X-ray Absorption Near-edge Spectroscopy Research Articles

Protein-bound calcium phosphate in uremic rat serum: a quantitative study.

Protein-bound calcium (prCa) constitutes about 40% of serum total calcium, in which albumin is the most dominant protein. Given the chemical interaction between calcium and phosphate (Pi), the increased serum Pi in chronic kidney disease may cause changes in the composition and structure of the prCa fraction. Here, we report the phosphate binding on the protein-bound calcium in uremic rat serum. Using adenine-fed rats as a uremic model, we separated the calcium and phosphate fractions in rat serum by ultrafiltration, and found that the level of protein-bound phosphate (prPi) in the uremic serum was markedly higher than in control. The elevated prPi level was comparable to the prCa level, consistent with the presence of protein-bound calcium phosphate pr(Ca)j-m(CaPi)m. We then confirmed its presence by ex vivo X-ray absorption near-edge structure spectroscopy, revealing the discrete state of the calcium phosphate clusters associated with protein. Finally, in a quantitative investigation using Ca- and Pi-boosted serum, we discovered the threshold concentration for the Pi binding on prCa, and determined the binding constant. The threshold, while preventing Pi from binding to prCa in normal condition, allows the reaction to take place in hyperphosphatemia conditions. The protein-bound calcium phosphate could act as a link between the metabolism of serum proteins and the homeostasis of phosphate and calcium, and it deserves further investigation whether the molar ratio of (prPi/prCa)⋅100% may serve as a serum index of the vascular calcification status in chronic kidney disease.

Toluene steam reforming using nickel based catalysts made from mining residues

Two nickel-based catalysts are used for toluene steam reforming: Ni-Olivine and Ni-UGSO (Nickel-UpGraded Slug Oxides). Both catalysts are made from mining residues and prepared by incipient wetness impregnation (IWI). The activity and stability of the two catalysts in toluene steam reforming are investigated and compared, at atmospheric pressure and 800 °C in a fixed bed reactor. Reaction temperature and Ni Loading effects are evaluated for the Ni-UGSO catalyst. The physicochemical properties of the catalysts were analyzed using the following characterization techniques: X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), X-ray absorption near edge spectroscopy (XANES), Temperature Programmed Reduction (TPR) and Brunauer-Emmett-Teller (BET) specific surface area. Results showed that toluene conversion, mainly into CO and H2, reached up to (98 w%). The catalyst activity was tested in multiple 24 h time-on-stream continuous isothermal runs and no signs of deactivation were observed. Ni in Ni-UGSO has a strong metal-support interaction, which, according to characterization results, is due to the formation of a NiO/MgO solid solution. This catalyst exhibited an elevated catalytic activity along with a high resistance to carbon formation. Ni in Ni-Olivine has shown a weak metal-support interaction leading to the formation of filamentous carbon at the catalyst’s surface.

Expression and Purification of Recombinant GHK Tripeptides Are Able to Protect against Acute Cardiotoxicity from Exposure to Waterborne-Copper in Zebrafish.

