Fluorescent probe for formaldehyde detection and preparation method and application thereof

Abstract

The invention discloses a fluorescent probe for formaldehyde detection and a preparation method and application thereof. The novel fluorescent probe is called HDBC for short, and the structural formula of the novel fluorescent probe is shown as the following formula I in the specification. The novel fluorescent probe HDBC has good response to formaldehyde and can be used for rapid detection of trace formaldehyde in the environment and organisms. The probe is simple in synthesis process and high in yield, and the used reagents are cheap and easy to obtain; the prepared probe is sensitive to formaldehyde response, and the defects that an existing formaldehyde fluorescent probe is complex in synthesis process, tedious in step, expensive in used reagent, insensitive to response and the like are overcome. Therefore, the formaldehyde probe HDBC has an application prospect.

Description

technical field

[0001] The invention belongs to the technical field of environmental monitoring, and relates to a fluorescent probe for formaldehyde detection, a preparation method and application thereof. The probe of the present invention can observe the color change of the solution with naked eyes, thereby judging whether there is formaldehyde in the solution. In addition, the approximate content of formaldehyde can be judged by observing the changes in the broad spectrum of fluorescence, so as to achieve the purpose of quantitative detection. Background technique

[0002] Formaldehyde (HCHO) is a colorless and irritating gas that is irritating to human eyes and nose. Long-term inhalation of formaldehyde can cause diseases such as nasal cancer, digestive tract cancer, lung cancer, and brain cancer. In addition, formaldehyde, as an endogenous substance in the human body, can be catalyzed by biological enzymes such as semicarbazide-sensitive amine oxidase. Studies have f...

Examples

Embodiment 1

[0042] Synthesis of Compound 1:

[0043] Under a nitrogen atmosphere, add 1.00g of 2-bromo-1,8-naphthalene anhydride to 100mL of absolute ethanol, then add 0.41g of 4-aminobutyric acid, and reflux at 80°C for 12h. After the reaction, crystals precipitated after cooling to room temperature, filtered, and washed three times with absolute ethanol to obtain 0.98 g of off-white intermediate compound 1 (yield 74.8%).

[0044] NMR characterization of compound 1: 1 H NMR (400MHz, DMSO-d 6 )δ (ppm): 12.04 (1H, s), 8.40 (2H, dd, J 1 =7.2Hz,J 2=8.2Hz), 8.17(1H,d,J=7.9Hz),8.07(1H,d,J=7.9Hz), 7.87(1H,t,J=6.9Hz),4.03(2H,t,J=6.9 Hz), 2.31(2H, t, J=7.2Hz), 1.84–1.91(2H, m). 13 C NMR (101MHz, DMSO-d 6 )δ (ppm): 174.48, 163.32, 163.27, 132.83, 131.84, 131.63, 131.21, 130.03, 129.43, 129.06, 128.57, 123.07, 122.30, 39.34, 31.79, 23.37.

[0045] Compound 1 1 H NMR spectrum and 13 The C NMR spectra are as follows figure 1 and figure 2 shown.

[0046] Synthesis of Probe HDBC:

[0047]...

Embodiment 2

[0051] Mass spectra of probe HDBC before and after reacting with formaldehyde aqueous solution

[0052] The probe HDBC prepared in Example 1 was dissolved in distilled water to make a test solution with a concentration of 0.1 mg / mL, and the relative molecular weight of the probe was tested by liquid chromatography-mass spectrometry (HPLC-MS), such as Figure 5 , where the signal peak at 312.1 is compound 1+[H + ]. Then add 150 μ M formaldehyde aqueous solution to the above-mentioned probe solution to be tested, after mixing evenly, test the relative molecular weight of the mixed solution with liquid mass spectrometry (HPLC-MS), such as Figure 6 As shown, the signal peak at 325.1 is the final product + [H + ]. Based on the above experimental conclusions, it can be preliminarily proved that the reaction process is consistent with the probe design concept of the present invention.

