含吡啶环香豆素酸性pH荧光探针的合成及应用
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摘要
为实现强酸性环境下pH的准确测量,设计并合成3个酸性p H荧光探针。经Knovengel反应得到3-乙酰基-7-二乙胺基香豆素(化合物1),再四组分一锅法得到2-氨基-3-氰基-6-(7-二乙胺基)香豆素吡啶衍生物(探针L-1、L-2、L-3),通过~1H NMR,~(13)C NMR,LC-MS对探针的结构进行表征,并用荧光光谱法对其光谱性能进行研究。探针L-1、L-2和L-3对H~+都有良好的选择性,其pKa分别为2. 68,2. 07和1. 99。探针L-1、L-2和L-3线性响应范围分别为pH 1. 59～3. 40,pH 1. 25～3. 43和pH 1. 14～3. 23,相关系数分别为0. 9930,0. 9919和0. 9907,3个探针均不受其他阳离子的干扰且具有可逆性。
In order to achieve accurate measurement of pH in strong acidic environment,three pH fluorescent probes were designed and synthesized. First, 3-acetyl-7-diethylaminocoumarin( Compound 1) was obtained by Knovengel reaction. Then,2-amino-6-( 7-( diethylamino)-2-oxo-2 H-chromen-3-yl) nicotinonitrile derivatives( L-1,L-2 and L-3) were synthesized by onepot four-components condensation reaction. The structures of these probes were characterized by ~1H NMR,~(13)C NMR and LC-MS and their spectral properties were studied by fluorescence spectroscopy. L-1,L-2 and L-3 probes displayed excellent pH dependent performance with p Ka of 2. 68,2. 07,1. 99,respectively. The pH titrations indicated that probe L-1 responded linearly( R~2= 0. 9930) to pH within the extremely acidic range of 1. 59 ～ 3. 40. Meanwhile,there was also a good linearity( R~2= 0. 9919) for L-2 between fluorescence intensity and pH in the range of 1. 25 ～ 3. 43. Similar results were obtained for probe L-3. Three probes displayed excellent stability and reversibility to hydrogen ion.
In order to achieve accurate measurement of pH in strong acidic environment,three pH fluorescent probes were designed and synthesized. First, 3-acetyl-7-diethylaminocoumarin( Compound 1) was obtained by Knovengel reaction. Then,2-amino-6-( 7-( diethylamino)-2-oxo-2 H-chromen-3-yl) nicotinonitrile derivatives( L-1,L-2 and L-3) were synthesized by onepot four-components condensation reaction. The structures of these probes were characterized by ~1H NMR,~(13)C NMR and LC-MS and their spectral properties were studied by fluorescence spectroscopy. L-1,L-2 and L-3 probes displayed excellent pH dependent performance with p Ka of 2. 68,2. 07,1. 99,respectively. The pH titrations indicated that probe L-1 responded linearly( R~2= 0. 9930) to pH within the extremely acidic range of 1. 59 ～ 3. 40. Meanwhile,there was also a good linearity( R~2= 0. 9919) for L-2 between fluorescence intensity and pH in the range of 1. 25 ～ 3. 43. Similar results were obtained for probe L-3. Three probes displayed excellent stability and reversibility to hydrogen ion.
引文
[1] Ma J B,Li W Q,Li J J,et al. Talanta,2018,182:464
[2] Zhang X,Jiang K,He H J,et al. Sens Actuators B,2018,254:1069
[3] Li Y. Mod Chem Res,2018(1):41李玥.当代化工研究,2018(1):41
[4] Niu W F,Nan M,Fan L,et al. Dyes Pigm,2016,126:224
[5] Chao J B,Wang H J,Song K L. Tetrahedron,2016,72(50):8342-8349
[6] Chao J B,Wang H J,Zhang Y B,et al. Anal Chim Acta,2017,975:52
[7] Ma Q J,Li X,FENG S X,et al. Spectrochim Acta A.,2017,177:6
[8] Yuan Y H,Yin Q Q,Feng F,et al. Chin J Anal Lab,2018,37(4):373袁跃华,殷强锋,冯锋,等.分析试验室,2018,37(4):373
[9] Ge Y Q,Liu A K,Dong J,et al. Sens Actuators B,2017,247:46
[10] Chao J B,Liu Y H,Sun J Y,et al. Sens Actuators B,2015,221:427
[11] Wysocki M L,Lavis D L. Curr Opin Chem Biol,2011,15(6):752
[12] He G J,Liu X L,Xu J H. Spectrochim Acta A,2018,190:116
[13] Hossain M S,Singh K,Lakma A,et al. Sens Actuators B,2017,239:1109
[14] Alizadeh A,Mohammadi R,Bayat F,et al. Tetrahedron,2018,74(16):2085
[15] Wang T,Wu P F,Shi M Q,et al. Acta Chim Sinica,2004,62(5):527王涛,吴飞鹏,施盟泉,等.化学学报,2004,62(5):527
[16] Wu Y C,You J Y,Jiang K. Dyes Pigm,2018,149:1
[2] Zhang X,Jiang K,He H J,et al. Sens Actuators B,2018,254:1069
[3] Li Y. Mod Chem Res,2018(1):41李玥.当代化工研究,2018(1):41
[4] Niu W F,Nan M,Fan L,et al. Dyes Pigm,2016,126:224
[5] Chao J B,Wang H J,Song K L. Tetrahedron,2016,72(50):8342-8349
[6] Chao J B,Wang H J,Zhang Y B,et al. Anal Chim Acta,2017,975:52
[7] Ma Q J,Li X,FENG S X,et al. Spectrochim Acta A.,2017,177:6
[8] Yuan Y H,Yin Q Q,Feng F,et al. Chin J Anal Lab,2018,37(4):373袁跃华,殷强锋,冯锋,等.分析试验室,2018,37(4):373
[9] Ge Y Q,Liu A K,Dong J,et al. Sens Actuators B,2017,247:46
[10] Chao J B,Liu Y H,Sun J Y,et al. Sens Actuators B,2015,221:427
[11] Wysocki M L,Lavis D L. Curr Opin Chem Biol,2011,15(6):752
[12] He G J,Liu X L,Xu J H. Spectrochim Acta A,2018,190:116
[13] Hossain M S,Singh K,Lakma A,et al. Sens Actuators B,2017,239:1109
[14] Alizadeh A,Mohammadi R,Bayat F,et al. Tetrahedron,2018,74(16):2085
[15] Wang T,Wu P F,Shi M Q,et al. Acta Chim Sinica,2004,62(5):527王涛,吴飞鹏,施盟泉,等.化学学报,2004,62(5):527
[16] Wu Y C,You J Y,Jiang K. Dyes Pigm,2018,149:1