CN113087902B - A kind of tetrazole-based porous organic polymer and its preparation method and application - Google Patents
A kind of tetrazole-based porous organic polymer and its preparation method and application Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000003536 tetrazoles Chemical class 0.000 title description 35
- YTNLBRCAVHCUPD-UHFFFAOYSA-N 5-(1$l^{2},2,3,4-tetrazol-5-yl)-1$l^{2},2,3,4-tetrazole Chemical compound [N]1N=NN=C1C1=NN=N[N]1 YTNLBRCAVHCUPD-UHFFFAOYSA-N 0.000 claims abstract description 34
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 21
- 239000011630 iodine Substances 0.000 claims abstract description 21
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002250 absorbent Substances 0.000 claims abstract description 8
- 230000002745 absorbent Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000011540 sensing material Substances 0.000 claims abstract description 8
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZKTARFAXHMRZEF-UHFFFAOYSA-N azane;5-(2h-tetrazol-5-yl)-2h-tetrazole Chemical compound N.N.N1N=NC(C2=NNN=N2)=N1 ZKTARFAXHMRZEF-UHFFFAOYSA-N 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- NGRXSVVLBWDAHG-UHFFFAOYSA-N n,n-bis(propan-2-ylamino)ethanamine Chemical compound CC(C)NN(CC)NC(C)C NGRXSVVLBWDAHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 6
- -1 phosphine cyanuric chloride Chemical compound 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000004815 dispersion polymer Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 3
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 3
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000013312 porous aromatic framework Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 125000003831 tetrazolyl group Chemical group 0.000 description 3
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000013317 conjugated microporous polymer Substances 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000013315 hypercross-linked polymer Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及荧光传感检测技术领域，尤其涉及一种联四唑基多孔有机聚合物及其制备方法、应用。The invention relates to the technical field of fluorescence sensing and detection, in particular to a bitetrazole-based porous organic polymer and a preparation method and application thereof.
背景技术Background technique
作为新一代可设计具有高稳定性和本征孔隙率、多孔性的有机聚合物，多孔有机聚合物(POPs)由于其在多相催化、气体分离和储存、电导性和光电子、荧光传感等潜在的应用前景而引起学术界和工业界的极大关注。为了满足其应用需求，有必要通过合理选择结构性砌块及聚合反应，优化多孔有机聚合物的结构和功能。到目前为止，已报道了各种多孔有机聚合物应用于缺电子分析物的荧光传感，如共轭微孔聚合物(CMPs)(J.Am.Chem.Soc.2012,134,8738-8741；J.Am.Chem.Soc.2013,135,8357-8362；J.Am.Chem.Soc.2014,136,2818-2824；Adv.Funct.Mater.2020,1910275)、多孔芳香骨架(PAFs)(J.Am.Chem.Soc.,2016,138,7603)、共价有机框架(COFs)(J.Am.Chem.Soc.2013,135,17310-17313；J.Am.Chem.Soc.2016,138,3031-3037；J.Am.Chem.Soc.2016,138,3302-3305；J.Am.Chem.Soc.,2017,139(6),2421–2427；J.Am.Chem.Soc.2017,139(25),8698-8704)、超交联聚合物(HCPs)(Eur.Polym.J.,130(2020)109674)、共价三嗪基骨架(CTFs)(J.Mater.Chem.A,2017,5,7612–7617；Macromolecules,2017,50(21),8512–8520；J.Mater.Chem.A,2020,8,2820–2826)、自具微孔聚合物(PIMs)和多孔聚合物网络(PPN)，等。研究表明，在多孔有机骨架中引入氮原子，构建富含氮原子的POPs，可以赋予材料更多的功能。As a new generation of organic polymers that can be designed with high stability and intrinsic porosity and porosity, porous organic polymers (POPs) are due to their applications in heterogeneous catalysis, gas separation and storage, electrical conductivity and optoelectronics, fluorescence sensing, etc. The potential application prospects have attracted great attention from academia and industry. In order to meet their application requirements, it is necessary to optimize the structure and function of porous organic polymers through rational selection of structural building blocks and polymerization reactions. So far, various porous organic polymers have been reported for fluorescence sensing of electron-deficient analytes, such as conjugated microporous polymers (CMPs) (J.Am.Chem.Soc.2012,134,8738-8741 ; J.Am.Chem.Soc.2013,135,8357-8362; J.Am.Chem.Soc.2014,136,2818-2824; Adv.Funct.Mater.2020,1910275), porous aromatic frameworks (PAFs) (J.Am.Chem.Soc.,2016,138,7603), Covalent Organic Frameworks (COFs) (J.Am.Chem.Soc.2013,135,17310-17313; J.Am.Chem.Soc.2016 , 138, 3031-3037; J.Am.Chem.Soc.2016, 138, 3302-3305; J.Am.Chem.Soc., 2017, 139(6), 2421–2427; J.Am.Chem.Soc. .2017,139(25),8698-8704), hypercrosslinked polymers (HCPs) (Eur.Polym.J., 130(2020)109674), covalent triazine-based frameworks (CTFs) (J.Mater. Chem.A, 2017, 5, 7612–7617; Macromolecules, 2017, 50(21), 8512–8520; J.Mater.Chem.A, 2020, 8, 2820–2826), self-porous polymers (PIMs ) and porous polymer network (PPN), etc. Studies have shown that introducing nitrogen atoms into porous organic frameworks to construct nitrogen-rich POPs can endow materials with more functions.
