Use of alkaline or enzymatic sample pretreatment prior to characterization of gold nanoparticles in animal tissue by single-particle ICPMS

Inductively coupled plasma mass spectrometry in single-particle mode (spICPMS) is a promising method for the detection of metal-containing nanoparticles (NPs) and the quantification of their size and number concentration. Whereas existing studies mainly focus on NPs suspended in aqueous matrices, not much is known about the applicability of spICPMS for determination of NPs in complex matrices such as biological tissues. In the present study, alkaline and enzymatic treatments were applied to solubilize spleen samples from rats, which had been administered 60-nm gold nanoparticles (AuNPs) intravenously. The results showed that similar size distributions of AuNPs were obtained independent of the sample preparation method used. Furthermore, the quantitative results for AuNP mass concentration obtained with spICPMS following alkaline sample pretreatment coincided with results for total gold concentration obtained by conventional ICPMS analysis of acid-digested tissue. The recovery of AuNPs from enzymatically digested tissue, however, was approximately four times lower. Spiking experiments of blank spleen samples with AuNPs showed that the lower recovery was caused by an inferior transport efficiency of AuNPs in the presence of enzymatically digested tissue residues.     

石墨炉原子吸收光谱法测定食品添加剂磷酸氢二铵中的铅含量

采用石墨炉原子吸收光谱法（GF．AAS）测定食品添加剂磷酸氢二铵中的铅含量,并且对样品中铅的线性范围、检测限、回收率和精密度进行了分析[1]。结果表明,在本实验条件下,铅的最低检测限为O．0082μg／g,线性回归方程为y=0．0091x＋0．00619,线性系数为0．9999,样品回收率都在97％以上。在采用同样前处...     

Detailed hydrocarbon analysis of gasoline by GC-MS (SI-PIONA)

A gas chromatographic – mass spectrometric (GC-MS) method has been developed for detailed analysis of the hydrocarbon content of gasoline. The method is equipped with special software and includes the analysis of oxygenated compounds in a single run. The technique utilizes three basic components: the separating power of high resolution capillary gas chromatography, a mass spectrometer with a controllable ion source and ion fragmentation ratios, and unique software for data handling and preparation of reports. The C₄ to C₁₂ range of hydrocarbons in gasoline is covered by the method. A sample of unleaded gasoline from a gas station was analyzed without sample preparation. The results are discussed.     

A sensitive method for determination of a broad range of perfluorinated compounds in serum suitable for large-scale human biomonitoring

A sensitive and reliable method based on column switching liquid chromatography (LC) coupled to a triple quadrupole mass spectrometer (MS) has been developed for quantification of 19 perfluorinated compounds (PFCs) in serum. A volume of only 150 μl serum is used and protein precipitation by methanol is the only sample preparation necessary prior to injection into the column switching system. Pseudo-MRM is used as a detection mode for determination of PFCs, resulting in reduced background noise and considerably increased sensitivity for the perfluorinated alkyl sulfonates and the perfluorinated alkyl sulfonamides. The estimated limits of detection for the method were as low as 0.0020–0.050 ng PFCs/ml serum. The accuracy determined from spiking experiments, reported as recovery of added amount, was between 85 and 121% in the range 0.20–50 ng PFC/ml serum, except for perfluorodecylsulfonate for which the accuracy was 146% at 0.20 ng PFC/ml serum. The low sample volume needed, the limited manual handling and the broad range of analytes which are included, make this method advantageous for large-scale epidemiological studies. This column-switching technique can easily be set up on standard LC–MS/MS instruments and is thus available to a wide range of laboratories.     

On-line sample preparation for high throughput reversed-phase LC/MS analysis of combinatorial chemistry libraries

An on-line sample preparation method utilizing a time-programmed autosampler is described for high throughput liquid chromatography/mass spectrometry (LC/MS). This approach is particularly helpful for the LC/MS analysis of samples which require solvents incompatible with HPLC in the sample preparation process. The on-line sample preparation approach minimizes a bottleneck in throughput and improves sample recovery under some circumstances.     

