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SCIENCE CHINA Materials, Volume 62, Issue 8: 1071-1086(2019) https://doi.org/10.1007/s40843-019-9414-4

Lanthanide-doped near-infrared II luminescent nanoprobes for bioapplications

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  • ReceivedJan 31, 2019
  • AcceptedMar 13, 2019
  • PublishedApr 17, 2019

Abstract

Luminescent biosensing in the second near-infrared (NIR-II) region is featured with superior spatial resolution and high penetration depth by virtue of the suppressed scattering of long-wavelength photons. Hitherto, the reported NIR-II nanoprobes are mostly based on carbon nanotubes, organic fluorophores or semiconducting quantum dots. As an alternative, trivalent lanthanide ions (Ln3+) doped nanoparticles have been emerging as a novel class of promising nanoprobes. In this review, we highlight the recent progress in the design of highly efficient Ln3+-doped NIR-II nanoparticles towards their emerging bioapplications, with an emphasis on autofluorescence-free bioimaging, sensitive bioassay, and accurate temperature sensing. Moreover, some efforts and challenges towards this rapidly expanding field are envisioned.


Funded by

the Strategic Priority Research Program of the CAS(XDB20000000)

the National Natural Science Foundation of China(21771185,11704380,51672272,21804134,U1805252)

the CAS/SAFEA International Partnership Program for Creative Research Teams

and Natural Science Foundation of Fujian Province(2017I0018)


Acknowledgment

This work was supported by the Strategic Priority Research Program of the CAS (XDB20000000), the National Natural Science Foundation of China (21771185, 11704380, 51672272, 21804134 and U1805252), the CAS/SAFEA International Partnership Program for Creative Research Teams, and the Natural Science Foundation of Fujian Province (2017I0018).


Interest statement

The authors declare no conflict of interest.


Contributions statement

Yu S, Tu D and Chen X conceived and wrote the manuscript and designed the figures. Lian W and Xu J prepared the materials of bioapplications. All authors contributed to the general discussion and revision of the manuscript.


Author information

Shaohua Yu earned her BSc degree from Fuzhou University (2015). She is currently a PhD student in condensed matter physics in the University of Chinese Academy of Sciences (UCAS). In September 2015, she joined Prof. Xueyuan Chen’s group in Fujian Institute of Research on the Structure of Matter (FJIRSM). Her current research focuses on the controlled synthesis and optical spectroscopy of inorganic luminescent nanomaterials.


Datao Tu earned his BSc degree (2006) from Wuhan University of Technology. He received his PhD degree (2011) in materials physics and chemistry from FJIRSM, Chinese Academy of Sciences. He joined Prof. Xueyuan Chen’s group as a research assistant professor in July 2011 and was promoted to research associate professor in 2014. His research focuses on the chemical synthesis, optical spectroscopy and biodetection of lanthanide-doped nanoprobes.


Xueyuan Chen earned his BSc degree from the University of Science and Technology of China (1993) and his PhD degree from FJIRSM, Chinese Academy of Sciences (1998). From 2001 to 2005, he was a postdoctoral research associate at the Chemistry Division of Argonne National Laboratory, U.S. Department of Energy, where he studied the photophysics and photochemistry of heavy elements. In 2005, he joined the faculty at FJIRSM, where he is currently professor and group leader in Material Chemistry and Physics. His research focuses on the chemistry, optical spectroscopy and bioapplications of lanthanide-doped luminescent nanomaterials.


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  • Figure 1

    Energy level diagrams of Ln3+ ions with typical emissions within the NIR-II region.

  • Figure 2

    Overview of Ln3+-doped NIR-II nanoprobes from design strategies to bioapplications.

  • Figure 3

    (a) Emission spectrum of SnO2:Er NPs upon excitation at 300 nm. (b) Excitation spectrum of SnO2:Er NPs by monitoring the emission at 1,551.2 nm. Adapted with permission from Ref. [78]. Copyright 2009, Optical Society of America.

