Synthesis of heterocyclic metal complexes and their evaluation as marine antifoulants

4-Amino-3-thio-1,24-triazolidine (L₁) and 4-amino-5-thio-1,3,4-thiadiazole (L_II) as well as their metal complexes of the general formulae ML_I·2H₂O and ML_IICl (M; Pb(II), Cd(II) and Zn(II)) were prepared. With Sn(II), we obtained Sn(L_I)₂·2H₂O and SnL_IICl, respectively. The structures of the compounds were identified through elemental analysis, and IR and UV spectra measurements, in addition to thermal analysis in case of the metal complexes. The antifouling properties of the compounds were tested by their incorporation into paint formulations which were applied to PVC substrates and tested in water from Alexandria western harbour. When the compounds were added at 17·5% by volume, the coated panels were fouled after 3 months of immersion. The addition of 6·7% by volume of tributyltin oxide to 15·8% of the prepared compounds in one formulation elevated the paint efficiency and prevented fouling for 11 months. Paint containing solely tributyltin oxide at the same concentration was inactive against algae.     

Fractionation and characterisation for antioxidant activity of hydrolysed whey protein

Whey protein isolate (WPI) was hydrolysed for 1 h using Alcalase, Protamex and Flavourzyme. Native WPI, hydrolysed WPI and two commercial WPI hydrolysates were subjected to fractionation by size exclusion chromatography. Antioxidant activity of WPI fractions was measured with a liposome‐oxidising system (50 µM FeCl₃/0.1 µM ascorbate, pH 7.0). Lipid oxidation was measured as thiobarbituric acid‐reactive substances (TBARS). Gel electrophoresis and amino acid analysis were run to identify the peptide composition. The influence of amino acid composition on antioxidant activity was evaluated using multivariate analysis methods (correlation analysis, principal component analysis, multiple linear regression and discriminant analysis). TBARS assays indicated the presence of antioxidant activity in all protein fractions, including non‐hydrolysed WPI. For native and hydrolysed WPI samples the first fraction (> 45 kDa) showed a higher TBARS inhibition effect (24–27%) when compared with lower‐molecular‐weight fractions and hydrolysate mixtures. In contrast, for commercial WPI hydrolysates a higher inhibitory effect was found in most of the lower‐molecular‐weight fractions (30–55%). The ability of WPI fractions to delay lipid oxidation was found to be related to the prevalence of histidine and hydrophobic amino acids. Copyright © 2004 Society of Chemical Industry     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

Biodegradability and improved mechanical performance of polyhydroxyalkanoates/agave fiber biocomposites compatibilized by different strategies

In this work, biocomposites made of polyhydroxyalkanoates (PHA) with natural fibers were produced via compression molding. In particular, polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-hydroxyvalerate (PHBV) were reinforced with 20 wt% of agave fibers. Different compatibilization strategies were investigated to improve the fiber-matrix interaction: fiber surface treatment in PHA solution, fiber surface treatment in maleated PHA solution, fiber propionylation, and extrusion with maleated PHA. The biocomposites were characterized in terms of morphology, mechanical properties, water absorption, and biodegradability by CO₂ production tracking. In general, fiber propionylation was the best strategy for mechanical properties enhancement and water uptake decreasing. Biocomposites with propionylated fibers showed improved flexural strength (170% for PHB and 84% for PHBV). The flexural modulus was also enhanced with propionylated fibers up to 19% and 18% compared to uncompatibilized biocomposites (PHB and PHBV, respectively). Tensile strength increased by 16% (PHB) and 14% (PHBV), and the water absorption was reduced using propionylated fibers going from 6.6% to 4.4% compared with biocomposites with untreated fibers. Most importantly, the impact strength was also improved for all biocomposites by up to 96% compared with the neat PHA matrices. Finally, it was found that the compatibilization did not negatively modify the PHA biodegradability.     

Dependency-based security risk assessment for cyber-physical systems

A cyber-physical attack is a security breach in cyber space that impacts on the physical environment. The number and diversity of such attacks against Cyber-Physical Systems (CPSs) are increasing at impressive rates. In times of Industry 4.0 and Cyber-Physical Systems, providing security against cyber-physical attacks is a serious challenge which calls for cybersecurity risk assessment methods capable of investigating the tight interactions and interdependencies between the cyber and the physical components in such systems. However, existing risk assessment methods do not consider this specific characteristic of CPSs. In this paper, we propose a dependency-based, domain-agnostic cybersecurity risk assessment method that leverages a model of the CPS under study that captures dependencies among the system components. The proposed method identifies possible attack paths against critical components of a CPS by taking an attacker’s viewpoint and prioritizes these paths according to their risk to materialize, thus allowing the defenders to define efficient security controls. We illustrate the workings of the proposed method by applying it to a case study of a CPS in the energy domain, and we highlight the advantages that the proposed method offers when used to assess cybersecurity risks in CPSs.

