Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys

Inorganic–organic hybrid materials are attracting a strong scientific interest mainly for their outstanding inherent mechanical and thermal properties, which can be traced back to the intimate coupling of both inorganic and organic components. By carefully choosing the experimental parameters used for their synthesis, chemically and thermally stable acrylate-based hybrid material embedding the zirconium oxocluster Zr₄O₄(OMc)₁₂, where OMcCH₂C(CH₃)C(O)O, can be deposited as UV-cured films on aluminium alloys.

In particular, the molar ratios between the oxocluster and the monomer, the polymerisation time, the amount of photo-initiator and the deposition conditions, by using an home-made spray-coating equipment, were optimised in order to obtain the best performing layers in terms of transparency and hardness to coat aluminium alloy (AA1050, AA6060 and AA2024) sheets. Furthermore, it was also evaluated whether the hybrid coatings behave as barrier to corrosion.

Several coated samples were prepared and characterised. Environmental scanning electronic microscopy (ESEM) and scratch test were used to investigate the morphology of the films and to evaluate their scratch resistance, respectively. Electrochemical impedance spectroscopy (EIS) was performed in order to evaluate if the coatings actually protect the metallic substrate from corrosion.

In order to measure shear storage modulus (G′) and loss modulus (G″) of the materials used for coatings, bulk samples were also obtained by UV-curing of the precursors solution. Dynamical mechanical thermal analysis (DMTA) was performed in shear mode on cured disks of both the hybrid materials and pristine polymer for comparison. The values of T_g were read off as the temperatures of peak of loss modulus. The length and mass of all the samples were measured before and after the DMTA analysis, so that the shrinkage of the materials in that temperature range was exactly evaluated.     

Molecular weight effect on the obtainment of parallel and perpendicular orientation in thermotropic poly(diethylene glycol <Emphasis Type="Italic">p,p′</Emphasis>-bibenzoate)

Summary The effect of molecular weight on the uniaxial orientation process has been analyzed in two samples of thermotropic poly(diethylene glycol p,p′-bibenzoate), evaluating the influence of that parameter on the type of orientation obtained. Several strain rates and deformation temperatures have been tested in order to map out the conditions for obtaining the two different kinds of orientation. The results show that in the lower molecular weight PDEB sample (M_w=31200) it is rather easy to get exclusively perpendicular “anomalous” orientation, with the molecular axes aligned transversely to the stretching direction. However, it is extremely difficult to obtain 100% parallel “normal” orientation. On the contrary, either type of orientation or a mixture of them can be easily developed for the higher molecular weight PDEB sample (M_w=102900).     

Use of recycled copper slag for blended cements

Copper slag is a by‐product generated during smelting to extract copper metal from the ore. The copper slag obtained may exhibit pozzolanic activity and may therefore be used in the manufacture of addition‐containing cements. In this paper the effect of the incorporation of the copper slag in cement is measured. Blends of copper slag with Portland cement generally possess properties equivalent to Portland cement containing fly ash, but very different to the silica fume incorporation. Copper slag and fly ash reduce the heat of hydration more effectively than silica fume in mortars. The replacement of 30% cement by copper slag reduces the flexural and compressive strength in a similar way to fly ash; however, after 28 days, the reduction is less than the percentage of substitution. Hydrated calcium aluminate phases were analysed using scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques. The pozzolanic activity of copper slag is similar to that of fly ash and higher than silica fume. In the presence of low water/cement ratios, certain pozzolanic materials produce a very compact cement paste that limits the space available for hydration products, a determining factor in the formation of hydrated calcium aluminates. SEM was found to be a useful analytical technique when aluminates are formed and can be clearly detected by XRD. Copyright © 2008 Society of Chemical Industry     

