RESUMO
Combining nuclear magnetic resonance (NMR), X-ray absorption spectroscopy near-edge structure (XANES), and density functional theory (DFT), we elucidate the structures of tungstate and molybdate with sugars of interest in the conversion of biomass to platform chemicals (glucose, mannose, and erythrose). We highlight a number of complexes, including one nearly isostructural structure that is formed with each metal-sugar combination. We also emphasize the singular reactivity of erythrose that undergoes retro-aldolization at room temperature.
RESUMO
The control of metal-sugar complexes speciation in solution is crucial in an energy transition context. Herein, the formation of tungstate-mannose complexes is unraveled in aqueous solution using a multitechnique experimental and theoretical approach. 13C nuclear magnetic resonance (NMR), as well as 13C-1H and 1H-1H correlation spectra, analyzed in the light of coordination-induced shift method and conformation analysis, were employed to characterize the structure of the sugar involved in the complexes. X-ray absorption near edge structure spectroscopy was performed to provide relevant information about the metal electronic and coordination environment. The calculation of 13C NMR chemical shifts for a series of tungstate-mannose complexes using density functional theory (DFT) is a key to identify the appropriate structure among several candidates. Furthermore, a parametric study based on several relevant parameters, namely, pH and tungstate concentration, was carried out to look over the change of the nature and concentrations of the complexes. Two series of complexes were detected, in which the metallic core is either in a ditungstate or a monotungstate form. With respect to previous proposals, we identify two new species. Dinuclear complexes involve both α- and ß-furanose forms chelating the metallic center in a tetradentate fashion. A hydrate form chelating a ditungstate core is also revealed. One monotungstate complex appears at high pH, in which a tetrahedral tungstate center is bound to α-mannofuranose through a monodentate site at the second deprotonated hydroxyl group. This unequalled level of knowledge opens the door to structure-reactivity relationships.
RESUMO
The cellular level of reactive oxygen species (ROS) has to be controlled to avoid some pathologies, especially those linked to oxidative stress. One strategy for designing antioxidants consists of modeling natural enzymes involved in ROS degradation. Among them, nickel superoxide dismutase (NiSOD) catalyzes the dismutation of the superoxide radical anion, O2â¢-, into O2 and H2O2. We report here Ni complexes with tripeptides derived from the amino-terminal CuII- and NiII-binding (ATCUN) motif that mimics some structural features found in the active site of the NiSOD. A series of six mononuclear NiII complexes were investigated in water at physiological pH with different first coordination spheres, from compounds with a N3S to N2S2 set, and also complexes that are in equilibrium between the N-coordination (N3S) and S-coordination (N2S2). They were fully characterized by a combination of spectroscopic techniques, including 1H NMR, UV-vis, circular dichroism, and X-ray absorption spectroscopy, together with theoretical calculations and their redox properties studied by cyclic voltammetry. They all display SOD-like activity, with a kcat ranging between 0.5 and 2.0 × 106 M-1 s-1. The complexes in which the two coordination modes are in equilibrium are the most efficient, suggesting a beneficial effect of a nearby proton relay.
Assuntos
Peróxido de Hidrogênio , Superóxido Dismutase , Espécies Reativas de Oxigênio , Peróxido de Hidrogênio/química , Superóxido Dismutase/química , Oxirredução , Superóxidos/química , Níquel/químicaRESUMO
The redox activity of Cu ions bound to the amyloid-ß (Aß) peptide is implicated as a source of oxidative stress in the context of Alzheimer's disease. In order to explain the efficient redox cycling between CuII -Aß (distorted square-pyramidal) and CuI -Aß (digonal) resting states, the existence of a low-populated "in-between" state, prone to bind Cu in both oxidation states, has been postulated. Here, we exploited the partial X-ray induced photoreduction at 10â K, followed by a thermal relaxation at 200â K, to trap and characterize by X-ray Absorption Spectroscopy (XAS) a partially reduced Cu-Aß1-16 species different from the resting states. Remarkably, the XAS spectrum is well-fitted by a previously proposed model of the "in-between" state, hence providing the first direct spectroscopic characterization of an intermediate state. The present approach could be used to explore and identify the catalytic intermediates of other relevant metal complexes.