In this study, an alternative method is developed to replace chemical synthesis to produce glycyl-histidyl-lysine (GHK) tripeptides with a bacterial fermentation system. The target GHK tripeptides are cloned into expression plasmids carrying histidine-glutathione-S-transferase (GST) double tags and TEV (tobacco etch virus) cleavage sites at the N-terminus. After overexpression in Escherichia coli (E. coli) BL21 cells, the recombinant proteins are purified and recovered by high-pressure liquid chromatography (HPLC). UV-vis absorption spectroscopy was used to investigate the chemical and biological properties of the recombinant GHK tripeptides. The results demonstrated that one recombinant GHK tripeptide can bind one copper ion to form a GHK-Cu complex with high affinity, and the recombinant GHK peptide to copper ion ratio is 1:1. X-ray absorption near-edge spectroscopy (XANES) of the copper ions indicated that the oxidation state of copper in the recombinant GHK-Cu complexes here was Cu(II). All of the optical spectrum evidence suggests that the recombinant GHK tripeptide appears to possess the same biophysical and biochemical features as the GHK tripeptide isolated from human plasma. Due to the high binding affinity of GHK tripeptides to copper ions, we used zebrafish as an in vivo model to elucidate whether recombinant GHK tripeptides possess detoxification potential against the cardiotoxicity raised by waterborne Cu(II) exposure. Here, exposure to Cu(II) induced bradycardia and heartbeat irregularity in zebrafish larvae; however, the administration of GHK tripeptides could rescue those experiencing cardiotoxicity, even at the lowest concentration of 1 nM, where the GHK-Cu complex minimized CuSO4-induced cardiotoxicity effects at a GHK:Cu ratio of 1:10. On the other hand, copper and the combination with the GHK tripeptide did not significantly alter other cardiovascular parameters, including stroke volume, ejection fraction, and fractional shortening. Meanwhile, the heart rate and cardiac output were boosted after exposure with 1 nM of GHK peptides. In this study, recombinant GHK tripeptide expression was performed, along with purification and chemical property characterization, which revealed a potent cardiotoxicity protection function in vivo with zebrafish for the first time.

Study of reactively sputtered nickel nitride thin films

Nickel nitride (Ni–N) thin film samples were deposited using reactive magnetron sputtering process utilizing the different partial flow of N2 (RN2). They were characterized using x-ray reflectivity (XRR), x-ray diffraction (XRD) and x-ray absorption near-edge spectroscopy (XANES) taken at N K-edge and Ni L-edges. From XRR measurements, we find that the deposition rate and the density of Ni–N films decrease due to successively progression in RN2, signifying that Ni–N alloys and compounds are forming both at Ni target surface and also within the thin film samples. The crystal structure obtained from XRD measurements suggest an evolution of different Ni–N compounds given by: Ni, Ni(N), Ni4N, Ni3N, and Ni2N with a gradual rise in RN2. XANES measurements further confirm these phases, in agreement with XRD results. Polarized neutron reflectivity measurements were performed to probe the magnetization, and it was found Ni–N thin films become non-magnetic even when N incorporation increases beyond few at.%. Overall growth behavior of Ni–N samples has been compared with that of rather well-known Fe–N and Co–N systems, yielding similarities and differences among them.

Nano-Scale Drinking Water Treatment Residuals Affect Arsenic Fractionation and Speciation in Biosolids-Amended Agricultural Soil

An incubation experiment was conducted to determine the effects of nanoscale drinking water treatment residuals (nWTRs) on arsenic (As) fractionation and speciation in agricultural soil amended with biosolids. The soils were treated with biosolids of 3% (w/w), along with nWTR application rates of 0, 0.25, 0.50, or 1.00% (w/w). The results revealed that the As adsorption rate increased with increasing the As treatment level from 50 to 800 mg/L. The maximum efficiency of As adsorption was 95%–98% in the soil treated with nWTRs of 1%, while the least As adsorption was 53%–91% in the soil treated with nWTRs of 0.25%. The overall As bioavailability in the biosolids-amended soil followed a descending order of nWTRs treatment: (0%) > 0.25% nWTRs, >0.50% nWTRs, and >1% nWTRs. The addition of nWTRs significantly changed As speciation in biosolids-amended soil. The X-ray absorption near-edge structure spectroscopy (XANES) and MINEQL+4.6 analyses showed that most of As was in a oxidized form of As5+ that likely incorporated in As pentoxide, and thus, with low mobility, bioavailability, and toxicity. This study demonstrated that nWTRs were effective in adsorbing and immobilizing As in biosolids-amended agricultural soils by forming stable As-nWTR surface complexes.

