罗丹明B-大环多胺缀合物的合成及其金属配合物与DNA的相互作用
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摘要
人工核酸酶,即应用化学的方法设计并合成既具有酶的高效催化作用,又比酶更简单稳定的仿酶化合物。人们通过研究人工核酸酶对DNA的氧化断裂,水解断裂机理等,寻找储存在DNA分子中的遗传信息,探索生命的奥秘,为各种遗传病,肿瘤等的医治建立理论基础。因此人工核酸酶的研究具有重要的理论意义和应用价值。
本论文设计合成了包括中间体在内的9个罗丹明B衍生物,其中有3个目标产物,均经过1HNMR、13C NMR、IR和ESI-MS确证。
通过琼脂糖凝胶电泳研究了目标产物与Cu2+,Zn2+, Co2+形成的配合物对pUC19质粒DNA的水解切割效率,并通过吸收光谱和荧光光谱考察了目标产物在离子识别变色荧光探针方面的应用。研究结果表明,合成的目标化合物形成的Co2+配合物在一定的缓冲溶液中对pUC19质粒DNA具有较好的切割作用。同时我们经过研究分析证实了本课题中所合成的目标产物对某些离子具有很强的识别功能,如配体1C和2C对Cr3+有较好的识别作用,而配体3C对Pb2+具有很好的识别作用。而且本课题的初步结果为以后本课题组其他同学研究罗丹明B衍生物配体在金属阳离子荧光探针方面奠定了一定的基础。
Artificial nuclease acid enzyme is named imitation enzyme compounds, it has the efficient catalysize like enzymes, and it is more simple and stable than enzyme. The people who study the oxidation and hydrolysis fracture mechanism of artificial nuclease acid enzyme on DNA for exploring the genetic information that is stored in the DNA, in order to explore the secret of life to establish theoretical basis for all sorts of genetic diseases, such as heal tumor. Therefore the research artificial nuclease enzymae has important theoretical significance and application value.
This paper has designed and synthesized nine RhB derivatives, including three RhB-cyclen conjugates as target product. All the target compounds were confirmed through'H NMR,13C NMR and IR and ESI-MS.
Through the agarose gel electrophoresis, preliminary studies on the cleavage of pUC19 DNA in the presence of Cu2+, Zn2+, Co2+complexes have been performed. We have investigated application of the target product in ion recognition discoloration fluorescence probe by the absorption spectrometry and fluorescence spectrum. Research results show that these Co2+ complexes have good cutting action on the pUC19 plasmid DNA. Meanwhile, through research and analysis we have investigated the target product have strong identification function to some ions. The ligands of 1C and 2C have strong fluorescence response to Cr3+ ion in acetonitrile, and the ligand 3C have strong fluorescence response to Pb2+. Furthermore, these fingdings lay a certain foundation for our team's other students in studying metal cations fluorescence probe by RhB derivatives ligands.
本论文设计合成了包括中间体在内的9个罗丹明B衍生物,其中有3个目标产物,均经过1HNMR、13C NMR、IR和ESI-MS确证。
通过琼脂糖凝胶电泳研究了目标产物与Cu2+,Zn2+, Co2+形成的配合物对pUC19质粒DNA的水解切割效率,并通过吸收光谱和荧光光谱考察了目标产物在离子识别变色荧光探针方面的应用。研究结果表明,合成的目标化合物形成的Co2+配合物在一定的缓冲溶液中对pUC19质粒DNA具有较好的切割作用。同时我们经过研究分析证实了本课题中所合成的目标产物对某些离子具有很强的识别功能,如配体1C和2C对Cr3+有较好的识别作用,而配体3C对Pb2+具有很好的识别作用。而且本课题的初步结果为以后本课题组其他同学研究罗丹明B衍生物配体在金属阳离子荧光探针方面奠定了一定的基础。
Artificial nuclease acid enzyme is named imitation enzyme compounds, it has the efficient catalysize like enzymes, and it is more simple and stable than enzyme. The people who study the oxidation and hydrolysis fracture mechanism of artificial nuclease acid enzyme on DNA for exploring the genetic information that is stored in the DNA, in order to explore the secret of life to establish theoretical basis for all sorts of genetic diseases, such as heal tumor. Therefore the research artificial nuclease enzymae has important theoretical significance and application value.
