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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
Ru3 was synthesized following the method of Ru1. Yield: 26%. 1H
NMR (400 MHz, DMSO) δ (ppm): 8.71 (dd, J = 1.2 Hz, 8.4 Hz, 1H),
were shown in supporting information.
DOI: 10.1039/D0DT01684E
8
8
7
7
.66 (dd, J = 1.2 Hz, 8.0 Hz, 1H), 8.54-8.48 (m, 3H), 8.33-8.23(m, 7H),
.15 (d, J = 8.8 Hz, 2H), 8.09-8.07 (m, 1H), 8.03-8.02 (m, 1H), 7.86-
.82 (m, 2H), 7.77 (dd, J = 0.8 Hz, 5.2 Hz, 1H), 7.68-7.63 (m, 3H),
Conflicts of interest
X. Liu, M. Xie, S. Liu and Qiang Zhao are mentioned as co-
inventors in patent application CN109021030A.
.39-7.35 (m, 5H), 7.14-7.10 (m, 9H). 13C NMR (100 MHz, CD
3
CN) δ
(ppm): 156.44, 155.90, 151.74, 151.63, 150.95, 150.90, 149.85,
1
1
1
1
1
49.79, 149.77, 149.76, 149.10, 148.69, 148.01, 147.18, 140.80,
36.17, 134.81, 133.67, 133.45, 132.54, 131.50, 131.36, 131.17,
31.07, 130.49, 138.86, 128.72, 128.53, 128.51, 128.35, 127.99,
Acknowledgements
This work was financially supported by the National Funds for
Distinguished Young Scientists (61825503), National Natural
Science Foundation of China (61775101), National Key
26.50, 126.01, 125.85, 125.69, 125.68, 124.81, 124.34, 122.74,
+
22.18, 113.72. MS (MALDI-TOF): m/z 923 ([M-PF
PF
6
] ). Anal. Calcd.
for C56
H (3.35), N (10.03).
37
H N
8
6
Ru: C (62.98), H (3.49), N (10.49), Found: C (63.54),
Research
and
Development
Program
of
China
(
2017YFA0205302), Priority Academic Program Development
Synthesis of Ru4
of Jiangsu Higher Education Institutions (YX03001) and the
Open Research Fund of State Key Laboratory of Bioelectronics,
Southeast University.
Ru4 was synthesized following a literature method.36 Yield: 56%. 1H
NMR (400 MHz, DMSO) δ (ppm): 9.00-8.83 (m, 2H), 8.55-8.49 (m,
4
7
7
H), 8.12-8.49 (m, 4H), 8.01-7.87 (m, 4H), 7.86 (d, J = 5.6 Hz, 2H),
.75 (t, J = 7.2 Hz, 2H), 7.60 (d, J = 5.2 Hz, 2H), 7.50-7.44 (m, 4H),
.41-7.36 (m, 2H), 7.24-7.06 (m, 10H). MS (MALDI-TOF): m/z 876
Notes and references
1
+
([M-PF
6
] ). Anal. Calcd. for C51
37
H N
9
P F
2
12Ru: Calcd: C (52.49), H
W. Fan, P. Huang and X. Chen, Chem. Soc. Rev., 2016, 45,
488.
(3.20), N (10.80), Found: C (52.70), H (3.21), N (10.20).
6
2
P. Agostinis, K. Berg, K.A. Cengel, T.H. Foster, A.W. Girotti,
S.O. Gollnick, S.M. Hahn, M.R. Hamblin, A. Juzeniene, D.
Kessel, M. Korbelik, J. Moan, P. Mroz, D. Nowis, J. Piette, B.C.
Wilson and J. Golab, CA: Cancer J. Clin, 2011, 61, 250.
Δ
Singlet oxygen quantum yields (Φ )
By monitoring the absorption variation of 1,3-
diphenylisobenzofuran (DPBF), singlet oxygen quantum yields
(Φ ) were detected. The mixture of the photosensitizer and
Δ
DPBF was irradiated with 475 nm light. UV-Vis
spectrophotometer was used to monitor the absorption of
Δ
DPBF. The values of Φ were calculated by the relative method
3
4
5
6
7
8
Z. Zhou, J. Song, L. Nie and X. Chen, Chem. Soc. Rev., 2016,
4
5, 6597.
M. Lismont, L. Dreesen and S. Wuttke, Adv. Funct. Mater.,
017, 27, 1606314.
