一种锌金属有机骨架(Zn-MOF)材料的荧光光谱法在食品Fe~(3+)检测中的应用
|
摘要
以2,5-呋喃二甲酸和六水硝酸锌为原料,N,N-二甲基甲酰胺为溶剂合成一种锌金属有机骨架材料[(Me_2NH_2)_2Zn_3(fdc)_4]_n·DMA(Zn-MOF)。用荧光光谱法对该材料的荧光特性进行研究,发现该材料在波长379 nm和398 nm处有很强的荧光发射峰。考察食品中可能存在的16种不同金属离子对该材料荧光强度的影响,研究表明,Fe~(3+)能选择性地令该材料产生荧光淬灭现象。此外,考察Fe~(3+)浓度、浸泡时间和2种混合金属离子(Fe~(3+)-M~(+/2+/3+))对荧光淬灭敏感度的影响。结果表明,锌金属有机骨架材料对Fe~(3+)具有高度选择性传感功能,可作为荧光探针应用到食品Fe~(3+)的检测中,并可以高效地检测出Fe~(3+)。
In this paper, a zinc-based metal organic framework, [(Me_2 NH_2)_2 Zn_3(fdc)_4]_n·DMA(Zn-MOF), was prepared from 2,5-furandicarboxylic acid and Zn(NO_3)_2·6H_2 O in N,N-dimethylformamide(DMF) under solvothermal condition. Fluorescence spectroscopic analysis revealed that the material showed emission maxima at 379 and 398 nm. The effects of 16 metal ions often coexisting in foods on the fluorescence intensity of the material were explored. The results indicated that Fe~(3+) could selectively quench the fluorescence of the material. In addition, the effects of Fe~(3+) concentration, soaking time and metal ion mixtures(Fe~(3+)-M~(+/2+/3+)) on the sensitivity of fluorescence quenching were also investigated. Our results showed that Zn-MOF exhibited high selectivity for Fe~(3+). Thus, this Zinc-based metal-organic framework material could be used as a fluorescent probe for the determination of Fe~(3+) in foods.
In this paper, a zinc-based metal organic framework, [(Me_2 NH_2)_2 Zn_3(fdc)_4]_n·DMA(Zn-MOF), was prepared from 2,5-furandicarboxylic acid and Zn(NO_3)_2·6H_2 O in N,N-dimethylformamide(DMF) under solvothermal condition. Fluorescence spectroscopic analysis revealed that the material showed emission maxima at 379 and 398 nm. The effects of 16 metal ions often coexisting in foods on the fluorescence intensity of the material were explored. The results indicated that Fe~(3+) could selectively quench the fluorescence of the material. In addition, the effects of Fe~(3+) concentration, soaking time and metal ion mixtures(Fe~(3+)-M~(+/2+/3+)) on the sensitivity of fluorescence quenching were also investigated. Our results showed that Zn-MOF exhibited high selectivity for Fe~(3+). Thus, this Zinc-based metal-organic framework material could be used as a fluorescent probe for the determination of Fe~(3+) in foods.
引文
[1]李国强,杨建君,何家洪,等.分光光度法测定铁(I I I)的研究进展[J].冶金分析,2014,34(1):34-44.DOI:10.13228/j.issn.1000-7571.2014.01.006.
[2]程辉,陆木丽,蒙一彬,等.分光光度法测定豆类中铁的含量(II)[J].广东微量元素科学,2005,7(12):62-64.DOI:10.16755/j.cnki.issn.1006-446x.2005.07.021.
[3]廖双,万燕,王敬凯,等.磺基水杨酸分光光度法测定黄豆和红豆中铁的含量[J].微量元素与健康研究,2018(1):40-41.
[4]苏圆.基于生物分子-金纳米簇的荧光光谱法在食品Fe3+和Al3+含量检测中的应用[D].泰安:山东农业大学,2016.
[5]宋娟.吡啶基类衍生配体及其过渡/稀土金属配合物的合成、晶体结构及性质研究[D].西安:西北大学,2014.
[6]薛铭,李雪阳,黄麟,等.新型三维金属-有机配位聚合物的合成、结构与性能[J].高等学校化学学报,2011,32(3):515-518.
[7]龙沛沛,程绍娟,赵强,等.金属-有机骨架材料的合成及其研究进展[J].山西化工,2008,28(6):21-25.DOI:10.3969/j.issn.1004-7050.2008.06.007.
[8]YUAN Y J,YU Z T,LI Y H,et al.A MoS2/6,13-pentacenequinone composite catalyst for visible-light-induced hydrogen evolution in water[J].Applied Catalysis B:Environmental,2016,181:16-23.DOI:10.1016/j.apcatb.2015.07.030.