  • Figure 4

    (a) Scheme illustration of the energy transfer between Nd3+, Yb3+ , Tm3+ and Gd3+ in NaGdF4:Nd/Yb/Tm NPs. (b) NIR emission spectra of NaGdF4:Nd/Yb/Tm and NaYF4:Nd/Yb/Tm, respectively. Adapted with permission from Ref. [56]. Copyright 2014, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature.

  • Figure 5

    (a) Scheme illustration of the SQAD model in NaYF4:Yb/Er@NaYF4 core/shell NPs. (b) Shell thickness-dependent UC QY (green) and NIR-II QY (gray) of Er3+ in NaYF4:Yb/Er@NaYF4 core/shell NPs upon excitation at 980 nm. Adapted with permission from Ref. [66]. Copyright 2016, American Chemical Society.

  • Figure 6

    (a) Comparison of the penetration depth of 1,532-nm emission from Er3+ and 1,060-nm emission from Nd3+. (b) Signal intensity curve obtained from (a). Reprinted with permission from ref. [102]. Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA. (c) Cerebral vascular image in NIR-II region with 20 ms exposure time and (d) corresponding principal component analysis of overlaid image showing arterial (red) and venous (blue) vessels. (e) Signal to background (SBR) analysis of cerebrovascular image in NIR-II region. Reprinted with permission from ref. [67]. Copyright 2017, Nature Publishing Group. (f) Bright field image of the tumor-bearing nude mouse. (g–i) NIR-II in vivo imaging after injecting NaYF4:Yb/Er and NaYF4:Yb/Ho NPs separately on left and right flank of the mouse. Reprinted with permission from ref. [46]. Copyright 2013, Nature Publishing Group.

  • Figure 7

    (a) Schematic diagram of in vivo NIR-II imaging based on PEGylated NaYF4:Yb/Er NPs upon excitation with X-ray light. (b) Bright field image of nude mouse and (c) NIR-II lymphatic mapping of the mouse injected with PEGylated NaYF4:Yb/Er NPs upon excitation with X-ray light. Adapted with permission from Ref. [86]. Copyright 2015, American Chemical Society.

  • Figure 8

    (a) PL decays of two types of NPs (NaY0.9−xYb0.1NdxF4@CaF2,x=0.2 and 0.3, respectively). In vivo multiplexed imaging of mouse after oral and intravenous injection of these two types of NPs based on (b) PL lifetime and (c) PL intensity. Adapted with permission from Ref. [109]. Copyright 2018, American Chemical Society.

  • Figure 9

    (a) Schematic illustration of the procedure for homogeneous assay of H2O2 with NaCeF4:Er/Yb NPs. (b) NIR-II emission intensity of ligand-free NaCeF4:Er/Yb NPs with different concentrations of H2O2, upon excitation at 980 nm. (c) Calibration curve for homogeneous assay of H2O2. Inset reveals the linear region of the calibration curve (0.078–10 μmol L−1). (d) Chemical equation for the generation of H2O2 via UA/uricase reaction. (e) NIR-II emission spectra of NaCeF4:Er/Yb NPs after adding H2O, uricase, UA and uricase + UA, respectively, upon excitation at 980 nm. (f) Calibration curve of UA assay. Inset reveals the linear region of the calibration curve (0.411–900 μmol L−1). Adapted with permission from Ref. [57]. Copyright 2018, the Royal Society of Chemistry.

  • Figure 10

    (a) Schematic illustration of ratiometric luminescent assay for H2O2. (b) UC emission spectra of NaErF4:Ho@NaYF4 NPs and IR1061 encapsulated polycaprolactone upon addition of different concentrations of H2O2. (c) Schematic illustration of the experiment for in vivo bioassay of H2O2. (d) UC luminescence images at 980 nm (top), 1,180 nm (middle), and the ratio of 980 to 1,180 nm (bottom) of microneedle patches taken at different times after lipopolysaccharide induced inflammation. (e) Photograph of the mouse treated with the microneedle patch. (f) Ratiometric luminescence of microneedle patches at different times with corresponding H2O2 concentration. Reprinted with permission from Ref. [87]. Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA.