Assuntos
Doença de Alzheimer , Peptídeos beta-Amiloides , Humanos , Peptídeos beta-Amiloides/metabolismo , Cobre/química , Raios X , Doença de Alzheimer/metabolismo , Oxirredução , Espectroscopia por Absorção de Raios XRESUMO
Soil is a major receptor of manufactured nanomaterials (NMs) following unintentional releases or intentional uses. Ceria NMs have been shown to undergo biotransformation in plant and soil organisms with a partial Ce(IV) reduction into Ce(III), but the influence of environmentally widespread soil bacteria is poorly understood. We used high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) with an unprecedented detection limit to assess Ce speciation in a model soil bacterium (Pseudomonas brassicacearum) exposed to CeO2 NMs of different sizes and shapes. The findings revealed that the CeO2 NM's size drives the biotransformation process. No biotransformation was observed for the 31 nm CeO2 NMs, contrary to 7 and 4 nm CeO2 NMs, with a Ce reduction of 64 ± 14% and 70 ± 15%, respectively. This major reduction appeared quickly, from the early exponential bacterial growth phase. Environmentally relevant organic acid metabolites secreted by Pseudomonas, especially in the rhizosphere, were investigated. The 2-keto-gluconic and citric acid metabolites alone were able to induce a significant reduction in 4 nm CeO2 NMs. The high biotransformation measured for <7 nm NMs would affect the fate of Ce in the soil and biota.
Assuntos
Cério , Nanopartículas Metálicas , Nanoestruturas , Tamanho da Partícula , Cério/química , Solo/química , Nanopartículas Metálicas/química , BactériasRESUMO
Nickel superoxide dismutase (NiSOD) is an enzyme that protects cells against O2·-. While the structure of its active site is known, the mechanism of the catalytic cycle is still not elucidated. Its active site displays a square planar NiII center with two thiolates, the terminal amine and an amidate. We report here a bioinspired NiII complex built on an ATCUN-like binding motif modulated with one cysteine, which demonstrates catalytic SOD activity in water (kcat = 8.4(2) × 105 M-1 s-1 at pH = 8.1). Its reactivity with O2·- was also studied in acetonitrile allowing trapping two different short-lived species that were characterized by electron paramagnetic resonance or spectroelectrochemistry and a combination of density functional theory (DFT) and time-dependent DFT calculations. Based on these observations, we propose that O2·- interacts first with the complex outer sphere through a H-bond with the peptide scaffold in a [NiIIO2·-] species. This first species could then evolve into a NiIII hydroperoxo inner sphere species through a reaction driven by protonation that is thermodynamically highly favored according to DFT calculations.
Assuntos
Materiais Biomiméticos/química , Complexos de Coordenação/química , Superóxidos/química , Catálise , Teoria da Densidade Funcional , Modelos Químicos , Estrutura Molecular , Níquel/química , Superóxido Dismutase/químicaRESUMO
In Rhodospirillum rubrum, the maturation of carbon monoxide dehydrogenase (CODH) requires three nickel chaperones, namely RrCooC, RrCooT and RrCooJ. Recently, the biophysical characterisation of the RrCooT homodimer and the X-ray structure of its apo form revealed the existence of a solvent-exposed NiII -binding site at the dimer interface, involving the strictly conserved Cys2. Here, a multifaceted approach that used NMR and X-ray absorption spectroscopies, complemented with structural bio-modelling methodologies, was used to characterise the binding mode of NiII in RrCooT. This study suggests that NiII adopts a square-planar geometry through a N2 S2 coordinating environment that comprises the two thiolate and amidate groups of both Cys2 residues at the dimer interface. The existence of a diamagnetic mononuclear NiII centre with bis-amidate/bis-thiolate ligands, coordinated by a single-cysteine motif, is unprecedented in biology and raises the question of its role in the activation of CODH at the molecular level.
