Structure of inorganic nanoclusters embedded in solid matrixes: an X-ray absorption study

Results of X-ray absorption studies of copper nanoclusters embedded in SiO₂ matrix and selenium chains confined in channels of cancrinite are reported. Initially randomly distributed copper atoms mainly surrounded by silicon species in an as-made film upon annealing form copper nanoclusters with a characteristic size of 80 Å and the structure identical to that of bulk copper. The characteristic size of the clusters does not increase with further annealing. Selenium in cancrinite is shown to form strongly oriented linear dimerised chains with a bond length much larger than that in bulk forms of selenium.     

Geometrical and electronic structure of small copper nanoclusters: XANES and DFT analysis

The geometrical and electronic structure of small copper nanoclusters was studied by density functional theory (DFT) and analysis of X-ray absorption spectra. It was shown that the icosahedral geometry of small copper nanoclusters of 13 atoms was energetically more stable than cuboctahedral geometry. The binding energies in these structures were compared; the theoretical XANES spectra were compared with experiment. The paper gives the results of ab initio calculations of the electronic structure of copper clusters differing in size.     

Atomic cluster calculation of the X-ray near-edge absorption of copper

The finite difference method for near-edge structure is used to calculate X-ray absorption near-edge structure (XANES) spectra. We extend the range of calculation for copper above the K-shell threshold and compare the results with recent experimental data in the X-ray absorption fine structure (XAFS) region. Qualitatively the calculation predicts the location of the peaks but fails to accurately describe relative amplitudes.     

X-ray photoelectron spectroscopic analysis of Si nanoclusters in SiO2 matrix

We investigated silicon nanoclusters Si(nc) in a SiO2 matrix prepared by the plasma-enhanced chemical vapor deposition technique, using X-ray photoelectron spectroscopy (XPS) with external voltage stimuli in both static and pulsed modes. This method enables us to induce an additional charging shift of 0.8 eV between the Si2p peaks of the oxide and the underlying silicon, both in static and time-resolved modes, for a silicon sample containing a 6 nm oxide layer. In the case of the sample containing silicon nanoclusters, both Si2p peaks of Si(nc) and host SiO2 undergo a charging shift that is 1 order of magnitude larger (>15 eV), with no measurable difference between them (i.e., no differential charging between the silicon nanoclusters and the oxide matrix could be detected). By use of a measured Auger parameter, we estimate the relaxation energy of the Si(nc) in the SiO2 matrix as -0.4 eV, which yields a -0.6 eV shift in the binding energy of the Si(nc) with respect to that of bulk Si in the opposite direction of the expected quantum size effect. This must be related to the residual differential charging between the silicon nanoclusters and the oxide host. Therefore, differential charging is still the biggest obstacle for extracting size-dependent binding energy shifts with XPS when one uses the oxide peak as the reference.     

X-ray absorption spectroscopic studies on novel microporous copper containing catalytic systems

Novel copper metal modified microporous aluminosilicate and aluminophosphate catalysts with the high phase purity were synthesized and characterized. CuK-edge XAS measurements were carried out over a series of copper containing SAPO-34 and ZSM-5 catalysts. EXAFS technique was used to obtain specific climacteric information related to the copper atomic distances, coordination and near neighbour environments. EXAFS studies indicated the presence of different of Cu species on ZSM-5/SAPO34 catalysts.     

Characterization of green copper phase pigments in Egyptian artifacts with X-ray absorption spectroscopy and principal components analysis

The characterization of materials in historical artifacts can contribute significantly to their preservation and understanding; however, sampling and characterization are ideally performed using non-destructive approaches. The analysis of green pigments from Egyptian artifacts presents a further challenge as responses to laboratory based techniques have proven unsuccessful in many cases. An alternative approach is the use of non-destructive X-ray absorption near-edge structure spectroscopy, which was performed on a reference set of copper-containing green minerals and other compounds. Data projection using principal component analysis was used to explore the spectral data structures and to illustrate the relationship between the spectra and copper speciation, resulting in a calibration or training set of the reference materials used. Data from the training set were compared with samples from Egyptian artifacts. The combination of X-ray absorption spectroscopy with principal components analysis provides a novel approach in archeometry and the characterization of objects of cultural heritage.     