  • Figure 11

    (a) Schematic diagram of subcutaneous temperature sensing of mouse based on LaF3:Nd@LaF3:Yb core/shell NPs with 808-nm laser as heating source. Thermal images of mouse (b) before and (c) after heating treatment. (d) Time evolution of the subcutaneous temperature measured by luminescent nanothermometer (gray) and skin temperature measured by IR thermal camera (orange), respectively. Adapted with permission from Ref. [118]. Copyright 2016, American Chemical Society.

  • Figure 12

    (a) Schematic illustration of the nanostructure consisting of NaGdF4:Nd3+ and PbS/CdS/ZnS QDs. (b) Temperature-dependent emission spectra of the hybrid nanocomposites upon excitation at 808 nm. (c) Schematic diagram of in vitro temperature measurement based on the hybrid nanocomposites upon excitation at 808 nm. (d) Evolution of the emission intensity of NaGdF4:Nd NPs and PbS/CdS/ZnS QDs in the hybrid nanocomposites injected in chicken breast tissue (top) and temperature evolution of tissue (bottom) determined by the hybrid nanocomposites during a heating/cooling cycle. Reprinted with permission from ref. [119]. Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA.

  • Figure 13

    (a) Schematic representation of experimental device for temperature sensing based on TTA-modified NaYF4:Nd NPs via double beam excitations (635 and 808 nm) and two detectors (PMT and InGaAs detectors). (b) Temperature-dependent emission spectra of TTA-modified NaYF4:Nd NPs from 283 to 323 K. Inset shows the temperature dependence of the integrated emission intensities of TTA and NIR-II emission from Nd3+. (c) Bright field image (left) and the ratiometric image based on TTA-modified NaYF4:Nd NPs in an inflammatory mode (right) showing temperature distributions in the two legs of a mouse. Adapted with permission from Ref. [124]. Copyright 2018, Nature Publishing Group.

  • Table 1   Optical characteristics and QYs of typical Ln-doped NIR-II NPs

    Nanoprobe

    Size (nm)

    Excitation (nm)

    Emission (nm)

    QY (%)

    Reference

    LiYF4:Nd

    18×25

    808

    900/1050

    28

    [8]

    NaYF4:Yb/Er

    183×113

    975

    1525

    0.2

    [44]

    NaGdF4:Nd/Yb/Tm

    21

    800

    980/1060

    1.06

    [56]

    NaCeF4:Er/Yb

    200.6

    980

    1530

    32.8

    [57]

    NaNdF4:Mn

    4.5

    808

    1058

    10

    [62]

    CaF2:Y/Nd

    10--15

    808

    989/1056/1328

    9.3

    [63]

    NaGdF4:Nd@NaGdF4

    15

    740

    900/1050/1330

    40

    [64]

    NaYF4:Yb/Er@NaLuF4

    26.2

    980

    1522

    14

    [66]

    NaYbF4:Er/Ce@NaYF4

    18

    980

    1550

    0.27–2.73

    [67]

    NaYF4:Yb/Nd@CaF2

    13

    800

    980/1060

    ~11

    [68]

    NaYF4:Yb/Nd@CaF2

    12

    808

    980

    20.7

    [69]

    NaYF4:Yb/Er@NaYbF4@NaYF4:Nd@ICG

    52

    800

    1000/1064/1530

    13.2

    [70]

    NaYF4:Er@ICG

    ~17

    808

    1520

    3.1

    [72]

    CsPbCl3:Yb

    16

    380

    980

    170

    [75]

    CsPbCl1.5Br1.5:Yb/Ce

    6.9

    365

    980

    119

    [77]

    InP@YF3:Yb@LuF3

    10

    440

    980

    0.5

    [79]

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