A method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds

Abstract

This invention relates to a method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds. The method utilizes the long afterglow induced by the specific interaction between the analyte and a matrix as the output signal to achieve naked-eye detection of the analyte. The aromatic compounds are aromatic pollutants and aromatic organic metabolites. This invention utilizes the organic long afterglow induced by mixing the analyte G with the host molecule H through methods such as heating and melting, solvent evaporation and crystallization, matrix adsorption, and paper chromatography as a monitoring signal to achieve ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds. The afterglow induced by the analyte G is highly dependent on the type and content of the analyte and matrix, which gives this detection method extremely high sensitivity and selectivity. The method is simple to operate, rapid, visible to the naked eye, requires inexpensive and readily available materials, and provides stable results.

Description

Technical Field

[0001] This invention relates to a method for the naked-eye detection of trace aromatic compounds (pollutants, organic metabolites, food additives, prohibited substances, etc.) with ultra-high sensitivity. Background Technology

[0002] In recent years, the high sensitivity and dependence between afterglow and dopants have made two-component room-temperature phosphorescent systems highly promising for ultra-high sensitivity detection. During detection, the long-lifetime emission of afterglow can be utilized to reduce or even eliminate the background signal of fluorescence emission by adjusting the delay time, significantly improving the signal-to-noise ratio. The afterglow emission induced by dopants is highly dependent on the dopant; different combinations of dopants and matrices induce afterglow with different emission wavelengths and durations. Furthermore, studies have shown that trace amounts of dopants (0.01%) can induce afterglow visible to the naked eye. Therefore, if the analyte can act as a dopant, interacting with a suitable matrix to induce afterglow emission, the color (wavelength), intensity, and other signals of the afterglow signal can be used as output signals to achieve highly sensitive and specific detection of the analyte. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and to achieve ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds (pollutants, organic metabolites, food additives, contraband, explosives, etc.) by using the analyte as guest molecule G and the matrix as host molecule H as a mixture induced by methods such as heating and melting, solvent evaporation and crystallization, matrix adsorption, or paper chromatography.

[0004] A method for detecting trace amounts of aromatic compounds with ultra-high sensitivity and specificity using the naked eye utilizes the long afterglow induced by the specific interaction between the analyte and a matrix after mixing as the output signal to achieve naked-eye detection of the analyte. The aromatic compounds are aromatic pollutants and aromatic organic metabolites.

[0005] Furthermore, the analyte is compound G, which has an aromatic structure and potential room-temperature phosphorescence emission properties. The molecular structure of compound G includes, but is not limited to, the following structures:

[0006]

[0007] In this context, the host molecule H serves as the matrix:

[0008]

[0009] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12R 13 The substituents are selected from hydrogen, methyl, methoxy, phenyl, hydroxyl, fluorine, chlorine, bromine, and amino atoms. The substituents can be located at the ortho, meta, or para positions.

[0010] Furthermore, the content of the analyte is higher than 0.01 nmol.

[0011] Furthermore, the ratio of the analyte to the main matrix is ​​greater than 1:10. 6 .

[0012] Furthermore, the mixing of the analyte and the matrix can be achieved by heating and melting: after the main molecule H and the analyte G are mixed evenly, they are heated and melted, and the sample is obtained after complete cooling.

[0013] Furthermore, the mixing of the analyte and the matrix can be achieved through solvent evaporation crystallization: the analyte G and the main molecule H are mixed in a flask, and a suitable amount of a good solvent such as dichloromethane is added to dissolve them completely, resulting in a mixed solution. The solvent is allowed to evaporate naturally at room temperature, and the solution is allowed to crystallize in a cool, dry place to obtain the material.

[0014] Furthermore, the mixing of the analyte and the matrix can be achieved through matrix adsorption: the solution of the analyte (1.0 × 10⁻⁶) is mixed with the matrix. -3 A solution of 0.1 g / mol and a matrix (0.1 g / mol) is mixed in a certain ratio, and 10 μL is dropped onto a filter paper with a diameter of 0.6 cm. The solvent is allowed to evaporate naturally at room temperature to obtain the desired filter paper.

[0015] Furthermore, the mixing of the analyte and the matrix can be achieved using paper chromatography: analyte G and the main molecule H are mixed in a beaker, and dichloromethane is added to dissolve them completely, yielding a mixed solution. A small amount of the mixed solution is used as the developing solvent in a developing tank. One end of a filter paper strip (50×5mm) is immersed in the developing solvent. When the solvent reaches a position 5mm from the top of the paper strip, the paper strip is removed, and the solvent is dried. A bright afterglow can be observed under ultraviolet light.

[0016] Furthermore, different afterglow colors can be used as detection signals to reflect the type of analyte.

[0017] Furthermore, the duration of the afterglow can be used as a detection signal to reflect the content of the analyte.

[0018] Furthermore, the intensity of phosphorescence can be used as a detection signal to reflect the content of the analyte.

