Chemistry - A European Journal
10.1002/chem.202001568
FULL PAPER
1
[12] J. Jia, Y. Zhang, M. Zheng, C. Shan, H. Yan, W. Wu, X. Gao, B.
Cheng, W. Liu and Y. Tang, Inorg. Chem. 2018, 57, 300-310.
emission, and of generating O
2
with efficiencies comparable to
known compounds. We have also explored their phototoxicity and
dark toxicity with HeLa cells, and determined IC50 values under
irradiation at 360 nm of 15.2 to 16.2 M. Further investigation
using flow cytometry indicates the presence of both necrotic and
late apoptotic cells. In the dark, the compounds are much less
cytotoxic towards HeLa cells, with decreases in cell viability to
10%. Although we attribute the cytotoxicity to the formation of
2
O , we cannot rule out the formation of other ROS species that
could contribute as well to the observed cell death.
[
13] F. Xu, Y. Zhao, M. Hu, P. Zhang, N. Kong, R. Liu, C. Liu and S.
K. Choi, Chem. Commun. 2018, 54, 9525-9528.
[14] S. Dasari, S. Singh, S. Sivakumar and A. K. Patra, Chem. Eur. J.
2016, 22, 17387-17396.
[
15] G.-L. Law, R. Pal, L. O. Palsson, D. Parker and K.-L. Wong,
Chem. Commun. 2009, 7321-7323.
16] P. Ung, M. Clerc, H. Huang, K. Qiu, H. Chao, M. Seitz, B. Boyd,
[
<
1
B. Graham and G. Gasser, Inorg. Chem. 2017, 56, 7960-7974.
[17] T. Zhang, C.-F. Chan, J. Hao, G.-L. Law, W.-K. Wong and K.-L.
Wong, RSC Adv. 2013, 3, 382-385.
[
5
[
18] K. R. Johnson and A. de Bettencourt-Dias, Inorg. Chem. 2019,
8, 13471-13480.
19] a) M. Ciofalo and G. Ponterini, Journal of Photochemistry and
The dual functionality of these compounds allows for a variety
1
of applications where
O
2
plays a vital role and provides
Photobiology A: Chemistry 1994, 83, 1-6; b) R. Boch, B. Mehta, T.
Connolly, T. Durst, J. T. Arnason, R. W. Redmond and J. C. Scaiano,
Journal of Photochemistry and Photobiology A: Chemistry 1996, 93,
III
simultaneous tracking of the complexes by Ln -centred
luminescence. While these complexes are water-soluble,
attempts to image luminescence within HeLa cells were not
fruitful, and is likely due to the low emission efficiencies in
aqueous environment. Nonetheless, these compounds provide a
design basis for the isolation of compounds with dual functionality,
39-47; c) T. Eicher, S. Hauptmann and A. Speicher, The Chemistry of
Heterocycles: Structures, Reactions, Synthesis, and Applications,
Wiley-VCH, 2012, p. 646 pp; d) R. J. Marles, J. B. Hudson, E. A.
Graham, C. Soucy-Breau, P. Morand, R. L. Compadre, C. M.
Compadre, G. H. N. Towers and J. T. Arnason, Photochem.
Photobiol. 1992, 56, 479-487; e) R. Boch, B. Mehta, T. Connolly, T.
Durst, J. T. Arnason, R. W. Redmond and J. C. Scaiano, J.
Photochem. Photobiol., A 1996, 93, 39-47; f) J. C. Scaiano, A.
MacEachern, J. T. Arnason, P. Morand and D. Weir, Photochem.
Photobiol. 1987, 46, 193-199; g) J. Pina and J. S. Seixas de Melo,
Phys. Chem. Chem. Phys. 2009, 11, 8706-8713; h) F. J. Gommers
and J. Bakker, Bioact. Mol. 1988, 7, 61-69; i) A. Parthasarathy, S.
Goswami, T. S. Corbitt, E. Ji, D. Dascier, D. G. Whitten and K. S.
Schanze, ACS Applied Materials & Interfaces 2013, 5, 4516-4520; j)
R. J. Marles, R. L. Compadre, C. M. Compadre, C. Soucy-Breau, R.
W. Redmond, F. Duval, B. Mehta, P. Morand, J. C. Scaiano and J. T.
Arnason, Pestic. Biochem. Physiol. 1991, 41, 89-100; k) J. B. Hudson,
E. A. Graham, N. Miki, G. H. N. Towers, L. L. Hudson, R. Rossi, A.
Carpita and D. Neri, Chemosphere 1989, 19, 1329-1343; l) M.
Herrnreiter, J. Kagan, X. Chen, K. Y. Lau, M. D'Auria and A. Vantaggi,
Photochem. Photobiol. 1993, 58, 49-52; m) A. Parthasarathy, S.
Goswami, T. S. Corbitt, E. Ji, D. Dascier, D. G. Whitten and K. S.
Schanze, ACS Appl. Mater. Interfaces 2013, 5, 4516-4520; n) H. D.
Burrows, J. Seixas de Melo, C. Serpa, L. G. Arnaut, A. P. Monkman,
I. Hamblett and S. Navaratnam, The Journal of Chemical Physics
that generate both 1O
emission.
and display the characteristic LnIII
2
Acknowledgements
The National Science Foundation (CHE 1800392 to AdBD) is
gratefully acknowledged for financial support. Shanti Rawat and
Carime V. da S. Rodrigues are acknowledged for their support
and guidance for biological experiments. Janina S. Ruprecht is
acknowledged for her support with mass spectrometry.
