CN110156734B - Fluorescent probe and fluorescent test paper for detecting nerve gas simulant and preparation method thereof - Google Patents
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a fluorescent probe for detecting a nerve gas simulant, fluorescent test paper and a preparation method thereof, wherein the structural formula of the fluorescent probe for detecting the nerve gas simulant is shown as
Wherein R is positioned at any substituted position on the benzene ring, and R is H, OCH3Or Cl. The fluorescent probe has fluorescence specificity for halophosphate nerve gas, and can be subjected to fluorescence lightening type fluorescence sensing, so that the halophosphate nerve gas can be detected, the detection sensitivity is high, and the detection limit is low; the prepared fluorescent test paper can be used for detecting halophosphate nervotoxic gas in the gas atmosphere, and has the advantages of simple detection method, low preparation cost and convenient carrying.
Description
Technical Field
The invention relates to the field of small molecule fluorescent probes, in particular to a fluorescent probe and a fluorescent test paper for detecting nerve gas simulants and a preparation method thereof.
Background
Sarin (GB) and soman (GD) are two representative nerve gases, both of which are halophosphates; the compounds can perform irreversible reaction with acetylcholinesterase in the central nerve of a human body, so that nerve impulse is damaged, and suffocation, cardiac arrest and other symptoms can be caused within minutes to cause death; and since war, such compounds have been used in large quantities in chemical weapons and pesticides. Therefore, the development of a sensing method for rapidly and accurately detecting halophosphate ester nerve gas is of great significance.
The fluorescence sensing method is a visual detection means with short response time, high sensitivity, high time and space resolution, and has been widely used for quantitative and qualitative detection of various environmental parameters and biochemical substrates. It has been reported that, taking Diethyl Chlorophosphate (DCP) as a nerve gas simulant, fluorescent materials applied to the detection of halophosphate class nerve gas include conjugated polymers, small molecule fluorescent materials, biological imprinting materials, aggregation-induced luminescent materials, nanometer materials and the like, and compared with other materials, the small molecule materials have the advantages of low cost, simple synthesis method and the like; however, the existing small-molecule fluorescent materials applied to the detection of halophosphate nervotoxic gas are still few, and the fluorescent test paper cannot be prepared at low cost.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a fluorescent probe, a fluorescent test strip and a preparation method thereof for detecting nerve gas mimics, which aims to solve the problems that the existing small-molecule fluorescent materials applied to the detection of halophosphate nerve gas are still few and the fluorescent test strip cannot be prepared at low cost.
The technical scheme of the invention is as follows:
the structural formula of the fluorescent probe for detecting the nerve gas simulant is shown in the specification
Wherein R is positioned at any substituted position on the benzene ring, and R is H, OCH3Or Cl.
The fluorescent probe for detecting the nerve gas simulant is characterized in that R is H.
A method for preparing a fluorescent probe for detecting nerve gas simulant as described above, comprising the steps of:
A. placing R-substituted 2-hydroxyacetophenone, 4- (diethoxymethyl) benzaldehyde and inorganic base in a polar solvent, and heating and refluxing for 12-36 h; cooling to room temperature, adding hydrogen peroxide, stirring at room temperature for 12-36 h, adding excessive hydrochloric acid, stirring, concentrating, and performing column chromatography to obtain a fluorescent probe intermediate;
B. fluorescent probe intermediate and hydroxylamine hydrochloride in CH2Cl2And carrying out medium reflux reaction for 4-36 h, and concentrating and recrystallizing to obtain the fluorescent probe.
The preparation method of the fluorescent probe for detecting the nerve gas simulant comprises the following steps of A, wherein in the step A, the inorganic base is KOH or NaOH; the polar solvent is methanol, ethanol or ethylene glycol.
The preparation method of the fluorescent probe for detecting the nerve gas simulant comprises the following steps of A, wherein in the step A, the molar ratio of the R-substituted 2-hydroxyacetophenone, the 4- (diethoxymethyl) benzaldehyde, the inorganic base and the hydrogen peroxide is 1: 3-5: 5-40: 10-50.
