基于苯并吡喃衍生物的近红外荧光探针用于二氧化硫衍生物的高灵敏检测与生物成像

doi:10.6023/cjoc202510002

摘要/Abstract

开发了一种近红外(NIR)荧光探针DCA-Tcf用于检测生物体系和食品样本中的二氧化硫衍生物($\mathrm{HSO}_{3}^{-} / \mathrm{SO}_{3}^{2-}$). 该探针以6-(二乙基氨基)-1,2-二氢环戊烯[b]苯并吡喃为荧光团, 通过引入吸电子基, 使其发射波长延伸至809 nm, 突破了小分子探针通常难以逾越的800 nm波长限制. 该发射波长可有效增强组织穿透深度并降低背景荧光干扰, 使该探针在生物成像应用中更具优势. 探针DCA-Tcf识别$\mathrm{HSO}_{3}^{-} / \mathrm{SO}_{3}^{2-}$表现出高选择性、快速响应(40 s)以及低至0.509 μmol/L的检测限, 并在真实水样和糖样中成功检测$\mathrm{HSO}_{3}^{-}$, 在活细胞荧光成像中展示出应用潜力. 本研究开发的DCA-Tcf在食品安全检测和生物成像领域可成为一种有力工具.

关键词: 近红外发射, 荧光探针, 二氧化硫衍生物, 生物成像, 食品样品

A novel near-infrared (NIR) fluorescent probe DCA-Tcf is developed for the detection of sulfur dioxide derivatives ($\mathrm{HSO}_{3}^{-} / \mathrm{SO}_{3}^{2-}$) in biological systems and food samples in this paper. Utilizing 6-(diethylamino)-1,2-dihydrocyclopentene- [b]benzopyran as the fluorophore, and incorporating electron-withdrawing groups, the emission wavelength of the probe is red-shifted to 809 nm, which surpasses the typical 800 nm barrier for small-molecule probes. The emission wavelength (809 nm) can effectively enhance the tissue penetration depth and reduce the background fluorescence interference, making this probe more advantageous in biological imaging applications. Probe DCA-Tcf exhibits high selectivity, rapid response within 40 s, and a detection limit as low as 0.509 μmol/L toward $\mathrm{HSO}_{3}^{-} / \mathrm{SO}_{3}^{2-}$. DCA-Tcf has been applied successfully to the detection of $\mathrm{HSO}_{3}^{-}$ in real water and sugar samples, and demonstrates promising potential for application in fluorescence imaging of living cells. The DCA-Tcf developed in this study can become a powerful tool in the fields of food safety detection and bioimaging.

Key words: near-infrared emission, fluorescent probe, sulfur dioxide derivatives, bioimaging, food samples

引用此文

刘琳, 周璐璐, 梁天宇, 钟克利, 燕小梅, 汤立军. 基于苯并吡喃衍生物的近红外荧光探针用于二氧化硫衍生物的高灵敏检测与生物成像[J]. 有机化学, 2026, 46(3): 866-871.

Lin Liu, Lulu Zhou, Tianyu Liang, Keli Zhong, Xiaomei Yan, Lijun Tang. Near-Infrared Fluorescent Probe Based on Benzopyran Derivative for Highly Sensitive Detection of SO₂ Derivative and Bioimaging[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 866-871.

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图/表 6

图式1. (a) DCA-Tcf对比相似结构探针的优势; (b)糖样和实际水样的制备过程及DCA-Tcf荧光检测${\text{HSO}}_{3}^{－}$的应用

Scheme 1. (a) Advantages of DCA-Tcf over similar-structured probes; (b) Preparation process of sugar and actual water samples and application of DCA-Tcf fluorescence detection for ${\text{HSO}}_{3}^{－}$

图1. (a) DCA-Tcf (10 μmol/L)在EtOH/PBS (V∶V=5∶5, pH=7.4)体系中加入500 μmol/L不同分析物(Br－、I－、$\mathrm{NO}_{2}^{-}$、$\mathrm{CO}_{3}^{2-}$、$\mathrm{HCO}_{3}^{-} 、 \mathrm{CH}_{3} \mathrm{COO}^{-} 、 \mathrm{HPO}_{4}^{2-} 、 \mathrm{~S}^{2-} 、 \mathrm{PO}_{4}^{3-} 、 \mathrm{CN}^{-} 、 \mathrm{SCN}^{-} 、 \mathrm{PPi} 、 \mathrm{SO}_{4}^{2-} 、 \mathrm{HSO}_{3}^{-} 、 \mathrm{~N}_{3}^{-} 、 \mathrm{Hcy} 、 \mathrm{GSH} 、 \mathrm{Cys} $和$\mathrm{HSO}_{4}^{-}$)后的荧光光谱变化; (b)探针加入不同分析物后继续加入${\text{HSO}}_{3}^{－}$在809 nm处的荧光强度变化(λex=690 nm)

