nanoscale advances
TRANSCRIPT
Nanoscale Advances
Supplementary Information
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
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Hydrochromic carbon dots as smart sensors for water sensing in organic solvents
Anitha Senthamizhan*a, Despina Fragouli*a, Brabu Balusamyb, Bhushan Patilc, Milan Paleie, Stefania Sabellab, Tamer Uyarc,d
and Athanassia Athanassiou*a
a. Smart Materials, Istituto Italiano di Tecnologia, 16163 Genova, Italy. [email protected], [email protected], [email protected], [email protected]
b. Nanoregulatory Platform, PharmaChemistry, Department of Drug Discovery and Development, Istituto Ital iano di Tecnologia, 16163 Genova, Italy c. Institute of Materials Science & Nanotechnology, Bilkent University, Ankara, 06800, Turkey d. Department of Fiber Science and Apparel Design, College of Human Ecology, Cornell University, Ithaca, NY, 14853, USA e. Nanochemistry Department, Istituto Italiano di Tecnologia, 16163 Genova, Italy
Electronic Supplementary Material (ESI) for Nanoscale Advances.This journal is © The Royal Society of Chemistry 2019
ARTICLE Journal Name
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Table of contents
Figure No
Description Page No
S1 Fourier-transform infrared spectra of the carbon dots 3
S2 XPS survey spectra of carbon dots 4
S3 XRD spectra of carbon dots 5
S4 Representative 2D excitation-emission contour map of carbon dots 6
S5 Biocompatibility studies of carbon dots 7
S6 Visual colorimetric changes in the emission of CD1 in THF upon addition of water 8
S7 Visual colorimetric changes in the emission of CD1 in THF upon addition of pure THF 8
S8 Selective water sensing performance of CD1/THF 9
S9 Time-resolved photoluminescence decay curves 9
S10 Excitation-emission contour maps of carbon dots in IPA and hydrated IPA 10
S11 Colorimetric sensing performance of hydrated Isopropyl alcohol 11
Supplementary Table
Supplementary Table 1: Comparison of the carbon dot based photoluminescent water sensor with other
works.
Supplementary Movie
Supplementary Movie 1: Demonstration of water sensing performance. An immediate distinguishable color change of CD1 is noticed upon exposure to water. Supplementary Movie 2: Demonstration of selective water sensing performance. The IPA, as an example
of polar protic solvent is introduced into CD1/THF (2 mL) to evaluate the selective sensing response
towards water. There is no significant change in the emission color of the CD1.
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Fig. S1 Fourier-transform infrared spectra of the carbon dots.
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Fig. S2 XPS survey spectra of carbon dots (a) and the table (b) containing atomic concentration of present
elements (%).
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Fig. S3 XRD spectra of carbon dots.
12 16 20 24 28 32 36 40
2 Theta (degree)
CD1
CD2
CD3
CD4
In
te
nsity(a
.u
.)
CD5
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Fig. S4 Representative 2D excitation-emission contour map of carbon dots (a) CD1 (b) CD2 (c) CD3 (d) CD4 and (e) CD5.
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Fig. S5 Biocompatibility studies of carbon dots. Cellular effects of carbon dots in Caco-2 human colon carcinoma cells using WST-1 cell viability and H2DCF-DA assay at 100 μg/mL (a&c) and 250 μg/mL (b&d). Error bars depict ± standard error of the mean for n=3.
(a) (b)
(c) (d)
Control CD1 CD2 CD3 CD4 CD5
0
20
40
60
80
100
120
140
160
Ce
ll V
ia
bility (%
)
24h 48h
Control CD1 CD2 CD3 CD4 CD5
0
20
40
60
80
100
120
140
160
Ce
ll V
ia
bility (%
)
24h 48h
Contr
ol
5m
M H
2O
2
CD
1
CD
2
CD
3
CD
4
CD
5
0
20
40
60
80
100
120
140
160
180
200
220
DC
F In
te
nsity (%
)
24h 48h
Contr
ol
5m
M H
2O
2
CD
1
CD
2
CD
3
CD
4
CD
5
0
20
40
60
80
100
120
140
160
180
200
220
DC
F In
te
nsity (%
)
24h 48h
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Fig. S6 Visual colorimetric changes in the emission of CD1 in THF upon addition of water under UV light (λmax-365
nm).
Fig. S7 Visual colorimetric changes in the emission of CD1 in THF upon addition of pure THF under UV light (λmax-
365 nm).
Control
H2O
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Fig. S8 Selective water sensing performance of CD1/THF. Photograph under UV light (λmax-365 nm) showing the
carbon dots in THF (2 mL) and subsequent addition of IPA (2 mL). The observed results indicated that there is no
significant chromatic transition.