四唑基金属有机骨架(MOFs)由于具有共轭的荧光基团和丰富的氮原子，具有荧光性能(科学通报，2014,59(15),1423-1428；无机化学学报,2014,30(6),1367-1372)，可用于金属离子的荧光传感(应用化学，2017,34(9),1046-1051)。但是现有纳米孔金属有机骨架的主要缺点是它们的物理化学稳定性较差。Tetrazolium-based metal-organic frameworks (MOFs) have fluorescent properties due to their conjugated fluorescent groups and abundant nitrogen atoms (Science Bulletin, 2014, 59(15), 1423-1428; Journal of Inorganic Chemistry, 2014, 30(6 ), 1367-1372), which can be used for the fluorescence sensing of metal ions (Applied Chemistry, 2017, 34(9), 1046-1051). But the main disadvantage of existing nanoporous MOFs is their poor physicochemical stability.
与大多数MOFs不同，多孔有机聚合物显示特殊的热和水热稳定性。但是四唑基多孔有机聚合物的研究较少。利用计算机辅助设计，加州大学Jiang课题组提出了新的含四唑的多孔芳香骨架，通过将含氮基团引入联苯单元，用蒙特卡罗模拟并预测它们的CO2吸附容量(J.Colloid Interf.Sci.438(2015)191–195)。目前，尚未见到联四唑基多孔有机聚合物的报道。Unlike most MOFs, porous organic polymers display exceptional thermal and hydrothermal stability. However, the studies on tetrazole-based porous organic polymers are less. Using computer-aided design, Jiang's group at the University of California proposed new tetrazole-containing porous aromatic frameworks, by introducing nitrogen-containing groups into biphenyl units, and using Monte Carlo to simulate and predict their CO2 adsorption capacity (J.Colloid Interf. Sci. 438(2015) 191–195). So far, there have been no reports on tetrazole-based porous organic polymers.
发明内容Contents of the invention
基于背景技术存在的技术问题，本发明提出了一种联四唑基多孔有机聚合物及其制备方法、应用，本发明用合适的结构性砌块，通过亲核取代反应制备出具有荧光性质的联四唑基多孔有机聚合物，可作为荧光传感材料，在其他物质存在的情况下，能够选择性地传感单质碘(I2)或对硝基苯酚(p-NP)；检测方法灵敏度高，选择性好。Based on the technical problems existing in the background technology, the present invention proposes a bitetrazole-based porous organic polymer and its preparation method and application. The present invention uses a suitable structural building block to prepare a fluorescent substance through a nucleophilic substitution reaction. The tetrazole-based porous organic polymer can be used as a fluorescent sensing material, which can selectively sense elemental iodine (I 2 ) or p-nitrophenol (p-NP) in the presence of other substances; the sensitivity of the detection method High, good selectivity.
