A compound for detecting organic phosphonate nerve agents and their hydrolysis products and its application

Abstract

The present invention belongs to the technical field of chemical sensor materials, and in particular to a compound for detecting organic phosphonate nerve agents and their hydrolyzates and their applications. The compound of the present invention is a mercaptopyridine amidoxime compound. The compound of the present invention can be pre-adsorbed on the surface of a noble metal substrate by self-assembly, and then the nerve agents and hydrolyzates in water and atmospheric environments are captured on the surface, thereby achieving rapid trace SERS detection.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical sensor materials, and in particular relates to a compound for detecting organic phosphonate nerve agents and hydrolyzates thereof and applications thereof. Background Art

[0002] Organophosphine nerve agents such as sarin, tabun, and soman are highly lethal. After skin contact or inhalation, they covalently bind to the body's acetylcholinesterase, affecting the function of the central nervous system and causing severe symptoms such as convulsions, respiratory depression, and cardiovascular failure. Therefore, the development of rapid trace detection technologies for organophosphine nerve agents is of strategic importance for public health and national security. Existing molecular detection technologies based on precious metal surface-enhanced Raman spectroscopy (SERS) offer the advantages of ultrasensitivity, fast response, fingerprint recognition, and non-destructive testing. They have been widely used in drug enforcement, pesticide residue detection, and rapid screening for illegal additives.

[0003] However, due to the small Raman scattering cross-section of organophosphonate molecules and their difficulty in stably adsorbing on precious metal substrates, there have been very few reports on the detection of nerve agents based on SERS technology in recent years. Therefore, there is an urgent need for a compound for detecting organophosphonate nerve agents and their hydrolysis products, and its application to address these issues. Summary of the Invention

[0004] In order to overcome the above-mentioned defects in the prior art, the present invention provides a compound for detecting organophosphonate nerve agents and their hydrolysis products and its application. The present invention can achieve rapid trace SERS detection.

[0005] To achieve one of the above purposes, the present invention adopts the following technical solutions:

[0006] A compound for detecting organic phosphonate nerve agents and their hydrolysis products is a mercaptopyridine amidoxime compound.

[0007] Preferably, the compound has the general structural formula:

[0008]

[0009] The value ranges of n1 and n2 are both 0-5, and n3 is 0 or 1.

[0010] To achieve the second objective, the present invention provides an application of a compound for detecting organophosphonate nerve agents and their hydrolysis products, comprising the following specific steps:

[0011] S1. Modify the compound on the surface of the noble metal solid substrate by molecular self-assembly;

[0012] S2, placing the noble metal solid substrate modified with the compound in an environment containing an organic phosphonate nerve agent;

[0013] S3. Finally, a Raman spectrometer is used to collect the SERS spectrum of the surface of the noble metal solid substrate.

[0014] Preferably, in step S2, the noble metal solid substrate modified with the compound is immersed in a solution containing an organic phosphonate nerve agent for 1-60 minutes, and then taken out and naturally dried.

[0015] Preferably, in step S2, the noble metal solid substrate modified with the compound is exposed to a gas atmosphere containing an organic phosphonate nerve agent for 5-10 minutes.

[0016] Preferably, in step S1, a compound solution is prepared, and then the noble metal solid substrate is immersed in the compound solution for 1-60 minutes, and then taken out and naturally dried.

[0017] Preferably, the compound solution is a solution prepared with methanol or ethanol as solvent and the compound as solute.

[0018] Preferably, the volume of the compound solution is 10-100 ml and the molar concentration is 10 -3 -10 -6 M.

[0019] Preferably, the size of the precious metal solid lining is 2-25 mm 2 .

[0020] Preferably, the noble metal solid substrate is composed of one of gold, silver and a gold-silver alloy.

[0021] The advantages of the present invention are:

[0022] (1) The compounds of the present invention can be modified on the surface of a precious metal solid substrate composed of gold, silver, copper and their alloys by molecular self-assembly, and then nerve agents and hydrolyzates in water and atmospheric environments are captured on the surface. The SERS characteristic peaks on the substrate surface are then detected by Raman spectrometry, thereby achieving rapid SERS detection of trace amounts of organophosphonate nerve agents and hydrolyzates.

[0023] (2) The compounds of the present invention have a high affinity for nerve agents and can effectively enrich nerve agents on the surface of the SERS substrate, thereby achieving not only efficient detection of nerve agents based on the SERS effect, but also detection of target molecules in liquid and gas environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the general structural formula of the compound of the present invention.

[0025] Figure 2This is a spectrum diagram of Example 1 of the present invention.

[0026] Figure 3 This is a spectrum diagram of Example 2 of the present invention. DETAILED DESCRIPTION

[0027] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0028] like Figure 1 As shown, a compound for detecting organophosphonate nerve agents and their hydrolysis products has the general structural formula:

[0029]

[0030] The value ranges of n1 and n2 are both 0-5, and n3 is 0 or 1.

[0031] Based on the principle of classic oximation reaction, the compound uses chlorocyanopyridine as raw material, which is first thiolated by the action of a sulfiding reagent, and then amidoximated by the action of hydroxylamine hydrochloride, thereby realizing the synthesis of pyridinethioamidooxime and finally preparing the compound of the present invention.