Fig. S9 Time-resolved photoluminescence decay curves.
ControlIPA
0 10 20 30 40 50
10
1
10
2
10
3
10
4
Co
un
ts
Time(ns)
CD1/THF
CD1/THF/THF
CD1/THF/H2O
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Fig. S10 Excitation-emission contour maps of carbon dots in (a) IPA and (b-f) hydrated IPA. (b) 0.2%, v/v
(c) 0.6%, v/v (d) 1.0%, v/v (e) 3.0%, v/v and (f) 5.0%, v/v.
400 420 440 460 480 500
300
320
340
360
380
Ex
cita
tio
n W
ave
le
ng
th
(n
m)
Emission Wavelength (nm)
0
1,563E6
3,125E6
4,688E6
6,250E6
7,813E6
9,375E6
1,094E7
1,250E7
1,406E7
1,563E7
1,719E7
1,875E7
400 420 440 460 480 500
300
320
340
360
380
Ex
cita
tio
n W
ave
le
ng
th
(n
m)
Emission Wavelength (nm)
0
1,550E6
3,100E6
4,650E6
6,200E6
7,750E6
9,300E6
1,085E7
1,240E7
1,395E7
1,550E7
1,705E7
1,860E7
400 420 440 460 480 500
300
320
340
360
380
Ex
cita
tio
n W
ave
le
ng
th
(n
m)
Emission Wavelength (nm)
0
1,567E6
3,133E6
4,700E6
6,267E6
7,833E6
9,400E6
1,097E7
1,253E7
1,410E7
1,567E7
1,723E7
1,880E7
400 420 440 460 480 500
300
320
340
360
380
Ex
cita
tio
n W
ave
le
ng
th
(n
m)
Emission Wavelength (nm)
0
1,563E6
3,125E6
4,688E6
6,250E6
7,813E6
9,375E6
1,094E7
1,250E7
1,406E7
1,563E7
1,719E7
1,875E7
400 420 440 460 480 500
300
320
340
360
380
Ex
cita
tio
n W
ave
le
ng
th
(n
m)
Emission Wavelength (nm)
0
1,208E6
2,417E6
3,625E6
4,833E6
6,042E6
7,250E6
8,458E6
9,667E6
1,088E7
1,208E7
1,329E7
1,450E7
400 420 440 460 480 500
300
320
340
360
380
Ex
cita
tio
n W
ave
le
ng
th
(n
m)
Emission Wavelength (nm)
0
1,563E6
3,125E6
4,688E6
6,250E6
7,813E6
9,375E6
1,094E7
1,250E7
1,406E7
1,563E7
1,719E7
1,875E7
(a) (b) (c)
(f)(e)(d)
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Fig. S11 Colorimetric sensing performance of hydrated Isopropyl alcohol. PL emission spectra (λex-330 nm) peak shift vs water content (0.2 % to 5.0% v/v).
ARTICLE Journal Name
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Supplementary Table 1: Comparison of the carbon dot based photoluminescent water sensor with other works.
Material Change in the spectral position
Visual demonstration of photo/video
Type of solvent
Response time
Solvent specific respons
e
Ref
2D oxamato‐based manganese(II)‐copper(II) mixed‐metal–organic framework
Increased/Shift (586 to 544 nm)
No Toluene Greater than 60 minutes
No 1
Mg2+ metal–organic framework
Increased/Shift No THF, EtOH and ACN
1–2 minutes
No 2
4′-N, N-dimethylamino-4-methylacryloylamino chalcone (DMC)
Decreased No ethanol, acetone, and THF
less than 90s
No 3
Europium Coordination Compound (Eu(DAF)2(NO3)3)
Decreased No acetonitrile - No 4
Copper nanoclusters Decreased No DMSO, DMF, THF, Acetonitrile
20 min No 5
Oxoporphyrinogens Absorption Spectra
No THF - No 6
Tetraphenylethene (TPE) derivatives
Increased Yes THF and dioxane
- No 7
Coumarin-decorated Schiff base
Increased/Shift No DMSO - No 8
Flexible Indium(III) Metal–Organic Polyhedra Materials
Decreased Yes acetonitrile - No 9
Zn-MOF (metal–organic framework, Zn(hpi2cf)(DMF)(H2
O))
Shift/Increased yes THF, MeOH, Acetone, ACN and DMF
Instantly No 10
Carbon dots Shift/Decreased-Aprotic solvents Increased- Protic solvents
yes THF, IPA, ACN, Acetone and ButOH.
Instantly Yes Current work
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