[9]LOISEAU T,FEREY G,VOLKRINGER C,et al.Method for preparing metal-organic framework crystallised and porous aluminium aromatic azocarboxylates:US8907114B2[P/OL].2014-12-09[2017-08-20].https://www.researchgate.net/publication/302806507_Method_for_preparing_metal-organic_framework_crystallised_and_porous_aluminium_aromatic_azocarboxylates.
[10]WU H,GONG Q,OLSON D H,et al.Commensurate adsorption of hydrocarbons and alcohols in microporous metal organic frameworks[J].Chemical Reviews,2012,112(2):836-868.DOI:10.1021/cr200216x.
[11]LI J,FU H R,ZHANG J,et al.Anionic metal-organic framework for adsorption and separation of light hydrocarbons[J].Inorganic Chemistry,2015,54(7):3093-3095.DOI:10.1021/acs.inorgchem.5b00316.
[12]许春慧,庄海棠,钟依均,等.金属有机骨架材料上气体吸附存储与分离的研究进[J].浙江师范大学学报,2011,34(4):429-435.DOI:10.3969/j.issn.1001-5051.2011.04.013.
[13]LV J,CAO R.Porous organic molecular frameworks with extrinsic porosity:a platform for carbon storage and separation[J].Angewandte Chemie International Edition,2016,55(33):9474-9480.DOI:10.1002/anie.201602116.
[14]ANDIROVA D,COGSWELL C F,LEI Y,et al.Effect of the structural constituents of metal organic frameworks on carbon dioxide capture[J].Microporous and Mesoporous Materials,2016,219:276-305.DOI:10.1016/j.micromeso.2015.07.029.
[15]RANDY W L,LUKASZ W.Photo-physical studies of ruthenium(II)tris(1,10-phenanthroline)confined within a polyhedral zinc(II)-trimesic acid metal organic framework[J].Inorganica Chimica Acta,2017,466:243-248.DOI:10.1016/j.ica.2017.06.007.
[16]LIU S J,HAN S D,CHANG Z,et al.Cluster-and chain based magnetic MOFsderived from 3 d metalions and 1,3,5-benzenetricarboxylate[J].New Journal of Chemistry,2016,40(3):2680-2686.DOI:10.1039/C5NJ02161H.
[17]王丹丹.基于HA和MOF功能材料的构建及其在离子吸附、载药和荧光传感方面的应用研究[D].合肥:安徽大学,2016.
[18]冷玲,李壹,熊晓辉.重金属检测荧光传感技术的研究进展[J].食品工业科技,2016,37(15):380-384;389.DOI:10.13386/j.issn1002-0306.2016.15.066.
[19]KRENO L E,LEONGl K,ALLENDORTF M,et al.Metal-orgnaic framework materials as chemical sensors[J].Chemical Reviews,2012,112(2):1105-1125.DOI:10.1021/cr200324t.
[20]MA D Y,WANG W,LI Y,et al.In situ 2,5-pyrazinedicarboxylate and oxalate ligands synthesis leading to a microporous europiumorganic framework capable of selective sensing of small molecules[J].Royal Society of Chemistry,2010,12(12):4372-4377.DOI:10.1039/C0CE00135J.
[21]刘兵,介素云,李伯耿.金属-有机框架化合物在非均相催化反应中的应用[J].化学进展,2013,25(1):36-45.
[22]CHEN L,DUAN B,LUO Q,et al.Facet-dependent catalytic activity of ZIF-8 nanocubes and rhombic dodecahedra based on tracing substrate diffusion in pores by sers:a case study for surface catalysis of MOFs[J].Catalysis Science&Technology,2016,6(6):1616-1620.DOI:10.1039/C5CY01882J.
[23]LIU L,HAN Z B,WANG S M,et al.Robust molecular bowl-based metal-organic frameworks with open metal sites:size modulation to increase the catalytic activity[J].Inorganic Chemistry,2015,54(8):3719-3721.DOI:10.1021/acs.inorgchem.5b00185.
[24]TAN L L,SONG N,ZHANG X A,et al.Ca2+,pH and thermo tripleresponsive mechanized Zr-based MOFs for on-command drug release in bone diseases[J].Journal of Materials Chemistry B,2015,4(1):135-140.DOI:10.1039/c5tb01789k.
[25]BAG P P,WANG D,CHEN Z,et al.Outstanding drug loading capacity by water stable microporous MOF:a potential drug carrier[J].Chemical Communications,2016,52(18):3669-36681.DOI:10.1039/C5CC09925K.
[26]WANG J,MA D Y,LIAO W L,et al.A hydrostable anionic zincorganic framework carrier with a bcu topology for drug delivery[J].Royal Society of Chemistry,2017,19:5244-5250.DOI:10.1039/C7CE01238A.
