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

doi:10.3866/PKU.WHXB201710271

Abstract

Abstract:

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.

Key words: Silver nanoclusters, Singlet oxygen, Photodynamic therapy, Organic dyes, FRET, Hybrid photosensitizers

Click here to download Supporting Info material in PDF type

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

References

1	Jin R. ; Zeng C. ; Zhou M. ; Chen Y. Chem. Rev. 2016, 116, 10346.
2	Goswami N. ; Yao Q. ; Chen T. ; Xie J. Coord. Chem. Rev. 2016, 329, 1.
3	Kurashige W. ; Niihori Y. ; Sharma S. ; Negishi Y. Coord. Chem. Rev. 2016, 320, 238.
4	Negishi Y. ; Nobusada K. ; Tsukuda T. J. Am. Chem. Soc. 2005, 127, 5261.
5	Zhu M. ; Lanni E. ; Garg N. ; Bier M. E. ; Jin R. J. Am. Chem. Soc. 2008, 130, 1138.
6	Xie J. ; Zheng Y. ; Ying J. Y. J. Am. Chem. Soc. 2009, 131, 888.
7	Negishi Y. ; Nakazaki T. ; Malola S. ; Takano S. ; Niihori Y. ; Kurashige W. ; Yamazoe S. ; Tsukuda T. ; H?kkinen H. J. Am. Chem. Soc. 2015, 137, 1206.
8	Zhou M. ; Zeng C. ; Chen Y. ; Zhao S. ; Sfeir M. Y. ; Zhu M. ; Jin R. Nat. Commun. 2016, 7, 13240.
9	Yamazoe S. ; Takano S. ; Kurashige W. ; Yokoyama T. ; Nitta K. ; Negishi Y. ; Tsukuda T. Nat. Commun. 2016, 7, 10414.
10	Kawasaki H. ; Hamaguchi K. ; Osaka I. ; Arakawa R. Adv. Funct. Mater. 2011, 21, 3508.
11	Li G. ; Jin R. Acc. Chem. Res. 2013, 46, 1749.
12	Yoshimoto J. ; Sangsuwan A. ; Osaka I. ; Yamashita K. ; Iwasaki Y. ; Inada M. ; Arakawa R. ; Kawasaki H. J. Phys. Chem. C 2015, 119, 14319.
13	Song X. R. ; Goswami N. ; Yang H. H. ; Xie J. Analyst 2016, 141, 3126.
14	Sangsuwan A. ; Kawasaki H. ; Matsumura Y. ; Iwasaki Y. Bioconjugate Chem. 2016, 27, 2527.
15	Chakraborty I. ; Pradeep T. Chem. Rev. 2017, 117, 8208.
16	Das T. ; Ghosh P. ; Shanavas M. S. ; Maity A. ; Mondal S. ; Purkayastha P. Nanoscale 2012, 4, 6018.
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.
18	Kawasaki H. ; Kumar S. ; Li G. ; Zeng C. ; Kauffman D. R. ; Yoshimoto J. ; Iwasaki Y. ; Jin R. Chem. Mater. 2014, 26, 2777.
19	Tao Y. ; Li M. ; Ren J. ; Qu X. Chem. Soc. Rev. 2015, 44, 8636.
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.
21	Yang D. ; Yang G. ; Gai S. ; He F. ; An G. ; Dai Y. ; Lv R. ; Yang P. Nanoscale 2015, 7, 19568.
22	Lei Q. ; Hu J. J. ; Rong L. ; Cheng H. ; Sun Y. X. ; Zhang X. Z. Molecules 2016, 21, 1103.
23	DeRosa M. C. ; Crutchley R. J. Coord. Chem. Rev. 2002, 233–234, 351.
24	Yamamoto M. ; Osaka I. ; Yamashita K. ; Hasegawa H. ; Arakawa R. J. Lumin. 2016, 180, 315.
25	Yu Y. ; Geng J. ; Ong E. Y. X. ; Chellappan V. Adv. Healthcare Mater. 2016, 5, 2528.
26	Yuan X. ; Setyawati M. I. ; Tan A. S. ; Ong C. N. ; Leong D. T. ; Xie J. NPG Asia Mater. 2013, 5, e39.
27	Sangsuwan A. ; Kawasaki H. ; Matsumura Y. ; Iwasaki Y. Bioconjugate Chem. 2016, 27, 2527.
28	Tominaga C. ; Hasegawa H. ; Yamashita K. ; Arakawa R. ; Kawasaki H. RSC Adv. 2016, 6, 73600.
29	Chakraborty I. ; Udayabhaskararao T. ; Pradeep T. Chem. Commun. 2012, 48, 6788.
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.
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.
32	Zou F. ; Zhou W. ; Guan W. ; Lu C. ; Tang B. T. Anal. Chem. 2016, 88, 9707.
33	Xiang H. ; Wei S. H. ; Gong X. J. Am. Chem. Soc. 2010, 132, 7355.
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.
35	Ai H. W. ; Hazelwood K. L. ; Davidson M. W. ; Campbell R. E. Nat. Methods 2008, 5, 401.
36	Zhou W. ; Cao Y. ; Sui D. ; Guan W. ; Lu C. ; Xie J. Nanoscale 2016, 8, 9614.
37	Browning D. J. Amer. J. Ophthalmol. 2004, 137, 577.
38	Solomon V. R. ; Almnayan. D ; Lee H. Eur. J. Med. Chem. 2017, 137, 156.

