CN115403514B - Compound and application thereof in detection of organic phosphate nerve agent simulator product - Google Patents

Compound and application thereof in detection of organic phosphate nerve agent simulator product Download PDF

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CN115403514B
CN115403514B CN202211200549.6A CN202211200549A CN115403514B CN 115403514 B CN115403514 B CN 115403514B CN 202211200549 A CN202211200549 A CN 202211200549A CN 115403514 B CN115403514 B CN 115403514B
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solution
nerve agent
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fluorescence
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CN115403514A (en
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付艳艳
张五昆
程建功
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Shanghai Institute of Microsystem and Information Technology of CAS
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Abstract

The invention discloses a compound and application thereof in detection of an organic phosphate nerve agent simulator product, and relates to the field of chemical sensor materials. The structural general formula is shown as the following formula (I):in formula (I), n is 0 or 1, n 1 Is taken from 1 to 3; n is n 2 And n 3 All from 0 to 6. The compound provided by the application has the advantages of simple preparation method, high yield, easy separation and high purity, can be used for preparing detection solution, a sensing film, detection test paper and the like, has sensitive response to the organophosphorus nerve agent simulant, and can be used for rapidly and accurately detecting the organophosphorus nerve agent simulant in liquid phase or gas phase.

Description

Compound and application thereof in detection of organic phosphate nerve agent simulator product
Technical Field
The invention relates to the field of chemical sensor materials, in particular to a compound and application thereof in detection of organic phosphate nerve agent simulant products.
Background
The detection of organophosphorus nerve agents such as sarin, takara, bowman and the like, which are frequently used as chemical weapons by terrorists, is increasingly being regarded by researchers in China and worldwide. Such neurotoxic agents are characterized by: can be used for treating dysfunction of central nervous system, and can be fatal when it is applied by skin, eye contact or inhalation through respiratory tract to inhibit the action of acetylcholinesterase. And the toxicants are mostly colorless, odorless and transparent liquid at normal temperature, are easy to dissolve in water, have extremely high volatility and easily enter human bodies. Therefore, the development of simple and convenient detection technology for the substances has important significance for public health and national defense safety. However, since the use of the sarin-type nerve agent is strictly regulated due to the extremely toxic nature, substances having a similar chemical structure to the sarin-type nerve agent but less toxic such as Diethyl Chlorophosphate (DCP) are generally selected as the mimics in practical studies. Whereas nerve agent chemical activity is generally higher than nerve agent mimics, in the same case, a chemical probe having high selectivity for the organophosphorus nerve agent mimics is more sensitive to the organophosphorus nerve agent, so that detection studies using nerve agent mimics are widely accepted as alternatives to those of nerve agents.
Currently, detection of nerve gas mimics can be accomplished by conventional detection methods such as mass spectrometry, ion mobility spectrometry, electrochemical sensors, and enzyme sensors. However, some of these conventional tests are limited by expensive test equipment, and some of them have too long test cycle to meet the requirement of on-site real-time rapid response to organophosphate nerve agents. Colorimetry and fluorescence detection have received much attention for their rapid response, visual recognition and instrument simplicity. To date, few literature reports have been made on detection of nerve agent mimics using colorimetry and fluorescence (Tetrahedron, 2014,2966-2970; J.Am.chem. Soc.2006,128,5041-5048;ACS Macro Lett,2015,4, 138-142), but most of these probes are limited to detection in solution, and few materials capable of achieving gas phase detection are generally complex in structure and cumbersome to synthesize. Therefore, there is still a difficulty in designing a simple and efficient organophosphorus nerve agent mimetic sensing material that can be used for both liquid and gas phase detection.
Disclosure of Invention
The invention provides a compound and application thereof in detection of an organic phosphate nerve agent simulator product, and the compound has the advantages of simple preparation method, high yield and easy separation, is sensitive to response of the organic phosphate nerve agent simulator, and can rapidly and accurately detect the organic phosphate nerve agent simulator in liquid phase or gas phase.
In order to solve the technical problems, one of the purposes of the invention is to provide a compound, the structural general formula of which is shown as the formula (I):
(I); in formula (I), n is 0 or 1, n 1 Is taken from 1 to 3; n is n 2 And n 3 All from 0 to 6.
