地质环境样品中挥发酚分析现状与进展

挥发酚被列为环境优先控制的有机污染物,已成为评价环境污染的重要指标之一。该文简述了挥发酚的化学性质及地质环境来源,概括了国内外挥发酚测定的相关标准方法,从样品预处理技术和检测技术两方面综述了近年来地质环境样品中挥发酚分析的研究现状。重点对溶剂萃取、蒸馏、固相萃取、固相微萃取和吹扫捕集等样品预处理技术,以及4-氨基安替比林分光光度法、紫外和荧光分光光度法、溴化容量法、气相色谱法、液相色谱法和酚生物传感器法等技术在地质环境样品中挥发酚分析上的应用进行了较为全面的总结,并对其未来的发展趋势进行了展望,为进一步研究挥发酚的分析技术及其环境应用提供参考。     

Gas chromatography/mass spectrometry versus liquid chromatography/fluorescence detection in the analysis of phenols in mainstream cigarette smoke

A new gas chromatographic/mass spectrometric (GC/MS) technique for the analysis of hydroxybenzenes (phenols) in mainstream cigarette smoke has been developed. The technique allows the measurement of 24 individual compounds, and the sum of a few other alkyl-dihydroxybenzenes. A critical evaluation is done for the new technique and for an established high-performance liquid chromatographic (HPLC) technique reported in the literature for the analysis of hydroxybenzenes in cigarette smoke, which uses fluorescence detection. Compared with the HPLC procedure, the new technique has similar accuracy, precision, and robustness. However, the GC/MS procedure allows for a larger number of phenols to be analyzed simultaneously, and eliminates any potential interference that may appear in the HPLC method. Using the GC/MS analysis, it was found that besides the main phenols typically measured in mainstream cigarette smoke such as phenol, catechol, hydroquinone, and cresols, many other phenols that are present at lower levels can be quantitated in mainstream cigarette smoke.     

Retention effects of oxidized polyphenols during analytical extraction of phenolic compounds of virgin olive oil

The hydrophilic extract of virgin olive oil contains several phenolic compounds such as simple phenols, lignans, and secoiridoids that have been widely studied in recent years. Interest in the hydrophilic extract has also been extended to the fraction of oxidized phenols that form during storage as a consequence of oxidative stress. The present investigation compares the two most commonly used extraction methods, namely liquid-liquid extraction and SPE, on fresh virgin olive oil and that kept at different temperatures in the presence of oxygen to promote the formation of oxidative products. The selective retention of these natural and oxidized phenolic compounds in relation to the extraction method was assessed. Quantification of eight identified phenolic molecules and 11 unknown peaks was performed by HPLC-DAD/MSD.     

Magnetic Titanium Dioxide Nanocomposites for Surface‐Enhanced Resonance Raman Spectroscopic Determination and Degradation of Toxic Anilines and Phenols

Mesoporous M‐TiO₂ NCs, functionalized by PATP, can capture toxic anilines and phenols by azo coupling. Loading these nanodevices with Ag NPs offers the possibility for a sensitive quantitative determination of target compounds by SERRS spectroscopy, which allows multiplex detection because of the specific vibrational fingerprints. Sensitivity and selectivity can be further enhanced by concentrating the hybrid particles by an external magnet and compound‐specific binding (anilines versus phenols). The bound toxic compounds can be degraded by TiO₂‐assisted photocatalysis after removal of the loaded hybrid particles from the sample solution with an external magnet. The degradation process can be enhanced in the presence of plasmonic Ag nanostructures.     

Tethering for Selective Synthesis of 2,2′‐Biphenols: The Acetal Method

2,2'‐Biphenols are a large and diverse group of compounds with exceptional properties both as ligands and bioactive agents. Traditional methods for their synthesis by oxidative dimerisation are often problematic and lead to mixtures of ortho‐ and para‐connected regioisomers. To compound these issues, an intermolecular dimerisation strategy is often inappropriate for the synthesis of heterodimers. The ‘acetal method’ provides a solution for these problems: stepwise tethering of two monomeric phenols enables heterodimer synthesis, enforces ortho regioselectivity and allows relatively facile and selective intramolecular reactions to take place. The resulting dibenzo[1,3]dioxepines have been analysed by quantum chemical calculations to obtain information about the activation barrier for ring flip between the enantiomers. Hydrolytic removal of the dioxepine acetal unit revealed the 2,2′‐biphenol target.     