Keywords: dual functionality • lanthanides • luminescence •
singlet oxygen • photodynamic therapy
[
1] A. T. Hoye, J. E. Davoren, P. Wipf, M. P. Fink and V. E. Kagan,
Acc. Chem. Res. 2008, 41, 87-97.
2] M. Ethirajan, Y. Chen, P. Joshi and R. K. Pandey, Chem. Soc. Rev.
011, 40, 340-362.
3] a) J. A. Leman and C. A. Morton, Expert Opin. Biol. Ther. 2002, 2,
5-53; b) Ophthalmology 2000, 107, 2314-2317.
4] a) F. Heinemann, J. Karges and G. Gasser, Acc. Chem. Res. 2017,
0, 2727-2736; b) S. Monro, K. L. Colón, H. Yin, J. Roque, P. Konda,
2
001, 115, 9601-9606; o) M. Ciofalo and G. Ponterini, J. Photochem.
Photobiol., A 1994, 83, 1-6.
20] L. Lilge, M. Roufaiel, S. Lazic, P. Kaspler, M. A. Munegowda, M.
[
2
[
4
[
5
[
Nitz, J. Bassan and A. Mandel, Translational Biophotonics 2020, n/a,
e201900032.
[
21] A. L. Capodilupo, V. Vergaro, F. Baldassarre, A. Cardone, G. A.
Corrente, C. Carlucci, S. Leporatti, P. Papadia, G. Gigli and G.
Ciccarella, Biochim. Biophys. Acta, Gen. Subj. 2015, 1850, 385-392.
S. Gujar, R. P. Thummel, L. Lilge, C. G. Cameron and S. A.
McFarland, Chem. Rev. 2018; c) T. Reynolds, J. Natl. Cancer Inst.
[
22] a) K. R. Johnson, S. B. Vittardi, M. A. Gracia-Nava, J. J. Rack
and A. de Bettencourt-Dias, Chem. Eur. J. 2020, DOI:
0.1002/chem.202000587; b) K. R. Johnson, S. B. Vittardi, M. A.
Gracia-Nava, J. Rack and A. de Bettencourt Dias, submitted 2020.
23] a) K. Liu, X. Yan, Y.-J. Xu, L. Dong, L.-N. Hao, Y.-H. Song, F. Li,
1997, 89, 112-114.
1
[
5] a) X.-J. Jiang, P.-C. Lo, Y.-M. Tsang, S.-L. Yeung, W.-P. Fong and
D. K. P. Ng, Chem.: Eur. J 2010, 16, 4777-4783; b) P.-C. Lo, J.-D.
Huang, D. Y. Y. Cheng, E. Y. M. Chan, W.-P. Fong, W.-H. Ko and D.
K. P. Ng, Chem.: Eur. J 2004, 10, 4831-4838.
6] F. Dumoulin, M. Durmuş, V. Ahsen and T. Nyokong, Coord. Chem.
Rev. 2010, 254, 2792-2847.
7] a) H. Dummin, T. Cernay and H. W. Zimmermann, J. Photochem.
[
Y. Su, Y.-D. Wu, H.-S. Qian, W. Tao, X.-Z. Yang, W. Zhou and Y. Lu,
Biomater. Sci. 2017, 5, 2403-2415; b) T. Vairapperumal, A.
Saraswathy, J. S. Ramapurath, S. Kalarical Janardhanan and N.
Balachandran Unni, Sci. Rep. 2016, 6, 34976.
[
[
[
24] L. Pellegatti, J. Zhang, B. Drahos, S. Villette, F. Suzenet, G.
Guillaumet, S. Petoud and É. Tóth, Chem. Commun. 2008, 6591-
593.
25] a) S. Laine, C. S. Bonnet, F. K. Kálmán, Z. Garda, A. Pallier, F.
Caillé, F. Suzenet, G. Tircsó and É. Tóth, New J. Chem. 2018, 42,
012-8020; b) C. S. Bonnet, F. Buron, F. Caillé, C. M. Shade, B.
Photobio. B 1997, 37, 219-229; b) A. E. O’Connor, W. M. Gallagher
and A. T. Byrne, Photochem. Photobiol. 2009, 85, 1053-1074.
6
[
[
7
[
2
8] R. W. Redmond and J. N. Gamlin, Photochem. Photobiol. 1999,
0, 391-475.
9] R. Baskaran, J. Lee and S.-G. Yang, Biomater. Res. 2018, 22, 25-
5.
10] A. de Bettencourt-Dias in Introduction to Lanthanide Ion
Luminescence (Ed. A. de Bettencourt-Dias), John Wiley & Sons, Ltd.,
Chichester, United Kingdom, 2014, pp. 1 - 48.
11] S. Dasari, S. Singh, P. Kumar, S. Sivakumar and A. K. Patra,
8
Drahoš, L. Pellegatti, J. Zhang, S. Villette, L. Helm, C. Pichon, F.
Suzenet, S. Petoud and É. Tóth, Chem. Eur. J 2012, 18, 1419-1431;
c) C. S. Bonnet, S. Laine, F. Buron, G. Tircsó, A. Pallier, L. Helm, F.
Suzenet and É. Tóth, Inorg. Chem. 2015, 54, 5991-6003.
[
[
Euro. J. Med. Chem. 2019, 163, 546-559.
7
This article is protected by copyright. All rights reserved.