An experimental design for the determination of Cu and Pb in marine sediments using taguchi's method

Taguchi's method appears to be an ideal statistical tool for the post-analysis correct determination of chemical composition in marine sediment samples. Using Taguchi's method in the chemistry laboratory, controllable factors such as mass per volume ratio, digestion temperature, digestion time and acids can be isolated to provide centring and variance control in Cu and Pb measurements or a “correct determination of Cu and Pb concentrations” minimizing the effect of noise factors. Statistical analysis is performed to identify the effect of parameters and their interactions. Also the expected cost savings under optimum condition is calculated. The results are confirmed by further measurements.     

Fundamental studies using ICP-MS for the measurement of technetium-99 in a dried-up deposition sample

In order to determine,⁹⁹Tc in the atmosphere, we analyzed a dried-up deposition sample obtained from rain and dry fallout. We carried out tracer experiments to investigate the loss of⁹⁹Tc during preparation of the sample by evaporation and drying and to examine a suitable separation method for measurement of the nuclide in the sample by using ICP-MS. The results showed no remarkable reduction of Tc during evaporation to dryness. The volatilization and trapping method with a combustion apparatus gave a clear and easy separation of Tc with a recovery of 77%.     

Application of PLE for the determination of essential oil components from Thymus vulgaris L

Essential plants, due to their long presence in human history, their status in culinary arts, their use in medicine and perfume manufacture, belong to frequently examined stock materials in scientific and industrial laboratories. Because of a large number of freshly cut, dried or frozen plant samples requiring the determination of essential oil amount and composition, a fast, safe, simple, efficient and highly automatic sample preparation method is needed.Five sample preparation methods (steam distillation, extraction in the Soxhlet apparatus, supercritical fluid extraction, solid phase microextraction and pressurized liquid extraction) used for the isolation of aroma-active components from Thymus vulgaris L. are compared in the paper. The methods are mainly discussed with regard to the recovery of components which typically exist in essential oil isolated by steam distillation.According to the obtained data, PLE is the most efficient sample preparation method in determining the essential oil from the thyme herb. Although co-extraction of non-volatile ingredients is the main drawback of this method, it is characterized by the highest yield of essential oil components and the shortest extraction time required. Moreover, the relative peak amounts of essential components revealed by PLE are comparable with those obtained by steam distillation, which is recognized as standard sample preparation method for the analysis of essential oils in aromatic plants.     

Fractional factorial design based microwave‐assisted extraction for the determination of organophosphorus and organochlorine residues in tobacco by using gas chromatography—mass spectrometry

Sample preparation is often the main bottleneck in analyzing biological samples. Particularly, effective evaluation of sample preparation conditions usually involves multiple factors and tedious and time‐consuming experiments. In this study, fractional factorial design, specifically orthogonal array testing, was employed to screen and optimize multiple extraction parameters in concise but representative experiments. An efficient and sensitive method was developed to determine organophosphorus and organochlorine pesticide residues in tobacco, via microwave‐assisted extraction and gas chromatography coupled with mass spectrometry detection. With orthogonal array design, screening, and optimization tests were subsequently conducted to determine the range, impact rank, and possible interactions of extraction temperature, time, microwave power, additive salt, and additive water. Orthogonal array testing selectively reduces the size and cost of experiments and meanwhile provides more information compared to the traditional experimental design that optimizes one factor at a time. A good linear range (0.02–2.00 μg/mL), limits of detection (0.001–0.098 μg/mL), and recovery rates (70.4–107.1%) were demonstrated by spiking known concentrations of multiple pesticide standards in tobacco samples. The established method was then successfully applied to the determination of multipesticide residues in raw tobacco leaves and commercial cigarettes.     

Analytical strategies for therapeutic monitoring of drugs and metabolites in biological fluids. Plenary lecture

Therapeutic drug monitoring can involve quantitation in either microgram, nanogram or picogram concentrations present in a complex biological matrix (whole blood, urine or tissue). The chemical structure of a compound influences not only the analytical method best suited to its quantitation, but also its acid/base character (pKa) and its extractability. The dose administered, the bioavailability of the dosage form, and the pharmacokinetic profile of the drug govern the circulating concentrations of either the parent drug and/or its metabolites present in vivo, and dictate the ultimate sensitivity nd specificity required of the analytical method. The degree of sample preparation required is dependent on the analytical method used (gas--liquid chromatography, thin-layer chromatography, high-performance liquid chromatography) and on the tolerance of the specific type of detection system to contamination. Factors leading to compound losses during sample preparation (adsorption, stability) are critical at low concentrations and can adversely affect the reliability of an assay, therefore maximizing the overall recovery of the assay is essential not only for high sensitivity but also for good precision and accuracy. Therefore, the criteria to be used in sample preparation should aim to optimize all of the above factors in the overall development of a reliable and validated method for the compound suitable for use in clinical therapeutic monitoring.     

