Studies of interactions between pesticides and target mammalian proteins are important steps toward understanding the pesticide's toxicity. Using calorimetric and spectroscopic methods, the interaction between triazole fungicide tebuconazole and human serum albumin has been investigated. The spectroscopic techniques showed that fluorescence quenching of human serum albumin by tebuconazole was the result of the formation of tebuconazole/human serum albumin complex with the static type as the dominant mechanism. The association constant was found to be 8.51 × 103 L/mol. The thermodynamic parameters were obtained as ΔH = -56.964 kJ/mol, ΔS = -115.98 J/mol·K. The main active interactions forming the tebuconazole/human serum albumin complex were identified as the interplay between hydrogen bonds and/or van der Waals forces, based on thermodynamic experiments. These binding modes were corroborated well by the predictions of molecular modeling. Hydrogen bonding of tebuconazole with Arg222, Ala215 and Ala291 of human serum albumin played a relevant role in binding. The conformation changes in secondary structure were characterized by circular dichroism and 3D fluorescence spectra.

• Klíčová slova
• human serum albumin, interaction, molecular modeling, spectroscopy, tebuconazole,
• MeSH
• diferenciální skenovací kalorimetrie MeSH
• fluorescenční spektrometrie MeSH
• fungicidy průmyslové farmakologie   MeSH
• ibuprofen farmakologie   MeSH
• ketoprofen farmakologie   MeSH
• lidé MeSH
• lidský sérový albumin chemie   metabolismus   MeSH
• simulace molekulového dockingu MeSH
• termodynamika MeSH
• triazoly chemie   farmakologie   MeSH
• vazba proteinů MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• fungicidy průmyslové MeSH
• ibuprofen MeSH
• ketoprofen MeSH
• lidský sérový albumin MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

The aim of the present study was to investigate tebuconazole sorption on common soil minerals (birnessite, ferrihydrite, goethite, calcite and illite) and humic acids (representing soil organic matter). Tebuconazole was used (i) in the commercial form Horizon 250 EW and (ii) as an analytical grade pure chemical. In the experiment with the commercially available tebuconazole, a significant pH-dependent sorption onto the oxides was observed (decreasing sorption with increasing pH). The highest sorption was found for ferrihydrite due to its high specific surface area, followed by humic acids, birnessite, goethite and illite. No detectable sorption was found for calcite. The sorption of analytical grade tebuconazole on all selected minerals was significantly lower compared to the commercial product. The sorption was the highest for humic acids, followed by ferrihydrite and illite and almost negligible for goethite and birnessite without any pH dependence. Again, no sorption was observed for calcite. The differences in sorption of the commercially available and analytical grade tebuconazole can be attributed to the additives (e.g., solvents) present in the commercial product. This work proved the importance of soil mineralogy and composition of the commercially available pesticides on the behavior of tebuconazole in soils.

• MeSH
• adsorpce MeSH
• huminové látky analýza   MeSH
• látky znečišťující půdu chemie   MeSH
• minerály chemie   MeSH
• pesticidy chemie   MeSH
• půda chemie   MeSH
• triazoly chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• huminové látky MeSH
• látky znečišťující půdu MeSH
• minerály MeSH
• pesticidy MeSH
• půda MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

Pesticide use worldwide exhibits a positive effect on agricultural production while it may negatively affect organisms living in soil, water or the air. Importantly, numerous negative health effects also occur in humans exposed to (accumulated) pesticides or their metabolites over a long period of time. To prevent both environmental catastrophes and adverse human health impacts, initial studies of the selected pesticides need to be performed together with the constant post-approval control; risk assessment analysis and on site monitoring have to be continuously carried out. Given this, Raman spectroscopy, especially surface-enhanced Raman spectroscopy (SERS), during the last decade has become a powerful analytical technique since it can offer quick, selective, and in situ detection of selected pollutants found in analyzed samples at very low concentrations. Moreover, the structural changes caused by the pollutant-biomacromolecule interaction can also be recognized in the molecule-specific Raman spectral signatures of biomolecules. In this study, we report a vibrational characterization of the fungicide molecule Tebuconazole (TB) which is listed to be a possible carcinogen. Even though its international and common use there is no evidence about the use of Raman/SERS spectroscopy to detect it sensitively and selectively as well as to analyse its impacts on biological systems. Therefore, we have recorded and calculated Raman and infrared spectra of TB. Furthermore, SERS spectra of TB were also registered and comprehensively analysed in view of the employed SERS substrates, dependence on the excitation wavelengths and pH of the analysed molecular systems. The molecule of TB interacts preferentially through the triazole moiety with the colloidal metal nanoparticles (NPs) whereas the silver NPs prepared by reduction of silver nitrate with hydroxylamine hydrochloride resulted to be the most effective ones. Consequently, the limit of detection was determined to be 1.4 μM≈430 ppb. The present paper thus could serve significantly for further investigations focused on both conducting vibrational analyses of structurally related molecules as well as providing a more precise explanation of the mechanism of action of TB and its influence on biological macromolecules.