This paper has designed and synthesized nine RhB derivatives, including three RhB-cyclen conjugates as target product. All the target compounds were confirmed through'H NMR,13C NMR and IR and ESI-MS.
Through the agarose gel electrophoresis, preliminary studies on the cleavage of pUC19 DNA in the presence of Cu2+, Zn2+, Co2+complexes have been performed. We have investigated application of the target product in ion recognition discoloration fluorescence probe by the absorption spectrometry and fluorescence spectrum. Research results show that these Co2+ complexes have good cutting action on the pUC19 plasmid DNA. Meanwhile, through research and analysis we have investigated the target product have strong identification function to some ions. The ligands of 1C and 2C have strong fluorescence response to Cr3+ ion in acetonitrile, and the ligand 3C have strong fluorescence response to Pb2+. Furthermore, these fingdings lay a certain foundation for our team's other students in studying metal cations fluorescence probe by RhB derivatives ligands.
引文
[1]沈同,王镜岩.生物化学(第二版),高等教育出版社,1990：329-330.
[2]Sigman, D. S. Biochemistry. Chemical nucleases [J].1990,29,9097.
[3]Yang, P.; Ren, R; Guo, M.; et al. Double-strand hydrolysis of DNA bya magnesium (II) complex with diethylenetriamine [J]. J Biol Inorg Chem,2004,9:495-506.
[4]Neves, A.; Terenzi, H.; Homer, R.; Horn, A. J.; Szpoganicz, B; Sugai, J. Hydrolytic DNA cleavage promoted by a dinuclear iron (III) complex [J]. Inorganic Chemistry Communications.2001,4 (8),388-391.
[5]Verheijen, J. C.; Deiman, B. A. L. M.; Yeheskiely, E.; Van Boom, J, H. Efficient hydrolysis of RNA bya PNA-diethyl-entriamine adduct [J]. Angewandte Chemie, International Edition. 2000,39 (2):369-372.
[6]白春礼,方哗,唐有棋.三链核酸的结构与生物化学[J].科学出版社,1996,176-183.
[7]Trawick, B. N.; Daniher, A. T.; Bashkin, J. K. Inorganic Mimics of Ribonucleases and Ribozymes:From Random Cleavage to Sequence-Specific Chemistry to Catalytic Antisense Drugs [J]. Chem, Rev.1998,98,939.
[8]王乐.郑州大学,博士学位论文,2010.
[9]万荣；王宁.赵玉芬.丝组二肽对DNA的切割作用的研究.高等学校化学学报,2001,22(4)：598-600.
[10]Sjoblom, T.; Jones, S.; Wood, L. D.; Parsons, D. W.; Lin, J.; Barber, T. D.; Mandelker, D.; Leary, R. J.; Ptak, J.; Velculescu, V. E. The consensus coding sequences of human breast and colorectal cancers. Science,2006,314 (5797):268-274.
[11]Neidle, S.; Thurston, D. E. Chemical approaches to the discovery and development of cancer therapies. Nature Rev,2005,5 (4):285-296.
[12]Wan, R.; Zhao, G.; Chen, J.; et al. Researeh progresses of artificial nucleie acid cleavage agents [J]. Chinese Science Bulletin,2000,45 (22):2017-2028.
[13]Tullius, T. D.; Dombroski, B. A. Hydroxyl radical "footPriniing":High-resolution Information about DNA-protein contacts and application to repressor and Cro Protein [J]. Proc. Nail. Acad. Sci. USA,1986,53:5469-5473.
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[15]Nielsen, P. E.; Jeppesen, C.; Buehardt, O. Uranyl salts as photochemical agents for cleavage of DNA and probing of Protein-DNA contacts [J]. FEBS Lett,1988,235; 122-124.
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[17]J. A. Cowan a.; Yan Jin. DNA Cleavage by Copper-ATCUN Complexes. J. Am. Chem, Soc, 2005,127:8408-8415.
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[19]Takeda, N.; Shibata, M.; Tajjima, N. J. Org. Chem,2000,65:4391.
[20]任颜卫,西北大学,博士学位论文.2006.
[21]Sitlani, A; Barton, J. K. DNA Photoecleavage by phenanthrenequinone diimine complexes of rhodium (III):Shape-selective recognition and reaction [J]. J. Am. Chem. Soe,1992,114: 2303-2312.