环境模拟样品中多环芳烃的超临界流体萃取I．利用正交设计选择最佳萃取条件

采用正交设计实验方法，研究了从环境模拟样品中超临界流体萃取（ＳＦＥ）多环芳烃（ＰＡＨ）的最佳萃取条件。着重考察了超临界流体的压力、温度和用量等对萃取效率的影响。结果表明，压力的影响居第一位，温度影响次之，超临界ＣＯ２的用量的影响居第三位。建立了选择超临界流体萃取条件的简单方法     

Measurement uncertainty from physical sample preparation: estimation including systematic error

A methodology is proposed, which employs duplicated primary sampling and subsequent duplicated physical preparation coupled with duplicated chemical analyses. Sample preparation duplicates should be prepared under conditions that represent normal variability in routine laboratory practice. The proposed methodology requires duplicated chemical analysis on a minimum of two of the sample preparation duplicates. Data produced from the hierarchical design is treated with robust analysis of variance (ANOVA) to generate uncertainty estimates, as standard uncertainties ('u' expressed as standard deviation), for primary sampling (ssamp), physical sample preparation (sprep) and chemical analysis (sanal). The ANOVA results allow the contribution of the sample preparation process to the overall uncertainty to be assessed. This methodology has been applied for the first time to a case study of pesticide residues in retail strawberry samples. Duplicated sample preparation was performed under ambient conditions on two consecutive days. Multi-residue analysis (quantification by GC-MS) was undertaken for a range of incurred pesticide residues including those suspected of being susceptible to loss during sample preparation procedures. Sampling and analytical uncertainties dominated at low analyte concentrations. The sample preparation process contributed up to 20% to the total variability and had a relative uncertainty (Uprep%) of up to 66% (for bupirimate at 95% confidence). Estimates of systematic errors during physical sample preparation were also made using spike recovery experiments. Four options for the estimation of measurement uncertainty are discussed, which both include and exclude systematic error arising from sample preparation and chemical analysis. A holistic approach to the combination and subsequent expression of uncertainty is advised.     

Variation of analytical results for peanuts in energy bars and milk chocolate

Peanuts contain proteins that can cause severe allergic reactions in some sensitized individuals. Studies were conducted to determine the percentage of recovery by an enzyme-linked immunosorbent assay (ELISA) method in the analysis for peanuts in energy bars and milk chocolate and to determine the sampling, subsampling, and analytical variances associated with testing energy bars and milk chocolate for peanuts. Food products containing chocolate were selected because their composition makes sample preparation for subsampling difficult. Peanut-contaminated energy bars, noncontaminated energy bars, incurred milk chocolate containing known levels of peanuts, and peanut-free milk chocolate were used. A commercially available ELISA kit was used for analysis. The sampling, sample preparation, and analytical variances associated with each step of the test procedure to measure peanut protein were determined for energy bars. The sample preparation and analytical variances were determined for milk chocolate. Variances were found to be functions of peanut concentration. Sampling and subsampling variability associated with energy bars accounted for 96.6% of the total testing variability. Subsampling variability associated with powdered milk chocolate accounted for >60% of the total testing variability. The variability among peanut test results can be reduced by increasing sample size, subsample size, and number of analyses. For energy bars the effect of increasing sample size from 1 to 4 bars, subsample size from 5 to 20 g, and number of aliquots quantified from 1 to 2 on reducing the sampling, sample preparation, and analytical variance was demonstrated. For powdered milk chocolate, the effects of increasing subsample size from 5 to 20 g and number of aliquots quantified from 1 to 2 on reducing sample preparation and analytical variances were demonstrated. This study serves as a template for application to other foods, and for extrapolation to different sizes of samples and subsamples as well as numbers of analyses.     

