X射线荧光与粒子激发X射线光谱分析

本文是《分析试验室》定期评述“Ｘ射线荧光光谱分析”系列评论第７篇,简述了１９９６年７月至１９９８年６月国内Ｘ射线荧光光谱分析技术发展的概况,从Ｘ射线荧光光谱仪的研制与改造、特殊激发方式的研究与应用、化学计量学与数据处理方法研究、化学态分析、标准物质与样品制备、测定方法研究与应用６个方面评述了国内Ｘ射线荧光与粒子激发Ｘ射线光谱分析进展。共收录国内学者论文及相关文集１４３篇。     

Atmospheric elemental concentration determined by Particle-Induced X-ray Emission at Tlaxcoapan in central Mexico, and its relation to Tula industrial-corridor emissions

The Tula-Vito-Apasco industrial corridor is considered one of the most contaminated zones in Mexico. In this corridor, at Hidalgo state, is located the Miguel Hidalgo refinery, the biggest in the country. Although ecology agencies monitor criterion contaminants in a routine basis, scarce data are available about elemental composition of particulate matter (PM). The PM₁₀ elemental composition of Tula vicinity is being analyzed and results of the field study performed in Tlaxcoapan, Hidalgo are presented here. This small agricultural town is located within a 7.5 km from Tula-Vito-Apasco industrial corridor. PM₁₀ fraction of atmospheric aerosols collected in filters from July to December 2007, was analyzed using Particle Induced X-ray Emission (PIXE) technique, and sixteen elements were detected. Temporal variations were observed during the studied period. Enrichment Factors were moderately high for S, Ca, V, Ni, Cu, Zn and Pb. Rain did not have strong influence but high amounts of sulfur were correlated to high amounts of Ni and V. Comparison of our results with other data from nearby allocations, shows good general agreement. A receptor model with principal component factor analysis (PCFA) and VARIMAX rotation was applied to data in order to estimate source apportionment. Four main sources were identified: soil that contributes to the elemental composition of filters with 26%, refinery and the power plant with 20% and two independent industrial emissions summed 26%. The last three polluting sources indicate that the industrial activities carried out in the corridor have a harmful impact in Tlaxcoapan, Hidalgo.     

Detection of synthetic components in food matrices using piezoelectric resonators

The adsorption of a mixture of volatile components from the vapor phase of synthetic flavoring agents on thin adsorbent films was studied using piezoelectric quartz microweighing. Conventional gas-chromatographic adsorbents and specific films of different nature were used as adsorbents. It was shown that synthetic flavoring agents, including those used in the production of foodstuffs, can be identified and their quality can be assessed. The use of an array of piezoelectric quartz microbalances with various films allowed the slightest changes in the composition of the equilibrium vapor phase of synthetic flavoring agents to be recorded. An algorithm using a universal database on piezoelectric quartz microweighing of flavoring agent vapors was proposed for detecting them in food products and revealing adulterations.     

Quantification of flupirtine maleate polymorphs using X-ray powder diffraction

Flupirtine maleate,a pharmaceutical compound for treating psychotic disease in clinics,has seven polymorphs.Form A,with better crystal stability and bioavailability,has been widely used as the pharmaceutical crystal form.Unfortunately,it is usually found in a polymorphic mixture with form B.In this study,pure crystal forms of A and B were prepared and characterized by X-ray powder diffraction (XRPD),Fourier transform infrared spectroscopy (FT-IR) and thermal analysis.An XRPD-based method for the quantitative determination of the amount of the flupirtine maleate polymorphs form A and form B was also established through a systematic optimization of instrumental parameters.The results of the analytical methodology validation showed that the XPRD method had a broad quantitative range of 0-100%(w/w),good linear relationship,with R²=0.999,excellent repeatability and precision and low limits of detection (LoD) of 0.15%(w/w) and quantification (LoQ) of 0.5%(w/w).The results also showed that the single-peak method was not as good as the whole pattern in reducing the influence of the preferred orientation,but this can be compensated for by a systematic optimization of instrumental parameters and validating the analytical methodology to reduce errors and obtain a good,repeatable,sensitive,and accurate method.This XRPD method can be used to analyze mixtures of flupirtine maleate polymorphs (forms A and B) quantitatively and control the quality of the bulk drug.     