Self-adjusting the intensity of assortative mating in genetic algorithms

Mate selection plays a crucial role in both natural and artificial systems. While traditional Evolutionary Algorithms (EA) usually engage in random mating strategies, that is, mating chance is independent of genotypic or phenotypic distance between individuals, in natural systems non-random mating is common, which means that somehow this mechanism has been favored during the evolutionary process. In non-random mating, the individuals mate according to their parenthood or likeness. Previous studies indicate that negative assortative mating (AM)—also known as dissortative mating—, which is a specific type of non-random mating, may improve EAs performance by maintaining the genetic diversity of the population at a higher level during the search process. In this paper we present the Variable Dissortative Mating Genetic Algorithm (VDMGA). The algorithm holds a mechanism that varies the GA’s mating restrictions during the run by means of simple rule based on the number of chromosomes created in each generation and indirectly influenced by the genetic diversity of the population. We compare VDMGA not only with traditional Genetic Algorithms (GA) but also with two preceding non-random mating EAs: the CHC algorithm and the negative Assortative Mating Genetic Algorithm (nAMGA). We intend to study the effects of the different methods in the performance of GAs and verify the reliability of the proposed algorithm when facing an heterogeneous set of landscapes. In addition, we include the positive Assortative Mating Genetic Algorithm (pAMGA) in the experiments in order test both negative and positive AM mechanisms, and try to understand if and when negative AM (or DM) speeds up the search process or enables the GAs to escape local optima traps. For these purposes, an extensive set of optimization test problems was chosen to cover a variety of search landscapes with different characteristics. Our results confirm that negative AM is effective in leading EAs out of local optima traps, and show that the proposed VDMGA is at least as efficient as nAMGA when applied to the range of our problems, being more efficient in very hard functions were traditional GAs usually fail to escape local optima. Also, scalability tests have been made that show VDMGA ability to decrease optimal population size, thus reducing the amount of evaluations needed to attain global optima. We like to stress that only two parameters need to be hand-tuned in VDMGA, thus reducing the tuning effort present in traditional GAs and nAMGA.     

Investigation of the relationships between the chain organization and rheological properties of atactic poly(vinyl alcohol) hydrogels

The structure and rheological behavior of atactic poly(vinyl alcohol) (a-PVA) hydrogels prepared by freeze/thaw cycles were investigated as a function of polymer concentration and number of freeze/thaw cycles. The presence of phases with different mobilities was observed using ¹³C CP/MAS and DP/MAS NMR experiments. The degree of crystallinity of the a-PVA-rich phase was determined by ¹H NMR free decay experiments. Measurements of the shear storage and loss modulus were performed at a fixed frequency of 1 Hz and a strain value of 0.1%, i.e. under conditions where the deformation imposed on the gel structure is entirely reversible. Results thus obtained showed that an increase in the number of freeze/thaw cycles induces an increase in the degree of crystallinity in the polymer-rich phase together with an increase in the storage modulus. The a-PVA hydrogels became more fragile as the number of freeze/thaw cycles was increased. Moreover, both the percentage of protons in a rigid environment measured by ¹H NMR and the storage modulus values tended to a limiting value after six freeze/thaw cycles. These results show that the first five or six freeze/thaw cycles play a very important role in determining the hydrogel structure and rheological properties. A more detailed comparison of NMR and rheological data led to the conclusion that the storage modulus is mainly controlled by the a-PVA crystallinity while the hydrogen bond interactions have a much smaller contribution.     

A new eicosapentaenoic acid formed from arachidonic acid in the coralline red algaeBossiella orbigniana

Aqueous extracts of the coralline red algaeBossiella orbigniana have been shown to catalyze the enzymatic oxidation of arachidonic acid to a previously unreported ω6 eicosapentaenoic acid product. This unique fatty acid contains a conjugated tetraene with absorption maxima at 293, 306, and 321 nm, and was identified by spectral methods as 5(Z),8(Z),10(E),12(E),14(Z)-eicosapentaenoic acid. The compound was given the trivial name bosseopentaenoic acid. Under experimental conditions, production of bosseopentaenoic acid was linear up to 2 hr and dioxygen was consumed. Bosseopentaenoic acid, along with several other conjugated tetraenes, was also present in the algae endogenously as revealed by a comparison of the ultraviolet (UV) spectra and the high-performance liquid chromatographic (HPLC) pattern of the purified product and the organic extract ofBossiella.     