[0019] Unlike current detection methods based on changes in certain chemical reactions or physical properties (such as absorption, emission, refractive index, photophysical properties, etc.), this invention utilizes the long afterglow induced by mixing the analyte G and matrix H through methods such as heating and melting, solvent evaporation and crystallization, matrix adsorption, and paper chromatography as a monitoring signal to achieve ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds (pollutants, organic metabolites, food additives, prohibited substances, etc.). The key to this invention is the use of the analyte as a dopant to form a two-component room-temperature phosphorescent material with ultra-long afterglow, using the long afterglow as the output signal to achieve analyte detection. The dependence between afterglow and the dopant gives the method of this invention ultra-high sensitivity and selectivity. The detection limit for aromatic compounds using matrix adsorption can be estimated to reach 0.01 ppm. This strategy has advantages such as speed, low cost, ease of operation, ultra-high sensitivity, and high selectivity. This strategy has extremely high feasibility and application value in the specific and rapid detection of aromatic environmental hazards, explosives, or biological metabolites. Attached Figure Description

[0020] To more intuitively illustrate the features of the embodiments of this invention, the invention will be further described below in conjunction with the accompanying drawings and embodiments. It is obvious that the described embodiments are only a partial application of the invention, and not all of it. Unless otherwise specified, the materials, reagents, etc., used in the following embodiments are all commercially available.

[0021] Figure 1 This is a photograph of the afterglow induced after the analyte and matrix are mixed under the detection method of Example 1.

[0022] Figure 2 This is a photograph of the afterglow induced after the analyte and matrix are mixed under the detection method of Example 2.

[0023] Figure 3 This is a photograph of the afterglow induced after the analyte and matrix are mixed under the detection method of Example 3.

[0024] Figure 4 This is a photograph of the afterglow induced after the analyte and matrix are mixed under the detection method of Example 4.

[0025] Figure 5 This image shows the relationship between the content of analyte G1 and the luminescence intensity under the heating-melting detection method.

[0026] Figure 6 These are emission spectra of analyte G1 mixed with matrix H1 in different molar ratios under the heating-melting detection method.

[0027] Figure 7 This is a photograph of the afterglow induced after the analyte and matrix are mixed under the detection method of Example 5. Detailed Implementation

[0028] This invention provides a method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds (pollutants, organic metabolites, food additives, contraband, explosives, etc.) using organic long afterglow as a monitoring signal. The following detailed and rigorous description of the patent's concept is provided in conjunction with specific embodiments. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the materials and reagents used in the following embodiments are commercially available. All other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0029] Example 1

[0030] The analyte guest molecule G29 (5 mg, 0.0284 mmol) and the host molecule H3 (0.28 g, 1.413 mmol) were mixed uniformly in a petri dish. Under this detection method, the molar ratio of analyte to matrix was 1:50. The mixture was heated to 50 °C until fully melted, and then slowly cooled to room temperature to obtain the desired material. This material exhibits a long yellow-green afterglow under ultraviolet light, with an afterglow time of 1 s. Figure 1 This indicates that analyte G29 can specifically interact with matrix compound H3, inducing a long afterglow. A response occurs when the molar ratio of analyte G29 to matrix compound H3 is greater than 1:50, producing a yellow-green long afterglow with a duration of 1 second.

[0031] Example 2

[0032] The analyte, guest molecule G3 (6.26 mg, 0.0274 mmol), and host molecule H1 (5 g, 0.0274 mol), were mixed in a flask and dissolved completely in 10 mL of dichloromethane to obtain a mixed solution. Under this detection method, the molar ratio of analyte to matrix is ​​1:1000. The solvent was allowed to evaporate naturally at room temperature, and the solution was allowed to crystallize in a cool, dry place to obtain the desired material. A bright red afterglow was observed under ultraviolet light, with an afterglow time of 0.5 s. Figure 2 The color of the afterglow differs from that of Example 1, indicating that the analyte G3 can specifically interact with the matrix compound H1, inducing a bright red long afterglow with a duration of 0.5 s.

[0033] Example 3

[0034] The analyte, guest molecule G16 (2.0 mg, 6.66 μmol) and host molecule H3 (13.20 g, 0.066 mol), were mixed in a beaker at a molar ratio of 1:10000. A small amount of dichloromethane was added and stirred thoroughly to dissolve the mixture, yielding a mixed solution. A small amount of the mixed solution was used as the developing solvent in a developing tank. Dry filter paper was cut into rectangular strips, and one end of the strip was immersed in the developing solvent. When the solvent reached 5 mm from the top of the strip, the strip was removed, and the solvent was dried. Under ultraviolet light, a bright yellow afterglow was observed, with an afterglow time of 8 s. Figure 3 Compared with Example 1, different analytes G29 and G16 showed different afterglow colors and durations in the same matrix H3, indicating that there is a high dependence between afterglow and analytes, and that afterglow color can be used as a detection signal to reflect the type of analyte.

