Supplementary Materials for · Figure S2. Structural characterizations of the five selected...
Transcript of Supplementary Materials for · Figure S2. Structural characterizations of the five selected...
advances.sciencemag.org/cgi/content/full/6/40/eabb6772/DC1
Supplementary Materials for
Full-color fluorescent carbon quantum dots
Liang Wang*, Weitao Li, Luqiao Yin, Yijian Liu, Huazhang Guo, Jiawei Lai, Yu Han, Gao Li, Ming Li, Jianhua Zhang,
Robert Vajtai, Pulickel M. Ajayan, Minghong Wu*
*Corresponding author. Email: [email protected] (L.W.); [email protected] (M.W.)
Published 2 October 2020, Sci. Adv. 6, eabb6772 (2020)
DOI: 10.1126/sciadv.abb6772
This PDF file includes:
Supplementary Text Figs. S1 to S7 Tables S1 to S3
Supplementary Text
Details for cytotoxicity test and cell imaging
Cytotoxicity test
First, the o-CQDs was converted to phosphate-buffered saline (PBS) through rotary evaporation.
Hela cells were cultured in DMEM medium with 1% penicillintreptomycin and 10% fetal bovine
serum (Hyclone, USA) at 37 oC in a Thermo cell incubator with 5% CO2. MTT method was taken
to estimate the cytotoxicity of o-CQDs. In short, cells were seeded in 96 wells plates, and about
5000 cells in each well. Different concentrations of o-CQDs (20, 40, 60, 80, and 100 mg·L-1) were
added to each group. After 24 and 48 hours in culture, MTT (5 mg·mL-1) was added and incubated
at 37 oC for four hours. Then, a microplate reader (ELX 00 UV, BIO-TEK, USA) was used to get
the result.
Cell imaging of o-CQDs
The method of cultivating o-CQDs and cells is the same as above. Approximately 2×105 cells were
seeded in a glass-bottom dish (35 mm dish with 14 mm glass-bottom well) with the 2 mL culture
medium. After 24 hours in culture, o-CQDs (20 mg·L-1) was added into the dish. Then after an
incubation of 30 min, the cells were examined under a confocal microscope (Leica TCS SP5, GER)
using lasers of 405, 488 and 543 nm.
Figure S1. Reaction acid reagent and solvent regulation of CQDs. (A) CQDs photographs under
UV light irradiation using different acid reagents with oPD. From left to right, these samples were
produced by solvothermal treatment of oPD with H2SO4, HNO3, uric acid, H3PO4, HCl, citric acid,
oxalic acid, edetic acid, and p-aminobenzoic acid, respectively. (B) CQDs photographs under UV
light irradiation using pure oPD and pure selected acid reagents. From left to right, these samples
were produced by solvothermal treatment of pure 4-ABSA, pure FA, pure BA, pure AA, pure TPA,
pure TA, and pure oPD, respectively. (C, D) Absorption and Normalized PL spectra of CQDs
produced in water solution. (E, F) Absorption and Normalized PL spectra of CQDs produced in
toluene solvent. (G, H) Absorption and Normalized PL spectra of CQDs produced in DMF solvent.
400 500 600Wavelength (nm)
700 800
PL Inte
nsity
(a. u.)
DTATPAAAFABA
400 500 600Wavelength (nm)
700 800
Inte
nsity
(a. u
.)
C
4-ABSA
TATPAAAFABA4-ABSA
300 300
400 500 600Wavelength (nm)
700 800
PL Inte
nsity
(a. u.)
FTATPAAAFABA
400 500 600Wavelength (nm)
700 800
Inte
nsity
(a. u
.)
E
4-ABSA
TATPAAAFABA4-ABSA
300
400 500 600Wavelength (nm)
700 800
PL Inte
nsity
(a. u.)
HTATPAAAFABA
400 500 600Wavelength (nm)
700 800
Inte
nsity
(a. u
.)
G
4-ABSA
TATPAAAFABA4-ABSA
300 300
A
B
Figure S2. Structural characterizations of the five selected CQDs. (A) FT-IR spectra of the five
selected CQDs. (B) 13C NMR spectra of the five selected CQDs. (C) 1H NMR spectra of the five
selected CQDs. (D) XPS survey spectra of the five selected CQDs. (E) High-resolution C1s spectra
of the five selected CQDs. (F) High-resolution N1s spectra of the five selected CQDs. (G) High-
resolution O1s spectra of the five selected CQDs. (H) High-resolution S2p spectrum of the b-CQDs.
(I) High-resolution B1s spectrum of the yg-CQDs. (J) XRD spectra of the five selected CQDs. (K)
Raman spectra of the five selected CQDs.
r-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
4000 3000 2000 1000Wavenumber (cm-1)
Inte
nsity
(a. u
.)
