咪唑类[PF6]^-型离子液体萃取胺类化合物

以眯唑类[PF6]^-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺、对氯苯胺等7种胺类化合物的萃取，考察了溶液初始浓度、相比、盐类、pH及离子液体眯唑基团上取代烷基对萃取平衡的影响，并研究了萃取过程的热效应。实验结果表明：溶液初始浓度对分配系数影响较小；相比10：1是离子液体对胺类化合物的溶解饱和临界点，当相比大于10：1时，分配系数降低；NaCl、K2SO4可以增大萃取分配系数，ZnSO4对分配系数几乎没有影响；pH增加，分配系数增大；离子液体对不同取代基的胺类萃取能力有较大的差异，咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著；萃取过程属于焓增大的吸热过程。     

温度对离子液体支撑膜捕集CO_2的影响

传统CO_2的捕集方法存在设备投资大、环境污染严重、再生能耗高等缺点,利用新型绿色工质离子液体负载于聚偏氟乙烯上制备离子液体支撑膜可以较好地解决该问题。在压力为0.2 MPa、流量为50 m L·min-1、温度在298～318 K范围内变化时,测定了CO_2在1-乙基-3甲基咪唑双三氟磺酰亚胺盐([Emim][Tf_2N])和1-乙基-3-甲基咪唑醋酸盐([Emim][AC])2种离子液体支撑膜中的渗透系数、溶解度和扩散系数,采用Van’t Hoff方程对溶解度数据进行关联、Arrhenius方程对渗透和扩散系数的数据进行关联。实验结果表明,CO_2在2种离子液体支撑膜中的渗透和扩散系数随着温度的升高而增大,溶解度随着温度的升高而降低。[Emim][Tf_2N]离子液体支撑膜对CO_2的捕集性能优于[Emim][AC]支撑膜,CO_2在[Emim][Tf2N]支撑膜中的溶解度最大值为0.447,在[Emim][AC]离子液体支撑膜中的最大溶解度为0.253,由此可确定离子液体支撑膜分离CO_2的最佳工作温度,为其在工业应用中奠定良好的基础。     

冠醚-离子液体体系对水相中铀酰离子的萃取

以二环己基-18-冠醚-6(DCH18C6)为萃取剂,一系列离子液体为溶剂的冠醚-离子液体萃取体系对水相中铀酰离子(UO2+2)进行萃取实验。结果表明:UO2+2在1-丁基-3-甲基咪唑双三氟磺酰亚胺盐([C4min]NTf2)体系的去除效率明显高于六氟磷酸盐类(PF-6)离子液体。在水相中当硝酸浓度在3 mol·L~(-1)左右时萃取效率最高,体系的萃取效率随着萃取剂浓度的增加而变大,共存离子的加入会降低体系的萃取效率,但是当加入的是硝酸根离子时,萃取率会相应增大。根据实验结果分析可以判断此萃取体系主要为阳离子交换过程。     

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,基咪唑溴化盐[C_nIm]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[C_(12)MIm]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。     

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。     

聚丙烯酸水凝胶对氯化-1-丁基-3-甲基咪唑离子液体的吸附热力学和动力学研究

通过水溶液聚合法制备了聚丙烯酸水凝胶（polyacrylic acid,PAA）,研究了溶液酸碱度和温度对聚丙烯酸水凝胶吸附氯化1-丁基3-甲基咪唑离子液体的影响。结果表明,水凝胶对氯化1-丁基3-甲基咪唑离子液体的吸附量随溶液pH值增大而逐渐增大,pH=2～4时增幅明显,而pH大于4时变化趋于缓慢;随温度的升高而逐渐降低。该等温吸附行为基本符合Langmuir吸附等温式,由二级吸附动力学模型获得的吸附过程活化能（Ea=52.470 kJ/mol）可以看出,PAA对氯化1-丁基3-甲基咪唑的吸附属于化学吸附范畴。     

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。     

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 NO_3)、十二烷基咪唑双氰胺盐(DDMIM DCA))作为研究对象寸模拟曱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J)DMIM 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 CKDDMIM NO_3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用苯的回收效率达到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。     