• Klíčová slova
• Density functional theory (DFT), Limit of detection (LOD), Pesticide (fungicide), Surface-enhanced Raman, Tebuconazole, Vibrational spectra,
• MeSH
• kovové nanočástice * MeSH
• lidé MeSH
• pesticidy * MeSH
• Ramanova spektroskopie MeSH
• triazoly MeSH
• vibrace MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• pesticidy * MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

Electrospray ionization mass spectrometry (ESI-MS) is used to probe the complex formation between tebuconazole (1) and copper(II) salts, which both are commonly used fungicides in agriculture. Experiments with model solutions containing 1 and CuCl(2) reveal the initial formation of the copper(II) species [(1)CuCl](+) and [(1)(2)CuCl](+) which undergo reduction to the corresponding copper(I) ions [(1)Cu](+) and [(1)(2)Cu](+) under more drastic ionization conditions in the ESI source. In additional experiments, copper/tebuconazole complexes were also detected in samples made from soil solutions of various origin and different amount of mineralization. The direct sampling of such solutions via ESI-MS is thus potentially useful for understanding of the interactions between copper(II) salts and tebuconazole in environmental samples.

• MeSH
• fungicidy průmyslové chemie   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací metody   MeSH
• měď chemie   MeSH
• oxidace-redukce MeSH
• triazoly chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• fungicidy průmyslové MeSH
• měď MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

Agriculture is today indispensably connected with enormous use of pesticides. Despite tough regulation, their entrance into soil cannot be excluded and they might enter soil organisms and plants and continue further to terrestrial food chains. This study was conducted to investigate the bioaccumulation of two pesticides currently used in large amounts, the insecticide chlorpyrifos (CLP) and the fungicide tebuconazole (TBZ). Their detailed uptake kinetics in the model earthworm species Eisenia andrei were measured in two arable soils differing in organic carbon content (1.02 and 1.93% respectively). According to our results, a steady state was reached after 3-5 days for both pesticides and soils. The values of bioaccumulation factors calculated at the steady state ranged from 4.5 to 6.3 for CLP and 2.2-13.1 for TBZ. Bioaccumulation factors were also calculated as the ratio of uptake and elimination rate constants with results comparable with steady-state bioaccumulation factors. The results suggested that the degradation and bioaccumulation of tested compounds might be influenced by other factors than only total organic carbon (e.g. clay content). The lower Koc and hydrophobicity of TBZ relative to CLP probably led to higher availability of TBZ through pore water exposure. On the other hand, CLP's higher hydrophobicity probably caused an increase in availability by its additional uptake via ingestion. To enable a proper ecological risk assessment of current pesticides in soils, it is necessary to accurately determine their bioaccumulation in soil invertebrates. We believe that our study not only brings such information for two specific pesticides but also addresses key methodological issues in this area.

• Klíčová slova
• Bioaccumulation, Chlorpyrifos, Currently used pesticides, Eisenia andrei, Soil, Tebuconazole, Toxicokinetics,
• MeSH
• dursban analýza   metabolismus   MeSH
• jíl MeSH
• kinetika MeSH
• látky znečišťující půdu analýza   metabolismus   MeSH
• monitorování životního prostředí MeSH
• Oligochaeta metabolismus   MeSH
• pesticidy analýza   metabolismus   MeSH
• půda chemie   MeSH
• silikáty hliníku analýza   MeSH
• triazoly analýza   metabolismus   MeSH
• zemědělství MeSH
• zvířata MeSH
• Check Tag
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika MeSH
• Názvy látek
• dursban MeSH
• jíl MeSH
• látky znečišťující půdu MeSH
• pesticidy MeSH
• půda MeSH
• silikáty hliníku MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