Figure 1. (a) Fluorescence spectral changes of DCA-Tcf (10 μmol/L) in EtOH/PBS solution (V∶V=5∶5, pH=7.4) addition of various analytes (Br－, I－, $\mathrm{NO}_{2}^{-}$、$\mathrm{CO}_{3}^{2-}$、$\mathrm{HCO}_{3}^{-} 、 \mathrm{CH}_{3} \mathrm{COO}^{-} 、 \mathrm{HPO}_{4}^{2-} 、 \mathrm{~S}^{2-} 、 \mathrm{PO}_{4}^{3-} 、 \mathrm{CN}^{-} 、 \mathrm{SCN}^{-} 、 \mathrm{PPi} 、 \mathrm{SO}_{4}^{2-} 、 \mathrm{HSO}_{3}^{-} 、 \mathrm{~N}_{3}^{-} 、 \mathrm{Hcy} 、 \mathrm{GSH} 、 \mathrm{Cys} $ and $\mathrm{HSO}_{4}^{-}$, 500 μmol/L); (b) Fluorescence intensity changes at 809 nm of DCA-Tcf (10 μmol/L) solution addition of various analytes and further adding ${\text{HSO}}_{3}^{－}$ (λex=690 nm)

图2. (a) DCA-Tcf (10 μmol/L)的EtOH/PBS (V∶V=5∶5, pH=7.4)溶液随${\text{HSO}}_{3}^{－}$浓度增加(0~500 μmol/L)的荧光光谱变化; (b)加入500 μmol/L ${\text{HSO}}_{3}^{－}$后DCA-Tcf溶液在809 nm处的荧光强度随时间变化曲线(λex=690 nm)

Figure 2. (a) Fluorescence spectral changes of DCA-Tcf (10 μmol/L) in EtOH/PBS solution (V∶V=5∶5, pH=7.4) upon the addition of varying concentrations of ${\text{HSO}}_{3}^{－}$ (0~500 μmol/L); (b) Time-dependent fluorescence intensity curve of DCA-Tcf solution at 809 nm after the addition of 500 μmol/L ${\text{HSO}}_{3}^{－}$ (λex=690 nm)

图3. (a) DCA-Tcf对${\text{HSO}}_{3}^{－}$的识别机制; (b) DCA-Tcf及DCA-Tcf-${\text{HSO}}_{3}^{－}$在S1态下的优化构型及前沿分子轨道电子跃迁示意图

Figure 3. (a) Recognition mechanism of DCA-Tcf for ${\text{HSO}}_{3}^{－}$; (b) Optimized configurations and schematic diagrams of the frontier molecular orbital electronic transitions of DCA-Tcf and DCA-Tcf-${\text{HSO}}_{3}^{－}$ in the S1 state

Sample	c/(μmol•L^－1)		Recovery/%	RSD/% (n=3)
Sample	Added	Found	Recovery/%	RSD/% (n=3)
Granulated sugar 1	5	5.12	102.41	0.18
	6	6.09	101.50	0.06
	7	6.97	99.57	0.08
Granulated sugar 2	5	4.88	97.60	0.09
	6	6.23	103.83	0.09
	7	7.19	102.71	0.15
Tap water	5	5.23	104.58	0.23
	6	6.43	107.17	0.40
	7	7.19	102.67	0.31
Lake water	5	4.94	98.81	0.30
	6	6.09	101.55	0.45
	7	7.14	101.97	0.15
River water	5	5.22	104.40	0.39
	6	6.14	102.27	0.18
	7	6.95	99.31	0.13

表1. DCA-Tcf检测白砂糖、自来水、湖水和河水中${\text{HSO}}_{3}^{－}$浓度的结果a

Table 1. Results of DCA-Tcf detection of ${\text{HSO}}_{3}^{－}$ concentration in white sugar, tap water, lake water, and river water

图4. MCF-7细胞在37 ℃下加入DCA-Tcf (10 μmol/L), 再加入不同浓度${\text{HSO}}_{3}^{－}$孵育后的荧光图

Figure 4. Fluorescence images of MCF-7 cells incubated with DCA-Tcf (10 μmol/L) and various concentrations of ${\text{HSO}}_{3}^{－}$at 37 ℃ Bright-field (a, d, g, j, m), dark-field (b, e, h, k, n), and overlay images (c, f, i, l, o).

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