基于镧系金属有机框架材料检测水体中酰胺类除草剂残留的可视化技术研究
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摘要
研发水体中酰胺类农药残留简便快捷的检测技术,对评估农药造成的水体污染和提出相应的治理对策具有重要意义。以共掺杂镧系金属离子(Eu~(3+)和Tb~(3+))作为配位金属离子,分别利用水热法和微波法制备了镧系金属有机框架材料(lanthanide metal-organic frameworks, LnMOF),对其结构和性质进行了表征,并采用所制备的Ln-MOF对水体中残留的5种常见酰胺类除草剂(乙草胺、异丙草胺、丙草胺、敌草胺和异丙甲草胺)进行了定性和定量分析。结果表明:与水热法相比,采用微波法制备的Ln-MOF样品呈蓬松的簇状、结晶度好,且具有更高的发光效率,故选择微波法制备Ln-MOF。农药残留检测试验结果表明,不同除草剂对Tb~(3+)和Eu~(3+)的发光会产生差别性猝灭,并使整体发射光发生变化,进而实现水体中农药的可视化检测。进一步研究发现,荧光强度比值I (Tb~(3+))/I (Eu~(3+))与丙草胺浓度在0.1～1 mmoL/L范围时呈线性相关,线性相关系数R~2=0.998,检测限(LOD)为0.08 mmoL/L。另外,该材料对于用湖水配制的除草剂溶液也具有一定的定性检测能力。本研究结果展现了Ln-MOF用于水体中酰胺类除草剂的定性、定量分析具有良好应用前景。
Convenient detection of amide herbicides in water is essential for assessing the herbicide pollution and proposing the corresponding countermeasures. In this work, Eu~(3+) and Tb~(3+) co-doped lanthanide metal-organic frameworks(Ln-MOF) were prepared using hydrothermal and microwave methods respectively. Their structure and optical properties were also characterized. Then the synthesized material was applied to the analysis of five amide herbicides(acetochlor, propisochlor,pretilachlor, napropamide and metolachlor) in water qualitatively and quantitatively. Results showed that the Ln-MOF prepared by microwave synthesis method was fluffy clusters with good crystallinity and high luminous efficiency. Therefore, the microwave synthesis method was selected. Test results show that diverse herbicides quench the fluorescence of Tb~(3+) and Eu~(3+) differently, which can change the color of emission light, then realizing the visual detection of amide herbicides in water. Further, when the concentration of pretilachlor is between 0.1 to 1 mmoL/L, the emission intensity ratio of I(Tb~(3+))/I(Eu~(3+)) increased with increase of the concentration of pretilachlor, with a correlation coefficient of R~2 =0.998. The limit of detection is 0.08 mmoL/L. Moreover, Ln-MOF can also be used for the qualitative analysis of the herbicide in lake water. These results indicated potential application of Ln-MOF for the qualitative and quantitative analysis of amide herbicides in water.
Convenient detection of amide herbicides in water is essential for assessing the herbicide pollution and proposing the corresponding countermeasures. In this work, Eu~(3+) and Tb~(3+) co-doped lanthanide metal-organic frameworks(Ln-MOF) were prepared using hydrothermal and microwave methods respectively. Their structure and optical properties were also characterized. Then the synthesized material was applied to the analysis of five amide herbicides(acetochlor, propisochlor,pretilachlor, napropamide and metolachlor) in water qualitatively and quantitatively. Results showed that the Ln-MOF prepared by microwave synthesis method was fluffy clusters with good crystallinity and high luminous efficiency. Therefore, the microwave synthesis method was selected. Test results show that diverse herbicides quench the fluorescence of Tb~(3+) and Eu~(3+) differently, which can change the color of emission light, then realizing the visual detection of amide herbicides in water. Further, when the concentration of pretilachlor is between 0.1 to 1 mmoL/L, the emission intensity ratio of I(Tb~(3+))/I(Eu~(3+)) increased with increase of the concentration of pretilachlor, with a correlation coefficient of R~2 =0.998. The limit of detection is 0.08 mmoL/L. Moreover, Ln-MOF can also be used for the qualitative analysis of the herbicide in lake water. These results indicated potential application of Ln-MOF for the qualitative and quantitative analysis of amide herbicides in water.
引文
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[25]GAO Y X,YU G,LIU K,et al.Luminescent mixed-crystal Ln-MOF thin film for the recognition and detection of pharmaceuticals[J].Sens Actnatnr B-Chem,2018,257:931-935.
[2]VASILAKOGLOU I B,ELEFTHEROHORINOS I G,DHIMA K B.Activity,adsorption and mobility of three acetanilide and two new amide herbicides[J].Weed Res,2001,41(6):535-546.
[3]ZHAO R S,DIAO C P,WANG X,et al.Rapid determination of amide herbicides in environmental water samples with dispersive liquid-liquid microextraction prior to gas chromatography-mass spectrometry[J].Anal Bioanal Chem,2008,391(8):2915-2921.
