Supporting information

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1 Supporting information Large Hollow Cavity Luminous Nanoparticles with Near-Infrared Persistent Luminescence and Tunable Sizes for Tumor Afterglow Imaging and Chemo/Photodynamic Therapies Jun Wang, Jinlei Li, Jiani Yu, Hongwu Zhang, and Bingbo Zhang* Institute of Photomedicine, Shanghai Skin Disease Hospital; The Institute for Biomedical Engineering & Nano Science, Tongji University School of Medicine, Shanghai , China. Key Lab of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, Fujian , China. Corresponding Authors *Bingbo Zhang: Tel: ; Fax: S1

2 Figure S1. 3-Dimensional TEM images of the hollow NIR PLNPs using 150 nm carbon spheres as a template (half sphere). S2

3 Figure S2. XRD of the hollow NIR PLNPs using different size of carbon spheres (150 nm, 300 nm and 500 nm) as the template. S3

4 Figure S3. Nitrogen adsorption desorption isotherms (A) and pore size distributions (B) of the as-synthesized hollow PLNPs (denoted HPLNPs here) by using of 150 nm carbon spheres as the template. S4

5 Figure S4. The effect of precursor ion amount on the shell formation. TEM images of the carbon spheres incubated with different molar ratio of Zn: Ga: Cr precursors (from 1x (A1), 2x (B1), 4x (C1), to 8x (D1)) using 150 nm carbon spheres as a template; TEM images of the resultant hollow NIR PLNPs under different molar ratio of Zn: Ga: Cr (from 1x (A2), 2x (B2), 4x (C2), to 8x (D2)) using 150 nm carbon spheres as a template under C for 2 h in the air atmosphere. S5

6 Figure S5. The fluorescence emission spectra (A1 and A2, 254 nm excitation, 1 mg/ml) and TEM images (B1 and B2) of the hollow NIR PLNPs prepared at different Cr contents using 150 nm carbon spheres as the template under C for 2 h in the air atmosphere. S6

7 Figure S6. The fluorescence emission spectra (A, 254 nm excitation, 1 mg/ml) and TEM images (B) of the hollow NIR PLNPs prepared at different calcination temperatures for 2 h in the air atmosphere using 150 nm carbon spheres as the template. S7

8 Figure S7. The fluorescence emission spectra (A, 254 nm excitation, 1 mg/ml) and TEM images (B) of the hollow NIR PLNPs prepared at different calcination times under C in the air atmosphere using 150 nm carbon spheres as the template. S8

9 Figure S8. FT-IR spectra of BSA, hollow PLNPs (denoted HPLNPs) and BSA-modified hollow PLNPs (denoted BSA-HPLNPs) (A), Zeta potentials (B), fluorescence spectra (C) and size distribution (D) of the hollow PLNPs and their counterparts with different modifications. Fluorescence spectrum was measured under an excitation of 254 nm. The hollow NIR PLNPs with a size of 50 nm was used in this study. S9

10 Figure S9. The emission spectrum of the hollow NIR PLNPs using 150 nm carbon spheres as a template. The inset photo image refers to the hollow NIR PLNPs aqueous solution (1 mg/ml) under 254 nm UV lamp excitation. S10

11 Figure S10. The emission spectrum of the hollow NIR PLNPs using 300 nm carbon spheres as a template. The inset photo image refers to the hollow NIR PLNPs aqueous solution (1 mg/ml) under 254 nm UV lamp excitation. S11

12 Figure S11. The emission spectrum of the hollow NIR PLNPs using 500 nm carbon spheres as a template. The inset photo image refers to the hollow NIR PLNPs aqueous solution (1 mg/ml) under 254 nm UV lamp excitation. S13

