Supplementary Figure 1 XRD and Raman spectrum characterization of GQDs. a, XRD pattern of GQDs. b, Raman spectrum of GQDs, the appearance of the mode

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1 Supplementary Figure 1 XRD and Raman spectrum characterization of GQDs. a, XRD pattern of GQDs. b, Raman spectrum of GQDs, the appearance of the mode at 1456 cm -1 is not fully understood. Nevertheless, this mode has been previously suggested to be characteristic to the stretching vibrations of the C=C bonds, as observed on transpolyacetylene 1.

2 Supplementary Figure 2 XPS spectra of GQDs. a, Atom concentrations of C, N, O, and S. b-d, High-resolution N1s, S2p, and O1s XPS spectra of the as-prepared GQDs, respectively. e, High-resolution O1s XPS spectra of GQDs after heating at 150 o C.

3 Supplementary Figure 3 In vitro photostability comparison of GQDs and CdTe QDs. a, The GQDs labeled HeLa cells yielded stable fluorescent signals during 90 minutes continuous observation, the scale bar is 20 μm. b, In contrast, for the control group using CdTe QDs as fluorescent labels, the signals were decreased gradually upon increasing irradiation time, the scale bar is 20 μm.

4 Supplementary Figure 4 Effects of ph. The fluorescence intensity at 680 nm of GQDs (λ ex = 500 nm) in a citric acid-na 2 HPO 4 buffer solution in the range of ph values from 2 to 8.

5 Supplementary Figure 5 Time-dependent ESR signals of GQDs. a, GQDs solution with TEMP. b, Pure water with TEMP. c, The signal intensity at G vs irradiation time, red dots represent GQDs solution and dark dots represent the pure water solution.

6 Supplementary Figure 6 Chemical trapping measurements of the 1 O 2 quantum yield of GQDs. a, Photodegradation of Na 2 -ADPA with GQDs. b, The absorption peak area of GQDs. c, The decomposition rate constants of Na 2 -ADPA by GQDs. d, Photodegradation of Na 2 -ADPA with RB. e, The absorption peak area of RB. f, The decomposition rate constants of Na 2 -ADPA by RB.

7 Supplementary Figure 7 The 1 O 2 quantum yields measurements of GQDs at the different excitation wavelengths. a, The absorption spectra of GQDs and RB in water solution, and the reduction in absorption of Na 2 -ADPA at 378 nm in the presence of GQDs or RB was plotted as a function of the irradiation time using different wavelengths. b, c with 538 nm, d, e with 549 nm and f, g with 562 nm.

8 Supplementary Figure 8 Amplified nucleus fluorescence images stained by Hoechst in the presence of GQDs. a, Before irradiation, the scale bar is 5 μm. b, After irradiation, the scale bar is 5 μm.

9 Supplementary Figure 9 Time-dependent confocal bright field images of HeLa cells in the absence of GQDs with different irradiation time,the scale bar is 50 μm.

10 Supplementary Figure 10 In vivo stability of GQDs.

11 Supplementary Figure 11 Fluorescence images of mice after various treatments at 1 st, 9 th, 17 th, and 25 th day.

12 Supplementary Figure 12 The photothermal effects of GQDs.

13 Supplementary Figure 13 Time-dependent weight of the mice with different treatments.

14 Supplementary Figure 14 Evaluation of the energy gap between S 1 and T 1. Decrease of Na 2 -ADPA absorption at 378 nm as a function of light irradiation time in the presence of (a) GQDs, (b) GQDs-tetracence, and (c) GQDs-pentacence mixture in aqueous solution. [Na 2 -ADPA]=40 μg ml -1, QDs]=[Tetracence]=[Pentacence]=20 μg ml -1.

15 Supplementary Figure 15 The route for synthesis of PT2.

16 Supplementary Table 1 Fluorescence properties of GQDs compare with 9, 10-Dicyanoanthracene Fluorescence Lifetime (ns) GQDs 9,10-Dicyanoanthr (H 2 O) a-cene (Benzene) Fluorescence quantum yield GQDs (H 2 O) 9,10-Dicyanoanthrace n-e (Benzene) N /1.21/ % 47.2% Air 0.39/1.23/ % 44.8% O /1.10/ % 30.6%

17 Supplementary Table 2 The 1 O 2 quantum yields of GQDs using different wavelengths λ ex A RB /A GQDs K GQDs K RB Ф GQDs 538 nm nm nm

18 Supplementary Table 3 The 1 O 2 quantum yields of GQD in different ph solutions ph A GQDs K GQDs A RB K RB Ф GQDs

19 Supplementary Table 4 Signal-to-background data of GQDs in vivo imaging Exciting wavelength Collected fluorescence channels a I signal b I background c S/B nm nm a and b refer to the fluorescence intensity of injection district and the background, respectively. c refers to the signal to background of the fluorescence intensity

20 Supplementary Note 1: In Supplementary Figure 6, the decomposition rate constants K GQDs and K RB can be determined to be 0.27 and 0.048, respectively. (Supplementary Figures 6c and 6f). In addition, A GQDs is 26.9 (Supplementary Figure 6b) and A RB is 8.26 (Supplementary Figure 6e). Thus, Substituting 0.75 (the 1 O 2 quantum yield of RB in water) into the following formula: Ф GQDs =Ф RB *K GQDs *A RB /(K RB *A GQDs ).(1) Thus, 1 O 2 quantum yield of GQDs in water, Ф GQDs, can be calculated to be 1.3.

21 Supplementary Note 2. As shown in Supplementary Figure 12, after irradiation for 20 min, the temperature of GQDs aqueous solution was only increased by 8.8 o C at a concentration of 27 µm. Therefore, the photothermal effect of the GQDs could be ruled out in the in vivo experiments 2, 3.

22 Supplementary Note 3: the S 1 energy of GQDs was estimated around 2.14 ev (49.30 kcal mol -1 ). T 1 energy could normally be estimated from the phosphorescence emission. However, we could not directly observe the phosphorescence of GQDs, which is probably due to the efficient energy gap law effect resulted from the close energy level to the ground state 4-7. The energy level of T 1 state was thus estimated by using triplet quenchers with different triplet energy 8, 9. In the present work, we used a standard method to monitor the conversion rate of disodium 9,10-anthracendipropionic acid (Na 2 -ADPA) to its endoperoxide by 1 O 2 oxidation in the presence of the triplet quenchers, i.e., tetracence and pentacence with T 1 energy levels of kcal mol -1 and 19.8 kcal mol -1, respectively 10. As shown in Supplementary Figure 14, the bleaching rate of Na 2 -ADPA with GQDs mixture pentacence was dropped by about 24% compared with the control solution. In contrast, the addition of tetracence did not induce obvious change. Based on these observations, we could estimate that the triplet energy level of GQDs was between kcal mol -1 and kcal mol -1, and the energy gap (ΔE ST ) between S 1 state and T 1 state was calculated to be about 22.80~26.80 kcal mol -1. This result suggested that the excited state of GQDs (S 1 and T 1 ) could be quenched by ground-state oxygen jointly through ET 1 and ET 2 (Figure 5), and the quantum yield of 1 O 2 generation over 1.0 could be

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