[4]XUE N D,LI F S,HOU H,et al.Occurrence of endocrine-disrupting pesticide residues in wetland sediments from Beijing,China[J].Environ Toxicol Chem,2008,27(5):1055-1062.
[5]李建中,储晓刚,蔡会霞,等.高效液相色谱法同时测定大豆中12种酰胺类除草剂的残留量[J].色谱,2006,24(6):585-588.LI J Z,CHU X G,CAI H X,et al.Simultaneous determination of residues of 12 amide herbicides in soybeans by high performance liquid chromatography[J].Chin J Chromatogr,2006,24(6):585-588.
[6]沈伟健,徐锦忠,杨雯筌,等.两种离子源技术气相色谱-质谱法检测茶叶中酰胺类除草剂的残留量[J].色谱,2007,25(5):753-757.SHEN W J,XU J Z,YANG W Q,et al.Determination of acetanilide herbicide residues in tea by gas chromatography-mass spectrometrywith two different ionization techniques[J].Chin J Chromatogr,2007,25(5):753-757.
[7]吴春英,白鹭,谷风,等·固相萃取-超高效液相色谱-串联质谱法同时测定地表水中的18种酰胺类除草剂[J].理化检验(化学分册),验2016,52(5):602-606.WU C Y,BAI L,GU F,et al.Simultaneous determination of 18amide herbicides in surface water by SPE-UPLC-MS/MS[J].Phys Test Chem Anal(Part B Chem Anal),2016,52(5):602-606.
[8]CADIAU A, BRITES C D S,COSTA P M F J,et al.Ratiometric nanothermometer based on an emissive Ln3+-organic framework[J].ACS Nano,2013,7(8):7213-7218.
[9]LONG J R,YAGHI O M.The pervasive chemistry of metal-organic frameworks[J].Chem Soc Rev,2009,38(5):1213-1214.
[10]LI B,WEN H M,CUI Y J,et al.Multifunctional lanthanide coordination polymers[J].Prog Polym Sci,2015(48):40-84.
[11]MOORE E G,SAMUEL A P S,RAYMOND K N.From antenna to assay:lessons learned in lanthanide luminescence[J].Accounts Chem Res,2009,42(4):542-552.
[12]CUI Y J,CHEN B L,QIAN G D.Lanthanide metal-organic frameworks for luminescent sensing and light-emitting applications[J].Coord Chem Rev,2014(273-274):76-86.
[13]DANG S,ZHANG J H,SUN Z M,et al.Luminescent lanthanide metal-organic frameworks with a large SHG response[J].Chem Commun,2012,48(90):11139-11141.
[14]LU W G,JIANG L,FENG X L,et al.Three-dimensional lanthanide anionic metal-organic frameworks with tunable luminescent properties induced by cation exchange[J].Inorg Chem,2009,48(15):6997-6999.
[15]XIAO Y Q,CUI Y J,ZHENG Q,et al.A microporous luminescent metal-organic framework for highly selective and sensitive sensing of Cu2+in aqueous solution[J].Chem Commun,2010,46(30):5503-5505.
[16]MA D Y,WANG W X,LI Y W,et al.In situ 2,5-pyrazinedicarboxylate and oxalate ligands synthesis leading to a microporous europium-organic framework capable of selective sensing of small molecules[J].CrystEngComm,2010,12(12):4372-4377.
[17]XIAO Y Q,WANG L B,CUI Y J,et al.Molecular sensing with lanthanide luminescence in a 3D porous metal-organic framework[J].J Alloy Compd,2009,484(1-2):601-604.
[18]CUI Y J,ZOU W F,SONG R J,et al.A ratiometric and colorimetric luminescent thermometer over a wide temperature range based on a lanthanide coordination polymer[J].Chem Common,2014,50(6),719-721.
[19]ZHAN C, OU S,ZOU C,et al.A luminescent mixed-lanthanideorganic framework sensor for decoding different volatile organic molecules[J].Anal Chem,2014,86(13):6648-6653.
[20]ROSI N L,KIM J,EDDAOUDI M,et al.Rod packings and metalorganic frameworks constructed from rod-shaped secondary building units[J].J Am Chem Soc,2005,127(5):1504-1518.
[21]HU Z C, DEIBERT B J,LI J.Luminescent metal-organic frameworks for chemical sensing and explosive detection[J].Chem Soc Rev,2014,43(16):5815-5840.
[22]BUNZLI J C G.Lanthanide luminescence for biomedical analyses and imaging[J].Chem Rev,2010,110(5):2729-2755.
[23]YANG W T,FENG J,SONG S Y,et al.Microwave-assisted modular fabrication of nanoscale luminescent metal-organic framework for molecular sensing[J].ChemPhysChem,2012,13(11):2734-2738.
[24]XU H,CAO C S,KANG X M,et al.Lanthanide-based metal-organic frameworks as luminescent probes[J].Dalton Trans,2016,45(45):18003-18017.
[25]GAO Y X,YU G,LIU K,et al.Luminescent mixed-crystal Ln-MOF thin film for the recognition and detection of pharmaceuticals[J].Sens Actnatnr B-Chem,2018,257:931-935.
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