Maximum likelihood mixture estimation to determine metal background values in estuarine and coastal sediments within the European Water Framework Directive

Some of the recently derived European Directives, such as the Water Framework and Marine Strategy, have, as ultimate aims, to achieve concentrations of hazardous substances in the marine environment near background values. Hence, the determination of natural background levels, in marine sediments, is highly relevant. The present study proposes the use of the maximum likelihood mixture estimation (MLME) to determine regional background levels and upper threshold of metal concentration, with the Basque Country as a case study (with a data set of 575 samples, from estuarine and littoral areas, including both intertidal and subtidal sediments). The heuristic procedure is applied with unimodal data distributions (Cd, Cr, Fe and Ni) and the mixture density estimations, based upon maximum likelihood, are carried out with polypopulational data distributions (As, Cu, Mn, Hg, Pb and Zn). The upper limits of the distribution are proposed, as the limits between 'High Status' and 'Good Status' (according to the Water Framework Directive terminology). The regional upper limits were 0.45 microg g(-1) for Cd, 71 microg g(-1) for Cr, 53,542 microg g(-1) for Fe, 57 microg g(-1) for Ni, 24 microg g(-1) for As, 64 microg g(-1) for Cu, 447 microg g(-1) for Mn, 0.27 microg g(-1) for Hg, 66 microg g(-1) for Pb, and 248 microg g(-1) for Zn. The results from this study can assist further in the determination of sediment reference conditions, to assess chemical status, within the above-mentioned directives; likewise, it will be studied as a useful methodology in determining regional metal backgrounds in other European countries.     

Understanding LAG-3 Signaling

Lymphocyte activation gene 3 (LAG-3) is a cell surface inhibitory receptor with multiple biological activities over T cell activation and effector functions. LAG-3 plays a regulatory role in immunity and emerged some time ago as an inhibitory immune checkpoint molecule comparable to PD-1 and CTLA-4 and a potential target for enhancing anti-cancer immune responses. LAG-3 is the third inhibitory receptor to be exploited in human anti-cancer immunotherapies, and it is considered a potential next-generation cancer immunotherapy target in human therapy, right next to PD-1 and CTLA-4. Unlike PD-1 and CTLA-4, the exact mechanisms of action of LAG-3 and its relationship with other immune checkpoint molecules remain poorly understood. This is partly caused by the presence of non-conventional signaling motifs in its intracellular domain that are different from other conventional immunoregulatory signaling motifs but with similar inhibitory activities. Here we summarize the current understanding of LAG-3 signaling and its role in LAG-3 functions, from its mechanisms of action to clinical applications.     

Evolution of the mechanical properties and estimation of the useful lifespan of poly(lactic acid) based compounds

The useful lifespans of a poly(lactic acid)/poly(methyl methacrylate) (PLA/PMMA) 80/20 (wt%) blend and a poly(lactic acid)/dioctyl adipate/talc (PLA/DOA/talc) compound have been estimated by applying an Arrhenius relationship to the evolution of the mechanical properties whilst ageing. The studied PLA based systems showed lower activation energies (ca 8 ? 20 kJ mol^?1) than those reported in the literature for other synthetic thermoplastics, indicating lower thermo‐oxidative stability. However, both systems were interesting choices for semi‐durable applications in terms of useful lifespan estimations. The PLA/PMMA blend showed a drastic loss in stiffness at T_g due to its almost amorphous structure whereas, in contrast, PLA/DOA/talc showed acceptable mechanical properties above its glass transition temperature due to its semicrystalline structure. © 2018 Society of Chemical Industry     

Effective incorporation of ZnO nanoparticles by miniemulsion polymerization in waterborne binders for steel corrosion protection

A nanohybrid waterborne binder was synthesized by miniemulsion polymerization with the incorporation of ZnO nanoparticles in order to increase the corrosion protection capability. This system was compared to a neat waterborne binder and to a physical blend of the binder with an aqueous ZnO nanoparticles dispersion. The hybrid dispersion was characterized by SEM and TEM, while the corrosion behavior of these latexes was investigated by electrochemical measurements (open circuit potential and electrochemical impedance spectroscopy in 3.5 wt% NaCl solution), evaluating the effect of the incorporation of these nanoparticles into the polymeric matrix. The incorporation of ZnO nanoparticles by blending showed similar behavior to the neat coating despite flash rust reduction on the metal surface. In contrast, the hybrid binder prepared by miniemulsion polymerization has shown the best performance according to the values of pore resistance (R _i ) and coating capacitance (C _c). In general, this study shows how useful can be the miniemulsion polymerization methodology to design hybrid coating formulations, obtaining homogenous distribution of ZnO nanoparticles within the film. Indeed, a heterogeneous distribution can hinder the effectiveness and the corrosion protection capabilities of promising nanoparticles.     

Low-Density Steels: Complex Metallurgy for Automotive Applications

The current aim in the development of third-generation steels for lightweighting automotive applications is to increase strength keeping at least the same formability as current steel concepts. In this philosophy, an optimal concept would be one that brings, in addition, a lower density. For this purpose, low-density steels have been designed with important aluminum additions obtaining density reductions of 8–10% or higher in comparison with low-carbon steels. At the levels required for lightweighting, aluminum introduces complex phenomena in steels. Here, some of the effects of aluminum in phase stability, CALPHAD-type modeling, and microstructure development are described, the latter in relation with mechanical properties. Finally, the potential of two families of lightweight steels for automotive applications is assessed by comparison with a steel currently present in automotive structures.     