Structural, optical, and dielectric investigations in bulk PrCrO3

The polycrystalline powder samples of PrCrO3 have been prepared using conventional solid-state synthesis method. Structural investigations are carried out using Raman spectroscopy and synchrotron X-ray diffraction (SXRD) followed by Rietveld refinement of diffraction data. Investigations of diffraction data suggest that these samples possess centrosymmetric orthorhombic structure with space group $$Pnma$$ $$(or\;Pbnm)$$ . The valence (charge) state of Cr in PrCrO3 has been determined from X-ray absorption near edge spectroscopy (XANES). Optical properties are studied using diffuse reflectance spectroscopy technique. Optical absorption study reveals that absorption in PrCrO3 ceramic is dominated by d–d electrons of chromium cation (Cr3+). The synthesized compound found to have energy bandgap of 3.20 eV. Based on the results observed, energy level diagram for PrCrO3 has been presented. High dielectric permittivity $$(\varepsilon {^{\prime}})$$ of the order $$3\times {10}^{3}$$ is observed for the studied sample. Impedance spectroscopy measurement at room temperature on sintered pellet indicates electronic inhomogeneity in the samples as demonstrated by the presence of dielectric relaxation processes associated with highly conducting grain and low conducting grain boundaries. The relaxation mechanism has been explained on the basis of Cole–Cole model. Observed high dielectric permittivity $$(\varepsilon {^{\prime}})$$ and optical energy bandgap $$({E}_{g})$$ indicates that PrCrO3 may find promising application in optoelectronic devices.

Electronic properties of DNA-related molecules containing a bromine atom

Purpose To clarify the radiosensitization mechanism masking the Auger effect of the cells possessing brominated DNA, the electronic properties of DNA-related molecules containing Br were investigated by X-ray spectroscopy and specific heat measurement. Materials and Methods X-ray absorption near-edge structure (XANES) and X-ray photoemission spectroscopy (XPS) were used to measure the electronic properties of the nucleotides with and without Br. We determined the specific heat of 5-bromouracil crystals with thymine as a reference molecule at low temperatures of 3–48 K to calculate the microscopic state numbers. Results Obtained XANES and XPS spectra indicated that both the lowest unoccupied molecular orbital (LUMO) and the core-levels were not affected by the Br incorporation. The state numbers of 5-bromouracil calculated from the specific heats obtained around 25 K was about 1.5 times larger than that for thymine below 20 K, although the numbers were almost the same below 5 K. Discussion Our results suggest that the Br atom may not contribute substantially to the LUMO and core-level electronic states of the molecule, but rather to the microscopic states related to the excitation of lattice vibrations, which may be involved in valence electronic states.

Morphological and electronic properties of titanium dioxide thin film

This paper describes the morphological and X-ray absorption near-edge spectroscopy (XANES) analysis of the titanium dioxide (TiO2) thin film. We fabricated a TiO2 thin film in the laboratory on a clean glass plate using a Physical vapour deposition technique (thermal evaporation method) and characterized. The structural, morphological, and electronic properties of the fabricated samples are presented by X-ray diffraction (XRD), atomic force microscope (AFM), and XANES. It observed from XRD the crystallite size was ∼ 25.66 nm with microstrain ∼ 0.0064 using the W-H plot. The fractal term such as grain size, roughness, kurtosis, and skewness was estimated using AFM. The grain size lies in the nanometric range and found that ∼ 177.21 nm. The electronic properties are studied using XANES. The XANES analysis well supported to XRD measurement and the result found that the fabricated TiO2 thin film was anatase phase.

Stabilizing Atomically Dispersed Catalytic Sites on Tellurium Nanosheets with Strong Metal-Support Interaction Boosts Photocatalysis.

The utilization of appropriate supports for constructing single-atom-catalysts is of vital importance to achieve high catalytic performances, as the strong mutual interactions between the atomically dispersed metal atoms and supports significantly influence their electronic properties. Herein, it is reported that atomic cobalt species (ACS) anchored 2D tellurium nanosheets (Te NS) can act as a highly active single-atom cocatalyst for boosting photocatalytic H2 production and CO2 reduction reactions under visible light irradiation, wherein Te NS serves as the ideal support material to bridge the light absorbers and ACS catalytic sites for efficient electron transfer. X-ray absorption near-edge structure spectroscopy reveals that the ACS are built by a Co center coordinated with five CoO bonding, which are anchored on Te NS through one CoTe bonding. The strong mutual interaction between the Te NS and ACS alters the electronic structure of Te NS, inducing the introduction of intermediate energy states, which act as trap sites to accommodate the photogenerated electrons for promoting photocatalytic reactions. This work may inspire further capability in designing other Te-based single-atom-catalysts for highly efficient solar energy conversion.

