Predicting mobility of alkylimidazolium ionic liquids in soils     

Wojciech Mrozik  Christian Jungnickel  Tomasz Ciborowski  William Robert Pitner  Jolanta Kumirska  Zbigniew Kaczyński  Piotr Stepnowski 《Journal of Soils and Sediments》2009,9(3):237-245

Background, aim, and scope  Ionic liquids (ILs) are a new class of alternative solvents that make ideal non-volatile media for a variety of industrial processes such as organic synthesis and biocatalysis, as alternative electrolytes, as phases and phase modifications in separation techniques, and as alternative lubricants. Once the large-scale implementation of ILs begins, the industrial application will follow. In view of their great stability, they could slip through classical treatment systems to become persistent components of the environment, where the long-term consequences of their presence are still unknown. Sorption on soils has a critical effect on the transport, reactivity, and bioavailability of organic compounds in the environment. So far, the IL sorption mechanism was investigated solely on the basis of batch experiments, which precluded any assessment of the dynamics of the process. An understanding of the mobility of ILs in soil columns is crucial for an accurate prediction of their fate in the soil. The aim of this study therefore was to investigate in detail the mobility of selected imidazolium ILs on three soil types. Moreover, it was decided to study these processes in soils from the coastal region (Gdańsk, Poland), which usually constitute a very important geochemical compartment, participating in the transport of contaminants on their way to the sea. Materials and methods  The mobility of alkylimidazolium ILs was investigated in columns containing soils from the coastal area. In addition, the sorption processes in all the soil systems studied were described isothermally and the equilibrium sorption coefficient was evaluated. The sorption capacities were determined according to OECD guidelines. Sorption dynamics was studied with use of polypropylene columns (diameter—10 mm, height—100 mm) packed with 10 g of soil. The ionic liquid solution was then injected into the soil column and left for 24 h to equilibrate. After this, a solution of 0.01 mM CaCl₂ was pumped through the column at a rate of 0.3 ml min^–1. Effluents were collected from the bottom of the column and analyzed by HPLC. Results  Sorption was strongest on the Miocene silt and the alluvial agricultural soil and weakest on the podsolic soil and Warthanian glacial till. The K _d value of long-chain ILs was far higher than that of the short-chain ones. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. Desorption of ILs is inversely correlated with sorption intensity. The experimental results of the column tests correlate well with those from batch experiments. In the cases of weakly binding soils, ILs were detected almost immediately in the eluent. The elution profiles of long-chain ILs indicate that these compounds are very strongly sorbed onto most soils, although certain amounts were transported through the soil. ILs exhibit a certain mobility in soils: in particular, salts with short and/or hydroxylated side chains are extremely mobile. Discussion  The results indicate a stronger binding of ILs in the first sorption layer; once the first layer is saturated, there are no more active sites on the soil surface (no free charged groups); hence, there are no more strong electrostatic binding sites, and dispersive interaction becomes the dominant interaction potential. The influence of the structure of the ILs, especially the side-chain length was also confirmed: The K _d value of long-chain ILs was far higher than that of the short-chain ones. The long alkyl side chain facilitates dispersive interactions with soil organic matter and intermolecular binding, and the build-up of a second layer becomes possible. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. The hydroxyl group in the side chain can alter the polarity of the compound so strongly that interaction with organic matter hardly occurs; these salts then remain in the aqueous phase. The experimental results from the column tests correlate well with those from batch tests. In the weakly binding soils (with low organic matter), the only binding to the soil surface must be via electrostatic interactions, although intermolecular van der Waals (ionic liquid–ionic liquid) interactions could also be taking place. The elution profile maxima for organic rich soils are far smaller than for the other soils. In the former, hydrogen bonding, dispersive and π…π interactions play a more important part than electrostatic interactions. The rapidly “disappearing” maxima of the elution peaks may indicate that, after elution of ILs from the second layer, it is difficult to extract further sorbed ILs. In the first layer, the ILs are bound by much stronger electrostatic interactions. To break these bonds, a greater energy is required than that sufficient to extract ILs from double sorption layers. Results indicate, moreover, that hydrophobic ILs will be sorbed in the first few centimeters of the soil; migration into the soil will therefore be almost negligible. Conclusions  Sorption of ILs was the strongest in soils with the highest cation exchange capacities and a high organic content. ILs were also more strongly bound to the first sorption layer. The sorption coefficients of long-chain ILs were far higher than those of short-chain ones; usually, hydroxylated derivatives were the least strongly sorbed. Results of soil column experiments to investigate the mobility of ILs in soils correlated well with those from batch tests, and the elution profiles were also well correlated with organic matter content. The observed rapidly disappearing elution peak maxima probably indicate that, after elution of the ILs from the second layer, it is difficult to extract further sorbed compounds. Recommendations and perspectives  Obtained results gave an interesting insight into mobility of ionic liquids in soil columns. However, several questions are now opened. It is therefore necessary to undertake further studies focused on total cycle of ionic liquids in the soil environment. This should include their evapotrasporation (lysimeter test), bioaccumulation by plants as well as degradation and transformation processes (chemical, biological, and physical) typically occurring in soils. Moreover, a further risk assessment of ILs is desirable since this study has indicated that these compounds, especially those with low lipophilicities, are generally mobile in the soil matrix. It is already known that short-chain ILs are characterized by low toxicities; should they enter the environment, they will probably migrate within the soil and pose a risk of contamination of surface and ground waters. This topic is relevant to the audience. Environmental threat of short-chain ionic liquids is currently unknown. From the predictive point of view, judging on known low acute toxic effects or high polarities of these compounds seems to be not enough to confirm their “environmental friendliness”. If we are to fully understand the potential environmental effects, one should also have an insight into long-term biological consequences of these ionic liquids, including chronic toxicity tests, bioaccumulation, and biotransformation rates as well as stability against natural elimination mechanisms.  相似文献   

