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Supplementary data
Flatbed-scanner-based colorimetric Cu2+ signaling system derived from a
coumarin–benzopyrylium conjugated dye
Myung Gil Choi, Yu Jeong Lee, In Jung Chang, Hyein Ryu, Sangwoon Yoon,* and Suk-Kyu Chang*
Department of Chemistry, Chung-Ang University, Seoul 06974, Republic of Korea
Contents
Fig. S1. Ratio of the absorbance at 650 nm and 423 nm (A650/A423) for sensor CB-1 in the
absence and presence of various metal ions.
Fig. S2. Fluorescence intensity at 476 nm (I/I0) of CB-1 in the absence and presence of
various metal ions.
Fig. S3. UVvis spectra of sensor CB-2 in the absence and presence of various metal ions.
Fig. S4. Fluorescence spectra of sensor CB-2 in the absence and presence of various metal
ions.
Fig. S5. Fast atom bombardment (FAB) mass spectrum of sensor CB-1 after treatment with
Cu2+.
Fig. S6. Job’s plot for complex formation between sensor CB-1 and Cu2+ ions.
Fig. S7. Effect of EDTA on the Cu2+ signaling solution of sensor CB-1.
Fig. S8. Changes in absorbance ratio (A650/A423) of sensor CB-1 as a function of Cu2+
concentration.
Fig. S9. Nonlinear curve fitting plot for the signaling of Cu2+ ions by sensor CB-1.
Fig. S10. Cu2+ concentration-dependent changes in red channel level (ΔRed value = 255 – red
channel level) of sensor CB-1.
Fig. S11. Competitive signaling of Cu2+ ions by sensor CB-1 in the presence of
environmentally relevant metal ions as background using a flatbed scanner.
Fig. S12. 1H NMR spectrum of CB in CDCl3.
Fig. S13. 13C NMR spectrum of CB in CDCl3.
Fig. S14. 1H NMR spectrum of CB-1 in CDCl3.
Fig. S15. 13C NMR spectrum of CB-1 in CDCl3.
Fig. S16. 1H NMR spectrum of CB-2 in CDCl3.
Fig. S17. 13C NMR spectrum of CB-2 in CDCl3.
S1
Fig. S18. FAB mass spectrum of CB-1.Fig. S19. FAB mass spectrum of CB-2.
0.01
2
0.00
5
0.00
6
0.00
2
0.00
2
0.00
5
0.00
4
0.00
5
0.00
8
0.00
1
0.00
5
0.00
6
0.00
6
0.00
3
0.00
4
0.00
6
3.89
0
1
2
3
4
A65
0 / A
423
CB-1
Cu2+ Li
+
Na+
K+
Mg2+
Ca2+
Ba2+
Mn2+
Fe3+
Co2+
Ni2+
Zn2+
Cd2+
Hg2+
Ag+
Pb2+
Fig. S1. Ratio of the absorbance at 650 nm and 423 nm (A650/A423) for sensor CB-1 in the absence and presence of various metal ions. [CB-1] = 5.0 10–6 M, [Mn+] = 1.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
0
0.2
0.4
0.6
0.8
1
1.2
I/I0
(at 4
76 n
m)
CB-1
Cu2+ Li
+
Na+
K+
Mg2+
Ca2+
Ba2+
Mn2+
Fe3+
Co2+
Ni2+
Zn2+
Cd2+
Hg2+
Ag+
Pb2+
S2
Fig. S2. Fluorescence intensity at 476 nm (I/I0) of CB-1 in the absence and presence of various metal ions. [CB-1] = 5.0 10–6 M, [Mn+] = 1.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile. ex = 423 nm.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
300 400 500 600 700 800
Wavelength (nm)
Abs
orba
nce CB-2 + Cu2+
CB-2,CB-2 + other metal ion
Fig. S3. UVvis spectra of sensor CB-2 in the absence and presence of various metal ions. [CB-2] = 1.0 10–5 M, [Mn+] = 2.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
S3
0
4
8
12
16
20
450 500 550 600 650 700 750
Wavelength (nm)
Fluo
resc
ence
inte
nsity
(au) CB-2,
CB-2 + other metal ions
CB-2 + Cu2+
Fig. S4. Fluorescence spectra of sensor CB-2 in the absence and presence of various metal ions. [CB-2] = 5.0 10–6 M, [Mn+] = 1.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile. ex = 423 nm.
