Method for detecting an amine compound

Abstract

This invention discloses a method for detecting amine compounds. The method includes: mixing an amine compound with a fluorescent solution to generate a fluorescence change for detecting the amine compound; the fluorescent solution includes a polymer and a fluorescent molecular probe; the polymer monomer is selected from at least one of acrylate compounds and butyrate compounds; the fluorescent molecular probe is selected from anti-rigid-chromic fluorescent molecular probes. Compared with existing amine detection technologies, the fluorescent probe composite system of this application has stronger ability to identify different types of amines, a lower detection limit (as low as 3.5 ppt), and can respond to amines in different physical states.

Description

Technical Field

[0001] This application relates to a method for detecting amine compounds, belonging to the field of analytical detection technology. Background Technology

[0002] Due to the widespread presence and high toxicity of amines, their detection is a crucial task. Exposure to toxic amines can lead to severe irritation or health problems, such as organ damage or even death. Amines are also important components of many pharmaceuticals. Therefore, accurate and sensitive amine detection is essential in fields such as industrial safety, environmental monitoring, and environmental surveillance. Continued research and development of sensing materials promises to improve the sensitivity and selectivity of amine detection. Optical / fluorescent amine detection materials are particularly promising due to their ease of handling, visual readability, and portability.

[0003] To date, reported fluorescent probes have limited sensitivity due to the inherent limitations of their "one-to-one" stoichiometric sensing mechanism. Typically, an amine molecule interacts with only one (or at most a few) fluorescent molecules, and its impact on the overall emission of the fluorescence system is negligible. Therefore, a large number of amine molecules are required to achieve a detectable signal change, resulting in low detection sensitivity. Furthermore, most previously reported fluorescent probes cannot distinguish between primary, secondary, and tertiary amines because these amines have fairly similar physical and chemical properties, making it difficult to produce relatively comparable fluorescence signal changes. Existing patents show that fluorescent probes for amine detection can only reach the mM level, such as development number CN115850174A, while this patent achieves a fluorescence detection limit of 10. -11 M. Summary of the Invention

[0004] To address the aforementioned challenges, this invention proposes a method for detecting amine compounds. The method includes: mixing the amine compound with a fluorescent solution to generate a fluorescence change for detection; the fluorescent solution comprises a polymer and a fluorescent molecular probe; the polymer monomer is selected from at least one of acrylate compounds and butyrate compounds; the fluorescent molecular probe is selected from anti-rigid-chromic fluorescent molecular probes. This application proposes a "one-to-many" chain reaction sensing mechanism, where an analyte can interact with multiple fluorophores or trigger / inhibit amplification of fluorescence signals in a chain reaction. This mechanism can be likened to a "domino effect," where one event triggers a series of events, gradually amplifying the scale and impact. Therefore, the effect of an analyte on the entire fluorescence system increases exponentially, resulting in unprecedentedly high sensitivity.

[0005] The inventors have creatively developed an amine-based fluorescent co-assembly resembling a domino chain, comprising a fluorescent molecule (PTF1) and up to 40 non-emitting polymer chains (pPFPAs). The fluorophore PTF1 acts as a domino trigger, interacting with surrounding polymer repeating units (PFPAs, equivalent to domino blocks) via polar π interactions. This interaction leads to the flattening of the polymer chains, resulting in well-aligned and tightly stacked repeating units, analogous to well-aligned dominoes. These well-aligned and tightly stacked repeating units facilitate efficient spatial conjugation (TSC) along the polymer chains. The intensity of the yellow emission from the fluorescent co-assembly increases with the number of polymer chains (or repeating units) surrounding PTF1. This function is analogous to the domino effect; the more dominoes there are, the stronger the signal produced.

[0006] According to one aspect of this application, a method for detecting amine compounds is provided, the method comprising: mixing an amine compound with a fluorescent solution to generate a fluorescence change to detect the amine compound;

[0007] The fluorescent solution comprises a polymer and a fluorescent molecular probe;

[0008] The polymer monomer is selected from at least one of acrylate compounds and butyrate compounds;

[0009] The fluorescent molecular probe is selected from anti-rigid color-changing fluorescent molecular probes.

[0010] Optionally, the acrylate compound is selected from at least one of methyl acrylate, methyl acrylate derivatives, phenolic acrylate, phenolic acrylate derivatives, pentafluorophenolic acrylate, pentafluorophenolic acrylate derivatives, and 4-cyanophenyl 2-methylbutyrate.

[0011] Optionally, the anti-rigid-chromic fluorescent molecular probe is the anti-rigid-chromic fluorescent molecular probe PTF1.

[0012] Optionally, the amine compound is selected from at least one of decylamine, isopropylamine, n-propylamine, S-1-isopropylamine, n-octylamine, m-bromoaniline, cyclopentylamine, cyclopropylamine, aniline, diethylamine, and triethylamine.

[0013] Optionally, obtaining the fluorescent solution includes:

[0014] The polymer solution and the fluorescent molecular probe solution are mixed to obtain the fluorescent solution.

[0015] Optionally, the polymer solution further includes solvent I; the fluorescent molecular probe solution further includes solvent II.