[27]JIN H G,YAN Y Z,LI J,et al.1-D to 3-D lanthanide coordination polymers constructed from 5-aminoisophthalic acid and oxalic acid[J].Inorganic Chemistry Communications,2012,23(27):25-30.DOI:10.1016/j.inoche.2012.05.040.
[28]郏佳,唐茜,何颖芳,等.基于有机小分子的Zn2+/Cd2+荧光探针研究新进展[J].有机化学,2012,32(10):1803-1811.DOI:10.6023/cjoc1203103.
[29]MA D Y,LI Y W,LI Z.Tuning the moisture stability of metalorganic frameworks by incorporating hydrophobic functional groups at different positions of ligands[J].Chemical Communications,2011,47(26):7377-7379.DOI:10.1039/c1cc11752a.
[30]WU Y,HENKE S,KKIESLICH G,et al.Time-resolved in situ X-ray diffraction reveals metal-dependent metal-organic framework formation[J].Angewandte Chemie International Edition,2016,128(45):14287-14290.DOI:10.1039/c1cc11752a.
[31]赵旭东.金属-有机骨架材料对液相中离子的荧光识别和吸附的研究[D].北京:北京化工大学,2016.
[32]赵旭东,张玉田,黄宏亮,等.Z n3-M O F用于硝基苯的高效荧光识别[J].化工学报,2015,66(8):3248-3254.DOI:10.11949/j.issn.0438-1157.20150640.
[33]曹丽慧.多孔金属有机框架材料的结构转变、分离及荧光性能研究[D].郑州:郑州大学,2016.
[2]程辉,陆木丽,蒙一彬,等.分光光度法测定豆类中铁的含量(II)[J].广东微量元素科学,2005,7(12):62-64.DOI:10.16755/j.cnki.issn.1006-446x.2005.07.021.
[3]廖双,万燕,王敬凯,等.磺基水杨酸分光光度法测定黄豆和红豆中铁的含量[J].微量元素与健康研究,2018(1):40-41.
[4]苏圆.基于生物分子-金纳米簇的荧光光谱法在食品Fe3+和Al3+含量检测中的应用[D].泰安:山东农业大学,2016.
[5]宋娟.吡啶基类衍生配体及其过渡/稀土金属配合物的合成、晶体结构及性质研究[D].西安:西北大学,2014.
[6]薛铭,李雪阳,黄麟,等.新型三维金属-有机配位聚合物的合成、结构与性能[J].高等学校化学学报,2011,32(3):515-518.
[7]龙沛沛,程绍娟,赵强,等.金属-有机骨架材料的合成及其研究进展[J].山西化工,2008,28(6):21-25.DOI:10.3969/j.issn.1004-7050.2008.06.007.
[8]YUAN Y J,YU Z T,LI Y H,et al.A MoS2/6,13-pentacenequinone composite catalyst for visible-light-induced hydrogen evolution in water[J].Applied Catalysis B:Environmental,2016,181:16-23.DOI:10.1016/j.apcatb.2015.07.030.
[9]LOISEAU T,FEREY G,VOLKRINGER C,et al.Method for preparing metal-organic framework crystallised and porous aluminium aromatic azocarboxylates:US8907114B2[P/OL].2014-12-09[2017-08-20].https://www.researchgate.net/publication/302806507_Method_for_preparing_metal-organic_framework_crystallised_and_porous_aluminium_aromatic_azocarboxylates.
[10]WU H,GONG Q,OLSON D H,et al.Commensurate adsorption of hydrocarbons and alcohols in microporous metal organic frameworks[J].Chemical Reviews,2012,112(2):836-868.DOI:10.1021/cr200216x.
[11]LI J,FU H R,ZHANG J,et al.Anionic metal-organic framework for adsorption and separation of light hydrocarbons[J].Inorganic Chemistry,2015,54(7):3093-3095.DOI:10.1021/acs.inorgchem.5b00316.
[12]许春慧,庄海棠,钟依均,等.金属有机骨架材料上气体吸附存储与分离的研究进[J].浙江师范大学学报,2011,34(4):429-435.DOI:10.3969/j.issn.1001-5051.2011.04.013.
[13]LV J,CAO R.Porous organic molecular frameworks with extrinsic porosity:a platform for carbon storage and separation[J].Angewandte Chemie International Edition,2016,55(33):9474-9480.DOI:10.1002/anie.201602116.
[14]ANDIROVA D,COGSWELL C F,LEI Y,et al.Effect of the structural constituents of metal organic frameworks on carbon dioxide capture[J].Microporous and Mesoporous Materials,2016,219:276-305.DOI:10.1016/j.micromeso.2015.07.029.
