Characterization of superficial modification of ferrous rusted substrates subjected to dechlorination-electrochemical process

Preservation of archaeological artefacts after their removal from saline media is a difficult task due to the chloride content of the oxide layers which are unstable in atmospheric conditions, especially if the relative humidity exceeds 85%. For this reason, removal of chlorides from rust layers is one of the priorities of conservationists or restorers of historical artefacts. However, removal of chloride ions is not an easy procedure because of the many considerations involved in the process. In this research, artificially pre-rusted iron samples and an actual historical cannonball were subject to a dechlorination process in a potassium hydroxide solution to measure constant chloride release in a bulk solution. After the chloride removal process, a commercial protective layer was applied to the rust for stabilization purposes. It was calculated that the kinetics of the dechlorination process is driven by diffusion behaviour following Fick’s second law. When this diffusion process prevails, the dechlorination extraction affects the integrity of rust layers as is demonstrated with scanning electron microscopy and X-ray diffraction analyses. It was proven that the chloride removal procedure causes the studied iron layers to stiffen, provoking superficial modification and, in some cases, fractures of the rust. By means of electrochemical impedance spectroscopy it was calculated that the magnitude of the positive effect of the dechlorinated samples depends on the protective features of the rust. Therefore, this research reveals that an efficient chloride removal procedure depends on the electrochemical properties of the dechlorination process and the initial morphology of the iron rust.     

Desktop‐Stereolithography 3D‐Printing of a Poly(dimethylsiloxane)‐Based Material with Sylgard‐184 Properties

The advantageous physiochemical properties of poly(dimethylsiloxane) (PDMS) have made it an extremely useful material for prototyping in various technological, scientific, and clinical areas. However, PDMS molding is a manual procedure and requires tedious assembly steps, especially for 3D designs, thereby limiting its access and usability. On the other hand, automated digital manufacturing processes such as stereolithography (SL) enable true 3D design and fabrication. Here the formulation, characterization, and SL application of a 3D‐printable PDMS resin (3DP‐PDMS) based on commercially available PDMS‐methacrylate macromers, a high‐efficiency photoinitiator and a high‐absorbance photosensitizer, is reported. Using a desktop SL‐printer, optically transparent submillimeter structures and microfluidic channels are demonstrated. An optimized blend of PDMS‐methacrylate macromers is also used to SL‐print structures with mechanical properties similar to conventional thermally cured PDMS (Sylgard‐184). Furthermore, it is shown that SL‐printed 3DP‐PDMS substrates can be rendered suitable for mammalian cell culture. The 3DP‐PDMS resin enables assembly‐free, automated, digital manufacturing of PDMS, which should facilitate the prototyping of devices for microfluidics, organ‐on‐chip platforms, soft robotics, flexible electronics, and sensors, among others.     

Solubilization of phospholipid bilayer caused by surfactants

The interaction of surfactants with liposomes eventually leads to the rupture of such structures and the solubilization of the phospholipid components. In this paper, solubilization is regarded as a decrease in light scattering of liposome suspensions. To this end, in accordance with the nomenclature, adopted by Lichtenberg, three parameters were considered as corresponding to the effective surfactant/lipid molar ratios (Re) at which light scattering starts to decrease, Re_sat; reaches 50% of the original value, Re₅₀; and shows no further decrease, Re_sol. These parameters corresponded to the Re at which the surfactant (i) saturated the liposomes, (ii) resulted in a 50% solubilization of vesicles and (iii) led to a total solubilization of liposomes. The surfactants tested were the nonionic surfactant octylphenol ethoxylated with 10 units of ethylene oxide or Triton X-100 (OP-10EO), two anionic surfactants, sodium dodecyl sulfate and sodium dodecyl ether sulfate, and an amphoteric surfactant dodecyl betaine (D-Bet). Unilamellar liposomes formed by egg phosphatidylcholine containing increasing amounts of phosphatidic acid were used. The Re parameters were the lowest for D-Bet, followed by OP-10EO, whereas the anionic surfactants always showed the highest values regardless of the electrical charge of the lipid bilayers. These parameters seem also to be inversely related to the critical micelle concentration (CMC) of the surfactant, except for OP-10EO. Moreover, the CMC values of the surfactant/lipid systems at 0.5 mM lipid concentration corresponded in all cases to the surfactant concentration at which liposomes were saturated by surfactants. As a consequence, this ratio can be regarded as an interesting parameter associated with the mixed micelle formation in liposome solubilization.     

