The present study describes an effect of reaction condition of pre-column derivatization of alkylphenols (APs): bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), and isomers of 4-nonylphenol (iso-NP) with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride, DNSC) on their LC-ESI-MS/MS determination in water samples. Chemical derivatization improves the sensitivity and selectivity of LC-MS/MS analysis. In principle, alkylphenols can be analyzed by LC-MS/MS without derivatization. However, pre-column derivatization of APs increases the sensitivity up to 1000 times in comparison with the analysis of underivatized alkylphenols. Reaction conditions affecting formation of the DNSC-derivatives, such as various solvent, reaction temperature, reaction time, DNSC concentration and pH values were tested. The most suitable conditions, in terms of achieving a high sensitivity, resulting from this study are: acetonitrile as reaction solvent, 60 min as reaction time, 60 °C as reaction temperature, pH values 10.5, 0.5 mg mL(-1) as DNSC concentration. Calibration curves are linear at least in the range of 1-1000 ng mL(-1), limits of detection (LOD) and limits of quantification (LOQ) ranging from 0.02 to 0.25 pg/injection and from 0.08 to 0.83 pg/injection, respectively. The improved procedure was successfully applied for the analysis of APs and BPA in real water samples. The median concentration of BPA and iso-NP obtained in bottled waters was 4.7 ng L(-1) and 33.5 ng L(-1), respectively. The median concentration of 4-t-OP was 1.3 ng L(-1.)

• Klíčová slova
• Alkylphenols, Chemical derivatization of alkylphenols, Electrospray ionization, Liquid chromatography, Tandem mass spectrometry,
• MeSH
• benzhydrylové sloučeniny analýza   MeSH
• chemické látky znečišťující vodu analýza   MeSH
• chromatografie kapalinová metody   MeSH
• fenoly analýza   MeSH
• indikátory a reagencie MeSH
• limita detekce MeSH
• pitná voda analýza   MeSH
• sloučeniny dansylu chemie   MeSH
• tandemová hmotnostní spektrometrie metody   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• 4-nonylphenol MeSH Prohlížeč
• 4-octylphenol MeSH Prohlížeč
• 4-tert-octylphenol MeSH Prohlížeč
• benzhydrylové sloučeniny MeSH
• bisphenol A MeSH Prohlížeč
• chemické látky znečišťující vodu MeSH
• dansyl chloride MeSH Prohlížeč
• fenoly MeSH
• indikátory a reagencie MeSH
• nonylphenol MeSH Prohlížeč
• pitná voda MeSH
• sloučeniny dansylu MeSH

Alkylphenols and their precursors, alkylphenol etoxylates, are a group of manmade chemicals used mainly as surfactants in domestic and industrial applications worldwide. It has been well established that they have endocrine disruption activity, hepatotoxic, genotoxic and other negative effects on animal and human health. In spite of the effort to reduce their use, they persist in the environment not only in industrial but also in remote regions, and were detected in the variety of natural matrices including air, water, soil as well as food products, and human blood and urine worldwide. This article summarizes their occurrence, fate in natural conditions, and toxicity including mode of action. A subject of our concern was the aquatic environment as the most important reservoir and target of their deleterious impact.

• MeSH
• chemické látky znečišťující vodu chemie   MeSH
• fenoly chemie   MeSH
• molekulární struktura MeSH
• odpad tekutý - odstraňování MeSH
• průmyslový odpad MeSH
• zvířata MeSH
• Check Tag
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH
• Názvy látek
• chemické látky znečišťující vodu MeSH
• fenoly MeSH
• průmyslový odpad MeSH

BACKGROUND: Alkylphenols are water contaminants of strong endocrine disruptive potential. Sample preparation is generally imperative to improve sensitivity and minimize matrix effects. Dispersive solid phase extraction is a powerful alternative to cartridge-based sorbent extraction omitting backpressure problems and reducing procedural time. Herein, solvent-dissolvable sorbents offer the advantages of easy and cost-efficient production, efficiency, and full analyte recovery, while eluates can be directly submitted to instrumental determination. Despite the potential to reduce environmental impact and enhance reproducibility, there is a lack of automation attempts. RESULTS: A fully automated solvent-assisted dispersive solid phase extraction method was developed for selected alkylphenols based on the technique Lab-In-Syringe. The void of automatic bidirectional syringe pump was used as mixing and extraction vessel. The iron(III) thenoyltrifluoroacetonate complex was used as novel dissolvable sorbent. 40 μL complex solution was dispersed in the sample, leading to the precipitation of 0.4 mg sorbent. Extraction occurred within 40 s and was accelerated by in-syringe magnetic stirring. The sorbent was retained on a melamine foam packing in the syringe inlet, dissolved in a methanolic solution of ascorbic acid, and injected into online-coupled HPLC. Linear working ranges were achieved from 1 to 1000 μg/L with sub-ppb detection limits and accuracies ranging from 98.3 to 110 %. SIGNIFICANCE: In this work, we explored for the first time automated in-syringe automated dispersive SPE based on a dissolvable sorbent. Parallel operation of sample pretreatment and separation enabled throughputs of 4.5/h with typically <5 % RSD and preconcentrations of 16.4-21.2. AGREE greenness evaluation yielded a score of 0.59.