Assuntos
Cisteína/química , Metalochaperonas/química , Níquel/química , Rhodospirillum rubrum/química , Sequência de Aminoácidos , Sítios de Ligação , Cátions Bivalentes/química , Complexos de Coordenação/química , Ligantes , Modelos Moleculares , Nitrogênio/química , Ligação Proteica , Conformação Proteica , Multimerização Proteica , Solventes/química , Enxofre/química , TermodinâmicaRESUMO
The superoxide dismutase (SOD) activity of mononuclear NiII complexes, whose structures are inspired by the NiSOD, has been investigated. They have been designed with a sulfur-rich pseudopeptide ligand, derived from nitrilotriacetic acid (NTA), where the three acid functions are grafted with cysteines (L3S). Two mononuclear complexes, which exist in pH-dependent proportions, have been fully characterized by a combination of spectroscopic techniques including 1H NMR, UV-vis, circular dichroism, and X-ray absorption spectroscopy, together with theoretical calculations. They display similar square-planar S3O coordination, with the three thiolates of the three cysteine moieties from L3S coordinated to the NiII ion, together with either a water molecule at physiological pH, as [NiL3S(OH2)]-, or a hydroxo ion in more basic conditions, as [NiL3S(OH)]2-. The 1H NMR study has revealed that contrary to the hydroxo ligand, the bound water molecule is labile. The cyclic voltammogram of both complexes displays an irreversible one-electron oxidation process assigned to the NiII/NiIII redox system with Epa = 0.48 and 0.31 V versus SCE for NiL3S(OH2) and NiL3S(OH), respectively. The SOD activity of both complexes has been tested. On the basis of the xanthine oxidase assay, an IC50 of about 1 µM has been measured at pH 7.4, where NiL3S(OH2) is mainly present (93% of the NiII species), while the IC50 is larger than 100 µM at pH 9.6, where NiL3S(OH) is the major species (92% of the NiII species). Interestingly, only NiL3S(OH2) displays SOD activity, suggesting that the presence of a labile ligand is required. The SOD activity has been also evaluated under catalytic conditions at pH 7.75, where the ratio between NiL3S(OH2)/ NiL3S(OH) is about (86:14), and a rate constant, kcat = 1.8 × 105 M-1 s-1, has been measured. NiL3S(OH2) is thus the first low-molecular weight, synthetic, bioinspired Ni complex that displays catalytic SOD activity in water at physiological pH, although it does not contain any N-donor ligand in its first coordination sphere, as in the NiSOD. Overall, the data show that a key structural feature is the presence of a labile ligand in the coordination sphere of the NiII ion.
Assuntos
Complexos de Coordenação/química , Cisteína/química , Níquel/química , Compostos de Enxofre/química , Superóxido Dismutase/química , Materiais Biomiméticos/química , Concentração de Íons de Hidrogênio , Ligantes , OxirreduçãoRESUMO
Mercury(II) is an unphysiological soft ion with high binding affinity for thiolate ligands. Its toxicity lies in the interactions with low molecular weight thiols including glutathione and cysteine-containing proteins that disrupt the thiol balance and alter vital functions. However, mercury can also be detoxified via interactions with Hg(II)-responsive regulatory proteins such as MerR, which coordinates Hg(II) with three cysteine residues in a trigonal planar fashion (HgS3 coordination). The model cyclodecapeptide P3C, c(GCTCSGCSRP) was designed to promote Hg(II) chelation in a HgS3 coordination environment through the parallel orientation of three cysteine side chains. The binding motif is derived from the dicysteine P2C cyclodecapeptide validated previously as a model for d10 metal transporters containing the binding sequence CxxC. The formation of the mononuclear HgP3C complex with a HgS3 coordination is demonstrated using electrospray ionization mass spectrometry, UV absorption, and 199Hg NMR. Hg LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopy indicates that the Hg(II) coordination environment is T-shaped with two short Hg-S distances at 2.45 Å and one longer distance at 2.60 Å. The solution structure of the HgP3C complex was refined based on 1H-1H NMR constraints and EXAFS results. The cyclic peptide scaffold has a rectangular shape with the three binding cysteine side chains pointing toward Hg(II). The HgP3CH complex has a p Ka of 4.3, indicating that the HgS3 coordination mode is stable over a large range of pH. This low p Ka value suggests that the preorientation of the three cysteine groups is particularly well-achieved for Hg(II) trithiolate coordination in P3C.