Use of Particle-Induced X-Ray Emission for Evaluation of Competitive Metal Binding on Algae

Elemental concentrations of a unicellular alga,Chlorella vulgaris,were evaluated by particle-induced X-ray emission (PIXE). The probed algal cells generated a significant amount of phosphorus and sulfur X-ray emission. Phosphorus- and sulfur-containing compounds can provide potential binding sites for metal ions. Competitive binding of six metal ions, Ag, Ba, Cd, Cu, Hg, and Pb, to the algae was studied. It was found that Ag, Ba, Cd, Cu, and Pb are attached to a similar binding site with a binding efficiency varying in the sequence Pb > Cu > Ag > Cd > Ba. The binding of Hg to algae involves a different binding site. Silver was found to increase the binding of mercuric chloride to the algae.     

Quantification of ligand packing density on gold nanoparticles using ICP-OES

In this study, a prototypical thiolated organic ligand, 3-mercaptopropionic acid (MPA), was conjugated on gold nanoparticles (AuNPs), and packing density was measured on an ensemble-averaged basis using inductively coupled plasma optical emission spectrometry. The effects of sample preparation, including centrifugation and digestion, as well as AuNP size and concentration, on recovery were investigated. For AuNPs with diameters of 5, 10, 30, 60, and 100 nm, calculated packing density is independent of size, averaging 7.8 nm⁻² and ranging from 6.7 to 9.0 nm⁻², and is comparable to reported values for MPA and similar short-chain ligands on AuNPs. These preliminary data provide fundamental information on the advantages and limitations of ICP-based analyses of conjugated AuNP systems. Moreover, they provide necessary information for the development of more broadly applicable methods for quantifying nanoparticle–ligand conjugates of critical importance to nanomedicine applications.     

Analysis of aluminosilicate particles in biological matrices using histochemistry and X-ray microanalysis

Aluminosilicates are a group of ubiquitous environmental particles that, in some cases, have been implicated in human disease. Characterisation of aluminosilicates in tissue samples requires, first, their in situ identification and, secondly, analysis of their aluminium and silicon content or, at least, aluminium:silicon ratio. Here, histochemical staining, microscopy and X-ray microanalysis were investigated as potential methods for the detection of aluminosilicates in biological samples. In contrast to aluminium phosphate or hydroxide, aluminosilicates were refractory to histochemical staining for aluminium. However, using electron microscopy, back scattered electrons allowed identification of aluminosilicates in tissue-like (gelatine) sections. X-ray microanalysis, using conventional peak:background ratios, did not provide a sufficiently accurate assessment of the aluminium content of various standard aluminosilicates to allow their identification. However, the similar spectral energies of aluminium and silicon allowed spectral peak heights to be directly compared and, using simple standards, aluminium:silicon ratios were found for a range of reference particles. Application of this technique should allow the localisation and identification of aluminosilicates in biological samples.     

Alignment of nanoparticles in polymer matrices

This paper briefly summarizes the state of the art in the field of designing composites containing semiconductor nanoparticles distributed in a polymer matrix. Special attention is focused on (i) nanocomposites based on block copolymers and (ii) LC polymer matrices capable of controlling the localization and alignment of nanoparticles.     

Microwave assisted cross-coupling reactions using palladium nanoparticles in aqueous media

Glucose stabilized palladium nanoparticles (PdNPs) have been prepared and the application of NPs in catalyzing both Suzuki and Heck reactions has been explored in aqueous media under microwave conditions. Both electron-rich and electron-deficient aryl halides can be coupled with a variety of boronic acids and styrene to access a wide variety of biaryl compounds and substituted alkenes in good to excellent yields. The catalyst can be recycled and reused four times with minimally affecting the morphology and efficiency of the nanoparticles. A plausible reaction mechanism has been proposed.     

