Determination of low levels of free fibres of chrysotile in contaminated soils by X-ray diffraction and FTIR spectroscopy

A new analytical method for the determination of low levels (0.01–1 wt%) of free fibres of chrysotile in contaminated clayey, sandy and sandy-organic soils is described. The detection limit of 0.01 wt% is reached with an enrichment of free fibres of chrysotile in the sample using a standard laboratory elutriator for sedimentation analysis. The chrysotile quantitative determination is performed both by X-ray powder diffraction, using the internal standard and reference intensity ratio methods, and by Fourier-transform infrared absorption spectroscopy. The procedure can be successfully applied to different soils after removal, by a thermal treatment, of the matrix components which can interfere. This straightforward method fulfils the request of public institutions and private companies for an appropriate quantitative determination of chrysotile-free fibres in contaminated soils.     

Electrospray ionization mass spectrometry for the quantitation of albumin in human serum

Capillary reversed-phase liquid chromatography was coupled to electrospray ionization mass spectrometry for determining the concentration of human serum albumin (HSA) in a fresh frozen serum reference material. A biotinylated HSA (bHSA) was prepared and used as an internal standard for the serum albumin determination. The average HSA concentration of the serum sample was determined by mass spectrometry to be 41.5 ± 2.8 g/L at the 95% confidence limit for the measured value. The HSA concentration of the fresh frozen serum was also assayed using the bromocresol green dye-binding method, producing a value of 42.3 ± 1.5 g/L. Calibration curves generated from HSA standards spiked with bHSA showed excellent linearity and the relative standard deviation for replicate analysis of a bHSA spiked serum sample was less than 3%.     

Determination of benzene at trace levels in air by a novel method based on solid-phase microextraction gas chromatography/mass spectrometry.

A new method for the determination of benzene at trace levels in air is presented. The method consists of the collection of air samples on adsorbent cartridges with simultaneous adsorption of pre-established amounts of D6-labeled internal standard. Desorption from the cartridge is performed by solid-phase microextraction (SPME) with analysis by gas chromatography/mass spectrometry (GC/MS) using an ion trap mass spectrometer. The influence of several parameters (type of SPME fiber, temperature, time, for example) was investigated, and good linearity in the range 10-400 ng of C6D6, with a coefficient of variance (CV) around 3-5%, was obtained. The method was tested by sampling air in a town center in Italy, and a benzene concentration of approximately 50 microg/m(3) was determined. The maximum limit recommended by the European Community is 10 microg/m(3).     

Precise determination of boron in titanium by inductively coupled plasma mass spectrometry

A method was developed for the determination of boron in titanium by inductively coupled plasma mass spectrometry (ICP-MS). A commercially available PTFE sample introduction system, leading to the desired low detection limits for boron, was used. The method is suitable for the determination of boron concentrations down to about 1 μg g^?1 in the solid material. The influence of the internal standard on the precision was studied and beryllium was selected as the internal standard. For the titanium analysed (BCR reference material 090), the ICP-MS result agreed with those obtained using other techniques. Several bars of titanium reference material were supplied and a study of the homogeneity of boron in this material was made. Using analysis of variance on the results obtained for the different bars, the homogeneity of boron in the reference material could be estimated to be better than 2.1%.     

Application of k 0-based internal mono-standard PGNAA for compositional characterization of cement samples

The k ₀-based internal mono-standard prompt gamma-ray neutron activation analysis (IM-PGNAA) method was used for compositional analysis of a cement standard provided by the International Atomic Energy Agency as a part of inter-laboratory comparison exercise. The PGNAA was also applied to a local cement sample for comparison purpose. The concentration ratios of elements with respect Ca were determined using the internal mono-standard method. The concentration ratios were then converted to the absolute concentrations by determining concentration of Ca in the cement using relative method. Concentrations of 11 elements were determined in both sample and standard of cement. The results of cement standard are found to be in good agreement with the certified values. The uncertainties on the elemental concentrations were in the range of 5–10 %.     