本发明提出了一种联四唑基多孔有机聚合物，其结构如式(I)或式(II)所示：The present invention proposes a kind of combined tetrazole-based porous organic polymer, its structure is as shown in formula (I) or formula (II):
本发明还提出了上述联四唑基多孔有机聚合物的制备方法，包括如下步骤：取物质A、5,5′-联四唑二铵盐，在酸吸收剂存在下，进行亲核取代反应，得到联四唑基多孔有机聚合物，其中，物质A为三聚氯化氰或三聚氯化膦氰。The present invention also proposes a method for preparing the above-mentioned bitetrazole-based porous organic polymer, which includes the following steps: taking substance A, 5,5'-bitetrazole diammonium salt, and performing a nucleophilic substitution reaction in the presence of an acid absorbent , to obtain a tetrazole-based porous organic polymer, wherein the substance A is cyanuric chloride or phosphinogen trichloride.
优选地，在惰性气体氛围中进行亲核取代反应。Preferably, the nucleophilic substitution reaction is performed in an inert gas atmosphere.
优选地，亲核取代反应的温度为60-140℃。Preferably, the temperature of the nucleophilic substitution reaction is 60-140°C.
优选地，亲核取代反应的时间为24-96h。Preferably, the time for the nucleophilic substitution reaction is 24-96h.
优选地，物质A、5,5'-联四唑二铵盐、酸吸收剂的摩尔比为(1-99):(1.5-300):(6-600)。Preferably, the molar ratio of substance A, 5,5'-diammonium tetrazolium salt, and acid absorbent is (1-99):(1.5-300):(6-600).
优选地，物质A、5,5'-联四唑二铵盐、酸吸收剂的摩尔比为1:(1.5-3.03):(6-13)。Preferably, the molar ratio of substance A, 5,5'-diammonium tetrazolium salt, and acid absorbent is 1:(1.5-3.03):(6-13).
优选地，酸吸收剂为三乙胺、N,N-二异丙胺基乙胺中的至少一种。Preferably, the acid absorbent is at least one of triethylamine and N,N-diisopropylaminoethylamine.
优选地，反应溶剂为乙腈、四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺中的至少一种。Preferably, the reaction solvent is at least one of acetonitrile, tetrahydrofuran, 1,4-dioxane, and N,N-dimethylformamide.
上述亲核取代反应后，提纯得到联四唑基多孔有机聚合物，提纯方法为：亲核取代反应后，固液分离，洗涤固体，抽提，干燥得到联四唑基多孔有机聚合物；干燥方式优选真空干燥，干燥温度优选50-150℃；抽提时间可以为24h。After the above-mentioned nucleophilic substitution reaction, purify to obtain the bitetrazole-based porous organic polymer, the purification method is: after the nucleophilic substitution reaction, separate the solid from the liquid, wash the solid, extract, and dry to obtain the bi-tetrazole-based porous organic polymer; The method is preferably vacuum drying, and the drying temperature is preferably 50-150°C; the extraction time can be 24h.
上述洗涤用溶剂可以为蒸馏水、乙醇、二氯甲烷、四氢呋喃等；抽提用溶剂可以为乙醇、二氯甲烷、四氢呋喃等。The above solvent for washing can be distilled water, ethanol, dichloromethane, tetrahydrofuran, etc.; the solvent for extraction can be ethanol, dichloromethane, tetrahydrofuran, etc.
本发明还公开了上述联四唑基多孔有机聚合物作为荧光传感材料的应用。The invention also discloses the application of the above-mentioned tetrazole-based porous organic polymer as a fluorescent sensing material.
优选地，所述联四唑基多孔有机聚合物作为荧光传感材料，用于荧光传感单质碘或对硝基苯酚。Preferably, the bitetrazole-based porous organic polymer is used as a fluorescent sensing material for fluorescent sensing of elemental iodine or p-nitrophenol.
本发明所述联四唑基多孔有机聚合物能够在其它物质存在的情况下，能选择性的荧光传感单质碘或对硝基苯酚，具有良好的灵敏性和选择性。The bitetrazole-based porous organic polymer of the present invention can selectively fluorescently sense elemental iodine or p-nitrophenol in the presence of other substances, and has good sensitivity and selectivity.
采用绘制Stern–Volmer曲线的方法，计算联四唑基多孔有机聚合物对单质碘、对硝基苯酚的荧光传感的灵敏性。Using the method of drawing Stern–Volmer curves, the sensitivity of fluorescent sensing of tetrazole-based porous organic polymers to elemental iodine and p-nitrophenol was calculated.
