![Page 1: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/1.jpg)
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
![Page 2: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/2.jpg)
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
![Page 3: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/3.jpg)
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
![Page 4: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/4.jpg)
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
![Page 5: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/5.jpg)
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
![Page 6: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/6.jpg)
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
![Page 7: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/7.jpg)
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
![Page 8: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/8.jpg)
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
![Page 9: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/9.jpg)
Fig. S12. 1H NMR spectrum of CB in CDCl3 (600 MHz).
CB
CB
S9
![Page 10: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/10.jpg)
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
![Page 11: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/11.jpg)
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
![Page 12: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/12.jpg)
Fig. S17. 13C NMR spectrum of CB-2 in CDCl3 (150 MHz).
Fig. S18. FAB mass spectrum of CB-1.
S12
![Page 13: Supplementary data - ars.els-cdn.com · Web viewn Jung Chang, Hyein Ryu, Sangwoon Yoon, * and Suk-Kyu Chang* Department of Chemistry, Chung-Ang University, Seoul 06974, Republic](https://reader031.vdocuments.net/reader031/viewer/2022022105/5bdc737d09d3f2b4758df233/html5/thumbnails/13.jpg)
Fig. S19. FAB mass spectrum of CB-2.
S13