RESUMO
Wetlands have been proposed to naturally attenuate U transfers in the environment via U complexation by organic matter and potential U reduction. However, U mobility may depend on the identity of particulate/dissolved uranium source materials and their redox sensitivity. Here, we examined the fate of uranium in a highly contaminated wetland (up to 4500 mg·kg-1 U) impacted by former mine water discharges. Bulk U LIII-EXAFS and (micro-)XANES combined with SEM-EDXS analyses of undisturbed soil cores show a sharp U redox boundary at the water table, together with a major U redistribution from U(IV)-minerals to U(VI)-organic matter complexes. Above the water table, U is fully oxidized into mono- and bidentate U(VI)-carboxyl and monodentate U(VI)-phosphoryl complexes. Minute amounts of U(VI)-phosphate minerals are also observed. Below the water table, U is fully reduced and is partitioned between U(IV)-phosphate minerals (i.e., ningyoite and a lermontovite-like phase), and bidentate U(IV)-phosphoryl and monodentate U(IV)-carboxyl complexes. Such a U redistribution from U-minerals inherited from mine water discharge deposits could result from redox cycling nearby the water table fluctuation zone. Oxidative dissolution of U(IV)-phosphate minerals could have led to U(VI)-organic matter complexation, followed by subsequent reduction into U(IV)-organic complexes. However, uranium(IV) minerals could have been preserved in permanently waterlogged soil.
Assuntos
Urânio , França , Minerais , Oxirredução , Fosfatos , Solo , Áreas AlagadasRESUMO
Sulfidation is a key process for silver nanoparticles released from consumer products in the environment. This study focuses on the impact of a model soil microorganism, Bacillus subtilis, on the fate of pristine and already sulfidized Ag-NPs. The nanoparticles were incubated with the initial growth medium, isolated secretome, and living bacteria, and characterized for their size and morphology, agglomeration state, structure, and Ag speciation. No Ag internalization or sorption on the cell wall was detected. A partial sulfidation, leading to an Ag-Ag2S core-shell structure, was observed in the presence of the secretome, and the rate limiting step of the reaction was the oxidation of Ag0, and it was favored near the crystal dislocations. The sulfidation was complete in the presence of the living bacteria and followed an indirect pathway. Both crystalline Ag2S and amorphous Ag2S and/or Ag-thiol were identified. At the opposite, the bacteria had no impact on Ag2S. These results suggest that microorganisms participate in the sulfidation of Ag-NPs in aerobic systems such as unsaturated soils, and thus affect the bioavailability of Ag. It is important to take these transformations into account during exposure experiments, since they drastically change the exposure conditions. Finally, the secretome of B. subtilis might be used for the green synthesis of Ag-Ag2S core-shell nanoparticles.
Assuntos
Nanopartículas Metálicas , Prata , Oxirredução , SoloRESUMO
Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3(-), form very stable and soluble complexes with Au(+) in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10-100 times more efficiently than sulfide and chloride only. As a result, S3(-) exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3(-) during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere.
RESUMO
The ISO-standardized RHIZOtest is used here for the first time to decipher how plant species, soil properties, and physical-chemical properties of the nanoparticles and their transformation regulate the phytoavailability of nanoparticles. Two plants, tomato and fescue, were exposed to two soils with contrasted properties: a sandy soil poor in organic matter and a clay soil rich in organic matter, both contaminated with 1, 15, and 50 mg·kg-1 of dissolved Ce2(SO4)3, bare and citrate-coated CeO2 nanoparticles. All the results demonstrate that two antagonistic soil properties controlled Ce uptake. The clay fraction enhanced the retention of the CeO2 nanoparticles and hence reduced Ce uptake, whereas the organic matter content enhanced Ce uptake. Moreover, in the soil poor in organic matter, the organic citrate coating significantly enhanced the phytoavailability of the cerium by forming smaller aggregates thereby facilitating the transport of nanoparticles to the roots. By getting rid of the dissimilarities between the root systems of the different plants and the normalizing the surfaces exposed to nanoparticles, the RHIZOtest demonstrated that the species of plant did not drive the phytoavailability, and provided evidence for soil-plant transfers at concentrations lower than those usually cited in the literature and closer to predicted environmental concentrations.
Assuntos
Cério/farmacocinética , Nanopartículas , Poluentes do Solo/farmacocinética , Solanum lycopersicum , Raízes de Plantas , Poaceae , SoloRESUMO
The study of the speciation of highly diluted elements by X-ray absorption spectroscopy (XAS) is extremely challenging, especially in environmental biogeochemistry sciences. Here we present an innovative synchrotron spectroscopy technique: high-energy resolution fluorescence detected XAS (HERFD-XAS). With this approach, measurement of the XAS signal in fluorescence mode using a crystal analyzer spectrometer with a â¼1-eV energy resolution helps to overcome restrictions on sample concentrations that can be typically measured with a solid-state detector. We briefly describe the method, from both an instrumental and spectroscopic point of view, and emphasize the effects of energy resolution on the XAS measurements. We then illustrate the positive impact of this technique in terms of detection limit with two examples dealing with Ce in ecologically relevant organisms and with Hg species in natural environments. The sharp and well-marked features of the HERFD-X-ray absorption near-edge structure spectra obtained enable us to determine unambiguously and with greater precision the speciation of the probed elements. This is a major technological advance, with strong benefits for the study of highly diluted elements using XAS. It also opens new possibilities to explore the speciation of a target chemical element at natural concentration levels, which is critical in the fields of environmental and biogeochemistry sciences.
