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This paper deals with the synthesis and characterization of iron-hexacyanocobaltate (FeHCC) and its antibacterial properties. The nanoparticles were prepared by a facile co-precipitation technique. Crystal structure, particle morphology, and elemental composition were determined using X-ray Powder Diffraction, X-ray fluorescence spectroscopy, Transmission Electron Microscopy (TEM), and Infrared Spectroscopy (IR). The antibacterial activity of the FeHCC nanoparticles was tested against Escherichia coli and Staphylococcus aureus as models for Gram-negative and Gram-positive bacteria, respectively, by bacterial counting method and microscopic visualization (TEM, FEG-SEM, and fluorescence microscopy). The results showed that the FeHCC nanoparticles bind to the bacterial cells, inhibit bacterial growth in a dose- and time-dependent manner, inducing a loss of the membrane potential, the production of reactive oxygen species and the release of macromolecules (nucleic acids and proteins) in the extracellular environment. To the best of our knowledge, this is the first study reporting the antimicrobial effects of metal-hexacyanometallates suggesting practical uses of these materials in different areas, such as self-cleaning surfaces or food packaging.
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Antibacterianos/síntesis química , Antibacterianos/farmacología , Cobalto/química , Cianuros/química , Hierro/química , Nanopartículas del Metal/química , Recuento de Colonia Microbiana , Escherichia coli/efectos de los fármacos , Escherichia coli/crecimiento & desarrollo , Pruebas de Sensibilidad Microbiana , Microscopía Electrónica de Rastreo , Microscopía Electrónica de Transmisión , Especies Reactivas de Oxígeno/metabolismo , Espectrometría de Fluorescencia , Staphylococcus aureus/efectos de los fármacos , Staphylococcus aureus/crecimiento & desarrolloRESUMEN
A combined X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) methodology is here presented on a series of partially and fully reduced Au(III) samples. This allows monitoring the relative fraction of Au(III) and Au(0) in the studied samples, displaying a consistent and independent outcome. The strategy followed is based, for the first time, on two structural models that can be fitted simultaneously, and it evaluates the correlation among strongly correlated parameters such as coordination number and the Debye-Waller factor. The results of the present EXAFS and XANES approach can be extended to studies based on X-ray absorption spectroscopy experiments for the in situ monitoring of the formation of gold nanoclusters.
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A charge transfer between Fe and Co in cobalt hexacyanoferrate has been observed for the first time by anatase doping. The charge transfer, which involves a spin transition at the Co site, is supported by high-resolution XANES spectra. EXAFS evidenced a consistent change (10%) of the Co-N first shell.
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Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH3)3SiOCH3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm-3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH3)3SiOCH3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN)64- at scan rates above 5 mVs-1 yielded currents controlled primarily by linear diffusion. Below 5 mVs-1, convection rather than the expected factor, radial diffusion, apparently limited the current.
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Many staple foods originate from durum wheat and its milling products; because of this, it is very important to know their characteristics. This study investigates elemental contents in these products and if differences exist because of organic farming. The concentrations of 28 elements in the whole seed and in milling products, that is, bran, semolina and flour, of durum wheat, were determined through ICP-OES. The wheats were grown under conventional or organic agronomic practices to verify the possibility of discriminating, using the elemental content, between products coming from one or the other practice. The elements were more abundant in the outer layer of the seed, the bran, but most of them were also present in the others. Traces of Sb were present only in 3% of the samples, while traces of Tl were detected in approximately half of the seed and bran samples but not in other samples. The absence of an element was more characteristic of specific products, e.g., most semolina and flour lacked Co, while other elements showed small differences between products from organic and conventional cultivation or between different milling products, which was the case, for example, for traces of Ag, B, and V. The concentrations of these elements were coupled with multivariate discriminant analysis, specifically PLS-DA, to identify the cultivation provenance of the milled products. A few elements, although different for each product, are sufficient to attain precision and accuracy of classification close to 1; small differences exist for different products. The worst is flour, where the predicted precision and accuracy are 0.92, although using only three elements: B, K, and Se. Semolina attains perfect prediction when also adding to the three previous elements, Ag, Cd, and Cu. Further elements are necessary for bran, while Fe and Mg replace K and Ag to classify seeds. In conclusion, five elements, B, Cd, Cu, K, and Se, are the most important in distinguishing between organic and conventional agriculture; these elements also permit some differentiation among products. The method could help in fraud prevention.
