Dicyanostilbene-derived Two-photon Fluorescence Probe for Mercury Ions†

doi:10.7503/cjcu20170139

Abstract

Abstract:

A novel water-soluble two-photon fluorescent probe for Hg²⁺(DHg) derived from dicyanostilbene(DCS) as a two-photon fluorophore and bis[2-(2-hydroxyethyl sulfanyl) ethyl]amino group(HAS) as a novel Hg²⁺ ligand was developed, and its structure was analyzed and identified. The results of UV-Vis absorption and absorption-titration experiments, one- and two-photon excited fluorescence experiments, as well as cellimaging and tissue-imaging experiments showed that the probe has a very high sensitivity and selectivity for the detection of Hg²⁺ in water. It can be used to detect trace Hg²⁺ in neutral or basic aqueous solution(pH=7—12), and its binding constant(lgK) for Hg²⁺ was determined from the one- and two-photon fluorescence-titration curves to be lgK=5.47±0.02 and lgK=5.34±0.02, respectively. Nitrogen atom property and the sulfur atom number on the ionophore are believed to be responsible of the unique selectivity of probe DHg for Hg²⁺. The fluorescent quantum yields of DHg in toluene, acetonitrile and water are 0.78, 0.42 and 0.20, respectively, and its two-photon absorption cross-section(δ_TPA) is as high as 840 GM in aqueous solution. The probe could selectively detect free Hg²⁺ ions in live cells without interference from other metal ions and the membrane-bound probes. Undoubtedly, the probe is an ideal two-photon excited fluorescence bioimaging candidate.

Key words: Two-photon fluorescence probe, Mercury ion, Live-imaging, Two-photon absorption across-section

CLC Number:

O657.3
O625

TrendMD:

HUANG Chibao, PAN Qi, CHEN Xiaoyuan, ZHAO Guanglian, CHEN Huashi, LIANG Xing, LÜ Guoling. Dicyanostilbene-derived Two-photon Fluorescence Probe for Mercury Ions^†[J]. Chem. J. Chinese Universities, 2017, 38(10): 1751.

Figures/Tables 5

Scheme 1 Molecular structures and synthetic procedures of the compounds

Fig.1 Relative fluorescence intensity of 1 μmol/L DHg in the presence of 20 mmol/L Ag+, Ca2+, Cd2+, Cr3+, Fe3+, Co2+, Ni2+, Fe2+, Na+, Cu2+, Zn2+, Mn2+, Mg2+, Hg2+, Pb2+, K+ and Ba2+ followed by the addition of 1 μmol/L Hg2+Data were measured in 30 mmol/L MOPS buffer(100 mmol/L KCl, 10 mmol/L EGTA, pH=7.2). λex1= 400 nm, λex2=790 nm.

Fig.2 Absorption(left) and one-photon emission(right) spectra(A) and two-photon emission spectra(B) of DHg(10 μmol/L and 1 μmol/L, respectively) in H2O(30 mmol/L MOPS+100 mmol/L KCl+10 mmol/L EGTA, pH=7.2) upon the addition of 0—6 and 0—2 mol/L Hg(ClO4)2·2H2O predissolved in MeCN(0.01 mol/L), respectively(λex1=400 nm, λex2=790 nm)c(Hg2+) from top to bottom/(mol·L-1): (A) 0, 3.3×10-7, 6.7×10-7, 1.0×10-6, 1.3×10-6, 1.7×10-6, 2.0×10-6, 2.3×10-6, 3.0×10-6, 3.7×10-6, 4.7×10-6, 5.7×10-6, 6.7×10-6; (B) 0, 1.5×10-7, 2.0×10-7, 3.0×10-7, 4.0×10-7, 6.0×10-7, 7.0×10-7, 1.0×10-6, 1.5×10-6, 2.0×10-6, 2.5×10-6, 3.5×10-6, 4.5×10-6, 5.5×10-6, 7.5×10-6; 1.0×10-5.

Fig.3 Bright-field two-photon excitation fluorescence images(A, D) and TPM images(B, C, E, F) of 1 μmol/L DHg-labeled mouse fibroblast collected at 550—650 nm(A), (D) Images were collected upon excitation at 790 nm with a femtosecond pulse; (B), (E) before addition of 6 μmol/L Hg2+ (20 mmol/L Zn2+) to the imaging solution; (C), (F) after addition of 6 μmol/L Hg2+ (20 mmol/L Zn2+) to the imaging solution. Cells shown are representative images from replicate experiments(n=5).

Fig.4 Calibration curve of the TPF intensities for DHg(1 μmol/L) at 600 nm vs. Hg2+ concentrations

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