Analysis of mixtures of compounds of copper using K-edge X-ray absorption spectroscopy

Summary A determination is described of copper metal, oxide, and hydroxide in samples containing both nickel and copper. The analysis was based on K-edge x-ray absorption spectra of the copper. This allowed us to consider the chemical states of copper and ignore the nickel also present. The method involved fitting linear combinations of copper standard spectra to the spectrum from copper in the sample. The fit composition that minimized the variance gave the sample composition. The work demonstrated that K-edge x-ray absorption spectra are sufficiently characteristic to allow their use for quantification of components in mixtures. This method of analysis is complemented by diffraction and less general techniques. It is a strength of x-ray absorption edge analysis that it is element-specific and applicable to most elements maintained under any conditions of temperatures, pressure, and atmosphere.     

X-ray absorption spectral analysis with a 9 V battery X-ray generator.

X-ray absorption spectral (XAS) analysis is performed with a combination of a 9 V dry electric battery X-ray generator and a portable Si PIN X-ray detector. The calcium K edge (4.0 keV) in paper is measured with a grazing incidence geometry, which suppressed the artifact due to the Kalpha X-ray fluorescence peak at 3.5 keV. The 9 V dry battery X-ray emitter is useful for portable XAS measurements.     

X-ray and UV photoelectron spectroscopy of Ag nanoclusters

The main purpose of the present work is to analyze a series of Ag nanoparticles (NPs) with different size or ligand functionalization by using X-ray photoelectron spectroscopy (XPS) and to identify the differences in the band-shape and energy peak position of photoemission spectra due to the particle dimension. A transmission electron microscopy characterization was performed, to verify the consistency of the results. Three types of samples were prepared starting from AgNO₃ water solution and adding different capping agents. In the first two cases, the formation of NPs was promoted by the reduction of silver ions Ag⁺¹ to metallic Ag⁰ through the addition of sodium borohydride, whereas in the last case, it was triggered by the exposure to UV light. Depending on the size of the NPs, a different physical behavior can be recognized. NPs with diameter of about 5 nm are characterized by the phenomenon of localized surface plasmon resonance (LSPR). The other type of samples having a diameter of about 1.5 nm presents discrete energy levels instead of electronic bands, and in this case, a typical fluorescence phenomenon can be observed. In the latter case, we can refer to such systems as nanoclusters. The XPS analyses were focused on the Ag 3D spectra looking for the possible shifts of the Ag doublet as a function of the particles size. The ultraviolet photoelectron spectroscopy with He II source was used for the investigation of possible changes in the valence band.     

基于铜纳米簇检测柠檬黄的方法研究EI北大核心CSCD

采用L-半胱氨酸经一步湿化学法合成了稳定的铜纳米簇(CuCNs),优化了其制备条件,分别运用XPS和FTIR对其性能进行表征。CuCNs的荧光能被柠檬黄(LY)淬灭,推测其机理主要来自内滤效应。基于此,该荧光探针能选择检测LY,线性范围和检出限分别为3.33~60.0μmol/L和1.90μmol/L。该方法用于矿泉水和饮料中LY检测,回收率为95.5%~104.4%。     

Particle size effects in X-ray absorption analysis: Formulae for size distributions

New equations have been derived to describe the dependence of X-ray transmitted intensity on particle size in heterogeneous specimens. The formulae include the effect of size distribution, a problem not covered in earlier theoretical work.     

X-ray absorption spectroscopy of hemes and hemeproteins in solution: multiple scattering analysis