所述绘制Stern–Volmer曲线的具体步骤为：The concrete steps of described drawing Stern–Volmer curve are:
使用荧光分光光度计，通过不断地激发-发射过程，找到最佳激发波长λex，在此激发波长下，测定联四唑基多孔有机聚合物分散液的荧光发射光谱，选择最高发射峰处的荧光强度记作I0；逐步滴加单质碘溶液或对硝基苯酚溶液，每次滴加混匀后，测定荧光发射光谱，选择最高发射峰处的荧光强度记作I；以相对荧光强度(I0/I)为纵坐标，单质碘或对硝基苯酚在联四唑基多孔有机聚合物分散液中的浓度为横坐标，绘制Stern–Volmer曲线，取直线部分，获得Stern–Volmer方程，其斜率即为Stern–Volmer常数(KSV)。Use a fluorescence spectrophotometer to find the optimal excitation wavelength λ ex through the continuous excitation-emission process. Under this excitation wavelength, measure the fluorescence emission spectrum of the tetrazole-based porous organic polymer dispersion, and select the highest emission peak. Fluorescence intensity is recorded as I 0 ; elemental iodine solution or p-nitrophenol solution is gradually added dropwise, and after each drop is mixed, the fluorescence emission spectrum is measured, and the fluorescence intensity at the highest emission peak is selected as I; the relative fluorescence intensity ( I 0 /I) is the ordinate, the concentration of elemental iodine or p-nitrophenol in the bitetrazole-based porous organic polymer dispersion is the abscissa, draws the Stern–Volmer curve, takes the straight line part, and obtains the Stern–Volmer equation, Its slope is the Stern–Volmer constant (K SV ).
上述联四唑基多孔有机聚合物分散液中，联四唑基多孔有机聚合物的浓度为0.01-1.0mg/mL；优选地，0.1mg/mL。In the aforementioned bitetrazole-based porous organic polymer dispersion, the concentration of the bitetrazole-based porous organic polymer is 0.01-1.0 mg/mL; preferably, 0.1 mg/mL.
不限定联四唑基多孔有机聚合物分散液的溶剂种类，能使单质碘、对硝基苯酚溶解、使联四唑基多孔有机聚合物均匀分散且荧光强度高的溶剂即可选用。The type of solvent for the bitetrazole-based porous organic polymer dispersion is not limited, and a solvent that can dissolve elemental iodine and p-nitrophenol, uniformly disperse the bitetrazole-based porous organic polymer and have high fluorescence intensity can be selected.
上述步骤中，使用荧光分光光度计进行检测，检测电压为220-700V，狭缝宽度为5-20nm。In the above steps, a fluorescence spectrophotometer is used for detection, the detection voltage is 220-700V, and the slit width is 5-20nm.
有益效果：Beneficial effect:
本发明选取合适的结构性砌块，通过亲核取代反应制备出具有荧光性能的联四唑基多孔有机聚合物，可以作为荧光传感材料，在其他物质存在的情况下，能够选择性地荧光传感单质碘、对硝基苯酚；且检测方法操作简便，信号直观、灵敏度高、选择性好，可实时原位检测。The present invention selects suitable structural building blocks and prepares bitetrazole-based porous organic polymers with fluorescent properties through nucleophilic substitution reactions, which can be used as fluorescent sensing materials and can selectively fluoresce in the presence of other substances. Sensing elemental iodine and p-nitrophenol; and the detection method is easy to operate, the signal is intuitive, high sensitivity, good selectivity, and can be detected in situ in real time.
附图说明Description of drawings
图1为实施例1中联四唑基多孔有机聚合物TBTZ在四氢呋喃中的发射光谱和激发光谱图。Figure 1 is the emission spectrum and excitation spectrum of the tetrazole-based porous organic polymer TBTZ in tetrahydrofuran in Example 1.
图2为碘淬灭实施例1中联四唑基多孔有机聚合物TBTZ的结果，其中，(a)为碘淬灭联四唑基多孔有机聚合物TBTZ在四氢呋喃中的发射光谱图；(b)为碘淬灭联四唑基多孔有机聚合物TBTZ在四氢呋喃中的Stern–Volmer曲线。Fig. 2 is the result that iodine quenches the tetrazole-based porous organic polymer TBTZ in Example 1, wherein, (a) is the emission spectrogram of iodine-quenched tetrazole-based porous organic polymer TBTZ in tetrahydrofuran; (b ) is the Stern–Volmer curve of the iodine-quenched tetrazole-based porous organic polymer TBTZ in tetrahydrofuran.
