荧光探针的发展和应用.doc

Supplementary materials for:
Perylene diimide based “turn-on” fluorescence sensor for detection of Pd2+ in mixed aqueous media
Hai-xia Wang a, b,*, Yue-he Lang a, Hui-xuan Wang a, Jing-jing Lou a, Hai-ming Guo a, b, Xi-you Li c,*
a School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions of Ministry of Education, Henan Normal University, Xinxiang 453007, China
b School of Environmental Science, Henan Normal University, Xinxiang 453007, China
email: hxwang5270@ (H. Wang)
c School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
email: xiyouli@ (X. Li)
Contents
Page S1: Title of the paper, authors along with the contents.
Page S2-S4: Copy of the 1H and 13C NMR spectra of PDI-1, PDI-2 and PDI-3.
Page S5: Photophysical properties of PDI-1, PDI-2 and PDI-3 derivatives in different solvents at room temperature; Fluorescence spectra change of PDI-2 and PDI-3 upon addition of different metal(8.0 equiv) ions; UV-vis spectra of PDI-1 (6.0 μM) in the presence of different metal ions (8.0 equiv).
Page S6: Job’s plots in DMF/H2O (v/v, 7/1) and acetonitrile; Fluorescence spectra changes of PDI-1 (5.0 μM) in the presence of Pd2+in acetonitrile and chloroform; ESI mass spectra of PDI-1 in the presence of 1.0 equiv PdCl2 in CH3CN.
Page S7: Job’s plots of PDI-1 (5.0 μM) in the presence of Pd2+in chloroform; Influence of pH on fluorescence intensity of PDI-1 (5.0 μM) in the absence and presence of 1.0 eq Pd2+; Benesi-Hildebrand analysis results.

Fig. S1 1H NMR (400 MHz) spectrum of PDI-1 in CDCl3.

Fig. S2 13C NMR (100MHz) spectrum of PDI-1 in CDCl3.

Fig. S3 1H NMR (400 MHz) spectrum of PDI-2 in CDCl3.

Fig. S4 13C NMR (100 MHz) spectrum of PDI-2 in CDCl3.

Fig. S5 1H NMR (400 MHz) spectrum of PDI-3 in CDCl3.

Fig. S6 13C NMR (100 MHz) spectrum of PDI-3 in CDCl3.
Table S1: Photophysical properties of PDI-1, PDI-2 and PDI-3 derivatives in different solvents at room temperature

Fig. S7 Fluorescence spectra change of PDI-2 (left) and PDI-3 (right) upon addition of different metal (8.0 equiv) ions including Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+, Hg2+, Pb2+ and Pd2+ in DMF/H2O (v/v, 7:1), λex = 540 nm, Slit: 2.5 nm; 5.0 nm.

Fig. S8 UV-vis spectra of chemosensor PDI-1 (6.0 μM) in the presence of different metal ions (8.0 equiv) of Mn2+, Co3+, Ni2+,Cu2+, Zn2+, Cd2+, Hg2+ and Pd2+ in DMF/H2O (v/v, 7:1). Inset showing the color change (left) before (right) after the addition of Pd2+ in visible light.

Fig. S9 Job’s plot of PDI-1 in DMF/H2O (v/v, 7/1) showing the 1:1 stoichiometry of the complex between Pd2+ ion and PDI-1. The total of the chemosensor and Pd2+ is 10 μM, λex = 540 nm, Slit: 2.5 nm; 5.0 nm.

Fig. S10 ESI mass spectra of PDI-1 in the presence of 1.0 equiv PdCl2 in CH3CN.

Fig. S11 (left) Fluorescence spectra changes of PDI-1 (5.0 μM) in the presence of different concentrations of Pd2+ in CH3CN after 30 minutes, λex = 510 nm, Slit: 2.5 nm; 5.0 nm; (right) Job’s plot of PDI-1 in CH3CN showing the 1:1 stoichiometry of the complex between Pd2+ and PDI-1. The total of the chemosensor and Pd2+ is 10 μM, λex = 510 nm, Slit: 2.5 nm; 5.0 nm.

Fig. S12 (left) fluorescence spectra of PDI-1 (5.0 μM) in the presence of different concentrations of Pd2+ in chloroform after 30 minutes, λex = 540 nm, Slit: 2.5 nm; 5.0 nm; (right) Job’s plot of PDI-1 in chloroform showing the 1:1 stoichiometry of the complex between Pd2+ and PDI-1, the total of the chemosensor and Pd2+ is 10 μM, λex = 540 nm, Slit: 2.5 nm; 5.0 nm.

Fig. S13 Influence of pH on fluorescence intensity of PDI-1 (5.0 μM) in the absence and presence of 1.0 eq Pd2+, λex = 540 nm, Slit: 5.0 nm; 5.0 nm. The pH of solution was adjusted by aqueous solution of NaOH (1.0 M) or HCl (1.0 M). Inset showing a influence of pH on fluorescence for PDI-1.

Benesi-Hildebrand equation and Benesi-Hildebrand analysis results are as follows:

Y = A + B * X

Parameter Value Error
------------------------------------------------------------
A -5.42365E-4 1.28771E-4
B 0.02425 3.35908E-4
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.99933 2.80162E-4 9 <0.0001
Ka = A/B = 5.42365E-4/0.02425 = 2.24×10-2 μM-1 = 2.24×104 M-1
S8