Preferably, in formula (I), the R 1 The radicals being
Preferably, in formula (I), the R 2 The radicals being
Preferably, in formula (I), the M group is Zn 2+ 、Cd 2+ 、Cu 2+ 、Ni 2+ 、Fe 2+ 、Mn 2+ Or Co 2+ 。
Preferably, in formula (I), the R 3 The radical being Cl - 、CH 3 COO - 、NO 3 - 、SO 4 - 、C 2 H 5 COO - Or CO 3 - 。
In order to solve the above technical problems, a second object of the present invention is to provide a method for preparing a compound, comprising the steps of:
(1) The compound represented by the following general formula (c) is prepared by a reaction using a compound represented by the following general formula (a) and a compound represented by the following general formula (b), and the reaction equation is as follows:
(2) Reacting a compound shown in the following general formula (c) with the following general formula (d) to obtain a compound shown in the following structural general formula (I), wherein the reaction equation is as follows:
wherein M, R in the formulae (a), (b), (c), (d), (I) 1 、R 2 、R 3 、n、n 1 、n 2 、n 3 Is the same as defined in the specification.
In order to solve the above technical problems, a third object of the present invention is to provide an application of a compound in detecting a nerve agent mimic product of an organic phosphoric acid.
Preferably, the product is a solution reagent, a sensing film or a test paper.
As a preferred embodiment, when the product is a solution reagent, the preparation method comprises dissolving the compound in a solvent to obtain a concentration of 10 -6 mol/L-10 -1 A mol/L solution reagent for detecting the organic phosphate nerve agent mimics according to the color or fluorescence change;
when the product is a sensing film, the preparation method comprises dissolving the compound in a solvent to obtain a concentration of 10 -6 mol/L-10 -1 Preparing a sensing film on a substrate by a spin coating method from a mol/L solution, and detecting an organophosphate nerve agent mimic according to the change of color or fluorescence;
when the product is a test paper, the preparation method comprises dissolving the compound in solventThe concentration of the agent is 10 -6 mol/L-10 -1 And (3) immersing filter paper in the mol/L solution or dripping the solution on test paper, naturally airing to obtain test paper, and detecting the organic phosphate nerve agent simulant according to the change of color or fluorescence.
Preferably, the solvent is one or more of tetrahydrofuran, dichloromethane, chloroform, acetonitrile, methanol and ethanol.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. the application provides a compound which has simple synthesis method, few steps, high yield and easy purification, has higher chemical modification, and can easily obtain fluorescent sensing materials with different emission wavelengths by introducing aromatic functional groups with different structures or changing the length of a flexible unit according to requirements; the structure is easy to adjust, the dissolubility is good, the film forming property is good, and the fluorescent material is an ideal raw material suitable for solution or solid state fluorescence sensing.
2. The compound material can interact with the organophosphorus nerve agent simulant to cause color and fluorescence change, and the change can be identified by naked eyes, so that the material is applicable to quantitative detection in laboratory solutions, can also be used for on-site rapid qualitative and semi-quantitative detection, is sensitive to response of the organophosphorus nerve agent simulant, can make rapid response within 3 seconds, and has good application prospect.
Drawings
FIG. 1 shows fluorescence changes of the solution reagent (left) and the solution reagent after DCP addition (right) of example 1 of the present application;
FIG. 2 shows fluorescence changes of the solution reagent (left) and the solution reagent after DCP addition (right) of example 2 of the present application;
FIG. 3 shows the fluorescence change of the test strip of example 3 of the present application before (left) and after (right) exposure to DCP vapors;
FIG. 4 shows the color change of the solution reagents (right) and after DCP addition (left) of example 4 of the present application;
FIG. 5 shows fluorescence changes of the solution reagents (right) and after DCP addition (left) of example 5 of the present application;
FIG. 6 shows the fluorescence change of the test strip of example 6 of the present application before (right) and after (left) exposure to DCP vapors;
FIG. 7 shows the fluorescence spectrum change results of the sensing film of example 7 of the present application before and after DCP placement;
FIG. 8 shows the fluorescence spectrum change results of the sensing film of example 3 of the present application before and after DCP placement;
FIG. 9 is a graph showing the fluorescence enhancement of the sensing film of example 8 of the present application before and after placement in DCP;
FIG. 10 is a graph showing the fluorescence enhancement of the sensing film of example 9 of the present application before and after DCP placement.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example one
A compound has a structural general formula shown in formula (I):
(I); in formula (i), n=0, n 1 ＝1，n 2 ＝n 3 ＝0；R 2 Is thatThe specific structure of the compound is shown as a formula (II): />
The preparation method of the compound comprises the following steps: 1g of 4'- (4-formylphenyl) -2,2':6', 2' -terpyridine and 100. Mu.L of hydrazine hydrate with a mass fraction of 85% are weighed and dissolved in 300ml of absolute ethanol, heated to 80 ℃ in a water bath, condensed and refluxed for 5 hours, and filtered while hot to obtain 0.66g of a pale yellow solid compound with a structure of formula (II).