Characterization of mesogen-jacketed liquid crystalline polymers by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

For synthetic polymers, a proper sample preparation method is essential for successful characterization by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. In this work, six synthetic mesogen-jacketed liquid crystalline polymers (MJLCPs) with different main-chain, spacer and mesogenic units were investigated by MALDI-TOF mass spectrometry. Several factors that affect the analysis of these polymers were examined. These factors include matrices used, cationization salts used, the concentration of polymers, and the ratio of sample to matrix. After testing different conditions, we found a suitable sample preparation method for these six polymers. The number average molecular weight (M(n)), weight average molecular weight (M(w)) and polydispersity (PD) were calculated using data obtained in the linear mode. The end groups of the polymers were proposed using data obtained in reflectron mode. Copyright 2000 John Wiley & Sons, Ltd.     

乙炔羰基化反应催化剂:由均相到多相

基于非石油路线制备的乙炔小分子,其羰基化反应可制备大量高附值化学品,在CO排放的环境治理以及化学品应用方面有着十分重要的意义.本文主要概述了乙炔羰基化反应的催化剂由均相到多相的研究进展,总结了乙炔单/双羰基化催化剂种类及添加剂对反应活性的影响.基于反应机理分析提出调控结构敏感性因素(尺寸效应及形貌效应)制备高效催化剂的...     

Optimization of a capillary zone electrophoresis–contactless conductivity detection method for the determination of nisin

Determination of natural preservatives using electrophoretic or chromatographic techniques in fermented milk products is a complex task due to the following reasons: (i) the concentrations of the analytes can be below the detection limits, (ii) complex matrix and comigrating/coeluting compounds in the sample can interfere with the analytes of the interest, (iii) low recovery of the analytes, and (iv) the necessity of complex sample preparation. The aim of this study was to apply capillary zone electrophoresis coupled with contactless conductivity detection for the separation and determination of nisin in fermented milk products. In this work, separation and determination of natural preservative–nisin in fermented milk products is described. Optimized conditions using capillary zone electrophoresis coupled with capacitance‐to‐digital technology based contactless conductivity detector and data conditioning, which filter the noise of the electropherogram adaptively to the peak migration time, allowed precise, accurate, sensitive (limit of quantification: 0.02 μg/mL), and most importantly requiring very minute sample preparation, determination of nisin. Sample preparation includes following steps: (i) extraction/dilution and (ii) centrifugation. This method was applied for the determination of nisin in real samples, i.e. fermented milk products. The values of different nisin forms were ranging from 0.056 ± 0.003 μg/mL to 9.307 ± 0.437 μg/g.     

Matrix removal in state of the art sample preparation methods for serum by charged aerosol detection and metabolomics-based LC-MS

Investigations into sample preparation procedures usually focus on analyte recovery with no information provided about the fate of other components of the sample (matrix). For many analyses, however, and particularly those using liquid chromatography-mass spectrometry (LC-MS), quantitative measurements are greatly influenced by sample matrix. Using the example of the drug amitriptyline and three of its metabolites in serum, we performed a comprehensive investigation of nine commonly used sample clean-up procedures in terms of their suitability for preparing serum samples. We were monitoring the undesired matrix compounds using a combination of charged aerosol detection (CAD), LC-CAD, and a metabolomics-based LC-MS/MS approach. In this way, we compared analyte recovery of protein precipitation-, liquid-liquid-, solid-phase- and hybrid solid-phase extraction methods. Although all methods provided acceptable recoveries, the highest recovery was obtained by protein precipitation with acetonitrile/formic acid (amitriptyline 113%, nortriptyline 92%, 10-hydroxyamitriptyline 89%, and amitriptyline N-oxide 96%). The quantification of matrix removal by LC-CAD showed that the solid phase extraction method (SPE) provided the lowest remaining matrix load (48–123 μg mL⁻¹), which is a 10–40 fold better matrix clean-up than the precipitation- or hybrid solid phase extraction methods. The metabolomics profiles of eleven compound classes, comprising 70 matrix compounds showed the trends of compound class removal for each sample preparation strategy. The collective data set of analyte recovery, matrix removal and matrix compound profile was used to assess the effectiveness of each sample preparation method. The best performance in matrix clean-up and practical handling of small sample volumes was showed by the SPE techniques, particularly HLB SPE. CAD proved to be an effective tool for revealing the considerable differences between the sample preparation methods. This detector can be used to follow matrix compound elution during chromatographic separations, and the facile monitoring of matrix signal can assist in avoiding unfavourable matrix effects on analyte quantification.     

