Rhodamine-based Cell Permeable Fluoresecent Turn-on Probes for Cupric Ion†

doi:10.7503/cjcu20160402

Abstract

Abstract:

Two rhodamine-based fluorescent turn-on probes L1 and L2 were designed and synthesized for the detection of Cu²⁺ ion. L1 and L2 exhibit high selectivity toward Cu²⁺ ion over a wide range of metal ions in MeCN/H₂O(volume ratio 1∶5). The detection limits of the probes are down to 10^-8 mol/L range. Moreover, L1 and L2 can function as excellent fluorescence probes for imaging of cellular Cu²⁺ by means of fluorescence microscopy.

Key words: Rhodamine, Hydrazide, Cupric ion, Fluorescence probe, Fluorescence imaging

CLC Number:

O657
O626

TrendMD:

MI Xiaolong, JIAO Xiaojie, LIU Chang, HE Song, ZENG Xianshun. Rhodamine-based Cell Permeable Fluoresecent Turn-on Probes for Cupric Ion^†[J]. Chem. J. Chinese Universities, 2016, 37(10): 1784.

Figures/Tables 8

Scheme 1 Synthetic routes for probes L1 and L2

Fig.1 UV-Vis spectra of probes L1(A) and L2(B)(1×10-5 mol/L) in the presence of nitrate salts of metal ions(5×10-5 mol/L ) in MeCN/H2O(volume ratio 1∶5) solventInset: histogram representing the absorbance enhancement of probe L1 at 553 nm and probe L2 at 521 nm, respectively, in the presence of different metal ions. a. No other ions; b. Ag+; c. Al3+; d. Ca2+; e. Cd2+; f. Co2+; g. Cr3+; h. Cu2+; i. Fe2+; j. Fe3+; k. Hg2+; l. K+; m. Mg2+; n. Na+; o. NH4+; p. Ni2+; q. Pb2+; r. Zn2+.

Fig.2 Fluorescence emission spectra of probes L1(A) and L2(B)(1×10-6 mol/L) in the presence of nitrate salts of metal ions(5×10-6 mol/L) in MeCN/H2O(volume ratio 1∶5)Inset: histogram representing the fluorescence enhancement of probe L in the presence of different metal ions. a. No other ions; b. Ag+; c. Al3+; d. Ca2+; e. Cd2+; f. Co2+; g. Cr3+; h. Cu2+; i. Fe2+; j. Fe3+; k. Hg2+; l. K+; m. Mg2+; n. Na+; o. NH4+; p. Ni2+; q. Pb2+; r. Zn2+. Excitation was performed at 520 nm(A) and 500 nm(B). Excitation/emission slit width: 2.5 nm/5 nm.

Fig.3 Fluorescent titration spectra of probes L1(1×10-6 mol/L) in the presence of different concentrations of Cu2+ in MeCN/H2O(volume ratio 1∶5)[Cu2+]/(μmol·L-1): 0, 0.2, 0.6, 1.0, 1.8, 2.6, 3.4, 5.0, 6.6, 8.2, 9.8, 11.4, 13.0, 14.6, 16.2, 19.4, 22.6, 25.8, 30.6. Excitation was performed at 520 nm. Excitation/emission slit width: 2.5 nm/5 nm. Inset: plot of fluorescent intensity of L1 at 580 nm versus [Cu2+].

Fig.4 Relative fluorescent intensity change ratios[(Fi-FL)/(FCu2+-FL)] of probes L1(A) and L2(B)(1×10-6 mol/L) upon addition of Cu2+(5×10-6 mol/L) in the presence of metal ions(5×10-6 mol/L) in MeCN/H2O(volume ratio 1∶5)a. Cu2+; b. Cu2++Ag+; c. Cu2++Al3+; d. Cu2++Ca2+; e. Cu2++Cd2+; f. Cu2++Co2+; g. Cu2++Cr3+; h. Cu2++Fe2+; i. Cu2++Fe3+; j. Cu2++Hg2+; k. Cu2++K+; l. Cu2++Mg2+; m. Cu2++Na+; n. Cu2++NH4+; o. Cu2++Ni2+; p. Cu2++Pb2+; q. Cu2++Zn2+. Excitation was performed at 520 nm(A) and 500 nm(B). Excitation/emission slit width: 2.5 nm/5 nm.

Fig.5 Profile of pH dependence of the fluorescence intensity of probes L1(A)(1×10-6 mol/L) at 580 nm and L2(B)(1×10-6 mol/L) at 550 nm in the absence(a) and presence(b) of Cu2+(5×10-6 mol/L) in MeCN/H2O(volume ratio 1∶5)Excitation was performed at 520 nm(A) and 500 nm(B). Excitation/emission slit width: 2.5 nm/5 nm.

Fig.6 Bright field images(A, D), fluorescence images(B, E) and overlay images(C, F) of INS-1 cells incubated with L1(A—C) as well as L1 and Cu2+(D—F) Excitation wavelength: 559 nm.

Fig.7 Bright field images(A, D), fluorescence images(B, E) and overlay images(C, F) of INS-1 cells incubated with L2(A—C) as well as L2 and Cu2+(D—F) Excitation wavelength: 488 nm.

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