The effect of the addition of poly(styrene‐co‐glycidyl methacrylate) copolymer on the properties of polylactide/poly(methyl methacrylate) blend

The effect of the addition of poly(styrene‐co‐glycidyl methacrylate) P(S‐co‐GMA) copolymer on the properties of melt blended polylactide/poly(methyl methacrylate) (PLA/PMMA) 80/20 (wt %) composition was studied. In the literature high ductility levels were achieved by melt blending PLA with different additives. However, the gained ductility was counter balanced with drastic drops in strength and modulus values. The novelty of this work was the preparation of PLA‐based blends with polylactide content higher than 75 wt % which showed an impact resistance value improvement of about 60% compared with the neat PLA and maintained similar tensile strength and modulus values as well as glass transition temperature to neat PLA. The addition of only 3 pph of copolymer to PLA/PMMA blend improved the impact resistance almost 100%. The chemical reaction between PLA/PMMA blend and P(S‐co‐GMA) copolymer were analyzed by FTIR, rotational rheometry, and GPC/SEC. Phase structure and morphology were studied by Differential Scanning Calorimetry and Scanning Electronic Microscopy. Tensile and impact properties as well as thermal stability were also studied. Results showed that as the amount of copolymer in the blend was increased then higher was average molecular weight and polydispersity index. After the addition of P(S‐co‐GMA) copolymer to the PLA/PMMA blend the impact resistance, elongation at break and thermal stability were improved while tensile strength and elastic modulus remained almost unaltered. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43935.     

Behavior of polyolefin blends with acetylated sisal fibers

The influence of acetylation on the mechanical, thermal and thermodegradative behavior of sisal fiber‐reinforced PP, PP/HDPE and PP/HDPE with functionalized and non‐functionalized EPR composites was studied. Acetylation of the fiber improves adhesion of the fiber to the polyolefin matrix. In general, acetylation of the sisal fiber was found to enhance the tensile strength and modulus of the resulting composites, except in some cases. Thermal properties suggest that the mixing and molding temperatures are between 160 and 230 °C and that when acetylated fiber is mixed with polyolefins, greater polymer‐fiber interactions takes place, which slightly favor stability of these composite materials. The results allow us to suggest that a satisfactory profit/cost relation justifies the addition of acetylated fiber to PP, PP/HDPE, and PP/HDPE/EPR. © 2000 Society of Chemical Industry     

Functionalization of Photosensitized Silica Nanoparticles for Advanced Photodynamic Therapy of Cancer

BODIPY dyes have recently attracted attention as potential photosensitizers. In this work, commercial and novel photosensitizers (PSs) based on BODIPY chromophores (haloBODIPYs and orthogonal dimers strategically designed with intense bands in the blue, green or red region of the visible spectra and high singlet oxygen production) were covalently linked to mesoporous silica nanoparticles (MSNs) further functionalized with PEG and folic acid (FA). MSNs approximately 50 nm in size with different functional groups were synthesized to allow multiple alternatives of PS-PEG-FA decoration of their external surface. Different combinations varying the type of PS (commercial Rose Bengal, Thionine and Chlorine e6 or custom-made BODIPY-based), the linkage design, and the length of PEG are detailed. All the nanosystems were physicochemically characterized (morphology, diameter, size distribution and PS loaded amount) and photophysically studied (absorption capacity, fluorescence efficiency, and singlet oxygen production) in suspension. For the most promising PS-PEG-FA silica nanoplatforms, the biocompatibility in dark conditions and the phototoxicity under suitable irradiation wavelengths (blue, green, or red) at regulated light doses (10–15 J/cm²) were compared with PSs free in solution in HeLa cells in vitro.     

Influence of cure conditions on properties of resol/layered silicate nanocomposites

The effects on clay exfoliation of organic modification of montmorillonite (MMT) and the nature of the catalyst used during the synthesis and curing of a MMT modified phenolic resol resin were investigated. The impact on the final properties of other parameters such as reactivity ratio and temperature of condensation were also analyzed in order to optimize the conditions to prepare a customized organoclay‐based nanocomposite. Nanocomposites were analyzed by means of wide angle X‐ray scattering (WAXS), optical microscopy (TOM), and atomic force microscopy (AFM) techniques. The formation of either intercalated or quasi‐exfoliated structure was assessed in some systems. Thermal and mechanical properties of the cured composites were evaluated and correlated to their morphologies. More homogenous clay dispersion was achieved for composites prepared with aminoacid‐modified MMT, triethylamine (TEA) as catalyst, formaldehyde/phenol molar ratio (F/P) 2.0, and curing at 80°C. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Heavy metal levels (Pb, Cd, Cr and Hg) in the adult general population near an urban solid waste incinerator

In 2005 an urban solid waste incinerator (SWI) was commissioned in Bilbao (Basque Country, Spain). Serum and urine samples were collected from 95 and 107 volunteers in 2006 and 2008 respectively, of which 62 were repeats from the same individuals. Blood lead levels (BPb) were determined, as were the concentrations of cadmium (Cd), chromium (Cr) and mercury (Hg) in urine (UCd, UCr and UHg). The town of Alonsotegi and a borough of Bilbao (Altamira, Rekalde) were considered to be close, less than 2 km from the plant, and correspond to an urban environment with high traffic density. The areas of reference were a borough of Bilbao (Santutxu-Zurbaran), 5 km from the plant, also in an urban area with high traffic density, and a small town with little industrial activity and low traffic density (Balmaseda) 20 km from the plant; neither of these is downwind from the site with respect to prevailing winds. There was a significant correlation for BPb, r = 0.63 (p < 0.001), between the two surveys. However, there was no linear correlation for the other three metals (UCd, UCr and UHg), between the two sampling periods (p > 0.05). Multiple linear regression models did not show increases over time of the levels of BPb, UCd, UCr and UHg in the areas close to the SWI compared to those of areas located further away, after adjusting for confounding variables. These results reinforce the hypothesis that populations near modern plants for solid waste incineration do not manifest increased levels of heavy metals.