Robert Biczak

The role of the anion in the toxicity of imidazolium ionic liquids.

From the environmental protection point of view, the growing interest of ionic liquids in various industrial branches has raised concerns for the toxicity assessment of these compounds. The paper discusses the effect of salts containing the shared 1-ethyl-3-methylimidazolium [EMIM] cation as coupled with five different anions: bromide [Br], nitrate [NO3], p-toluenesulfonate (tosylate) [Ts], dimethylphosphate [dMP] and methanesulfonate [MS] on the growth and development of higher land plants - spring barley and common radish. The experiment was done according to the ISO Standard 11269-2:1995 and the OECD/OCDE Guide 208/2006. As the indications of phytotoxicity, the percentage of sprouts and the level of dry and fresh plant mass were used; in addition, the visual assessment of any signs of damage to the examined plant species, such as growth inhibition and chlorotic changes, was also made. Results of our study has proved the negative impact of ILs on the tested plants and the toxic effect of imidazolium salts was dependent primarily on the applied ionic liquids concentration. The common radish revealed the higher tolerance to the imidazolium as compared to spring barley. The anion type of ionic liquid was crucial for the toxicity against common radish.

Phytotoxicity of new furan-derived aminophosphonic acids, N-aryl furaldimines and 5-nitrofuraldimine.

The aim of this work was to synthesize selected furaldimines and their aminophosphonic derivatives and evaluation the phytotoxicity of new obtained products according to OECD 208 Guideline. Four Schiff bases, N-furfurylidene-p-anisidine (1a), N-furfurylidene-p-toluidine (1b), N-furfurylidene-benzhydrylamine (1c), and N-(2-nitrofurfurylidene)-p-toluidine (1d) were synthesized and three new furan-derived N-substituted aminomethylphosphonic acids, namely: 2-furyl N-(p-methoxyphenyl)-aminomethylphosphonic acid (2a), 2-furyl N-(p-methylphenyl)-aminomethylphosphonic acid (2b) and 2-furyl N-(diphenylmethyl)-aminomethylphosphonic acid (2c) were synthesized by the addition of in situ generated bis-(trimethylsilyl) phosphite to azomethine bond of corresponding Schiff bases 1a-c. Three Schiff bases 1a-b and 1d as well as all three aminophosphonic acids 2a-c were analyzed in regard with their phytotoxicity toward two plants, radish (Raphanus sativus) and oat (Avena sativa). It has been found that tested N-furfurylidene-p-anisidine (1a), N-(2-nitrofurfurylidene)-p-toluidine (1d) and aminophosphonic acids 2a-c are toxic for selected plants. N-furfurylidene-p-toluidine (1b) did not show any ecotoxicological impact in used plant growth test.

Quaternary ammonium salts with tetrafluoroborate anion: Phytotoxicity and oxidative stress in terrestrial plants.

This paper discusses the impact of four quaternary ammonium salts (QAS) such as tetraethylammonium tetrafluoroborate [TEA][BF4], tetrabutylammonium tetrafluoroborate [TBA][BF4], tetrahexylammonium tetrafluoroborate [THA][BF4], and tetraoctylammonium tetrafluoroborate [TOA][BF4] on the growth and development of spring barley and common radish. Analogous tests were performed with the inorganic salt ammonium tetrafluoroborate [A][BF4] for comparison purposes. Results indicated that the phytotoxicity of the QAS applied is dependent on the concentration of the substance and their number of carbon atoms. The most toxic compound was [TBA][BF4], causing the greatest drop in fresh weight of both study plants, similar to the phytotoxic effects of [A][BF4]. All the tested compounds caused oxidative stress in spring barley and common radish seedlings due to a drop in the chlorophyll content. Stress was also observed in plants, which was indicated by the increased level of ROS (reactive oxygen species) such as H2O2 and lipid peroxidation of MDA (malondialdehyde). Due to the stress, both plants displayed changes in the activity of antioxidative enzymes such as superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD). Based on the results of the study, it was concluded that changes in chlorophyll levels and peroxidase activity are the best biomarkers to determine oxidative stress in plants.

Evaluation of the effect of tetraethylammonium bromide and chloride on the growth and development of terrestrial plants.