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A measurement campaign was conducted on San Domino Island, part of the Tremiti Islands archipelago, located in Foggia, Italy. The area is almost entirely covered by vegetation, dominated by the following main species: Juniperus turbinata, Helichrysum italicum, Myrtus communis, Rosmarinus officinalis, Pistacia lentiscus and Pinus halepensis.This study focused on the BVOCs emitted by plants and the ground, employing a simple, economical, and efficient sampling and analysis method. The main known BVOC species emitted by Mediterranean plant species as α-pinene, ß-pinene, camphene and limonene were detected. The measurements highlighted a daily complementarity between plant and soil emissions. The daily variations in BVOCs emitted by both plants and the soil are differ, ensuring an almost constant concentration throughout the day. At the same time, the composition of sea spray aerosol (SSA) was also measured. The measurement sites were selected based on botanical characterization to account for the predominant species on San Domino Island, and the sampling was conducted at human height to accurately identify the species for potential use. The combination of beneficial effects of the substances emitted by plant species and soil, along with the simultaneous presence of SSA, are factors that could enhance the effectiveness of forest therapy in a previously unexplored location.
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Wheat spikes could directly absorb lead (Pb) from atmospheric depositions. However, the mechanism by which the spikes contribute to Pb accumulation in the grain remains unclear. To investigate this mechanism, a field experiment was conducted using three comparative spikes shading treatments: 1) exposed to atmospheric deposition and light (CK), 2) non-exposed to atmospheric deposition and light (T1), and 3) non-exposed to atmospheric deposition but light-transmitting (T2). Spikes shading treatments reduced the average rate and peak value of the accumulation of Pb in grains, which significantly decreased the grain Pb concentration by 57.44 % and 50.26 % in T1 and T2 treatments, respectively. Moreover, Pb isotopic analysis shows that the Pb in spike and grain was mainly from atmospheric deposition, and the percentage of the grain Pb originated from atmospheric Pb decreased from 85.98 % in CK to 72.87 % and 79.59 % in T1 and T2, respectively. In addition, the spikes, rather than the leaves/roots, were the largest wheat tissue source of Pb in grains, and the relative contribution of spikes to grain Pb accumulation increased to 65.57 % at the maturity stage, of which the stored Pb re-translocation of spikes and the newly absorbed Pb by spikes during the filling stage contributed 13.37 % and 52.20 % to the grain Pb, respectively. Thus, the contribution of the spike to the grain Pb was mainly from the newly absorbed Pb from the atmospheric deposition during the grain filling phase, and grain filling phase is the key stage for the absorption of Pb by the grain. In brief, the newly absorbed atmospheric Pb by wheat spike during filling stage is the primary cause of grain Pb contamination, which provided a new insight for effective control of wheat Pb pollution.
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Plomo , Triticum , Suelo , Contaminación Ambiental , Grano ComestibleRESUMEN
Lead (Pb) accumulation in wheat grains depends on two aspects: i) Pb uptake by the roots and shoots, and ii) the translocation of organ Pb into the grain. However, the underlying mechanism of the uptake and transport of Pb in wheat remains unclear. This study explored this mechanism by establishing field leaf-cutting comparison treatments. Interestingly, as the organ with the highest Pb concentration, only 20.40 % of the root's relative contribution to grain Pb. The relative contributions of the spike, flag leaf, second leaf, and third leaf to grain Pb were 33.13 %, 23.57 %, 13.21 %, and 9.69 %, respectively, which was opposite to their Pb concentration distribution trends. According to Pb isotope analysis, it was found leaf-cutting treatments reduced the proportion of atmospheric Pb in grain, and grain Pb predominantly comes from atmospheric deposition (79.60 %). Furthermore, from the bottom to the top, the concentration of Pb in internodes decreased gradually, and the proportions of Pb originating from soil in the nodes also decreased, revealing that wheat nodes hindered the translocation of Pb from roots and leaves to the grain. Therefore, the hindering effect of nodes on the migration of soil Pb in wheat resulted in atmospheric Pb having a more convenient pathway to the grain than soil Pb, and further leading grain Pb accumulation primarily depended on the contribution of the flag leaf and spike.
