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应用化学  2020, Vol. 37 Issue (1): 80-87    DOI: 10.11944/j.issn.1000-0518.2020.01.190165
  研究论文 本期目录 | 过刊浏览 | 高级检索 |
基于蒽-苯并咪唑鎓的荧光传感器对H2PO4-的高选择性识别
董智云,张晓宇,曾政权,席福贵()
忻州师范学院化学系 山西 忻州 034000
Anthracene-Benzimidazolium Based Fluorescent Chemosensor for Highly Selective Recogniton of H2PO4-
DONG Zhiyun,ZHANG Xiaoyu,ZENG Zhengquan,XI Fugui()
Department of Chemistry, Xinzhou Teachers University,Xinzhou,Shanxi 034000,China
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摘要 

设计合成了基于蒽-苯并咪唑鎓的受体分子12,通过荧光发射光谱研究了受体分子12对F-、Cl-、Br-、I-、AcO-、HSO4-、H2PO4-、NO3-、ClO4-等阴离子的识别性能。 研究发现,在受体分子12的乙腈溶液(5.0×10-6 mol/L)中加入10倍化学计量的H2PO4-时,受体分子1的荧光猝灭百分数为13%,受体分子2的荧光猝灭百分数高达94%,表明受体分子2在构型上与H2PO4-更匹配,可作为H2PO4-的荧光关闭型(turn-off)探针。 受体分子2与H2PO4-的结合比为1:1,结合常数为(3.70±0.16)×104 L/mol,检出限为3.77×10-6 mol/L。

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董智云
张晓宇
曾政权
席福贵
关键词 苯并咪唑鎓磷酸二氢根荧光探针    
Abstract

Two novel anthracene-benzimidazolium based receptors 1 and 2 were synthesized. The anion (F-, Cl-, Br-, I-, AcO-, HSO4-, H2PO4-, ClO4-,NO3-) binding properties of receptors 1 and 2 were evaluated in acetonitrile by fluorescence spectroscopy. The receptors 1 and 2 display fluorescent quenching effect with H2PO4-, the quench percentage for receptor 1 is 13%,and for receptor 2 is as much as 94%. The results indicate that receptor 2 is more closely matched to H2PO4- in configuration, and receptor 2 can behave as a “turn-off” fluorescence sensor for H2PO4-. Job-plot shows that receptor 2 and H2PO4- form a 1:1 complex, the binding constant is (3.70±0.16)×104 L/mol, and the detection limit is 3.77×10-6 mol/L.

Key wordsanthracene    benzimidazolium    dihydrogen phosphate    fluorescent chemosensor
收稿日期: 2019-06-05           接受日期: 2019-09-05
基金资助:山西省1331工程重点学科建设计划经费(2019)资助
通讯作者: 席福贵     E-mail: xifuguig@163.com
引用本文:   
董智云, 张晓宇, 曾政权, 席福贵. 基于蒽-苯并咪唑鎓的荧光传感器对H2PO4-的高选择性识别[J]. 应用化学, 2020, 37(1): 80-87.
DONG Zhiyun, ZHANG Xiaoyu, ZENG Zhengquan, XI Fugui. Anthracene-Benzimidazolium Based Fluorescent Chemosensor for Highly Selective Recogniton of H2PO4-. Chinese Journal of Applied Chemistry, 2020, 37(1): 80-87.
链接本文:  
http://yyhx.ciac.jl.cn/CN/10.11944/j.issn.1000-0518.2020.01.190165      或      http://yyhx.ciac.jl.cn/CN/Y2020/V37/I1/80
Scheme 1Synthesis of recpetors 1 and 2
图1受体分子1和2的乙腈溶液(5.0×10-6 mol/L)中加入10倍化学计量不同阴离子后的荧光强度变化
Fig.1Relative emission changes as difference between the emission intensity of receptors 1 and 2(5.0×10-6 mol/L) in the presence of 10 stoichiometric corresponding anions(I) and the receptors alone(I0) in acetonitrile
图2在受体分子1(A)和2(B)的乙腈溶液(浓度均为5.0×10-6 mol/L)中加入不同量H2PO4- (沿箭头方向:受体1:0,0.1,0.2,0.4,0.6,0.8,1.0,2.0,3.0,……,10.0倍化学计量;受体2:0,0.1,0.2,0.4,0.6,0.8,1.0,2.0,3.0,……,15.0倍化学计量)时的荧光光谱变化图
Fig.2Fluorescence titrations of receptors 1(A) and 2(B)(5.0×10-6 mol/L) with H2PO4-(along the arrows:0→10 stoichiometry for receptor 1; 0→15 stoichiometry for receptor 2) in CH3CN; Insets:normalized emission developments at 402 nm as a function of c(G)/c(H), and fluorescent color of receptors 1 and 2 in the absence and presence of H2PO4- under UV lamp excited at 365 nm
图3其它阴离子干扰受体分子2识别H2PO4-的荧光光谱图
Fig.3Fluorescence spectra of receptor 2 and H2PO4- upon addition of other anions
图4受体分子1和2与H2PO4-作用的Job曲线(总浓度为5.0×10-6 mol/L)
