Synthesis of Novel Fluorescein-Thiospirolactams Hg2+ Fluorescent Probes and Its Application in vivo†

doi:10.7503/cjcu20180077

Abstract

Abstract:

The aldehyde compounds such as p-hydroxybenzaldehyde, pyrrole formaldehyde and acetaldehyd were introduced into the fluorescein thiohydrazide via the Schiff base reaction, the resulting compounds of TFP3, TFP4 and TFP5 could detect mercury with high selectivity and sensitivity. In further study, it was found that when the 7.5 μmol/L Hg²⁺was added, the fluorescence enhancement of TFP3, TFP4 and TFP5 at 530 nm of fluorescence spectrum appeared more than 30 times and the detection limits were 7.22×10^-8, 1.03×10^-7 and 1.28×10^-8 mol/L, respectively. In addition, the cellular imaging experiment exhibited that the probe had good biocompatibility and low toxicity, and may have practical application in the biological system.

Key words: Fluorescein thiohydrazide, Fuorescent probe, Mercury ion, Cellular imaging

CLC Number:

O657

TrendMD:

LIU Dahai, ZHANG Xueyan, FENG Yusha, DU Xianlong, XUE Longqi, DU Jianshi, ZHANG Guirong, YANG Qingbiao, LI Yaoxian. Synthesis of Novel Fluorescein-Thiospirolactams Hg²⁺ Fluorescent Probes and Its Application in vivo^†[J]. Chem. J. Chinese Universities, 2018, 39(7): 1412.

Figures/Tables 11

Scheme 1 Synthetic routes of probes TFP2, TFP3, TFP4 and TFP5

Fig.1 Selectivity of probes TFP2(A), TFP3(B), TFP4(C) and TFP5(D) for metal ions^Other ions include Cu2+, Mg2+, Na+, Mn2+, Cd2+, Co2+, Zn2+, Fe3+, Ni2+, Ba2+, K+, Ca2+, Pb2+, free.

Fig.2 UV absorption spectra of probe TFP3(5 μmol/L) in EtOH-HEPES (1∶1, volume ratio, pH=7.4) buffer solution upon the addition of different amounts of Hg2+ions(0—7.5 μmol/L)(A) and absorption enhancement at 509 nm as a function of Hg2+ concentration(B)

Fig.3 Fluorescence intensity of probe TFP3(5 μmol/L) in EtOH/HEPES(1∶1, volume ratio, pH=7.4) buffer solution upon the addition of different amounts of Hg2+ions(0—7.5 μmol/L)(λex=509 nm)(A), fluorescence enhancement at 530 nm as a function of Hg2+ concentration(B) and plot of emission intensity of TFP3 at 530 nm vs. Hg2+cation concentration(C)

Fig.4 Fluorescence intensity of TFP3(5 μmol/L) in the absence(a) and presence(b) of Hg2+(7.5 μmol/L) in EtOH-water(1∶1, volume ratio) solution under different pH conditions(λex=509 nm)

Fig.5 Fluorescence response of TFP3(5 μmol/L) in the presence of various metal ions in EtOH-HEPES (1∶1, volume ratio, pH=7.4) buffer solution(530 nm)^a. Hg2+; b. Cu2+; c. Mg2+; d. Na+; e. Mn2+; f. Cd2+; g. Co2+; h. Zn2+; i. Fe3+; j. Ni2+; k. Ba2+; l. K+; m. Ca2+; n. Pb2+.

Fig.6 Reversibility of Hg2+(5 μmol/L) coordination to TFP3 by Na2S

Fig.7 Job’s plot of TFP3 in EtOH-HEPES(1∶1, volume ratio, pH=7.4) buffer solution with a total concentration of [Hg2+]+[TFP3]=2×10-5 mol/L(λ=509 nm)

Fig.8 Benesi-Hildebrand plot(λex=509 nm) of 1/(F-F0) vs. 1/[Hg2+] for the association based on a 1∶2 association stoichiometry between TFP3 and Hg2+

Scheme 2 Proposed binding mechanism between the receptor probe TFP3 and Hg2+

Fig.9 Fluorescence images of Hg2+ ions in Hela cells with 20 μmol/L TFP3^ Bright-field transmission images(A, C) and fluorescence images(B, D) of Hela cells incubated with 0(A, B) and 40 μmol/L(C, D) of Hg2+ ions for 30 min.

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Synthesis of Novel Fluorescein-Thiospirolactams Hg²⁺ Fluorescent Probes and Its Application in vivo^†

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