A full quantitative analysis of Fe K-edge X-ray absorption spectra has been performed for hemes in two porphynato complexes, that is, iron(III) tetraphenylporphyrin chloride (Fe(III)TPPCl) and iron(III) tetraphenylporphyrin bis(imidazole) (Fe(III)TPP(Imid)2), in two protein complexes whose X-ray structure is known at atomic resolution (1.0 A), that is, ferrous deoxy-myoglobin (Fe(II)Mb) and ferric aquo-myoglobin (Fe(III)MbH2O), and in ferric cyano-myoglobin (Fe(III)MbCN), whose X-ray structure is known at lower resolution (1.4 A). The analysis has been performed via the multiple scattering approach, starting from a muffin tin approximation of the molecular potential. The Fe-heme structure has been obtained by analyzing independently the Extended X-ray Absorption Fine Structure (EXAFS) region and the X-ray Absorption Near Edge Structure (XANES) region. The EXAFS structural results are in full agreement with the crystallographic values of the models, with an accuracy of +/- 0.02 A for Fe-ligand distances, and +/-6 degrees for angular parameters. All the XANES features above the theoretical zero energy (in the lower rising edge) are well accounted for by single-channel calculations, for both Fe(II) and Fe(III) hemes, and the Fe-N p distance is determined with the same accuracy as EXAFS. XANES evaluations of Fe-5th and Fe-6th ligand distances are determined with 0.04-0.07 A accuracy; a small discrepancy with EXAFS (0.01 to 0.05 A beyond the statistical error), is found for protein compounds. Concerns from statistical correlation among parameters and multiple minima in the parameter space are discussed. As expected, the XANES accuracy is slightly lower than what was found for polarized XANES on Fe(III)MbCN single crystal (0.03-0.04 A), and states the actual state-of-the-art of XANES analysis when used to extract heme-normal parameters in a solution spectrum dominated by heme-plane scattering.     

Particle size effects in X-ray absorption analysis: General equation for transmitted intensity

An equation has been derived to describe the dependence of transmitted X-ray intensity on particle size in heterogeneous specimens containing r-types of grains. The equation includes the effect of random distribution of grains in any volume element of the sample, a problem not covered in earlier theoretical work.     

X-ray absorption microscopy of bacterial surface protein layers: X-ray damage

The electronic structure of individual sheets of the bacterial surface protein layer (S layer) of Bacillus sphaericus NCTC 9602 was studied using a photoemission electron microscope (PEEM) operating in near-edge X-ray absorption fine structure spectroscopy mode. The laterally resolved measurements performed at the C 1s, N 1s, and O 1s thresholds on fresh samples revealed characteristic differences compared to the laterally integrated data, where substrate contributions were taken along with the protein signals. During the PEEM experiments an irradiation-induced increase of the C-C bond density at the cost of the densities of the C-O and C-N bonds related to a rearrangement of the contributing atoms of the S layer deposited onto a Si substrate was observed. The critical irradiation doses for the C-O and C-N bond breaking and formation of the new C-C bonds were derived.     

Towards a unified understanding of the copper sites in particulate methane monooxygenase: an X-ray absorption spectroscopic investigation

The enzymatic conversion of the greenhouse gas, methane, to a liquid fuel, methanol, is performed by methane monooxygenases (MMOs) under mild conditions. The copper stoichiometry of particulate MMO (pMMO) has been long debated, with a dicopper site previously proposed on the basis of a 2.51 Å Cu–Cu feature in extended X-ray absorption fine structure (EXAFS) data. However, recent crystallographic data and advanced electron paramagnetic resonance (EPR) characterization support the presence of only mononuclear copper sites. To reconcile these data, we have collected high-energy resolution fluorescence detected (HERFD) and partial fluorescence yield (PFY) EXAFS spectra of Methylococcus (M.) capsulatus (Bath) pMMO. Both methods reveal only monocopper sites. These data were compared to previously published pMMO PFY-EXAFS data from M. capsulatus (Bath) and Methylomicrobium alcaliphilum 20Z, supporting dicopper and monocopper sites, respectively. The FT-EXAFS feature previously attributed to a dicopper site can be reproduced by the inclusion of a metallic copper background signal. The exact position of this feature is dependent on the nature of the sample and the percentage of background contamination, indicating that visual inspection is not sufficient for identifying background metallic contributions. Additionally, an undamaged X-ray absorption spectrum was obtained, consistent with the copper oxidation-state speciation determined by EPR quantification. X-ray photodamage studies suggest that the previously observed Cu(i) XAS features are in part attributable to photodamage. This study illustrates the complex array of factors involved in EXAFS measurement and modeling of pMMO and more generally, dilute metalloproteins with multiple metal centers.