The preparation method of the fluorescent probe for detecting the nerve gas simulant comprises the step B, wherein the molar ratio of the fluorescent probe intermediate to hydroxylamine hydrochloride is 1: 2-10.
A preparation method of a fluorescent test paper for detecting nerve gas simulants comprises the following steps:
C. placing the fluorescent probe for detecting nerve gas simulant according to claim 1 or 2 and a matrix material in an organic solvent, and uniformly mixing;
D. and then spreading the mixed solution on a substrate, drying to form a film, and cutting to obtain the film.
The preparation method of the fluorescent test paper for detecting the nerve gas simulant comprises the following steps of C, wherein the weight ratio of the fluorescent probe for detecting the nerve gas simulant to the matrix material is 1: 10-1000; the matrix material is PEG, PP or PB; the boiling point of the organic solvent is less than 100 ℃.
The fluorescent test paper for detecting the nerve gas simulant is prepared by the preparation method of the fluorescent test paper for detecting the nerve gas simulant.
Has the advantages that: the fluorescent probe has a novel structure, takes the flavone dye with high fluorescence quantum yield, good light stability, clear light-emitting mechanism, simple and convenient synthesis and low toxicity as a fluorescent probe matrix, and takes the oxime group with high reaction activity as the identification group of the halophosphate nervous gas to realize fluorescent lighting type fluorescent sensing, thereby realizing the detection of the halophosphate nervous gas; the fluorescent probe has fluorescence specificity for the halophosphate nerve gas, can be directly used for qualitatively and quantitatively detecting the halophosphate nerve gas in a solution, and has high sensitivity and low detection limit; the prepared fluorescent test paper can be used for detecting halophosphate nervotoxic gas in the gas atmosphere, the detection method is simple, the preparation cost of the fluorescent test paper is low, and the fluorescent test paper is convenient to carry.
Drawings
FIG. 1 is a graph showing the change of the fluorescence response of HOFO with respect to a test solution containing DCP at different concentrations with time in example 1 of the present invention.
FIG. 2 is a graph showing the fluorescence response of HOFO to test solutions containing DCP at different concentrations in example 1 of the present invention.
FIG. 3 is a graph comparing the fluorescence response of HOFO in example 1 of the present invention to test solutions containing different compounds (at the same concentration).
FIG. 4 is a graph showing the fluorescence response of solid HOFO in the fluorescence test paper of example 1 of the present invention to gas atmosphere with different DCP vapor concentration.
FIG. 5 is a graph comparing the fluorescence response of solid HOFO in the fluorescence test strip of example 1 of the present invention to different compound vapors (vapor concentrations are the same).
Detailed Description
The invention provides a fluorescent probe and a fluorescent test paper for detecting nerve gas simulant and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a fluorescent probe for detecting a nerve gas simulant, wherein the structural formula of the fluorescent probe for detecting the nerve gas simulant is shown in the specification
Wherein R is positioned at any substituted position on the benzene ring, and R is H, OCH3Or Cl; further, R ═ H.
The fluorescent probe has a novel structure, takes the flavone dye with high fluorescence quantum yield, good light stability, clear light-emitting mechanism, simple and convenient synthesis and low toxicity as a fluorescent probe matrix, and takes an oxime group with high reaction activity as a recognition group of halophosphate nerve gas; that is, the oxime hydroxyl group of the fluorescent probe of the present invention can be used as a nucleophile to attack the phosphorus (V) center of the halophosphate nervoxic gas, so that the Photoinduced Electron Transfer (PET) process between the oxime substituent and the flavone skeleton is inhibited to cause fluorescence enhancement, thereby realizing fluorescence sensing of the halophosphate nervoxic gas, and further realizing detection thereof. The fluorescent probe as a fluorescent lighting sensor is more convenient for naked eye observation than a fluorescent quenching sensor, and meets the requirement of accurate detection of halophosphate nerve gas.
