Pyrazole-substituted Near-infrared Cyanine Dyes Exhibit PH-dependent Fluorescence Lifetime Properties

Overview

Journal Photochem Photobiol

Specialties Biochemistry
Biology
Chemistry

Date 2012 Oct 26

PMID 23094959

Citations 6

Authors

Hyeran Lee

Mikhail Y Berezin

Rui Tang

Natalia Zhegalova

Samuel Achilefu

Affiliations

Soon will be listed here.

Abstract

Near-infrared heptamethine cyanine dye is functionalized with pyrazole derivatives at the meso-position to induce pH-dependent photophysical properties. The presence of pyrazole unsubstituted at (1) N-position is essential to induce pH-dependent fluorescence intensity and lifetime changes in these dyes. Replacement of meso-chloro group of cyanine dye IR820 with (1) N-unsubstituted pyrazole resulted in the pH-dependent fluorescence lifetime changes from 0.93 ns in neutral media to 1.27 ns in acidic media in DMSO. Time-resolved emission spectra (TRES) revealed that at lower pH, the pyrazole consists of fluorophores with two distinct lifetimes, which cor-responds to pH-sensitive and non-pH-sensitive species. In contrast, (1) N-substituted pyrazoles do not exhibit pH response, suggesting excited state electron transfer as the mechanism of pH-dependent fluorescence lifetime sensitivity for this class of compounds.

Citing Articles

Synthesis and Antiproliferative Activity of 2,4,6,7-Tetrasubstituted-2-pyrazolo[4,3-]pyridines.

Razmiene B, Reznickova E, Dambrauskiene V, Ostruszka R, Kubala M, Zukauskaite A Molecules. 2021; 26(21).

PMID: 34771163 PMC: 8588486. DOI: 10.3390/molecules26216747.

Copper-Catalyzed Syntheses of Pyrene-Pyrazole Pharmacophores and Structure Activity Studies for Tubulin Polymerization.

Sar D, Srivastava I, Misra S, Ostadhossein F, Fathi P, Pan D ACS Omega. 2018; 3(6):6378-6387.

PMID: 30221233 PMC: 6130796. DOI: 10.1021/acsomega.8b00320.

Synthesis and Optical Properties of Near-Infrared meso-Phenyl-Substituted Symmetric Heptamethine Cyanine Dyes.

Levitz A, Marmarchi F, Henary M Molecules. 2018; 23(2).

PMID: 29364846 PMC: 6017188. DOI: 10.3390/molecules23020226.

In vivo quantitative imaging of tumor pH by nanosonophore assisted multispectral photoacoustic imaging.

Jo J, Lee C, Kopelman R, Wang X Nat Commun. 2017; 8(1):471.

PMID: 28883396 PMC: 5589864. DOI: 10.1038/s41467-017-00598-1.

Cyanine polyene reactivity: scope and biomedical applications.

Gorka A, Nani R, Schnermann M Org Biomol Chem. 2015; 13(28):7584-98.

PMID: 26052876 PMC: 7780248. DOI: 10.1039/c5ob00788g.

References

Benson R, Kues H . Fluorescence properties of indocyanine green as related to angiography. Phys Med Biol. 1978; 23(1):159-63. DOI: 10.1088/0031-9155/23/1/017. View

Hassan M, Riley J, Chernomordik V, Smith P, Pursley R, Lee S . Fluorescence lifetime imaging system for in vivo studies. Mol Imaging. 2007; 6(4):229-36. PMC: 3512197. View

Boens N, Qin W, Basaric N, Orte A, Talavera E, Alvarez-Pez J . Photophysics of the fluorescent pH indicator BCECF. J Phys Chem A. 2006; 110(30):9334-43. DOI: 10.1021/jp0615712. View

Murtaza Z, Chang Q, Rao G, Lin H, Lakowicz J . Long-lifetime metal-ligand pH probe. Anal Biochem. 1997; 247(2):216-22. PMC: 6816250. DOI: 10.1006/abio.1997.2057. View

