Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
Electronic Supplementary Information
Solvent assisted selective detection of sub-micromolar levels of Cu2+ ions in aqueous samples and live-cells Narendra Reddy Chereddya, Subramaniyan Janakipriyaa, Purna Sai Korrapatib, Sathiah Thennarasu*a and Asit Baran Mandal*c a
Organic Chemistry Division, bBiomaterials Laboratory, cChemical Laboratory, CSIR-Central Leather Research Institute, Adyar, Chennai-600 020, India Corresponding author Tel.: +91 44 24913289; Fax: +91 44 24911589 E-Mail:
[email protected],
[email protected] Table of contents
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1
S2-S3
ESI-MS analytical data of fluorescent probe 1 (Figure S3)
S4
1
S5-S6
ESI-MS analytical data of fluorescent probe 2 (Figure S6)
S7
Metal ion selectivity of 2 in presence of other metal ions (Figure S7)
S8
The linear range of detection using fluorescent probe 2 (Figure S8)
S9
ESI-MS analytical data of 2-Cu2+ complex (Figure S9)
S10
pH dependent variation in the fluorescence intensity of 2 (Figure S10)
S11
Metal ion selectivity of 2 in presence of various amino acids (Figure S11)
S12
Comparative account of the characteristics of probe 2 and other Cu2+ probes (Table S1)
S13
H- and 13C-NMR spectra of fluorescent probe 1 (Figures S1-S2)
H- and 13C-NMR spectra of fluorescent probe 2 (Figures S4-S5)
S1
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
O N
N H
O
NH
N
N H
Fig. S1. 1H NMR spectrum of 1 in DMSO-d6
S2
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
O N
N H
O
NH
N
N H
Fig. S2. 13C NMR spectrum of 1 in DMSO-d6
S3
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
O N
N H
O
NH
N
N H
Fig. S3. ESI Mass spectrum of 1
S4
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
N N
Bn N
O N
N H
O
N
N
N H
Fig. S4. 1H NMR spectrum of 2 in CDCl3
S5
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
N N
Bn N
O N
N H
O
N
N
N H
Fig. S5. 13C NMR spectrum of 2 in CDCl3
S6
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
N N
Bn N
O N
N H
O
N
N
N H
Fig. S6. ESI Mass spectrum of 2
S7
Fluorescence Intensity at 555 nm
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
450 400 350 300 250
200 150 100 50 0
Fig. S7. Metal-ion selectivity of 2 (10 µM) in 1:1 v/v 0.01M Tris HCl-CH3CN, pH 7.4. The dark bars represent the fluorescence emission of a solution of 2 (10 µM) and 5 equiv of the cation of interest. The light bars show the fluorescence change that occurs upon addition of 1 equiv of Cu(II) to the solution containing 2 (10 µM) and the cation (50 µM).
S8
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
Fig. S8. The linear range of detection using fluorescent probe 2
S9
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
M+Cu2+ +Cl-
Fig. S9. ESI Mass spectrum of 2-Cu2+ complex
S10
Fluorescence Intensity (a.u)
Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
450 450 400 350 300 250 200 150 100 50 0
400 350 300 250 200 150 100
0
2
4
8
10
pH
50 0 525
6
550
575
600
625
650
Wavelength (nm) Fig. S10. pH dependant variation in fluorescence intensity of 2 (10 μM).
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Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
Fluorescence Intensity at 555 nm
450.0 400.0 350.0 300.0 250.0 200.0 150.0 100.0
50.0 0.0
Fig. S11. Cu2+ ion selectivity of 2 (10 µM) in 1:1v/v 0.01M Tris HCl-CH3CN, pH 7.4 in the presence of various amino acids. The dark bars represent the fluorescence emission intensity of 2 (10 µM) and 5 equiv of the amino acid of interest. The grey bars show the fluorescence emission intensity upon addition of 1.0 equiv. of Cu2+ to the solution of 2 (10 µM) and 5.0 equiv. of the amino acid of interest.
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Electronic Supplementary Material (ESI) for Analyst This journal is © The Royal Society of Chemistry 2012
Table S1. Comparative account of the characteristics of probe 2 and other Cu2+ probes Cu2+ Sensor
Reversibility
Competing metal ion(s)
Linear range (µM)
Detection limit (µM)
Ref 1
NA
Co2+
0.1-70
0.23
Ref 2
Irreversible
-
2.5-35
1.8
Ref 3
Reversible
-
0.1-1
0.045
Ref 4
Irreversible
-
0.08-30
0.013
Ref 5
Irreversible
Cr3+, Hg2+
-
0.3
Ref 6
NA
Fe3+, Hg2+
-
-
This work
Reversible
-
0.05-8
0.03
Remarks Interference from other metal ions Large response time (8 min) and high detection limit narrow linear range of detection Low excitation wavelength (365 nm) may be harmful to living organisms Interference from other metal ions Interference from other metal ions No interference from other metal ions; Wide linear range of detection; Low detection limit; Excitation in visible region (525 nm)
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