离子液体对三种农作物发芽和生长的毒性研究

为了考察离子液体的生态毒性,研究了5种离子液体及其浓度变化对3种农作物发芽及生长状况的影响。结果表明：就种子发芽这一生态毒理指标而言,不同作物对离子液体毒性的敏感程度不同,其次序为黄瓜>玉米>白菜;在一定浓度下,离子液体对白菜、黄瓜和玉米均具有一定的毒害作用;对于所考察的5种离子液体,阴离子为卤素的［EMIM］Br和［BMIM］Cl对植物发芽和生长的抑制作用远大于阴离子为烷基硫酸酯和烷基磷酸酯的同类离子液体 ［EMIM］［ES］、［EMIM］［DEP］和［MMIM］［DMP］。这种毒性顺序可能与卤素离子对细胞膜较强的穿透能力和由于离子液体的稳定性所造成的阴阳“离子对”的共迁移有关。     

Relevant parameters for assessing the environmental impact of some pyridinium, ammonium and pyrrolidinium based ionic liquids

Several physico-chemical properties relevant to determine the environmental impact of ionic liquids - aqueous solubility, octanol/water partition coefficient, chromatographically derived lipophilicity and infinite dilution diffusion coefficients in water - were measured in ionic liquids based on pyridinium, ammonium and pyrrolidinium cations with bis(trifluoromethylsulfonyl)imide anions. The influence of the presence of hydroxyl or ester groups in the physico-chemical properties of these liquids was checked. It appeared that the presence of functional oxygenated moieties reduces the lipophilicity of ionic liquids and so decreases the risk of bioaccumulation in environment.     

Absorption of NO and NO2 in caprolactam tetrabutyl ammonium halide ionic liquids

To explore environmentally benign solvents for the absorption of NO and NO2, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO2 was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO2 in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO2 decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO2 was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO2.     

Cytotoxicity estimation of ionic liquids based on their effective structural features

Cytotoxicity of a diverse set of 227 ionic liquids (taken from UFT/Merck Ionic Liquids Biological Effects Database) containing 94 imidazolium, 53 pyridinium, 23 pyrrolidinium, 22 ammonium, 15 piperidinium, 10 morpholinium, 5 phosphanium, and 5 quinolinium cations in combination with 25 different types of anions to Leukemia Rat Cell Line (IPC-81) was estimated from their structural parameters using quantitative structure - toxicity relationship “QSTR” methodology. Linear and nonlinear models were developed using genetic algorithm (GA), multiple linear regressions (MLR) and multilayer perceptron neural network (MLP NN) approaches. Robustness and reliability of the constructed models were evaluated through internal and external validation methods. Furthermore, chemical applicability domain was determined via leverage approach. In this work, it was revealed that the cationic moieties make the major contribution to cytotoxicity and the anionic parts play a secondary role in cytotoxicity of the ionic liquids studied here. Structural information represented in this work, can be used for a rational design of safer ILs.     

Sorption and desorption of imidazolium based ionic liquids in different soil types

This study investigates the influence of the two different clay minerals kaolinite and smectite as well as of organic matter on the cation sorption and desorption behaviour of three imidazolium based ionic liquids -1-butyl-3-methyl-imidazolium tetrafluoroborate (IM14 BF(4)), 1-methyl-3-octyl-imidazolium tetrafluoroborate (IM18 BF(4)) and 1-butyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide (IM14 (CF(3)SO(2))(2)N) - in soil. The German standard soil Lufa 2.2 - a natural soil classified as a loamy sand - was the basis substrate for the different soil compositions and also served as a reference soil. The addition of organic matter and clays increases the sorption of the substances and in particular smectite had striking effects on the sorption capacity for all three ionic liquids indicating that ionic interactions play an important role for sorption and desorption processes of ionic liquids in soil. One exception was for kaolinite-containing soils and the IM14 cation: with (CF(3)SO(2))(2)N(-) as an anion the sorption was identical at either 10 wt% or 15 wt% clay content, and with BF(4)(-) sorption was even lower at 15 wt% kaolinite than at 10 wt%. Desorption was weak for IM18 BF(4), presumably owing to the longer alkyl side chain. With regard to the influence of kaolinite on desorption, the same pattern was observed as it was found for the sorption of IM14 BF(4) and IM14 (CF(3)SO(2))(2)N.     