Mordon S, Devoisselle J, Soulie S . Fluorescence spectroscopy of pH in vivo using a dual-emission fluorophore (C-SNAFL-1). J Photochem Photobiol B. 1995; 28(1):19-23. DOI: 10.1016/1011-1344(94)07100-3. View

Lee H, Berezin M, Henary M, Strekowski L, Achilefu S . Fluorescence lifetime properties of near-infrared cyanine dyes in relation to their structures. J Photochem Photobiol A Chem. 2009; 200(2-3):438-444. PMC: 2630462. DOI: 10.1016/j.jphotochem.2008.09.008. View

Szmacinski H, Lakowicz J . Optical measurements of pH using fluorescence lifetimes and phase-modulation fluorometry. Anal Chem. 1993; 65(13):1668-74. PMC: 6816262. DOI: 10.1021/ac00061a007. View

Amali A, Awwad N, Rana R, Patra D . Nanoparticle assembled microcapsules for application as pH and ammonia sensor. Anal Chim Acta. 2011; 708(1-2):75-83. DOI: 10.1016/j.aca.2011.10.001. View

Qin W, Baruah M, Van der Auweraer M, De Schryver F, Boens N . Photophysical properties of borondipyrromethene analogues in solution. J Phys Chem A. 2006; 109(33):7371-84. DOI: 10.1021/jp052626n. View

10.

Kuwana E, Sevick-Muraca E . Fluorescence lifetime spectroscopy for pH sensing in scattering media. Anal Chem. 2003; 75(16):4325-9. DOI: 10.1021/ac034059a. View

11.

Lee H, Berezin M, Guo K, Kao J, Achilefu S . Near-infrared fluorescent pH-sensitive probes via unexpected barbituric acid mediated synthesis. Org Lett. 2008; 11(1):29-32. PMC: 2725187. DOI: 10.1021/ol802363x. View

12.

Lee H, Mason J, Achilefu S . Heptamethine cyanine dyes with a robust C-C bond at the central position of the chromophore. J Org Chem. 2006; 71(20):7862-5. DOI: 10.1021/jo061284u. View

13.

Han J, Burgess K . Fluorescent indicators for intracellular pH. Chem Rev. 2009; 110(5):2709-28. DOI: 10.1021/cr900249z. View

14.

Zhang Z, Berezin M, Kao J, Davignon A, Bai M, Achilefu S . Near-infrared dichromic fluorescent carbocyanine molecules. Angew Chem Int Ed Engl. 2008; 47(19):3584-7. DOI: 10.1002/anie.200800475. View

15.

Sanders R, Draaijer A, Gerritsen H, Houpt P, Levine Y . Quantitative pH imaging in cells using confocal fluorescence lifetime imaging microscopy. Anal Biochem. 1995; 227(2):302-8. DOI: 10.1006/abio.1995.1285. View

16.

Rosch U, Yao S, Wortmann R, Wurthner F . Fluorescent H-aggregates of merocyanine dyes. Angew Chem Int Ed Engl. 2006; 45(42):7026-30. DOI: 10.1002/anie.200602286. View

17.

Zhang Z, Achilefu S . Design, synthesis and evaluation of near-infrared fluorescent pH indicators in a physiologically relevant range. Chem Commun (Camb). 2005; (47):5887-9. DOI: 10.1039/b512315a. View

18.

Baruah M, Qin W, Flors C, Hofkens J, Vallee R, Beljonne D . Solvent and pH dependent fluorescent properties of a dimethylaminostyryl borondipyrromethene dye in solution. J Phys Chem A. 2006; 110(18):5998-6009. DOI: 10.1021/jp054878u. View

19.

Berezin M, Kao J, Achilefu S . pH-dependent optical properties of synthetic fluorescent imidazoles. Chemistry. 2009; 15(14):3560-6. PMC: 2844652. DOI: 10.1002/chem.200801784. View

20.

Baruah M, Qin W, Basaric N, De Borggraeve W, Boens N . BODIPY-based hydroxyaryl derivatives as fluorescent pH probes. J Org Chem. 2005; 70(10):4152-7. DOI: 10.1021/jo0503714. View