Fluorescent probe for selectively detecting singlet oxygen in solution phase and application

Abstract

The invention relates to a fluorescent probe with enhanced fluorescence generation in the presence of singlet oxygen. The invention provides a fluorescent probe which can be used for selectively detecting singlet oxygen generated in various chemical reaction, photosensitization reaction and photocatalysis reaction systems in a solution phase. Fluorescent dye BODIPY with absorption and emission overlapped to a certain extent is adopted as a fluorescent parent, an anthracene functional group is introduced into the fluorescent parent to serve as an active center for selectively reacting with thesinglet oxygen, and alkynyl is innovatively connected with two groups, so that the fluorescence intensity is changed before and after the reaction with the singlet oxygen; and the ratio change of theabsorption intensity is generated by utilizing the change of the conjugated structure of the probe molecule before and after the reaction of the anthracene functional group and the singlet oxygen.

Description

technical field

[0001] The present invention relates to a class of fluorescent probes for selectively detecting singlet oxygen in a solution phase, specifically, a class of fluorescent probes in 1 o 2 Fluorescent probes whose fluorescence is enhanced or whose emission wavelength is changed in the presence of a fluorescent probe. Background technique

[0002] 1 o 2 It is a highly reactive reactive oxygen species (ROS), which can chemically react with a variety of organic molecules, and plays a vital role in the fields of life sciences and photocatalysis. 1 o 2 The detection methods mainly include the following: 1270nm 1 o 2 Direct detection of luminescence, electron spin resonance (ESR), chemiluminescent probe and fluorescent probe methods (Nosaka Y; Nosaka A.Y. Chemical Reviews, 2017, 117, 11302). Fluorescent probes are effective in detecting 1 o 2 It is an important method with strong specificity, good repeatability, and high sensitivity. It can also perform single...

Examples

Embodiment 1

[0026] Embodiment 1 (synthesis of probe):

[0027] Such as image 3 As shown, the structure of the probe compound used in the examples is represented by the code BA, and the boron pyrrole precursor used in the synthesis of the probe compound is represented by the code B.

[0028] Synthesis of BA: Under nitrogen protection, B (0.09g, 0.2mmol) and A (0.085g, 0.42mmol) were dissolved in a mixed solvent of 5ml of anhydrous triethylamine and 10ml of anhydrous tetrahydrofuran, and Pd(PPh 3 ) 2 Cl 2 (14mg, 0.02mmol), PPh 3 (10.5mg, 0.04mmol), CuI (7.6mg, 0.04) and stirred at reflux for 8 hours. The solvent was evaporated under vacuum, and the obtained solid was purified by silica gel column chromatography to obtain the target compound BA.

[0029] 1 H NMR (400MHz, CDCl 3 )δ(ppm):8.57-8.55(d,2H),8.40(s,1H),8.01-7.99(d,2H),7.57-7.47(m,7H),7.36-7.34(m,2H),6.07 (s,1H),2.91(s,3H),2.62(s,3H),1.72(s,3H),1.43(s,3H).ESI-HRMS):m / z, Calcd for[M+H] + C 35 h 28 BYZGR 2 + :525.2308,foun...

Embodiment 2

[0030] Embodiment 2 (BA produces to photosensitizer MB illumination 1 o 2 quantitative detection):

[0031] Add 3.0ml of 10μM BA and 10μM MB air-saturated dichloromethane / acetonitrile (v / v=1:1) mixed solution into a quartz cuvette, shake well, then add a 650nm high-pass filter in front of the xenon lamp, power About 0.2mW. Shake the solution evenly after a certain period of light, and measure the absorption spectrum and fluorescence spectrum. 1 o 2 Schematic diagram of yield variation.

[0032] Figure 5(a) shows the change of the absorption intensity of the system, indicating that with 1 o 2 As production increases, BA absorption intensity decreases while BA EPO The absorption intensity rises, and the absorption spectrum shifts blue; Figure 5(b) shows the linear fitting curve of the 518nm / 545nm absorbance ratio with the illumination time, and the linear regression constant of the linear fitting curve is 0.9991, indicating that the probe can quantitatively determine the ...

