具有双态发光性质的双光子丹磺酰类荧光探针的合成及其在硫化氢检测中的应用研究

doi:10.6023/cjoc202402010

有机化学 ›› 2024, Vol. 44 ›› Issue (9): 2869-2875.DOI: 10.6023/cjoc202402010 上一篇下一篇

研究论文

具有双态发光性质的双光子丹磺酰类荧光探针的合成及其在硫化氢检测中的应用研究

何春, 刘姝祺, 成奋民, 郝远强, 陈述, 张培盛^*(), 曾荣今^*()

湖南科技大学化学化工学院湖南湘潭 411201

收稿日期:2024-02-20 修回日期:2024-04-10 发布日期:2024-05-10
通讯作者: 张培盛, 曾荣今
基金资助:
国家自然科学基金(52273290); 国家自然科学基金(52173278); 国家自然科学基金(52073087); 湖南省自然科学基金(2024JJ2033); 湖南省科技创新计划(2022RC1075)

Synthesis of Two-Photon Dansyl-Based Fluorescent Probe with Dual-State Emission Properties for Hydrogen Sulfide Detection

Chun He, Shuqi Liu, Fenmin Cheng, Yuanqiang Hao, Shu Chen, Peisheng Zhang(), Rongjin Zeng()

School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201

Received:2024-02-20 Revised:2024-04-10 Published:2024-05-10
Contact: Peisheng Zhang, Rongjin Zeng
Supported by:
National Natural Science Foundation of China(52273290); National Natural Science Foundation of China(52173278); National Natural Science Foundation of China(52073087); Natural Science Foundation of Hunan Province(2024JJ2033); Science and Technology Innovation Program of Hunan Province(2022RC1075)

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摘要/Abstract

硫化氢(H₂S)是一种具有刺激性和挥发性的环境有毒气体, 同时也是生物体内的重要功能小分子, 因此开发能检测不同状态下(如溶液态和气态)H₂S的荧光探针至关重要. 研究合成了一种具有双态发光(DSE)性质和高荧光量子产率的丹磺酰类荧光团DNs-HPP, 进一步引入2,4-二硝基苯磺酰基, 合成得到了一种用于检测H₂S的荧光探针DNs-HPP-DNBS. 基于DNs-HPP的DSE性质, 探针DNs-HPP-DNBS不仅能实现溶液中H₂S的灵敏检测(检测限为1.16 μmol•L^－1), 同时负载于固相基底后还能实现对气态H₂S的监测. 此外, 该探针独特的双光子性能还使其在生物成像等领域具有良好的应用潜力.

关键词: 双态发光, 双光子, 荧光探针, 硫化氢

Hydrogen sulfide (H₂S) is a kind of irritant and volatile environmental toxic gas. It is also an important functional small molecule in organisms. Therefore, it is very important to develop fluorescent probes that can detect H₂S in different states (such as solution and gas). In this study, a dansyl-based fluorophore (DNs) with dual-state emission (DSE) properties and high fluorescence quantum yields was successfully synthesized. Furthermore, a 2,4-dinitrobenzenesulfonyl moiety was introduced to synthesize a fluorescent probe, DNs-HPP-DNBS, for H₂S detection. Leveraging the DSE properties of DNs, the DNs-HPP-DNBS probe not only achieved sensitive detection of H₂S in solution, with a detection limit of 1.16 μmol•L^－1. At the same time, it can monitor gaseous H₂S after loading on solid substrate. In addition, its two-photon performance is expected to play its good application potential in biology and cell imaging.

Key words: dual-state emission, two-photon, fluorescent probe, hydrogen sulfide

引用此文

何春, 刘姝祺, 成奋民, 郝远强, 陈述, 张培盛, 曾荣今. 具有双态发光性质的双光子丹磺酰类荧光探针的合成及其在硫化氢检测中的应用研究[J]. 有机化学, 2024, 44(9): 2869-2875.

Chun He, Shuqi Liu, Fenmin Cheng, Yuanqiang Hao, Shu Chen, Peisheng Zhang, Rongjin Zeng. Synthesis of Two-Photon Dansyl-Based Fluorescent Probe with Dual-State Emission Properties for Hydrogen Sulfide Detection[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2869-2875.

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图/表 10

图式1. DNs-HPP和DNs-HPP-DNBS的合成路线图

Scheme 1. Synthesis of DNs-HPP and DNs-HPP-DNBS

图1. DNs-HPP在溶液(THF)中和固态的归一化单光子荧光发射光谱

Figure 1. Normalized fluorescence emission spectra of DNs- HPP in solution (THF) and in solid state Ex=350 nm, the inset is an image of DNs-HPP illuminated by 365 nm ultraviolet lamp

图2. DNs-HPP在THF中的双光子荧光发射光谱(Ex=760 nm)

Figure 2. Fluorescence emission spectra of DNs-HPP in THF (Ex=760 nm)

图3. DNs-HPP-DNBS与H2S反应前后的荧光发射光谱

Figure 3. Fluorescence spectra of DNs-HPP-DNBS before and after reaction with H2S Ex=350 nm, the inset is an image of DNs-HPP illuminated by 365 nm ultraviolet lamp

图式2. DNs-HPP-DNBS对H2S的识别机理图

Scheme 2. Proposed sensing mechanism of DNs-HPP-DNBS toward H2S

图4. DNs-HPP-DNBS在不同浓度的H2S溶液(0~50 μmol? L－1)中的荧光光谱图

Figure 4. Fluorescence spectra of DNs-HPP-DNBS in the presence of H2S (0~50 μmol?L－1)

图5. DNs-HPP-DNBS对不同的干扰物的荧光响应

Figure 5. Fluorescent response of DNs-HPP-DNBS to different species

图6. 在不同的干扰物的存在下DNs-HPP-DNBS对H2S的荧光响应

Figure 6. Effect of H2S on DNs-HPP-DNBS in the presence of different interferent

样品	H₂S加入量/ (μmol•L^－1)	H₂S检出量^a/(μmol•L^－1)	RSD/% (n=3)	回收率/ %
自来水	0	—	—	—
	10.00	9.89	1.39	98.90
	20.00	19.93	1.36	99.70
明湖水	0	—	—	—
	10.00	9.90	6.30	99.00
	20.00	20.02	1.39	100.1

表1. 自来水和明湖水中的H2S的检测

Table 1. Detection of H2S in tap water and lake water

图7. 沾有探针DNs-HPP-DNBS的棉片暴露于不同浓度的气态H2S后在365 nm紫外灯照射下的图像

Figure 7. Images of cotton stained with probe DNs-HPP-DNBS at different H2S concentrations under ultraviolet light irradiation

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具有双态发光性质的双光子丹磺酰类荧光探针的合成及其在硫化氢检测中的应用研究

Synthesis of Two-Photon Dansyl-Based Fluorescent Probe with Dual-State Emission Properties for Hydrogen Sulfide Detection

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