分析测试学报2025，Vol.44Issue(7)：1321-1330,10.DOI:10.12452/j.fxcsxb.241002435
1,6-二取代芘基共轭微孔聚合物荧光传感检测苦味酸和邻硝基苯酚的研究
The Study on 1,6-Disubstituted Pyrene-based Conjugated Microporous Polymers for Fluorescence Sensing of Picric Acid and o-Nitrophenol
摘要
Abstract
The 1,6-disubstituted pyrene-based conjugated microporous polymers(1,6-disubstitut-ed pyrene-based CMPs,TTPDP and TDTPAP)were synthesized by Friedel-Crafts arylation reac-tions with the 1,6-disubstituted pyrene derivatives(TPDP and DTPAP)and 2,4,6-trichloride-1,3,5-triazine(TCT)at 140℃for 48 h.After washing,extracted with Soxhlet's apparatus,and vac-uum drying,TTPDP and TDTPAP gave 84.85%and 82.17%yield,respectively.The structures of the 1,6-disubstituted pyrene-based CMPs were characterized with FT-IR,solid state 13 C NMR,and solid-state UV-visible spectroscopy and confirmed to be the target products.The morphology of the 1,6-disubstituted pyrene-based CMPs was analyzed by powder X-ray diffraction(PXRD)and scanning electron microscope(SEM).The 1,6-disubstituted pyrene-based CMPs showed an amor-phous network structures which have massive structures.TTPDP and TDTPAP are insoluble in any solvent and have excellent thermal stability with the high decomposition temperatures of 563 and 573℃,respectively.The pore properties of 1,6-disubstituted pyrene-based CMPs were investigat-ed by nitrogen adsorption-desorption measurements of at 77.3 K.TTPDP and TDTPAP fit the typeⅠ and Ⅱ gas adsorption isotherms and some hysteresis,respectively.The micropore diameters of TTPDP and TDTPAP are around 1.88 and 1.22 nm,respectively,and the BET surface areas are 187.5 and 695.2 m2·g-1,V0.1/Vtot values are higher than 0.40,respectively,indicating the predomi-nance of micropores in the networks.The fluorescent sensing properties of TTPDP and TDTPAP for the nitroaromatic compounds(NACs)were studied.TTPDP and TDTPAP have good fluorescence properties either in the solid state or dispersed in the solvent.The TTPDP and TDTPAP are easily dis-persed in N,N-dimethylformamide(DMF)and 1,4-dioxane(DOX)and can emit bright cyan fluo-rescence under UV light at 365 nm,which is basically consistent with the colors in the CIE dia-grams.Both TTPDP and TDTPAP can detect picric acid(PA)and o-nitrophenol(o-NP)in real time,showing high sensitivity and selectivity.The quenching coefficient(KSV)of TTPDP to PA and TDT-PAP to o-NP are 1.59×104 and 7.80×103 L·mol-1,with the limit of detection(LODs)of 2.82×10-12 and 1.92×10-10 mol·L-1,respectively.The mechanisms of TTPDP and TDTPAP fluorescence sensing PA and o-NP were explored by theoretical calculations using the program Gaussian 09 D.01 at the B3LYP/6-31G level and contrasting the UV-visible spectra of the analytes and the fluorescence spec-tra of the 1,6-disubstituted pyrene-based CMPs.TTPDP fluorescence sensing PA is the result of the combined action of electron transfer and energy transfer processes,whereas TDTPAP fluorescence detecting to o-NP is only the electron transfer process.1,6-Disubstituted pyrene-based CMPs have potential applications for the detection of NACs in environmental pollutants.关键词
共轭微孔聚合物/1,6-二取代芘/荧光传感/苦味酸/邻硝基苯酚Key words
conjugated microporous polymers/1,6-disubstituted pyrene/fluorescence sensing/picric acid/o-nitrophenol分类
化学化工引用本文复制引用
任丽英,汪雅晨,桂云龙,王越,胡佳敏,耿同谋..1,6-二取代芘基共轭微孔聚合物荧光传感检测苦味酸和邻硝基苯酚的研究[J].分析测试学报,2025,44(7):1321-1330,10.基金项目
安徽省教育厅自然科学基金(2024AH051141,2023AH040406,2022AH052545) （2024AH051141,2023AH040406,2022AH052545）
