双氰基二苯代乙烯型双光子荧光汞离子探针

doi:10.7503/cjcu20170139

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (10): 1751.doi: 10.7503/cjcu20170139

双氰基二苯代乙烯型双光子荧光汞离子探针

黄池宝^1,²(), 潘淇¹, 陈晓远², 赵光练¹, 陈华仕¹, 梁兴¹, 吕国岭¹

1. 遵义师范学院化学化工学院, 遵义563002
2. 韶关大学农业科学与工程学院, 韶关 512005

收稿日期:2017-03-08 出版日期:2017-10-10 发布日期:2017-09-20
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 Mercury Ions^†

HUANG Chibao^1,^2,^*(), PAN Qi¹, CHEN Xiaoyuan², ZHAO Guanglian¹, CHEN Huashi¹, LIANG Xing¹, LÜ Guoling¹

1. Chemistry and Chemical Engineering College, Zunyi Normal University, Zunyi 563002, China
2. College of Agricultural Science and Engineering, Shaoguan University, Shaoguan 512005, China

Received:2017-03-08 Online:2017-10-10 Published:2017-09-20
Contact: HUANG Chibao E-mail:huangchibao@163.com
Supported by:
† Supported by the Guizhou Provincial High-Level Innovative Talents Training Project-Hundred 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], 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 Honghuagang District in Zunyi City, China(No.[2015]18)

摘要/Abstract

摘要：

分别以双氰基二苯代乙烯(DCS)和双[2-(2-羟乙基硫基)乙基]氨(HSA)为双光子荧光团和汞离子受体, 合成了双光子荧光汞离子探针(DHg), 并对其结构进行了分析. 实验结果表明, DHg在甲苯、乙腈和水中的荧光量子产率(Φ)分别为0.78, 0.42和0.20, 对汞离子的络合常数通过单、双光子荧光滴定分别拟合为lgK=5.47±0.02和lgK=5.34±0.02. DHg在水溶液中对汞离子具有优良的选择性和高的灵敏性, 可用于中性环境中汞离子的检测. DHg的双光子吸收截面(δ_TPA)在水溶液中高达840 GM, 可用于细胞中汞离子的检测与成像.

关键词: 双光子荧光探针, 汞离子, 活体成像, 双光子吸收截面

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

中图分类号:

O657.3
O625

TrendMD:

黄池宝, 潘淇, 陈晓远, 赵光练, 陈华仕, 梁兴, 吕国岭. 双氰基二苯代乙烯型双光子荧光汞离子探针. 高等学校化学学报, 2017, 38(10): 1751.

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

图/表 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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双氰基二苯代乙烯型双光子荧光汞离子探针

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

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双氰基二苯代乙烯型双光子荧光汞离子探针

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

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