Structural studies of ITO films using grazing incidence x-ray diffractometry

Tin doped indium oxide (ITO) films deposited by e-beam evaporation were investigated using grazing incidence x-ray diffractometry (GIXRD). With increasing doping concentration the x-ray peak positions are shifted to lower angles and the line profiles become broader. Rietveld refinements show that tin in small concentrations occupies regular In sites. Line profile analysis reveals that higher tin concentrations cause an increasing of lattice defects, as grain boundaries and microstrains. The results of the structural investigations correlate with resistivity measurements.     

Determination of indomethacin polymorphic contents by chemometric near-infrared spectroscopy and conventional powder X-ray diffractometry

A chemoinfometric method for the quantitative determination of the crystal content of indomethacin (IMC) polymorphs, based on Fourier-transform near-infrared (FT-NIR) spectroscopy, was established. A direct comparison of the data with those collected using the conventional powder X-ray diffraction method was performed. Pure alpha and gamma forms of IMC were prepared using published methods. Powder X-ray diffraction profiles and NIR spectra were recorded for six kinds of standard material with various contents of the gamma form of IMC. Principal component regression (PCR) analyses were performed on the basis of the normalized NIR spectral sets of standard samples with known contents of the gamma form of IMC. A calibration equation was determined to minimize the root mean square error of the prediction. The predicted gamma form contents were reproducible and had a relatively small standard deviation. The values of the gamma form contents predicted by the two methods were in close agreement. The results indicated that NIR spectroscopy provides an accurate quantitative analysis of crystallinity in polymorphs compared with the results obtained by conventional powder X-ray diffractometry.     

Systematic and statistical errors in quantitative evaluation using TLC and HPTLC. 2. Internal and external standard methods

The error propagation is given for routine analysis by in situ evaluation in TLC using the methods with internal or external standard. The internal standard method will need four different measurements of peak height or area, while the external standard method uses only two measurements. Therefore in the latter case the error of the spotting volume will cause errors in the determined concentration. By error propagation it can be shown, that the internal standard method gives better results, if the error in measuring peak height or area is less than the error of the spotting volume.     

Determination of streptomycin in serum by high-performance liquid chromatography

A high-performance liquid chromatographic method was developed for monitoring the serum concentration of streptomycin. The method includes clean-up using a Sep-Pak C18 cartridge and quantitation using dihydrostreptomycin as an internal standard. Streptomycin and dihydrostreptomycin were separated by reversed-phase ion-pair chromatography on LiChrosorb RP-18 and detected by UV absorption (195 nm). The calibration graph of serum streptomycin concentration was linear over the range 5-50 micrograms/ml. Streptomycin was added to serum at the level of 20.0 micrograms/ml and its concentration was determined to be 18.9 micrograms/ml with a coefficient of variation of 2.07% (n = 5). The clinical application of this method was confirmed by comparison with fluorescence polarization immunoassay.     

Determination of trace elements in zeolites by laser ablation ICP-MS

Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation conditions employed (lambda: 266 nm, repetition frequency: 10 Hz, pulse energy: 10 mJ, laser power density: 6 x 10(9) W/cm2) fractionation effects of the determined elements relative to the internal standard element Ti were not observed.     

Interaction of bovine serum albumin with chrysotile: spectroscopic and morphological studies

The biodurability of chrysotile fibers, which is related to their cytotoxicity and mutagenic responses, is strongly affected by the surface chemical adsorption of biological molecules. Natural chrysotile is a heterogeneous material in both structure and composition. The availability of synthetic stoichiometric chrysotile of constant structure and uniform morphology has allowed us to investigate its interaction with bovine serum albumin (BSA). By using transmission electron microscopy (TEM) and atomic force microscopy (AFM), we have obtained the first morphological evidence of albumin adsorption onto chrysotile nanocrystals. FTIR spectroscopy was used to quantify modifications of BSA secondary structure that were induced by the surface interaction. The protein transition to beta-turns allows a stronger interaction between the protein hydrophilic side-chains and the charged asbestos surface, which is consistent with hydrogen bonds involving the superficial OH groups. Synthetic stoichiometric chrysotile nanocrystals were shown to be an ideal reference standard with which to study the interaction of asbestos fibers with biological systems, in order to elucidate the chemical mechanisms of asbestos toxicity.     