S. Shao, V. Rajendiran, J.F. Lovell, Coord. Chem. Rev., 2019,
79, 99.
2
3
according to eqn (S1)
A. Jańczyk, E. Krakowska, G. Stochel and W. Macyk, J. Am.
Chem. Soc., 2006, 128, 15574.
푆
푥
퐹
푠푡푑
Φ
∆(푥) = Φ∆(std) 푆
(
)(
)
(S1)
푠푡푑
퐹
푥
X. Li, N. Kwon, T. Guo, Z. Liu and J. Yoon, Angew. Chem. Int.
Ed., 2018, 57, 11522.
J.S. Nam, M.-G. Kang, J. Kang, S.-Y. Park, S.J.C. Lee, H.-T. Kim,
J.K. Seo, O.-H. Kwon, M.H. Lim, H.-W. Rhee and T.-H. Kwon,
J. Am. Chem. Soc., 2016, 138, 10968.
N. Kotagiri, G.P. Sudlow, W.J. Akers and S. Achilefu, Nat.
Nanotech., 2015, 10, 370.
0 R.C. Gilson, K.C.L. Black, D.D. Lane and S. Achilefu, Angew.
Chem. Int. Ed., 2017, 56, 10717.
where subscripts x and std represent Ru1-Ru4 and Ru(bpy)
3
2+,
respectively; S is the slope of the plots of the absorbance of
DPBF (410 nm) vs the irradiation time; F means the correction
factor of absorption, which is given by F = 1-10 (OD indicates
-OD
9
1
2
+
25
the optical density of Ru1-Ru4 and Ru(bpy)
3
at 475 nm).
−•
O
2
detection
1
1
1 J.-N. Liu, W. Bu and J. Shi, Chem. Rev., 2017, 9, 6160.
2 Z. He, X. Huang, C. Wang, X. Li, Y. Liu, Z. Zhou, S. Wang, F.
Zhang, Z. Wang, O. Jacobson, J.-J. Zhu, G. Yu, Y. Dai and X.
Chen, Angew. Chem. Int. Ed., 2019, 58, 8752.
−
•
As O
monitor O
and DHR123 were prepared as 10 µM in phosphate buffer saline
PBS)/DMSO (99:1, v/v) and irradiated with a xenon lamp (400-800
2
indicator, dihydrorhodamine 123 (DHR123) is used to
−•
2
generation. The mixed solutions of Ru(II) complexes
(
13 Z. Zhou, J. Liu, T.W. Rees, H. Wang, X. Li, H. Chao and P.J.
-2
Stang, Proc. Nati. Acad. Sci. USA, 2018, 115, 5664.
nm, 30 mW cm ). The fluorescence spectra were monitored
immediately after each irradiation for different time (1, 2, 3, 4, 5, 6,
, 8, 9 and 10 min). As control, DHR123 was observed without
1
1
1
1
1
4 L. Misba, S. Zaidi and A.U. Khan, J. Photochem. Photobiol. B,
2
018, 183, 16.
7
5 Q. Chen, L. Feng, J. Liu, W. Zhu, Z. Dong, Y. Wu and Z. Liu,
Adv. Mater., 2016, 28, 7129.
photosensitizers under light irradiation.
6 H. Chen, J. Tian, W. He and Z. Guo, J. Am. Chem. Soc., 2015,
137, 1539.
7 H. Cheng, J.-Y. Zhu, S.-Y. Li, J.-Y. Zeng, Q. Lei, K.-W. Chen, C.
Zhang and X.-Z. Zhang, Adv. Funct. Mater., 2016, 26, 7847.
8 Q. Jia, J. Ge, W. Liu, X. Zheng, S. Chen, Y. Wen, H. Zhang and
P. Wang, Adv. Mater., 2018, 30, 1706090.
OH• detection
For OH• evaluation, the mixed solutions of Ru(II) complexes and
hydroxyphenyl fluorescein (HPF) were prepared as 10 µM in
PBS/DMSO (99:1, v/v), and others procedure were consistent with
−•
19 M. Li, J. Xia, R. Tian, J. Wang, J. Fan, J. Du, S. Long, X. Song,
that of O
2
measurement.
J.W. Foley and X. Peng, J. Am. Chem. Soc., 2018, 140, 14851.
Cell culture and intracellular experiments
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