图3为对硝基苯酚淬灭实施例2中联四唑基多孔有机聚合物HBTZ的结果，其中，(a)为对硝基苯酚淬灭联四唑基多孔有机聚合物HBTZ在N,N-二甲基甲酰胺中的发射光谱图；(b)为对硝基苯酚淬灭联四唑基多孔有机聚合物HBTZ在N,N-二甲基甲酰胺中的Stern–Volmer曲线。Fig. 3 is the result of p-nitrophenol quenching the tetrazole-based porous organic polymer HBTZ in Example 2, wherein, (a) is the p-nitrophenol quenching bi-tetrazole-based porous organic polymer HBTZ in N,N -Emission spectrum in dimethylformamide; (b) is the Stern–Volmer curve of p-nitrophenol quenched tetrazole-based porous organic polymer HBTZ in N,N-dimethylformamide.
图4为单质碘、硝基芳香族化合物或苯酚对实施例1和实施例2中联四唑基多孔有机聚合物相对荧光强度影响的柱状图，其中，(a)为实施例1，(b)为实施例2。Fig. 4 is the histogram that elemental iodine, nitroaromatic compound or phenol affect relative fluorescence intensity of tetrazole-based porous organic polymer in embodiment 1 and embodiment 2, wherein, (a) is embodiment 1, (b ) is embodiment 2.
图5为实施例1和实施例2中联四唑基多孔有机聚合物对单质碘或对硝基苯酚的选择性荧光传感结果，其中，(a)为实施例1，(b)为实施例2。Fig. 5 is the selective fluorescence sensing result of elemental iodine or p-nitrophenol in the joint tetrazole-based porous organic polymer in embodiment 1 and embodiment 2, wherein, (a) is embodiment 1, (b) is implementation Example 2.
具体实施方式Detailed ways
下面，通过具体实施例对本发明的技术方案进行详细说明。Below, the technical solution of the present invention will be described in detail through specific examples.
实施例1Example 1
一种联四唑基多孔有机聚合物的制备方法，包括如下步骤：A preparation method of a tetrazole-based porous organic polymer, comprising the steps of:
快速称取三聚氯化氰(TCT，0.5554g，3.0mmol)，并加入到一个N2填充的100mL两颈圆形底部烧瓶中，配备磁力搅拌棒和冷凝器；然后加入5,5'-联四唑二铵盐(TBZ，0.7919g，4.5mmol)；接着将三乙胺(2.70mL，19.5mmol)和四氢呋喃(48mL)的混合物转移到圆底烧瓶中；再将烧瓶放置在油浴中，浴温升高到80℃，反应混合物搅拌回流72h后，冷却，抽滤，固体产物分别用蒸馏水、乙醇和四氢呋喃各洗涤三次；再用乙醇、四氢呋喃和二氯甲烷在索氏提取器中各抽提取24h，最后在50℃真空干燥箱中干燥，得到联四唑基多孔有机聚合物，为淡黄色粉末，记为TBTZ。Quickly weigh cyanuric chloride (TCT, 0.5554g, 3.0mmol) and add it to a N2- filled 100mL two-neck round bottom flask equipped with a magnetic stirring bar and a condenser; then add 5,5'- Diammonium tetrazolium salt (TBZ, 0.7919 g, 4.5 mmol); then a mixture of triethylamine (2.70 mL, 19.5 mmol) and tetrahydrofuran (48 mL) was transferred to a round bottom flask; the flask was then placed in an oil bath , the bath temperature was raised to 80°C, the reaction mixture was stirred and refluxed for 72 hours, cooled, filtered with suction, and the solid product was washed three times with distilled water, ethanol and tetrahydrofuran respectively; After extracting for 24 hours, and finally drying in a vacuum oven at 50°C, the bitetrazole-based porous organic polymer was obtained as light yellow powder, denoted as TBTZ.