Synthesis and anti-microbial activity of hydroxylammonium ionic liquids

Eight hydroxylammonium-based room temperature ionic liquids (ILs) have been synthesized by acid-base neutralization of ethanolamines with organic acids. The ILs were characterized by infrared and nuclear magnetic resonance spectroscopies and elemental analysis. Their anti-microbial activities were determined using the well-diffusion method. All eight ILs were toxic to Staphylococcus aureus, while 2-hydroxyethylammonium lactate and 2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium acetate showed high anti-microbial activity against a wide range of human pathogens.     

Ecotoxicity of biocomposites based on renewable feedstock - preliminary studies

The aim of the work was to study the biodegradation process of biocomposites prepared from renewable resources and the ecotoxicological assessment of their biodegradation products. Biocomposites from modified starch reinforced with various cellulose fibers were prepared by the extrusion process. Biodegradation studies were carried out according to the ISO respirometic method. Ecotoxicity of biodegradation products was assessed by the luminescent bacteria test. It was found that biodegradation of biocomposites was above 60% within 24 days according to the results of respirometric test. Increase in the amount of natural fiber reinforcement, as well as smaller fiber size increased the biodegradability of biocomposites. On the basis of the preliminary results of the ecotoxicological test using luminescent bacteria it seems that the biodegradation products of the biocomposites studied are ecologically safe.     

咪唑类离子液体用于处理油田污水的研究

采用油浴法合成了疏水性咪唑类离子液体[omim]PF6。研究了这种离子液体对油田污水的萃取,考察了萃取时间、离子液体加量、pH值对萃取效果的影响。实验结果表明,萃取15 min就可以达到平衡。污水COD的去除率随pH值的增大而减小,同时对再生离子液体处理油田污水的效果进行了探讨,离子液体的循环使用次数对处理污水的效果影响不大。     

Sorption of imidazolium-based ionic liquids to aquatic sediments

Ionic liquids (ILs) have received much attention as "green" alternatives to traditional solvents because they do not evaporate, eliminating concerns over fugitive emissions. However, if ionic liquids are used in industrial applications, they may enter aquatic systems via effluent, and their fate and transport may be influenced by sorption to sediments. In this study, we conducted batch mixing experiments with four alkylmethylimidizolium-based ILs and four types of aquatic sediments to asses the capacity for natural aquatic sediments to remove these chemicals from the water column. The concentration isotherms were non linear with point estimates of the distribution coefficient (K(d)) decreasing with increasing concentration. Apparent distribution coefficients ranged from 7.9 to 95.7l kg(-1) at an initial concentration of 0.5mM and were positively related to sediment organic matter (SOM) content. These K(d) values indicate that the ILs did not sorb strongly to the tested sediments. Increased alkyl chain length did not lead to increased sorption suggesting that hydrophobic interactions were not the most important sorption mechanism. We conclude that aquatic sediments have a limited capacity to sorb alkylmethylimidazolium ILs and that the transport of these contaminants in aquatic systems will not be strongly attenuated by sediments.     

