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Dalton Transactions
Page 5 of 7
DOI: 10.1039/C7DT04850E
Journal Name
ARTICLE
missing the hydrophobic unit (compound 3) does not show this
effect, but only a slight modification of the absorption spectrum,
Table 1. IC50 values (in mM) after 72 hours exposure for 1 and 2 with different
cancer cell lines.
due to the low solubility (see absorption spectrum of
ESI, Fig. S5).
3 in the
Cell lines
¶ With the verb to illuminate here we mean the localization of a
dye into a cell compartment plus its photoemission behavior.
MDA-MB-
A2780 A549
18.1±1.0a >30
SKMel28 SHSY5Y MCF7
231
>30
>30
1
The literature on this topic is too large to be exhaustively
quoted; for some recent reviews and few representative
papers, see: (a) A. S. Stender, K. Marchuk, C. Liu, S. Sander,
M. W. Meyer, E. A. Smith, B. Neupane, G. Wang, J. Li, J.-X.
Cheng, B. Huang and N. Fang, Chem. Rev., 2013, 113, 2469–
1
2
26.5±6.3
>30
>30
>30
8.0±2.8
>30
>30
>30
a Mean±SD of 4-7 experiments.
2527. (b) M. Schaeferling, Angew. Chem. Int. Ed., 2012, 51
,
3532–3554. (c) K. Chung, J. Wallace, S.-Y. Kim, S.
Kalyanasundaram, A. S. Andalman, T. J. Davidson, J. J.
Mirzabekov, K. A. Zalocusky, J. Mattis, A. K. Denisin, S. Pak, H.
Bernstein, C. Ramakrishnan, L. Grosenick, V. Gradinaru and
K. Deisseroth, Nature, 2013, 497, 332–337. (d) H. Xiao, P. Li,
Conclusions
X. Hu, X. Shi, W. Zhang and B. Tang, Chem. Sci., 2016,
6153-6159. (e) X. Zhang, R. Li, Y. Chen, S. Zhang, W. Wang
and F. Li, Chem. Sci., 2016, , 6182-6189.
7,
In conclusion, we have prepared a new bichromophoric
species , made of two different bodipy subunits, belonging to
the class of ratiometric probes. The two subunits of have
been selected in such way that intercomponent,
1
7
1
2
(a) Z. Guo, S. Park, J. Yoon and I. Shin, Chem. Soc. Rev., 2014,
43, 16-29. (b) A. Yadav, T. Janaratne, A. Krishanan, S. S.
Singhal, S. Yadav, A. S. Dayoub, D. L. Hawkins, S. Awasthi and
F. M. MacDonnell, Mol. Cancer Ter., 2013, 12, 643-653. (c) J.
Lantoine, T. Grevesse, A. Villers, G. Delhaye, C. Mestdagh, M.
Versaevel, D. Mohammed, C. Bruyere, L. Alaimo, S. P. Lacour,
L. Ris and S. Gabriele, Biomaterials, 2016, 89, 14-24. (d) E. M.
Surender, S. Comby, B. L. Cavanagh, O. Brennan, T. C. Lee
a
photoinduced energy transfer is depending on the
environment, so the emission output also becomes
environment dependent. As a direct consequence,
1 exhibits a
quite rare, interesting property: it can simultaneously and
differentially illuminate different cell compartments, due to an
unusual control of intercomponent photoinduced EnT
efficiency governed by the environment. The efficiency of lipid
and T. Gunnlaugsson, Chem, 2016, 1, 438-455.
3
4
(a) P. Sengupta, S. B. van Engelenburg and J. Lippincott-
Schwartz, Chem. Rev., 2014, 114, 3189-3202, and refs.
therein. (b) A. Hense, B. Prunsche, P. Gao, Y. Ishitsuka, K.
droplets illumination by
1 is also of particular interest in the
light of recent suggestions on the role of lipid droplets on cell
health.18 The results here reported can contribute to pave the
way to the use of environment-controlled intercomponent
energy transfer in multichromophoric species for the study of
cell structures based on luminescence imaging. Analogous
bichromophoric systems in which the acceptor subunit can
significantly modify its absorption spectrum by interaction
with different environments – for example by hydrogen
bonding or self-aggregation phenomena – could exhibit similar
environment-dependence EnT properties and assist in
identifying anomalous situations in cell apparatuses.