[0035] Example 4

[0036] Prepare 25 ml of a good solvent solution of analyte G1 (1.0 × 10⁻⁶). -3 A 10 mL solution of a 0.1 g / mol concentration good solvent for matrix H1 was prepared. Mixed solutions were prepared according to different doping ratios of the analyte guest molecule G1 and the host molecule H1. 10 μL of each solution was dropped onto a 0.6 cm diameter filter paper. The solvent was allowed to evaporate naturally at room temperature to obtain the desired filter paper. Under ultraviolet light irradiation, filter paper with different ratios exhibited different lifetimes and luminescence intensities of yellow afterglow; that is, luminescence intensity and lifetime can reflect the content of the analyte. Under this detection method, the detection limit can reach 0.01 ppm. Figure 4 This indicates that different combinations of analyte G1 and matrix H1 induce different emission intensities and durations of afterglow. Stronger phosphorescence intensity and longer afterglow duration indicate a higher analyte content; therefore, phosphorescence intensity and afterglow duration can be used as detection signals to reflect the analyte content.

[0037] Example 5

[0038] Guest molecule G1 and host molecule H1 were mixed uniformly in a petri dish at different molar ratios (0.01‰ to 2.0‰). The mixture was heated to 50°C until fully melted, and then slowly cooled to room temperature to obtain the desired material. When the molar ratio increased from 0.02‰ to 0.2‰, the luminescence intensity at 560 nm increased rapidly, while the increase slowed when the molar ratio increased from 0.2‰ to 2.0‰. Fitting analysis revealed an exponential relationship between the luminescence intensity at 560 nm and the doping ratio. Figure 5 Similarly, in the emission spectrum, as the content of the analyte G1 increases from 0.01‰ to 2‰, the emission peak at 560 nm gradually increases. Figure 6The relationship between doping ratio and phosphorescence intensity provides a possibility for the quantitative detection of polycyclic aromatic hydrocarbons.

[0039] Example 6

[0040] Two roast ducks were randomly purchased from different markets. After pretreatment, residues of 1.86g and 2.42g (named 1 and 2) were obtained from the two ducks (30.00g each). 1 / 40 of the extract was mixed with BPO (0.4g), heated to a melting point, and thoroughly mixed. The mixture was then slowly cooled to room temperature to obtain the desired crystalline material. Under ultraviolet light irradiation, a clear yellow afterglow of 1 / BPO was observed, but its duration was very limited. Figure 7 No significant afterglow was observed in 2 / BPO, indicating that the polycyclic aromatic hydrocarbon (PAH) content was below the detection limit. The PAH concentration of sample 1 was calculated to be 10.67 mg / kg.

[0041] The above are preferred embodiments of the present invention. It should be stated that, without inventive effort, those skilled in the art can make modifications to the present invention and apply it to other embodiments. The present invention is not limited to the above embodiments, and any modifications made without departing from the principle of the present invention should fall within the protection scope of the present invention.

Claims

1. A method for detecting trace amounts of aromatic compounds with ultra-high sensitivity and specificity using the naked eye, characterized in that, The naked-eye detection of the analyte is achieved by using the long afterglow induced by the specific interaction between the analyte and the matrix as the output signal; the aromatic compound is an aromatic pollutant or an aromatic organic metabolite; the analyte is compound G, which has an aromatic structure and potential room-temperature phosphorescence emission properties, and the molecular structure of compound G is as follows: The matrix is ​​the host molecule H: wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 are selected from a hydrogen atom, a methyl group, a methoxy group, a phenyl group, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom and / or an amino group; the position of the substituent is ortho, meta or para.

2. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The content of the analyte is higher than 0.01 nmol.

3. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The ratio of the analyte to the main matrix is ​​greater than 1:10 6 .

4. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The mixing of the analyte and the matrix is ​​achieved by heating and melting: the host molecule H and the analyte G are mixed evenly, heated and melted, and then completely cooled to obtain the desired sample.

5. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The mixing of the analyte and the matrix is ​​achieved by solvent evaporation crystallization: the analyte G and the main molecule H are mixed in a flask, and an appropriate amount of dichloromethane solvent is added to dissolve them completely to obtain a mixed solution; the solvent is allowed to evaporate naturally at room temperature, and the solution is allowed to stand in a cool and dry place to crystallize and obtain the material.

6. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The mixing of the analyte and the matrix is ​​achieved by matrix adsorption: the solution of the analyte and the solution of the matrix are mixed in a certain ratio, 10 μL is taken and dropped onto a filter paper with a diameter of 0.6 cm, and the solvent is allowed to evaporate naturally at room temperature to obtain the desired filter paper.

7. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The mixing of the analyte and the matrix was achieved by paper chromatography: the analyte G and the main molecule H were mixed in a beaker and dissolved completely in dichloromethane to obtain a mixed solution; a small amount of the mixed solution was taken as the developing solvent in the developing tank, one end of the filter paper strip was immersed in the developing solvent, and when the solvent reached a position 5 mm from the top of the paper strip, the paper strip was removed and the solvent was dried; a bright afterglow was observed under ultraviolet light.

8. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, Different afterglow colors can be used as detection signals to reflect the type of analyte.

9. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The duration of the afterglow serves as a detection signal, reflecting the content of the analyte.

10. The method for ultra-high sensitivity and specific naked-eye detection of trace aromatic compounds according to claim 1, characterized in that, The intensity of phosphorescence serves as a detection signal, reflecting the content of the analyte.

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