Extended X-ray absorption fine structure spectroscopic analysis of particulate methane monooxygenase reveals only monocopper sites and investigates the possible origins of the previous observed dicopper signals.     

X-ray absorption near edge structure and extended X-ray absorption fine structure analysis of Fe(II) aqueous and acetone solutions

X-ray absorption spectroscopy measurements were used to determine the structure of the first coordination shell of Fe(II) ions in aqueous and acetone based solutions. Extended X-ray absorption fine structure analysis coupled with ab initio X-ray absorption near edge structure calculations confirms the octahedral coordination of the iron ion in water based solution. Data collected for acetone rich solutions can be reproduced assuming coexistence of the octahedral Fe(H(2)O)(6)(2+) and tetrahedral [FeCl(4)](2-) complexes. Distortion of the tetrahedral coordination of ion was detected in some of the acetone based solutions.     

Rapid fluorescence assay for Sudan dyes using polyethyleneimine-coated copper nanoclusters

We report that the intensity of the blue fluorescence of copper nanoclusters coated with polyethyleneimine (PEI) is strongly reduced in the presence of the food dyestuffs Sudan I-IV. This finding was exploited in a label-free fluorescence assay for these Sudan dyes both in ethanol and aqueous solutions. The PEI-capped nanoclusters have an average diameter of 1.8 nm and are displaying, under 355 nm excitation, a blue emission at 480 nm that matches the absorption bands of the Sudan dyes. The clusters are stable in solution for at least 1 month. Under optimum conditions, this assay can be applied to the quantification of the dyes Sudan I, II, III, and IV, respectively, in the 0.1?30, 0.1–30, 0.1–25, and 0.1–25 μM concentration ranges, and the detection limits (3σ/slope) are 65, 70, 45, and 50 nM, respectively. The capability of reducing the fluorescence of the PEI-capped copper nanoclusters is directly related to the number of the functional groups in that Sudan III and IV give lower detection limits. This analytical scheme exhibits a remarkably high selectivity for the Sudan dyes over potentially interfering substances. The method was successfully applied to determine Sudan I, II, III, and IV in hot chilli powder.

Dodecanethiol-protected copper/silver bimetallic nanoclusters and their surface properties

Dodecanethiol-protected copper/silver bimetallic nanoclusters were prepared by a liquid-phase method using different copper to silver feed ratios. The morphology and size of the prepared nanoclusters were analyzed with X-ray diffraction (XRD) and transmission electron microscopy (TEM), while their spectroscopic and surface properties were characterized by infrared (IR) and X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and 13C cross-polarization magic angle spinning NMR (13C CPMAS NMR). TEM analysis indicated that all the bimetallic clusters prepared are approximately 4-6 nm in size. On the other hand, the results of XRD, XPS, and Fourier transform infrared (FTIR) spectroscopy suggested that the surfaces of the alloy nanoclusters are mostly enriched with the less noble metal copper atoms. This surface enrichment of copper may be attributed to a galvanic exchange process during preparation, and the extent of enrichment is directly related to the copper feed ratio used. Interestingly, DSC studies showed two melting transitions in some of these alloy samples, suggesting different packing behavior of the dodecanethiol chains onto the heterogeneously intercalated silver- and copper-rich surfaces.     

Trace analysis of high-purity copper by total reflection X-ray fluorescence spectrometry

Total reflection X-ray fluorescence (TXRF) analysis after the separation of matrix element was studied for the determination of trace impurity elements (Ca, Sc, V, Cr, Mn, Fe, Co, Ni and Zn) in high purity copper. Matrix copper was removed by electrolysis (0.2 A, 8 h) of a nitric acid solution. A 10 μL aliquot of the remaining solution of the electrolysis was dropped on a silicon-wafer sample-carrier and dried in a vacuum. This was repeated five times and the precipitate of five 10 μL-aliquots was analyzed by TXRF using a W-Lβ beam with an incident angle of 0.05?°. TXRF analytical values were obtained by using relative sensitivity factors of the analytes to the internal standard element (Pd). Detection limits of the analytes ranges from 0.077 ng for Zn to 0.785 ng for Ca.