Supporting Information
Fluorogenic recognition of Zn2+, Al3+ and F- ions by a new multi-analyte chemosensor based bisphenol A-quinoline
Serkan Erdemir*, Ozcan Kocyigit and Sait Malkondu
Selcuk University, Science Faculty, Department of Chemistry, Konya, Turkey 42031
Figure S1. 1H NMR (400 MHz, CDCl3) spectra of 1
Figure S2. 13C NMR (100 MHz, CDCl3) spectra of 1
Figure S3. FT-IR spectra of BFQ
Figure S4. 1H NMR (400 MHz, DMSO-d6) spectra of BFQ
Figure S5. 13C NMR (100 MHz, DMSO-d6) spectra of BFQ
Figure S6. COSY NMR (400 MHz, DMSO-d6) spectra of BFQ
Figure S7. APT (100 MHz, DMSO-d6) spectra of BFQ
Figure S8. Flourescence intensities of BFQ (10 μM) in presence of Zn2+ and Al3+ ions in the different solvent system
Figure S9. Flourescence intensities of BFQ (10μM) in presence of Zn2+ and Al3+ ions in the different solvent ratio (EtOH:H2O)
Figure S10. Benesi–Hildebrand plots assuming 1:2 stoichiometry from Fluorometric titration data of BFQ (10 μM) with Zn2+ (a) and Al3+ (b)
Figure S11. The plots of emission intensity of BFQ at 530 and 560 nm versus with Zn2+ (a) and Al3+ (b) cation concentration
Table S1. The quantum yields of BFQ and its Zn2+/Al3+ complexes
Figure S12. Plot of integrated fluorescence intensity against absorbance for BFQ and its Zn2+/Al3+ complexes
Figure S13: Benesi–Hildebrand plots assuming 1:2 stoichiometry from UV-vis titration data of BFQ (10 μM) with Zn2+ (a) and Al3+ (b)
Figure S14. Fluorescence enhancing profile of addition of Zn2+ and Al3+ ions (10 equiv) to BFQ (10 μM) in EtOH-H2O (9/1, v/v) from 1 to 10 min
Figure S15. Job's plot for interaction of BFQ (10 μM) with F- at 610 nm
Figure S16. Benesi–Hildebrand plot assuming 1:2 stoichiometry from Fluorometric titration data of BFQ (10 μM) with F-
Figure S17. The plot of emission intensity of BFQ at 610 nm versus with F- anion concentration
Table S2. The quantum yields of BFQ and its F- complex
Figure S18. Plot of integrated fluorescence intensity against absorbance for BFQ and its F- complex
Figure S1. 1H NMR (400 MHz, CDCl3) spectra of 1
Figure S2. 13C NMR (100 MHz, CDCl3) spectra of 1
Figure S3. FT IR spectra of BFQ
Figure S4. 1H NMR (400 MHz, DMSO-d6) spectra of BFQ
Figure S5. 13C NMR (100 MHz, DMSO-d6) spectra of BFQ
Figure S6. COSY NMR (400 MHz, DMSO-d6) spectra of BFQ
Figure S7. APT (100 MHz, DMSO-d6) spectra of BFQ
Figure S8. Flourescence intensities of BFQ (10 μM) in presence of Zn2+ and Al3+ ions in the different solvent system
Figure S9. Flourescence intensities of BFQ (10μM) in presence of Zn2+ and Al3+ ions in the different solvent ratio (EtOH:H2O)
Association constant determination:
Binding constants were calculated according to the Benesi-Hildebrand equation [1]. K was calculated following the equation stated below.
1/(A-Ao) = 1/{K(Amax–Ao) [M]n} + 1/[Amax-Ao] (UV-vis studies)
1/(I-Io) = 1/{K(Imax–Io) [M]n} + 1/[Imax-Io] (Fluorescence studies)
Here Ao and Io are the absorbance and the fluorescent intensity of receptor in the absence of guest, A and I are the absorbance and the fluorescent intensity recorded in the presence of added guest, Amax and Imax are the absorbance and the fluorescent intensity in presence of added [M]max and K is the association constant (M-1). The association constant (K) could be determined from the slope of the straight line of the plot of 1/(I-Io) or 1/(A-Ao) against 1/[M]n. The association constants (Ka) were determined by UV-vis and Fluorometric titration methods for BFQ with Zn2+/Al3+ and F- ions.
Determination of detection limit
The detection limits DL of BFQ for Zn2+/Al3+ and F- ions were determined from the following equation [2-3].
DL = 3S/K
Where S is the standard deviation of the blank solution; K is the slope of the calibration curve.
Fig. S11 and S16 show the plot of I versus the Zn2+/Al3+ cation concentration in EtOH-H2O (9/1, v/v) and the F- concentration in MeCN, respectively.
Determination of quantum yields
The quantum yields [4] were calculated with the following equation.
where Φ is the fluorescence quantum yield and Grad is the gradient from a plot of integrated fluorescence intensity vs. absorbance. The subscripts X and ST denote the tested and the reference fluorophore, respectively. Here, the referencence is quinine sulphate, which has a quantum yield of 0.54 when dissolved in 0.1 M H2SO4. Refractive index values (η) of solventswere determinedwith arefractometerfrom Milton Roy, Inc.
Figure S10. Benesi–Hildebrand plots assuming 1:2 stoichiometry from Fluorometric titration data of BFQ (10 μM) with Zn2+ (a) and Al3+ (b)
Figure S11. The plots of emission intensity of BFQ at 530 and 560 nm versus with Zn2+ (a) and Al3+ (b) cation concentration
Table S1. The quantum yields of BFQ and its Zn2+/Al3+ complexes
ΦBFQ / ΦBFQ-Zn2+ / ΦBFQ-Al3+0.0107 / 0.172 / 0.239
Figure S12. Plot of integrated fluorescence intensity against absorbance for BFQ and its Zn2+/Al3+ complexes
Figure S13. Benesi–Hildebrand plots assuming 1:2 stoichiometry from UV-vis titration data of BFQ (10 μM) with Zn2+ (a) and Al3+ (b)
Figure S14. Fluorescence enhancing profile of addition of Al3+ (a) and Zn2+ (b) ions (10 equiv) to BFQ (10 μM) in EtOH-H2O (9/1, v/v) from 1 to 10 min
Figure S15. Job's plot for interaction of BFQ (10 μM) with F- at 610 nm
Figure S16. Benesi–Hildebrand plot assuming 1:2 stoichiometry from Fluorometric titration data of BFQ (10 μM) with F-
Figure S17. The plot of emission intensity of BFQ at 610 nm versus with F- anion concentration
Table S2. The quantum yields of BFQ and its F- complex.
ΦBFQ / ΦBFQ-F-0.0061 / 0.172
Figure S18. Plot of integrated fluorescence intensity against absorbance for BFQ and its F- complex
References
[1] H.A. Benesi, J.H. Hildebrand, A Spectrophootometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons. J Am Chem Soc. 71 (1949) 2703–2707.
[2] M. Zhu, M.J. Yuan, X.F. Liu, J.L. Xu, J. Lv, C.S, Huang, H.B. Liu, Y.Y. Li, S. Wang, D. B. Zhu, Visible Near-Infrared Chemosensor for Mercury Ion, Org Lett. 10 (2008) 1481–1484.
[3] H.T. Niu, D.D. Su, X.L. Jiang, W.Z. Yang, Z.M. Yin, J.Q. He, J.P. Cheng, A simple yet highly selective colorimetric sensor for cyanide anion in an aqueous environment, Org Biomol Chem. 6 (2008) 3038–3040.