Determination in plasma of angiotensin-converting enzyme inhibitor by inhibitor-binding assay.

A method of determining a new angiotensin-converting enzyme inhibitor (CS-622) and its active metabolite (RS-5139) in plasma by inhibitor-binding assay has been developed using high-performance liquid chromatography. The assay is based on the principle that the amount of inhibitor bound to the enzyme is inversely related to the amount of hippuric acid liberated on hydrolysis from the artificial substrate (hippuryl-L-histidyl-L-leucine). Plasma was heated at 60 degrees C for 15 min, to inactivate endogenous enzyme, and preincubated with rabbit-lung angiotensin-converting enzyme at 37 degrees C for 3 min. The artificial substrate (5.75 mg/ml in pH 8.3 phosphate buffer containing sodium chloride) was added to the resulting solution, and the mixture was incubated for 30 min. The reaction was terminated by the addition of 2 M hydrochloric acid. The hippuric acid liberated on hydrolysis was extracted with ethyl acetate and determined by reversed-phase chromatography using methylparaben as an internal standard. The total concentration of the inhibitor and its metabolite were determined by this method after de-esterification by rat-plasma esterase. The standard curve was obtained by the regression analysis of log concentration against logit response. The within-day and day-to-day precision were satisfactory. The proposed method is simple, rapid and sensitive enough to determine angiotensin-converting enzyme inhibitor in plasma.     

悬浮物测定的质量控制方法

为完善现行国标法GB 11901–1989《水质悬浮物的测定重量法》中质量控制与质量保证相关内容,促进悬浮物标准品的研发,利用高岭土研制的标准溶液建立了悬浮物测定的质量控制方法。根据水样的属性,取样体积范围在50 m L~200 m L区间,采用水系0.45μm滤膜和三联抽滤装置对水样进行预处理操作,以重量法测定水样悬浮物的含量。确定方法的空白测定值稳定于上下警告线内波动,检出限为5 mg/L,样品6次测定结果的相对标准偏差小于10%,标准样品10次测定相对误差在±10%内,满足分析质量控制要求。     

氯磺隆的高效液相色谱分析方法研究

本文研究了用高效液相色谱法测定新型除草剂氯磺隆含量的方法,在反相ODS柱上,用甲醇—水作流动相进行洗脱,紫外225nm检测,以萘作内标定量,方法快速、灵敏、准确,氯磺隆的最小检出量为0.8ng,变异系数为1.4%,回收率为100.7%,一次分析仅需3分钟。     

Analysis of tetracyclines from milk powder by molecularly imprinted solid‐phase dispersion based on a metal–organic framework followed by ultra high performance liquid chromatography with tandem mass spectrometry

A novel molecularly imprinted polymer that could selectively recognize tetracyclines in milk powder was synthesized using a metal–organic framework as a support material, tetracycline as template molecule, and 3‐aminophenylboronic acid as a functional monomer and a cross‐linking agent. The novel molecularly imprinted polymer was characterized by Fourier transform infrared spectrometry, transmission electron microscopy, X‐ray diffractometry, thermogravimetric analysis, and N₂ adsorption/desorption measurements. The adsorption isotherms, adsorption kinetics, adsorption thermodynamics, and selective adsorption experiments of the novel molecularly imprinted polymer to tetracycline were also studied. The novel molecularly imprinted polymer was used as dispersant of matrix solid‐phase dispersion to extraction tetracyclines. After that, the tetracyclines extracted from milk powder were determined by ultra high performance liquid chromatography with tandem mass spectrometry. Under the optimal conditions, the detection limits of tetracyclines were 0.217–0.318 ng/g. The relative standard deviations of intra‐ and interday precision ranged from 3.8 to 6.9% and from 2.8 to 7.4%, respectively. In all three concentration levels (1.0, 10, 50 ng/g), the recoveries of tetracyclines ranged from 84.7 to 93.9%. The method was successfully applied to the determination of tetracyclines in milk powder.     