[0016] Solvent I and solvent II are each independently selected from at least one of toluene, dichloromethane, and tetrahydrofuran.

[0017] Optionally, the molar ratio of the polymer to the fluorescent molecular probe is 5000:1 to 20000:1; wherein the polymer is calculated based on the molar mass of the polymer monomer molecules themselves.

[0018] Optionally, the molar ratio of the polymer to the fluorescent molecular probe is 10000:1; wherein the polymer is calculated based on the molar mass of the polymer monomer molecules themselves.

[0019] Optionally, the concentration of the anti-rigid-chromic fluorescent molecular probe in the fluorescent molecular probe solution is 2.5 × 10⁻⁶. -5 mol / L mol / L.

[0020] Optionally, the detection method includes:

[0021] Step S1: Prepare a fluorescent solution and test the fluorescence data I of the fluorescent solution;

[0022] Step S2: Mix the amine compound with the fluorescent solution to produce a fluorescence change, and test the fluorescence data II after the fluorescence change.

[0023] Step S3: Compare the fluorescence data I with the fluorescence data II to detect the type and concentration of the amine compound.

[0024] As a specific implementation, the detection method includes: adding a solution of the amine-containing compound to be tested into a fluorescent solution for detection; by sequentially and quantitatively adding the solution of the amine-containing compound, the color of the fluorescent system changes, and the effect of distinguishing different amines is achieved by the change in fluorescent color.

[0025] Optionally, the solvent in the solution containing the amine compound is toluene, and the concentration of the solution containing the amine compound is 0.001 mol / L.

[0026] Optionally, the fluorescence data I and the fluorescence data II are tested using a fluorescence spectrometer.

[0027] Optionally, the excitation wavelength of the fluorescence spectrometer is 360 nm.

[0028] The beneficial effects that this application can produce include:

[0029] In this invention, a supramolecular domino sensor was developed to detect amines via a "one-to-many" chain reaction mechanism. The supramolecular domino consists of a fluorescent molecule and up to 40 non-emissive polymer chains (pPFPAs), comprising over a thousand repeating units (PFPAs). Amine insertion into the domino chain causes disintegration, thus significantly quenching the yellow fluorescence. Due to these advantages, we have achieved near-picomolar amine detection, with a sensitivity four orders of magnitude lower than conventional fluorescent amine sensors based on a "one-to-one" sensing mechanism.

[0030] Furthermore, the varying reactivity of pPFPA to different amines allows for the differentiation of primary, secondary, and tertiary amines. Moreover, these sensors show great promise for air quality monitoring and drug detection. This study proposes a previously unreported "domino effect" sensing mechanism and provides a universal method for chemical detection that is unattainable by conventional approaches. Attached Figure Description

[0031] Figure 1 This is a schematic flowchart of the triethylamine detection method according to Embodiment 1 of the present invention;

[0032] Figure 2 This is the standard curve for the quantitative detection of triethylamine using a fluorescence spectrometer in Example 1 of the present invention;

[0033] Figure 3 This is the fluorescence detection limit curve of Example 1 of the present invention;

[0034] Figure 4 This is a comparison image of the fluorescence changes shown in Example 2 of the present invention under 254nm ultraviolet light irradiation. Detailed Implementation

[0035] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0036] Unless otherwise specified, the raw materials and reagents used in the embodiments of this application were all purchased commercially.

[0037] Example 1

[0038] like Figure 1 As shown, the triethylamine detection method of this embodiment includes the following steps:

[0039] (1) Construction of the domino fluorescence system

[0040] Preparation of the anti-rigid-chromic fluorescent molecule PTF1 solution:

[0041]

[0042] The anti-rigid chromogenic fluorescent molecule PTF1 was dissolved in toluene to prepare a concentration of 2.5 × 10⁻⁶ molar concentration.-4 A solution of mol / L.

[0043] Preparation of polymer solution (pPFPA):

[0044]

[0045] The polymer pPFPA was dissolved in toluene to prepare a 0.25 mol / L solution.

[0046] The polymer solution and the anti-rigid fluorescent molecule solution were prepared into a 10000:1 domino fluorescence system. (At this time, the PTF1 concentration was 2.5 × 10⁻⁶). -7 mol / L)

[0047] (2) Preparation of triethylamine solution:

[0048] Triethylamine solution was prepared sequentially in toluene to a molar concentration of 10. -3 mol / L, 10 -4 mol / L, 10 -5 mol / L, 10 -6 mol / L, 10 -7 mol / L, 10 -8 mol / L and 10 -9 mol / L.

[0049] Take 3 ml of the prepared fluorescence system and measure the standard fluorescence curve using a fluorescence spectrometer.

[0050] 10 μL of different amine solutions were added to the fluorescence system. It was found that as the amine concentration increased, the color of the fluorescence system gradually changed from yellow to blue. The standard fluorescence curve after the addition of amine solutions was measured using a fluorescence spectrometer.

[0051] like Figure 2 As shown in the figure, the detection fluorescence curves of different amine concentrations measured in this embodiment show that as the amine concentration increases, the peak at 570 nm gradually decreases, the peak at 455 nm gradually increases, and the fluorescence color changes from yellow to blue.