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Contaminantes del Suelo , Suelo , Triticum/metabolismo , Plomo/análisis , Contaminantes del Suelo/análisis , Raíces de Plantas/metabolismo , Grano Comestible/químicaRESUMEN
Vanadium pentoxide materials prepared through sol-gel processes act as excellent intercalation hosts for lithium as well as polyvalent cations. A chemometric approach has been applied to study the X-ray absorption near-edge structure (XANES) evolution during in situ scanning of the Cu(0.1)V(2)O(5) xerogel/Li ions battery. Among the more common techniques, the fixed size windows evolving factor analysis (FSWEFA) permits the number of species involved in the experiment to be determined and the range of existence of each of them. This result, combined with the constraints of the invariance of the total concentration and non-negativity of both concentrations and spectra, enabled us to obtain the spectra of the pure components using a multivariate curve resolution refined by an alternate least squares fitting procedure. This allowed the normalized concentration profile to be understood. This data treatment evidenced the occurrence, for the first time, of three species during the battery charging. This fact finds confirmation by comparison of the pure spectra with the experimental ones. Extended X-ray absorption fine structure (EXAFS) analysis confirms the occurrence of three different chemical environments of Cu during battery charging.
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The structural parameters in selected cobalt and mixed cobalt/nickel hexacyanoferrates have been determined by X-ray absorption spectroscopy. The presence of two or three metals in the sample requires the use of a highly efficient multiple edge analysis. The typical structure of mixed hexacyanoferrates coupled with a suitable data analysis program, GNXAS, allow us to determine structural parameters considering a very high number of experimental points. The first data analysis of three contiguous edges (Fe, Co, and Ni K-edges), the structural parameters of which are entirely correlated, is presented. The advantages and limitations of the multiple edge approach are underlined and placed in the context of the previous studies. The CN bond length has been determined with a statistical error of few thousandths of an angstrom.
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The product obtained by the intercalation of hexacyanoferrate(III) inside a Ni, Al hydrotalcite-like compound (Htlc) has been characterized using XRD, FT-IR, Raman, and XAS spectroscopy. The intercalation was carried out by anionic exchange of the originally existing chloride ions. The combined use of those techniques gave more insight on the insertion chemistry of Htlcs. Extended X-ray absorption fine structure spectra of the intercalated Htlc demonstrated that the native structure was stable during the iron complex insertion, whereas the exchange process occurred with a partial reduction of hexacyanoferrate(III). Both Raman and FT-IR spectroscopy pointed out the concomitant formation of K(2)NiFe(II)(CN)(6) and KNiFe(III)(CN)(6). The effect of aging on the intercalated product is also addressed.
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The oxidation of 5-hydroxytryptophan (5-HTPP) yielded a passivating polymeric film at an indium tin oxide (ITO) electrode. Coating ITO with a nanoscale sol-gel film with a mesoporous structure was shown to change the pathway of the chemical reaction coupled to the electron transfer. The sol-gel film was deposited by an electrochemically assisted process, and the mesoporosity was imparted by including generation-4 poly(amidoamine) dendrimer in the precursor solution. The dendrimer was removed subsequently with an atmospheric oxygen plasma. This electrode remained active during cyclic voltammetry and controlled potential electrolysis of 5-HTPP, which was attributed to dimer, rather than polymer, formation from the oxidation product. Mass spectrometry confirmed this hypothesis. The anodic current was limited by the electron-transfer kinetics. Modification of the sol-gel film by inclusion of cobalt hexacyanoferrate, which catalyzes the oxidation, resulted in a diffusion-limited current. Determination of 5-HTPP by flow-injection amperometry had a detection limit of 17nM.
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5-Hidroxitriptófano/análisis , Electrodos , Análisis de Inyección de Flujo , Nanotecnología , Microscopía Electrónica de Rastreo , Oxidación-Reducción , Espectrometría de Masa por Láser de Matriz Asistida de Ionización DesorciónRESUMEN
X-ray absorption spectroscopy (XAS) was used to investigate the local structure arrangements of submicrocrystalline lithium iron phosphate and its precursors. The former material, proven to be very promising as active cathode material in lithium metal and lithium-ion batteries, was synthesized through a new procedure that combines a simple sol-gel precipitation with a moderate temperature (e.g., low cost) heat treatment. X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra taken at the Fe K-edge pointed out the modification of the Fe site during the synthesis steps that allow one to produce the submicrometer size crystalline LiFePO4 (active material) useful for batteries applications. The XAS investigation has shown that such a material is different from the conventional crystalline LiFePO4 on the short-range order. The difference is attributed to the synthesis procedure.