Zhang Jingyu, Li Shang, Yao Liping, Han Yulin, Chen Kexian, Qian Mingrong, Li Zuguang, Lin Hui
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, China; Key Laboratory of Pollution Exposure and Health Intervention of Zhejiang Province, Interdisciplinary Research Academy, Zhejiang Shuren University, Hangzhou, 310015, China.
Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
Anal Chim Acta. 2024 Jul 4;1311:342714. doi: 10.1016/j.aca.2024.342714. Epub 2024 May 10.
Antibiotics residues can accelerate the growth of drug-resistant bacteria and harm the ecological environment. Under the effect of enrichment and biomagnification, the emergence of drug-resistant pathogenic bacteria may eventually lead to humans being ineffective to drugs in the face of bacterial or fungal disease infections in the future. It is urgent to develop an efficient separation medium and analytical method for simultaneous extraction and determination of antibiotics in the water environment.
This work doped 2,6-Di-O-methyl-β-cyclodextrin, randomly methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin with thymol:fatty acid respectively to construct non-covalent interaction-dominated pH-responsive ternary supramolecular deep eutectic solvents (SUPRADESs), which can undergo a hydrophilic/hydrophobic transition with aqueous phase to achieve an efficient microextraction. Semi-empirical method illustrated that SUPRADESs have a wide range of hydrogen bond receptor sites. We developed a SUPRADES-based analytical method combined with liquid chromatography-triple quadrupole mass spectrometry for the extraction and determination of trace quinolones and sulfonamides in wastewater. The overall limits of detection of the method were 0.0021-0.0334 ng mL and the limits of quantification were 0.0073-0.1114 ng mL. The linearity maintained good in the spiked level of 0.01-100 ng mL (R > 0.99). The overall enrichment factors of the method were 157-201 with lower standard deviations (≤8.7).
The method gave an extraction recovery of 70.1-115.3 % for 28 antibiotics in livestock farming wastewater samples from Zhejiang, China, at trace levels (minimum 0.5 ng mL). The results demonstrated that inducing the phase transition between SUPRADES and aqueous phase by adjusting pH for extraction is a novel and efficient pretreatment strategy. To our knowledge, this is the first application of cyclodextrin-based ternary SUPRADESs with pH-responsive reversible hydrophobicity-hydrophilicity transition behavior in wastewater analysis.
抗生素残留会加速耐药菌的生长并危害生态环境。在富集和生物放大作用的影响下，耐药病原菌的出现最终可能导致未来人类在面对细菌或真菌感染时无药可用。开发一种高效的分离介质和分析方法用于同时萃取和测定水环境中的抗生素迫在眉睫。
本研究分别将百里酚与脂肪酸掺杂到2,6-二-O-甲基-β-环糊精、随机甲基化-β-环糊精、2-羟丙基-β-环糊精中，构建以非共价相互作用为主的pH响应型三元超分子低共熔溶剂（SUPRADESs），其可与水相发生亲水/疏水转变以实现高效微萃取。半经验方法表明SUPRADESs具有广泛的氢键受体位点。我们开发了一种基于SUPRADESs的分析方法，结合液相色谱-三重四极杆质谱用于萃取和测定废水中的痕量喹诺酮类和磺胺类药物。该方法的总体检测限为0.0021 - 0.0334 ng/mL，定量限为0.0073 - 0.1114 ng/mL。在0.01 - 100 ng/mL的加标水平下线性良好（R > 0.99）。该方法的总体富集因子为157 - 201，标准偏差较低（≤8.7）。
该方法对来自中国浙江的养殖废水样品中28种痕量抗生素（最低0.5 ng/mL）的萃取回收率为70.1 - 115.3%。结果表明通过调节pH诱导SUPRADESs与水相之间的相变进行萃取是一种新颖且高效的预处理策略。据我们所知，这是基于环糊精的具有pH响应可逆疏水-亲水性转变行为的三元SUPRADESs在废水分析中的首次应用。