实验1Experiment 1
取实施例1制得的联四唑基多孔有机聚合物TBTZ对单质碘进行荧光传感，结果如图1-2所示。图1为实施例1中联四唑基多孔有机聚合物TBTZ在四氢呋喃中的发射光谱和激发光谱图；图2为碘淬灭实施例1中联四唑基多孔有机聚合物TBTZ的结果，其中，(a)为碘淬灭联四唑基多孔有机聚合物TBTZ在四氢呋喃中的发射光谱图；(b)为碘淬灭联四唑基多孔有机聚合物TBTZ在四氢呋喃中的Stern–Volmer曲线。The bitetrazole-based porous organic polymer TBTZ prepared in Example 1 was used for fluorescence sensing of elemental iodine, and the results are shown in Figure 1-2. Fig. 1 is the emission spectrum and excitation spectrogram of tetrazole-based porous organic polymer TBTZ in tetrahydrofuran in embodiment 1; Fig. 2 is the result of iodine quenching embodiment 1 in-linked tetrazole-based porous organic polymer TBTZ, wherein , (a) is the emission spectrum of the iodine-quenched bitetrazole-based porous organic polymer TBTZ in THF; (b) is the Stern–Volmer curve of the iodine-quenched bitetrazole-based porous organic polymer TBTZ in THF.
由图2可以看出，联四唑基多孔有机聚合物TBTZ对单质碘的相对荧光强度与单质碘的浓度之间呈现良好的线性关系，Stern–Volmer常数KSV达1.67×104L/mol，表明联四唑基多孔有机聚合物TBTZ能荧光传感单质碘，具有很高的灵敏性。It can be seen from Figure 2 that there is a good linear relationship between the relative fluorescence intensity of the tetrazole-based porous organic polymer TBTZ for elemental iodine and the concentration of elemental iodine, and the Stern–Volmer constant K SV reaches 1.67×10 4 L/mol , indicating that the tetrazole-based porous organic polymer TBTZ can fluorescently sense elemental iodine with high sensitivity.
实施例2Example 2
一种联四唑基多孔有机聚合物的制备方法，包括如下步骤：A preparation method of a tetrazole-based porous organic polymer, comprising the steps of:
快速称取三聚氯化膦氰(HCCP，1.0430g，3.0mmol)，并加入到一个N2填充的150mL两颈圆形底部烧瓶中，配备磁力搅拌棒和冷凝器；然后加入5,5'-联四唑二铵盐(TBZ，1.5839g，9.0mmol)；接着将三乙胺(5.40mL，39mmol)和四氢呋喃(96mL)的混合物转移到圆底烧瓶中；再将烧瓶放置在油浴中，浴温升高到80℃，反应混合物搅拌回流72h后，冷却，抽滤，固体产物分别用蒸馏水、乙醇和四氢呋喃各洗涤三次；再用乙醇、四氢呋喃和二氯甲烷在索氏提取器中各抽提取24h，最后在50℃真空干燥箱中干燥，得到联四唑基多孔有机聚合物，为白色粉末，记为HBTZ。Quickly weigh phosphacyanine chloride (HCCP, 1.0430 g, 3.0 mmol) and add to a N filled 150 mL two - neck round bottom flask equipped with a magnetic stirring bar and condenser; then add 5,5' - diammonium tetrazolium salt (TBZ, 1.5839 g, 9.0 mmol); then a mixture of triethylamine (5.40 mL, 39 mmol) and tetrahydrofuran (96 mL) was transferred to a round bottom flask; the flask was then placed in an oil bath , the bath temperature was raised to 80°C, the reaction mixture was stirred and refluxed for 72 hours, cooled, filtered with suction, and the solid product was washed three times with distilled water, ethanol and tetrahydrofuran respectively; Extract for 24 hours, and finally dry in a vacuum oven at 50°C to obtain a bitetrazole-based porous organic polymer as a white powder, which is designated as HBTZ.
实验2Experiment 2
取实施例2制得的联四唑基多孔有机聚合物HBTZ对对硝基苯酚进行荧光传感，结果如图3所示。图3为对硝基苯酚淬灭实施例2中联四唑基多孔有机聚合物HBTZ的结果，其中，(a)为对硝基苯酚淬灭联四唑基多孔有机聚合物HBTZ在N,N-二甲基甲酰胺中的发射光谱图；(b)为对硝基苯酚淬灭联四唑基多孔有机聚合物HBTZ在N,N-二甲基甲酰胺中的Stern–Volmer曲线。The tetrazole-based porous organic polymer HBTZ prepared in Example 2 was used for fluorescence sensing of p-nitrophenol, and the results are shown in FIG. 3 . Fig. 3 is the result of p-nitrophenol quenching the tetrazole-based porous organic polymer HBTZ in Example 2, wherein, (a) is the p-nitrophenol quenching bi-tetrazole-based porous organic polymer HBTZ in N,N -Emission spectrum in dimethylformamide; (b) is the Stern–Volmer curve of p-nitrophenol quenched tetrazole-based porous organic polymer HBTZ in N,N-dimethylformamide.