[1]	Shiyang He, Dandan Chu, Zhixin Pang, Yuhang Du, Jiayi Wang, Yuhong Chen, Yumeng Su, Jianhua Qin, Xiangrong Pan, Zhan Zhou, Jingguo Li, Lufang Ma, Chaoliang Tan. Pt Single-Atom-Functionalized 2D Al-TCPP MOF Nanosheets for Enhanced Photodynamic Antimicrobial Therapy [J]. Acta Phys. -Chim. Sin., 2025, 41(5): 100046-.
[2]	Zhen Wei, Minjie Li, Wencong Lu. Theoretical Study of High-Efficiency Organic Dyes with Different Electron-Withdrawing Groups Based on R6 toward Dye-Sensitized Solar Cells [J]. Acta Phys. -Chim. Sin., 2021, 37(10): 1905084-.
[3]	Peixuan BU,Chenhui HE,Xinsheng ZHAO. Single-Molecule Study on the Folding of OmpT in Tween-20 Micelles [J]. Acta Phys. -Chim. Sin., 2019, 35(5): 546-554.
[4]	Shizhao WANG, Weijun LI, Yue YU, Jin LIU, Cheng ZHANG. Aggregation-Induced Emission Property of a Novel Pt(Ⅱ) Metal Complex and Its Self-Sensitized Oxidation Reaction in Photo-Excitation State [J]. Acta Physico-Chimica Sinica, 2019, 35(11): 1276-1281.
[5]	Jiao LIU,Jicun HUO,Min ZHANG,Xiandui DONG. Ultrafast Photoluminescence Dynamics of Organic Photosensitizers with Conjugated Linkers Containing Different Heteroatoms [J]. Acta Phys. -Chim. Sin., 2018, 34(4): 424-436.
[6]	GUO Chuang-Long, OU Zhi-Ze, GAO Yun-Yan, WANG Zhong-Li, JIN He-Lin, LI Hai-Xia. Photophysical and Photobiological Properties of Coordination Polymers of Hypocrellin B Complexes Containing Magnesium and Zinc [J]. Acta Phys. -Chim. Sin., 2011, 27(11): 2682-2690.
[7]	OGUNSIPE Abimbola, NYOKONG Tebello. Solvent Effects on the Photophysicochemical Properties of Tetra(tert-butylphenoxy)phthalocyaninato Zinc(II) [J]. Acta Phys. -Chim. Sin., 2011, 27(05): 1045-1052.
[8]	GUO Su;LIAO Wei;WEI Fang;QIAN Min-Xie;ZHAO Xin-Sheng . Protein Biosensors Based on Scanning Potential Hairpin Denaturation and Fluorescence Resonance Energy Transfer [J]. Acta Phys. -Chim. Sin., 2006, 22(08): 917-920.
[9]	Huang Jian-Dong,Liu Er-Sheng,Yang Su-Ling,Ouyang Rui-Zhen,Chen Nai-Sheng,Huang J. The Ability of Photosensitization and Anti-cancer of ZnPcSP under Different Exciting Wavelength [J]. Acta Phys. -Chim. Sin., 1997, 13(03): 247-251.
[10]	Ma Si-Yu; Ding Yan-Bo; Fu Xiao-Yuan. Theoretical Studies on the 1,2-Cycloaddition Reaction of Singlet Molecular Oxygen (¹O₂) with Imidazole [J]. Acta Phys. -Chim. Sin., 1992, 8(02): 181-185.

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

RichHTML

PDF

Like

Knowledge

Abstract

Supporting Info

Cite this article

share this article

References

Related Articles 10

Metrics

Recommended 0