Cd1−xZnxS solid solutions supported on ordered mesoporous silica (SBA-15): Structural features and photocatalytic activity under visible light

A series of Cd_1−xZn_xS (x = 0.05–0.3) photocatalysts supported on ordered mesoporous silica (SBA-15) were prepared and investigated for hydrogen production from water splitting under visible light. Textural, structural and surface photocatalyst properties are determined by N₂ adsorption isotherms, UV–vis, Raman and XPS and related to the activity results in hydrogen production. Raman and XRD results indicated a mutual interaction between Cd and Zn, forming nanoparticles of Cd_1−xZn_xS solid solutions. All Cd_1−xZn_xS/SBA-15 samples showed relatively high activities for hydrogen evolution. The hydrogen production rate is found to increase gradually when the zinc concentration on photocatalysts increases from 0.05 to 0.2, achieving a maximum for the photocatalyst with zinc concentration equal to 0.2. Variation in photoactivity is discussed in terms of modification in the conduction band and light absorption ability of Cd_1−xZn_xS particles derived from the changes in the Zn concentration in the Cd_1−xZn_xS solid solution.     

Hedgehog Signalling Modulates Immune Response and Protects against Experimental Autoimmune Encephalomyelitis

The Hedgehog (Hh) pathway is essential for the embryonic development and homeostatic maintenance of many adult tissues and organs. It has also been associated with some functions of the innate and adaptive immune system. However, its involvement in the immune response has not been well determined. Here we study the role of Hh signalling in the modulation of the immune response by using the Ptch-1-LacZ^+/− mouse model (hereinafter referred to as ptch^+/−), in which the hemizygous inactivation of Patched-1, the Hh receptor gene, causes the constitutive activation of Hh response genes. The in vitro TCR stimulation of spleen and lymph node (LN) T cells showed increased levels of Th2 cytokines (IL-4 and IL-10) in ptch^+/−cells compared to control cells from wild-type (wt) littermates, suggesting that the Th2 phenotype is favoured by Hh pathway activation. In addition, CD4⁺ cells secreted less IL-17, and the establishment of the Th1 phenotype was impaired in ptch^+/− mice. Consistently, in response to an inflammatory challenge by the induction of experimental autoimmune encephalomyelitis (EAE), ptch^+/− mice showed milder clinical scores and more minor spinal cord damage than wt mice. These results demonstrate a role for the Hh/ptch pathway in immune response modulation and highlight the usefulness of the ptch^+/− mouse model for the study of T-cell-mediated diseases and for the search for new therapeutic strategies in inflammatory diseases.     

Asymmetric bihomologous crosslinkers for bicomponent gels—The way to strongly increased elastic moduli

2‐Hydroxyethylmethacrylate (HEMA) and acrylamide (AA) have been copolymerized via free radical mechanism, in the presence of 5 mol % of four different crosslinker systems, the symmetric ethylenglycoldimethacrylate (EGDMA), bisacrylamide (BIS), a mixture of EGDMA and BIS, and the asymmetric acrylamideethylenmethacrylate (METAA). The polymerizations have been monitored with a rheometer, exhibiting the gel obtained with the asymmetric METAA, an elastic modulus that is dramatically increased compared with those of the gels prepared with the other three crosslinker systems. A kinetic analysis using the terminal model has been used to build probabilistic surfaces that give information about how the crosslinker is incorporated into the network. This analysis shows a high dissimilarity between the reactions using the asymmetric and the mixture of symmetric crosslinkers, what has been correlated to the difference in modulus. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enrichment of marsh soils with heavy metals by effect of anthropic pollution

The impact of waste disposal on marsh soils was assessed in topsoil samples collected at eight randomly selected points in the salt marsh in Ramallosa (Pontevedra, Spain) at 4-month intervals for 2 years. Polluted soil samples were characterized in physico-chemical terms and their heavy metal contents determined by comparison with control, unpolluted samples. The results revealed a marked effect of waste discharges on the soils in the area, which have low contents in heavy metals under normal environmental conditions. In fact, the studied soils were found to contain substantial amounts of total and DTPA-extractable Cd, Cu, Pb and Zn. Based on the relationship of the redox potential with the DTPA-extractable Cd, Cu, Pb, and Zn contents of the soils, strongly reductive conditions raised the total contents in these elements by effect of their remaining in the soils as precipitated sulphides. Such contents, however, decreased as oxidative conditions gradually prevailed. The contents in DTPA-extractable metals increased with increasing Eh through the release of the metals in ionic form to the soil solution under oxidative conditions. The contents in heavy metals concentrating in the polluted soils were several times higher than those in the control soils (viz. 2 vs. 6 for Cd, 4 vs. 6 for Cu, 4 vs. 20 for Pb, and 2 vs. 15 for Zn, all in mg kg⁻¹). This can be expected to influence the amounts of available heavy metals present in the soils, and hence the environmental quality of the area, in the near future. Based on its geoaccumulation index (Class ≥3 for Cd and Cu, and 1–4 for Pb and Zn), the Ramallosa marsh is highly polluted with Cd and moderately to highly polluted with Cu, Pb and Zn. The enrichment factors obtained confirm that the salt marsh is highly polluted (especially with Cd) as the primary result of anthropic activity.     

