基于咪唑并吡啶pH探针的合成及其光谱性质
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摘要
为了得到适用于极酸性环境的pH荧光探针,选用咪唑并[1,2-a]吡啶类化合物作为受体,以双键作为桥梁连接供电体吩噻嗪,设计合成了化合物10-(2-(2-甲氧基乙氧基)乙基)-3-(2-(2-苯基咪唑并[1,2-a]吡啶-7-基)乙烯基)-10H-吩噻嗪. pH滴定实验表明,随着体系中pH值的降低(7. 0～0. 4),化合物在399 nm的紫外吸收强度逐渐降低,在419 nm的紫外吸收强度逐渐增强,在573 nm处的荧光发射峰强度随pH值的降低而逐渐减弱.此外,该化合物的解离常数pKa为3. 07.实验数据表明,该化合物可作为一种新型的pH荧光探针适用于极酸性环境.
In order to obtain a pH fluorescent probe suitable for extremely acidic environment,we use imidazo[1,2-a]pyridine compounds as receptors and double bonds as bridge-connected donor phenothiazine to synthesize a compound 10-( 2-( 2-methoxyethoxy) ethyl-3-( 2-( 2-phenylimidazo [1,2-a]pyridin-7-yl) vinyl)-10 H-phenothiazine.The results of pH titration show that with the pH decrease from 7. 0 to 0. 4,the UV absorption intensity of the compound gradually reduces at 399 nm but gradually increases at 419 nm,and the fluorescence emission peak intensity gradually reduces at 573 nm. The pKa of the compound is 3. 07. The synthesized compound can be used as a new pH fluorescent probe suitable for extremely acidic environment.
In order to obtain a pH fluorescent probe suitable for extremely acidic environment,we use imidazo[1,2-a]pyridine compounds as receptors and double bonds as bridge-connected donor phenothiazine to synthesize a compound 10-( 2-( 2-methoxyethoxy) ethyl-3-( 2-( 2-phenylimidazo [1,2-a]pyridin-7-yl) vinyl)-10 H-phenothiazine.The results of pH titration show that with the pH decrease from 7. 0 to 0. 4,the UV absorption intensity of the compound gradually reduces at 399 nm but gradually increases at 419 nm,and the fluorescence emission peak intensity gradually reduces at 573 nm. The pKa of the compound is 3. 07. The synthesized compound can be used as a new pH fluorescent probe suitable for extremely acidic environment.
引文
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[2]WANG Qianqian,ZHOU Liyi,QIU Liping,et al. An efficient ratiometric fluorescent probe for tracking dynamic changes in lysosomal p H[J]. Analyst, 2015, 140(16):5563-5569.
[3]QI Jing,LIU Daying,LIU Xiaoyan,et al. Fluorescent p H sensors for broad-range p H measurement based on a single fluorophore[J]. Analytical Chemistry,2015,87(12):5897-5904.
[4]HOU Jiting,REN Wenxiu,LI Kun,et al. Fluorescent bioimaging of p H:from design to applications[J].Chemical Society Reviews,2017,46(8):2076-2090.
[5]KIM H J,HEO C H,KIM H M. Benzimidazole-based ratiometric two-photon fluorescent probes for acidic p H in live cells and tissues[J]. Journal of the American Chemical Society,2013,135(47):17969-17977.
[6]GLASER T A,BAATZ J E,KREISHMAN G P,et al. p H homeostasis in leishmania donovani amastigotes and promastigotes[J]. Proceedings of the National Academy of Sciences of the United States of America,1988,85(20):7602-7606.
[7]MIAO Fang,UCHINOMIYA S,NI Yong,et al. Development of p H-responsive BODIPY probes for staining late endosome in live cells[J]. Chem Plus Chem,2016,81(11):1209-1215.
[8]MICHAEL S. Nanoparticle-based luminescent probes for intracellular sensing and imaging of p H[J]. Wiley Interdisciplinary Reviews Nanomedicine&Nanobiotechnology,2016,8(3):378-413.
[9]FOSTER J W. Escherichia coli acid resistance:tales of an amateur acidophile[J]. Nature Reviews Microbiology,2004,2(11):898-907.
[10]LUND P,TRAMONTI A,DE BIASE D. Coping with low p H:molecular strategies in neutralophilic bacteria[J].FEMS Microbiology Reviews, 2014, 38(6):1091-1125.
[11]RUGGE M,FASSAN M,GRAHAM D Y. Clinical guidelines:secondary prevention of gastric cancer[J]. Nature reviews Gastroenterology&hepatology, 2012, 9(3):128-129.
[12]BLAKE P A,WEAVER R E,HOLLIS D G. Diseases of humans(other than cholera)caused by vibrios[J].Annual Review of Microbiology,1980,34(34):341-367.
[13]ENGEN R M,KILLIEN E Y,DAVIS J L,et al. C septicum complicating hemolytic uremic syndrome:survival without surgical intervention[J]. Pediatrics,2017,139(3):e20161362.
[14]KANJEE U,HOURY W A. Mechanisms of acid resistance in Escherichia coli[J]. Annual Review of Microbiology,2013,67(67):65-81.
[15]LOVING G, IMPERIALI B. A versatile amino acid analogue of the solvatochromic fluorophore 4-N,N-dimethylamino-1,8-naphthalimide:a powerful tool for the study of dynamic protein interactions[J]. Journal of the American Chemical Society,2008,130(41):13630-13638.
[16]HUANG Huawen,JI Xiaochen,TANG Xiaodong,et al.Conversion of pyridine to imidazo[1,2-a]pyridines by copper-catalyzed aerobic dehydrogenative cyclization with oxime esters[J]. Organic Letters,2013, 15(24):6254-6257.