Lanthanide-doped fluorapatite(FAp:Ln^(3+))upconversion luminescence(UCL)probes exhibit good biocompatibility but suffer from low quantum yields under near-infrared(NIR)excitation.Here,we propose a universal MoO_(4)^(2...Lanthanide-doped fluorapatite(FAp:Ln^(3+))upconversion luminescence(UCL)probes exhibit good biocompatibility but suffer from low quantum yields under near-infrared(NIR)excitation.Here,we propose a universal MoO_(4)^(2−)doping strategy that achieves 74-fold green UCL enhancement in FAp:Yb/Er/Mo(FYEM)under 980 nm excitation(quantum yield:0.004%at 50 W cm^(−2)).Remarkably,stable Ln^(3+)/MoO_(4)^(2−)dimers induce 4d–4f orbital hybridization,as validated by density functional theory(DFT)and X-ray photoelectron spectroscopy(XPS).This mechanism extends to self-sensitized systems:FAp:Er/Mo(FEM)achieves 156-fold UCL enhancement under 980 nm excitation,while FAp:Nd/Mo(FNM)integrates 84-fold UCL amplification with photothermal synergy(ΔT=53.5℃).Critically,the optimized FYEM material enables dual-mode imaging,with 808/980 nm excitation UCL and NIR-II downconversion luminescence for deep-tissue imaging,besides outstanding thermal sensitivity(SA=1.04%K−1@323 K).This work establishes a biocompatible,multi-wavelength platform for deep-tissue diagnostics,photothermal therapy,and multimodal sensing and imaging.展开更多
基金supported by the National Key Research and Development Program of China(Grants No.2021YFA1201302)the Fund from Science and Technology Department of Sichuan Province,China(Grant No.2023NSFSC1930)Tianfu Qingcheng Plan-Youth Science and Technology Talent Project,Sichuan,China(Grant No.1710).
文摘Lanthanide-doped fluorapatite(FAp:Ln^(3+))upconversion luminescence(UCL)probes exhibit good biocompatibility but suffer from low quantum yields under near-infrared(NIR)excitation.Here,we propose a universal MoO_(4)^(2−)doping strategy that achieves 74-fold green UCL enhancement in FAp:Yb/Er/Mo(FYEM)under 980 nm excitation(quantum yield:0.004%at 50 W cm^(−2)).Remarkably,stable Ln^(3+)/MoO_(4)^(2−)dimers induce 4d–4f orbital hybridization,as validated by density functional theory(DFT)and X-ray photoelectron spectroscopy(XPS).This mechanism extends to self-sensitized systems:FAp:Er/Mo(FEM)achieves 156-fold UCL enhancement under 980 nm excitation,while FAp:Nd/Mo(FNM)integrates 84-fold UCL amplification with photothermal synergy(ΔT=53.5℃).Critically,the optimized FYEM material enables dual-mode imaging,with 808/980 nm excitation UCL and NIR-II downconversion luminescence for deep-tissue imaging,besides outstanding thermal sensitivity(SA=1.04%K−1@323 K).This work establishes a biocompatible,multi-wavelength platform for deep-tissue diagnostics,photothermal therapy,and multimodal sensing and imaging.