Evaluation of Salt-Induced Damage to Aged Wood of Historical Wooden Buildings.

Salt is a common cause of damage to building materials used in cultural and historical buildings. The damage to aged wood in historical wooden buildings has not been extensively studied, resulting in the need for a more detailed analysis. In this work, Yingxian Wooden Pagoda, a typical historical wooden structure, was taken as the research object. Multichemical analyses were conducted to evaluate and understand the salt-induced damage to the aged wood using a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer, sulphur K-edge X-ray absorption near-edge structure spectroscopy, X-ray fluorescence spectroscopy, X-ray powder diffraction, and attenuated total reflectance fourier transformed infrared spectroscopy. The results showed the presence of invasive salt crystallisations and ions in the aged samples. The source of these invasive elements was deduced by identifying the type, amount, and valency of the elements; they were found to be derived from environmental factors such as acid rain and atmospheric pollutant. The unique damage mechanism and route induced by salt in historical buildings made of wood were summarised; the damage was attributed to the accumulation of sulphate salt causing hydrolysis of the carbohydrates and salt crystallisation resulting in mechanical damage. This interdisciplinary study is significant for decision making in studies related to the preservation and evaluation of historical wooden buildings.

A new internally heated diamond anvil cell system for time-resolved optical and x-ray measurements

We have developed a new internally heated diamond anvil cell (DAC) system for in situ high-pressure and high-temperature x-ray and optical experiments. We have adopted a self-heating W/Re gasket design allowing for both sample confinement and heating. This solution has been seldom used in the past but proved to be very efficient to reduce the size of the heating spot near the sample region, improving heating and cooling rates as compared to other resistive heating strategies. The system has been widely tested under high-temperature conditions by performing several thermal emission measurements. A robust relationship between electric power and average sample temperature inside the DAC has been established up to about 1500 K by a measurement campaign on different simple substances. A micro-Raman spectrometer was used for various in situ optical measurements and allowed us to map the temperature distribution of the sample. The distribution resulted to be uniform within the typical uncertainty of these measurements (5% at 1000 K). The high-temperature performances of the DAC were also verified in a series of XAS (x-ray absorption spectroscopy) experiments using both nano-polycrystalline and single-crystal diamond anvils. XAS measurements of germanium at 3.5 GPa were obtained in the 300 K-1300 K range, studying the melting transition and nucleation to the crystal phase. The achievable heating and cooling rates of the DAC were studied exploiting a XAS dispersive setup, collecting series of near-edge XAS spectra with sub-second time resolution. An original XAS-based dynamical temperature calibration procedure was developed and used to monitor the sample and diamond temperatures during the application of constant power cycles, indicating that heating and cooling rates in the 100 K/s range can be easily achieved using this device.

Synthesis and structural investigation of stoichiometric iron mononitride thin films

We report the synthesis of iron mononitride (FeN) thin films having zinc blende (ZB) type structure, deposited using a direct current magnetron sputtering process on amorphous quartz substrates. The effect of substrate temperature (Ts) on the structure of FeN thin films was systematically investigated by varying the Tsfrom 300 to 500 K(in close intervals of 25K). The long-range as well as the local structure of samples was studied using x-ray diffraction (XRD), x-ray absorption near edge spectroscopy (XANES) at N K-edge, Fe L and K-edge and extended x-ray absorption fine structure (EXAFS) at Fe K-edge. The lattice parameter (LP) obtained from XRD and the presence of an intense pre-edge feature in Fe K-edge XANES confirms the ZB-structure of FeN samples. It was found in this work that the stoichiometric FeN with a LP close to its theoretical value can only be obtained in a narrow temperature regime due to minimization of stresses generated during the growth near the thermodynamic equilibrium conditions. These findings were further validated by EXAFS results yielding Fe–N and Fe–Fe bond distances, in conformity with the theoretically predicted values for FeN in ZB type structure.

