Citation: TOMINAGA Chiaki, HIKOSOU Dailo, OSAKA Issey, KAWASAK Hideya. Ag₇(MBISA)₆ Nanoclusters Conjugated with Quinacrine for FRET-Enhanced Photodynamic Activity under Visible Light Irradiation[J]. Acta Physico-Chimica Sinica, ;2018, 34(7): 805-811. doi: 10.3866/PKU.WHXB201710271 shu

Ag₇(MBISA)₆ Nanoclusters Conjugated with Quinacrine for FRET-Enhanced Photodynamic Activity under Visible Light Irradiation

1.
Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita-shi, Osaka 564-8680, Japan
2.
Center for Nano Materials and Technology, Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi-shi, Ishikawa 923-1292, Japan

Corresponding author: KAWASAK Hideya, hkawa@kansai-u.ac.jp
Received Date: 11 September 2017
Revised Date: 14 October 2017
Accepted Date: 20 October 2017
Available Online: 27 July 2017
Fund Project: The project was supported by the JSPS KAKENHI, Japan (15H03520, 15H03526, and 26107719), and the MEXT-Supported Program for the Strategic Research Foundation at Private Universities, Japanthe JSPS KAKENHI, Japan 15H03526the JSPS KAKENHI, Japan 26107719the JSPS KAKENHI, Japan 15H03520