[22]Alexander, V. Design and Synthesis of macrocyclic ligands and their complexes of lanthanides and actinides. Chem. Rev,1995,95:273-342.
[23]Caravan, P.; Lauffer, R. B. Gadolinium (III) Chelates as MRI Contrast Agents Structure, Dynamics, and Applications. Chem. Rev,1999,99:2293-2352.
[24]Shionoya, M.; Kimura, E. Highly selective recognition of thymidine and its related nucleosides by a zinc (II) macrocyclic tetraamine complex with novel complementary associations. J. Am.Chem. Soc,1993,115:6730-6737.
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[26]Reany, O.; Parker, D. Selective signalling of zinc ions by modulation of terbium luminescence. Chem. Commun,2000,473-474.
[27]Lim, N. C.; Freake, H. C.; Bruckner, C. Synthesis of a fluorescent chemosensor suitable for the imaging of zinc (II) in live cells Bioorg. Med. Chem. Lett,2003,2251-2254.
[28]Epstein, D. M.; Chappell, L. L. Eu (III) Macrocyclic Complexes Promote Cleavage of and Bind to Models for the 5'-Cap of mRNA.Chem,2000,39:2130-2134.
[29]Reichert, D. E.; Anderson, C. J. Metal complexes as diagnostic tools Coord. Chem. Rev, 1999,184:3-66.
[30]Kimura, E.; Yamada, Y. A model for catalytically active zinc (II) ion in liver alcohol dehydrogenase.J. Am. Chem. Soc,1992,114:10134.
[31]Zhang, X.; Eldik, R. A functional model for carbonic anhydrase. Inorg. Chem,1995,34: 5606.
[32]Bianchi, A.; Paleari, L.; Valtancoli, B. Thermodynamic and structural properties of Gd (III) complexes with polyamino polycarboxylic ligands. Chem. Rev,2000,204:309-393.
[33]Gunnlaugsson, T.; Parker, D. Lanthanide Macrocyclic Quinolyl Conjugates as Luminescent MolecularLevel Devices. J. Am. Chem. Soc,2001,123:12866-12876.
[34]Shiraishi, Y.*; Kohno, Y.; Hirai, T. Fluorometric Detection of pH and Metal Cations by Cyclen Bearing two anthrylmethyl groups. Ind. Eng. Chem. Res,2005,44:847-851.
[35]Gunnlaugsson, T.; Chal, K. S.; Harte, A. J. Novel "Off-On-Off'Lumine-scent Signaling in the Physiological pH Range. J. Am. Chem. Soc,2003,125:12062-12063.
[36]Yasuhiro Shiraishi;* Shigehiro Sumiya; Yoshiko Kohno; Takayuki Hirai. A Rhodamine-Cyclen Conjugate as a Highly Sensitive and Selective Fluorescent Chemosensor for Hg (II). J. Org. Chem, Vol.73, No.21,2008:8571-8574.
[37]Aoki, S.; Kimura, E. Metal Chelation-Controlled Twisted Intramolecular Charge Transfer and Its Application to Fluorescent Sensing of Metal Ions and Anions. J. Am. Chem. Soc, 2004,126:13377-13390.
[38]Burdette, S. C.; Lippard, S. J. The Rhodafluor Family:An Initial Study of Potential Ratiometric Fluorescent Sensors for Zn21. Inorg. Chem,2002,41,6816-6823.
[39]乔仁忠.聚酞胺与大环多胺缀合物的合成及活性[D].北京：清华大学化学系,2005.
[40]Komiyama, M.; Sumaoka, J.; Yonezawa, K.; Mastsumoto, Y. Chem.. Soc. PerkinTrans, 1997,75.
[41]a. Chang, A.; Rowland, M. E. Inorg. Chem,1983,22:3866. b. Andergg, Chim. Acta,1981,64:1790. c. Araud-Neu, F. Chem. Soc. Rev,1994.235.
[42]Chin, K. O. A.; Morrow, J. R. Inorg. Chem,1991,30:4295.
[43]Amin, S.; Morrow, J. R. Restoration of Catalytic Activity by Replacement of a Coordinated Amide Group. Inorg. Chem,1996,55:7466-7470.
[44]Chin, K. O. A.; Morrow, J. R.; Churchill, M. R. Synthesis and solution properties of lanthanum (III), europium (III), and lutetium (III) THP complexes and an x-ray diffraction study of a crystal containing four stereoisomers of a europium (III) THP complex. Inorg. Chem,1994,33:656-659.