Cholinesterases activities and lipid peroxidation levels in muscle from shelf and slope dwelling fish from the NW Mediterranean: its potential use in pollution monitoring

We selected muscle tissue from nine commercial fish species, seven teleosts and two elasmobranchs, frequently caught in the NW Mediterranean trawling grounds in two different habitats (the continental shelf at 53 m and the slope at 660 m) for cholinesterases (ChEs) characterisation and activities determination, as well as the measure of lipid peroxidation (LP) levels. Acethyl- (AChE), butyryl- (BChE) and propionyl- (PrChE) cholinesterase were chosen as exposure markers of neurotoxic chemicals/molecules and LP as an effect marker of oxidative damage. The use of diagnose inhibitors: eserine sulphate, iso-OMPA and BW284c51 confirmed the measurement of true ChEs as well as the presence of pseudocholinesterases. The present study has evidenced the existence of interspecies differences, especially between teleosts and elasmobranchs but not in relation to depth. Moreover, the good correlation observed between all ChEs in most of the studied fish, supports the use of AChE as neurotoxic marker in field pollution monitoring. The non-metric multidimensional scaling analysis identified the commercial species hake Merluccius merluccius, among teleosts, and the shark, Galeus melastomus, as more adequate sentinel species in commercial fishing grounds. AChE activity showed a relationship with the fish trophic level, while all ChEs revealed a relationship with the feeding habits (benthic, suprabenthic, pelagic) and the stomach fullness. BChE activity and LP levels were the only markers to show a relationship with their swimming capacity.     

Exposure to volatile organic compounds (VOC) in public buses of Pamplona, Northern Spain

This study examines the exposure level of passengers and drivers to VOC in public buses in a medium-size metropolitan area (Northern Spain). In-vehicle monitoring was performed on different routes, on peak and non-peak hours, during January and February 2007. A total of 112 air samples were collected onto adsorbent tubes and analysed by thermal desorption (TD) and gas chromatography/mass selective detector (GC/MSD) technique. Statistical differences were found among route to route concentrations, with those routes with major prevalence in the commercial area of the city displaying higher values; differences between peak and non-peak hours were also observed. A decrease in VOC concentrations was also registered during the weekend. BTEX ratios were estimated and found to be related to traffic emissions and similar for all the surveyed routes. Correlations confirmed traffic as the main emission source for BTEX and trimethylbenzene, their concentrations being highly associated to changes in meteorological conditions.     

The preparation of high conversion polymeric systems containing eugenol residues and their rheological characterization

Copolymeric systems bearing eugenol covalently linked to the macromolecular chains have been prepared and characterised in terms of thermal, rheological and in vitro behaviour. Eugenyl methacrylate (EgMA) and ethoxyeugenyl methacrylate (EEgMA) were polymerized and copolymerized with ethyl methacrylate (EMA) in a wide range of feed composition by bulk at high conversion. Glass transition temperature (T_g) increased with the content of EgMA in the copolymer whereas T_g decreased with the content of EEgMA. The presence of any of the eugenyl monomers in the copolymer increased the thermal stability of the materials. Rheological analysis showed that EMA-co-EgMA copolymers present a higher density of crosslinking or entanglements among the chains compared with EMA-co-EEgMA materials, and copolymers containing more than 40% EgMA exhibited a pseudo-solid like behaviour with G′ relatively independent of the frequency. The average molecular weight between cross-links (M_c) for the latter copolymers was in the order of 10⁴ Da. For EEgMA copolymers, tan δ was lower than unity and G′ showed a gradual and slight dependency with frequency over the whole range of composition. In vitro behaviour showed a higher hydrophilicity of the EEgMA containing copolymers manifested in higher water sorption values, lower water contact angle values and higher surface free energy due to an increase in polarity. All systems presented a good cytocompatibility with human fibroblasts assessed through direct and indirect assays.     

Quantification of unidirectional nonlinear associations between multidimensional signals

In this paper, we present a rigorous, general definition of the nonlinear association index, known as h2. Proving equivalence between different definitions we show that the index measures the best dynamic range of any nonlinear map between signals. We present also a construction for removing the influence of one signal from another, providing, thus, the basis of an independent component analysis. Our definition applies to arbitrary multidimensional vector-valued signals and depends on an aperture function. In this way, the bin-related classic definition of h2 can be generalized. We show that upon choosing suitable aperture functions the bin-related intuitive definition can be deduced. Special attention is dedicated to the direction of the association index that in general is taken in only one sense. We show that for linearly coupled signals high associations are always bidirectional. As a consequence, high asymmetric nonlinear associations are indicators of nonlinear relations, possibly critical, between the dynamic systems underlying the measured signals. We give a simple simulated example to illustrate this property. As a potential clinical application, we show that unidirectional associations between electroencephalogram (EEG) and electromyogram (EMG) recorded from patient with pharmacologically intractable epilepsy can be used to study the cortical involvement in the generation of motor seizures.     