Extraction of perfluorinated compounds from food matrices using fluorous solvent partitioning

Perfluorinated compounds (PFCs) such as perfluorooctane sulfonic acid (PFOS) have emerged as a new class of global environmental pollutant; they bioaccumulate and are persistent in the environment and in wildlife. Fluorine-fluorine interactions have been investigated as a means to isolate PFCs for mass spectrometric quantification. A novel sample extraction and cleanup procedure has been developed for fat-containing samples based on fluorous liquid-liquid extraction (F-LLE) in a triphasic solvent system consisting of hybrid:fluorous:organic solvent (trifluoroethanol:perfluorohexane/dichloromethane-saturated with water). This system partially separates fluorous from non-fluorous compounds, allowing removal of co-extractants, which had previously resulted in liquid chromatography mass spectrometry (LC-MS/MS) peak suppression preventing low-level detection of PFCs. The developed F-LLE was coupled with an existing extraction protocol allowing the limits of detection of PFCs to be lowered an order of magnitude for high fat samples. The developed workflow was used to show the absence of a range of eleven PFCs in nine UK and one Irish cheese samples. This representative application demonstrates a new application of fluorous-organic extraction in sample cleanup for measurement of fluorinated analytes in food, environment and broader analytical chemistry.     

Quantification in grazing-emission X-ray fluorescence spectrometry

In grazing-emission X-ray fluorescence (GEXRF) spectrometry wavelength-dispersive detection can be applied. Much softer radiation and hence lighter elements than in total-reflection X-ray (TXRF) spectrometry can thus be detected. We used simulations to investigate methods of quantification of GEXRF results involving soft characteristic radiation. From these studies, it is concluded that for ultra-thin layers, e.g. the sub-monolayer amounts encountered in semiconductor contamination analysis, calibration plots are linear. For thicker layers, quantification should be performed very carefully because of deviations from linearity due to absorption of radiation and to oscillations in the calibration curve. These oscillations are caused by interference of fluorescence radiation emitted directly towards the detector and radiation reflected at the sample–substrate interface. Suggestions for a judicious choice of measurement conditions are made and the benefits of internal standardisation are discussed.     

CdS semiconductor nanoparticles in silica sonogel matrices

SiO₂ gels obtained by sonocatalytic method combined with DCCA were used as host-matrices for extremely fine dispersions of CdS semiconductor particles. Small crystallites were produced in situ by H₂S gas diffusion method. The particles were characterized by TEM and HRTEM, EXAFS, UV-Vis and Raman spectroscopies. The size of crystallites ranged from 5 to 10 nm. The optical transmission spectra showed the characteristic blue shift as a function of the particles size, as predicted by the theory. The optical and mechanical qualities of the samples were substantially improved by an infiltration method using a sono-sol which sealed the superficial pores thus ensuring greater longevity and the possibility of obtaining transparent gels by polishing.     

Emission properties of dihydropterins in aqueous solutions

Pterins belong to a class of heterocyclic compounds present in a wide range of living systems and accumulate in the skin of patients affected by vitiligo, a depigmentation disorder. The study of the emission of 7,8-dihydropterins is difficult because these compounds are more or less unstable in the presence of O(2) and their solutions are contaminated with oxidized pterins which have much higher fluorescence quantum yields (Φ(F)). In this work, the emission properties of six compounds of the dihydropterin family (6-formyl-7,8-dihydropterin (H(2)Fop), sepiapterin (Sep), 7,8-dihydrobiopterin (H(2)Bip), 7,8-dihydroneopterin (H(2)Nep), 6-hydroxymethyl-7,8-dihydropterin (H(2)Hmp), and 6-methyl-7,8-dihydropterin (H(2)Mep)) have been studied in aqueous solution. The fluorescence characteristics (spectra, Φ(F), lifetimes (τ(F))) of the neutral form of these compounds have been investigated using the single-photon-counting technique. Φ(F) and τ(F) values obtained lie in the ranges 3-9 × 10(-3) and 0.18-0.34 ns, respectively. The results are compared to those previously reported for oxidized pterins.     