[45]谭新禹.博士学位论文.四川大学,2007.
[46]Kim, J. H. Selective hydrolysis of 4-nitrophenyl phosphate by a dinuclear Cu (II) complex. Chem. Lett,2000.156.
[47]Kimura, E.; Koike, T. Phosphodiester Hydrolysis by a New Zinc (II) Macrocyclic Tetraamine Complex with an Alcohol Pendant. J. Am. Chem. Soc,1995,117:8304.
[48]Shiranoya, M.; Shiro, M. Novel "Multipoint" Molecular Recognition of Nucleobases by a New Zinc (II) Complex of Acridine-Pendant Cyclen. J. Am. Chem. Soc,1994,116:3848.
[49]D Y Kong.; C Qin.; L H Meng. Bioorg. Med. Chem. Lett,1999,9:1087-1092.
[50]赵玉芬,乔仁忠,余孝其等.中国专利：200410004532.9,2004.
[51]赵玉芬,乔仁忠,张祯.中国专利：200410004766.3,2004.
[52]W Peng.; P Yliu.; N Jiang. Bioorg. Chem,2005,33:374-385.
[53]C Q Xia.; N Jiang.; J Zhang. Bioorg. Med. Chem,2006,14:5756-5764.
[54]张丽珠,大连理工大学,博士学位论文,2007.
[55]Zhang M.; Gao, Y. H.; Li, M. Y. A selective turn-on fluorescent sensor for Fe (III) and application to bioimaging. Tetrahedron Letters.2007.48 (21) 3709-3712.
[56]Maciej. A.; Jonathan, G. Synthesis of Probes with Broad pH Range Fluorescence. Bioorganic & Medicinal Chemistry Letters,2003,73 (14) 2327-2330.
[57]Dujols, V.; Ford, F.; Czarnik, A. W. Long-wavelength fluorescent chemodosimeter selective for Cu (II) ion in water. Journal of the American Chemical Society.1997,119 (31) 7386-7387.
[58]Zheng, H.; Qian, Z. H.; Xu, L. Switching the Recognition Preference of Rhodamine B Spirolactam by Replacing One Atom:Design of Rhodamine B Thiohydrazide for Recognition of Hg (II) in Aqueous Solution.Organic Letters,2006,8 (5) 859-861.
[59]Zhang, X.; Shiraishi, Y.; Hirai, T. Cu (II)-selective green fluorescence of a Rhodamine-diacetic acid conjugate. Organic letters,2007,9 (24):5039-5042.
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[63]沈同等编著, 《生物化学》(上册)高等教育出版社.1990.p.329.
[64]Anderson, R. A. Essentiol of chromium in humans. Sci. Tot. Enviroment,1989,86:75-81.
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[2]Sigman, D. S. Biochemistry. Chemical nucleases [J].1990,29,9097.
[3]Yang, P.; Ren, R; Guo, M.; et al. Double-strand hydrolysis of DNA bya magnesium (II) complex with diethylenetriamine [J]. J Biol Inorg Chem,2004,9:495-506.
[4]Neves, A.; Terenzi, H.; Homer, R.; Horn, A. J.; Szpoganicz, B; Sugai, J. Hydrolytic DNA cleavage promoted by a dinuclear iron (III) complex [J]. Inorganic Chemistry Communications.2001,4 (8),388-391.
[5]Verheijen, J. C.; Deiman, B. A. L. M.; Yeheskiely, E.; Van Boom, J, H. Efficient hydrolysis of RNA bya PNA-diethyl-entriamine adduct [J]. Angewandte Chemie, International Edition. 2000,39 (2):369-372.
[6]白春礼,方哗,唐有棋.三链核酸的结构与生物化学[J].科学出版社,1996,176-183.
[7]Trawick, B. N.; Daniher, A. T.; Bashkin, J. K. Inorganic Mimics of Ribonucleases and Ribozymes:From Random Cleavage to Sequence-Specific Chemistry to Catalytic Antisense Drugs [J]. Chem, Rev.1998,98,939.
[8]王乐.郑州大学,博士学位论文,2010.
[9]万荣；王宁.赵玉芬.丝组二肽对DNA的切割作用的研究.高等学校化学学报,2001,22(4)：598-600.
