2ZnSnS4 thin films

A dc magnetron sputtering-based method to grow high-quality Cu2ZnSnS4 (CZTS) thin films, to be used as an absorber layer in solar cells, is being developed. This method combines dc sputtering of metallic precursors with sulfurization in S vapour and with post-growth KCN treatment for removal of possible undesired Cu2−xS phases. In this work, we report the results of a study of the effects of changing the precursors’ deposition order on the final CZTS films’ morphological and structural properties. The effect of KCN treatment on the optical properties was also analysed through diffuse reflectance measurements. Morphological, compositional and structural analyses of the various stages of the growth have been performed using stylus profilometry, SEM/EDS analysis, XRD and Raman Spectroscopy. Diffuse reflectance studies have been done in order to estimate the band gap energy of the CZTS films. We tested two different deposition orders for the copper precursor, namely Mo/Zn/Cu/Sn and Mo/Zn/Sn/Cu. The stylus profilometry analysis shows high average surface roughness in the ranges 300–550 nm and 230–250 nm before and after KCN treatment, respectively. All XRD spectra show preferential growth orientation along (1 1 2) at 28.45◦. Raman spectroscopy shows main peaks at 338 cm−1 and 287 cm−1 which are attributed to Cu2ZnSnS4. These measurements also confirm the effectiveness of KCN treatment in removing Cu2−xS phases. From the analysis of the diffuse reflectance measurements the band gap energy for both precursors’ sequences is estimated to be close to 1.43 eV. The KCN-treated films show a better defined absorption edge; however, the band gap values are not significantly affected. Hot point probe measurements confirmed that CZTS had p-type semiconductor behaviour and C–V analysis was used to estimate the majority carrier density giving a value of 3.3 × 1018 cm−3.

Study of optical and structural properties of Cu2ZnSnS4 thin films

Cu2ZnSnS4 is a promising semiconductor to be used as absorber in thin film solar cells. In this work, we investigated optical and structural properties of Cu2ZnSnS4 thin films grown by sulphurization of metallic precursors deposited on soda lime glass substrates. The crystalline phases were studied by X-ray diffraction measurements showing the presence of only the Cu2ZnSnS4 phase. The studied films were copper poor and zinc rich as shown by inductively coupled plasma mass spectroscopy. Scanning electron microscopy revealed a good crystallinity and compactness. An absorption coefficient varying between 3 and 4×104cm−1 was measured in the energy range between 1.75 and 3.5 eV. The band gap energy was estimated in 1.51 eV. Photoluminescence spectroscopy showed an asymmetric broad band emission. The dependence of this emission on the excitation power and temperature was investigated and compared to the predictions of the donor-acceptor-type transitions and radiative recombinations in the model of potential fluctuations. Experimental evidence was found to ascribe the observed emission to radiative transitions involving tail states created by potential fluctuations.

Properties of tantalum oxynitride thin films produced by magnetron sputtering: the influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaNxOy) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaNxOy films was prepared by varying the reactive gases flow rate, using a N2/O2 gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta2O5, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0. The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.

Antioxidant properties of hydroxycinnamic acids: a review of structure- activity relationships

Hydroxycinnamic acids (HCAs) are important phytochemicals possessing significant biological properties. Several investigators have studied in vitro antioxidant activity of HCAs in detail. In this review, we have gathered the studies focused on the structure-activity relationships (SARs) of these compounds that have used medicinal chemistry to generate more potent antioxidant molecules. Most of the reports indicated that the presence of an unsaturated bond on the side chain of HCAs is vital to their activity. The structural features that were reported to be of importance to the antioxidant activity were categorized as follows: modifications of the aromatic ring, which include alterations in the number and position of hydroxy groups and insertion of electron donating or withdrawing moieties as well as modifications of the carboxylic function that include esterification and amidation process. Furthermore, reports that have addressed the influence of physicochemical properties including redox potential, lipid solubility and dissociation constant on the antioxidant activity were also summarized. Finally, the pro-oxidant effect of HCAs in some test systems was addressed. Most of the investigations concluded that the presence of ortho-dihydroxy phenyl group (catechol moiety) is of significant importance to the antioxidant activity, while, the presence of three hydroxy groups does not necessarily improve the activity. Optimization of the structure of molecular leads is an important task of modern medicinal chemistry and its accomplishment relies on the careful assessment of SARs. SAR studies on HCAs can identify the most successful antioxidants that could be useful for management of oxidative stress-related diseases.