Mycological survey for potential aflatoxin and ochratoxin producers and their toxicological properties in harvested Brazilian black pepper.

A mycological survey was carried out on 115 samples of whole dried black pepper seeds, from two main production regions of Brazil (Pará and Espírito Santo). A high incidence of contamination was verified in both regions when 99.1% of the samples showed filamentous fungi contamination. A total of 497 species of nine different genera were isolated (Aspergillus, Eurotium, Rhizopus, Penicillium, Curvularia, Cladosporium, Absidia, Emericella and Paecilomyces). The genus Aspergillus was the predominant (53.5%) followed by species from the Eurotium genus (24.5%). Eurotium chevalieri (16.4%) was the most predominant species followed by A. flavus (14.6%) present on 55 samples of black pepper (47.8%) analysed. Twenty-five samples (21.7%) were contaminated with aflatoxigenic strains of A. flavus and A. parasiticus. In relation to the types of aflatoxins produced by mycotoxigenic strains, it was observed that 25 strains (44.6%) of 56 isolated of A. flavus produced aflatoxins. From 12 samples, A. ochraceus species were isolated in low frequency (3.5%). Two strains of A. ochraceus from 16 isolated were producers of ochratoxin A. With respect to the aflatoxins and ochratoxin A natural contamination, none of the samples presented detectable levels of these mycotoxins using thin-layer chromatographic analysis.     

Karyotype description of Pomacea patula catemacensis (Caenogastropoda, Ampullariidae), with an assessment of the taxonomic status of Pomacea patula.

Mitotic chromosomes of the freshwater snail Pomacea patula catemacensis (Baker 1922) were analyzed on gill tissue of specimens from the type locality (Lake Catemaco, Mexico). The diploid number of chromosomes is 2n = 26, including nine metacentric and four submetacentric pairs; therefore, the fundamental number is FN = 52, No sex chromosomes could be identified. The same chromosome number and morphology were already reported for P. flagellata, i.e., the other species of the genus living in Mexico. The basic haploid number for family Ampullariidae was reported to be n = 14 in the literature; so, its reduction to n = 13 is probably an apomorphy of the Mexican Pomacea snails. Lanistes bolteni, from Egypt, also shows n = 13, but its karyotype is much more asymmetrical, and seems to have evolved independently from P. flagellata and P. patula catemacensis. The nominotypical subspecies, P. patula patula (Reeve 1856), is a poorly known taxon, whose original locality is unknown. A taxonomical account is presented here, and a Mexican origin postulated as the most parsimonious hypothesis.     

Genotoxic effect of Physalis angulata L. (Solanaceae) extract on human lymphocytes treated in vitro

Physalis angulata L (Solanaceae) is a medicinal plant from North of Brazil, whose different extracts and infusions are commonly used in the popular medicine for the treatment of malaria, asthma, hepatitis, dermatitis and rheumatism. However, the genotoxic effects of P. angulata on human cells is not well known. The main purpose of the present study was to evaluate the in vitro genotoxic effects of aqueous extract of P. angulata using the comet assay and the micronucleus assay in human lymphocytes provided from 6 healthy donors. Treatments with P. angulata extracts were performed in vitro in order to access the extent of DNA damage. The comet assay has shown that treatments with P. angulata at 0.5, 1.0, 2.0, 3.0 and 6.0 microg/mL in culture medium were genotoxic. Lymphocytes treated with P. angulata at the concentrations of 3.0 and 6.0 microg/mL in culture medium showed a statistically significant increase in the frequency of micronucleus (p<0.05), however, the cytokinesis blocked proliferation index (CBPI) was not decreased after P. angulata treatment. In conclusion, the present work demonstrated the genotoxic effects of P. angulata extract on human lymphocytes in vitro.