• Klíčová slova
• Alkylphenols, High performance liquid chromatography, Iron(III) thenoyltrifluoroacetonate complex, Lab-in-syringe automation, Solvent-assisted dispersive solid phase Extraction,
• MeSH
• automatizace MeSH
• chemické látky znečišťující vodu analýza   izolace a purifikace   MeSH
• chromatografie kapalinová metody   MeSH
• fenoly * izolace a purifikace   analýza   chemie   MeSH
• injekční stříkačky * MeSH
• limita detekce MeSH
• mikroextrakce na pevné fázi * metody   MeSH
• vysokoúčinná kapalinová chromatografie MeSH
• železité sloučeniny chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• chemické látky znečišťující vodu MeSH
• fenoly * MeSH
• železité sloučeniny MeSH

Stagnant water bodies have generally received little attention regarding the presence of endocrine disruptive compounds, although they can integrate diverse pollutants from multiple different sources. Many compounds of anthropogenic as well as natural origin can contribute to the overall estrogenicity of surface waters and some of them can exhibit adverse effects on aquatic biota even in very low concentrations. This study focused on freshwater ponds and reservoirs affected by water blooms and determined the estrogenic activity of water by in vitro bioassay as well as concentrations of several important groups of estrogenic compounds (estrogenic hormones, alkylphenols, and phytoestrogens) by LC-MS/MS analyses. Estrogenic hormones were found at concentrations up to 7.1 ng.L-1, similarly to flavonoids, whose concentrations did not exceed 12.5 ng.L-1. Among alkylphenols, only bisphenol A and 4-tert-octylphenol were detected in levels reaching 100 ng.L-1 at maximum. Estrogenic activity of water samples varied from below the quantification limit to 1.95 ng.L-1. There does not seem to be any general causal link of the massive phytoplankton occurrence with the estrogenicity of water or concentration of phytoestrogens, since they showed no direct relationship with the phytoplankton abundance or composition across sites. The contribution of the analysed compounds to the estrogenic activity was calculated in three scenarios. In minimum scenario, just the compounds above quantification limit (LOQ) were taken into account and for most samples, only minor part (<6%) of the biological activity could be explained. In the mean and maximum scenarios, we included also compounds below LOQ into the calculations at the level of LOQ/2 and LOQ, respectively. In these cases, a considerable part of the estrogenic activity could be attributed to the possible presence of steroid estrogens below LOQ. However, for the samples with estrogenic activity greater than 1 ng.L-1, more than 50% of the estrogenic activity remained unexplained even in the maximum scenario. Probably other compounds or possible interactions between individual substances cause the estrogenic activity in these types of water bodies and in this case, the results of LC-MS/MS analyses cannot sufficiently predict the biological effects. A complex approach including bioassays is needed when assessing the estrogenicity of these types of surface waters.

• Klíčová slova
• Alkylphenols, Estrogenicity, Estrogens, Flavonoids, Surface water,
• MeSH
• chemické látky znečišťující vodu analýza   metabolismus   MeSH
• chromatografie kapalinová MeSH
• endokrinní disruptory analýza   metabolismus   MeSH
• estrogeny analýza   metabolismus   MeSH
• fytoplankton chemie   metabolismus   MeSH
• sladká voda chemie   MeSH
• tandemová hmotnostní spektrometrie MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• chemické látky znečišťující vodu MeSH
• endokrinní disruptory MeSH
• estrogeny MeSH

Aquatic biotests are important tools targeting various effects in ecotoxicology, including endocrine disruption. Unintentional exposure of bioassay organisms to endocrine disruptors during cultivation or testing may interfere with assessed endpoints. We illustrate this issue on the example of laboratory phytoplankton cultivation, where possible sources of estrogenic compounds have been revealed. Fifty-four blank samples (water and fresh or cultivated growth media) were assessed by in vitro biotests for their estrogenicity, and major known estrogens originating from plastic materials, bisphenol A and alkylphenols, were analyzed in selected samples. The samples of freshly prepared growth medium elicited weak estrogenic response in bioassays and some samples of the aerated media caused responses even above the 50% of maximum of the reference compound (17β-estradiol, E2), while the samples from diverse laboratory water sources did not show significant estrogenic activity. The results identified substances contained in the growth medium as minor but reproducible contributors to estrogenicity in the cultivations. Sporadic but significant effects (up to 4.9 ng E2 equivalent/L) can be ascribed to compounds released from the used plastic materials during aeration of the cultivations. The potential sources of unintentional exposure to estrogenic compounds need to be considered in aquatic cultivations and biotests, since they could impact their outcomes, especially in arrangements assessing reproduction or whole life cycle biotests, or production of bioactive compounds by phytoplankton. The findings emphasize the necessity to assess all relevant blanks, ideally by sensitive high throughput in vitro assays that reflect also unknown pollutants and minimize all potential sources of background contamination. In vitro assays show very good applicability for this purpose since they enable to screen for any background estrogenicity of the used media and materials without the need of analyzing individual compounds, which often might not be known.