Magnetosomes could be protective shields against metal stress in magnetotactic bacteria

Magnetotactic bacteria are aquatic microorganisms with the ability to biomineralise membrane-enclosed magnetic nanoparticles, called magnetosomes. These magnetosomes are arranged into a chain that behaves as a magnetic compass, allowing the bacteria to align in and navigate along the Earth’s magnetic field lines. According to the magneto-aerotactic hypothesis, the purpose of producing magnetosomes is to provide the bacteria with a more efficient movement within the stratified water column, in search of the optimal positions that satisfy their nutritional requirements. However, magnetosomes could have other physiological roles, as proposed in this work. Here we analyse the role of magnetosomes in the tolerance of Magnetospirillum gryphiswaldense MSR-1 to transition metals (Co, Mn, Ni, Zn, Cu). By exposing bacterial populations with and without magnetosomes to increasing concentrations of metals in the growth medium, we observe that the tolerance is significantly higher when bacteria have magnetosomes. The resistance mechanisms triggered in magnetosome-bearing bacteria under metal stress have been investigated by means of x-ray absorption near edge spectroscopy (XANES). XANES experiments were performed both on magnetosomes isolated from the bacteria and on the whole bacteria, aimed to assess whether bacteria use magnetosomes as metal storages, or whether they incorporate the excess metal in other cell compartments. Our findings reveal that the tolerance mechanisms are metal-specific: Mn, Zn and Cu are incorporated in both the magnetosomes and other cell compartments; Co is only incorporated in the magnetosomes, and Ni is incorporated in other cell compartments. In the case of Co, Zn and Mn, the metal is integrated in the magnetosome magnetite mineral core.

The magneto-elastic and optical properties of multiferroic GaFeO3-δ

Temperature-dependent Raman spectroscopy, X-ray absorption near-edge spectroscopy (XANES), optical absorption spectroscopy (OAS) and ac-susceptibility measurements have been carried out on GaFeO3 samples to understand the effect of sintering temperature (TS) on optical and magneto-elastic properties. The temperature-dependent ac-susceptibility measurements suggest the systematic scaling in the values of ferri-magnetic transition temperature (TC) with TS. The observed variation has been understood in terms of enhancement in the Goodenough-Kanamori-Anderson coupling. Instead of expected anharmonic behavior in Raman spectra around TC, several vibrational modes of rigid FeO6 units were found to show anomalous behavior, which suggests the significant magneto-elastic coupling contributions to phonon frequencies. The strength of magneto-elastic coupling has been quantified by using the phonon renormalization function (Δw) and is found to scale systematically with TS. Further, optical absorption study demonstrates the increase in intensity and red shift in charge-neutral d-d transitions, which infers the increase in oxygen non-stoichiometry with TS. The oxygen non-stoichiometry has been further quantified by the XANES measurements. The present investigations on GaFeO3 samples reveal that TC can be tuned by varying the oxygen stoichiometry and can be very beneficial for spintronic devices applications.

Human red blood cell uptake and sequestration of arsenite and selenite: Evidence of seleno-bis(S-glutathionyl) arsinium ion formation in human cells