     

Ontology-driven web-based semantic similarity

Estimation of the degree of semantic similarity/distance between concepts is a very common problem in research areas such as natural language processing, knowledge acquisition, information retrieval or data mining. In the past, many similarity measures have been proposed, exploiting explicit knowledge—such as the structure of a taxonomy—or implicit knowledge—such as information distribution. In the former case, taxonomies and/or ontologies are used to introduce additional semantics; in the latter case, frequencies of term appearances in a corpus are considered. Classical measures based on those premises suffer from some problems: in the first case, their excessive dependency of the taxonomical/ontological structure; in the second case, the lack of semantics of a pure statistical analysis of occurrences and/or the ambiguity of estimating concept statistical distribution from term appearances. Measures based on Information Content (IC) of taxonomical concepts combine both approaches. However, they heavily depend on a properly pre-tagged and disambiguated corpus according to the ontological entities in order to compute accurate concept appearance probabilities. This limits the applicability of those measures to other ontologies –like specific domain ontologies- and massive corpus –like the Web-. In this paper, several of the presented issues are analyzed. Modifications of classical similarity measures are also proposed. They are based on a contextualized and scalable version of IC computation in the Web by exploiting taxonomical knowledge. The goal is to avoid the measures’ dependency on the corpus pre-processing to achieve reliable results and minimize language ambiguity. Our proposals are able to outperform classical approaches when using the Web for estimating concept probabilities.     

Time series prediction evolving Voronoi regions

Time series prediction is a complex problem that consists of forecasting the future behavior of a set of data with the only information of the previous data. The main problem is the fact that most of the time series that represent real phenomena include local behaviors that cannot be modelled by global approaches. This work presents a new procedure able to find predictable local behaviors, and thus, attaining a better level of total prediction. This new method is based on a division of the input space into Voronoi regions by means of Evolution Strategies. Our method has been tested using different time series domains. One of them that represents the water demand in a water tank, through a long period of time. The other two domains are well known examples of chaotic time series (Mackey-Glass) and natural phenomenon time series (Sunspot). Results prove that, in most of cases, the proposed algorithm obtain better results than other algorithms commonly used.     

Ontology-based semantic similarity: A new feature-based approach

Estimation of the semantic likeness between words is of great importance in many applications dealing with textual data such as natural language processing, knowledge acquisition and information retrieval. Semantic similarity measures exploit knowledge sources as the base to perform the estimations. In recent years, ontologies have grown in interest thanks to global initiatives such as the Semantic Web, offering an structured knowledge representation. Thanks to the possibilities that ontologies enable regarding semantic interpretation of terms many ontology-based similarity measures have been developed. According to the principle in which those measures base the similarity assessment and the way in which ontologies are exploited or complemented with other sources several families of measures can be identified. In this paper, we survey and classify most of the ontology-based approaches developed in order to evaluate their advantages and limitations and compare their expected performance both from theoretical and practical points of view. We also present a new ontology-based measure relying on the exploitation of taxonomical features. The evaluation and comparison of our approach’s results against those reported by related works under a common framework suggest that our measure provides a high accuracy without some of the limitations observed in other works.     

The impracticalities of R. B. Stuart's practical multicultural competencies.

Comment in response to Stuart's recent article (see record 2004-10365-001) on multicultural competence. This comment includes three distinct voices. One voice is of a Brazilian woman, living in the United States, who experienced a visceral reaction to the article. The second voice is from a European American man who appreciates Stuart's efforts but is troubled by a disguised ideology that possibly objectifies culture and ignores sociopolitical realities. The third voice is from an Italian-Catholic-Austrian-Jewish man who can see himself and his clinical psychology training in what he considers Stuart's Western/White-male scientific multicultural metatheory. To the three of us, the practical suggestions Stuart offered seem useful, on the surface. However, we fear that when put into practice, these suggestions could not only be culturally insensitive, but in extreme cases might undermine some of the important progress made in the field of multicultural psychology over the past 2 decades. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A novel chromatographic separation technique using tertiary pyridine resin for the partitioning of trivalent actinides and lanthanides

A novel chromatographic separation technique using a tertiary pyridine type resin has been applied to the partitioning of the trivalent actinides (An) and lanthanides (Ln) and several successful results have been shown. In an alcoholic hydrochloric acid system, the trivalent An were clearly separated from the Ln, while no such group separation was achieved in an alcoholic nitric acid system. On the other hand, the nitric acid system was more effective for the intragroup (i.e. individual) separation of the trivalent An and the Ln than the hydrochloric acid system. On the basis of these results, a novel concept for the partitioning of the trivalent An and Ln using the present separation technique and its flowchart have been proposed with its advantages and disadvantages.