Dissolved carbon and nitrogen release from deadwood of different tree species in various stages of decomposition     

Ewa Błońska  Jarosław Lasota  Wojciech Piaszczyk 《Soil Science and Plant Nutrition》2019,65(1):100-107

The aim of study was to estimate how the deadwood of different tree species in various stages of decomposition releases dissolved organic carbon (DOC) and total nitrogen concentration. The deadwood of seven species (Common alder, Common aspen, Common ash, Silver fir, Norway spruce, Common hornbeam, and Silver birch) were selected. Three logs from each species in the third, fourth, and fifth decay classes were chosen for analysis. The investigation was carried out in Czarna Rózga Reserve in Central Poland. The leachate from deadwood was collected in lysimeters. Concentrations of total carbon (TC), inorganic carbon (IC), total organic carbon (TOC), and total nitrogen (TN) were determined. In our investigations, the concentration of TOC measure in filtered water samples was equal to DOC. Additionally, pH and electrical conductivity (EC) values were determined in water samples. The results confirmed the importance of the wood species and the stage of decomposition on the concentration of DOC and TN. Significant differences in the concentration of DOC and TN in leachates released between coniferous and deciduous species were noted. Most DOC and TN were released from decomposing hornbeam and aspen wood, the least DOC, and TN were released into the soil from coniferous species, especially the spruce.  相似文献   

In vitro immunomodulatory effect of nisin on porcine leucocytes     

Joanna Ma&#x;aczewska  Edyta Kaczorek‐&#x;ukowska  Roman Wjcik  Wojciech R&#x;kawek  Andrzej K. Siwicki 《Journal of animal physiology and animal nutrition》2019,103(3):882-893

Nisin, a lantibiotic bacteriocin, has been used for years as a natural food preservative. In addition to its antimicrobial activity, nisin also shows immunomodulatory properties, and the nisin‐producing Lactococcus lactis strain has been successfully tested as a probiotic in weaned piglets. However, the impact of nisin on porcine immune cells has not yet been explored. The objective of the present study was to examine the in vitro immunomodulatory effect of nisin on porcine peripheral blood leucocytes. The whole heparinized blood samples or freshly isolated peripheral blood mononuclear cells (PBMCs) were incubated with different nisin concentrations (0, 1.56, 3.125, 6.25, 12.5, 25 or 50 µg/ml) for 1, 24, 48 or 72 hr. Escherichia coli bacteria were used to stimulate blood phagocytes, while concanavalin A and lipopolysaccharide from E. coli were used as mitogens. Control cells remained unstimulated. MTT colorimetric assay was used to evaluate PBMCs viability and mitogenic response. Phagocyte activity and T‐cell proliferation were measured by flow cytometry. Flow cytometer was also used for immunophenotyping of T cells. Cytokine levels in the culture media were determined using commercial immunoassay (ELISA) kits. The highest concentration of nisin exhibited proliferative activity (p ? 0.05), stimulated interleukin‐1 beta (IL‐1β) and interleukin‐6 (IL‐6) production (both at p ? 0.001), and increased the percentage of CD4⁺CD8⁺ T cells (p ? 0.001) among unstimulated leucocytes. After cell stimulation, however, the highest nisin concentration showed antiproliferative activity (p ? 0.05), decreased phagocytic functions (p ? 0.05) and inhibited the synthesis of IL‐6 (time‐ and concentration‐dependent effect). As a typical bacterial product, nisin had a stronger impact on innate immune cells, and its effect on T cells was likely a consequence of the modulation of the activity of antigen‐presenting cells. Nisin may be a good candidate as an immunomodulator in pig breeding.  相似文献   