[10]Sjoblom, T.; Jones, S.; Wood, L. D.; Parsons, D. W.; Lin, J.; Barber, T. D.; Mandelker, D.; Leary, R. J.; Ptak, J.; Velculescu, V. E. The consensus coding sequences of human breast and colorectal cancers. Science,2006,314 (5797):268-274.
[11]Neidle, S.; Thurston, D. E. Chemical approaches to the discovery and development of cancer therapies. Nature Rev,2005,5 (4):285-296.
[12]Wan, R.; Zhao, G.; Chen, J.; et al. Researeh progresses of artificial nucleie acid cleavage agents [J]. Chinese Science Bulletin,2000,45 (22):2017-2028.
[13]Tullius, T. D.; Dombroski, B. A. Hydroxyl radical "footPriniing":High-resolution Information about DNA-protein contacts and application to repressor and Cro Protein [J]. Proc. Nail. Acad. Sci. USA,1986,53:5469-5473.
[14]Pogozelski, W. K.; Tullius, T. D. Routes initiated by hydrogen abstraction from the sugar moiety [J]. Che, Rev,1998,1089-1108.
[15]Nielsen, P. E.; Jeppesen, C.; Buehardt, O. Uranyl salts as photochemical agents for cleavage of DNA and probing of Protein-DNA contacts [J]. FEBS Lett,1988,235; 122-124.
[16]Burger R M. Cleavage of nucleic acids by bleomycin [J].Chem. Rev,1998,3:1153-1171.
[17]J. A. Cowan a.; Yan Jin. DNA Cleavage by Copper-ATCUN Complexes. J. Am. Chem, Soc, 2005,127:8408-8415.
[18]Komiyama, M.; Shigekawa, H. Che. Comm,1999,1443.
[19]Takeda, N.; Shibata, M.; Tajjima, N. J. Org. Chem,2000,65:4391.
[20]任颜卫,西北大学,博士学位论文.2006.
[21]Sitlani, A; Barton, J. K. DNA Photoecleavage by phenanthrenequinone diimine complexes of rhodium (III):Shape-selective recognition and reaction [J]. J. Am. Chem. Soe,1992,114: 2303-2312.
[22]Alexander, V. Design and Synthesis of macrocyclic ligands and their complexes of lanthanides and actinides. Chem. Rev,1995,95:273-342.
[23]Caravan, P.; Lauffer, R. B. Gadolinium (III) Chelates as MRI Contrast Agents Structure, Dynamics, and Applications. Chem. Rev,1999,99:2293-2352.
[24]Shionoya, M.; Kimura, E. Highly selective recognition of thymidine and its related nucleosides by a zinc (II) macrocyclic tetraamine complex with novel complementary associations. J. Am.Chem. Soc,1993,115:6730-6737.
[25]Shionoya, M.; Ikeda, T.; Kimura, E. Novel "Multipoint" Molecular Recognition of Nucleobases by a New Zinc (II) Complex of Acridine-Pendant Cyclen. J. Am. Chem. Soc, 1994,116:3848-3859.
[26]Reany, O.; Parker, D. Selective signalling of zinc ions by modulation of terbium luminescence. Chem. Commun,2000,473-474.
[27]Lim, N. C.; Freake, H. C.; Bruckner, C. Synthesis of a fluorescent chemosensor suitable for the imaging of zinc (II) in live cells Bioorg. Med. Chem. Lett,2003,2251-2254.
[28]Epstein, D. M.; Chappell, L. L. Eu (III) Macrocyclic Complexes Promote Cleavage of and Bind to Models for the 5'-Cap of mRNA.Chem,2000,39:2130-2134.
[29]Reichert, D. E.; Anderson, C. J. Metal complexes as diagnostic tools Coord. Chem. Rev, 1999,184:3-66.
[30]Kimura, E.; Yamada, Y. A model for catalytically active zinc (II) ion in liver alcohol dehydrogenase.J. Am. Chem. Soc,1992,114:10134.
[31]Zhang, X.; Eldik, R. A functional model for carbonic anhydrase. Inorg. Chem,1995,34: 5606.
[32]Bianchi, A.; Paleari, L.; Valtancoli, B. Thermodynamic and structural properties of Gd (III) complexes with polyamino polycarboxylic ligands. Chem. Rev,2000,204:309-393.