[0052] The detection method in this embodiment has a short detection time, low error, and a visual detection limit of 35 ppm. The visual results can be directly observed and judged by the naked eye under natural light.

[0053] like Figure 3 As shown, to determine the detection limit of triethylamine, three sets of fluorescence systems and triethylamine solutions of the same concentration were prepared, and tested using a fluorescence spectrometer to obtain standard fluorescence curves. I 455 / I 570 The ratio of fluorescence intensity was used as a standard to calculate the mean and standard deviation.

[0054] The detection limit for triethylamine was determined to be 3.5 ppt based on a signal-to-noise ratio greater than 3.

[0055] All experiments were repeated three times, demonstrating good accuracy.

[0056] Example 2

[0057] like Figure 4 As shown, the method for distinguishing different types of amine solutions based on a fluorescence color-changing system includes the following steps:

[0058] Eleven amines—decylamine, isopropylamine, n-propylamine, S-1-phenylethylamine, n-octylamine, m-bromoaniline, cyclopentylamine, cyclopropylamine, aniline, diethylamine, and triethylamine—were prepared into a 0.001 mol / L toluene solution.

[0059] The prepared fluorescence system was added in 400 μL drops into 11 identical NMR tubes.

[0060] Each of the eleven amine solutions was added dropwise in 10 μL to the fluorescent system prepared in Example 1, and the changes in fluorescence color were observed.

[0061] As the number of drops increases, the color of the fluorescent system can be observed to gradually change from yellow to blue under a 254nm UV lamp, and the rate of color change of the fluorescent system is also different due to the different types of amines.

[0062] Table 1. Eleven amines and their corresponding pKa values.

[0063] name CAS pKa decylamine 2016-57-1 10.64 Isopropylamine 75-31-0 10.63 n-Propylamine 107-10-8 10.71 S-1-Phenylacetylamine 2627-86-3 9.04 octylamine 111-86-4 10.65 m-bromoaniline 591-19-5 3.58 Cyclopentanylamine 1003-03-8 10.65 Cyclopropylamine 765-30-0 9.1 aniline 62-53-3 4.6 Diethylamine 109-89-7 11.09 Triethylamine 121-44-8 10.78

[0064] like Figure 4 As shown, the fluorescence color change rate is triethylamine > diethylamine > S-1-phenylethylamine > cyclopentylamine > n-octylamine > decanamine > n-propylamine > cyclopropylamine > isopropylamine > aniline > m-bromoaniline.

[0065] Different fluorescence change rates can be used to differentiate between different types of amines.

[0066] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for detecting amine compounds, characterized in that, The detection method includes: mixing an amine compound with a fluorescent solution to generate a fluorescence change in order to detect the amine compound; The fluorescent solution comprises a non-emissive polymer chain (pPFPA) and a fluorescent molecular probe; The non-emissive polymer chain (pPFPA) monomer is selected from at least one of acrylate compounds and butyrate compounds; The molar ratio of the non-emissive polymer chain (pPFPA) to the fluorescent molecular probe is 10000:1; wherein the non-emissive polymer chain (pPFPA) is calculated based on the molar mass of the non-emissive polymer chain (pPFPA) monomer molecule itself. The fluorescent molecular probe is the antirigor chromogenic fluorescent molecular probe PTF1; The detection method includes the following steps: S1, Prepare a fluorescent solution and test the fluorescence data I of the fluorescent solution; S2, mix the amine compound with the fluorescent solution to produce a fluorescence change, and test the fluorescence data II after the fluorescence change; S3, compare the fluorescence data I with the fluorescence data II to detect the type and concentration of the amine compound.

2. The detection method according to claim 1, characterized in that, The acrylate compound is selected from at least one of methyl acrylate, methyl acrylate derivatives, phenolic acrylate, phenolic acrylate derivatives, pentafluorophenolic acrylate, and pentafluorophenolic acrylate derivatives.

3. The detection method according to claim 1, characterized in that, The amine compound is selected from at least one of decylamine, isopropylamine, n-propylamine, S-1-isopropylamine, n-octylamine, m-bromoaniline, cyclopentylamine, cyclopropylamine, aniline, diethylamine, and triethylamine.

4. The detection method according to claim 1, characterized in that, The fluorescent solution is obtained by: The fluorescent solution is obtained by mixing a non-emissive polymer chain (pPFPA) solution and a fluorescent molecular probe solution.

5. The detection method according to claim 4, characterized in that, The non-emissive polymer chain (pPFPA) solution also includes solvent I; the fluorescent molecular probe solution also includes solvent II. Solvent I and solvent II are each independently selected from at least one of toluene, dichloromethane, and tetrahydrofuran.

6. The detection method according to claim 4, characterized in that, In the fluorescent molecular probe solution, the concentration of the anti-rigid-chromic fluorescent molecular probe is 2.5 × 10⁻⁶. -5 mol / L.

7. The detection method according to claim 1, characterized in that, The fluorescence data I and fluorescence data II were tested using a fluorescence spectrometer.

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