A solid-phase fluorescent biosensor for the determination of phenolic compounds and peroxides in samples with complex matrices

A solid-phase fluorescent biosensor for the determination of phenolic compounds (simple substituted phenols and catecholamines) and peroxides has been developed. The biosensor has a simple construction and the analytical signal is measured directly in a biosensitive layer {peroxidase-chitosan} on the sensor surface. This approach allowed analyzing samples with complex matrices (including water-insoluble samples and nontransparent solutions) without their preliminary pretreatment. Two novel fluorescent indicator reactions for the determination of the above-mentioned analytes in wide concentration ranges (from nmol l^?1 to mm l^?1) which provided an analytical signal registration on a solid phase were proposed. The developed sensor was applied successfully for the analysis of urine, cosmetics, pharmaceuticals preparations, etc.     

Simultaneous Determination of Epinephrine and Dopamine by Using Candida tropicalis Yeast Cells Immobilized in a Carbon Paste Electrode Modified with Single Wall Carbon Nanotube

A new electrochemical microbial biosensor system based on Candida tropicalis was developed for the fast detecting of dopamine and epinephrine. Candida tropicalis was immobilized in a carbon paste electrode (CPE) with single wall carbon nanotube (SWCNT). Immobilized cells were used as a origin of the polyphenol oxidase (PPO) to develop voltammetric epinephrine and dopamine biosensor. Voltammetric determination of phenolic compounds such as epinephrine and dopamine a simple technique which is available. Direct oxidation of phenols can be used, but the oxidation potentials of this compounds are similar and they can not be detected distinctively. Another possibility is the use of biosensors based on the polyphenol oxidase (tyrosinase) enzyme that oxidizes the phenolic compounds into their related quinones. By this way, phenolic compounds are epinephrine and dopamine which were used in this study as well detected at different potentials. In this study differential pulse voltammetry and amperometry techniques were used for the determination of dopamine and epinephrine. The effect of varying the amounts of SWCNT and the response of microorganism to epinephrine was investigated to find the optimum composition of the sensor. The effects of pH and temperature were also examined. Increases in biosensor responses obtained by amperometric measurements were linearly related to dopamine concentrations between 0.025 and 0.25 mM and epinephrine concentrations between 0.01 and 0.1 mM. Limits of detection of the biosensor for dopamine and epinephrine were calculated to be 0.008 and 0.0023 mM, respectively. Finally, proposed system was applied to epinephrine and dopamine analysis in pharmaceutical drugs and synthetic serum and the results were compared with LC MS MS method.     

Enzyme entrapped nanoporous scaffolds formed through flow-induced gelation in a microfluidic filter device for sensitive biosensing of organophosphorus compounds

A novel and versatile processing method was developed for the formation of gel scaffolds with in situ AChE-AuNPs immobilization for biosensing of organophosphorus compounds. The biosensor designed by our new approach shows high sensitivity, selectivity and reactivation efficiency. This flow-induced immobilization technique opens up new pathways for designing a simple, fast, biocompatible, and cost-effective process for enhanced sensor performance and on-site monitoring of a variety of toxic organophosphorus compounds.     

Studies towards an amperometric phosphate ion biosensor for urine and water analysis

An amperometric biosensor for phosphate ion is described that is based on a cobalt phthalocyanine modified screen-printed carbon electrode (CoPC-SPCE). The biosensor operation is based on the enzyme pyruvate oxidase (PyOd) which catalyses the oxidative decarboxylation of pyruvate, in the presence of inorganic phosphate and O₂, to acetyl phosphate, hydrogen peroxide (H₂O₂) and CO₂. The transducer allows the electrocatalytic oxidation of H₂O₂ in order to generate the analytical signal. The enzyme was immobilised onto the CoPC-SPCE using a sandwich format. The inner membrane was formed in situ by depositing an acetone solution containing cellulose acetate first onto the transducer surface. The enzyme and cofactors were then deposited onto this layer and allowed to dry; finally a second aliquot of the cellulose acetate solution was deposited onto the enzyme layer and allowed to dry. The biosensor was characterised by amperometry in stirred solution to produce current-voltage curves and for calibration studies. From these it was deduced that a reliable electrocatalytic response was obtained for phosphate ion; an operating potential of +0.4 V was selected for the analysis of urine samples. The precision of the response for urine analysis and recovery data for potable water suggests that the biosensor could have applications in clinical and environmental monitoring.     