Nienhaus and G. U. Nienhaus, Sci. Rep., 2015, 5, 18006.
(a) F. D. Dip, T. Ishizawa and N. Kokudo, Fluorescence
Imaging for Surgeons: Concepts and Applications, Springer,
New York, 2015. (b) Q. T. Nguyen and R. Y. Tsien, Nat. Rev.
Cancer, 2013, 13, 653-662. (c) S. B. Mondal, S. Gao, N. Zhu, R.
Liang, V. Gruev and S. Achlefu, Adv. Cancer Res., 2014, 124
171-211.
,
5
6
M. Montalti, G. Battistelli, A. Cantelli and D. Genovese,
Chem. Commun., 2014, 50, 5326, and refs therein.
For some examples of dual-color cell imaging, see: (a) J.
Chen, W. Zhong, Y. Tang, Z. Wu, Y. Li, P. Yi and J. Jiang,
Macromolecules, 2015, 48, 3500-3508. (b) M. Yeng, L. Li, P.
Jiang, A. R. Moossa, S. Penman and R. M. Hoffman, Proc.
Natl. Ac. Sci., 2003, 100, 14259-14262. (c) Z. Yang, J. Cao, Y.
He, J. H. Yang, T. Kim, X. Peng and J. S. Kim Chem. Soc. Rev.
2014, 43, 4563–4601. (d) A. S. Klymchenko, Acc. Chem. Res.
2017, 50, 366−375.
Acknowledgements
We acknowledge MIUR (FIRB Project NANOSOLAR) for funding.
7
T. Papalia, G. Siracusano, I. Colao, A. Barattucci, M. C. Aversa,
S. Serroni, S. Campagna, M. T. Sciortino, F. Puntoriero and P.
Bonaccorsi, Dyes and Pigments, 2014, 110, 67-71, and refs
therein.
Notes and references
8
9
P. Bonaccorsi, M. C. Aversa, A. Barattucci, T. Papalia, F.
,
‡ Reasons for the dependence of the absorption spectrum of the
blue dye of 1 will be studied in detail in a future work. A
pioneering example of EnT dependence on environment can be
found in ref. 14.
Puntoriero and S. Campagna, Chem. Commun., 2012, 48
10550-10552.
(a) V. Balzani, P. Ceroni and A. Juris, Photochemistry and
Photophysics. Concepts, Research, Applications, Wiley-VCH,
2014. (b) N. J. Turro, V. Ramamurthy and J. C. Scaiano,
Principles of Molecular Photochemistry, University Science
Books, Sausalito, Ca., 2009.
¥ The absorption spectrum of
1 in oil evidences a significant loss
of structure and a strong reduced molar absorption of the
contribution due to the lowest-energy bodipy subunit. This can
be tentatively attributed to formation of micelles in which the
(hydrophilic) polar subunits of the bichromophoric dye is
protected from the environment, with the simultaneous
interaction (i.e., aggregation) of the lowest-energy bodipy units,
responsible for the severe effects on the light absorption
features. The role of the hydrophobic high-energy bodipy
subunit also appears to be important, since the precursor
10 M. Ortega-Muñoz, F. Perez-Balderas, J. Morales-Sanfrutos, F.
Hernandez-Mateo, J. Isac-García and F. Santoyo-Gonzalez,
Eur. J. Org. Chem., 2009, 2454–2473.
11 R. Ziessel, G. Ulrich, A. Harriman, M. A. H. Alamiry, B. Stewart
and P. Retailleau, Chem.–Eur. J., 2009, 15, 1359-1369.
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J. Name., 2013, 00, 1-3 | 5
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