[33]Gunnlaugsson, T.; Parker, D. Lanthanide Macrocyclic Quinolyl Conjugates as Luminescent MolecularLevel Devices. J. Am. Chem. Soc,2001,123:12866-12876.
[34]Shiraishi, Y.*; Kohno, Y.; Hirai, T. Fluorometric Detection of pH and Metal Cations by Cyclen Bearing two anthrylmethyl groups. Ind. Eng. Chem. Res,2005,44:847-851.
[35]Gunnlaugsson, T.; Chal, K. S.; Harte, A. J. Novel "Off-On-Off'Lumine-scent Signaling in the Physiological pH Range. J. Am. Chem. Soc,2003,125:12062-12063.
[36]Yasuhiro Shiraishi;* Shigehiro Sumiya; Yoshiko Kohno; Takayuki Hirai. A Rhodamine-Cyclen Conjugate as a Highly Sensitive and Selective Fluorescent Chemosensor for Hg (II). J. Org. Chem, Vol.73, No.21,2008:8571-8574.
[37]Aoki, S.; Kimura, E. Metal Chelation-Controlled Twisted Intramolecular Charge Transfer and Its Application to Fluorescent Sensing of Metal Ions and Anions. J. Am. Chem. Soc, 2004,126:13377-13390.
[38]Burdette, S. C.; Lippard, S. J. The Rhodafluor Family:An Initial Study of Potential Ratiometric Fluorescent Sensors for Zn21. Inorg. Chem,2002,41,6816-6823.
[39]乔仁忠.聚酞胺与大环多胺缀合物的合成及活性[D].北京：清华大学化学系,2005.
[40]Komiyama, M.; Sumaoka, J.; Yonezawa, K.; Mastsumoto, Y. Chem.. Soc. PerkinTrans, 1997,75.
[41]a. Chang, A.; Rowland, M. E. Inorg. Chem,1983,22:3866. b. Andergg, Chim. Acta,1981,64:1790. c. Araud-Neu, F. Chem. Soc. Rev,1994.235.
[42]Chin, K. O. A.; Morrow, J. R. Inorg. Chem,1991,30:4295.
[43]Amin, S.; Morrow, J. R. Restoration of Catalytic Activity by Replacement of a Coordinated Amide Group. Inorg. Chem,1996,55:7466-7470.
[44]Chin, K. O. A.; Morrow, J. R.; Churchill, M. R. Synthesis and solution properties of lanthanum (III), europium (III), and lutetium (III) THP complexes and an x-ray diffraction study of a crystal containing four stereoisomers of a europium (III) THP complex. Inorg. Chem,1994,33:656-659.
[45]谭新禹.博士学位论文.四川大学,2007.
[46]Kim, J. H. Selective hydrolysis of 4-nitrophenyl phosphate by a dinuclear Cu (II) complex. Chem. Lett,2000.156.
[47]Kimura, E.; Koike, T. Phosphodiester Hydrolysis by a New Zinc (II) Macrocyclic Tetraamine Complex with an Alcohol Pendant. J. Am. Chem. Soc,1995,117:8304.
[48]Shiranoya, M.; Shiro, M. Novel "Multipoint" Molecular Recognition of Nucleobases by a New Zinc (II) Complex of Acridine-Pendant Cyclen. J. Am. Chem. Soc,1994,116:3848.
[49]D Y Kong.; C Qin.; L H Meng. Bioorg. Med. Chem. Lett,1999,9:1087-1092.
[50]赵玉芬,乔仁忠,余孝其等.中国专利：200410004532.9,2004.
[51]赵玉芬,乔仁忠,张祯.中国专利：200410004766.3,2004.
[52]W Peng.; P Yliu.; N Jiang. Bioorg. Chem,2005,33:374-385.
[53]C Q Xia.; N Jiang.; J Zhang. Bioorg. Med. Chem,2006,14:5756-5764.
[54]张丽珠,大连理工大学,博士学位论文,2007.
[55]Zhang M.; Gao, Y. H.; Li, M. Y. A selective turn-on fluorescent sensor for Fe (III) and application to bioimaging. Tetrahedron Letters.2007.48 (21) 3709-3712.
[56]Maciej. A.; Jonathan, G. Synthesis of Probes with Broad pH Range Fluorescence. Bioorganic & Medicinal Chemistry Letters,2003,73 (14) 2327-2330.
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