[0032] Application of a compound for detecting organophosphonate nerve agents and their hydrolysis products:

[0033] S1, using methanol or ethanol as solvent, prepare a volume of 10-100ml, a concentration of 10 -3 -10 -6 M compound solution, the size of which is 2-25mm 2 The precious metal solid substrate is immersed in the compound solution for 1-60 minutes, taken out and dried naturally;

[0034] S2, immersing the noble metal solid substrate in a solution containing an organic phosphonate nerve agent, taking it out after 1-10 minutes and letting it dry naturally;

[0035] or exposing the noble metal solid substrate to a gas atmosphere containing an organic phosphonate nerve agent for 5-10 minutes;

[0036] S3. Use handheld, portable or micro-confocal Raman spectrometer to collect SERS spectra on the surface of noble metal solid substrates at 710-770 cm -1 The characteristic peaks and intensities within the wavenumber range are used as criteria for qualitative identification and semi-quantitative detection of organophosphonate nerve agents and their hydrolysis products.

[0037] Example 1

[0038] The general structural formula of the compound is:

[0039]

[0040] Specific applications:

[0041] S1, using ethanol as solvent, with a volume of 50 ml and a concentration of 10 -5 M compound solution, the size of 9mm 2 The silver ball array substrate was immersed in the compound solution for 10 minutes, taken out and dried naturally;

[0042] S2, soaking the dried silver ball array substrate in a 1 ppm taben solution for 1 minute, taking it out and letting it dry naturally;

[0043] S3. Use a portable Raman spectrometer with an excitation wavelength of 785 nm to collect the SERS spectrum of the substrate surface. The spectrum is shown in the figure below. Figure 2 shown.

[0044] Example 2

[0045] The general structural formula of the compound is:

[0046]

[0047] Specific applications:

[0048] S1, using methanol as solvent, with a volume of 10 ml and a concentration of 10 -6 M compound solution, the size of 9mm 2 The gold ball array substrate was immersed in the compound solution for 5 minutes, taken out and dried naturally;

[0049] S2, exposing the dried gold ball array substrate to a 10 ppm sarin atmosphere for 2 minutes;

[0050] S3. Use a portable Raman spectrometer with an excitation wavelength of 785 nm to collect the SERS spectrum of the substrate surface. The spectrum is shown in the figure below. Figure 3 shown.

[0051] Depend on Figure 2-3 It can be seen that Figure 2-3The characteristic peaks of organic phosphonate nerve agents are obtained, which are the Raman vibrations of carbon-phosphine bonds unique to organic phosphonate nerve agents, and the peaks at other positions are all peaks of the mercaptopyridine amidoxime molecules selected in Examples 1-2; thus, it can be concluded that the compounds in Examples 1-2 have a high affinity for nerve agents and can effectively enrich nerve agents on the surface of the SERS substrate, thereby realizing efficient detection of nerve agents based on the SERS effect, and further realizing the detection of target molecules in liquid and gas environments.

[0052] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A compound for detecting organophosphonate nerve agents and their hydrolysis products, characterized in that: The compound is a mercaptopyridine amidoxime compound; the general structural formula of the compound is: One of them.

2. A use of the compound for detecting organophosphonate nerve agents and their hydrolysis products as claimed in claim 1, characterized in that: The specific steps are as follows: S1. Modify the compound on the surface of the precious metal solid substrate by molecular self-assembly; S2, placing the noble metal solid substrate modified with the compound in an environment containing an organic phosphonate nerve agent; S3. Finally, a Raman spectrometer is used to collect the SERS spectrum of the surface of the precious metal solid substrate.

3. The use of a compound for detecting organic phosphonate nerve agents and their hydrolysis products according to claim 2, characterized in that: In step S2, the noble metal solid substrate modified with the compound is immersed in a solution containing an organic phosphonate nerve agent for 1-60 minutes, and then taken out and naturally dried.

4. The use of a compound for detecting organic phosphonate nerve agents and their hydrolysis products according to claim 2, characterized in that: In step S2, the noble metal solid substrate modified with the compound is exposed to a gas atmosphere containing an organic phosphonate nerve agent for 5-10 minutes.

5. The use of a compound for detecting organic phosphonate nerve agents and their hydrolysis products according to claim 2, characterized in that: In step S1, a compound solution is prepared, and then the precious metal solid substrate is immersed in the compound solution for 1-60 minutes, and then taken out and naturally dried.

6. The use of a compound for detecting organic phosphonate nerve agents and their hydrolysis products according to claim 5, characterized in that: The compound solution is a solution prepared with methanol or ethanol as solvent and the compound as solute.

7. The use of a compound for detecting organic phosphonate nerve agents and their hydrolysis products according to claim 5, characterized in that: The volume of the compound solution is 10-100 ml, and the molar concentration is 10 -3 -10 -6 M.

8. The use of a compound for detecting organic phosphonate nerve agents and their hydrolyzates according to claim 2, characterized in that: The size of the precious metal solid lining is 2-25 mm 2 .

9. The use of a compound for detecting organic phosphonate nerve agents and their hydrolysis products according to claim 2, characterized in that: The precious metal solid substrate is composed of one of gold, silver and a gold-silver alloy.

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