Silica matrices for embedding of magnetic nanoparticles

This paper presents a study regarding the formation of hybrid gels starting from tetraethyl orthosilicate (TEOS), polyvinyl alcohol (PVA) and 1,3-propanediol (PD) and their thermal evolution to mesoporous silica matrices. The possibility of obtaining homogenously dispersed cobalt ferrite inside the silica matrix starting from (TEOS–PVA–PD–Metal Nitrates) gels was also studied. The formation of the hybrid gels TEOS/PVA/PD with different compositions was studied by FT-IR spectrometry and thermal analysis, in order to evidence the interaction between the diol with the organic and the inorganic polymers. Both thermal analysis and FT-IR spectrometry have evidenced the formation of physical and chemical interaction between polyols and the siloxane network. Elemental mapping performed by SEM-EDX technique evidenced the formation of homogenous hybrids both in the presence of the absence of 1,3-propanediol. SEM images of the powders obtained by annealing the hybrid xerogels at 600 °C have evidenced the formation of mesoporous silica. By thermal treatment of the (TEOS–PVA–PD–Metal Nitrates) gels, 30%CoFe₂O₄/70%SiO₂ (mass percent) nanocomposites uniformly dispersed in silica matrix with characteristic magnetic properties, have been successfully synthesized.     

SERS-based DNA detection in aqueous solutions using oligonucleotide-modified Ag nanoprisms and gold nanoparticles

Oligonucleotide-modified nanoparticle conjugates show highly promising potential for SERS-based DNA detection. However, it remains challenging to carry out the SERS-based DNA detection in aqueous solutions directly using oligonucleotide-modified nanoparticles, because the Raman reporters would exhibit lower signals when they are dispersed in aqueous solutions than laid on “dry” metal nanoparticles. Here, we synthesized stable oligonucleotide-modified Ag nanoprism conjugates, and performed SERS-based DNA detection in aqueous solution directly by using such conjugates in combination with Raman reporter-labeled, oligonucleotide-modified gold nanoparticles. The experimental results indicate that this SERS-based DNA detection approach exhibited a good linear correlation between SERS signal intensity and the logarithm of target DNA concentration ranging from 10^?11～10^?8 M. This sensitivity is comparable to those SERS-based DNA detection approaches with the “dry” process. Additionally, a similar correlation could also be observed in duplex target DNA detection by SERS hybrid probes. Our results suggest that the oligonucleotide-modified Ag nanoprisms may be developed as a powerful SERS-based DNA detection tool.

Determination of pyromellitic acid in aqueous matrices by HPLC

Summary A rapid method for the HPLC determination of pyromellitic acid in aqueous media used as food simulants has been developed and is described in this paper. The proposed method can determine pyromellitic acid at ppb trace levels and is based on an ionic exchange separation mechanism. The method herein developed has been applied to the determination of pyromellitic acid residues leached from plastic bottles.Research partially supported by National Research Council of Italy, Special Project RAISA, sub-project 4, Paper N.696.     

Semi-quantitative determination of cationic surfactants in aqueous solutions using gold nanoparticles as reporter probes

Concentrations of cationic surfactants in aqueous solutions have been estimated on the basis of changes in the color of gold nanoparticles, used as reporter probes. We have shown that the colors of gold nanoparticles with anionic protective groups on their surfaces shift from red to indigo/purple and then back to red in a range of cationic surfactant solutions in which concentrations vary from very low to above the theoretical CMCs. The color changes occur near the theoretical CMCs, presumably because the presence of surfactant micelles in the solution prevents the gold nanoparticles from aggregating. We have used gold nanoparticles as reporter probes to determine the concentrations of cationic surfactants in products such as hair conditioners, which often contain large amounts of alkyltrimethylammonium halides. Although this approach can only provide an estimate, it can be performed simply by addition of a given amount of gold nanoparticles to a series of diluted solutions, without the need for instruments or labor-intensive procedures. Figure Photographs of a series of diluted hair conditioner solutions with added gold nanoparticles

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Degradation of scarlet 4BS in aqueous solution using bimetallic Fe/Ni nanoparticles

A reactive-template vapor phase polymerization method for the preparation of bamboo-like polypyrrole (PPy) nanotubes has been successfully demonstrated in this paper. Herein, electrospun V(2)O(5) nanofibers were chosen as templates to deposit PPy, which served as the oxidants as well. This method can provide the fabrication of PPy nanostructures more easily than conventional routes due to its independence of removing template, which is usually a complex and tedious experimental process. The application of bamboo-like PPy nanotubes for Cr(VI) ions removal in aqueous solution has been explored. The resulting bamboo-like PPy nanotubes exhibited much higher adsorption performance than traditional PPy nanoparticles.