A Nondestructive Methodology for the Study of Colored Enamels: Insights into Manufacturing and Weathering Processes

We studied ancient enamels on gilded copper from a collection of archeological horse harness pendants of the Museo Instituto Valencia de Don Juan (Madrid, Spain) to test the benefits of a new, nondestructive analytical methodology based on chemometric analysis (i.e., Principal Component Analysis, PCA) on micro‐ATR‐FTIR spectral data and chemical quantification using SEM‐EDS. The novelty of this approach was threefold: (i) PCA allowed the discrimination of the different harness pendants of known origin and attributed to the 14th and 15th centuries according to the chemical complex composition, nanostructure, glass weathering, and/or coloring mechanisms of each colored enamel, separately (i.e., red, purple, blue, and white), (ii) it is a cheap, easily available and nondestructive methodology that enables us to (iii) draw archeological conclusions about the quality of the manufacturing process, reassess the chronology of these objects and attempt to attribute them to different workshops according to the different traditional recipes identified. In particular, the enamels were made of alkali and/or alkaline earth lead‐glass with a wide range of chemical compounds in the form of pigments or opacifiers. Two types of coloring mechanisms were identified, colloidal particles such as copper‐ruby for red enamels, and ionic mechanisms such as Fe(II) and Co(II) to achieve a blue pigments; Mn(III) in the purple pigment; and two kind of white enamels were identified, i.e., tin oxide as an opacifier and uranium oxide. In addition, we established the reason for the poor state of conservation of some of the enamels by means of the identification of depolymerization and ion exchanges, well‐known harmful effects of glass weathering, and finally a chronology was assigned for some of these pieces according to the enamel composition.     

One‐Pot Synthesis of Functional Helicoidal Hybrid Organic–Inorganic Nanofibers with Periodically Organized Mesoporosity

The one‐pot synthesis and properties of multifunctional hybrid mesoporous organosilica fibers with helical shapes are described. These hybrid mesoporous fibers are prepared without chiral elements and functionalized with a large variety of organic R functions (R = alkylthiols, phenylsulfonates, alkylphosphonates, dansyl, aminopropyl, fluoroalkyl, etc.). The resulting nanomaterials are thoroughly characterized by a variety of techniques. The use of a synergetic combination of achiral molecules as co‐directing structuring agents, a surfactant, and an organofunctional silica precursor R‐Si(OR)₃ allows, via carefully tuning of the main synthesis parameters and processing conditions, to control the shape, which is the anisotropic factor, of the hybrid nanofibers. The functionalization of the hybrid materials with fluorescent molecules (dansyl) and gold nanoparticles opens possibilities for sensor and catalytic applications, respectively. Moreover, these hybrid nanofibers can be easily transferred in organic solvents or in a “green” solvent such as water to make stable colloidal dispersions. This tunable functionality of nanofibers also allows their transferability into a variety of polymeric hosts (PVDF, PVBu, and PVP) allowing the formation of functional homogeneous nanocomposite hybrid membranes.     

Detection of anisakids in fish and seafood products by real-time PCR

Anisakids are a group of widely distributed nematodes which have acquired high social relevance due to their involvement in foodborne infections caused by consumption of raw or undercooked seafood. A TaqMan^®-LNA probe real-time assay targeting the cytochrome oxidase subunit I (COI) was developed allowing the simultaneous detection of the most important anisakids species present in fish and seafood products.The determination of the detection limit in terms of ppm was 1 ppmFor the validation of method developed, twenty fish and cephalopod samples were experimentally contaminated with anisakid. It was checked that in cases in any anisakids species was present, it was detected because the Ct was always less than 35 and did not produce any case false negatives. The main novelty of this work lies in the fact that it can be applied to all kinds of processed products, including those undergoing intensive processes of transformation, as for instance canned foods. The proposed methodology is rapid, robust, highly sensitive and readily adaptable in routine molecular diagnostic laboratories, and can be employed as molecular screening method in order to assess the food security.     