Embodiment 3

[0033] Embodiment 3 (BA is to 1 o 2 optional):

[0034] Add 2.0ml of 10μM BA air-saturated dichloromethane / acetonitrile (v / v=1:1) mixed solution into a quartz cuvette, then add 300.0μM oxidizing substances (oxidizing substances include hydrogen peroxide, hypochlorite, single line Oxygen, tert-butanol peroxide, nitrosyl peroxide (ONOO - )) in ethanol solution 1.0ml, shake the solution, equilibrate for 1h, measure the fluorescence spectrum. Add 1.0ml of ethanol as a control group. Figure 6 Indicates the change in fluorescence of the system after adding oxidative compounds to probe BA, it can be seen that probe BA is 1 o 2 Be selective.

technical field

[0001] The present invention relates to a class of fluorescent probes for selectively detecting singlet oxygen in a solution phase, specifically, a class of fluorescent probes in 1 o 2 Fluorescent probes whose fluorescence is enhanced or whose emission wavelength is changed in the presence of a fluorescent probe. Background technique

[0002] 1 o 2 It is a highly reactive reactive oxygen species (ROS), which can chemically react with a variety of organic molecules, and plays a vital role in the fields of life sciences and photocatalysis. 1 o 2 The detection methods mainly include the following: 1270nm 1 o 2 Direct detection of luminescence, electron spin resonance (ESR), chemiluminescent probe and fluorescent probe methods (Nosaka Y; Nosaka A.Y. Chemical Reviews, 2017, 117, 11302). Fluorescent probes are effective in detecting 1 o 2 It is an important method with strong specificity, good repeatability, and high sensitivity. It can also perform single...

Examples

Embodiment 1

[0026] Embodiment 1 (synthesis of probe):

[0027] Such as image 3 As shown, the structure of the probe compound used in the examples is represented by the code BA, and the boron pyrrole precursor used in the synthesis of the probe compound is represented by the code B.

[0028] Synthesis of BA: Under nitrogen protection, B (0.09g, 0.2mmol) and A (0.085g, 0.42mmol) were dissolved in a mixed solvent of 5ml of anhydrous triethylamine and 10ml of anhydrous tetrahydrofuran, and Pd(PPh 3 ) 2 Cl 2 (14mg, 0.02mmol), PPh 3 (10.5mg, 0.04mmol), CuI (7.6mg, 0.04) and stirred at reflux for 8 hours. The solvent was evaporated under vacuum, and the obtained solid was purified by silica gel column chromatography to obtain the target compound BA.

[0029] 1 H NMR (400MHz, CDCl 3 )δ(ppm):8.57-8.55(d,2H),8.40(s,1H),8.01-7.99(d,2H),7.57-7.47(m,7H),7.36-7.34(m,2H),6.07 (s,1H),2.91(s,3H),2.62(s,3H),1.72(s,3H),1.43(s,3H).ESI-HRMS):m / z, Calcd for[M+H] + C 35 h 28 BYZGR 2 + :525.2308,foun...

Embodiment 2

[0030] Embodiment 2 (BA produces to photosensitizer MB illumination 1 o 2 quantitative detection):

[0031] Add 3.0ml of 10μM BA and 10μM MB air-saturated dichloromethane / acetonitrile (v / v=1:1) mixed solution into a quartz cuvette, shake well, then add a 650nm high-pass filter in front of the xenon lamp, power About 0.2mW. Shake the solution evenly after a certain period of light, and measure the absorption spectrum and fluorescence spectrum. 1 o 2 Schematic diagram of yield variation.

[0032] Figure 5(a) shows the change of the absorption intensity of the system, indicating that with 1 o 2 As production increases, BA absorption intensity decreases while BA EPO The absorption intensity rises, and the absorption spectrum shifts blue; Figure 5(b) shows the linear fitting curve of the 518nm / 545nm absorbance ratio with the illumination time, and the linear regression constant of the linear fitting curve is 0.9991, indicating that the probe can quantitatively determine the ...

Embodiment 3

[0033] Embodiment 3 (BA is to 1 o 2 optional):

[0034] Add 2.0ml of 10μM BA air-saturated dichloromethane / acetonitrile (v / v=1:1) mixed solution into a quartz cuvette, then add 300.0μM oxidizing substances (oxidizing substances include hydrogen peroxide, hypochlorite, single line Oxygen, tert-butanol peroxide, nitrosyl peroxide (ONOO - )) in ethanol solution 1.0ml, shake the solution, equilibrate for 1h, measure the fluorescence spectrum. Add 1.0ml of ethanol as a control group. Figure 6 Indicates the change in fluorescence of the system after adding oxidative compounds to probe BA, it can be seen that probe BA is 1 o 2 Be selective.

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