13 Figure S12. NIR persistent luminescent afterglow decay images of the hollow NIR PLNPs powder (A) and aqueous solution (B) (20 mg, 100 nm size) after 10 min irradiation by 254 nm UV lamp and 5 min re-activation by a white LED lamp (1100 lm); NIR persistent luminescence afterglow decay images of the hollow NIR PLNPs powder (C) and aqueous solution (D) (20 mg, 250 nm size) after 10 min irradiation by 254 nm UV lamp and 5 min re-activation by a white LED lamp (1100 lm). S15

14 Figure S13. The effects of ion strength (A, B and C) and ph (D, E and F) on the fluorescence (A and D) and the persistent luminescence (B, E, C and F) intensities of the hollow PLNPs. The NIR afterglow images at 5 min, 10 min, 15 min of the BSA-modified hollow NIR PLNPs in different concentrations (0, 25 mm, 50 mm and 100 mm) of NaCl aqueous and different ph values (ph=4.0, ph=7.4 and ph=9.0) of PBS solution were recorded after 10 min irradiation by a 254 nm UV lamp (B and E). The NIR afterglow intensities were quantified as shown in C and F. S16

15 Figure S14. Fluorescence stability of the hollow NIR PLNPs aqueous solution (1 mg/ml) with a size of 50 nm in deionized water (A) and PBS 7.4 (B). S17

16 Figure S15. The UV-vis absorption spectra of DOX, the hollow NIR PLNPs and the DOX-hollow NIR PLNPs (A) ; The fluorescence spectra of DOX, the hollow NIR PLNPs and the DOX-hollow NIR PLNPs under 480 nm excitation (B). S19

17 Figure S16. The standard curve of concentration-dependent DOX absorbance at 480 nm in water. S20

18 Figure S17. Cell viabilities of the hollow NIR PLNPs using 150 nm carbon spheres as the template against 4T1cells at different concentrations for 24 h. S21

19 Figure S18. Cell viabilities of the hollow NIR PLNPs using 300 nm carbon spheres as the template against 4T1cells at different concentrations for 24 h. S22

20 Figure S19. Cell viabilities of the hollow NIR PLNPs using 500 nm carbon spheres as the template against 4T1cells at different concentrations for 24 h. S23

21 Figure S20. The standard curve of concentration-dependent Si-Pc absorbance at 675 nm in DMSO. S24

22 Figure S21. Fluorescence emission spectra of DFPB (410 nm excitation) for Si-Pc, Si-Pc (with 1 min LED irradiation), and Si-Pc plus hollow PLNPs (after 1 min LED excitation). S25

23 Figure S22. H&E-staining images of major organs (heart, liver, spleen, lung, kidney and intestines) of the mice collected from the blank mice and the ones 15 days after intravenous injection of 50 nm-sized BSA-modified hollow NIR PLNPs. Scale bar is 100 µm. S26

24 Table S1. Fabrication parameters of the hollow NIR PLPNs at different amounts of Zn 2+, Ga 3+, Cr 3+ Number Carbon spheres Zn 2+ Ga 3+ Cr 3+ Weight Size (mmol) (mmol) (mmol) (mg) (nm) T ( C) t (h) Table S2. Fabrication parameters of the hollow NIR PLNPs at different concentrations of Cr 3+ Number Carbon spheres Zn 2+ Ga 3+ Cr 3+ Weight Size (mmol) (mmol) (mmol) (mg) (nm) T ( C) t (h) Table S3. Fabrication parameters of the hollow NIR PLNPs at different calcination temperatures Number Carbon spheres Zn 2+ Ga 3+ Cr 3+ Weight Size (mmol) (mmol) (mmol) (mg) (nm) T ( C) t (h) S27

25 Table S4. Fabrication parameters of the hollow NIR PLNPs at different times Number Carbon spheres Zn 2+ Ga 3+ Cr 3+ Weight Size (mmol) (mmol) (mmol) (mg) (nm) T ( C) t (h) Table S5. Fabrication parameters of different sizes of the hollow NIR PLNPs Number Carbon spheres Zn 2+ Ga 3+ Cr 3+ Weight Size (mmol) (mmol) (mmol) (mg) (nm) T ( C) t (h) S28