Evaluation of interaction between imidazolium-based chloride ionic liquids and calf thymus DNA.

With ionic liquids (ILs) being widely used, the toxicity of many ILs has been studied and verified. However the mechanism underlying the interaction between ILs and DNA needs to be investigated. In this study, the interaction of three imidazolium-based ILs ([C8mim]Cl, [C12mim]Cl, and [C16mim]Cl) with calf thymus DNA (ctDNA) was investigated by UV absorption spectroscopy and fluorescence spectroscopy. An intense interaction between [Cnmim]Cl and ctDNA was observed, involving a hypochromic effect or even a hyperchromic effect, in the UV absorption spectrum of ctDNA at 260nm. The Tm of ctDNA increased over 10°C after binding with [Cnmim]Cl, and the KSV values of [Cnmim]Cl-ctDNA quenched by potassium iodide (KI) were lower than those of [Cnmim]Cl. The fluorescence intensity of ctDNA-ethidium bromide (EB) was gradually quenched as the [Cnmim]Cl concentration increased. The results indicated that ctDNA interacted with [Cnmim]Cl through an intercalation binding mode. The mechanism of fluorescence quenching of [Cnmim]Cl with ctDNA involved static quenching. The binding constant between [Cnmim]Cl and ctDNA were 1443, 11169, and 67189, and the number of binding sites were 0.89, 1.10, and 1.27 at 298K, for [C8mim]Cl, [C12mim]Cl, and [C16mim]Cl, respectively. The results indicated that the intercalation binding between the three [Cnmim]Cl and ctDNA increased with increasing IL-alkyl chain length. These results will aid in the understanding of the mechanism of toxicity and of the biologically mediated environmental processes of ILs.

Enantioselective toxicities of chiral ionic liquids 1-alkyl-3-methyl imidazolium tartrate on Scenedesmus obliquus.

Ionic liquids (ILs) are being used in various industries during the last few decades, while the good solubility and high stability of ILs may pose a potential threat to the aquatic environment. Effect of chiral ionic liquids (CILs) 1-alkyl-3-methyl imidazolium tartrate (RMIM T) on Scenedesmus obliquus (S.obliquus) was studied. The growth rate inhibition and cell membrane permeability increased with increasing RMIM T concentration and increasing alkyl chain lengths. The IC50 values of D-(-)-tartrate 1-hexyl-3-methyl imidazolium (D-(-)-HMIM T) were 28.30, 12.23,10.15 and 14.41 mg/L, respectively, at 24, 48, 72 and 96h. While that of L-(+)-tartrate 1-hexyl-3-methyl imidazolium (L-(+)-HMIM T) were 15.97, 7.91, 9.43 and 12.04 mg/L respectively. The concentration of chl a, chl b and chl (a+b) decreased with increasing RMIM T concentration. The chlorophyll fluorescence parameters (F0, Fv/Fm, Fv/F0, Y(II), ETR and NPQ) were affected by RMIM T, indicating that the RMIM T will damage the PSII, inhibit the transmission of excitation energy, decrease the efficiency of photosynthesis. The results showed that there were enantioselective toxicity of RMIM T to algae, and the toxicity of L-(+)-RMIM T was greater than that of D-(-)-RMIM T, but the enantioselective difference becomes smaller with increasing exposure time, and with the increasing carbon chain length of cation, indicating that cation properties may have a larger effect on toxicity than anion properties.

Effects of imidazolium chloride ionic liquids and their toxicity to Scenedesmus obliquus.

The low volatility of ionic liquids effectively eliminates a major pathway for environmental release and contamination; however, the good solubility, low degree of environmental degradation and biodegradation of ILs may pose a potential threat to the aquatic environment. The growth inhibition of the green alga Scenedesmus obliquus by five 1-alkyl-3-methylimidazolium chloride ionic liquids (ILs) ([Cnmim]Cl, n=6, 8, 10, 12, 16) was investigated, and the effect on cellular membrane permeability and the ultrastructural morphology by ILs ([Cnmim]Cl, n=8, 12, 16) were studied. The results showed that the growth inhibition rate increased with increasing IL concentration and increasing alkyl chain lengths. The relative toxicity was determined to be [C6mim]Cl<[C8mim]Cl<[C10mim]Cl<[C12mim]Cl<[C16mim]Cl. The algae were most sensitive to imidazolium chloride ILs at 48 h according to the results from the growth inhibition rate and cellular membrane permeability tests. The ultrastructural morphology showed that the ILs had negative effects on the cellular morphology and structure of the algae. The cell wall of treated algae became wavy and separated from the cell membrane. Chloroplast grana lamellae became obscure and loose, osmiophilic material was deposited in the chloroplast, and mitochondria and their cristae swelled. Additionally, electron-dense deposits were observed in the vacuoles.

[Combined toxicity of cadmium and S-metolachlor to Scenedesmus obliquus].

The single and combined effects of Cd2+ and S-metolachlor on acute toxicity, total soluble protein content, superoxide dismutase (SOD) activity and cell membrane permeability of Scenedesmus obliquus (S. obliquus) were studied using the standard toxic testing methods. The results showed that the EC50 of Cd2+ and S-metolachlor decreased with time, and the acute toxicity of S-metolachlor was higher than that of Cd2+, EC(50-24h) of Cd2+ and S-metolachlor was 0.27 mg x L(-1) and 0.24 mg x L(-1), respectively, and EC(50.96h) was 0.16 mg x L(-1) and 0.13 mg x L(-1), respectively. The combined toxicity of Cd2+ and S-metolachlor showed a synergistic effects at low concentration, and antagonism effects at high concentration. After 96h-exposure, the total soluble protein content of S. obliquus decreased, the SOD activity first increased and then decreased, and the cell membrane permeability increased with the increasing concentration of both single and combined treatment.