Mass spectrometry (EI): m/z670.
Nuclear magnetic hydrogen spectrum 1 H-NMR(600MHz,THF)δ8.64–8.62(m,6H),8.62–8.60(m,4H),8.06(d,J＝8.2Hz,4H),7.98(d,J＝8.2Hz,4H),7.82(td,J＝7.7,1.7Hz,4H),7.31–7.27(m,8H)。
Preparation example two
A compound has a structural general formula shown in formula (I); in formula (i), n=n 1 ＝1，n 2 ＝n 3 ＝0，R 1 Is thatR 2 Is->The specific structure of the compound is shown as a formula (III):
the preparation method of the compound comprises the following steps: 168mg of '4' - (4-formylphenyl) -2,2':6', 2' -terpyridine and 54mg of p-phenylenediamine are weighed and dissolved in 50ml of absolute ethanol, heated to 80 ℃ in a water bath, condensed and refluxed for 5 hours, and filtered while hot to obtain 104mg of a pale yellow solid compound with a structure of formula (III).
Mass spectrometry (EI): m/z746.
Nuclear magnetic hydrogen spectrum 1H-NMR (500 mhz, cdcl 3) delta 8.80 (s, 2H), 8.76 (dd, j=4.3, 1.2hz, 2H), 8.70 (d, j=8.0 hz, 2H), 8.62 (s, 1H), 8.07 (q, j=8.4 hz, 4H), 7.91 (td, j=7.8, 1.8hz, 2H), 7.40-7.38 (m, 2H), 7.37 (s, 2H).
Preparation example three
A compound has a structural general formula shown in formula (I); in formula (i), n=0, n 1 ＝n 2 ＝1，n 3 ＝2，R 2 Is thatM is Zn, R 3 CH3COO-; the specific structure of the compound is shown as a formula (IV):
the preparation method of the compound comprises the following steps: 6.7mg of the compound having the structure of formula (II) is weighed and dissolved in 5mL of tetrahydrofuran to prepare a solution A, 4.4mg of zinc acetate dihydrate is weighed and dissolved in 5mL of methanol to prepare a solution B, and A, B solutions are mixed to form a compound solution having the structure of formula (IV).
Mass spectrometry (EI): m/z 1049.
Preparation example IV
A compound has a structural general formula shown in formula (I); in formula (i), n=n 1 ＝n 2 ＝1，n 3 ＝2，R 1 Is thatR 2 Is->M is Zn, R 3 Is CH 3 COO - The method comprises the steps of carrying out a first treatment on the surface of the The specific structure of the compound is shown as a formula (V):(Ⅴ)。
the preparation method of the compound comprises the following steps: 6.5mg of the compound having the structure of formula (III) is weighed and dissolved in 5mL of chloroform to prepare a solution A, 4.4mg of zinc acetate dihydrate is weighed and dissolved in 5mL of methanol to prepare a solution B, and A, B solutions are mixed to form the compound having the structure of formula (V).
Mass spectrometry (EI): m/z 1125.
Preparation example five
A compound has a structural general formula shown in formula (I); in formula (I), n is 0, n 1 ＝n 2 ＝1，n 3 2, M is Cd 2+ ，R 2 Is thatR 3 Is CH 3 COO - The specific structure of the compound is shown as a formula (VI):
preparation example six
A compound has a structural general formula shown in formula (I); in formula (I), n is 0, n 1 ＝n 2 ＝1，n 3 Is 2, M is Zn, R 2 Is thatR 3 Is Cl - The specific structure of the compound is shown as a formula (VII):
example 1
A solution reagent for detecting an organophosphate nerve agent mimic, comprising the following preparation method: tetrahydrofuran was used as solvent, and the compound obtained in preparation one was used to prepare a concentration of 1×10 -3 mol/L of compound solution reagent.