Singlet oxygen (¹O₂) plays an important role in various applications, such as in the photodynamic therapy (PDT) of cancers, photodynamic inactivation of microorganisms, photo-degradation of toxic compounds, and photo-oxidation in synthetic chemistry. Recently, water-soluble metal nanoclusters (NCs) have been utilized as photosensitizers for the generation of highly reactive ¹O₂ because of their high water solubility, low toxicity, and surface functionalizability for targeted substances. In the case of metal NC-based photosensitizers, the photo-physical properties depend on the core size of the NCs and the core/ligand interfacial structures. A wide range of atomically precise gold NCs have been reported; however, reports on the synthesis of atomically precise silver NCs are limited due to the high reactivity and low photostability (i.e., easy oxidation) of Ag NCs. In addition, there have been few reports on what kinds of metal NCs can generate large amounts of ¹O₂. In this study, we developed a new one-pot synthesis method of water-soluble Ag₇(MBISA)₆ (MBISA = 2-mercapto-5-benzimidazolesulfonic acid sodium salt) NCs with highly efficient ¹O₂ generation ability under the irradiation of white light emitting diodes (LEDs). The molecular formula and purity were determined by electrospray ionization mass spectrometry and gel electrophoresis. To the best of our knowledge, this is the first report on atomically precise thiolate silver clusters (Ag_n(SR)_m) for efficient ¹O₂ generation under visible light irradiation. The ¹O₂ generation efficiency of Ag₇(MBISA)₆ NCs was higher than those of the following known water-soluble metal NCs: bovine serum albumin (BSA)-Au₂₅ NCs, BSA-Ag₈ NCs, BSA-Ag₁₄ NCs, Ag₂₅(dihydrolipoic acid)₁₄ NCs, Ag₃₅(glutathione)₁₈ NCs, and Ag₇₅(glutathione)₄₀ NCs. The metal NCs examined in this study showed the following order of ¹O₂ generation efficiency under white light irradiation: Ag₇(MBISA)₆ > BSA-Ag₁₄ > Ag₇₅(SG)₄₀ > Ag₃₅(SG)₁₈ > BSA-Au₂₅ ≫ BSA-Ag₈ (not detected) and Ag₂₅(DHLA)₁₄ (not detected). For further improving the ¹O₂ generation of Ag₇(MBISA)₆ NCs, we developed a novel fluorescence resonance energy transfer (FRET) system by conjugating Ag₇(MBISA)₆ NCs with quinacrine (QC) (molar ratio of Ag NCs to QC is 1 : 0.5). We observed the FRET process, from QC to Ag₇(MBISA)₆ NCs, occurring in the conjugate. That is, the QC works as a donor chromophore, while the Ag NCs work as an acceptor chromophore in the FRET process. The FRET-mediated process caused a 2.3-fold increase in ¹O₂ generation compared to that obtained with Ag₇(MBISA)₆ NCs alone. This study establishes a general and simple strategy for improving the PDT activity of metal NC-based photosensitizers.
- Silver nanoclusters,
- Singlet oxygen,
- Photodynamic therapy,
- Organic dyes,
- FRET,
- Hybrid photosensitizers
1. [1]
  Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Chem. Rev. 2016, 116, 10346. doi: 10.1021/acs.chemrev.5b00703 doi: 10.1021/acs.chemrev.5b00703
2. [2]
  Goswami, N.; Yao, Q.; Chen, T.; Xie, J. Coord. Chem. Rev. 2016, 329, 1. 10.1016/j.ccr.2016.09.001 doi: 10.1016/j.ccr.2016.09.001
3. [3]
  Kurashige, W.; Niihori, Y.; Sharma, S.; Negishi, Y. Coord. Chem. Rev. 2016, 320, 238. 10.1016/j.ccr.2016.02.013 doi: 10.1016/j.ccr.2016.02.013
4. [4]
  Negishi, Y.; Nobusada, K.; Tsukuda, T. J. Am. Chem. Soc. 2005, 127, 5261. doi: 10.1021/ja042218h doi: 10.1021/ja042218h
5. [5]
  Zhu, M.; Lanni, E.; Garg, N.; Bier, M. E.; Jin, R. J. Am. Chem. Soc. 2008, 130, 1138. doi: 10.1021/ja0782448 doi: 10.1021/ja0782448
6. [6]
  Xie, J.; Zheng, Y.; Ying, J. Y. J. Am. Chem. Soc. 2009, 131, 888. doi: 10.1021/ja806804u doi: 10.1021/ja806804u
7. [7]
  Negishi, Y.; Nakazaki, T.; Malola, S.; Takano, S.; Niihori, Y.; Kurashige, W.; Yamazoe, S.; Tsukuda, T.; Häkkinen, H. J. Am. Chem. Soc. 2015, 137, 1206. doi: 10.1021/ja5109968 doi: 10.1021/ja5109968
8. [8]
  Zhou, M.; Zeng, C.; Chen, Y.; Zhao, S.; Sfeir, M. Y.; Zhu, M.; Jin, R. Nat. Commun. 2016, 7, 13240. doi: 10.1038/ncomms13240 doi: 10.1038/ncomms13240
9. [9]
  Yamazoe, S.; Takano, S.; Kurashige, W.; Yokoyama, T.; Nitta, K.; Negishi, Y.; Tsukuda, T. Nat. Commun. 2016, 7, 10414. doi: 10.1038/ncomms10414 doi: 10.1038/ncomms10414
10. [10]
  Kawasaki, H.; Hamaguchi, K.; Osaka, I.; Arakawa, R. Adv. Funct. Mater. 2011, 21, 3508. doi: 10.1002/adfm.201100886 doi: 10.1002/adfm.201100886
11. [11]
  Li, G.; Jin, R. Acc. Chem. Res. 2013, 46, 1749. doi: 10.1021/ar300213z doi: 10.1021/ar300213z
12. [12]
  Yoshimoto, J.; Sangsuwan, A.; Osaka, I.; Yamashita, K.; Iwasaki, Y.; Inada, M.; Arakawa, R.; Kawasaki, H. J. Phys. Chem. C 2015, 119, 14319. doi: 10.1021/acs.jpcc.5b03934 doi: 10.1021/acs.jpcc.5b03934