C=CC-O
B-CB-O
SO3
O-H/N-H
C=O
10 20 30 40 50 60 70 80
r-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
Inte
nsity
(a. u
.)
2 Theta (degree)
B
500 1000 1500 2000Raman shift (cm-1)
Inte
nsity
(a. u
.)
2500
DG r-CQDs
o-CQDsyg-CQDsc-CQDsb-CQDs
Ar-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
200 150 100 0ppm
Inte
nsity
(a. u
.)
50
Sp2 C
DMSO
Cr-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
10 8 6 0ppm
Inte
nsity
(a. u
.)
4 2
Aromatic ring
hy drogen+Ph-NH2
H2O
DMSO
J
0 200 400 800Binding energy (eV)
Inte
nsity
(a. u
.)
ED
280 285 290 300Binding energy (eV)
Inte
nsity
(a. u
.)
295
F
390 395 400 410Binding energy (eV)
Inte
nsity
(a. u
.)
405600
525 530 535 545Binding energy (eV)
Inte
nsity
(a. u
.)
HG
155 160 165 175Binding energy (eV)
Inte
nsity
(a. u
.)
170
I
180 185 190 200Binding energy (eV)
Inte
nsity
(a. u
.)
195540
B1sS2pO1s
N1sC1s
B1s
S2p
C1s N1s O1s
C=O C-O
NH2C=C/C-C C-N/C-O
C=O
C-B
-SO3/2p3/2
-SO3/2p1/2
B-OB-C
KJ
r-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
b-CQDs yg-CQDs
r-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
r-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
r-CQDs
o-CQDs
yg-CQDs
c-CQDs
b-CQDs
Figure S3. Optimized preparation conditions of the five selected CQDs using PL QYs as a
reference. (A) 4-ABSA concentration optimization of the b-CQDs. (B) Temperature optimization
of the b-CQDs. (C) FA concentration optimization of the c-CQDs. (D) Temperature optimization
of the c-CQDs. (E) BA concentration optimization of the yg-CQDs. (F) Temperature optimization
of the yg-CQDs. (G) AA concentration optimization of the o-CQDs. (H) Temperature optimization
of the o-CQDs. (I) TPA concentration optimization of the r-CQDs. (J) Temperature optimization
of the r-CQDs. (K) Photographs of Rhodamine 6G and yg-CQDs under daylight (left) and UV light
(right), respectively.
Rhodamine 6G yg-CQDs
K
PL Q
Ys (
%)
120 150 180 200T (oC)
B 50
40
30
20
10
0
50
40
30
20
10
0
4-ABSA (mg)
PL Q
Ys (
%)
A
10 20 50 100 150 200 300
PL Q
Ys (
%)
120 150 180 200T (oC)
J 60
50
40
30
20
10
0
60
50
40
30
20
10
TPA (mg)
PL Q
Ys (
%)
I
10 50 100 150 200 250 3000
PL Q
Ys (
%)
120 150 180 200T (oC)
F
60
50
40
30
20
10
0
70
80
60
50
40
30
20
10
0
PL Q
Ys (
%)
G
0.05 0.1 0.2 0.4 0.6 0.8 1
70
AA (mL)
PL Q
Ys (
%)
120 150 180 200T (oC)
D 50
40
30
20
10
0
50
40
30
20
10
0
FA (mg)
PL Q
Ys (
%)
C
5 10 30 50 70 90 100
60
50
40
30
20
10
0
BA (mg)
PL Q
Ys (
%)
E
10 20 50 100 150 200
70
80yg-CQDs
PL Q
Ys (
%)
120 150 180 200T (oC)
H
60
50
40
30
20
10
0
70o-CQDs
b-CQDs c-CQDs
r-CQDs
g-CQDs
y-CQDs
dr-CQDs
b-CQDs c-CQDs
yg-CQDs o-CQDs
r-CQDs
Figure S4. Optical properties of the five selected CQDs. (A) PL spectra of the b-CQDs excited
at different wavelengths. (B) PL spectra of the c-CQDs excited at different wavelengths. (C) PL
spectra of the yg-CQDs excited at different wavelengths. (D) PL spectra of the o-CQDs excited at
different wavelengths. (E) PL spectra of the r-CQDs excited at different wavelengths. (F)
Corresponding PLE spectra of the five selected CQDs. (G) The relationship between the maximum
excitation wavelength and the corresponding excitonic absorption peak of the five selected CQDs.
(H) Photostability data for the b-CQDs under continuous irradiation with UV light for ten hours.