Over 200 million people worldwide are exposed to the human carcinogen, arsenic, in contaminated drinking water. In laboratory animals, arsenic and the essential trace element, selenium, can undergo mutual detoxification through the formation of the seleno-bis(S-glutathionyl) arsinium ion [(GS)2AsSe]−, which undergoes biliary and fecal elimination. [(GS)2AsSe]−, formed in animal red blood cells (RBCs), sequesters arsenic and selenium, and slows the distribution of both compounds to peripheral tissues susceptible to toxic effects. In human RBCs, the influence of arsenic on selenium accumulation, and vice versa, is largely unknown. The study aims were to characterize arsenite (AsIII) and selenite (SeIV) uptake by human RBCs, to determine if SeIV and AsIII increase the respective accumulation of the other in human RBCs, and ultimately to determine if this occurs through the formation and sequestration of [(GS)2AsSe]−. 75SeIV accumulation was temperature and Cl−-dependent, inhibited by 4,4′-diisothiocyanatodihydrostilbene-2,2′-disulfonic acid (H2DIDS) (IC50 1 ± 0.2 µM), and approached saturation at 30 µM, suggesting uptake is mediated by the erythrocyte anion-exchanger 1 (AE1 or Band 3, gene SLC4A1). HEK293 cells overexpressing AE1 showed concentration-dependent 75SeIV uptake. 73AsIII uptake by human RBCs was temperature-dependent, partly reduced by aquaglyceroporin 3 inhibitors, and not saturated. AsIII increased 75SeIV accumulation (in the presence of albumin) and SeIV increased 73AsIII accumulation in human RBCs. Near-edge X-ray absorption spectroscopy revealed the formation of [(GS)2AsSe]− in human RBCs exposed to both AsIII and SeIV. The sequestration of [(GS)2AsSe]− in human RBCs potentially slows arsenic distribution to susceptible tissues and could reduce arsenic-induced disease.

Investigating mineralization species in cultured bone from human mesenchymal stem cells using synchrotron-based XANES

In this context, we successfully demonstrate the use of X-ray absorption near edge spectroscopy (XANES) to identify calcium species and compare the mineralization of bone-like materials from human mesenchymal stem cells (MSC) in 3 culture conditions in vitro; non-osteogenic medium (non-OM), osteogenic medium (OM) and OM supplemented with bone morphogenetic protein 9 (OM-BMP9). X-ray photoelectron spectroscopy (XPS) was also used to examine the bonding of mineralized species on the surface of MSC-mediated mineralization. The results from Alizarin Red staining exhibited calcium deposits in all 3 culture conditions with different degrees of calcium deposition (OM-BMP9> OM > non-OM). While XANES disclosed that the majority of calcium species deposited in the non-OM culture was calcium sulfate (CaSO4; 27.7%), tricalcium phosphate (TCP; 27.1%) and calcium chloride (CaCl2; 22.2%) with lower levels of calcium carbonate (CaCO3; 10.5%) and calcium hydroxide (Ca(OH)2; 12.5%). Hydroxyapatite (HA) was not detected in the non-OM sample. On the other hand, the majority of calcium species in OM and OM-BMP9 cultures presented in calcium phosphate forms. The amount of calcium species in the OM-BMP9 culture comprised 33.1% HA, 40.5% TCP, 5.7% CaCl2, 15.4% CaSO4, and 5.0% CaCO3 and the OM culture comprised 22% HA, 33.5% TCP, 8.5% CaCl2, 24.3% CaSO4, 5% CaCO3 and 3.9% Ca(OH)2. Amorphous calcium phosphate (APC) was not detected in all the 3 groups. XPS results confirmed the existence of calcium phosphate species on the surface of MSC-mediated biomineralization. The successful use of XANES and XPS to qualitatively and quantitatively determine calcium phosphates in vitro is highly beneficial and provides not only an insight into chemical composition of the mineral deposit in the cultured bone but also presents more biologically-relevant information than those from conventional analytical methods. This is also the first report to demonstrate, by synchrotron-based XANES, the osteogenic role of BMP9 in enhancing HA formation specifically. This will help optimizing culture conditions to produce highly osteogenic bone-like materials containing similar compositions and functions to native human bone.

Abundance of Fe(III) during cultivation affects the microbiologically influenced corrosion (MIC) behaviour of iron reducing bacteria Shewanella putrefaciens

The effect of the presence of Fe(III) during the cultivation on the electrochemical activity and corrosion behaviour of dissimilatory iron reducing bacteria Shewanella putrefaciens was studied by means of ex situ and in situ X-ray absorption near-edge spectroscopy (XANES). Stainless steel AISI 304 and thin iron films were studied as substrates. XANES analysis indicated an accelerated iron dissolution and growth of an oxide/hydroxide film for the culture grown with Fe(III) in comparison to the culture grown in absence of Fe(III). Electrochemical analysis indicated that the biofilm resulted in acceleration of the general corrosion but provides protection against local corrosion.

