Cholinesterases Inhibition, Anticancer and Antioxidant Activity of Novel Benzoxazole and Naphthoxazole Analogs.

Benzoxazole and naphthoxazole fused systems are found in many biologically active molecules. Novel benzoxazole and naphthoxazole analogs functionalized by the 2,4-dihydroxyphenyl moiety were designed, obtained and evaluated as a broad spectrum of biological potency compounds. Sulfinylbis[(2,4-dihydroxyphenyl)methanethione] or its analogs and 2-aminophenols or 1-amino-2-naphthol were used as starting reagents. 4-(Naphtho[1,2-d][1,3]oxazol-2-yl)benzene-1,3-diol was identified as the most promising compound of the nanomolar activity against AChE (IC50 = 58 nM) of the mixed-type inhibition and of the moderate activity against BChE (IC50 = 981 nM). The higher antiproliferative potency against a panel of human cancer cell lines for naphtho[1,2-d][1,3]oxazoles than for benzoxazoles was found. The activity of the analog with chlorine atom was in the range of 2.18-2.89 µM (IC50) against all studied cells and it is similar to that of cisplatin studied comparatively. Moreover, this compound was not toxic at this concentration to human normal breast cells and keratinocytes. For some compounds it also has proved antioxidant properties at the level of IC50 = 0.214 µM, for the most active compound. The lipophilicity of all compounds, expressed as log p values, is within the range recommended for potential drugs. The biological activity profile of the considered analogs and their lipophilic level justify the search for agents used in AD or in anticancer therapy in this group of compounds.

Mechanisms of Tebuconazole Adsorption in Profiles of Mineral Soils.

The study attempted to identify the soil components and the principal adsorption mechanisms that bind tebuconazole in mineral soils. The KF values of the Freundlich isotherm determined in 18 soils from six soil profiles in batch experiments after 96 h of shaking ranged from 1.11 to 16.85 µg1-1/n (mL)1/n g-1, and the exponent 1/n values from 0.74 to 1.04. The adsorption of tebuconazole was inversely correlated with the soil pH. Both neutral and protonated forms of this organic base were adsorbed mainly on the fraction of humins. The adsorption of the protonated form increased in the presence of hydrogen cations adsorbed in the soil sorption sites. Fourier transform infrared spectroscopy coupled with the molecular modeling studies and partial least squares regression analysis indicated that the tebuconazole molecule is bound in the organic matter through the formation of hydrogen bonds as well as hydrophobic and π-π interactions. Ion exchange was one of the adsorption mechanisms of the protonated form of this fungicide. The created mathematical model, assuming that both forms of tebuconazole are adsorbed on the organic matter and adsorption of the protonated form is affected by the potential acidity, described its adsorption in soils well.

Modeling the effect of adsorption on the degradation rate of propiconazole in profiles of Polish Luvisols.

Laboratory adsorption and degradation studies were carried out to determine the effect of time-dependent adsorption on propiconazole degradation rates in samples from three Polish Luvisols. Strong propiconazole adsorption (organic carbon normalized adsorption coefficients Koc in the range of 1217-7777 mL/g) was observed in batch experiments, with a typical biphasic mechanism with a fast initial step followed by the time-dependent step, which finished within 48 h in the majority of soils. The time-dependent step observed in incubation experiments was longer (duration from 5 to 23 d), and its contribution to total adsorption was from 20% to 34%. The half-lives obtained at 25 °C and 40% maximum water holding capacity of soil, were in the range of 34.7-112.9 d in the Ap horizon and in the range of 42.3-448.8 d for subsoils. The very strong correlations, between degradation rates in pore water and soil organic carbon and soil microbial activity, indicated that microbial degradation of propiconazole was most likely the only significant process responsible for the decay of this compound under aerobic conditions for the whole of the examined soil profiles. Modeling of the processes showed that only models coupling adsorption and degradation were able to correctly describe the experimental data. The analysis of the bioavailability factor values showed that degradation was not limited by the rate of propiconazole desorption from soil, but sorption affected the degradation rate by decreasing its availability for microorganisms.

Modeling of Bentazone Leaching in Soils with Low Organic Matter Content.

