Trtić-Petrović Tatjana, Dimitrijević Aleksandra, Zdolšek Nikola, Đorđević Jelena, Tot Aleksandar, Vraneš Milan, Gadžurić Slobodan
Laboratory of Physics, Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, Belgrade, 11001, Serbia.
Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, Novi Sad, 21000, Serbia.
Anal Bioanal Chem. 2018 Jan;410(1):155-166. doi: 10.1007/s00216-017-0705-z. Epub 2017 Nov 2.
In this study, four hydrophilic ionic liquids (ILs) containing 1-alkyl-3-methylimidazolim cation and either salicylate or chloride anions were synthetized and studied as new task-specific ionic liquids (TSILs) suitable for aqueous biphasic system (ABS) formation and selective one-step extraction of copper(II). TSILs are designed so that the anion is responsible for forming the complex with metal(II) and preventing hydrolysis of metal cations at very strong alkaline pH, whereas the cation is responsible for selective extraction of metal(II)-salicylate complexes. It was found that 1-butyl-3-methylimidazolium salicylate could be used for selective extraction of Cu(II) in the presence of Zn(II), Cd(II), and Pb(II) at very alkaline solution without metal hydroxide formation. It was assumed that formation of metal(II)-salicylate complexes prevents the hydrolysis of the metal ions in alkaline solutions. The determined stability constants for Cu(II)-salicylate complexes, where salicylate was derived from different ionic liquids, indicated that there was no significant influence of the cation of the ionic liquid on the stability of the complexes. The ABS based on 1-butyl-3-methylimidazolium salicylate has been applied as the sample preparation step prior to voltammetric determination of Cu(II). The effect of volume of aqueous sample and IL and extraction time were investigated and optimum extraction conditions were determined. The obtained detection limits were 8 ng dm. The optimized method was applied for the determination of Cu(II) in tap water, wastewater, and urine. The study indicated that application of the ABS based on 1-butyl-3-methylimidazolium salicylate ionic liquid could be successfully applied as the sample preparation method for the determination of Cu(II) from various environmental samples. Graphical abstract Aqueous biphasic system based on task-specific ionic liquid as a sample pretreatment for selective determination of Cu(II) in biological and environmental sample.
在本研究中,合成了四种含有1-烷基-3-甲基咪唑阳离子以及水杨酸根或氯离子阴离子的亲水性离子液体(ILs),并将其作为适用于形成双水相体系(ABS)和选择性一步萃取铜(II)的新型任务特定离子液体(TSILs)进行研究。TSILs的设计使得阴离子负责与金属(II)形成络合物,并在极强碱性pH值下防止金属阳离子水解,而阳离子负责选择性萃取金属(II)-水杨酸络合物。研究发现,在强碱性溶液中,1-丁基-3-甲基咪唑水杨酸酯可用于在锌(II)、镉(II)和铅(II)存在下选择性萃取铜(II),且不会形成金属氢氧化物。据推测,金属(II)-水杨酸络合物的形成可防止金属离子在碱性溶液中水解。对于源自不同离子液体的水杨酸与铜(II)形成的络合物,所测定的稳定常数表明离子液体的阳离子对络合物的稳定性没有显著影响。基于1-丁基-3-甲基咪唑水杨酸酯的ABS已被用作伏安法测定铜(II)之前的样品制备步骤。研究了水样和离子液体体积以及萃取时间的影响,并确定了最佳萃取条件。获得的检测限为8 ng dm。该优化方法用于测定自来水、废水和尿液中的铜(II)。研究表明,基于1-丁基-3-甲基咪唑水杨酸酯离子液体的ABS可成功用作从各种环境样品中测定铜(II)的样品制备方法。图形摘要基于任务特定离子液体的双水相体系作为生物和环境样品中选择性测定铜(II)的样品预处理方法。