由图3可以看出，联四唑基多孔有机聚合物HBTZ对对硝基苯酚的相对荧光强度与对硝基苯酚的浓度之间呈现良好的线性关系，Stern–Volmer常数KSV达5.89×104L/mol，表明联四唑基多孔有机聚合物HBTZ能荧光传感对硝基苯酚，具有很高的灵敏性。It can be seen from Figure 3 that there is a good linear relationship between the relative fluorescence intensity of the tetrazole-based porous organic polymer HBTZ to p-nitrophenol and the concentration of p-nitrophenol, and the Stern–Volmer constant K SV is 5.89×10 4 L/mol, indicating that the tetrazole-based porous organic polymer HBTZ can fluorescently sense p-nitrophenol with high sensitivity.
实验3Experiment 3
分别取实施例1和实施例2制得的联四唑基多孔有机聚合物TBTZ和HBTZ，对单质碘、硝基芳香族化合物(简称NACs)及苯酚(PhOH)进行荧光传感，其中，硝基芳香族化合物有：二硝基甲苯(DNT)、间二硝基苯(m-DNB)、硝基苯(NB)、邻硝基苯酚(o-NP)、对硝基甲苯(p-NT)、苦味酸(PA)、对二硝基苯(p-DNB)、对硝基苯酚(p-NP)、间硝基苯酚(m-NP)、2,4-二硝基苯酚(DNP)。Take the bitetrazole-based porous organic polymer TBTZ and HBTZ obtained in Example 1 and Example 2 respectively, and carry out fluorescence sensing to elemental iodine, nitroaromatic compounds (NACs for short) and phenol (PhOH), wherein, nitro The base aromatic compounds are: dinitrotoluene (DNT), m-dinitrobenzene (m-DNB), nitrobenzene (NB), o-nitrophenol (o-NP), p-nitrotoluene (p-NT ), picric acid (PA), p-dinitrobenzene (p-DNB), p-nitrophenol (p-NP), m-nitrophenol (m-NP), 2,4-dinitrophenol (DNP) .
具体检测方法为：The specific detection method is:
取适量浓度为0.1mol/L单质碘、硝基芳香族化合物或苯酚溶液加入到浓度为0.1mg/mL联四唑基多孔有机聚合物分散液中，混合均匀，使TBTZ分散液中单质碘、硝基芳香族化合物或苯酚的浓度为2.5×10-4mol/L，使HBTZ分散液中单质碘、硝基芳香族化合物或苯酚的浓度为1.0×10-4mol/L，测试荧光发射光谱，并记录测试结果。Take an appropriate amount of 0.1mol/L elemental iodine, nitroaromatic compound or phenol solution and add it into the 0.1mg/mL bitetrazole-based porous organic polymer dispersion, mix evenly, so that the elemental iodine, nitroaromatic compound or phenol in the TBTZ dispersion The concentration of nitroaromatic compound or phenol is 2.5×10 -4 mol/L, so that the concentration of elemental iodine, nitroaromatic compound or phenol in the HBTZ dispersion is 1.0×10 -4 mol/L, and the fluorescence emission spectrum is tested , and record the test results.
具体测试结果如图4所示，图4为单质碘、硝基芳香族化合物或苯酚对实施例1和实施例2中联四唑基多孔有机聚合物相对荧光强度影响的柱状图，其中，(a)为实施例1，(b)为实施例2。The specific test results are as shown in Figure 4, and Figure 4 is a bar graph showing the influence of elemental iodine, nitroaromatic compounds or phenol on the relative fluorescence intensity of the tetrazole-based porous organic polymer in Example 1 and Example 2, wherein, ( a) is Example 1, and (b) is Example 2.
由图4可以看出，除苦味酸、对硝基苯酚外，其他硝基芳香族化合物以及苯酚对实施例1所述TBTZ的荧光强度影响较小；除苦味酸和二硝基苯酚外，其他硝基芳香族化合物以及苯酚对实施例2所述HBTZ的荧光强度影响较小。表明实施例1和实施例2所述联四唑基多孔有机聚合物对单质碘或对硝基苯酚具有优异的选择性。As can be seen from Figure 4, except picric acid and p-nitrophenol, other nitroaromatic compounds and phenol have little influence on the fluorescence intensity of TBTZ described in Example 1; except picric acid and dinitrophenol, other Nitroaromatic compounds and phenol have little effect on the fluorescence intensity of HBTZ described in Example 2. It shows that the tetrazole-based porous organic polymer described in Example 1 and Example 2 has excellent selectivity to elemental iodine or p-nitrophenol.