The detection method comprises the following steps: 3mL was pipetted into a clear quartz cell and 0.5mL DCP was pipetted into the compound solution reagent, at which time the solution fluorescence was observed to change from non-fluorescent to yellowish green fluorescence at around 4s, as shown in FIG. 1.
Example two
A solution reagent for detecting an organophosphate nerve agent mimic, comprising the following preparation method: tetrahydrofuran and methanol are selected according to the volume ratio of 1:1 as solvent, the compound obtained in preparation example 1 was used to prepare a solution with a concentration of 1 x 10 - 3 mol/L of compound solution reagent.
The detection method comprises the following steps: 3mL of the solution was pipetted into a clear quartz cell, 0.5mL of DCP was pipetted into the compound solution reagent, at which point the solution fluorescence was observed to change from non-fluorescent to yellowish green fluorescence, as shown in FIG. 2.
Example III
A sensing film for detecting an organophosphate nerve agent mimetic, comprising the following preparation method: tetrahydrofuran and methanol are selected according to the volume ratio of 1:1 as solvent, the compound obtained in preparation III is selected to prepare the composition with concentration of 1 x 10 - 3 The compound solution of mol/L is used for preparing the sensing film based on the compound on the quartz plate substrate by a spin coating method.
The detection method comprises the following steps: a small amount of DCP is placed at the bottom of a transparent quartz pool, a group of absorbent cotton is padded above the DCP to avoid direct contact with a sensing film, the sensing film is covered and sealed after being placed in the quartz pool, and the fluorescence of the sensing film is changed from non-fluorescence to yellowish green fluorescence within about 4 seconds, as shown in figure 3. The front-back change of the fluorescence emission spectrum of the sensing film is measured after the sensing film is placed in a quartz cell for 300 seconds, and the data show that the film with weak original fluorescence and DCP steam have obvious fluorescence emission spectrum with the maximum emission peak at 513nm after the action, as shown in figure 8.
Example IV
A solution reagent for detecting an organophosphate nerve agent mimic, comprising the following preparation method: selecting chloroform as solvent, selecting compound obtained in preparation II, and preparing into 1 x 10 concentration -3 mol/L of compound solution reagent.
The detection method comprises the following steps: 2mL was pipetted into a clear quartz cell and 0.5mL DCP was pipetted into the compound solution reagent, at which point the solution color was observed to change from pale yellow to dark yellow fluorescence, as shown in FIG. 4.
Example five
A solution reagent for detecting an organophosphate nerve agent mimic, comprising the following preparation method: selecting chloroform as solvent, selecting compound obtained in preparation III, and preparing into 1×10 concentration -3 mol/L of compound solution reagent.
The detection method comprises the following steps: 2mL of the solution was pipetted into a clear quartz cell and 0.5mL of DCP was pipetted into the compound solution reagent, at which point the solution fluorescence was observed to change from non-fluorescent to yellow fluorescence, as shown in FIG. 5.
Example six
The detection filter paper for detecting the organic phosphate nerve agent mimics comprises the following preparation methods: selecting chloroform as solvent, selecting compound obtained in preparation II, and preparing into 1 x 10 concentration -3 And (3) taking the mol/L compound solution, using a disposable straw to suck the solution, dripping a drop of the solution onto common filter paper, and naturally airing to prepare the detection test paper.
The detection method comprises the following steps: after the test paper was placed in DCP vapor, after five minutes, the change of fluorescence of the test paper before and after the test paper was placed in DCP saturated vapor was observed under an ultraviolet lamp, and the test paper was found to change from non-fluorescence to yellowish fluorescence, as shown in FIG. 6.
Example seven
A sensing film for detecting an organophosphate nerve agent mimetic, comprising the following preparation method: selecting chloroform as solvent, selecting compound obtained in preparation four, and preparing concentration of 1×10 -3 The compound solution of mol/L is used for preparing the sensing film based on the compound on the quartz plate substrate by a spin coating method.
The detection method comprises the following steps: placing a small amount of DCP at the bottom of a quartz pool, filling a group of absorbent cotton above the quartz pool to avoid direct contact with a sensing film, placing the sensing film in the quartz pool, covering and sealing the quartz pool, and measuring the front-back change of the fluorescence emission spectrum after 300 s. The data show that a film with weak fluorescence and DCP vapor showed a distinct fluorescence emission spectrum with a maximum emission peak at 547nm, as shown in FIG. 7.