Fig.4Job’s plot between receptors 1/2 and AcO- with a total concentration of 5.0×10-6 mol/L
Anion Receptor 1 Receptor 2
K/(L·mol-1) R2 Binding ratio K/(L·mol-1) R2 Binding ratio
F- (3.54±0.07)×103 0.9960 1:1 (5.88±0.03)×103 0.9906 1:1
AcO- (3.71±0.05)×103 0.9962 1:1 (6.65±0.08)×103 0.9927 1:1
HSO4- (3.27±0.03)×103 0.9980 1:1 (3.02±0.08)×103 0.9919 1:1
H2PO4- (3.70±0.16)×104 0.9902 1:1 (5.31±0.06)×105 0.9912 1:1
表1受体分子1和2与阴离子的结合常数
Table 1Binding constants of receptors 1 and 2 with various anions
图5DFT模拟计算受体分子1和2与H2PO4-的结合模式
Fig.5Optimized geometries of receptor 1 and 2 with H2PO4-
Receptor 1 Receptor 2
Heavy atom distance H-bond distance Heavy atom distance H-bond distance
C27—O58 0.2912 H30—O58 0.1875 C42—O90 0.2919 H45—O90 0.1891
C40—O58 0.3444 H42—O58 0.2556 C30—O91 0.2935 H33—O91 0.1913
C46—O61 0.3732 H42—O61 0.2546 C73—O92 0.3487 H75—O92 0.2419
C40—O61 0.3551 H48—O61 0.2753 C57—O94 0.3474 H59—O94 0.2388
表2受体分子1和2与H2PO4-结合后的键长参数(nm)
Table 2Bond distances of receptors 1 and 2 with H2PO4-(nm)
HOMO LUMO HLG
1-H2PO4- -5.57 -2.06 3.51
2-H2PO4- -5.86 -2.45 3.41
表3DFT模拟计算的HOMO、LUMO、HOMO-LUMO能隙差值HLG(eV)
Table 3DFT calculated HOMO, LUMO, HOMO-LUMO gap HLG(eV)
106c(H2PO4-) in samples/(mol·L-1) 106Detected c(H2PO4-)/(mol·L-1) RSD/% Recovery/%
2.5 2.486±0.036 0.88 99.4
5.0 5.221±0.055 0.59 104.4
7.5 7.513±0.048 1.06 100.2
表4基于受体分子2的乙腈溶液中H2PO4-离子检测结果
Table 4Determination of H2PO4- in acetonitrile using the receptor 2
[1] Zhao J,Yang D,Yang X J,et al. Anion Coordination Chemistry:From Recognition to Supramolecular Assembly[J]. Coord Chem Rev,2019,378(8):415-444.
[2] Yang J,Dong C C,Chen X L,et al. Excimer Disaggregation Enhanced Emission:A Fluorescence “Turn-On” Approach to Oxoanion Recognition[J]. J Am Chem Soc,2019,141(11):4597-4612.
[3] Tepper R,Schubert U S.Halogen Bonding in Solution:Anion Recognition, Templated Self-assembly, and Organocatalysis[J]. Angew Chem Int Ed,2018,57(21):6004-6016.
[4] YAN Jijun,KANG Chuanqing,GAO Lianxun.Anion-Naphthalenediimide Interactions and Their Applications[J]. Prog Chem,2018,30(7):902-912(in Chinese). 闫吉军,康传清,高连勋. 阴离子-萘四酸双酰亚胺相互作用及其应用[J]. 化学进展,2018,30(7):902-912.
[5] Nieto S,Hargrove A E,Zhang T,et al. Artificial Receptors for the Recognition of Phosphorylated Molecules[J]. Chem Rev,2011,111(11):6603-6782.
[6] Warwick C,Guerreiro A,Soares A.Sensing and Analysis of Soluble Phosphates in Environmental Samples:A Review[J]. Biosens Bioelectron,2012,41(1):1-11.
[7] Law A A T,Adeloju S B. Progress and Recent Advances in Phosphate Sensors:A Review[J]. Talanta,2013,114:191-203.
[8] Zhang D,Cochrane J R,Martinez A,et al. Recent Advances in H2PO4-Fluorescent Sensors[J]. RSC Adv,2014,4(56):29735-29749.
[9] Patra C,Bhanja A K,Sen C,et al. Imine-Functionalized Thioether Zn(Ⅱ) Turn-On Fluorescent Sensor and Its Selective Sequential Logic Operations with H2PO4-, DFT Computation and Live Cell Imaging[J]. RSC Adv,2016,6(58):53378-53388.
[10] Ghosh K,Saha I.Ortho-Phenylenediamine-Based Open and Macrocyclic Receptors in Selective Sensing of H2PO4-, ATP and ADP under Different Conditions[J]. Org Biomol Chem,2012,10(47):9383-9392.
[11] Kondo S I,Takai R.Selective Detection of Dihydrogen Phosphate Anion by Fluorescence Change with Tetraamide-Based Receptors Bearing Isoquinolyl and Quinolyl Moieties[J]. Org Lett,2013,15(3):538-541.
