4.8 Article

Boosting the Near-Infrared Emission of Ag2S Nanoparticles by a Controllable Surface Treatment for Bioimaging Applications

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 14, Issue 4, Pages 4871-4881

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c19344

Keywords

silver sulfide; PL enhancing; NIR imaging; surface traps; QY; PL lifetimes; surface etching

Funding

  1. Comunidad de Madrid [S2017/BMD-3867 RENIM-CM]
  2. European Structural and Investment Fund
  3. Ministerio de Economia y Competitividad-MINECO [MAT2017-83111R, PID2019-106211RB-I00]
  4. REACT ANTICI-PA-UCM
  5. European Union [801305]
  6. COST action [CA17140]
  7. UCM-Santander [CT63/19-CT64/19]
  8. European Commission [895932, 797945]
  9. China Scholarship Council (CSC) [201806870023]
  10. Juan de la Cierva scholarship [FJC 2018-036734-I]
  11. Marie Curie Actions (MSCA) [797945, 895932] Funding Source: Marie Curie Actions (MSCA)

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This study presents a simple methodology to improve the photoluminescence efficiency of Ag2S nanoparticles, achieving a quantum yield of 10% and a photoluminescence lifetime of 3.8 μs through the partial removal of sulfur atoms from the nanoparticle's surface. The enhanced photoluminescence is attributed to the reduction in surface traps responsible for nonradiative de-excitation processes. The study also compares the performance of these nanoparticles with other near-infrared luminescent probes in in vitro and in vivo experiments, demonstrating their cytocompatibility and superior optical properties when used in vivo for higher resolution imaging.
Ag2S nanoparticles are the staple for high-resolution preclinical imaging and sensing owing to their photochemical stability, low toxicity, and photoluminescence (PL) in the second near-infrared biological window. Unfortunately, Ag2S nanoparticles exhibit a low PL efficiency attributed to their defective surface chemistry, which curbs their translation into the clinics. To address this shortcoming, we present a simple methodology that allows to improve the PL quantum yield from 2 to 10%, which is accompanied by a PL lifetime lengthening from 0.7 to 3.8 mu s. Elemental mapping and X-ray photoelectron spectroscopy indicate that the PL enhancement is related to the partial removal of sulfur atoms from the nanoparticle's surface, reducing surface traps responsible for nonradiative de-excitation processes. This interpretation is further backed by theoretical modeling. The acquired knowledge about the nanoparticles' surface chemistry is used to optimize the procedure to transfer the nanoparticles into aqueous media, obtaining water-dispersible Ag2S nanoparticles that maintain excellent PL properties. Finally, we compare the performance of these nanoparticles with other near-infrared luminescent probes in a set of in vitro and in vivo experiments, which demonstrates not only their cytocompatibility but also their superb optical properties when they are used in vivo, affording higher resolution images.

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