• Klíčová slova
• Aeration, Alkylphenols, Aquatic medium, Bisphenol A, Estrogenicity,
• MeSH
• chemické látky znečišťující vodu * toxicita   MeSH
• endokrinní disruptory * analýza   toxicita   MeSH
• estrogeny analýza   toxicita   MeSH
• fytoplankton MeSH
• monitorování životního prostředí metody   MeSH
• plastické hmoty MeSH
• voda MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• chemické látky znečišťující vodu * MeSH
• endokrinní disruptory * MeSH
• estrogeny MeSH
• plastické hmoty MeSH
• voda MeSH

Lignin can be converted into useful precursors of fuels and fine chemicals by thermochemical conversion followed by catalytic hydrogenation using metal catalysts at severe reaction conditions. Thus, mild hydrogenation would significantly improve the sustainability of lignin valorization. Here, hydrogenation of phenols, alkylphenols, and methoxyphenols was achieved at mild reaction conditions (70 °C and atmospheric pressure) via H-transfer hydrogenation over Raney-Ni catalyst in 2-propanol and 2-butanol solvents. The transfer hydrogenation was feasible at the mild conditions, but the complexity of the reactant greatly decreased or even completely suppressed its reactivity. The position of the functional group (o-, m-, p-position) had a great effect on the reactivity of phenols. Moreover, 2-butanol enhanced the conversion of phenols in comparison with 2-propanol. When comparing classic hydrogenation with H-transfer hydrogenation in presence of external H2 , it was found that external H2 not only regenerated H-donor solvent and ensured stable performance but also increased conversion of phenols and alkylphenols. On the other hand, the absence of external H2 boosted the conversion of methoxy phenols. Finally, phenols extracted from a pyrolysis oil aqueous phase were hydrogenated. The conversion of phenols was greatly affected by competitive adsorption of different compounds present in the reaction mixture. External H2 promoted hydrogenation of the complex reaction mixture and prevented condensation of the reactive species in contrast to the H-transfer hydrogenation.

• Klíčová slova
• Raney-Ni, biomass conversion, deoxygenation, hydrogenation, phenols,
• MeSH
• fenoly * MeSH
• katalýza MeSH
• lignin * MeSH
• regenerace MeSH
• rozpouštědla MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• fenoly * MeSH
• lignin * MeSH
• rozpouštědla MeSH

Development of direct competitive enzyme-linked immunoadsorbent assays (ELISAs) based on polyclonal and monoclonal antibodies raised against 4-n-alkylphenol hapten mimics is described. A strong tendency to recognize 4-nonylphenol (NP) and 4-octylphenol (OP) as a total analyte amount was indicated by cross-reactivity pattern established for two polyclonal antibodies. These antibodies were employed for development of class-selective assays exhibiting IC(50) values around 40 microg.L(-1) for technical 4-NP. Specificity of the monoclonal antibody 4H6 and additional two polyclonal antibodies allowed sensitive detection of linear long-chain forms of 4-n-alkylphenols (4-n-AP). The assays incorporating these antibodies offer a potential for detecting the minor fraction of NP/OP isomer spectrum having IC(50) = 11.5 microg.L(-1) for 4-n-NP. No cross-reactivity interference was indicated for linear alkylbenzene sulfonates and phenolic compounds. To interpret the measured data in terms of analytical equivalents, a reliable relationship between the assay responses and AP content of contaminated samples should be verified and validated.

• MeSH
• ELISA metody   MeSH
• fenoly analýza   chemie   MeSH
• králíci MeSH
• myši MeSH
• zkřížené reakce MeSH
• zvířata MeSH
• Check Tag
• králíci MeSH
• myši MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• fenoly MeSH
• nonylphenol MeSH Prohlížeč
• octylphenol MeSH Prohlížeč

The method employing molecularly imprinted polymers for the extraction and clean up of endocrine-disrupting compounds (estrogens, bisphenol A, and alkylphenols) from water and sediment is described. The identical extraction/clean-up and LC-MS/MS condition were used for the analysis of both types of samples. The method showed high recoveries ranging from 90 to 99% with excellent precision (intrabatch: 3.6-9.3%; interbatch: 5.6-11.4% for water; intrabatch: 4.3-8.5%; interbatch: 6.1-9.6% for sediment). The LOD was in the range of 0.7-1.9 ng/L and 0.3-0.6 ng/g for water and sediment, respectively. Overall extraction on molecularly imprinted polymers substantially enhanced sample clean-up. The difference in efficiency of clean-up was particularly pronounced when a large sample volume/weight was extracted and analyzed. Finally, the method was successfully applied for the analysis of 20 water and sediment samples.

