双氰基二苯代乙烯型双光子荧光铅离子探针

doi:10.7503/cjcu20170672

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 897.doi: 10.7503/cjcu20170672

双氰基二苯代乙烯型双光子荧光铅离子探针

黄池宝, 潘淇, 陈华仕, 梁兴, 吕国岭

遵义师范学院化学化工学院, 遵义 563002

收稿日期:2017-10-11 出版日期:2018-04-08 发布日期:2018-04-08
作者简介:
联系人简介: 黄池宝, 男, 博士, 教授, 主要从事双光子荧光探针方面的研究. E-mail: huangchibao@163.com
基金资助:
贵州省高层次创新型人才培养计划项目“百”层次人才(批准号: 黔科合平台人才[2016]5683)、国家自然科学基金(批准号: 21562050)、贵州省第八批科技创新人才团队建设专项基金[批准号: 黔科合人才团队(2015)4007]、贵州省科学技术基金项目(批准号: 黔科合J字[2015]2146)、贵州省教育厅自然科学重点研究项目(批准号: 黔教合KY字[2014]296)、贵州省教育厅省级本科教学工程建设项目(批准号: 黔教[2014]JXGChcb)、遵义市“15851人才精英工程”项目[批准号: (2015)4007]和遵义市红花岗区科学技术项目(批准号: 遵红科合社字[2015]18)资助.

Dicyanostilbene-derived Two-photon Fluorescence Probe for Lead Ions^†

HUANG Chibao^*, PAN Qi, CHEN Huashi, LIANG Xing, LÜ Guoling

Chemistry and Chemical Engineering College, Zunyi Normal University, Zunyi 563002, China

Received:2017-10-11 Online:2018-04-08 Published:2018-04-08
Contact: HUANG Chibao
Supported by:
† Supported by the Guizhou Provincial High-level Innovative Talents Training ProjectHundred Talents Program, China(No.[2016]5683), the National Natural Science Foundation of China(No.21562050), the Special Fund Project of the Construction of the Eighth Batch of Scientific and Technological Innovation Talent Team in Guizhou Province, China[No.(2015)4007], the Guizhou Science and Technology Fund Project, China(No.J[2015]2146), the Key Project of Education Department of Guizhou Province, China(No.KY[2014]296), the Teaching Contents and Curriculum System Reform Project of Higher Education in Guizhou Province, China(No.KY[2014]JXGChcb), the Project of “15851 Talents Elite Project” in Zunyi City, China(No.[2015]4007) and the Science and Technology Project of Zunyi City Honghuagang District, China(No.[2015]18).

摘要/Abstract

摘要：

以4-甲基-2,5-二氰基-4'-氨基二苯代乙烯(DCS)和双[2-(2-氨基苯基硫基)乙基]胺(BSA)分别作为双光子荧光团和铅离子配体, 构建了1个新型的双光子荧光Pb²⁺探针(DPb), 并对其结构和性能进行了表征. 结果表明, 该探针具有分子尺寸小、双光子吸收截面大(δ_TPA, 1020 GM)、长波长发射(λ_max=609 nm)、斯托克斯位移大(209 nm)、光稳定性好、水溶性适宜、细胞渗透性优良、无细胞毒性及在生理环境下对pH不依赖等优点. 该探针能选择性地检测细胞与组织中的Pb²⁺, 猝灭常数 $K sv TP$ =7.58×10⁵ L/mol.

关键词: 双光子荧光探针, 铅离子, 活体成像, 双光子吸收截面

Abstract:

