Green synthesis of multimodal ‘OFF ON’ switchable MRI ... · J. Gallo1*, N. Vasimalai2, M.T....
Transcript of Green synthesis of multimodal ‘OFF ON’ switchable MRI ... · J. Gallo1*, N. Vasimalai2, M.T....
Green synthesis of multimodal ‘OFF-ON’ switchable MRI/optical
probes
J. Gallo1*, N. Vasimalai2, M.T. Fernandez-Arguelles2, M. Bañobre-López1*
1 Advanced (magnetic) Theranostic nanostructures group, INL – International Iberian Nanotechnology Laboratory,
Av. Mestre José Veiga, 4715-330 Braga, Portugal 2 Life Sciences department, INL – International Iberian Nanotechnology Laboratory, Av. Mestre José Veiga, 4715-
330 Braga, Portugal
Electronic supporting information
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016
Table S1. CQDs characterisation summary.
Parameters Results
Excitation/emission
maximum
λex: 370 nm
λem: 462 nm
Stokes shift 92 nm
FWHM 145 nm
Size (TEM) 4.3 ± 0.5 nm
d-spacing (TEM) 0.32 nm
D band
G band (Raman)
1340.6 cm-1
1567.5 cm-1
ID/IG (Raman) 1.44
Zeta potential -16.3 mV
Quantum yield
(quinine sulfate std)
38.31 %
Figure S1. (a) UV-vis and (b) emission spectra of CQDs (λex/λem = 370 nm/462 nm). Inset:
photographs of CQDs water solutions (i) day light (ii) UV light (320 nm).
Figure S2. Emission spectra of CQDs under different excitation wavelengths. Left, from 290 to
370 nm, and right, from 370 to 600 nm.
400 500 600 700
0.0
2.0x106
4.0x106
6.0x106
8.0x106
1.0x107
Inte
nsit
y
Wavelength (nm)
290 nm
300 nm
310 nm
320 nm
330 nm
340 nm
350 nm
360 nm
370 nm
400 500 600 700
0.0
2.0x106
4.0x106
6.0x106
8.0x106
1.0x107
Inte
nsit
y
Wavelength (nm)
370 nm
380 nm
390 nm
400 nm
410 nm
420 nm
430 nm
440 nm
450 nm
460 nm
470 nm
480 nm
490 nm
500 nm
510 nm
520 nm
530 nm
540 nm
550 nm
560 nm
570 nm
580 nm
590 nm
600 nm
400 500 600 700
0.0
2.0x106
4.0x106
6.0x106
8.0x106
1.0x107
Inte
nsit
y
Wavelength (nm)
200 300 400 500 600 700
0
1
2
3
4
5A
bso
rban
ce
Wavelength (nm)
n-
(ii) (i)
(a) (b)
Figure S3. FT-IR spectrum of CQDs
Figure S4. Raman spectrum of CQDs showing D and G bands.
4000 3500 3000 2500 2000 1500 1000 5000.0
0.2
0.4
0.6
0.8
1.0
33
90
29
66
11
14
14
02
C-O
C-H
C=O
16
02
C-H
Tra
ns
mit
tan
ce
(%
)
Wavenumber (cm-1)
O-H
1000 1200 1400 1600 1800
Inte
ns
ity
(a
.u.)
Raman shift (cm-1)
D G
Figure S5. Left, overview SEM image of MnO2_CQDS nanosheets deposited on a silicon
surface. Right, high resolution TEM image of CQDs.
Figure S6. High resolution TEM image of MnO2_CQDs showing the polycrystalline nature of
the sample.
Figure S7. SAED pattern obtained on a sample of MnO2_CQDs and the assignment of the
structure.
Figure S8. Energy dispersive X-ray spectra (EDXS) of a MnO2_CQDs sample showing clear
peaks from Mn, O and C.
Figure S9. Raman spectra and tentative assignment of the peaks of a sample of MnO2_CQDs.
30 40 50 60 70 80 90
MnO2-CQDs
Inte
nsity (
a. u
.)
2 (º)
Figure S10. XRD diffractogram of MnO2_CQDs nanosheets showing a pattern matching the
JCPDS pattern of MnO2 (JCPDS 44-0141, J.Phys.Chem.C, 2015, 119, 6604). The baseline signal
has been subtracted by adjacent-averaging smoothing method considering 20 anchor points
connected by Spline interpolation.
Figure S11. FT-IR spectra of MnO2-CQDs nanocomposites.
Figure S12. TGA curve showing the mass loss from MnO2 nanosheets (after solvent loss) against
temperature.
0
0.2
0.4
0.6
0.8
1
1.2
4008501300175022002650310035504000
Wavelength/cm-1
ν(OH)str
ν(OH)bendv (C=O)
ν(Mn-O)
Figure S13. TGA curve showing the mass loss from MnO2-CQDs nanocomposites (after solvent
loss) against temperature.
Figure S14. Left, white light image of water solutions of MnO2_CQDs nanocomposites (left
column) before (upper) and after (bottom) reduction with GSH, and CQDs (bottom right column);
center, green channel fluorescence of the same samples; right, overlay image. MnO2_CQDs
concentration: 1 and 3, 0.9 mg Mn/mL; 2 and 4, 1.8 mg Mn/mL. CQDs concentration: 5, 0.9
mg/mL; 6, 1.8 mg/mL. GSH concentration 5 mM.
1 2
3 4 5 6
Figure S15. Left, evolution of the fluorescence spectra of a 11 µg Mn/mL solution of MnO2-
CQDs nanocomposites in completed (10% foetal bovine serum) DMEM medium upon the addition
of increasing concentrations of GSH (from 0 to1.80 mM). Right, evolution of the fluorescence at
443 nm versus the concentration of GSH.
Figure S16. Investigation of the de-quenching mechanism of CQDs PL from MnO2 nanosheets in
the presence of increasing concentrations of H2O2.
Figure S17. A, T1-weigthed MR image of different phantoms: First column, H2O only (top) and
MnO2_CQDs in H2O (bottom). Second column, DMEM only (top) and MnO2_CQDs in DMEM
(bottom). Rest of columns, MnO2_CQDs in DMEM or H2O (top) and MnO2_CQDs in DMEM or
H2O after the addition of Glc, Tyr, or GSH (bottom). B, Signal intensity analysis from phantoms
in A showing a clear OFF-ON transition both in water and DMEM cell culture media.
Figure S18. Evolution of the T1-weigthed signal intensity of a phantom containing 6 ug Mn/mL
of MnO2-CQDs in water (orange) or completed DMEM cell culture media (blue) as a function of
the concentration of GSH in the solution.
Figure S19. r1 and r2 relaxivity plots of MnO2_CQDs nanocomposites in water before (A) and
24h after (B) the addition of 100 mM GSH.
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70
I Sam
ple
/IB
lan
k
mM GSH
DMEM
H2O
Figure S20. Viability test of A549 cells incubated for 4h at 37oC and 5% CO2 in the presence of
increasing concentrations of MnO2-CQDs (0 to 100 µg Mn/mL).
Figure S21. Representative fluorescence confocal images of A549 cells incubated only in
completed DMEM cell culture media (A), completed cell culture media plus 1.8 mg/mL of
turmeric CQDs (B), and completed cell culture media plus 1.8 mg Mn/mL of MnO2_CQDs
nanocomposites (C).
0
20
40
60
80
100
120
140
0 2 5 10 25 50 75 100
Cytotoxicity MnO2_CQDs nanosheets