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

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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.

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

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