One-photon microscopy(OPM) uses a single photon of higher energy to excite the fluorophore, while two-photon microscopy(TPM) uses two photons of lower energy as the excitation source. Therefore, TPM has such distinct advantages as improvement of penetration depth, localized two-photon excitation, reduction of photo-damage and photobleaching, small absorption coefficient of light in tissue, and lower tissue autofluorescence. These advantages make TPM more popular among biologists. Lead is a common contaminant and has inherent toxic effects on human health and environment. Pb²⁺ ion contamination can affect a wide variety of diseases such as anemia, irritability, memory loss, and muscle paralysis. For these reasons, there is an urgent need to develop some effective two-photon fluorescence probes to detect trace amounts of Pb²⁺ ions in live cells and tissues. A novel two-photon fluorescence probe for Pb²⁺ derived from 4-methyl-2,5-dicyano-4'-amino stilbene as a two-photon fluorophore and bis[2-(2-aminophenylsulfanyls)ethyl]amine as a novel Pb²⁺ ligand was developed. The probe possessed small molecule size, large two-photon absorption cross-section(1020 GM), noncytotoxic effect, long-wavelength emission at 609 nm, large Stokes shift(209 nm), excellent photostability, moderate water-solubility, good cell-permeability and pH-insensitivity in the biologically relevant range. The probe was able to selectively detect Pb²⁺ ions in live cells and living tissues without interference from other metal ions and the membrane-bound probes, and its quenching constant( $K sv TP$ ) was 7.58×10⁵ L/mol.

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

中图分类号:

O625

TrendMD:

黄池宝, 潘淇, 陈华仕, 梁兴, 吕国岭. 双氰基二苯代乙烯型双光子荧光铅离子探针. 高等学校化学学报, 2018, 39(5): 897.

HUANG Chibao,PAN Qi,CHEN Huashi,LIANG Xing,LÜ Guoling. Dicyanostilbene-derived Two-photon Fluorescence Probe for Lead Ions^†. Chem. J. Chinese Universities, 2018, 39(5): 897.

图/表 7

Fig.1 Structure of DPb chelating lead ion

Fig.2 Relative fluorescence intensity of 1 μmol/L DPb in the presence of 20 mmol/L Pb2+ and other ions(empty bars) followed by addition of 40 μmol/L Pb2+(filled bars) Note：a—q: Pb2+, K+, Ca2+, Mg2+, Ba2+, Fe2+, Fe3+, Zn2+, Co2+, Ni2+, Cr3+, Cd2+, Mn2+, Cu2+, Ag+, Na+, 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.3 Absorption(A) and emission spectra(B) of DPb(1 μmol/L) in 30 mmol/L MOPS buffer(100 mmol/L KCl+10 mmol/L EGTA, pH=7.2) upon the addition of Pb2+(0—40 μmol/L), respectively Note：λex1=400 nm, λex2=790 nm. (A) Left: absorption spectra; right: one-photon emission spectra; (B) two-photon emission spectra.

Fig.4 Best fitting curve between changes in one-photon absorption intensities of DPb(10 μmol/L) at 400 nm and Pb2+ concentrations Note：Data were measured in 30 mmol/L MOPS buffer (100 mmol/L KCl+10 mmol/L EGTA, pH=7.2).

Fig.5 TPM images of 1 μmol/L DPb-labeled mouse fibroblast collected at 550—650 nm before(A) and after(B) the addition of 20 μmol/L Pb2+ to the imaging solution Note： The two-photon excitation fluorescence(TPEF) images were collected upon excitation at 790 nm with a femtosecond pulse. Cells shown are representative images from replicate experiments(n=5).

Fig.6 TPM images of a mouse brain tissue slice stained with 10 μmol/L DPb at a depth of ca. 120 μm with magnification 100× before(A) and after(B) the addition of 20 μmol/L Pb2+ to the imaging solution Note：The two-photon excitation fluorescence(TPEF) images were collected at 550—650 nm upon excitation at 790 nm with a femtosecond pulse. Cells shown are representative images from replicate experiments(n=5).

Fig.7 Normalized fluorescence decay curves of DPb(10 μmol/L) solutions at 609 nm before and after the addition of Pb2+ excited by one-photon absorption(403 nm) and two-photon absorption(790 nm) Note：(A) OPFL(DPb-Pb2+); (B) TPFL(DPb-Pb2+); (C) OPFL(DPb); (D) TPFL(DPb). OPFL and TPFL abbreviated from one- and two-photon fluorescence lifetime, respectively.

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双氰基二苯代乙烯型双光子荧光铅离子探针

Dicyanostilbene-derived Two-photon Fluorescence Probe for Lead Ions^†

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双氰基二苯代乙烯型双光子荧光铅离子探针

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

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Dicyanostilbene-derived Two-photon Fluorescence Probe for Lead Ions^†