BiVO_4催化剂的离子液体辅助水热合成及其可见光催化活性

采用溴化1-丁基-3-甲基咪唑([Bmim]Br)离子液体辅助水热合成法制备了光催化剂Bi VO4。以高压氙灯作为可见光源,亚甲基蓝为目标污染物,考察反应温度、p H、反应时间和离子用量等制备条件对Bi VO4的可见光催化活性的影响,确定了最佳制备条件。并采用XRD、SEM和UV-Vis漫反射等分析手段对催化剂的晶相、形貌和光学特性进行了表征。结果表明,在离子液体加入量为2 m L、p H=4、反应温度为180℃、反应时间为4 h的条件下,制得的Bi VO4催化剂的可见光光催化活性最高。制得的Bi VO4为单斜相,呈分散的、大小均匀的片状,在200~500 nm范围有一个较宽的强吸收平台,具有良好的可见光催化活性,在可见光照射下对浓度为5 mg/L的亚甲基蓝的光催化脱色率达97%以上。     

生物柴油萃取高浓度吡啶废水

农药、医药等行业的生产过程中产生含有高浓度吡啶的废水,采用溶剂萃取法萃取废水中的吡啶既可改善废水的可生化性,又可实现吡啶的循环利用.实验以生物柴油为萃取剂,讨论了体系的pH值、温度、相比及时间等条件对萃取分配系数(D)及吡啶去除率的影响.结果表明,较为适宜吡啶萃取的条件是:萃取时间为30 min,pH值为6,温度为30℃,相比为1:1.在上述萃取条件下,生物柴油与吡啶水溶液进行六级错流萃取后,水中吡啶浓度从15%降至0.84%,吡啶去除率达到94.40%.     

Expression alterations of cytochromes P4501A1, 2E1, and 3A,and their receptors AhR and PXR caused by 1-octyl-3-methylimidazolium chloride in mouse mammary carcinoma cells

Cytochrome P450s (CYPs) play a key role in the metabolism of a wide range of environmental xenobiotics and endogenous compounds. The expression and activity levels of CYPs can be elevated by a process of induction involving the activation of nuclear receptors. The effects of the ionic liquid 1-octyl-3-methylimidazolium chloride ([C₈mim][Cl]) on the expression of cytochrome P450 members, including CYP1A1, CYP2E1, and CYP3A, as well as on aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) in mouse mammary carcinoma cells (EMT6) were investigated by using quantitative real-time PCR in the present study. The results reveal that [C₈mim][Cl]-exposure up-regulates the expressions of CYP1A1, CYP2E1, and CYP3A at mRNA level, suggesting that imidazolium-based ionic liquids can activate CYPs. Our results also suggest that [C₈mim][Cl]-mediated CYP3A induction be PXR-dependent. This result may be beneficial to evaluating the environmental toxicity of imidazolium-based ionic liquids and investigating the metabolism of imidazolium-derivative drugs.     

Toxicity of imidazolium- and pyridinium-based ionic liquids and the co-metabolic degradation of N-ethylpyridinium tetrafluoroborate

We examined the effects of the ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆], N-ethylpyridinium tetrafluoroborate [EtPy][BF₄], and N-ethylpyridinium trifluoroacetate [EtPy][CF₃COO] on Pseudomonas fluorescens, a ubiquitous soil bacterium. In the presence of 0.5- and 1% of [BMIM][PF₆] or [EtPy][CF₃COO] the growth of bacteria was inhibited, whereas exposing them to 1% [EtPy][BF₄] increased the lag period wherein bacteria adapt to growth conditions before continuing to grow. However, at higher concentrations (5% and 10%), no growth was observed. The inhibitory effects were evident by a decrease in the optical density of the culture, a decline in the consumption of the carbon source, citric acid, and a change in the size of the bacterium. At concentrations below 1%, [EtPy][BF₄] was metabolized by P. fluorescens in the presence of citric acid. Oxidation of the side alkyl-chain of [EtPy][BF₄] caused the accumulation of N-hydroxylethylpyridinium and pyridinium as major degradation products.     