Quaternary ammonium salts (QAS), which also include ionic liquids, constitute a vast group of chemical compounds that are increasingly common in the commercial use. This situation may lead to the contamination of the natural environment and may constitute a potential threat to all its elements, including terrestrial higher plants. This paper presents the effect of tetraethylammonium chloride [TEA][Cl] and tetraethylammonium bromide [TEA][Br] on the growth and development of spring barley and common radish. The applied QAS were characterized with phytotoxicity dependent on the concentration of compound and characteristics of the study plants. Spring barley turned out to be highly susceptible plant to the analyzed compounds, which was confirmed by % inhibition of length of plants, root length and fresh weight of plants and by calculated values for EC50, NOEC as well as LOEC. On the contrary, a common radish revealed the resistance to QAS used in the study; although, phytotoxic symptoms were still observed when high concentrations of dry weight of soil were applied (1000, 3000 and 5000 mg/kg). The applied QAS caused oxidative stress symptoms, mainly in spring barley seedlings, which were manifested by decreased assimilation of pigments content, increased hydrogen peroxide (H2O2) and malondialdehyde (MDA) content in plant cells and with a changed activity of superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD).

Comparison of Phytotoxicity of Selected Phosphonium Ionic Liquid

Abstract Ionic liquids have attracted considerable interest in various areas as new, non-volatile and non-flammable organic solvents, catalysts, reaction additives, ligands, drugs and other dedicated materials etc. Their general use, sometimes in bulky quantities, requires determination of their potential ecotoxicity on selected organisms. In the present work, influence of triphenylmethylphosphonium iodide (1) and triphenylhexadecylphosphonium iodide (2), introduced to soil, on germination and early stages of growth and development of superior plants was investigated using the plant growth test based on the OECD/OCDE 208/2006. In this test, the seeds of selected species, i.e. land superior plants - spring barley (Hordeum vulgare) and common radish (Raphanus sativus L. subvar. radicula Pers.) were planted in pots containing soil to which a test chemical compound had been added and in pots with control soil. To evaluate the phytotoxicity of ionic liquids 1 and 2 germination and weight (dry and fresh) of control plant seedlings were determined and compared with the germination and weight (dry and fresh) of the seedlings of plants grown in the soil watered with appropriate amounts of the test chemicals. The visual assessment of any types of damage to the test species, such as growth inhibition, chlorosis and necrosis, was also carried out and documented by digital photographs. Based on the obtained results, magnitudes of the LOEC - the lowest concentration causing observable effects in the form of reduction in growth and germination compared with the control and the NOEC - the highest concentration not causing observable, toxic effects - were also determined.

The phytotoxicity of ionic liquids from natural pool of (-)-menthol with tetrafluoroborate anion.

Over the last several decades, ionic liquids have become a promising alternative to conventional organic solvents. Initially, ionic liquids were described as “environmentally friendly” substances. However, the results of numerous studies proved that the effects of these compounds on individual ecosystems might be adverse. The presented paper discusses the effect of ionic salts containing natural chiral substituent: (1R,2S,5R)-(−)-menthol in cation and a tetrafluoroborate anion of a general formula of [Cn-Im-Men][BF4] of implementation into the soil on the growth of spring barley and common radish in their early development stages. The obtained results showed that the greatest phytotoxicity was exhibited by ionic liquids containing substituents with the smallest possible number of carbon atoms. The further increase in the length of the chain did not increase the toxicity of these salts for terrestrial plants. Moreover, a compound with a substituent having a chain length of 11 carbon atoms was found to be non-toxic to common radish. The experiment under discussion showed also the effect of these tetrafluoroborates, used in the form of spray, on the development of common sorrel, gallant soldier and white goosefoot. The tests carried out also showed that the most toxic were the compounds with 1 and 3 carbon atoms. The phytotoxicity of tetrafluoroborates was positively correlated with the concentration of these compounds in the soil and was dependent on the genetic features of the genres and varieties of plants used in the experiment.

The effect of the number of alkyl substituents on imidazolium ionic liquids phytotoxicity and oxidative stress in spring barley and common radish seedlings.