Electrochromatographic solid-phase extraction for determination of cimetidine in serum by micellar electrokinetic capillary chromatography.

A highly effective electrochromatographic solid-phase extraction and preconcentration method is reported for the determination of cimetidine in serum in the concentration range 0.233-11.4 micrograms/ml. Preconcentrated samples were determined by micellar electrokinetic capillary chromatography while ranitidine was used as an internal standard. Sample preparation included retention of the analyte on a C18 solid-phase cartridge, followed by elution assisted by an applied voltage of 150 V. From 0.5-ml serum samples, 20-50-microliters aliquots were collected for electrophoretic analysis. Within the studied concentration range, the method was linear and provided adequate precision.     

X-Ray Fluorescence Determination of Iron in Polluted Streams

Abstract

The method involves the addition of chromium as an internal standard and requires no other chemical pretreatment. Samples are spotted directly onto chromatographic paper discs and analyzed by x-ray fluorescence spectrometry. The method is rapid, and is best in the concentration range 5–400 p.p.m.     

Simultaneous determination of free carnitine and total choline by liquid chromatography/mass spectrometry in infant formula and health-care products: single-laboratory validation

A single-laboratory validation study was conducted for a liquid chromatographic/mass spectrometric (LCIMS) method for the simultaneous determination of the free carnitine and total choline in milk-based infant formula and health-care products. The sample preparation used for both carnitine and choline was adapted from AOAC Official Method 999.14, with an acidic and enzymatic hydrolysis of esterified forms of choline. Carnitine and choline were quantified by ion-pair chromatography with single-quadrupole MS detection, using their respective deuterated internal standards. The repeatability relative standard deviation was < or =2.5 and 2.1%, respectively, for carnitine and choline. The intermediate reproducibility relative standard deviation was <4.7 and 2.4%, respectively, for carnitine and choline. The ranges of the average product-specific recoveries were 92-98 and 94-103%, respectively, for carnitine and choline. Choline concentration determined in infant formula reference material SRM 1846 was in agreement with the reference value. The proposed method was compared with the enzymatic methods for a range of products; good correlation (r = 0.99) was obtained, although a significant bias was observed for both analytes. The method, with a short chromatographic run time (7 min), is convenient for routine analysis to enhance analytical throughput and is a good alternative to enzymatic assays.     

Bulk and microprobe analysis for trace elements with synchrotron radiation

Blood serum samples were irradiated by monochromatic synchrotron radiation (15 keV) and by 2.4-MeV protons to compare their performance for the detection of trace elements by x-ray fluorescence (XRF) spectrometry. Absolute concentration assignment was based on the addition of an internal standard and on a method which uses the incoherent and coherent radiation as a flux monitor of the incoming beam. Preliminary experiments with a synchrotron XRF microprobe are reported.     

Liquid Chromatographic Determination of Valproic Acid in Human Serum

Abstract

The concentration of the antiepilepsy drug valproic acid (2-propylpentanoic acid) was determined in both a processed freeze dried human serum material and patient serum samples obtained from a clinical laboratory. The freeze dried material is being issued by the National Bureau of Standards as Standard Reference Material 1599. The analytical procedure developed involves organic extraction of valproic acid and an internal standard (cyclohexane-carboxylic acid) from the serum matrix; derivatization of the carboxylic acids to phenacyl esters; measurement of the analyte and internal standard species by reversed-phase high performance liquid chromatography. The results obtained on both types of samples compare favorably with results obtained using more conventional gas chromatographic approaches.