实验4Experiment 4
取实施例1、实施例2中的联四唑基多孔有机聚合物TBTZ、HBTZ，荧光传感单质碘或对硝基苯酚，在含有其他硝基芳香族化合物(如DNT、m-DNB、NB、o-NP、p-NT、PA、p-DNB、m-NP、DNP)时对单质碘、对硝基苯酚的竞争性，结果如图5所示。Get the combined tetrazole-based porous organic polymer TBTZ, HBTZ in embodiment 1, embodiment 2, fluorescent sensing elemental iodine or p-nitrophenol, in containing other nitroaromatic compounds (such as DNT, m-DNB, NB , o-NP, p-NT, PA, p-DNB, m-NP, DNP) to elemental iodine, p-nitrophenol competition, the results are shown in Figure 5.
图5为实施例1和实施例2中联四唑基多孔有机聚合物对单质碘或对硝基苯酚的选择性荧光传感结果，其中，(a)为实施例1，(b)为实施例2。Fig. 5 is the selective fluorescence sensing result of elemental iodine or p-nitrophenol in the joint tetrazole-based porous organic polymer in embodiment 1 and embodiment 2, wherein, (a) is embodiment 1, (b) is implementation Example 2.
由图5可以进一步看出，当单质碘或对硝基苯酚与其他硝基芳香族化合物同时存在时，其荧光强度与只含单质碘或对硝基苯酚的荧光强度无明显变化；实施例1和实施例2所述联四唑基多孔有机聚合物对单质碘或对硝基苯酚具有优异的选择性。As can be further seen from Fig. 5, when elemental iodine or p-nitrophenol exist simultaneously with other nitroaromatic compounds, its fluorescence intensity has no significant change with the fluorescence intensity containing only elemental iodine or p-nitrophenol; Example 1 And the tetrazole-based porous organic polymer described in Example 2 has excellent selectivity to elemental iodine or p-nitrophenol.
实施例3Example 3
一种联四唑基多孔有机聚合物的制备方法，包括如下步骤：A preparation method of a tetrazole-based porous organic polymer, comprising the steps of:
快速称取三聚氯化氰(TCT，0.5554g，3.0mmol)，并加入到一个N2填充的100mL两颈圆形底部烧瓶中，配备磁力搅拌棒和冷凝器；然后加入5,5'-联四唑二铵盐(TBZ，0.7919g，4.5mmol)；接着将N,N-二异丙胺基乙胺(3.22mL，19.5mmol)和1,4-二氧六环(48mL)的混合物转移到圆底烧瓶中；再将烧瓶放置在油浴中，浴温升到120℃，反应混合物搅拌回流48h后，冷却，抽滤分离固体产物，分别用蒸馏水、乙醇和四氢呋喃各洗涤三次；再用乙醇、四氢呋喃和二氯甲烷在索氏提取器中对粉末各提取24h，最后在100℃真空干燥箱中干燥得到联四唑基多孔有机聚合物，为棕黄色粉末。Quickly weigh cyanuric chloride (TCT, 0.5554g, 3.0mmol) and add it to a N2- filled 100mL two-neck round bottom flask equipped with a magnetic stirring bar and a condenser; then add 5,5'- Diammonium tetrazolium salt (TBZ, 0.7919 g, 4.5 mmol); then a mixture of N,N-diisopropylaminoethylamine (3.22 mL, 19.5 mmol) and 1,4-dioxane (48 mL) was transferred into a round-bottomed flask; then place the flask in an oil bath, raise the bath temperature to 120°C, stir and reflux the reaction mixture for 48 hours, cool, and separate the solid product by suction filtration, wash three times with distilled water, ethanol and tetrahydrofuran respectively; Ethanol, tetrahydrofuran and dichloromethane were extracted in a Soxhlet extractor for 24 hours respectively, and finally dried in a vacuum oven at 100° C. to obtain a bitetrazole-based porous organic polymer in the form of a brown yellow powder.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
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