10.1002/chem.201802875
Chemistry - A European Journal
FULL PAPER
[1]
[2]
R. Weissleder, M. J. Pittet, Nature 2008, 452, 580-589.
(20% O2) and different hypoxic (10%, 5% and 1% O2) conditions
A. N. Butkevich, G. Y. Mitronova, S. C. Sidenstein, J. L. Klocke, D. Kamin,
D. N. H. Meineke, E. D'Este, P.-T. Kraemer, J. G. Danzl, V. N. Belov, S.
W. Hell, Angew. Chem. Int. Ed. 2016, 55, 3290-3294.
J. B. Grimm, A. K. Muthusamy, Y. Liang, T. A. Brown, W. C. Lemon, R.
Patel, R. Lu, J. J. Macklin, P. J. Keller, N. Ji, L. D. Lavis, Nat. Methods
2017, 14, 987-994.
for
8 h before treated with the PRB2-NTR, respectively.
Corresponding fluorescence gradually enhanced with the
decrease of O2 level, as shown in Figure S19. In cells pretreated
with 0.1 mM dicoumarin, an inhibitor for NTR, fluorescence faded
down, indicating the profound specificity of PRB2-NTR in vivo.
[3]
[4]
[5]
[6]
L. D. Lavis, R. T. Raines, ACS Chem. Biol. 2014, 9, 855-866.
L. D. Lavis, Annu. Rev. Biochem. 2017, 86, 825-843.
X. Chen, T. Pradhan, F. Wang, J. S. Kim, J. Yoon, Chem. Rev. 2012,
112, 1910-1956.
Conclusions
[7]
G. Lukinavičius, C. Blaukopf, E. Pershagen, A. Schena, L. Reymond, E.
Derivery, M. Gonzalez-Gaitan, E. D'Este, S. W. Hell, D. W. Gerlich and
K. Johnsson, Nat Commun. 2015, 6, 8497.
The advances in fluorophore and fluorogenic strategy have
mutually promoted the understanding of complicated biophysical
structures and processes. As an aged family of dyes, xanthene
fluorophore has been rejuvenated by the replacement of bridging
oxygen with other atoms for further tuning and improvement of
photophysical properties. Phosphorus was introduced into
rhodamine scaffold as the key bridging atom, resulting in a series
of NIR PRBs. Accompanied with the bathochromic shift in spectra
to over 700 nm, excellent water solubility and photostability have
also been fulfilled by the organophosphorus in PRBs, further
facilitating their application of bioimaging in vivo. The manifold
bridging organophosphorus caged by an organo-phosphinate
ester has also been proved to be a promising fluorescence-
controller based on bridge-caging strategy, a new concept for
rational design of fluorescent probes. Three paradigms, PRB2-hv,
PRB2-H2O2 and PRB2-NTR for photon illumination, H2O2 and
enzyme, respectively, have manifested the modularity and
flexibility of the bridge-caging strategy by phosphorus-bridged
rhodamine for tailored structures in respect to specific stimuli of
interest in vivo. We believe that the disclosure of the novel bridge-
caging strategy and theoretical calculation have extended the
design principles of fluorophores, boosting the application of
fluorescent probes in bioimaging.
[8]
[9]
R. Weissleder, Nat. Biotechnol. 2001, 19, 316-317.
L. Yuan, W. Lin, K. Zheng, L. He, W. Huang, Chem. Soc. Rev. 2013, 42,
622-661.
[10] M. Fu, Y. Xiao, X. Qian, D. Zhao, Y. Xu, Chem. Commun. 2008, 0, 1780-
1782.
[11] Y. Koide, Y. Urano, K. Hanaoka, W. Piao, M. Kusakabe, N. Saito, T. Terai,
T. Okabe, T. Nagano, J. Am. Chem. Soc. 2012, 134, 5029-5031.
[12] T. Wang, Q.-J. Zhao, H.-G. Hu, S.-C. Yu, X. Liu, L. Liu, Q.-Y. Wu, Chem.
Commun. 2012, 48, 8781-8783.
[13] G. Lukinavičius, K. Umezawa, N. Olivier, A. Honigmann, G. Yang, T.