The aim of this study was to estimate bentazone's potential to leach to groundwater in the Arenosols developed from sand, Luvisols developed from loamy sand or sandy loam, and Luvisols or Cambisols developed from loess, and to identify the major factors influencing bentazone's fate in the soils. Potato and maize cultivations were simulated using the FOCUS PELMO 5.5.3 pesticide leaching model. The amount of bentazone reaching groundwater was highly sensitive to degradation parameters, water-holding capacity, evapotranspiration, organic carbon content, and pH. The highest bentazone concentrations in percolate were noted in Arenosols. The risk of bentazone concentration exceeding 0.1 µg/L was low only in Arenosols with high organic carbon content (3.0% for topsoil or higher). In Luvisols developed from loamy sand or sandy loam, the estimated bentazone concentrations in percolate were highly dependent on the climate. In Luvisols or Cambisols developed from loess, concentrations of >0.1 µg/L were the least likely due to the high water-holding capacity and high organic carbon content of these soils. The study also revealed that the FOCUS Hamburg scenario, representing the coarsest soils in the European Union with relatively low organic carbon content, does not reflect the leaching potential of Arenosols and Luvisols.

Adsorption and desorption processes of MCPA in Polish mineral soils.

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.

Occurrence and transformation of phenoxy acids in aquatic environment and photochemical methods of their removal: a review.

The article presents the behavior of phenoxy acids in water, the levels in aquatic ecosystems, and their transformations in the water environment. Phenoxy acids are highly soluble in water and weakly absorbed in soil. These highly mobile compounds are readily transported to surface and groundwater. Monitoring studies conducted in Europe and in other parts of the world indicate that the predominant phenoxy acids in the aquatic environment are mecoprop, 4-chloro-2-methylphenoxyacetic acid (MCPA), dichlorprop, 2,4-dichlorophenoxyacetic acid (2,4-D), and their metabolites which are chlorophenol derivatives. In water, the concentrations of phenoxy acids are effectively lowered by hydrolysis, biodegradation, and photodegradation, and a key role is played by microbial decomposition. This process is determined by the qualitative and quantitative composition of microorganisms, oxygen levels in water, and the properties and concentrations of phenoxy acids. In shallow and highly insolated waters, phenoxy acids can be decomposed mainly by photodegradation whose efficiency is determined by the form of the degraded compound. Numerous studies are underway on the use of advanced oxidation processes (AOPs) to remove phenoxy acids. The efficiency of phenoxy acid degradation using AOPs varies depending on the choice of oxidizing system and the conditions optimizing the oxidation process. Most often, methods combining UV radiation with other reagents are used to oxidize phenoxy acids. It has been found that this solution is more effective compared with the oxidation process carried out using only UV.

Adsorption of bentazone in the profiles of mineral soils with low organic matter content.

The current laboratory adsorption study aimed at determination of the values of adsorption distribution coefficient (Kd) of bentazone in the profiles of Arenosols, Luvisols, and Cambisols, which are the most common arable mineral soils in Poland. The study attempted to identify the soil components that bind bentazone and the principal adsorption mechanisms of this compound as well as create a model capable of predicting its adsorption in soils. The Kd values determined in batch experiments after 24 h of shaking were very low, and ranged from 0.05 to 0.30 mL/g for the Ap horizon and 0 to 0.07 mL/g for subsoils. The results indicated that the anionic form of bentazone was adsorbed on organic matter, while in acidic soils the neutral form of bentazone was adsorbed on organic matter and sand. The detailed analyses of mineralogical composition revealed that the principal mineral that was responsible for the adsorption of bentazone was quartz, which content was strongly positively correlated with the sand fraction. In soils with pH < 5 and an organic carbon content of < 0.35%, quartz exhibited much greater affinity for the neutral bentazone form than organic matter. Fourier transform infrared photoacoustic spectroscopy analyses supported by computational methods have shown the most probable mechanisms behind the adsorption of bentazone on quartz. The created model, assuming the adsorption of bentazone on organic matter and on sand and using the spectrophotometrically determined dissociation constant of bentazone, very well explained the Kd variance in the 81 examined soils, while correctly predicting the adsorption based on soil properties described in the published data.

Adsorption and degradation of phenoxyalkanoic acid herbicides in soils: A review.