Conazole fungicides are currently used pesticides with considerable chronic toxicity and ecotoxicity that are also on EU list for substitution. They enter the soil forming short- or long-term residues. In this study two of their representatives, epoxiconazole (EPC) and tebuconazole (TBC), have been tested with 20 soils from the Czech Republic for their adsorption. Adsorption, by means of Kd coefficients, was compared to "basic" (TOC, pH, clay …) and "advanced" (surface area, minerals ..) soil properties. After doing multivariate analysis of the variables it was apparent that adsorption of both pesticides was highly associated with pH (negatively correlated), and less associated with soil organo-mineral complex (TOC, clay and surface area) and C and N in soil organic matter (OM). Particle sizes or cation exchange capacity (CEC) did not show correlation with adsorption, but showed an association in multidimensional space in factor analysis (FA). Some correlations were revealed between EPC adsorption and soil organic matter parameters. Recalculating Kd to Koc and to Gibb's free energy (ΔG) and its values indicated that the adsorption of EPC and TBC is mainly weak physical adsorption - partitioning. Also, ΔG values gave better correlation with pH(H2O) than Kd. Surface area impacted EPC adsorption. From the several soil minerals, kaolinite showed EPC and TBC adsorption. EPC adsorption was not highly influenced with pH changes compared to TBC. The number and types of H-bonds with molecular geometry govern the sorption, which might crucially affect leachibility in soil, and this may indicate that TBC is more leachable than EPC for the same soil.

• Klíčová slova
• Adorption, Conazole fungicides, Epoxiconazole, Soil, Tebuconazole,
• MeSH
• adsorpce MeSH
• epoxidové sloučeniny chemie   MeSH
• jíl MeSH
• kationty MeSH
• látky znečišťující půdu chemie   MeSH
• minerály chemie   MeSH
• pesticidy chemie   MeSH
• půda chemie   MeSH
• triazoly chemie   MeSH
• velikost částic MeSH
• zemědělství MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika MeSH
• Názvy látek
• epoxiconazole MeSH Prohlížeč
• epoxidové sloučeniny MeSH
• jíl MeSH
• kationty MeSH
• látky znečišťující půdu MeSH
• minerály MeSH
• pesticidy MeSH
• půda MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

The aim of this study is to investigate how the presence of Cu influences tebuconazole (Teb) sorption onto contrasting soil types and two important constituents of the soil sorption complex: hydrated Fe oxide and humic substances. Tebuconazole was used in commercial form and as an analytical-grade chemical at different Teb/Cu molar ratios (1:4, 1:1, 4:1, and Teb alone). Increased Cu concentrations had a positive effect on tebuconazole sorption onto most soils and humic substances, probably as a result of Cu-Teb tertiary complexes on the soil surfaces. Tebuconazole sorption increased in the following order of different Teb/Cu ratios 1:4>1:1>4:1>without Cu addition, with the only exception for the Leptosol and ferrihydrite. The highest K f value was observed for humic substances followed by ferrihydrite, the Cambisol, the Arenosol, and the Leptosol. The sorption of analytical-grade tebuconazole onto all matrices was lower, but the addition of Cu supported again tebuconazole sorption. The Teb/Cu ratio with the highest Cu addition (1:4) exhibited the highest K f values in all matrices with the exception of ferrihydrite. The differences in tebuconazole sorption can be attributed to the additives present in the commercial product. This work proved the importance of soil characteristics and composition of the commercially available pesticides together with the presence of Cu on the behavior of tebuconazole in soils.

• MeSH
• adsorpce MeSH
• chemické jevy MeSH
• huminové látky * MeSH
• látky znečišťující půdu chemie   MeSH
• měď chemie   MeSH
• pesticidy chemie   MeSH
• půda chemie   MeSH
• triazoly chemie   MeSH
• železité sloučeniny chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• ferric oxyhydroxide MeSH Prohlížeč
• huminové látky * MeSH
• látky znečišťující půdu MeSH
• měď MeSH
• pesticidy MeSH
• půda MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH
• železité sloučeniny MeSH

Pesticide compounds can influence denitrification processes in groundwater in many ways. This study observed behavior of three selected pesticides under denitrifying conditions. Alachlor, terbuthylazine, and tebuconazole, in a concentration of 0.1 mL L-1, were examined using two laboratory denitrifications assays: a "short" 7-day and a "long" 28-day test. During these tests, removal of pesticides via adsorption and biotic decomposition, as well as the efficiency of nitrate removal in the presence of the pesticides, were measured. No considerable inhibition of the denitrification process was observed for any of the pesticides. On the contrary, significant stimulation was observed after 21 days for alachlor (49%) and after seven days for terbuthylazine (40%) and tebuconazole (36%). Adsorption was in progress only during the first seven days in the case of all tested pesticides and increased only negligibly afterwards. Immediate adsorption of terbuthylazine was probably influenced by the mercuric chloride inhibitor. A biotic loss of 4% was measured only in the case of alachlor.