Plass, V. Mueller, L. Reymond, I. R. Corrêa Jr, Z.-G. Luo, C. Schultz, E.
A. Lemke, P. Heppenstall, C. Eggeling, S. Manley, K. Johnsson, Nat.
Chem. 2013, 5, 132-139.
[14] S. L. Niu, G. Ulrich, R. Ziessel, A. Kiss, P.-Y. Renard, A. Romieu, Org.
Lett. 2009, 11, 2049-2052.
[15] S. Zhu, J. Zhang, G. Vegesna, F.-T. Luo, S. A. Green, H. Liu, Org. Lett.
2011, 13, 438-441.
[16] A. P. Gorka, M. J. Schnermann, Curr. Opin. Chem. Biol. 2016, 33, 117-
125.
[17] X. Chai, X. Cui, B. Wang, F. Yang, Y. Cai, Q. Wu, T. Wang, Chem. Eur.
J. 2015, 21, 16754-16758.
[18] M. Grzybowski, M. Taki, S. Yamaguchi, Chem. Eur. J. 2017, 23, 13028-
13032.
[19] X. Zhou, R. Lai, J. R. Beck, H. Li, C. I. Stains, Chem. Commun. 2016, 52,
12290-12293.
[20] B. Wang, X. Chai, W. Zhu, T. Wang, Q. Wu, Chem. Commun. 2014, 50,
14374-14377.
Acknowledgements
[21] R. Ditchfield, W. J. Hehre, J. A. Pople, J. Chem. Phys. 1971, 54, 724-728.
[22] A. Fukazawa, S. Suda, M. Taki, E. Yamaguchi, M. Grzybowski, Y. Sato,
T. Higashiyama, S. Yamaguchi, Phospha-fluorescein: a red-emissive
fluorescein analogue with high photobleaching resistance. Chem.
Commun. 2016, 52, 1120-1123.
This work was financially supported by National Natural Science
Foundation of China (21205135, 21602250, 21705049),
Shanghai Pujiang program (17PJ1402000), Innovation Program
of
Shanghai
Municipal
Education
Commission
[23] F. L. Hirshfeld, Theor. Chim. Acta. 1977, 44, 129-138.
[24] T. Lu, F. Chen, J. Comput. Chem., 2012, 33, 580-592.
[25] Y. Tang, D. Lee, J. Wang, G. Li, J. Yu, W. Lin, J. Yoon, Chem. Soc. Rev.
2015, 44, 5003-5015.
(201701070005E00020) and The Program for Professor of
Special Appointment (Eastern Scholar) at Shanghai Institutions of
Higher Learning. We thank Supercomputer Center of East China
Normal University for the computational time. We also sincerely
thank Dr. Tong Zhu from East China Normal University for his help
in theoretical calculation and Dr. Limin Zhang from East China
Normal University for her help in the cyclic voltammetry
experiments.
[26] N. Karton-Lifshin, E. Segal, L. Omer, M. Portnoy, R. Satchi-Fainaro, D.
Shabat, J. Am. Chem. Soc. 2011, 133, 10960-10965.
[27] O. Redy-Keisar, E. Kisin-Finfer, S. Ferber, R. Satchi-Fainaro, D. Shabat,
Nat. Protoc. 2013, 9, 27-36.
[28] M. Fernandez-Suarez, A. Y. Ting, Nat. Rev. Mol. Cell Bio. 2008, 9, 929-
943.
[29] B. D'Autreaux, M. B. Toledano, Nat. Rev. Mol. Cell Bio. 2007, 8, 813-824.
[30] A. R. Lippert, G. C. V. De Bittner, C. J. Chang, Acc. Chem. Res., 2011,
44, 793-804.
Keywords: Rhodamine • Phosphorus • Near-infrared •
Fluorescent probe • Imaging
[31] J. M. Brown, W. R. William, Nat. Rev. Cancer 2004, 4, 437-447.
[32] M. Gao, F. Yu, C. Lv, J. Choo, L. Chen, Chem. Soc. Rev. 2017, 46, 2237-
2271.
This article is protected by copyright. All rights reserved.