The primary aim of the present review on phenoxyalkanoic acid herbicides-2-(2,4-dichlorophenoxy) acetic acid (2,4-D), 2-(4-chloro-2-methylphenoxy) acetic acid (MCPA), (2R)-2-(2,4-dichlorophenoxy) propanoic acid (dichlorprop-P), (2R)-2-(4-chloro-2-methylphenoxy) propanoic acid (mecoprop-P), 4-(2,4-dichlorophenoxy) butanoic acid (2,4-DB), and 4-(4-chloro-2-methylphenoxy) butanoic acid (MCPB)-was to compare the extent of their adsorption in soils and degradation rates to assess their potential for groundwater contamination. The authors found that adsorption decreased in the sequence of 2,4-DB > 2,4-D > MCPA > dichlorprop-P > mecoprop-P. Herbicides are predominantly adsorbed as anions-on organic matter and through a water-bridging mechanism with adsorbed Fe cations-and their neutral forms are adsorbed mainly on organic matter. Adsorption of anions of 2,4-D, MCPA, dichlorprop-P, and mecoprop-P is inversely correlated with their lipophilicity values, and modeling of adsorption of the compounds based on this relationship is possible. The predominant dissipation mechanism of herbicides in soils is bacterial degradation. The contribution of other mechanisms, such as degradation by fungi, photodegradation, or volatilization from soils, is much smaller. The rate of bacterial degradation decreased in the following order: 2,4-D > MCPA > mecoprop-P > dichlorprop-P. It was found that 2,4-D and MCPA have the lowest potential for leaching into groundwater and that mecoprop-P and dichlorprop-P have slightly higher potential. Because of limited data on adsorption and degradation of 2,4-DB and MCPB, estimation of their leaching potential was not possible.

Modeling of pH-dependent adsorption and leaching of MCPA in profiles of Polish mineral soils.

This study aimed to determine the leaching potential of MCPA and the contribution of major soil components to its retention in 27 profiles of common Polish arable soils. Results of experiments and modeling of the pH-dependent adsorption indicated that the adsorption of the neutral and anionic forms of MCPA on soil organic matter are the predominant adsorption mechanisms, even in soil horizons with very low organic matter contents. The third most important mechanism was the adsorption of MCPA anions, most likely through the water bridging mechanism on sorption sites created by exchangeable Fe cations adsorbed in soil. It was found that in acidic soils with very low organic matter contents, the neutral form of MCPA was also adsorbed on the quartz and silica sorption sites of silt and sand. The value of r(2) was 78% when it was assumed that MCPA was adsorbed only on organic matter and 93% when all indicated mechanisms of adsorption on mineral soil components were included in the model fitted to data from all soil profiles. Simulations using FOCUS PELMO indicated that in two profiles, the 80th percentiles of the average yearly concentrations of MCPA in the leachate exceeded the European Union (EU) contamination limit of 0.1 µgL(-1). It was shown that when an assumption was made in the model of pH-dependent adsorption that MCPA was adsorbed only on organic matter, the leaching potential of MCPA was overestimated in the examined soils. Much better predictions were obtained when adsorption on mineral soil components was also included in the model.

Effect of pH on the adsorption of carbendazim in Polish mineral soils.

The study aimed to determine the influence of pH on the adsorption of carbendazim in soil profiles of three mineral agricultural soils: Hyperdystric Arenosol, Haplic Luvisol and Hypereutric Cambisol. In the examined pH range between 3 and 7 the adsorption of carbendazim was inversely correlated to the pH of the soil. The adsorption coefficients were in the range between 0.3 and 151.8 m Lg(-1). Decreasing the pH in the soil suspensions from 7 to 3 increased the value of this coefficient by 3 to 70 times. A decrease in the amounts of organic matter down the soil profiles was not associated with weaker carbendazim adsorption. In the samples from all soil horizons, at pH values between 3 and 6, the predominant sorption process was carbendazim adsorption on clay minerals. The adsorption of carbendazim on organic matter prevailed over that on clays only at pH>6 and only in the Ap horizon of the examined soils. The developed mathematical models yielded very good results when the adsorption of the protonated form of carbendazim was assumed to be the predominant adsorption process on clays together with the adsorption of neutral molecules on organic matter and clays. The results from both the model fitting and the experiments revealed the negative effect of Al oxides and hydroxides and Al cations on the adsorption of the protonated form of carbendazim on clay minerals. The developed models successfully described the pH-dependent adsorption processes of carbendazim for both data from particular soil horizons and those from all three examined soil profiles.