Polyphenolic contents in Citrus fruit juices: authenticity assessment

The contents of 49 polyphenols in sweet orange, tangerine, lemon and grapefruit juices from 18 cultivars grown in Spain were determined by reversed-phase high-performance liquid chromatography with photodiode array detection. Citrus polyphenolic profiles consist of 81–97 % of flavanones, 0.3–13.6 % of flavones, 0.1–6.0 % of flavonols, 0.6–9.6 % of hydroxycinnamic acids and 0.2–0.4 % of coumarins (only found in grapefruit juices). Several markers that allow to distinguish with practical certainty grapefruit and lemon juices between them and from the other Citrus species are reported. Each of these markers is a reliable and useful tool to detect juice adulteration. Grapefruit juice markers were naringenin-7-O-neohesperidoside, naringenin-7-O-neohesperidoside-4′-O-glucose, naringenin-O-hexosylhexoside, hesperetin-7-O-neohesperidoside, naringenin-O-rhamnosylmalonylhexoside, isosakuranetin-7-O-neohesperidoside, hesperetin-7-O-rutinoside, apigenin-6-C-hexoside-O-hexoside, apigenin-7-O-neohesperidoside and scopoletin-O-hexoside. Lemon juice markers were eriodictyol-7-O-rutinoside-4′-O-glucoside, eriodictyol-7-O-rutinoside, diosmetin-6,8-di-C-glucoside, diosmetin-8-C-glucoside, luteolin-7-O-rutinoside, diosmetin-6-C-glucoside and diosmetin-6,8-di-C-hexosideacylhexoside. The markers naringenin-O-hexosylhexoside, apigenin-6-C-hexoside-O-hexoside, scopoletin-O-hexoside, diosmetin-8-C-glucoside and diosmetin-6,8-di-C-hexosideacylhexoside were detected, characterized and quantitatively determined in grapefruit and lemon juices for the first time by our research group, as far as the authors know. Classification models provided by LDA and PLS-DA correctly identify all sweet orange and tangerine juices. Moreover, PLS regression model determines the percentage (10–70 %) of tangerine juice used to adulterate sweet orange juice with a suitable confidence interval (RMSEP = 7 %).     

Characterization by culture-dependent and culture-independent methods of the bacterial population of suckling-lamb packaged in different atmospheres

This study offers insight into the dynamics of bacterial populations in fresh cuts of suckling lamb under four different atmospheric conditions: air (A), and three Modified Atmosphere Packaging (MAP) environments, 15%O₂/30%CO₂/55%N₂ (C, commercial), 70%O₂/30%CO₂ (O), and 15%O₂/85%CO₂ (H) for 18 days. Microbial analyses by both conventional methods and PCR-DGGE were performed. Controversial and surprising results emerged from comparing both methods in relation to the genus Pseudomonas. Thus, conventional methods detected the presence of high numbers of Pseudomonas colonies, although PCR-DGGE only detected this genus in air-packaged samples. PCR-DGGE detected higher microbial diversity in the control samples (A) than in the modified atmospheres (C, O, H), having atmosphere H the fewest number of species. Brochothrix thermosphacta, LAB (Carnobacterium divergens and Lactobacillus sakei), and Escherichia spp. were detected in all the atmospheres throughout storage. Moreover, previously undescribed bacteria from lamb meat such as Enterobacter hormaechei, Staphylococcus equorum and Jeotgalicoccus spp. were also isolated in this study by DGGE. Additionally, qPCR analysis was used to detect and characterize strains of Escherichia coli. Virulence genes (stx₁, stx₂ and eae) were detected throughout storage in 97% of the samples. A high CO₂ atmosphere was the most effective packaging combination doubling storage time in comparison with commercial atmosphere.     

Proteins as Possible Targets for Cytotoxic trans‐Platinum(II) Complexes with Aliphatic Amine Ligands: Further Exceptions to the DNA Paradigm

The reactivity of three cytotoxic trans‐Pt^II complexes bearing aliphatic amine ligands, with transferrin and single‐stranded oligonucleotides as DNA models, was investigated by ESI‐MS and the results obtained are discussed in comparison with cisplatin. Tandem MS studies provided additional information on the preferential Pt binding sites. To determine whether trans‐Pt^II complexes can migrate from a peptide to an oligonucleotide, transfer experiments were also performed using ESI‐MS, and competitive binding of the trans‐Pt^II complexes toward a model peptide and different oligonucleotides was also investigated. Significant differences in the reactivity of the trans complexes with respect to cisplatin were observed. In general, adduct formation with the selected peptide is favored for the trans compounds, whereas cisplatin shows a preference for oligonucleotides, especially if adjacent G–G residues are present. The results are discussed in relation to the possible mechanism of action of the trans‐Pt^II complexes.