Assuntos
Monitoramento Ambiental , Espectroscopia por Absorção de Raios X , EcologiaRESUMO
We have studied the local structure and valence electronic unoccupied states of thermoelectric CsBi4Te6 and superconducting CsBi3.5Pb0.5Te6 (Tc â¼ 3 K) by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) measurements. The Bi-L3 edge EXAFS reveals wide Bi-Te distance distribution for both compounds indicating complex atomic arrangements in the studied system. The mean square relative displacements (MSRDs) of the Bi-Te bond distances appear largely increased in Pb substituted system due to larger overall local disorder, however, one of the Bi-Te bonds shows a reduced disorder. On the other hand, the Bi-L3 edge XANES is hardly affected by Pb substitution while the Te-L1 edge XANES reveals increased density of unoccupied Te 5p states. This suggests that the carriers introduced by the Pb substitution in CsBi4-xPbxTe6 preferentially goes on Te sites. Similarly, the Cs-L3 edge XANES also shows small changes due to Pb-substitution and reduced local disorder indicated by the reduced width of the Cs-L3 edge white line. We have also shown that the X-ray photoemission spectroscopy (XPS) measurements on various electronic core levels are in a qualitative agreement with the XANES results. These findings are consistent with carrier doping and a reduced disorder in one direction to be likely factors to drive the thermoelectric CsBi4Te6 into a bulk superconductor by Pb-substitution in CsBi4-xPbxTe6.
RESUMO
Gold(I) complexes such as auranofin or aurothiomalate have been used as therapeutic agents for the treatment of rheumatoid arthritis for several decades. Several gold(I) and gold(III) complexes have also shown in vitro anticancer properties against human cancer cell lines, including cell lines resistant to cisplatin. Because of the thiophilicity of gold, cysteine-containing proteins appear as likely targets for gold complexes. Among them, zinc finger proteins have attracted attention and, recently, gold(I) and gold(III) complexes have been shown to inhibit poly(adenosine diphosphate ribose)polymerase-1 (PARP-1), which is an essential protein involved in DNA repair and in cancer resistance to chemotherapies. In this Article, we characterize the reactivity of the gold(III) complex [Au(III)(terpy)Cl]Cl2 (Auterpy) with a model of Zn(Cys)4 "zinc ribbon" zinc finger by a combination of absorption spectroscopy, circular dichroism, mass spectrometry, high-performance liquid chromatography analysis, and X-ray absorption spectroscopy. We show that the Zn(Cys)4 site of Zn·LZR is rapidly oxidized by Auterpy to form a disulfide bond. The Zn(2+) ion is released, and the two remaining cysteines coordinate the Au(+) ion that is produced during the redox reaction. Subsequent oxidation of these cysteines can take place in conditions of excess gold(III) complex. In the presence of excess free thiols mimicking the presence of glutathione in cells, mixing of the zinc finger model and gold(III) complex yields a different product: complex (Au(I))2·LZR with two Au(+) ions bound to cysteines is formed. Thus, on the basis of detailed speciation and kinetic measurements, we demonstrate herein that the destruction of Zn(Cys)4 zinc fingers by gold(III) complexes to achieve the formation of "gold fingers" is worth consideration, either directly or mediated by reducing agents.
Assuntos
Compostos Organoáuricos/química , Dedos de Zinco , Humanos , Estrutura MolecularRESUMO
We present herein the first in situ site-selective XAS experiment performed on a proof-of-principle transformation of a mixed-valence compound: the calcination of the K0.1Co(II)4[Co(III)(CN)6]2.7·20H2O Prussian Blue analogue (containing Co(2+) and Co(3+) ions in two different Oh sites) into Co3O4 (containing Co(2+) ions in a Td site and Co(3+) in an Oh site). By recording the Co K-edge X-ray absorption spectra using a spectrometer aligned at the Co Kß1,3 emission line, the evolution of each species was singly monitored from 20 °C up to the oxide formation. The experimental spectrum of the Co(2+)(Td) and Co(3+) (Oh) species in Co3O4 is reported for the first time. Our results demonstrate the possibilities offered by site-selective XAS for the investigation of chemical transformations and the study of materials under working conditions whenever the chemical element of interest is present in several states and/or sites.