Growth inhibition and effect on photosystem by three imidazolium chloride ionic liquids in rice seedlings.

The effects of three imidazolium chloride ionic liquids (ILs) including 1-octyl-3-methylimidazolium chloride ionic liquid ([OMIM]Cl), 1-decyl-3-methylimidazolium chloride ionic liquid ([DMIM]Cl) and 1-dodecyl-3-methylimidazolium chloride ionic liquid ([C12MIM]Cl) were studied in hydroponically grown rice seedlings. The growth inhibition rate increased and the Hill reaction activity of isolated rice chloroplasts decreased with increasing ILs concentrations. The IC50,5d for stem length was 0.70 mg/L of [OMIM]Cl, 0.15 mg/L of [DMIM]Cl, and 0.055 mg/L of [C12MIM]Cl, respectively. The SOD, POD and CAT activities of chloroplast exhibited initial increases followed by decreases in activity with increasing ILs concentrations. Chlorophyll fluorescence parameters such as the maximum effective quantum yield of PSII(Fv/Fm), the potential activity of PSII(Fv/F0), the yield of photochemical quantum [Y(II)], the photochemical quenching coefficient (qP), the non-photochemical quenching coefficient (NPQ) and the relative electron transport ratio (rETR) were affected, showing that ILs will damage the PSII. The results demonstrated that imidazolium chloride ILs are phytotoxic to rice growth and their photosystem, the toxicity increased as the alkyl chain length increased with the following order: [OMIM]Cl<[DMIM]Cl<[C12MIM]Cl. The results will help to better understand the possible role of the defense mechanism in rice caused by ILs exposure.

[Influence of S-metolachlor and Cd2+ on photosynthesis of Scenedesmus obliquus].

The single and combined effects of Cd2+ and S-metolachlor on the chlorophyll content and chlorophyll fluorescence parameters of Scenedesmus obliquus were studied by using standard toxic testing method. Both Cd2+ and S-metolachlor had effects on the chlorophyll content and fluorescence parameters such as F0, FV/Fm, FV/F0, Y( II), qP, NPQ and rETR after 96 h-exposure, showing that Cd2+ and S-metolachlor damaged the PS II in algae, inhibited the primary reaction of photosynthesis, stopped the process of photosynthetic electron transport, and destroyed its ability of heat dissipation. The effects of Cd2 + on the chlorophyll content and fluorescence parameters were greater than those of S-metolachlor, and the effects increased with the increasing concentration. The average drop of Y( II ) was 62. 5% in the control group when the light intensity was 231 µmol (m2.s) -1 , and it was 68. 0% , 82. 5% and 100% respectively in Cd2+ -treated groups, and 66. 1% , 72. 1% and 79.6% respectively in S-metolachlor-treated group with the increasing concentration. The combined effects of Cd2+ and S-metolachlor on the chlorophyll fluorescence parameters were mainly due to the impacts of Cd2+.

[Influence of the coexistence of Zn2+ on the enantioselective toxicity of metolachlor to Scenedesmus obliquus].

To evaluate the enantioselective toxicity of chiral pesticide coexisting with heavy metal, the enantioselective toxicity of Rac-, S-metolachlor alone and coexisting with Zn2+ on Scenedesmus obliquus was studied by using standard toxic testing method. The results showed that the trend of the enantioselective toxicity of Rac- and S-metolachlor coexisting with Zn2+ was similar to that of Rac- and S-metolachlor alone. The growth inhibition rate of Scenedesmus obliquus was decreased by the coexistence of Zn2+ with high concentrations of metolachlor. The inhibition rates with 0.30 mg x L(-1) Rac- and S-metolachlor alone at 24 h were 49.61% and 59.73%, and in the coexistence of Zn2+ the values were 38.41% and 42.52%, respectively. The enantioselective toxicity of Rac- and S-metolachlor was expanded and the toxicity of S-metolachlor increased greater than that of Rac-metolachlor. The coexistence of Zn2+ showed partial increase in toxicity of metolachlor in low concentrations, while there was antagonistic effect in high content of metolachlor. The trend of Chlorophyll content of Scenedesmus obliquus at 96 h was in accordance with the growth inhibition.

Phytotoxicity and oxidative stress effect of 1-octyl-3-methylimidazolium chloride ionic liquid on rice seedlings.

The effects of the ionic liquid 1-octyl-3-methylimidazolium chloride ([OMIM]Cl) was studied in hydroponically grown rice seedlings. Observed effects included increased root length and weight at concentrations of 0.1 mg/L [OMIM]Cl, however, as concentrations increased a reversed response was observed where roots and stems grew shorter and the weight decreased. The inhibitory concentration 50 (IC50,5d) values for root length and stem length were 0.59 mg/L and 0.70 mg/L, respectively. The Hill reaction activity and root system activity in [OMIM]Cl-treated rice seedlings were observed to be lower than the controls, however, root membrane permeability increased. The antioxidant enzyme activity in roots decreased, while in leaves there was an initial stimulation followed by a decrease. Malondialdehyde (MDA) content was found to be greater in seedlings subjected to [OMIM]Cl treatment. The cellular structures, such as chloroplasts, mitochondria and rough endoplasmic reticulum in rice root and leaf cells were affected at concentrations of 0.6 mg/L [OMIM]Cl.