Toxicity of imidazolium salt with anion bromide to a phytoplankton Selenastrum capricornutum: effect of alkyl-chain length

Room-temperature ionic liquids are regarded as environmentally benign alternatives to volatile organic solvents. However, the product designs for this promising group of compounds should take account, not only the technological needs, but also the eco-toxicological hazards. Therefore, this study aimed to evaluate the toxicity of some important ionic liquids on the growth of the freshwater alga, Selenastrum capricornutum. The ionic liquids examined in this study included 1-propyl-3-methylimidazolium [PMIM], 1-butyl-3-methylimidazolium [BMIM], 1-hexyl-3-methylimidazolium [HMIM] and 1-octyl-3-methylimidazolium [OMIM] with a bromide anion. The susceptibility of alga to ionic liquids was strongly dependent on the alkyl-chain length. According to our results, a longer alkyl-chain resulted in stronger inhibition of algal growth. In general, the toxicity could be summarized as decreasing in the following order: [OMIM]>[HMIM]>[BMIM]>or=[PMIM]. Among the ionic liquids examined, [OMIM] [Br] was found to be most toxic to S. capricornutum, with EC(50) values ranging from 26.3 microM to 54.9 microM after an incubating time of 96 h. Although [BMIM] [Br] and [PMIM] [Br] was relatively less toxic than [OMIM] and [HMIM], their toxicity increased as increasing the incubation time from 48 h to 96 h. This fact indicates that these kinds of ionic liquids may become more toxic after being released and contacted to freshwater ecosystem.     

Role of cation structure in the phytotoxicity of ionic liquids: growth inhibition and oxidative stress in spring barley and common radish

The present study determines the influence of three ionic liquids (ILs) containing cations with diversified structure on the growth and development of spring barley seedlings and common radish leaves. Increasing amounts of 1-butyl-1-methylpyrrolidinium hexafluorophosphate [Pyrrol][PF₆], 1-butyl-1-methylpiperidinium hexafluorophosphate [Piper][PF₆], and 1-butyl-4-methylpyridinium hexafluorophosphate [Pyrid][PF₆] were added to the soil on which both plants were cultivated. The results of this studies showed that the applied ILs were highly toxic for plants, demonstrated by the inhibition of length of plant shoots and roots, decrease of fresh mass, and increase of dry weight content. Common radish turned out to be the plant with higher resistance to the used ILs. The differences in the cation structure did not influence phytotoxity of ILs for spring barley. Furthermore, all ILs led to a decrease of photosynthetic pigments, which was directly followed by decreased primary production in plants. Oxidative stress in plants occurred due to the presence of ILs in the soil, which was demonstrated by the increase of malondialdehyde (MDA) content, changes in the H₂O₂ level, and antioxidant enzymes such as superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD). The changes in the chlorophyll contents and the increase of POD activity turned out to be the most significant oxidative stress biomarkers in spring barley and common radish. Both spring barley and radish exposed to ILs accumulated a large amount of fluoride ion.

     

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.     

Experimental investigation of density,viscosity, and surface tension of aqueous tetrabutylammonium-based ionic liquids

Environmental Science and Pollution Research - The physical properties such as density, dynamic viscosity, and surface tension of aqueous tetrabutylammonium-based ionic liquids were measured...     

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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The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Rapid quantification of polycyclic aromatic hydrocarbons in hydroxypropyl-beta-cyclodextrin (HPCD) soil extracts by synchronous fluorescence spectroscopy (SFS)

Synchronous fluorescence spectroscopy (SFS) was directly applied to rapidly quantify selected polycyclic aromatic hydrocarbons (PAHs: benzo[a]pyrene and pyrene) in aqueous hydroxypropyl-beta-cyclodextrin (HPCD) soil extract solutions from a variety of aged contaminated soils containing four different PAHs. The method was optimized and validated. The results show that SFS can be used to analyse benzo[a]pyrene and pyrene in HPCD based soil extracts with high sensitivity and selectivity. The linear calibration ranges were 4.0x10(-6)-1.0x10(-3)mM for benzo[a]pyrene and 6.0x10(-6)-1.2x10(-3)mM for pyrene in 10mM HPCD aqueous solution alone. The detection limits according to the error propagation theory for benzo[a]pyrene and pyrene were 3.9x10(-6) and 5.4x10(-6)mM, respectively. A good agreement between SFS and HPLC was reached for both determinations of PAHs in HPCD alone and in soil HPCD extracts. Hence, SFS is a potential means to simplify the present non-exhaustive hydroxypropyl-beta-cyclodextrin (HPCD)-based extraction technique for the evaluation of PAH bioavailability in soil.