RESUMO
In this paper we report a systematic XAS study of a set of samples in which Cu(II) was progressively added to complexes in which Zn(II) was bound to the tetra-octarepeat portion of the prion protein. This work extends previous EPR and XAS analysis in which, in contrast, the effect of adding Zn(II) to Cu(II)-tetra-octarepeat complexes was investigated. Detailed structural analysis of the XAS spectra taken at both the Cu and Zn K-edge when the two metals are present at different relative concentrations revealed that Zn(II) and Cu(II) ions compete for binding to the tetra-octarepeat peptide by cross-regulating their relative binding modes. We show that the specific metal-peptide coordination mode depends not only, as expected, on the relative metal concentrations, but also on whether Zn(II) or Cu(II) was first bound to the peptide. In particular, it seems that the Zn(II) binding mode in the absence of Cu(II) is able to promote the formation of small peptide clusters in which triplets of tetra-octarepeats are bridged by pairs of Zn ions. When Cu(II) is added, it starts competing with Zn(II) for binding, disrupting the existing peptide cluster arrangement, despite the fact that Cu(II) is unable to completely displace Zn(II). These results may have a bearing on our understanding of peptide-aggregation processes and, with the delicate cross-regulation balancing we have revealed, seem to suggest the existence of an interesting, finely tuned interplay among metal ions affecting protein binding, capable of providing a mechanism for regulation of metal concentration in cells.
Assuntos
Cobre/farmacologia , Príons/química , Príons/metabolismo , Zinco/metabolismo , Sequência de Aminoácidos , Relação Dose-Resposta a Droga , Dados de Sequência Molecular , Fragmentos de Peptídeos/química , Fragmentos de Peptídeos/metabolismo , Ligação Proteica/efeitos dos fármacosRESUMO
Among trace metal pollutants, zinc is the major one in the rivers from the Paris urban area, such as the Orge River, where Zn concentration in the suspended particulate matter (SPM) can reach 2000 mg/kg in the most urbanized areas. In order to better understand Zn cycling in such urban rivers, we have determined Zn speciation in SPM as a function of both the seasonal water flow variations and the urbanization gradient along the Orge River. Using TEM/SEM-EDX and linear combination fitting (LCF) of EXAFS data at the Zn K-edge, we show that Zn mainly occurs as tetrahedrally coordinated Zn(2+) sorbed to ferrihydrite (37-46%), calcite (0-37%), amorphous SiO2 (0-21%), and organic-P (0-30%) and as octahedrally coordinated Zn(2+) in the octahedral layer of phyllosilicates (18-25%). Moreover, the Zn speciation pattern depends on the river flow rate. At low water flow, Zn speciation changes along the urbanization gradient: geogenic forms of Zn inherited from soil erosion decrease relative to Zn bound to organic-phosphates and amorphous SiO2. At high water flow, Zn speciation is dominated by soil-borne forms of Zn regardless the degree of urbanization, indicating that erosion of Zn-bearing minerals dominates the Zn contribution to SPM under such conditions.
Assuntos
Cidades , Material Particulado/química , Rios , Estações do Ano , Urbanização , Zinco/isolamento & purificação , França , Espectrometria por Raios X , Poluentes Químicos da Água/análiseRESUMO
Platinum nanoclusters highly dispersed on γ-alumina are widely used as heterogeneous catalysts. To understand the chemical interplay between the Pt nanoparticles, the support, and the reductive atmosphere, we performed X-ray absorption near edge structure (XANES) inâ situ experiments recorded in high energy resolution fluorescence detection (HERFD) mode. Spectra are assigned by comparison with simulated XANES spectra on models obtained by molecular dynamics (DFT-MD). We propose platinum cluster morphologies and quantify the hydrogen coverages compatible with XANES spectra recorded at variable hydrogen pressures and temperatures. Using cutting-edge methodologies to assign XANES spectra, this work gives unequalled atomic insights into the characterization of supported nanoclusters.