Physical and Antioxidant Characterization of Edible Films Added with Red Prickly Pear (<Emphasis Type="Italic">Opuntia ficus-indica</Emphasis> L.) cv. San Martín Peel and/or Its Aqueous Extracts

The aim of this research was to investigate the effect of the addition of peel powder and/or its aqueous extract on physical and antioxidant characteristics of carboxymethyl cellulose (CMC) edible films. Prickly pear peel powder and aqueous extract (2 and 4%) were characterized in color, bioactive compounds (betalains and total phenolic compounds), antioxidant capacity and reducing power. Edible films were prepared with CMC, glycerol, varying the dissolution medium (0, 2, or 4% aqueous extract from prickly pear peel) and peel powder (0, 1, or 2%) using a face-centered central composite design. Physical, mechanical, bioactive compounds, and antioxidant capacity properties were investigated in edible films. Prickly pear peel powder presented 58.8 ± 0.08 mg of betacyanins/100 g, 53.8 ± 0.2 mg of betaxanthins/100 g, 967.8 ± 20 mg Gallic acid equivalent (GAE)/100 g for total phenolic compounds, an antioxidant capacity equivalent to 420.9 ± 4.9 mg GAE/100 g and a reducing power of 879.1 ± 115.9 mg ascorbic acid equivalent (AAE)/100 g. High concentration of aqueous extract and peel powder in CMC films increased the bioactive compounds content, antioxidant capacity and reducing power. Films mechanical properties were not affected by the aqueous extract; nevertheless, were strongly affected by the peel powder. Response surface methodology was used to optimize edible films formulation with high antioxidant characteristics, being the optimal formulation 1.7% of peel powder plus 3.3% of aqueous extract. This study may be the base for exploitation of prickly pear peel as source of bioactive compounds with antioxidant capacity for their use in edible coatings.     

Lentil protein: a review of functional properties and food application. An overview of lentil protein functionality

There is an increased interest, driven by environmental sustainability and food security points of view, in seeking new protein sources as alternatives to replace animal proteins (Day, Trends in Food Science and Technology, 32 , 2016, 25). Pulse proteins, including lentil proteins (LP), are promising good substitutes as the wide variety of functional properties shown by them (Alsohaimy et al., World Journal of Agricultural Sciences, 3 , 2007, 123; Boye et al., Food Research International, 43 , 2010a, 537). Interest in LP has grown due to its high nutritional value, good Leu/Ile and Leu/Lys ratios (1.24–1.98 and 1.08–2.03, respectively) (Urbano et al., Lentil: An Ancient Crop for Modern Times, 2007, 47, Berlin: Springer), high digestibility (~83%) (Barbana & Boye, Food & Function, 4 , 2013, 310), and its potential use in food product applications (Farooq & Boye, Novel Food and Industrial Applications of Pulse Flours and Fractions. Pulse Foods, 1st edn, 2011, Amsterdam: Elsevier Ltd; Aider et al., Journal of Food Research, 1 , 2012, 160; De la Hera et al., LWT – Food Science and Technology, 49 , 2012, 48; Turfani et al., LWT – Food Science and Technology, 78 , 2017, 361). On the other hand, great progress has been made lately to reveal the good functionality of LP such as solubility and emulsifying, foaming and gelation capacities (Avramenko et al., Food Research International, 81 , 2016, 17; Jarpa‐Parra et al., Food Hydrocolloids, 61 , 2016, 903; Primozic et al., Food Chemistry, 237 , 2017, 65). However, the relatively unknown relationship between its molecular structure and functionalities and the lack of knowledge of the impact of the extraction and environmental conditions on those properties has hindered the exploitation of their full potential. This review describes the current knowledge of the LP structure, physical chemistry and functional properties, and its potential role as an ingredient for the development of food grade products. The gap between the current knowledge and what remains to be known is emphasised.     

Effect of different cooking methods on lipid oxidation and formation of free cholesterol oxidation products (COPs) in Latissimus dorsi muscle of Iberian pigs

The aim of this work was to study the influence of different cooking methods (grilled (GR), fried (FP), microwave (MW) and roasted (RO)) on lipid oxidation and formation of free cholesterol oxidation products (COPs) of meat from Iberian pigs that have been fed on an intensive system. Moisture and total lipid content, TBARs, hexanal and COPs were measured in Latissimus dorsi muscle samples. Cooking did not produce changes in total lipid content in meat but induced significantly higher lipid oxidation (TBARs and hexanal values) (p < 0.001) and cholesterol oxidation (COPs) (p < 0.01). When the different cooking methods were studied, the grilled method was the least affected by lipid oxidation (TBARs and hexanal) compared to the others. There were no significant differences among different cooking methods on COPs values. The most abundant cholesterol oxides were both 7α-hydroxycholesterol and 7β-hydroxycholesterol in all groups studied.