(I) Photostability data for the c-CQDs under continuous irradiation with UV light for ten hours. (J)
Photostability data for the yg-CQDs under continuous irradiation with UV light for ten hours. (K)
Photostability data for the o-CQDs under continuous irradiation with UV light for ten hours. (L)
Photostability data for the r-CQDs under continuous irradiation with UV light for ten hours. (M)
The temperature stability test of b-CQDs. (N) The temperature stability test of c-CQDs. (O) The
temperature stability test of yg-CQDs. (P) The temperature stability test of o-CQDs. (Q) The
temperature stability test of r-CQDs.
400 500 600Wavelength (nm)
700300
PLE I
nte
nsity
(a. u.)
FPLE
T (oC)4025154
o-CQDs
PL Inte
nsity
(a. u.)
I t/I 0
(%)
0Time (h)
1 2 3 4 5 6 7 8 9 10
100
80
60
40
20
Jyg-CQDs
I t/I 0
(%)
0Time (h)
1 2 3 4 5 6 7 8 9 10
100
80
60
40
20
Ko-CQDs
I t/I 0
(%)
0Time (h)
1 2 3 4 5 6 7 8 9 10
100
80
60
40
20
Lr-CQDs
I t/I 0
(%)
0Time (h)
1 2 3 4 5 6 7 8 9 10
100
80
60
40
20
I
c-CQDs
Excito
nic
absorp
tion p
eak
(nm
)
350 400 450Maximum excitation w avelength (nm)
500 550 600
400
500
550
450
600
G
I t/I 0
(%)
0Time (h)
1 2 3 4 5 6 7 8 9 10
100
80
60
40
20
H
b-CQDs
Inte
nsity
(a. u.)
600 700Wavelength (nm)
E
800500
510530550570590
r-CQDs
Inte
nsity
(a. u.)
400 500 600Wavelength (nm)
C
700 800
360380400420440
Inte
nsity
(a. u.)
300 400 500 600Wavelength (nm)
A
700
330350370390
Inte
nsity
(a. u.)
400 500 600Wavelength (nm)
B
700 800
380400420440460
300
b-CQDs yg-CQDsc-CQDs
PL Inte
nsity
(a. u.)
4 15 25 40T (oC)
b-CQDs
T (oC)4025154
c-CQDs
PL Inte
nsity
(a. u.)
O
T (oC)4025154
yg-CQDs
PL Inte
nsity
(a. u.)
Inte
nsity
(a. u.)
500 600Wavelength (nm)
700
480500520540560
Do-CQDs
N PM
Q
T (oC)4025154
r-CQDs
PL Inte
nsity
(a. u.)
650
350
Figure S5. Bandgap energy levels of the five selected CQDs. (A) Ultraviolet photoelectron
spectroscopy data of b-CQDs. (B) Ultraviolet photoelectron spectroscopy data of c-CQDs. (C)
Ultraviolet photoelectron spectroscopy data of yg-CQDs. (D) Ultraviolet photoelectron
spectroscopy data of o-CQDs. (E) Ultraviolet photoelectron spectroscopy data of r-CQDs. (F)
Dependence of the HOMO and LUMO energy levels with respect to the particle size of the five
selected CQDs.
E
Inte
nsity (
Arb
. U
nits)
19 18 17Binging Energy (eV)
20 16 15
19.79 eV
Inte
nsity (
Arb
. U
nits)
6 2Binging Energy (eV)
10 0
2.42 eV
21 8 412 -2
r-CQDs
C
Inte
nsity (
Arb
. U
nits)
19 18 17Binging Energy (eV)
20 16 15
18.91 eV Inte
nsity (
Arb
. U
nits)
6 2Binging Energy (eV)
10 0
2.28 eV
21 8 412 -2
yg-CQDs
AIn
tensity (
Arb
. U
nits)
19 18 17Binging Energy (eV)
20 16 15
18.75 eV Inte
nsity (
Arb
. U
nits)
6 2Binging Energy (eV)
10 0
2.77 eV
21 8 412 -2
b-CQDs
D
Inte
nsity (
Arb
. U
nits)
19 18 17Binging Energy (eV)
20 16 15
19.98 eV
Inte
nsity (
Arb
. U
nits)
6 2Binging Energy (eV)
10 0
2.96 eV
21 8 412 -2
o-CQDs
Energ
y level (e
V)
1.7 1.8 1.9 2.0Lateral size (nm)
2.1 2.2 2.3 2.4 2.5
-3
-4
-2
-5HOMOLUMO
B
Inte
nsity (
Arb
. U
nits)
19 18 17Binging Energy (eV)
20 16 15
18.71 eV Inte
nsity (
Arb
. U
nits)
6 2Binging Energy (eV)
10 0
2.36 eV
21 8 412 -2
c-CQDs
F
Figure S6. Stability and structural characterizations of the w-CQDs. (A) Photostability data
for the w-CQDs under continuous irradiation with UV light for ten hours. (B) The temperature
stability test of w-CQDs. (C) XRD spectrum of the w-CQDs. (D) Raman spectrum of the w-CQDs.