[15]RANDY W L,LUKASZ W.Photo-physical studies of ruthenium(II)tris(1,10-phenanthroline)confined within a polyhedral zinc(II)-trimesic acid metal organic framework[J].Inorganica Chimica Acta,2017,466:243-248.DOI:10.1016/j.ica.2017.06.007.
[16]LIU S J,HAN S D,CHANG Z,et al.Cluster-and chain based magnetic MOFsderived from 3 d metalions and 1,3,5-benzenetricarboxylate[J].New Journal of Chemistry,2016,40(3):2680-2686.DOI:10.1039/C5NJ02161H.
[17]王丹丹.基于HA和MOF功能材料的构建及其在离子吸附、载药和荧光传感方面的应用研究[D].合肥:安徽大学,2016.
[18]冷玲,李壹,熊晓辉.重金属检测荧光传感技术的研究进展[J].食品工业科技,2016,37(15):380-384;389.DOI:10.13386/j.issn1002-0306.2016.15.066.
[19]KRENO L E,LEONGl K,ALLENDORTF M,et al.Metal-orgnaic framework materials as chemical sensors[J].Chemical Reviews,2012,112(2):1105-1125.DOI:10.1021/cr200324t.
[20]MA D Y,WANG W,LI Y,et al.In situ 2,5-pyrazinedicarboxylate and oxalate ligands synthesis leading to a microporous europiumorganic framework capable of selective sensing of small molecules[J].Royal Society of Chemistry,2010,12(12):4372-4377.DOI:10.1039/C0CE00135J.
[21]刘兵,介素云,李伯耿.金属-有机框架化合物在非均相催化反应中的应用[J].化学进展,2013,25(1):36-45.
[22]CHEN L,DUAN B,LUO Q,et al.Facet-dependent catalytic activity of ZIF-8 nanocubes and rhombic dodecahedra based on tracing substrate diffusion in pores by sers:a case study for surface catalysis of MOFs[J].Catalysis Science&Technology,2016,6(6):1616-1620.DOI:10.1039/C5CY01882J.
[23]LIU L,HAN Z B,WANG S M,et al.Robust molecular bowl-based metal-organic frameworks with open metal sites:size modulation to increase the catalytic activity[J].Inorganic Chemistry,2015,54(8):3719-3721.DOI:10.1021/acs.inorgchem.5b00185.
[24]TAN L L,SONG N,ZHANG X A,et al.Ca2+,pH and thermo tripleresponsive mechanized Zr-based MOFs for on-command drug release in bone diseases[J].Journal of Materials Chemistry B,2015,4(1):135-140.DOI:10.1039/c5tb01789k.
[25]BAG P P,WANG D,CHEN Z,et al.Outstanding drug loading capacity by water stable microporous MOF:a potential drug carrier[J].Chemical Communications,2016,52(18):3669-36681.DOI:10.1039/C5CC09925K.
[26]WANG J,MA D Y,LIAO W L,et al.A hydrostable anionic zincorganic framework carrier with a bcu topology for drug delivery[J].Royal Society of Chemistry,2017,19:5244-5250.DOI:10.1039/C7CE01238A.
[27]JIN H G,YAN Y Z,LI J,et al.1-D to 3-D lanthanide coordination polymers constructed from 5-aminoisophthalic acid and oxalic acid[J].Inorganic Chemistry Communications,2012,23(27):25-30.DOI:10.1016/j.inoche.2012.05.040.
[28]郏佳,唐茜,何颖芳,等.基于有机小分子的Zn2+/Cd2+荧光探针研究新进展[J].有机化学,2012,32(10):1803-1811.DOI:10.6023/cjoc1203103.
[29]MA D Y,LI Y W,LI Z.Tuning the moisture stability of metalorganic frameworks by incorporating hydrophobic functional groups at different positions of ligands[J].Chemical Communications,2011,47(26):7377-7379.DOI:10.1039/c1cc11752a.
[30]WU Y,HENKE S,KKIESLICH G,et al.Time-resolved in situ X-ray diffraction reveals metal-dependent metal-organic framework formation[J].Angewandte Chemie International Edition,2016,128(45):14287-14290.DOI:10.1039/c1cc11752a.
[31]赵旭东.金属-有机骨架材料对液相中离子的荧光识别和吸附的研究[D].北京:北京化工大学,2016.
[32]赵旭东,张玉田,黄宏亮,等.Z n3-M O F用于硝基苯的高效荧光识别[J].化工学报,2015,66(8):3248-3254.DOI:10.11949/j.issn.0438-1157.20150640.
[33]曹丽慧.多孔金属有机框架材料的结构转变、分离及荧光性能研究[D].郑州:郑州大学,2016.