13. [13]
  Song, X. R.; Goswami, N.; Yang, H. H.; Xie, J. Analyst 2016, 141, 3126. doi: 10.1039/C6AN00773B doi: 10.1039/C6AN00773B
14. [14]
  Sangsuwan, A.; Kawasaki, H.; Matsumura, Y.; Iwasaki, Y. Bioconjugate Chem. 2016, 27, 2527. doi: 10.1021/acs.bioconjchem.6b00455 doi: 10.1021/acs.bioconjchem.6b00455
15. [15]
  Chakraborty, I.; Pradeep, T. Chem. Rev. 2017, 117, 8208. doi: 10.1021/acs.chemrev.6 doi: 10.1021/acs.chemrev.6
16. [16]
  Das, T.; Ghosh, P.; Shanavas, M. S.; Maity, A.; Mondal, S.; Purkayastha, P. Nanoscale 2012, 4, 6018. doi: 10.1039/C2NR31271A doi: 10.1039/C2NR31271A
17. [17]
  Shibu, E. S.; Sugino, S.; Ono, K.; Saito, H.; Nishioka, A.; Yamamura, S.; Sawada, M.; Nosaka, Y.; Biju, V. Angew. Chem. Int. Ed. 2013, 52, 10559. doi: 10.1002/anie.201304264 doi: 10.1002/anie.201304264
18. [18]
  Kawasaki, H.; Kumar, S.; Li, G.; Zeng, C.; Kauffman, D. R.; Yoshimoto, J.; Iwasaki, Y.; Jin, R. Chem. Mater. 2014, 26, 2777. doi: 10.1021/cm500260z doi: 10.1021/cm500260z
19. [19]
  Tao, Y.; Li, M.; Ren, J.; Qu, X. Chem. Soc. Rev. 2015, 44, 8636. doi: 10.1039/C5CS00607D doi: 10.1039/C5CS00607D
20. [20]
  He, F.; Yang, G.; Yang, P.; Yu, Y.; Lv, R.; Li, C.; Dai, Y.; Gai, S.; Lin, J. Adv. Funct. Mater. 2015, 25, 3966. doi: 10.1002/adfm.201500464 doi: 10.1002/adfm.201500464
21. [21]
  Yang, D.; Yang, G.; Gai, S.; He, F.; An, G.; Dai, Y.; Lv, R.; Yang, P. Nanoscale 2015, 7, 19568. doi: 10.1039/C5NR06192J doi: 10.1039/C5NR06192J
22. [22]
  Lei, Q.; Hu, J. J.; Rong, L.; Cheng, H.; Sun, Y. X.; Zhang, X. Z. Molecules 2016, 21, 1103. doi: 10.3390/molecules21081103 doi: 10.3390/molecules21081103
23. [23]
  DeRosa, M. C.; Crutchley, R. J. Coord. Chem. Rev. 2002, 233–234, 351. doi: 10.1016/S0010-8545(02)00034-6 doi: 10.1016/S0010-8545(02)00034-6
24. [24]
  Yamamoto, M.; Osaka, I.; Yamashita, K.; Hasegawa, H.; Arakawa, R., J. Lumin. 2016, 180, 315. doi: 10.1016/j.jlumin.2016.08.059 doi: 10.1016/j.jlumin.2016.08.059
25. [25]
  Yu, Y.; Geng, J.; Ong, E. Y. X.; Chellappan, V. Adv. Healthcare Mater. 2016, 5, 2528. doi: 10.1002/adhm.201600312 doi: 10.1002/adhm.201600312
26. [26]
  Yuan, X.; Setyawati, M. I.; Tan, A. S.; Ong, C. N.; Leong, D. T.; Xie, J. NPG Asia Mater. 2013, 5, e39. doi:10.1038/am.2013.3 doi: 10.1038/am.2013.3
27. [27]
  Sangsuwan, A.; Kawasaki, H.; Matsumura, Y.; Iwasaki, Y. Bioconjugate Chem. 2016, 27, 2527. doi: 10.1021/acs.bioconjchem.6b00455 doi: 10.1021/acs.bioconjchem.6b00455
28. [28]
  Tominaga, C.; Hasegawa, H.; Yamashita, K.; Arakawa, R.; Kawasaki, H. RSC Adv. 2016, 6, 73600. doi: 10.1039/C6RA10892J doi: 10.1039/C6RA10892J
29. [29]
  Chakraborty, I.; Udayabhaskararao, T.; Pradeep, T. Chem. Commun. 2012, 48, 6788. doi: 10.1039/C2CC33099G doi: 10.1039/C2CC33099G
30. [30]
  Chin, P. T.; van der Linden, M.; van Harten, E. J.; Barendregt, A.; Rood, M. T.; Koster, A. J.; van Leeuwen, F. W.; de Mello Donega, C.; Heck, A. J.; Meijerink, A. Nanotechnology 2013, 22, 075703. doi: 10.1088/0957-4484/24/7/075703 doi: 10.1088/0957-4484/24/7/075703
31. [31]
  Bootharaju, M. S.; Burlakov, V. M.; Besong, T. M. D.; Joshi, C. P.; AbdulHalim, L. G.; Black, D. M.; Whetten, R. L.; Goriely, A.; Bakr, O. M. Chem. Mater. 2015, 27, 4289. doi: 10.1021/acs.chemmater.5b00650 doi: 10.1021/acs.chemmater.5b00650
32. [32]
  Zou, F.; Zhou, W.; Guan, W.; Lu, C.; Tang, B. T. Anal. Chem. 2016, 88, 9707. doi: 10.1021/acs.analchem.6b02611 doi: 10.1021/acs.analchem.6b02611
33. [33]
  Xiang, H.; Wei, S. H.; Gong, X. J. Am. Chem. Soc. 2010, 132, 7355. doi: 10.1021/ja9108374 doi: 10.1021/ja9108374
34. [34]
  Xu, S.; Yuan, Y.; Cai, X.; Zhang, C. J.; Hu, F.; Liang, J.; Zhang, G.; Zhang, D.; Liu, B. Chem. Sci. 2015, 6, 5824. doi: 10.1039/c5sc01733e doi: 10.1039/c5sc01733e
35. [35]
  Ai, H. W.; Hazelwood, K. L.; Davidson, M. W.; Campbell, R. E. Nat. Methods 2008, 5, 401. doi: 10.1038/nmeth.1207 doi: 10.1038/nmeth.1207
36. [36]
  Zhou, W.; Cao, Y.; Sui, D.; Guan, W.; Lu, C.; Xie, J. Nanoscale 2016, 8, 9614. doi: 10.1039/C6NR02178F doi: 10.1039/C6NR02178F
37. [37]
  Browning, D. J. Amer. J. Ophthalmol. 2004, 137, 577. doi: 10.1016/j.ajo.2003.08.047 doi: 10.1016/j.ajo.2003.08.047
38. [38]
  Solomon, V. R.; Almnayan. D; Lee, H. Eur. J. Med. Chem. 2017, 137, 156. doi: 10.1016/j.ejmech.2017.05.052 doi: 10.1016/j.ejmech.2017.05.052
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Ag7(MBISA)6 Nanoclusters Conjugated with Quinacrine for FRET-Enhanced Photodynamic Activity under Visible Light Irradiation

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Ag₇(MBISA)₆ Nanoclusters Conjugated with Quinacrine for FRET-Enhanced Photodynamic Activity under Visible Light Irradiation