Automated evaluation of the effect of ionic liquids on catalase activity

An automated assay for the evaluation of the influence of ionic liquids on the activity of catalase was developed. The activity and inhibition assays were implemented in a sequential injection analysis (SIA) system and intended to contribute for the estimation of the toxicity of the tested compounds. The fast developed methodology was based on the oxidation of the non-fluorescent probe amplex red, in the presence of H₂O₂, to produce resorufin, a strong fluorescent compound. Catalase activity was monitored by the decreased of the fluorescence intensity due to the consumption of H₂O₂ by the enzyme. The activity assays were performed in strictly aqueous media and in the presence of increasing concentrations of seven commercially available ionic liquids and sodium azide, a strong inhibitor of catalase. IC₅₀ values between 0.15 and 2.77 M were obtained for the tested compounds, revealing distinct inhibitory effects. This allowed us to perform some considerations about the toxicity of the tested cations and anions. The developed SIA methodology showed to be robust and exhibited good repeatability in all the assay conditions. On the other hand, it proved to be in good agreement with the actual concerns of “Green Chemistry” since it involved the consumption of less than 200 μL of reagents and the production of only 1.7 mL of effluent (per cycle) and at the same time reduced the operator exposure resulting in increased environmental and human safety.     

Removal of imidazolium- and pyridinium-based ionic liquids by Fenton oxidation

The oxidation of imidazolium (1-hexyl-3-methylimidazolium chloride, HmimCl) and pyridinium (1-butyl-4-methylpyridinium chloride, BmpyrCl) ionic liquids (ILs) by Fenton’s reagent has been studied. Complete conversion was achieved for both ILs using the stoichiometric H₂O₂ dose at 70 °C, reaching final TOC conversion values around 45 and 55% for HmimCl and BmpyrCl, respectively. The decrease in hydrogen peroxide dose to substoichiometric concentrations (20–80% stoichiometric dose) caused a decrease in TOC conversion and COD removal and the appearance of hydroxylated oxidation by-products. Working at these substoichiometric H₂O₂ doses allowed the depiction of a possible degradation pathway for the oxidation of both imidazolium and pyridinium ILs. The first step of the oxidation process consisted in the hydroxylation of the ionic liquid by the attack of the ·OH radicals, followed by the ring-opening and the formation of short-chain organic acids, which could be partially oxidized up to CO₂ and H₂O. At H₂O₂ doses near stoichiometric values (80%), the resulting effluents showed non-ecotoxic behaviour and more biodegradable character (BOD₅/COD ratio around 0.38 and 0.58 for HmimCl and BmpyrCl, respectively) due to the formation of short-chain organic acids.

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Biodegradation of oxygenated and non-oxygenated imidazolium-based ionic liquids in soil

Aerobic biodegradation of ionic liquids in soil was monitored for the first time. The tests, followed over six months according to ASTM D 5988-96, were carried out on the four ionic liquids obtained from 1-R-3-methylimidazolium cations, with R=CH(3)(CH(2))(3) and CH(3)O(CH(2))(2), and the tetrafluoroborate and dicyanamide counter anions. The n-butyl derivatives, after an induction period of about two months, were found to be degradable, although the degradation rate with the dicyanamide anion was smaller. In contrast, no significant production of CO(2) was observed in the tests with the methoxyethyl derivatives. Calculations at the B3LYP/6-31G(d) level were carried out to characterize the atomic charge distributions and frontier orbital structures of 1-alkyl-3-methylimidazolium cations and point out the changes caused by replacement of a CH(2) group of the alkyl chain with an oxygen atom. The calculations predict an overall negative charge on the nitrogen atoms of the imidazolium-based cations. The energies of the highest occupied (pi) MO and lowest empty (pi( *)) MO are only slightly perturbed by the length and nature of the alkyl chain. However, the electron-donor properties of the oxy derivatives are radically increased. The HOMO becomes a lone pair orbital mainly localized on the oxygen atom, and its ionization energy is sizeably smaller than that of the outermost ring pi MO.     

Study of sorption kinetics of some ionic liquids on different soil types

In the present contribution sorption kinetics experiments under static conditions were utilized in three selected ionic liquids cations (1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium chlorides) study with five type of soil, differing in total organic carbon (TOC) content. The experimental results indicate the sorption capacity growth with increase in TOC content and hydrophobicity of ionic liquid cation. The obtained kinetic sorption parameters as well as distribution coefficients (K_d) were used to estimate the sorption properties of the soil types towards the ionic liquids in question. The Gibbs free energy values indicate that ionic liquid cations sorption on soils could be generally considered as a physical adsorption with exothermic effect. But the values of −dG for studied cations sorption on soil with very high of TOC content in soil (45%) may testify to nature of chemical adsorption. Sorption of the analyzed compounds occurs probably by means of hydrogen bonds, electrostatic and π  π interaction with the organic matter and the clay minerals of the soils.     