Evaluation of the Effect of Pear Stone Cells on the Recovery of Multi-Class Pesticides

The widespread sample preparation method for the extraction of pesticide residues, the QuEChERS method, sometimes yields different pesticide recovery values for different food matrices. Pear (Pyrus communis L.) is an example of a matrix that can be characterized with somewhat lower pesticide recoveries. In order to investigate the reason for this result, the most characteristic structural feature of pears, the stone cells, possessing a specific surface due to their greater cellulose and lignin contents, were isolated and purified. The isolated stone cells were used for the preparation of a model sample in combination with tomato, a food matrix showing high pesticide recovery values, in a pesticide spiking experiment. Eleven multi-class pesticides were selected for the study where the quantification was carried out with HPLC-ESI-MS/MS. No significant differences were found between the pesticide recoveries obtained from the tomato and the combined tomato-pear stone cells matrices, which indicates the reason behind the lower pesticide recoveries in pear matrices is still to be determined.     

Characterization of humic substances by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and laser desorption/ionization (LDI-)TOFMS have been used to characterize Suwannee River humic substances, obtained from the International Humic Substances Society (IHSS), and Armadale soil fulvic acid (ASFA). An array of MALDI matrices were tested for use with humic substances, including alpha-cyano-4-hydroxycinammic acid (CHCA), 2-(4-hydroxyphenylazo)benzoic acid (HABA), 2,5-dihydroxybenzoic acid (DHBA), sinapinic acid, dithranol and norharmane. DHBA yielded the best results, exhibiting superior ionization efficiency, low noise, broad applicability to the analytes of interest, and most importantly producing an abundance of high mass ions, the highest observed being m/z 1848. A number of sample preparation modes were investigated; the overlayer method improved sample/matrix homogeneity and hence shot-to-shot reproducibility. The choice of the matrix, mass ratio of analyte to matrix, and the sample preparation protocol, were found to be the most critical factors governing the quality of the mass spectra. Matrix suppression was greatly enhanced by ensuring good mixing of matrix and analyte in the solid phase, proper optimization of the matrix/analyte ratio, and optimizing delayed extraction to ensure complete matrix-analyte reaction in the plume before ions are moved to the flight tube. A number of common features, in particular specific ions which could not be attributed to the matrices or to contaminants, were present in the spectra of all the humic substances, regardless of origin or operational definition. Additionally, a prominent repeating pattern of peaks separated by 55, 114 and 169 Da was clearly observed in both LDI and MALDI, suggesting that the humic compounds studied here may have quasi-polymeric or oligomeric features.     

Gel electrophoresis/electroelution sorting fractionator combined with filter-aided sample preparation for deep proteomic analysis

Sample preparation and protein fractionation are important issues for proteomic studies. Protein extraction procedures strongly affect the performance of fractionation methods by provoking protein dispersion in several fractions. The most notable exception is the gel-based electrophoretic protein fractionation due to its resolution and effectiveness of sodium dodecyl sulfate as a solubilizing agent, while its main limitation lies in the poor recovery of the gel-trapped proteins. We created a fractionator device to separate complex mixture of proteins and peptides that is based on the continuous gel electrophoresis/electroelution sorting of these molecules. In an unsupervised process, complex mixtures of proteins or peptides are fractionated into the gel while separated fractions are simultaneously and sequentially electroeluted to the solution containing wells. The performance of the device was studied for protein fractionation in terms of reproducibility, protein recovery, and loading capacity. In a setup free of sodium dodecyl sulfate, complex peptide mixtures can also be fractionated. More than 11,700 proteins were identified in the whole-cell lysate of the CaSki cell line by using the fractionator combined with the filter-aided sample preparation method and mass spectrometry analysis. Fractionator-based proteome characterization increased 1.7-fold the number of identified proteins compared to the unfractionated sample analysis.