Cycle time properties of the PROFIBUS timed-token protocol

A recent trend in distributed computer-controlled systems (DCCS) is to interconnect the distributed computing elements by means of multi-point broadcast networks. Since the network medium is shared between a number of network nodes, access contention exists and must be solved by a medium access control (MAC) protocol. Usually, DCCS impose real-time constraints. In essence, by real-time constraints we mean that traffic must be sent and received within a bounded interval, otherwise a timing fault is said to occur. This motivates the use of communication networks with a MAC protocol that guarantees bounded access and response times to message requests. PROFIBUS is a communication network in which the MAC protocol is based on a simplified version of the timed-token protocol. In this paper we address the cycle time properties of the PROFIBUS MAC protocol, since the knowledge of these properties is of paramount importance for guaranteeing the real-time behaviour of a distributed computer-controlled system which is supported by this type of network.

Impact of prescribed fire on the chemical properties of soil

Prescribed fire is a common forest management tool used in Portugal to reduce the fuel load availability and minimize the occurrence of wildfires. In addition, the use of this technique also causes an impact to ecosystems. In this presentation we propose to illustrate some results of our project in two forest sites, both located in Northwest Portugal, where the effect of prescribed fire on soil properties were recorded during a period of 6 months. Changes in soil moisture, organic matter, soil pH and iron, were examined by Principal Component Analysis multivariate statistics technique in order to determine impact of prescribed fire on these soil properties in these two different types of soils and determine the period of time that these forest soils need to recover to their pre-fire conditions, if they can indeed recover. Although the time allocated to this study does not allow for a widespread conclusion, the data analysis clearly indicates that the pH values are positively correlated with iron values at both sites. In addition, geomorphologic differences between both sampling sites, Gramelas and Anjos, are relevant as the soils’ properties considered have shown different performances in time. The use of prescribed fire produced a lower impact in soils originated from more amended bedrock and therefore with a ticker humus covering (Gramelas) than in more rocky soils with less litter covering (Anjos) after six months after the prescribed fire occurrence.

Stress Ratio Effects on the fatigue Properties of Biaxially Loaded Tubular FRP-Specimens – Experimental Study

In this work tubular fiber reinforced specimens are tested for fatigue life. The specimens are biaxially loaded with tension and shear stresses, with a load angle β of 30° and 60° and a load ratio of R=0,1. There are many factors that affect fatigue life of a fiber reinforced material and the main goal of this work is to study the effects of load ratio R by obtaining S-N curves and compare them to the previous works (1). All the other parameters, such as specimen production, fatigue loading frequency and temperature, will be the same as for the previous tests. For every specimen, stiffness, temperature of the specimen during testing, crack counting and final fracture mode are obtained. Prior to testing, a study if the literature regarding the load ratio effects on composites fatigue life and with that review estimate the initial stresses to be applied in testing. In previous works (1) similar specimens have only been tested for a load ratio of R=-1 and therefore the behaviour of this tubular specimens for a different load ratio is unknown. All the data acquired will be analysed and compared to the previous works, emphasizing the differences found and discussing the possible explanations for those differences. The crack counting software, developed at the institute, has shown useful before, however different adjustments to the software parameters lead to different cracks numbers for the same picture, and therefore a better methodology will be discussed to improve the crack counting results. After the specimen’s failure, all the data will be collected and stored and fibre volume content for every specimen is also determinate. The number of tests required to make the S-N curves are obtained according to the existent standards. Additionally are also identified some improvements to the testing machine setup and to the procedures for future testing.

Anti-neoplastic properties of hydralazine in prostate cancer

Prostate cancer (PCa) is a major cause of cancer-related morbidity and mortality worldwide. Although early disease is often efficiently managed therapeutically, available options for advanced disease are mostly ineffective. Aberrant DNA methylation associated with gene-silencing of cancer-related genes is a common feature of PCa. Therefore, DNA methylation inhibitors might constitute an attractive alternative therapy. Herein, we evaluated the anti-cancer properties of hydralazine, a non-nucleoside DNA methyltransferases (DNMT) inhibitor, in PCa cell lines. In vitro assays showed that hydralazine exposure led to a significant dose and time dependent growth inhibition, increased apoptotic rate and decreased invasiveness. Furthermore, it also induced cell cycle arrest and DNA damage. These phenotypic effects were particularly prominent in DU145 cells. Following hydralazine exposure, decreased levels of DNMT1, DNMT3a and DNMT3b mRNA and DNMT1 protein were depicted. Moreover, a significant decrease in GSTP1, BCL2 and CCND2 promoter methylation levels, with concomitant transcript re-expression, was also observed. Interestingly, hydralazine restored androgen receptor expression, with upregulation of its target p21 in DU145 cell line. Protein array analysis suggested that blockage of EGF receptor signaling pathway is likely to be the main mechanism of hydralazine action in DU145 cells. Our data demonstrate that hydralazine attenuated the malignant phenotype of PCa cells, and might constitute a useful therapeutic tool.