咪唑类离子液体对油基钻屑的处理

合成3种结构和性质呈规律性递变的离子液体1-烷基-3-甲基咪唑溴化盐[CnMIm]Br（n=8、10、12）,作为萃取剂替代有机溶剂用于油基钻屑的萃取处理。研究了离子液体结构对油去除率的影响规律,发现随着阳离子烷基链长的增加,油去除率提高。通过考察离子液体种类、加量、萃取时间及pH值等对萃取效果的影响,优选[C12MIm]Br为最佳萃取剂,油基钻屑与萃取液质量比为1：1、pH大于7时,萃取在20 min时就可以达到平衡,油基钻屑中油去除率大于85%,离子液体吸附损失率小于1%,分离后的离子液体可直接重复利用6次。     

水溶性离子液体对甲苯的吸收效果及影响因素

选择3种水溶性离子液体（十二烷基咪唑氯盐（DDMIM Cl）、十二烷基咪唑硝酸盐（DDMIM NO3）、十二烷基咪唑双氰胺盐（DDMIM DCA））作为研究对象,对模拟甲苯废气进行吸收实验,研究了吸收液的吸收性能、甲苯浓度、吸收液浓度、进气气速以及盐度等因素对吸收效果的影响以及加热蒸馏法对吸收液的再生与甲苯回收的可行性。结果表明：不同的离子液体对甲苯的吸收率不同,DDMIM DCA的吸收效果最好,在质量分数为5%时,初始吸收率达到98%,饱和吸收量为53.39 mg·L-1,而DDMIM Cl、DDMIM NO3对甲苯的初始吸收率在92%左右,饱和吸收量分别为33.60、37.01 mg·L-1;甲苯饱和吸收量与吸收液浓度、甲苯进气浓度呈正相关,与进气气速、含盐度呈负相关;传质系数与甲苯进气浓度、进气气速以及含盐度呈正相关,与吸收液浓度呈负相关;采用加热蒸馏法进行甲苯回收及吸收液再利用时,甲苯的回收效率达到85%~90%,且甲苯的饱和吸收量随着重复利用次数的增加而基本保持不变。因此利用离子液体溶液处理甲苯废气理论上是可行的。     

Toxic effect and mechanism of four ionic liquids on seedling taproots of Arabidopsis thaliana

Arabidopsis thaliana was selected as model organisms to investigate the toxic effect and mechanism of four kinds of imidazolium and pyridinium ionic liquids (ILs) on plant seedling taproots. After exposure to ILs, the growth of seedling taproots was significantly inhibited in a dose-dependent manner. The toxicity of ILs on seedling taproots was [Bmim][BF₄] > [Bmpy][BF₄] > [Bmim][Br] > [Bmpy][Br]. The reduction of seedling root cell vitality, aggravation of seedling root cell death, and repression of gravitropic growth responses were observed. The amounts of H₂O₂ and ROS in seedlings were enhanced with increasing concentrations of ILs. Moreover, the expression levels of cdc2a and pcna1 genes were decreased after exposure to ILs. Our results suggest that ILs can induce the overproduction of ROS in A. thaliana seedling taproots and thus cause oxidative damage to seedling taproots. Meanwhile, ILs alter the expression patterns of two cell cycle-related genes and hence cause the seedling taproot growth inhibition. This work provides an integrated understanding of the toxic effect and mechanism of ILs on A. thaliana seedlings at the molecular and physiological level and also provides theoretical basis and reference for the environmental safety evaluation of ILs, prior to their widespread use and release.