Amperometric detection of mono- and diphenols at Cerrena unicolor laccase-modified graphite electrode: correlation between sensitivity and substrate structure

Graphite electrode modified with laccase from Cerrena unicolor served as a biosensor for detection of 30 phenolic compounds with different structures. Some correlations of the sensor response to the structures of substrates are discussed. This biosensor responded to: (i) nanomolar concentrations of some of the selected phenolic compounds, e.g., 2,6-dimethoxyphenol, coniferyl alcohol, caffeic acid, DOPAC and hydroquinone, (ii) micromolar concentrations, e.g., ferulic acid, syringic acid, dopamine, 3,4-dihydroxybenzoic acid and dl-noradrenaline, and (iii) millimolar concentrations in the case of phenol and 4-hydroxybenzaldehyde. Among the ortho- or para-substituted phenols, the sensitivity of the C. unicolor laccase-modified electrode increased in the following order H, CH(3), OH, OCH(3) and NH(3)(+) but in the case of para-substituted phenols, the K(m)(app) values were lower. The sensitivity of the laccase electrode increased with an additional OH group in para-substituted phenols. In the case of the selected compounds, kinetic data from electrochemical flow injection system were compared with those obtained from experiments in solution.     

Determination of formaldehyde and cyanide ion in human nasal discharge by using simple spectrophotometric methods

Environmental tobacco smoke (ETS) contains many toxic compounds which include substances classified as aldehydes (e.g. formaldehyde) and inorganic substances such as cyanide ions. The information on the determination of these compounds in water is available, but the monitoring data on the level of these substances in human body fluids are still lacking. In this work the procedure for determining cyanide ions and formaldehyde in samples of human nasal discharge by simple spectrophotometric technique is presented.     

Feasibility of application of conductometric biosensor based on acetylcholinesterase for the inhibitory analysis of toxic compounds of different nature

This study was aimed at the development of a conductometric biosensor based on acetylcholinesterase considering the feasibility of its application for the inhibitory analysis of various toxicants. In this paper, the optimum conditions for enzyme immobilization on the transducer surface are selected as well as the optimum concentration of substrate for inhibitory analysis. Sensitivity of the developed biosensor to different classes of toxic compounds (organophosphorus pesticides, heavy metal ions, surfactants, aflatoxin, glycoalkaloids) was tested. It is shown that the developed biosensor can be successfully used for the analysis of pesticides and mycotoxins, as well as for determination of total toxicity of the samples. A new method of biosensor analysis of toxic substances of different classes in complex multicomponent aqueous samples is proposed.     

Bromination of Some Aromatic Compounds with Potassium Bromide in the Presence of Benzyltriphenylphosphonium Peroxodisulfate

A simple, efficient, and mild method for selective bromination of some activated aromatic compounds using potassium bromide in the presence of benzyltriphenylphosphonium peroxodisulfate in nonaqueous solution is reported. The results obtained revealed good to excellent selectivity between ortho and para positions of phenols and methoxyarenes.     

Optimisation of stir bar sorptive extraction for the analysis of volatile phenols in wines

An easy, fast and reliable analytical method is proposed for the determination of the concentration of volatile phenols (ethyl- and vinylphenols) in wines. The novel stir bar sorptive extraction (SBSE) technique is employed, following a simple and fast procedure that allows 15 samples to be extracted simultaneously using very small sample volume. Extracts are desorbed in a thermodesorption system (TDS) coupled on-line to a gas chromatograph-mass spectrometry system. The SBSE offers better recovery and linear regression coefficient (r2) for the four volatile phenols than solid-phase extraction (SPE). The mass spectrometric detection in selected ion monitoring mode contributes to the lower detection limit and good sensibility obtained with this method.     

Silver‐Mediated Oxidative Trifluoromethylation of Phenols: Direct Synthesis of Aryl Trifluoromethyl Ethers

Aryl trifluoromethyl ethers (ArOCF₃) are prevalent in pharmaceuticals, agrochemicals, and materials. However, methods for the general and efficient synthesis of these compounds are extremely underdeveloped and limited. Herein, we describe a highly efficient and general procedure for the direct O‐trifluoromethylation of unprotected phenols through a silver‐mediated cross‐coupling reaction using CF₃SiMe₃ as the CF₃ source and exogenous oxidants. This novel oxidative trifluoromethylation provides access to a wide range of aryl trifluoromethyl ethers from simple phenols. The mild process was also applied to the late‐stage trifluoromethylation of a medicinally relevant compound.     

