Screening and determination of drugs in human saliva utilizing microextraction by packed sorbent and liquid chromatography–tandem mass spectrometry

This study presents a new method for collecting and handling saliva samples using an automated analytical microsyringe and microextraction by packed syringe (MEPS). The screening and determination of lidocaine in human saliva samples utilizing MEPS and liquid chromatography–tandem mass spectrometry (LC‐MS/MS) were carried out. An exact volume of saliva could be collected. The MEPS C₈‐cartridge could be used for 50 extractions before it was discarded. The extraction recovery was about 60%. The pharmacokinetic curve of lidocaine in saliva using MEPS‐LC‐MS/MS is reported. Copyright © 2013 John Wiley & Sons, Ltd.     

Derivatisation in gas chromatographic determination of acidic herbicides in aqueous environmental samples

This paper reviews derivatisation processes applied in chromatographic determination of acidic herbicides (with carboxyl and phenol groups), mainly in aqueous environmental samples. The discussion focuses on the basic derivatisation reactions used to convert herbicides to derivatives to make them analysable by gas chromatography, and possibly to reduce detection limits and/or increase extraction recovery from aqueous samples. The reactions are transesterification, esterification, silylation, alkylation, and extractive and pyrolytic alkylation. The reagents used to conduct the reactions are numerous. Diazomethane is a very efficient methylation reagent but explosive and toxic. Methyl iodide also ensures rapid and efficient methylation. Benzyl bromide can be used directly in water but derivatisation yield is low and reproducibility is poor. Butyl chloroformate and dimethyl sulfite can also be used for derivatisation in water, and acetic anhydride can be used for in-situ derivatisation of phenolic herbicides. For increasing selectivity of GC detection pentafluorobenzyl bromide (for ECD) and (2-cyanethyl)dimethyl(diethylamino)silane (for NPD) have been applied. Very characteristic ions are produced in mass spectra if silyl groups are introduced, e.g. by using bis(trimethylsilyl)trifluoroacetamide. Tetramethylammonium, trimethylphenylammonium, tetraalkylammonium, and trimethylsulfonium hydroxides and salts can by used for derivatisation at elevated temperature in the GC injection port. Extractive alkylation is relatively efficient if tetraalkylammonium salts with long chain alkyl groups are used.     

The Extraction of Polycyclic Aromatic Hydrocarbons from Atmospheric Particulate Matter Samples by Accelerated Solvent Extraction (ASE)

Abstract

The Accelerated solvent extraction (ASE) of PAHs (23 2- to 6-ring species) spiked onto glass fibre filters (GFFs) was studied as a function of variable extraction solvents, pressure, temperature and extraction times. Acceptable recoveries (85% ± 15%) were obtained for certain combinations of conditions and a tentative method (1500 psi, 150°C, 70:30 hexane:acetone mixture, 7 min heat-up time, 5 min static extraction time, 60% flush volume, 2 static cycles was selected for further testing. However, this method did not prove as effective as the traditional Soxhlet method of extraction when these parameters were used to extract native PAHs from ambient atmospheric particulate matter collected on a GFF by Integrated Atmospheric Deposition Network (IADN) sampling protocols. The extraction recovery study for spiked GFFs was repeated using slightly different extraction conditions: 2000 psi, 100°C, 70:30 hexane:acetone, 5 min heat-up time, 5 min static extraction time, 150% flush volume, 3 static cycles. When this method was applied to the extraction of native PAHs from ambient atmospheric particulate matter collected on GFFs, the results showed equivalent or better recoveries to that of the Soxhlet method. The total time of extraction was 25 min requiring only 30 mL of solvent. This ASE method is presently used to quantitatively determine PAHs in IADN particle-phase samples.     

Rapid and easy quantification of elemental sulphur in aqueous samples from biological reactors: the turbidimetric method revisited

Recent developments in wastewater treatment have led to a renewed interest to obtain elemental sulphur (S°) as a by-product from bioreactors. However, practical studies are limited by the gap of adequate analytical techniques for its determination. This paper provides a statistical study and matrix effect evaluation of an adapted spectrophotometric method for routine S° analyses in aqueous samples, based on a methodology previously described by Hart (1961). Four complex matrices were tested: domestic sewage and effluent samples from three different bioreactors. Tested performance criteria included linearity, matrix effect, limit of detection and quantification and S° recovery. Results were linear (R² = 0.99994) in the studied range (5 to 100 mg S° L^?1) and no matrix effect was observed. The accuracy was based on recovery values that varied from 100% to 106%. The colloidal S° separation and extraction protocol was also considered suitable for aqueous samples, reaching more than 99.0% of S° recovery.     