Estimation of mechanical properties of seeds of common vetch accessions (Vicia sativa L.) and their chemical composition     

Wojciech Rybiński  Maciej Bańda  Jan Bocianowski  Andreas Börner  Michał Starzycki  Boguslaw Szot 《Genetic Resources and Crop Evolution》2015,62(3):361-375

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Induction time of Fe-SOD synthesis and activity determine different tolerance of two Desmodesmus (green algae) strains to chloridazon: A study with synchronized cultures     

Wojciech Pokora  Zbigniew Tukaj 《Pesticide biochemistry and physiology》2013

Cells of two Desmodesmus armatus strains (276-4a and 276-4d) grown asynchronously in batch cultures after 24-h treatment revealed different tolerance to chloridazon (photosynthetic herbicide) applied at a concentration of 3.45 mg L⁻¹. To find time- and cell cycle-dependent biochemical reasons leading to such a difference, a population of young autospores of both strains synchronized by a light/dark (14/10) regime were exposed to chloridazon at the initiation of the light period. Chloridazon reduced the growth and number of divisions of cell strain 276-4d. In consequence, at the end of the dark phase the number of released autospores was reduced by 50% compared with the control. In contrast, the growth and reproductive processes of cell strains 276-4a was unaffected. Moreover, chloridazon treatment speeded up cell development, as a result of which the release of autospores took this process observed in the control cells over. There is a relationship between photosynthetic activity response to chloridazon and time-dependent changes in Fe-SOD content and activity. The energy trapped in the reaction centre (RC) was similar in both strains, but the amount of energy absorbed by RCs was twice as high in strain 276-4d as in 276-4a. In consequence, non-photochemical energy dissipation occurring in the cells of 276-4d strain far exceed the value obtained for 276-4a strain. The control cells of both strains differed significantly in the content of FSD 1 and FSD 2 proteins, whereas the differences in Fe-SOD isoforms activities were slight. The 8-fold increase in SOD content in CHD treated cells of strain 276-4a was associated with the transience of photosynthetic efficiency impairment. In CHD treated cells of strain 276-4d, neither activity of Fe-SOD nor FSDs protein content was instantly affected. Different response of developing cells of two Desmodesmus strains to CHD is influenced by the inherent features of cells; the short time required to induce stress adaptive mechanism involving chloroplastic Fe-SOD activity and biosynthesis in the cells of CHD tolerant strain 276-4a seems to play the key role, being an overriding on the high, but not induced in response to stress, FSD protein level and activity in cells of strain 276-4d.  相似文献   

In Vitro Studies on Atrazine Effects on Human Intestinal Cells     

Anna M. Olejnik  Roman Marecik  Wojciech Białas  Paweł Cyplik  Włodzimierz Grajek 《Water, air, and soil pollution》2010,213(1-4):401-411

Considering the importance of the oral route for human exposure to atrazine, we have investigated the possible effect of this herbicide on the human intestinal cells and the integrity of the epithelial barrier, using Caco-2 cells as the intestinal model in vitro. We evaluated possibile cytotoxic and genotoxic effects of atrazine in concentrations ranging from 1 to 250 μM on the Caco-2 cells at different stages of growth after short- and long-term exposure. Results from the tetrazolium blue (MTT) test and the Trypan blue exclusion assay showed that atrazine cytotoxicity was dose- and time-dependent. Obtained data indicated that atrazine at high concentrations (50 and 250 μM) was able to induce effects on Caco-2 proliferation and viability. Moreover, it was found that the long-term exposure to atrazine at the non-cytotoxic dose caused inhibition of the intestinal cell maturation and decreased the transepithelial electrical resistance, the indicator of the epithelial barrier integrity. Studies on the atrazine genotoxicity determined using the single cell microelectrophoresis assay indicated that atrazine did not induce DNA damages in the Caco-2 cells at concentrations of up to 50 μM, whereas enhancement in the DNA damage was observed at 250 μM. Altogether, our results indicate that atrazine at expected human oral exposure concentrations is not able to induce effects on the Caco-2 cell proliferation and viability, but may suppress the intestinal cell differentiation and reduce the cell monolayer integrity. We suggest that chronic exposure on low levels of atrazine may lead to alteration in the expression of the morphological and functional features of the Caco-2 cells related to the transport and barrier function of small intestinal enterocytes. In consequence, this may lead to alterations in the intestinal absorption process.  相似文献   

Genetic diversity of European pear cultivars (<Emphasis Type="Italic">Pyrus communis</Emphasis> L.) and wild pear (<Emphasis Type="Italic">Pyrus pyraster</Emphasis> (L.) Burgsd.) inferred from microsatellite markers analysis     