Increasing amounts of two ILs: 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6] and 1-butyl-2,3-dimethylimidazolium hexafluorophosphate [BMMIM][PF6], were introduced to soil in which spring barley (Hordeum vulgare) and common radish (Raphanus sativus L. subvar. radicula Pers.) seedlings were cultivated, in order to evaluate the phytotoxicity of ionic liquids with imidazolium cation with two or three alkyl substituents attached. The results of the study i.e. the inhibition of the length of plants and their roots, as well as the yield of fresh weight of plants, clearly showed that differences in the number of substituents did not affect the toxicity of these ILs. Although, radish was more resistant to the applied ionic liquids than barley. Ionic liquids led to a decrease in the content of all assimilation pigments and induced oxidative stress in the plants, as showed by an increase in malondialdehyde (MDA) content, and changes in the level of H2O2 and antioxidant enzymes: superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD). The best biomarkers of oxidative stress in both plants were the changes in chlorophyll content and the increase in POD activity. Both spring barley and radish exposed to [BMIM][PF6] and [BMMIM][PF6] accumulated a large amount of fluoride ions, which further increased the toxicity of these compounds for both plants.

Phytotoxicity and Cytotoxicity of Imidazolium Ionic Liquids Containing Sulfur Atom

Abstract Ionic liquids have attracted considerable interest in various areas as new, nonvolatile and nonflammable organic solvents, catalysts, reaction additives, ligands, drugs, and other dedicated materials. Ionic liquids exhibit solubility both in organic solvents and in water. They also constitute very good solvents for many inorganic, organic, and organometallic compounds. Yet, the most important feature of ionic liquids is that they provide the possibility of obtaining substances of optimal properties for a given process through modification of the cation structure and selection of the appropriate anion. Therefore, the term designer solvents has been invented for these salts. The above characteristics and relatively low production cost may soon lead to the situation, in which huge amounts of these chemicals will be brought into environment via industry, agriculture, and commercial trading. Their general use, sometimes in bulky quantities, requires determination of their potential ecotoxicity on selected plant and animal organisms. Other biological tests, are also very important. GRAPHICAL ABSTRACT

Growth inhibition and efficiency of the antioxidant system in spring barley and common radish grown on soil polluted ionic liquids with iodide anions

Ionic liquids (ILs) constitute a huge group of substances that are increasingly common in the commercial use. This situation may lead to the contamination of the soil environment which being the basic of plants vegetation. This paper presents the effect of four ILs with I- anion on the growth and development of spring barley (Hordeum vulgare) and common radish (Raphanus sativus L. subvar. radicula Pers) and changes in metabolism of the plants. Seedlings of spring barley and common radish cultivated on soil with increasing ILs concentration exhibited typical phytotoxicity symptoms. A considerable reduction of shoot and root lengths, decrease of fresh weight (FW) and increase of dry weight (DW) occurred in both test plants. Ionic liquids concentration increase in soil was correlated with the decrease of concentrations of all photosynthetic pigments in the plants. The observed increase of malondialdehyde (MDA) concentration and changes in the H2O2 level indicated presence of oxidative stress in spring barley and common radish, which usually led to the increase of superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD) activity. The most reliable biomarker of oxidative stress was chlorophyll level and changes in POD activity.

Changes in growth and physiological parameters of spring barley and common radish under the influence of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate

Ionic liquids (ILs) constitute a large group of chemical substances, which, thanks to their desirable properties, still attract attention of scientists and representatives of the industry. This may lead to a greater commercial use of these compounds, which will undoubtedly lead to the contamination of soils, constituting the basis of plant vegetation, with these substances. This paper presents effect of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BMMIM][BF4] on the growth and development of spring barley and common radish and on the physiological and biochemical changes in these plants. The used IL was characterized by relatively high toxicity for the monocotyledonous plant, which was exhibited by shortening of the plant length and their root length, decreasing the fresh weight yield. Moreover, [BMMIM][BF4] led to the decrease in the content of all photosynthetic pigments in spring barley seedlings, reflecting the decrease in the fresh yield. Furthermore, the increase of malondialdehyde (MDA) level and changes in contents of hydrogen peroxide (H2O2) and the activity of antioxidant enzymes, that is, superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) may suggest the occurrence of oxidative stress in spring barley. The decrease in the content of photosynthetic pigment and the increase of POD activity constitute the most reliable markers of oxidative stress and, at the same time, the signs of early aging of spring barley plants. Common radish was the plant with a very high tolerance for the used IL, which can be indicated by, that is, EC50 values, determined based on inhibition of root length, plant length, and fresh weight yield.