Double-imprinted polymer based on cross-linked poly(vinylimidazole–trimethylolpropane trimethacrylate) in solid phase extraction for determination of lead from wastewater samples by UV–vis spectrophotometry

The monitoring of the heavy metal pollution in wastewater is increasingly becoming a crucial global issue since they tend to accumulate in food chains and can cause many biological abnormalities. In this work, it was developed a novel lead ion-imprinted polymer (IIP) using sodium dodecyl sulphate (SDS) as a second template to be used as adsorbent in solid phase extraction (SPE) for determination of lead from wastewater samples by UV–vis spectrophotometry. The polymer called IIP–SDS was synthesised by a double-imprinting process with lead (template) and SDS (template). IIP–SDS was characterised by infrared spectroscopy Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. IIP–SDS showed good recovery for lead (around 82.0%), while the IIP (only lead as template) was 72.2% and non-IIP was 44.9%. Thus, the double-imprinting process for the preconcentration of Pb²⁺ proved to be a more adequate methodology than IIP with a single template. The optimised parameters of sample preparation were washing solvent (2.0 mL of tetrahydrofuran), type and volume of eluent (5 mL of 1 mol L^?1 hydrochloric acid), sample amount (30 mL of water spiked with 10.0 µg mL^?1), amount of IIP–SDS (400 mg) and sample pH (pH = 4.5). Linearity ranged from 10 to 125 µg L^?1 with r > 0.992. The limit of detection and quantification were 6.3 and 10 µg L^?1, respectively. The precision (relative standard deviation, %) and accuracy (relative error, %) were lower than 15%. Finally, IIP–SDS may be an alternative and effective adsorbent for SPE procedures in monitoring of wastewater samples.     

元素周期表实物展窗:元素化学性质的形象化展示

以展示元素单质、化合物和矿物样品为形式制作的元素周期表实物展窗能够形象化地展示各种元素的化学特性。元素周期表实物展窗将实物样品展示度与样品背后的化学内涵相结合,可以展示元素和化学学科的风貌。     

Electrochemical Determination of Lead(II) in Environmental Waters Using a Sulfydryl Modified Covalent Organic Framework by Square Wave Anodic Stripping Voltammetry (SWASV)

A novel sulfhydryl-modified covalent organic framework was designed for the selective determination of lead(II) using square wave anodic stripping voltammetry. The introduction of sulfhydryl groups enhanced the selectivity and sensitivity of the covalent organic framework for analytes. The sulfhydryl-modified covalent organic framework was characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. Under the optimized conditions, a sulfhydryl-modified covalent organic framework/gold electrode was successfully used for the determination of lead(II) in water samples. The newly developed square wave anodic stripping voltammetry method exhibited wide linearity (0.05 to 20?ng mL^?1, r?=?0.991), a low limit of detection (0.015?ng mL^?1) and good precision, with a relative standard deviation values <5.1%. The limit of detection was lower than 10?ng mL^?1, the level of lead(II) in drinking water permitted by the World Health Organization. The recoveries of three spiked samples ranged from 90.0% to 104.0%, with relative standard deviations <4.9%. Satisfactory reproducibility and good repeatability demonstrated that the newly developed method is very suitable for the detection of lead(II) in real water samples, with significant advantages over existing methods.     

胶体金修饰电极测定鱼样中组胺的方法研究

基于胶体金修饰的玻碳电极,利用电流～时间曲线法建立了一种简便、灵敏的组胺检测方法。优化了底液的pH值和组胺的电化学测试方法及条件,考察了修饰电极的电化学性能。结果表明,组胺在胶体金修饰电极上的响应电流(-I,μA)与其浓度(c,μmol/L)在0. 1～64μmol/L范围内呈良好的线性关系,检出限为0. 033μmol/L,在带鱼和黄花鱼样品中的加标回收率分别为94. 4%～106%、91. 8%～106%,相对标准偏差分别为3. 2%、2. 5%。该法操作简单、检测速度快、成本低,适用于带鱼和黄花鱼等鱼样中组胺的测定。     

Field‐amplified sample injection combined with capillary electrophoresis for the simultaneous determination of five chlorophenols in water samples

A sensitive method of CZE‐ultraviolet (UV) detection based on the on‐line preconcentration strategy of field‐amplified sample injection (FASI) was developed for the simultaneous determination of five kinds of chlorophenols (CPs) namely 4‐chlorophenol (4‐CP), 2‐chlorophenol (2‐CP), 2,4‐dichlorophenol (2,4‐DCP), 2,4,6‐trichlorophenol (2,4,6‐TCP), and 2,6‐dichlorophenol (2,6‐DCP) in water samples. Several parameters affecting CZE and FASI conditions were systematically investigated. Under the optimal conditions, sensitivity enhancement factors for 4‐CP, 2‐CP, 2,4‐DCP, 2,4,6‐TCP, and 2,6‐DCP were 9, 27, 35, 43, and 43 folds, respectively, compared with the direct CZE, and the baseline separation was achieved within 5 min. Then, the developed FASI‐CZE‐UV method was applied to tap and lake water samples for the five CPs determination. The LODs (S/N = 3) were 0.0018–0.019 µg/mL and 0.0089–0.029 µg/mL in tap water and lake water, respectively. The values of LOQs in tap water (0.006–0.0074 µg/mL) were much lower than the maximum permissible concentrations of 2,4,6‐TCP, 2,4‐DCP, and 2‐CP in drinking water stipulated by World Health Organization (WHO) namely 0.3, 0.04, and 0.01 µg/mL, respectively, and thereby the method was suitable to detect the CPs according to WHO guidelines. Furthermore, the method attained high recoveries in the range of 83.0–119.0% at three spiking levels of five CPs in the two types of water samples, with relative standard deviations of 0.37–8.58%. The developed method was proved to be a simple, sensitive, highly automated, and efficient alternative to CPs determination in real water samples.