Fig. S5. Fast atom bombardment (FAB) mass spectrum of sensor CB-1 after treatment with Cu2+.
S4
0
0.02
0.04
0.06
0.08
0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction = [CB-1]/([CB-1] + [Cu2+])
A65
0
Fig. S6. Job’s plot for complex formation between sensor CB-1 and Cu2+ ions. [CB-1] + [Cu2+] = 5.0 10–6 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
S5
0
0.1
0.2
0.3
0.4
350 450 550 650 750
Wavelengh (nm)
Abs
orba
nce
CB-1,CB-1 + Cu2+ + EDTA
CB-1 + Cu2+
Fig. S7. Effect of EDTA on the Cu2+ signaling solution of sensor CB-1. [CB-1] = 5.0 10–6 M, [Cu2+] = 1.0 10–4 M, [EDTA] = 2.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
y = 0.1756x + 0.0546R2 = 0.9951
0
0.5
1
1.5
2
2.5
3
0 3 6 9 12 15
[Cu2+] (mM)
A65
0 / A
423
Detection limit:3 x Blank SD (0.00235) / slope (0.1756)= 0.040 mM
Fig. S8. Changes in the absorbance ratio (A650/A423) of sensor CB-1 as a function of Cu2+
concentration. [CB-1] = 5.0 10–6 M, [Cu2+] = 0–1.5 10–5 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
S6
Fig. S9. Nonlinear curve fitting plot for the signaling of Cu2+ ions by sensor CB-1. [CB-1] = 5.0 10–6 M, [Cu2+] = 0–1.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
y = 5.517x + 3.1899R2 = 0.9961
0
10
20
30
40
50
60
0 1 2 3 4 5 6 7 8 9
[Cu2+] (mM)
DRed
val
ue
Detection limit:3 x Blank SD (0.2012) / slope (5.517)= 0.11 mM
Fig. S10. Cu2+ concentration-dependent changes in red channel level (ΔRed value = 255 – red channel level) of sensor CB-1. [CB-1] = 1.0 10–5 M, [Cu2+] = 0–9.0 10–6 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile. The inset image was obtained using a flatbed scanner in transmittance mode, and the error bars were obtained from three independent
S7
measurements.
0
0.2
0.4
0.6
0.8
1
1.2L
met
al +
Cu(
II) / L
Cu(
II) (L
= DRed
val
ue)
Li+
Na+
K+
Mg2+
Ca2+
Ba2+
Mn2+
Fe3+
Co2+
Ni2+
Zn2+
Cd2+
Hg2+
Ag+
Pb2+
Fig. S11. Competitive signaling of Cu2+ ions by sensor CB-1 in the presence of environmentally relevant metal ions as background using a flatbed scanner. [CB-1] = 1.0 10–5 M, [Cu2+] = [Mn+] = 2.0 10–4 M in a 1:1 (v/v) mixture of acetate buffer solution (pH 4.7, 20 mM) and acetonitrile.
S8
Fig. S12. 1H NMR spectrum of CB in CDCl3 (600 MHz).
CB
CB
S9
Fig. S13. 13C NMR spectrum of CB in CDCl3 (150 MHz).
Fig. S14. 1H NMR spectrum of CB-1 in CDCl3 (600 MHz).
CB-1
CB-1
S10
Fig. S15. 13C NMR spectrum of CB-1 in CDCl3 (150 MHz).
Fig. S16. 1H NMR spectrum of CB-2 in CDCl3 (600 MHz).
CB-2
CB-2
S11
Fig. S17. 13C NMR spectrum of CB-2 in CDCl3 (150 MHz).
Fig. S18. FAB mass spectrum of CB-1.
S12
Fig. S19. FAB mass spectrum of CB-2.
S13