[12] Kumar A,Kumar V,Upadhyay K K.An Al3+ and H2PO4-/HSO4- Selective Conformational Arrest and Bail to a Pyrimidine-Naphthalene Anchored Molecular Switch[J]. Analyst,2013,138(6):1891-1897.
[13] Kui D,Niu S Z,Li Q,et al. A Highly Selective Ratiometric Fluorescent Probe for the Cascade Detection of Zn2+ and H2PO4- and Its Application in Living Cell Imaging[J]. RSC Adv,2017,7(64):40615-40620.
[14] Du K,Liu J,Shen R,et al. Design and Synthesis of a New Fluorescent Probe for Cascade Detection of Zn2+ and H2PO4- in Water and Targeted Imaging of Living Cells[J]. Luminescence,2019,34(4):407-414.
[15] Zhang Y H,Huang H W,Yang S S,et al. A New Ferrocenophane with Amide and Triazole Donors for Recognition of Dihydrogenphosphate Anion[J]. J Organomet Chem,2018,871:74-78.
[16] Du K,Niu S,Chen X,et al. A Novel Highly Selective Ratiometric Fluorescent Sensor for Relay Recognition of Zn2+ and H2PO4-[J]. Tetrahedron Lett,2018,59(4):356-360.
[17] Zhang Y M,Li Y F,Zhong K P,et al. A Novel Pillar[5]arene-Based Supramolecular Organic Framework Gel to Achieve an Ultrasensitive Response by Introducing the Competition of Cation…π and π…π Interactions[J]. Soft Matter,2018,14:3624-3631.
[18] Feng X,Fu Y,Jin J,et al. A Highly Selective and Sensitive Fluorescent Sensor for Relay Recognition of Zn2+ and HSO4-/H2PO4- Fluorescent Responses[J]. Anal Biochem,2018,563:20-24.
[19] Du W,Jia C,Zhang Y,et al. A Sc-3-HF Complex as a Fluorescent Chemosensor for the Selective Detection of Dihydrogen Phosphate[J]. Anal Methods,2018,10:1993-1998.
[20] Das R,Pathak N,Choudhury S,et al. Dihydrogenphosphate Recognition:Assistance from the Acidic OH Moiety of the Anion[J]. J Mol Struct,2017,1148:81-88.
[21] Su Y,Zhang D,Jia P,et al. Highly Selective and Sensitive Long Fluorescence Lifetime Polyurethane Foam Sensor Based on Tb-Complex as Chromophore for the Detection of H2PO4- in Water[J]. Spectrochim Acta A,2019,217:86-92.
[22] Wang K P,Zhang S J,Lv C D,et al. A Highly Sensitive and Selective Turn-On Fluorescent Sensor for Dihydrogen Phosphate in Living Cells[J]. Sens Actuators B:Chem,2017,247:791-796.
[23] Molina P,Zapata F,Caballero A.Anion Recognition Strategies Based on Combined Noncovalent Interactions[J]. Chem Rev,2017,117(15):9907-9972.
[24] Liu Q X,Hu Z L,Zhao Z X.A New Fluorescent-Colorimetric Chemosensor for Fluoride Anion Based on Benzimidazolium Salt[J]. Tetrahedron,2018,74(46):6710-6716.
[25] Kim J,Morozumi T,Nakamura H.Control Between TICT and PET Using Chemical Modification of N-Phenyl-9-anthracenecarboxamide and Its Application to a Crown Ether Type Chemosensor[J]. Tetrahedron,2008,64(47):10735-10740.
[26] Zhou L,Sun Q F.A Self-assembled Pd2L4 Cage that Selectively Encapsulates Nitrate[J]. Chem Commun,2015,51(94):16767-16770.
[27] Herbert J M,Woodgate P D,Denny W A. Potential Antitumor Agents.53.Synthesis, DNA Binding Properties, and Biological Activity of Perimidines Designed as Minimal DNA-Intercalating Agents[J]. J Med Chem,1987,30(11):2081-2086.
[28] Liu G,Zhao L.A Simple Colorimetric and On-Off Fluorescent Chemosensor for Biologically Important Anions Based on Thiourea Groups[J]. Spectrosc Lett,2012,45(6):424-429.
[29] HUANG Xiaomei,DENG Xiang.Preparation of New Photoluminescent Carbon Dots and Its Application in Hg2+ Detection[J]. Chinese J Appl Chem,2019,36(5):603-610(in Chinese). 黄小梅,邓祥. 新型荧光碳点的制备及其在Hg2+检测中的应用[J]. 应用化学,2019,36(5):603-610.
[30] Valeur B,Pouget J,Bourson J.Tuning of Photoinduced Energy Transfer in a Bichromophoric Coumarin Supermolecule by Cation Binding[J]. J Phys Chem,1992,96:6545-6549.
[31] Zapata F,Gonzalez L,Caballero A,et al. Dual Role of the 1,2,3-Triazolium Ring as a Hydrogen-Bond Donor and Anion-π Receptor in Anion-Recognition Processes[J]. Chem-Eur J,2015,21(27):9797-9808.
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