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Sorption of ionic liquids onto soils: experimental and chemometric studies

Chemometric analyses are a great tool to support typical experimental studies of the interactions of xenobiotics with natural environment. Such interpretations are able to determine statistically significant correlations and finally lead to identification of the major sorption factors. However, to effectively use chemometrics a bigger data set is required. Even though the ionic liquids are intensively studied, their complete fate or prediction of their behavior in the natural environment is still unclear. Therefore, to evaluate and distinguish the patterns of interactions of ILs in soil environment by chemometrics, sorption of nine ionic liquids (imidazolium and pyridinium chlorides) on 11 types of various soils was tested. Experimental studies indicated that compounds with longer alkyl side chains were sorbed far more strongly than weakly lipophilic ones. Moreover, salts with short and/or hydroxylated derivatives were more mobile in soils/sediments and thus, might cause a danger of contamination of surface or ground waters. Cluster analysis revealed that ionic liquids form two major clusters according to interaction with soil surface - one grouping compounds with short and hydroxylated alkyl side chains and the second with the rest of compounds. Pairwise scatterplots for correlations between soil variables and sorption coefficients indicated that the main soil parameter responsible for the sorption was cation exchange capacity. Correlation of sorption coefficients, K(d), with pH indicated the existence of lower sorption potency in lower pH values.     

5种吸附剂对水中离子液体的吸附性能

实验研究了蒙脱土、活性白土、人造沸石、活性炭和水滑石5种吸附材料在25℃和50℃下对[Bmim]Cl的吸附过程,结果表明,蒙脱土对离子液体的去除效果最好,温度对活性炭的吸附有一定的影响,而对其他吸附剂的影响不大,说明这些无机矿物发生了离子交换型吸附过程。实验进一步研究了蒙脱土在25℃下对[Bmim]Cl、[Bmim]BF4、[Bmim]PF6、[Bmim]DBP、[Hmim]Cl和[Omim]Cl 6种离子液体的吸附行为,结果表明,对于阳离子相同的离子液体,阴离子对吸附影响不大;对于阴离子相同的离子液体,其饱和吸附量随着阳离子链长的增加而减小。     

光催化法与生物法结合降解咪唑类离子液体

采用纳米TiO2光催化与生物降解相结合的方法,考察了3种1,3-二烷基咪唑类氯型离子液体的降解过程,并用HPLC-MS方法鉴定了光催化降解的碎片和可能的结构。结果表明,在相同条件下3,种离子液体光催化降解的速率次序为1-丁基-3-甲基咪唑氯盐（BmimCl）〉1-己基-3-甲基咪唑氯盐（HmimCl）≈1-辛基3-甲基咪唑氯盐（OmimCl）。BmimCl的光催化降解曲线符合一级动力学方程,最佳催化剂用量为0.5 g/L。HPLC-MS分析表明,光催化降解是咪唑开环氧化的过程,生成众多部分氧化碎片。离子液体水溶液的光催化预处理有利于提高其后续的活性污泥生物降解性能。     

Ecotoxicity prediction using mechanism- and non-mechanism-based QSARs: a preliminary study

In ecotoxicology, mechanism-based quantitative structure-activity relationships (QSARs) are usually developed with higher quality than QSARs without regard to toxicity mechanism. Correctly determining the mechanism of a compound, which is not always easy, is required to use mechanism-based QSARs for toxicity prediction. The mechanism determination step may introduce extra errors in addition to the intrinsic prediction errors of mechanism-based QSARs, thus compromising these QSARs' performance compared with QSARs regardless of mechanism. In this study, the mechanism identification-toxicity prediction (MI-TP) approach was compared with the direct toxicity prediction (DTP) approach using a data set containing phenol toxicity to Tetrahymena pyriformis. A statistical mechanism classification model for mechanism prediction, four mechanism-based QSARs and a single QSAR without discriminating between mechanisms were developed for toxicity prediction. Toxicity of phenols in an external data set was predicted following the MI-TP and DTP approaches. Results indicated that the mechanisms of several phenols in the external test set were incorrectly predicted which led to significant over- or under-estimation of their toxicity. Overall, the MI-TP approach did not yield more accurate toxicity prediction than the DTP approach.