(E) FT-IR spectrum of the w-CQDs. (F) XPS survey spectrum of the w-CQDs. (G) High-resolution
C1s spectrum of the w-CQDs. (H) High-resolution N1s spectrum of the w-CQDs. (I) High-
resolution O1s spectrum of the w-CQDs.
I t/
I 0(%
)
0Time (h)
1 2 3 4 5 6 7 8 9 10
100
80
60
40
20
280 285 290 295 300
Inte
nsity (
a.
u.)
Binding energy (eV)
C1s
C=C/C-C
C-N/C-O
C=O
G
-COOHC-O
4000 3000 2000 1000Wavenumber (cm-1)
Inte
nsity (
a.
u.)
O-H/N-H
C=C
E
T (oC)4025154
PL I
nte
nsity (
a. u.)
O1sN1s
C1s
0 200 400 600 800
Inte
nsity (
a.
u.)
Binding energy (eV)
F
395 405 410
N1s
Inte
nsity (
a.
u.)
Binding energy (eV)
NH2
H
400390
500 1000 1500 2000Raman shift (cm-1)
Inte
nsity (
a.
u.)
2500
DG
D
10 20 30 40 50 60 70
Inte
nsity (
a.
u.)
2 Theta (degree)80
CB
O1s
525 530 535 540 545
C=O
C-O
Inte
nsity (
a.
u.)
Binding energy (eV)
I
550
A
Figure S7. The applications of the CQDs. (A) Photographs of the CQDs doped PMMA composite
films under daylight. (B) Cytotoxicity of the o-CQDs toward HeLa cells. (C) Confocal bright field
image of HeLa cells incubated with o-CQDs. (D) Confocal fluorescence image of HeLa cells
incubated with o-CQDs excited at 405 nm. (E) Confocal fluorescence image of HeLa cells
incubated with o-CQDs excited at 488 nm. (F) Confocal fluorescence image of HeLa cells
incubated with o-CQDs excited at 543 nm.
Cell
Via
bility
(%
)
24 h 48 h100
80
60
40
20
020 40 60 80 100
[o-CQDs] (mg·L-1)
B
Cyan YellowYellow-green (YG) OrangeYellow+Green Green+Orange
Deep-red+BlueRed+Deep-redYG+Orange White
Blue Green
Red Cyan+Yellow+RedDeep-red (DR) Blue+YG+DR
25 μm 25 μm
C D
25 μm25 μm
E F
A
Table S1. The electron-withdrawing and electron-donating group ratios of the five selected
CQDs in XPS spectra and elemental analysis.
Samples b-CQDs c-CQDs yg-CQDs o-CQDs r-CQDs
XPS
C (%) 57.67 62.95 59.06 67.26 68.65
N (%) 14.77 14.51 13.11 11.95 8.69
O (%) 21.15 22.54 22.57 20.79 22.66
S (%) 6.41 — — — —
B (%) — — 5.26 — —
N/C 0.26 0.23 0.22 0.18 0.12
C=O 45.51 55.08 60.3 67.9 71.64
C-O 54.49 44.92 39.7 32.1 28.36
Elemental
analysis
C (%) 68.3 60.0 73.1 63.7 71.9
N (%) 20.2 16.6 17.1 13.4 12.4
H (%) 3.8 3.7 4.3 5.6 5.2
N/C 0.29 0.27 0.23 0.21 0.17
Table S2. PL scan conditions and QY data for the as-prepared CQDs.
Samples Excitation
(nm)
Emission
(nm)
PL range
(nm)
Quantum
yields (%)
b-CQDs 355 450 360-600 25
c-CQDs 410 490 410-620 36
g-CQDs 420 500 420-630 28
yg-CQDs 440 540 450-660 72
y-CQDs 470 550 480-670 45
o-CQDs 535 600 540-690 59
r-CQDs 600 665 550-750 47
dr-CQDs 640 700 650-760 52
w-CQDs 360 560 370-800 39
Table S3. The PL lifetimes and energy levels of the five selected CQDs.
Samples b-CQDs c-CQDs yg-CQDs o-CQDs r-CQDs
PL
lifetimes
λex (nm) 355 410 440 535 600
λem (nm) 450 490 540 600 665
A1 2350.72 2444.23 2980.54 4303.28 6125.37
t1 (ns) 10.91 7.87 4.50 3.08 2.49
R2 0.994 0.987 0.988 0.991 0.990
Energy
levels
HOMO (eV) -5.22 -4.85 -4.57 -4.18 -3.83
LUMO (eV) -2.46 -2.32 -2.23 -2.18 -1.95
λedge (nm) 450 490 530 620 660
Egopt (eV) 2.76 2.53 2.34 2.00 1.88