Compact Plasmonic Blackbody for Cancer Theranosis in Near-Infrared II Window

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1 Supporting Information for Compact Plasmonic Blackbody for Cancer Theranosis in Near-Infrared II Window Jiajing Zhou,, Yuyan Jiang,, Shuai Hou, Paul Kumar Upputuri, Di Wu,, Jingchao Li, Peng Wang, Xu Zhen, Manojit Pramanik, Kanyi Pu*, and Hongwei Duan*, School of Chemical and Biomedical Engineering, Nanyang Technological University, 70 Nanyang Drive, Singapore Department of Chemistry, Zhejiang University, Hangzhou , China J. J. Zhou and Y. Y. Jiang contributed equally to this work. Materials and Characterization Dopamine, tris(hydroxymethyl)aminomethane (TRIS), and bicine were purchased from Sigma Aldrich. Hydrogen tetrachloroaurate(iii) trihydrate (HAuCl4 3H2O) was from Alfa Aesar. Ultrapure water (18.2 MΩ cm) was purified using a Sartorius AG arium system and used in all experiments. Methoxy-poly(ethylene glycol)-thiol (PEG-SH, 5 kda) was purchased from Laysan Bio, Inc. Cleaved caspase-3 antibody was purchased from Cell Signaling Technology Inc. Alexa Fluor 488 conjugated donkey anti-rabbit secondary antibody was purchased from Thermo Fisher Scientific. All the other bioreagents were purchased from Sigma Aldrich unless otherwise declared. Transmission electron microscopy (TEM) observations were conducted on a Jeol JEM 2010 electron microscope at an acceleration voltage of 300 kv. Scanning electron microscopy (SEM) images were acquired on a FESEM (JSM-6700F, Japan). UV Vis NIR spectra were recorded using a Cary5000 UV Vis NIR. Particle size was measured by a Malvern Nano-ZS Particle Sizer. Inductively coupled plasma mass spectroscopy (ICP-MS) data was obtained by S1

2 a Prodigy High Dispersion ICP-MS. Temperature was determined by a FLIR T420 camera or Extech TM 300 Type K/J thermocouple dual input thermometer. A home-made PAT system was used for PA imaging. S2

3 Figure S1. TEM image of 45 nm AuPBs at low magnification. Figure S2. The ratio of molar extinction coefficient (ε) of AuPBs at 1064 nm and 808 nm. S3

4 Figure S3. a) Photographs of the reaction mixture of AuPBs at 5 min (left) and 8 h (right). b,c) TEM images of AuPBs at different magnification. d) Photographs of the reaction mixture of HAuCl4 and pyrocatechol at 5 min (left) and 8 h (right). e,f) TEM images of Au nanoparticles at different magnification. Figure S4. a-e) TEM image of AuPBs of different particle sizes. f,g) SEM and TEM images of 250 nm AuPBs. h) UV-Vis-NIR absorbance spectra of 250 nm AuPBs. S4

5 Figure S5. HRTEM image of branches in the AuPBs Figure S6. Schematic illustration of PDA surface functionalization with HS-PEG via the Michael Addition. S5

6 Figure S7. (a) Hydrodynamic diameter distribution of AuPB and AuPB-PEG. AuPB has a size of 44.8 ± 3.0 nm with a PDI of and AuPB-PEG has a size of 56.2 ± 3.7 nm with a PDI of (b) Agarose gel electrophoresis of AuPB (lane 1) and AuPB modified by PEG-SH of different concentrations (lane 2: 0.5 μg/ml, lane 3: 1.0 μg/ml, lane 4: 2.0 μg/ml, lane 5: 5.0 μg/ml). Negatively charged polydopamine-coated AuPBs showed rapid migration in electrophoresis, which significantly reduced and eventually stopped after PEGylation due to the decrease of surface potential. S6

7 Figure S8. (a) Temperature of AuPB solution (100 µg/ml) irradiated for 30 min with a 808 nm laser at a power density of 1 W/cm2 in quartz cuvettes. (b) Linear time versus -lnθ were obtained from the cooling period in Figure S8a. (c) Temperature of the AuPB dispersion (100 µg/ml) irradiated for 30 min with a 1064 nm laser at a power density of 1 W/cm2 in quartz cuvettes. (d) Linear time versus -lnθ were obtained from the cooling period in Figure S8c. S7

8 Figure S9. Calculated extinction, scattering and absorption cross section spectra (Mie theory) of 45 nm Au nanosphere (AuNS) and AuPB. For AuNS, 91.2% of the total extinction at 527 nm comes from the absorption, while only 59.5% and 70.7% of the total extinction at 808 nm and 1064 nm come from the absorption. For AuPB, 98.5% and 99.2% of the total extinction at 808 nm and 1064 nm come from the absorption. S8

9 Figure S10. (a) Photothermal stability of AuPBs under 808 nm laser heating and natural cooling cycles. (b) TEM image of AuPBs after 6 cycles of heating and cooling. (c) Photothermal stability of AuPBs under 1064 nm laser heating and natural cooling cycles. (d) TEM image of AuPBs after 6 cycles of heating and cooling. S9

10 Figure S11. Simulation results of the electric field enhancement ( E/E0 ) at 808 nm (a) and 1064 nm (b). Figure S12. (a) The amplitude of in vivo PA signals as a function of time from a 4T1 tumor-bearing mouse collected before and after the injection of the AuBP dispersion (2 mg/ml). (b) PA signals from tumor and different organs at 48 h post-injection. The error bars represent standard deviations (n = 3) S10

11 Figure S13. Body weights of different groups of mice after treatment. The error bars represent standard deviations (n=3). Figure S14. Histological analysis. (a) H&E staining and (b) immunofluorescence staining of caspase-3 of livers, spleens, kidneys and tumors for 4T1-bearing mice after photothermal ablation. Scale bar: 100 m. S11