Elaboration of Urease Adsorption on Silicalite for Biosensor Creation

A possibility of efficient urease adsorption on silicalite for the purpose of biosensor creation was investigated. The procedure of urease adsorption on silicalite is notable for such advantages as simple and fast performance and non‐use of toxic or auxiliary compounds. Optimal conditions for modifying transducer surfaces with silicalite and subsequent urease adsorption on these surfaces were selected. The working parameters of the created biosensor were optimized. The developed biosensor with adsorbed urease was characterized by good intra‐reproducibility (RSD – 4.5 %), improved inter‐reproducibility (RSD of urea determination is 9 %) and operational stability (less than 10 % loss of activity after 10 days). Besides, the developed method for enzyme adsorption on silicalite was compared with the traditional methods of urease immobilization in biosensorics. Working conditions of the produced biosensor (pH and ionic strength) were shown to be close to those of the biosensor based on urease immobilized in GA vapor. For these reasons, it was concluded that the method of enzyme adsorption on silicalite is well‐suited for biosensor standardization aimed at its further manufacture.     

Rapid screening of alkylphenol exposure in fish bile using an enzymatic peroxidase biosensor

This article deals with the development and novel application of an amperometric peroxidase biosensor for monitoring fish exposure to petroleum-related discharges, in particular, to alkyl phenols (AP) using fish bile as the main sample material. The biosensor consisted of a screen-printed electrode coupled with peroxidase immobilized by glutaraldehyde cross-linking. The sensor was optimized with regards to factors such as immobilization procedures, substrate selectivity, and matrix effects. The biosensor was used for the analysis of fish bile samples from Atlantic cod (Gadus morhua L.) exposed in the laboratory during a 2 week period to different petroleum related compounds. The biosensor could distinguish between bile samples of fish exposed to water containing high concentrations (a mixture of C₄–C₇) to moderate levels (mainly C₀–C₅) of alkylphenols and that of the control group.     

Fructose-selective calorimetric biosensor in flow injection analysis

A highly selective, interference free biosensor for the measurement of fructose in real syrup samples was developed. The assay is based on the phosphorylation of d(−)fructose to fructose-6-phosphate by hexokinase and subsequent conversion of fructose-6-phosphate to fructose-1,6-biphosphate by fructose-6-phosphate-kinase. The heat liberated in the second reaction is monitored using an enzyme thermistor. The major advantages of this biosensor are rapid and selective measurement of fructose without the need to eliminate glucose and inexpensive FIA-based, mediator-free calorimetric measurement suitable for regular fructose analysis. This method was optimised for parameters, such as pH, ionic strength, interference, operational stability and shelf life. Good and reproducible linearity (0.5-6.0 mM) with a detection limit of 0.12 mM was obtained. Fructose determination in commercial syrup samples and spiked samples confirmed the reliability of this set-up and technique. The biosensor gave reproducible results with good overall stability for continuous measurements over a period of three months besides a useful shelf life of six months. The method could be used for routine fructose monitoring in food samples.     

Spectrophotometric bioanalytical flow-injection system for control of hemodialysis treatment

A spectrophotometric flow-injection analysis (FIA) system for monitoring clinical hemodialysis is demonstrated. The role of a dialysate urea detector incorporated in this bioanalytical system is played by an optical flow-through biosensor based on Prussian Blue film with chemically linked urease forming a monomolecular layer of the enzyme. This pH-enzyme optode-FIA system is useful for the selective determination of post-dialysate urea in the range of concentration corresponding to its level in real clinical samples (2-16 mmol l(-1)). This bioanalytical system allows the analysis of about 15 samples of spent dialysate per hour. The operational and storage stabilities of the applied biosensor are longer than 2 weeks and 2 months, respectively. Clinical evaluation of the bioanalytical system was performed.     

环境水质中酚类优先监测物的气相色谱法测定

以气相色谱法（ＧＣ）测定了环境水质中的重点酚类污染物。选择乙酸酐作衍生化试剂、甲苯为萃取剂,比较了不同的衍生ｐＨ条件,给出了氢火焰离子化检测器（ＦＩＤ）分离测定酚类污染物的精密度和检出限。方法简便实用,经５家实验室验证表明：适用于监测地表水和污水中的酚类物质。６种酚类优先监测物的检测限为０．６～７μｇ／Ｌ。