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Synthesis of Near-Infrared Emitting Gold Nanoclusters for Biological Applications

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Two-photon brightness of NIR-emitting, atomically precise DNA-stabilized silver nanoclusters.

Agata Hajda¹, Rweetuparna Guha², Stacy Marla Copp^2,3,4,5

¹Institute of Advanced Materials, Wroclaw University of Science and Technology Wrocław Poland joanna.olesiak-banska@pwr.edu.pl.

Chemical Science

|December 25, 2024

Summary

DNA-stabilized silver nanoclusters show promise as near-infrared (NIR) two-photon absorbers for in vivo imaging. These Ag-DNAs exhibit high two-photon absorption (2PA) cross-sections, enabling brighter NIR-to-NIR imaging probes.

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Area of Science:

Materials Science
Nanotechnology
Biophotonics

Background:

Near-infrared (NIR) emitters with high two-photon absorption (2PA) are crucial for deep tissue imaging due to reduced light scattering.
DNA-stabilized silver nanoclusters (Ag-DNAs) are explored as potential water-soluble probes for biological applications.
Understanding the photophysical properties of Ag-DNAs, including their 2PA behavior, is essential for their development.

Purpose of the Study:

To investigate the two-photon absorption (2PA) properties of various DNA-stabilized silver nanocluster (Ag-DNA) species.
To evaluate the potential of these Ag-DNAs as NIR-to-NIR two-photon probes for in vivo imaging.
To correlate nanocluster composition and ligand environment with 2PA cross-sections and emission characteristics.

Main Methods:

Synthesis and characterization of four distinct atomically precise Ag-DNA species.
Determination of 2PA cross-sections (σ₂) using the two-photon excited luminescence (2PEL) technique across a broad wavelength range (810–1400 nm).
Analysis of the relationship between one-photon and two-photon absorption spectra to understand photophysical complexities.

Main Results:

Ag-DNAs demonstrated reversed transition strengths in the two-photon regime compared to one-photon absorption, indicating complex photophysics.
A maximal 2PA cross-section of ~582 GM was observed for (DNA)₃[Ag₂₁]¹⁵⁺.
(DNA)₂[Ag₁₆Cl₂]⁸⁺ exhibited unique 2PA behavior with a high cross-section of 176 GM at 1050 nm, distinct from Ag-DNAs without chlorido ligands.

Conclusions:

Ag-DNAs are promising water-soluble NIR-to-NIR two-photon probes with high 2PA cross-sections and fluorescence quantum yields.
The observed two-photon brightness (up to ~10² GM) surpasses that of many water-soluble organic fluorophores.
These findings support the utility of Ag-DNAs for advanced bioimaging applications requiring efficient NIR excitation and emission.