Łukasz Wolko  Wojciech Antkowiak  Elżbieta Lenartowicz  Jan Bocianowski 《Genetic Resources and Crop Evolution》2010,57(6):801-806

The aim of this study was to identify the group of highly polymorphic microsatellite markers for the identification of six pear cultivars (P. communis) and two individuals of wild pear (P. pyraster). From among 40 tested SSR markers, 19 were selected to profile genetic diversity in pear genotypes due to high polymorphisms. These markers showed high heterozygosity levels (0.5–1) and, on average, 6.4 alleles per marker were found. The set of microsatellite markers employed in this study demonstrated usefulness of microsatellite markers for the identification of pear genotypes. The examined wild forms were represented in this study by only two individuals of P. pyraster. It can be assumed that these forms were distinctly different from the cultivated pear cultivars.  相似文献   

Morphological characteristics of some accessions of grass pea (<Emphasis Type="Italic">Lathyrus sativus</Emphasis> L.) grown in Europe and nutritional traits of their seeds     

Eugeniusz R. Grela  Wojciech Rybiński  Renata Klebaniuk  Jan Matras 《Genetic Resources and Crop Evolution》2010,57(5):693-701

Thirty-one European accessions of grass pea (Lathyrus sativus L.) originating from Italy, Spain, Northern France, Germany and Poland grown in the same soil-climatic conditions in Poland were investigated. The morphological traits as well as the seed morphology and nutrient contents were studied. Substantial differentiation in some morphological characteristics was noticed. The plants could be assigned to two groups: one group comprising the lines from the Mediterranean basin (Italy and Spain) and the other group containing the accessions from West-central Europe (Northern France, Germany and Poland). The grass pea plants produced from the seeds obtained from West-central Europe appeared to be about 10 cm taller than the Mediterranean accessions and had predominantly white flowers. Their seeds were more than two times smaller than seeds of the accessions of Italian or Spanish origin. There were not noted any considerable differences in nutrient contents or antinutritional factors in seeds between these two groups of Lathyrus accessions. A negative correlation between β-ODAP and tannin contents (r = −0.379, P ≤ 0.05) and a positive correlation (r = 0.843, P ≤ 0.01) between a tannin content and flower color intensity were found. A white or crème colour was associated with a low tannin level in the seeds, while the colourful blooming accessions had higher tannin contents.  相似文献   

A universal method to produce low-work function electrodes for organic electronics     

Zhou Y  Fuentes-Hernandez C  Shim J  Meyer J  Giordano AJ  Li H  Winget P  Papadopoulos T  Cheun H  Kim J  Fenoll M  Dindar A  Haske W  Najafabadi E  Khan TM  Sojoudi H  Barlow S  Graham S  Brédas JL  Marder SR  Kahn A  Kippelen B 《Science (New York, N.Y.)》2012,336(6079):327-332

Organic and printed electronics technologies require conductors with a work function that is sufficiently low to facilitate the transport of electrons in and out of various optoelectronic devices. We show that surface modifiers based on polymers containing simple aliphatic amine groups substantially reduce the work function of conductors including metals, transparent conductive metal oxides, conducting polymers, and graphene. The reduction arises from physisorption of the neutral polymer, which turns the modified conductors into efficient electron-selective electrodes in organic optoelectronic devices. These polymer surface modifiers are processed in air from solution, providing an appealing alternative to chemically reactive low-work function metals. Their use can pave the way to simplified manufacturing of low-cost and large-area organic electronic technologies.  相似文献   

Antioxidant capacity manipulation in transgenic potato tuber by changes in phenolic compounds content   总被引：1，自引：0，他引：1  

Lukaszewicz M  Matysiak-Kata I  Skala J  Fecka I  Cisowski W  Szopa J 《Journal of agricultural and food chemistry》2004,52(6):1526-1533

The main goal of this study was to generate potato tubers with increased levels of flavonoids and thus modified antioxidant capacities. To accomplish this, the vector carrying multigene construct was prepared and several transgenic plants were generated, all overexpressing key biosynthesis pathway enzymes. The single-gene overexpression or simultaneous expression of genes encoding chalcone synthase (CHS), chalcone isomerase (CHI), and dihydroflavonol reductase (DFR) resulted in a significant increase of measured phenolic acids and anthocyanins. The increase in phenolic compounds synthesis is accompanied by decreases in starch and glucose levels in transgenic plants. The flavonoids-enriched plants showed improved antioxidant capacity; however, there is a complex relationship between antioxidant capacity and flavonoids content, suggesting the great participation of other compounds in the antioxidant potential of the plants. These other compounds are not yet recognized.  相似文献