• MeSH
• chemické látky znečišťující vodu analýza   izolace a purifikace   MeSH
• endokrinní disruptory analýza   izolace a purifikace   MeSH
• extrakce na pevné fázi přístrojové vybavení   metody   MeSH
• geologické sedimenty analýza   MeSH
• molekulový imprinting MeSH
• polymery chemická syntéza   chemie   MeSH
• tandemová hmotnostní spektrometrie metody   MeSH
• vysokoúčinná kapalinová chromatografie metody   MeSH
• Publikační typ
• časopisecké články MeSH
• hodnotící studie MeSH
• práce podpořená grantem MeSH
• Názvy látek
• chemické látky znečišťující vodu MeSH
• endokrinní disruptory MeSH
• polymery MeSH

Lignins are the most abundant biopolymers that consist of aromatic units. Lignins are obtained by fractionation of lignocellulose in the form of "technical lignins". The depolymerization (conversion) of lignin and the treatment of depolymerized lignin are challenging processes due to the complexity and resistance of lignins. Progress toward mild work-up of lignins has been discussed in numerous reviews. The next step in the valorization of lignin is the conversion of lignin-based monomers, which are limited in number, into a wider range of bulk and fine chemicals. These reactions may need chemicals, catalysts, solvents, or energy from fossil resources. This is counterintuitive to green, sustainable chemistry. Therefore, in this review, we focus on biocatalyzed reactions of lignin monomers, e.g., vanillin, vanillic acid, syringaldehyde, guaiacols, (iso)eugenol, ferulic acid, p-coumaric acid, and alkylphenols. For each monomer, its production from lignin or lignocellulose is summarized, and, mainly, its biotransformations that provide useful chemicals are discussed. The technological maturity of these processes is characterized based on, e.g., scale, volumetric productivities, or isolated yields. The biocatalyzed reactions are compared with their chemically catalyzed counterparts if the latter are available.

• Klíčová slova
• alkyl phenols, biotransformation, eugenol, ferulic acid, guaiacol, isoeugenol, lignin, p-coumaric acid, valorization, vanillin,
• MeSH
• fenoly * chemie   MeSH
• katalýza MeSH
• lignin * chemie   MeSH
• rozpouštědla chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH
• Názvy látek
• fenoly * MeSH
• lignin * MeSH
• rozpouštědla MeSH

Biodegradation of phenolic compounds is a promising alternative to physical and chemical methods used to remove these toxic pollutants from the environment. The ability of various microorganisms to metabolize phenol and its derivatives (alkylphenols, nitrophenols and halogenated derivatives) has therefore been intensively studied. Knowledge of the enzymes catalyzing the individual reactions, the genes encoding these enzymes and the regulatory mechanisms involved in the expression of the respective genes in bacteria serves as a basis for the development of more efficient degraders of phenols via genetic engineering methods. Engineered bacteria which efficiently degrade phenolic compounds were constructed in laboratories using various approaches such as cloning the catabolic genes in multicopy plasmids, the introduction of heterologous genes or broadening the substrate range of key enzymes by mutagenesis. Efforts to apply the engineered strains in in situ bioremediation are problematic, since engineered strains often do not compete successfully with indigenous microorganisms. New efficient degraders of phenolic compounds may be obtained by complex approaches at the organism level, such as genome shuffling or adaptive evolution. The application of these engineered bacteria for bioremediation will require even more complex analysis of both the biological characteristics of the degraders and the physico-chemical conditions at the polluted sites.

• Klíčová slova
• Adaptive evolution, Genome shuffling, In situ bioremediation, Phenol biodegradation, Phenolic compounds, Synthetic biology,
• MeSH
• Bacteria enzymologie   genetika   metabolismus   MeSH
• bakteriální geny genetika   MeSH
• bakteriální proteiny genetika   MeSH
• biodegradace * MeSH
• DNA shuffling MeSH
• fenoly chemie   metabolismus   MeSH
• genetické inženýrství metody   MeSH
• nitrofenoly metabolismus   MeSH
• regulace genové exprese u bakterií genetika   MeSH
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH
• Názvy látek
• bakteriální proteiny MeSH
• fenoly MeSH
• nitrofenoly MeSH