Embodiment 3

[0054] Changes of Titration Absorbance of Probe HDBC to Formaldehyde Aqueous Solution with Different Concentrations

[0055] The probe HDBC prepared in Example 1 was dissolved in DMSO to prepare a probe mother solution with a concentration of 1 mM; 37% formaldehyde was added to distilled water to prepare a formaldehyde mother solution with a formaldehyde concentration of 1 mM. The above 1 mM probe mother solution was diluted to 10 μM with DMSO to prepare the test solution, and the solution used was sonicated for 10 min with an ultrasonic instrument before use. At room temperature, use a disposable pipette to pipette 3mL of the above-mentioned solution to be tested and add it to a quartz cuvette to start the test; , 80, 90, 100 (unit: μM). The above-mentioned formaldehyde solutions of different concentrations are added to the above-mentioned liquid to be tested, and after mixing evenly, the change of the absorbance of the reaction between the liquid to be tested and different ...

technical field

[0001] The invention belongs to the technical field of environmental monitoring, and relates to a fluorescent probe for formaldehyde detection, a preparation method and application thereof. The probe of the present invention can observe the color change of the solution with naked eyes, thereby judging whether there is formaldehyde in the solution. In addition, the approximate content of formaldehyde can be judged by observing the changes in the broad spectrum of fluorescence, so as to achieve the purpose of quantitative detection. Background technique

[0002] Formaldehyde (HCHO) is a colorless and irritating gas that is irritating to human eyes and nose. Long-term inhalation of formaldehyde can cause diseases such as nasal cancer, digestive tract cancer, lung cancer, and brain cancer. In addition, formaldehyde, as an endogenous substance in the human body, can be catalyzed by biological enzymes such as semicarbazide-sensitive amine oxidase. Studies have f...

Examples

Embodiment 1

[0042] Synthesis of Compound 1:

[0043] Under a nitrogen atmosphere, add 1.00g of 2-bromo-1,8-naphthalene anhydride to 100mL of absolute ethanol, then add 0.41g of 4-aminobutyric acid, and reflux at 80°C for 12h. After the reaction, crystals precipitated after cooling to room temperature, filtered, and washed three times with absolute ethanol to obtain 0.98 g of off-white intermediate compound 1 (yield 74.8%).

[0044] NMR characterization of compound 1: 1 H NMR (400MHz, DMSO-d 6 )δ (ppm): 12.04 (1H, s), 8.40 (2H, dd, J 1 =7.2Hz,J 2=8.2Hz), 8.17(1H,d,J=7.9Hz),8.07(1H,d,J=7.9Hz), 7.87(1H,t,J=6.9Hz),4.03(2H,t,J=6.9 Hz), 2.31(2H, t, J=7.2Hz), 1.84–1.91(2H, m). 13 C NMR (101MHz, DMSO-d 6 )δ (ppm): 174.48, 163.32, 163.27, 132.83, 131.84, 131.63, 131.21, 130.03, 129.43, 129.06, 128.57, 123.07, 122.30, 39.34, 31.79, 23.37.

[0045] Compound 1 1 H NMR spectrum and 13 The C NMR spectra are as follows figure 1 and figure 2 shown.

[0046] Synthesis of Probe HDBC:

[0047]...

Embodiment 2

[0051] Mass spectra of probe HDBC before and after reacting with formaldehyde aqueous solution

[0052] The probe HDBC prepared in Example 1 was dissolved in distilled water to make a test solution with a concentration of 0.1 mg / mL, and the relative molecular weight of the probe was tested by liquid chromatography-mass spectrometry (HPLC-MS), such as Figure 5 , where the signal peak at 312.1 is compound 1+[H + ]. Then add 150 μ M formaldehyde aqueous solution to the above-mentioned probe solution to be tested, after mixing evenly, test the relative molecular weight of the mixed solution with liquid mass spectrometry (HPLC-MS), such as Figure 6 As shown, the signal peak at 325.1 is the final product + [H + ]. Based on the above experimental conclusions, it can be preliminarily proved that the reaction process is consistent with the probe design concept of the present invention.

Embodiment 3

[0054] Changes of Titration Absorbance of Probe HDBC to Formaldehyde Aqueous Solution with Different Concentrations

[0055] The probe HDBC prepared in Example 1 was dissolved in DMSO to prepare a probe mother solution with a concentration of 1 mM; 37% formaldehyde was added to distilled water to prepare a formaldehyde mother solution with a formaldehyde concentration of 1 mM. The above 1 mM probe mother solution was diluted to 10 μM with DMSO to prepare the test solution, and the solution used was sonicated for 10 min with an ultrasonic instrument before use. At room temperature, use a disposable pipette to pipette 3mL of the above-mentioned solution to be tested and add it to a quartz cuvette to start the test; , 80, 90, 100 (unit: μM). The above-mentioned formaldehyde solutions of different concentrations are added to the above-mentioned liquid to be tested, and after mixing evenly, the change of the absorbance of the reaction between the liquid to be tested and different ...

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