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Stabilizing Dye-Sensitized Upconversion Nanosystems via Singlet Oxygen Spin Flipping.

Chang Jiang¹, Yang Li¹, Tao Jia¹

¹MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering and Key Laboratory of Micro-systems and Micro-structures, Ministry of Education, Harbin Institute of Technology, Harbin, 150001, China.

Small (Weinheim an Der Bergstrasse, Germany)

|July 31, 2025

Summary

Stabilizing near-infrared dye-sensitized upconversion nanoparticles (UCNPs) is crucial for bioapplications. This study introduces 4-aminotriphenylamine (4A-TPA) to prevent singlet oxygen damage, significantly enhancing UCNP photostability and enabling robust bioimaging.

Keywords:

intersystem crossing near‐infrared dye photobleaching singlet oxygen triplet state upconversion nanoparticles

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Area of Science:

Nanotechnology
Materials Science
Biomedical Engineering

Background:

Near-infrared (NIR) dye sensitization enhances lanthanide-doped upconversion nanoparticle (UCNP) brightness.
Stability issues in dye-sensitized UCNPs arise from singlet oxygen (¹O₂) damage to NIR dyes.

Purpose of the Study:

To develop a strategy for stabilizing dye-sensitized UCNPs against ¹O₂-induced degradation.
To improve the photostability and applicability of UCNPs in biological environments.

Main Methods:

Surface anchoring of 4-aminotriphenylamine (4A-TPA) to UCNPs to facilitate ¹O₂ spin flipping.
Utilizing the electron-rich triphenylamine group for ¹O₂ adsorption and intersystem crossing.
Coating UCNPs with amphiphilic polymers for aqueous stability.

Main Results:

4A-TPA incorporation improved photostability of IR806-sensitized UCNPs by 27-fold after 30 min of irradiation.
Enhanced UCNPs demonstrated stable cellular upconversion luminescence imaging under high laser power density (1200 W cm⁻²).
The strategy effectively protected NIR dyes from ¹O₂-induced photodegradation.

Conclusions:

Surface-anchored 4A-TPA provides a robust method to stabilize dye-sensitized UCNPs by converting harmful ¹O₂ to triplet oxygen (³O₂).
This stabilization strategy significantly broadens the potential of UCNPs for advanced bioimaging and photodynamic therapy applications.
The developed nanosystems exhibit enhanced durability in aqueous media, crucial for in vivo applications.