Supporting Information

Transcription

1 Supporting Information Toward High-Efficient Red Emissive Carbon Dots: Facile Preparation, Unique Properties, and Applications as Multifunctional Theranostic Agents Shan Sun,, Ling Zhang, Kai Jiang, Aiguo Wu, and Hengwei Lin*, Key Laboratory of Additive Manufacturing Materials of Zhejiang Province & Ningbo Institute of Materials Technology & Engineering (NIMTE), Chinese Academy of Sciences (CAS), Ningbo 31521, P. R. China University of Chinese Academy of Sciences, Beijing, 149, P. R. China * Tel: ; Fax:

2 Supporting Figures (S1-S16) a) O1s Intensity (a.u.) C1s N1s Bindng Energy (ev) b) c) Intensity (a.u.) Measured Fitting Pyrrolic N Graphitic N /N-H Intensity (a.u.) Measured Fitting C=O C-OH /C-O-C Binding Energy (ev) Binding Energy (ev) Figure S1. (A) Wide scan XPS survey; (B) N1s XPS spectra; (C) O1s XPS spectra of the R-CDs. D band Raman Intensity (a.u.) pyridine-ring breathing pyrrole-ring breathing C C G band N=N OCH 2 / OCH Raman Shift (cm -1 ) Figure S2. Raman spectrum of the R-CDs and the corresponding peak attributions. 2

3 a) b) Absorbance with ph increase ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph 8 ph 9 ph 1 ph 11 ph 12 PL Intensity (a.u.) ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph 8 ph 9 ph 1 ph 11 ph c) d) PL Intensity (a.u.) PLE Intensity (a.u.) ph 2 ph 3 ph 4 ph 5 ph 6 ph 7 ph 8 ph 9 ph 1 ph 11 ph ph Figure S3. ph effects of the optical properties to the R-CDs. a) UV-Vis absorption, b) PL emission spectra, c) PL emission intensities, and d) PL excitation spectra water Methanol Ethanol Dichloromethane Abs Figure S4. The effects of solvent to the UV-Vis absorption of the R-CDs. 3

4 FL Intensity (a.u.) IRF R-CDs Fitted line Time (ns) Figure S5. PL delay (red lines) and fitting (blue lines) curves of the R-CDs measured at emission wavelength of 655 nm with excitation at 588 nm. TPEF Intensity (a.u.) nm 85 nm 9 nm 95 nm 1 nm Figure S6. TPEF spectra of the R-CDs under excitation with various wavelengths of femtosecond pulse lasers. 4

5 N-PL intensity Time (min) Figure S7. Photostability of the R-CDs under continuous irradiation with a xenon lamp (15 W). a) b) Number (Percent) Size (d.nm) c) 4 3 Total Counts Apparent Zeta Potencial (mv) Figure S8. a) Photos of the R-CDs in water (1), PBS (2), and cell culture medium (3, including 1% serum) after standing for 48 h; b) DLS measurement of the size distribution of the R-CDs in cell culture medium (with an averaged diameter 6.8 nm); c) Zeta potential of the R-CDs in water with an average value of mv. 5

6 12 MCF-7 HeLa Cell viability (%) Concentration (μg ml -1 ) Figure S9. The viability of MCF-7 and HeLa cells after incubating with various concentrations of the R-CDs (-2 μg/ml) for 24 h. A) HeLa B) PL intensity (a.u.) Distance (μm) Figure S1. Cells imaging properties of the R-CDs in living HeLa cells. (A) One-photon confocal fluorescent images. (B) Quantitative figure of selected HeLa cells. (λ ex =543 nm, λ em =55-75 nm, scale bar =2 μm). 6

7 Merged Hoechst R-CDs Control HeLa RNase Figure S11. Fluorescent images of the R-CDs and Hoechst without (control) and with the RNase treatment in HeLa cells. (Hoechst: λ ex =45 nm, λ em =42-5 nm; R-CDs: λ ex =543 nm, λ em =55-75 nm; scale bar =2 μm). a b c Figure S12. 3D fluorescent images of living MCF-7 cells after being counterstained with the R-CDs and Hoechst. (a) xy cross section (inset: bright-filed image). (b) yz cross section. (c) xz cross section. (Hoechst: λ ex =45 nm, λ em =42-5 nm; the R-CDs: λ ex =543 nm, λ em =55-75 nm; scale bar =2 μm). 7

8 a) PL intensity (a. u.) μg/ml 5 μg/ml 1 μg/ml 15 μg/ml 2 μg/ml 25 μg/ml b) F/F RNA (μg ml -1 ) Figure S13. a) Fluorescence spectra of the R-CDs (1 μg/ml) toward addition of various concentrations of RNA in PBS buffer (1 mm, ph=7.4) under excitation of 54 nm; b) Fluorescence intensity ratio versus the different concentrations of RNA, F and F stand for the emission peak intensity of the R-CDs (i.e. 64 nm) before and after the addition of RNA. FITC Transmittance (%) RCD S FITC-RCD S Wavenumbers (cm -1 ) Figure S14. FT-IR spectra of the R-CDs (red line), FITC (blue line) and RCDs-FITC (black line). 8

9 a) b) FL intensity (a.u.) Y= X R 2 =. 997 PL Intensity (a.u.) g/ml FITC (μg/ml) Figure S15. a) Plot of PL intensity of FITC with different concentrations (i.e. calibration line); b) PL emission spectrum of the RCDs-FITC (5 μg/ml). The amount of FITC linked to the R-CDs can be easily calculated based on this calibration line (i.e mg per gram of the R-CDs). a) b) 1.6 before irradiation after irradiation PLE before irradiation PLE after irradiation PL before irradiation PL after irradiation Absorbance PL Intensity (a.u.) c).21 nm Precentage (%) Diameter (nm) d) Transmittance before irridation after irridation Wavenumbers (cm -1 ) Figure S16. Stability of the R-CDs (5 μg/ml) before and after continuous laser irradiation for 2 h (2.5 W cm -2 ). a) UV-Vis absorbance; b) photoluminescence excitation (PLE) and emission (PL); c) TEM (after irradiation); and d) FT-IR. 9

10 Supporting Tables (S1-S2) Table S1. Fitting results of the fluorescence lifetime of the R-CDs under excitation of 588 nm (based on the Figure S2). λ ex /nm λem/nm B[%] τ1/ns B[%] τ2/ns τ(ave)/ns χ Table S2. QYs of the R-CDs under excitation at 54 nm. sample solvent λ ex /nm Φ 1 Φ 2 Φ 3 Φ 4 Φ 5 Φ ave Φ corr. Rhodamine 6G RCDs EtOH % 89.2% 89.7% 88.7% 89.3% 89.3% 95% MeOH % 2.1% 21.% 22.9% 22.2% 21.5% 22.9% H 2 O % 13.4% 13.8% 13.5% 14.1% 13.8% 16.2% 1