Example eight
A sensing film for detecting an organophosphate nerve agent mimetic, comprising the following preparation method: selecting chloroform as solvent, selecting compound obtained in preparation five, and preparing concentration of 1×10 -3 The compound solution of mol/L is used for preparing the sensing film based on the compound on the quartz plate substrate by a spin coating method.
The detection method comprises the following steps: placing a small amount of DCP at the bottom of a quartz pool, filling a group of absorbent cotton above the quartz pool to avoid direct contact with a sensing film, placing the sensing film in the quartz pool, covering and sealing the quartz pool, and measuring the front-back change of the fluorescence emission spectrum after 300 s. As shown in fig. 9, the fluorescence curve is increased from the original curve with weak fluorescence intensity for about 15s to form a curve with strong fluorescence.
Example nine
A sensing film for detecting an organophosphate nerve agent mimetic, comprising the following preparation method: selecting chloroform as solvent, selecting compound obtained in preparation six, and preparing concentration of 1×10 -3 The compound solution of mol/L is used for preparing the sensing film based on the compound on the quartz plate substrate by a spin coating method.
The detection method comprises the following steps: placing a small amount of DCP at the bottom of a quartz pool, filling a group of absorbent cotton above the quartz pool to avoid direct contact with a sensing film, placing the sensing film in the quartz pool, covering and sealing the quartz pool, and measuring the front-back change of the fluorescence emission spectrum after 300 s. As shown in fig. 10, the fluorescence curve is increased from the original curve with weak fluorescence intensity at about 45s to form a curve with strong fluorescence.
The foregoing embodiments have been provided for the purpose of illustrating the general principles of the present invention, and are not to be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art without departing from the spirit and principles of the present invention are intended to be included in the scope of the present invention.

Claims (6)

1. A compound is characterized in that the structural general formula is shown in the formula (I):
in formula (I), n is 0 or 1,n 1 taking 1; n is n 2 And n 3 All taken from 0, or n 2 Taken from 1 and n 3 Taken from 2, said R 1 The radical is->The R is 2 The radical is->The M group is Zn 2+ Or Cd 2+ The R is 3 The radical being Cl - Or CH (CH) 3 COO - 。
2. A process for the preparation of a compound as claimed in claim 1, comprising the steps of:
(1) The compound represented by the following general formula (c) is prepared by a reaction using a compound represented by the following general formula (a) and a compound represented by the following general formula (b), and the reaction equation is as follows:
(2) Reacting a compound shown in the following general formula (c) with the following general formula (d) to obtain a compound shown in the following structural general formula (I), wherein the reaction equation is as follows:
wherein M, R in the formulae (a), (b), (c), (d), (I) 1 、R 2 、R 3 、n、n 1 、n 2 、n 3 Are as defined in claim 1.
3. Use of a compound according to claim 1 for the detection of a neurotoxic agent mimetic product.
4. Use of a compound according to claim 3 for the detection of a nerve agent mimetic product, wherein said product is a solution reagent, a sensing membrane or a test strip.
5. The use of a compound according to claim 4 for detecting a neurotoxic agent mimetic product, wherein:
when the product is a solution reagent, the preparation method comprises dissolving the compound in a solvent to obtain a solution with a concentration of 10 -6 mol/L-10 - 1 A mol/L solution reagent for detecting the organophosphate nerve agent mimic according to a change in color or fluorescence;
when the product is a sensing film, the preparation method comprises dissolving the compound in a solvent to obtain a concentration of 10 -6 mol/L-10 - 1 Preparing a sensing film on a substrate by a spin coating method from a mol/L solution, and detecting an organophosphate nerve agent mimic according to the change of color or fluorescence;
when the product is a test paper, the preparation method comprises dissolving the compound in a solvent to obtain a solution with a concentration of 10 -6 mol/L-10 - 1 And (3) immersing filter paper in the mol/L solution or dripping the solution on test paper, naturally airing to obtain test paper, and detecting the organic phosphate nerve agent simulant according to the change of color or fluorescence.
6. The use of a compound according to claim 5 for detecting a neurotoxic agent mimetic product wherein the solvent is one or more of tetrahydrofuran, dichloromethane, chloroform, acetonitrile, methanol, and ethanol.
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