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.     

Critical Configurations for 1-View in Projections from ℙ<Superscript>k</Superscript> → ℙ<Superscript>2</Superscript>

In this paper we describe, from a theoretical point of view, critical configurations for the projective reconstruction of a set of points, for a single view, i.e. for calibration of a camera, in the case of projections from ℙ^k to ℙ² for k ≥ 4. We give first a general result describing these critical loci in ℙ^k, which, if irreducible, are algebraic varieties of dimension k−2 and degree 3. If k=4 they can be either a smooth ruled surface or a cone and if k = 5 they can be a smooth three dimensional variety, ruled in planes, or a cone. If k≥ 6, the variety is always a cone, the vertex of which has dimension at least k − 6. The reducible cases are studied in Appendix A. These results are then applied to determine explicitly the critical loci for the projections from ℙ^k which arise from the dynamic scenes in ℙ³ considered in [13]. Marina Bertolini is currently Associate Professor of Geometry at the Department of Mathematics at the Università degli Studi di Milano, Italy. Her main field of research is Complex Projective Algebraic Geometry, with particular interest for the classification of projective varieties and for the geometry of Grassmann varieties. On these topics M. Bertolini has published more than twenty reviewed papers on national and international journals. She has been for some years now interested also in applications of Algebraic Geometry to Computer Vision problems. Cristina Turrini is Associate Professor of Geometry at the Department of Mathematics of Università degli Studi di Milano, Italy. Her main research interest is Complex Projective Algebraic Geometry: subvarieties of Grassmannians, special varieties, automorphisms, classification. In the last two years she has started to work on applications of Algebraic Geometry to problems of Computer Vision. She is author or co-author of about thirty reviewed papers. She is also involved in popularization of Mathematics, and on this subject she is co-editor of some books.     

Estimates of intakes: methodology and results of some studies carried out in Italy.

The methods which may be applied to estimating population intakes of food additives are outlined. The applications in studies of the intakes of some preservatives and food colours in Italy are reported. It was concluded that there is a need to investigate comparability between the various methods used. The surveys carried out indicated that, in general, the levels of consumption of the additives studied did not present a health risk.     

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.     

Endogenous games with goals: side-payments among goal-directed agents

Boolean games have been developed as a paradigm for modelling societies of goal-directed agents. In boolean games agents exercise control over propositional variables and strive to achieve a goal formula whose realization might require the opponents’ cooperation. The presence of agents that are goal-directed makes it difficult for an external authority to be able to remove undesirable properties that are inconsistent with agents’ goals, as shown by recent contributions in the multi-agent literature. What this paper does is to analyse the problem of regulation of goal-direct agents from within the system, i.e., what happens when agents themselves are given the chance to negotiate the strategies to be played with one another. Concretely, we introduce endogenous games with goals, obtained coupling a general model of goal-directed agents (strategic games with goals) with a general model of pre-play negotiations (endogenous games) coming from game theory. Strategic games with goals are shown to have a direct correspondence with strategic games (Proposition 1) but, when side-payments are allowed in the pre-play phase, display a striking imbalance (Proposition 4). The effect of side-payments can be fully simulated by taxation mechanisms studied in the literature (Proposition 7), yet we show sufficient conditions under which outcomes can be rationally sustained without external intervention (Proposition 5). Also, integrating taxation mechanisms and side-payments, we are able to transform our starting models in such a way that outcomes that are theoretically sustainable thanks to a pre-play phase can be actually sustained even with limited resources (Proposition 8). Finally, we show how an external authority incentivising a group of agents can be studied as a special agent of an appropriately extended endogenous game with goals (Proposition 11).     

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.     

Camera re-calibration after zooming based on sets of conics

We describe a method to compute the internal parameters (focal and principal point) of a camera with known position and orientation, based on the observation of two or more conics on a known plane. The conics can even be degenerate (e.g., pairs of lines). The proposed method can be used to re-estimate the internal parameters of a fully calibrated camera after zooming to a new, unknown, focal length. It also allows estimating the internal parameters when a second, fully calibrated camera observes the same conics. The parameters estimated through the proposed method are coherent with the output of more traditional procedures that require a higher number of calibration images. A deep analysis of the geometrical configurations that influence the proposed method is also reported.