Psychometric Properties of the Portuguese Version of the Posttraumatic Growth Inventory Short Form Among Divorced Adults

The aim of this study was to develop and validate a Portuguese version of the Short Form of the Posttraumatic Growth Inventory (PTGI-SF). Using an online convenience sample of Portuguese divorced adults (N = 482), we confirmed the oblique five-factor structure of the PTGI-SF by confirmatory factor analysis. The results demonstrated the measurement invariance across divorce initiator status groups. Total score and factors of PTGI-SF showed good internal consistency, with the exception of the New Possibilities factor, which revealed an acceptable reliability. The Portuguese PTGI-SF showed a satisfactory convergent validity. In terms of discriminant validity, posttraumatic growth assessed by the Portuguese PTGI-SF was a distinct factor from posttraumatic psychological adjustment. These preliminary findings suggest the cultural adaptation and also psychometric properties of the present Portuguese PTGI-SF to measure posttraumatic growth after personal crisis.

Effect of selenization conditions on the growth and properties of Cu2ZnSn(S,Se)4 thin films

The opto-electronic properties of copper zinc tin sulfide can be tuned to achieve better cell efficiencies by controlled incorporation of selenium. In this paper we report the growth of Cu2ZnSn(S,Se)4 (CZTSSe) using a hybrid process involving the sequential evaporation of Zn and sputtering of the sulfide precursors of Cu and Sn, followed by a selenization step. Two approaches for selenization were followed, one using a tubular furnace and the other using a rapid thermal processor. The effects of annealing conditions on the morphological and structural properties of the films were investigated. Scanning electron microscopy and energy dispersive spectroscopy were employed to investigate the morphology and composition of the films. Structural analyses were done using X-ray diffraction (XRD) and Raman spectroscopy. Structural analyses revealed the formation of CZTSSe. This study shows that regardless of the selenization method a temperature above 450 °C is required for conversion of precursors to a compact CZTSSe layer. XRD and Raman analysis suggests that the films selenized in the tubular furnace are selenium rich whereas the samples selenized in the rapid thermal processor have higher sulfur content.

Mechanical properties of chemically modified portuguese pinewood

To turn wood into a construction material with enhanced properties, many methods of chemical modification have been developed in the last few decades. In this work, mechanical properties of pine wood were chemically modified, compared and evaluated. Maritime pine wood (Pinus pinaster) was modified with four chemical processes: 1,3-dimethylol-4,5- dihydroxyethyleneurea, N-methylol melamine formaldehyde, tetra-alkoxysilane and wax. The following mechanical properties were assessed experimentally: Modulus of elasticity measured statically, stiffness stabilization efficiency in different climates (30 and 87% of relative humidity), modulus of rupture, work maximum load, impact bending strength, compression, tensile and shear strength at indoor conditions (65% of relative humidity). In both types of active principle of modification, cell wall or lumen fill, no significant changes on the bending stiffness (modulus of elasticity) were found. In the remaining properties analysed significant changes in the modified wood-material took place compared to unmodified wood control: - Cell wall modification was the most effective method to achieve high stiffness stabilization efficiency (up to 60%) and also increased compression strength (up to 230%). However, modulus of rupture, tensile, shear and the impact bending strength were reduced by both resins, but in a varying extent, where the N-methylol melamine formaldehyde endured less reduction than 1,3-dimethylol-4,5-dihydroxyethyleneurea resin. In the latter, reduction up to 60% can take place. - In the lumen fill modification: tetra-alkoxysilane has no effect in the mechanical properties. Although, a slight increase in shear strength parallel to the grain was found. Wax specimens have shown a slight increase in bending strength, compression, tensile and shear strength as well as in the absorption energy capacity.