First-principles modeling of X-ray absorption spectra enlightens the processes of scandium sequestration by iron oxides

Abstract Scandium is often associated with iron oxides in the environment. Despite the use of scandium as a geochemical tracer and the existence of world-class supergene deposits, uncertainties on speciation obscure the processes governing its sequestration and concentration. Here, we use first-principles approaches to interpret experimental K-edge X-ray absorption near-edge structure spectra of scandium either incorporated in or adsorbed on goethite and hematite, at concentrations relevant for the environment. This modeling helps to interpret the characteristic spectral features, providing key information to determine scandium speciation when associated with iron oxides. We show that scandium is substituted into iron oxides at low concentrations without modifying the crystal structure. When scandium is adsorbed onto iron oxide surfaces, the process occurs through outer-sphere complexation with a reduction in the coordination number of the hydration shell. Considering available X-ray absorption spectra from laterites, the present results confirm that scandium adsorption onto iron oxides is the dominant mechanism of sequestration in these geochemical conditions. This speciation explains efficient scandium recovery through mild metal-lurgical treatments of supergene lateritic ores. The specificities of scandium sorption mechanisms are related to the preservation of adsorbed scandium in million-years old laterites. These results demonstrate the emerging ability to precisely model fine X-ray absorption spectral features of trace metals associated with mineral phases relevant to the environment. It opens new perspectives to accurately determine trace metals speciation from high-resolution spatially resolved X-ray absorption near-edge structure spectroscopy in order to constrain the molecular mechanisms controlling their dynamics.

Hydrogen production by steam reforming of LPG using supported perovskite type precursors

Perovskites supported on Al2O3 (LaNi/AL) and CeO2–SiO2 (LaNi/CS) were tested as catalyst precursors for steam reforming of liquefied petroleum gas (SRLPG). The role of different supports in perovskites-derived catalysts performances was evaluated. A non-supported LaNiO3 (LaNi) was also synthesized for comparison. According to the in-situ X-Ray Diffraction analyses, a reduction temperature of 700 °C was enough to generate Ni0 and La2O3, except for LaNi/AL. X-ray absorption Near Edge Spectroscopy (XANES) showed a direct influence of the supports on the reducibility of the samples. At 600 °C, the supported precursors LaNi/AL and LaNi/CS were more stable than LaNi during the SRLPG reaction. The alumina support provided a higher activity to LaNi/AL mainly due to the strong metal-support interaction. At 700 °C, the LPG conversion of LaNi/CS was near 100%. At both temperatures, the lowest carbon accumulation rate was obtained by LaNi/CS likely due to ceria oxygen mobility.

A New Near‐Infrared Long Persistent Luminescence Material with Its Outstanding Persistent Luminescence Performance and Promising Multifunctional Application Prospects

AbstractIn this work, a novel near‐infrared (NIR) persistent luminescence (PersL) material Na2CaGe5SiO14 (NCGSO):Cr3+ is designed and prepared. The phase composition and crystal structure are analyzed by X‐ray diffraction (XRD) and Rietveld structural refinement. The band gap of NCGSO is calculated to be 4.245 eV by density functional theory (DFT) and confirmed by diffuse reflection spectroscopy (DRS). It is determined by the photoluminescence (PL) spectra, X‐ray absorption near‐edge spectroscopy (XANES), and time‐resolved emission spectra (TRES) that three Ge4+ sites can be superseded simultaneously when Cr3+ ions are doped. In addition, the PL, photoluminescence excitation (PLE), and PersL performance are analyzed systematically. Under the radiation of 254 nm ultraviolet (UV) lamp, the samples exhibit excellent PL and PersL performance in the range of 600–900 nm, and the optimal afterglow duration lasts for more than 10 h. According to results, a possible mechanism is proposed to explain the PersL phenomenon. In the end, a set of information encrypted digital labels is designed and biological tissue penetration experiments are performed. The results reveal the potential of NCGSO:Cr3+ for information encryption and biological imaging applications.