• Klíčová slova
• alachlor, inhibition, laboratory denitrification assay, tebuconazole, terbuthylazine,
• Publikační typ
• časopisecké články MeSH

Resveratrol is antioxidant naturally occurring in wine grapes. It is thought to have a preventive biological activity against number of diseases. However, it has been recently shown that in the presence of metal ions, such as Cu2+, resveratrol forms oxidative radicals. Cu2+ is usually present in wine due to former usage of bluestone in vineyards. Fungicide tebuconazole has substituted bluestone and is presently one of the most widely used agrochemicals in wine industry; wine thus may contain traces of tebuconazole. Here, we study the ternary system of resveratrol, Cu2+, and tebuconazole experimentally and theoretically (using mass spectrometry, antioxidant capacity assay and quantum-chemical calculations) to model the redox behaviour of resveratrol in wine. We show that tebuconazole prevents formation of oxidative resveratrol radicals (induced by Cu2+ reaction with resveratrol) via preferential Cu2+ capture and protection of the binding sites of resveratrol. This positive effect of tebuconazole has not been observed before.

• Klíčová slova
• Antioxidant capacity, Copper, DFT, ESI-MS, FRAP, Polyphenols, Triazoles,
• MeSH
• antioxidancia analýza   chemie   MeSH
• fungicidy průmyslové chemie   MeSH
• hmotnostní spektrometrie MeSH
• měď chemie   MeSH
• oxidace-redukce MeSH
• resveratrol MeSH
• stilbeny analýza   chemie   MeSH
• triazoly chemie   MeSH
• víno analýza   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• antioxidancia MeSH
• fungicidy průmyslové MeSH
• měď MeSH
• resveratrol MeSH
• stilbeny MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH

Biochar usage in agriculture becomes increasingly important for the improvement of soil properties. However, from the perspective of pesticides, biochar can influence exposure to pesticides of both target and non-target organisms and also pesticides' fate in soil. Our study investigated degradation and bioaccumulation (in the Eisenia andrei earthworm) of two conazole fungicides, epoxiconazole and tebuconazole, added to high- and low-sorbing soils (by means of fungicides' sorption measured beforehand) amended with low-, moderate- and high-sorbing biochars at 0.2% and 2% doses. We aimed to investigate the effects of contrasting soil and biochar properties, different doses of biochar in soil-biochar mixtures, and different compounds on the degradation and bioaccumulation. We also wanted to explore if the beforehand determined sorption of fungicides on individual soils and biochars is manifested somehow in their degradation and/or bioaccumulation in soil-biochar mixtures. The biochars' presence in the soils promoted the degradation of fungicides with a clear effect of dose and soil, but less clear effect of biochar or compound. The bioaccumulation factors were higher in low-sorbing soil variants and also decreased with increasing biochar dose. For low-sorbing soil variants, the bioaccumulation was also influenced by the type of biochar corresponding to its sorbing potential and the possible effect on the bioavailability of the fungicides. Our results show that mixing of biochars with soils changes the fate and bioaccumulation of the conazole fungicides. However, the sorption results from original materials are not straightforwardly manifested in the more complex soil-biota system.

• Klíčová slova
• Bioaccumulation, Biochar, Conazole fungicides, Degradation, Eisenia andrei, Soil,
• MeSH
• bioakumulace MeSH
• dřevěné a živočišné uhlí MeSH
• epoxidové sloučeniny MeSH
• fungicidy průmyslové * analýza   MeSH
• látky znečišťující půdu * analýza   MeSH
• Oligochaeta * MeSH
• půda MeSH
• triazoly MeSH
• zvířata MeSH
• Check Tag
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• biochar MeSH Prohlížeč
• dřevěné a živočišné uhlí MeSH
• epoxiconazole MeSH Prohlížeč
• epoxidové sloučeniny MeSH
• fungicidy průmyslové * MeSH
• látky znečišťující půdu * MeSH
• půda MeSH
• tebuconazole MeSH Prohlížeč
• triazoly MeSH