The invention also provides a preparation method of the fluorescent probe for detecting the nerve gas simulant, which comprises the following steps:
A. placing R-substituted 2-hydroxyacetophenone, 4- (diethoxymethyl) benzaldehyde and inorganic base in a polar solvent, and heating and refluxing for 12-36 h; cooling to room temperature, adding hydrogen peroxide, stirring at room temperature for 12-36 h, adding excessive hydrochloric acid, stirring, concentrating, and performing column chromatography to obtain a fluorescent probe intermediate;
B. fluorescent probe intermediate and hydroxylamine hydrochloride in CH2Cl2And carrying out medium reflux reaction for 4-36 h, and concentrating and recrystallizing to obtain the fluorescent probe.
The preparation route of the fluorescent probe for detecting the nerve gas simulant comprises the following steps
The invention firstly prepares a fluorescent probe intermediate (flavonoid dye) by a one-pot two-step method through Claisen-Schmidt condensation reaction and Algar-Flynn-Oyamada oxidation cyclization reaction in sequence at low cost; and then carrying out Schiff base condensation reaction to obtain the fluorescent probe. Further, in the step A, the inorganic base is KOH or NaOH; the polar solvent is methanol, ethanol or ethylene glycol; the molar ratio of the R-substituted 2-hydroxyacetophenone, 4- (diethoxymethyl) benzaldehyde, inorganic base and hydrogen peroxide is 1: 3-5: 5-40: 10-50; the eluent for column chromatography is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 10-4: 1. In the step B, the molar ratio of the fluorescent probe intermediate to hydroxylamine hydrochloride is 1: 2-10; the solvent for recrystallization is Tetrahydrofuran (THF).
The preparation method of the fluorescent probe is simple, low in cost and suitable for actual expanded production.
The invention also provides a preparation method of the fluorescent test paper for detecting the nerve gas simulant, wherein the preparation method comprises the following steps:
C. placing the fluorescent probe for detecting the nerve gas simulant and the substrate material in an organic solvent, and uniformly mixing;
D. and then spreading the mixed solution on a substrate, drying to form a film, and cutting to obtain the film.
Further, in step C, the matrix material may be selected from, but not limited to, one of polyethylene glycol (PEG), Polypropylene (PP), Polybutadiene (PB); the weight ratio of the fluorescent probe for detecting the nerve gas simulant to the matrix material is 1:10 to 1000; the boiling point of the organic solvent is less than 100 ℃, preferably ethyl acetate. In step D, the substrate may be selected from, but not limited to, one of a glass sheet and a quartz sheet; the drying temperature is 60-90 ℃.
The invention also provides a fluorescent test paper for detecting the nerve gas simulant, wherein the fluorescent test paper is prepared by adopting the preparation method of the fluorescent test paper for detecting the nerve gas simulant.
The invention adopts the preparation method of swelling first and drying second to prepare the fluorescent test paper, is simple and convenient, is easy to realize, and is suitable for actual large-scale production; the invention uses cheap high molecular material as substrate material, greatly reduces the usage amount of the fluorescent probe and further reduces the production cost. The fluorescent test paper prepared by the invention keeps higher detection sensitivity to halophosphate nerve gas and is convenient to carry. The method for detecting halophosphate nervotoxic gas in gas is simple and convenient.
The following examples are provided to describe in detail the fluorescent probe of the fluorescent test strip for nerve gas simulant detection, the preparation method of the fluorescent test strip, and the performance thereof.
Example 1
(1) Dissolving 2-hydroxyacetophenone (40mmol) and terephthalaldehyde diethylacetal (160mmol) in ethanol, adding KOH (400mmol), heating and refluxing for 24h, and cooling to room temperature; adding hydrogen peroxide (20mL) and continuing to react for 24H, adding hydrochloric acid until the pH value is 1, stirring for 5min, removing the solvent under reduced pressure, and performing column chromatography (the eluent is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 7: 1) to obtain a fluorescent probe intermediate 4- (3-hydroxy-4-oxo-4H-chromen-2-yl) benzaldehyde (abbreviated as HOFA), wherein the yield is 45%, and the structural formula of the fluorescent probe intermediate is shown in the specification
1H-NMR(600MHz,DMSO-d6),:10.09(br s,2H),8.44(d,J＝8.2Hz,2H),8.13(d,J＝7.9Hz,1H),8.09(d,J＝8.2Hz,2H),7.84(t,J＝7.7Hz,1H),7.80(d,J＝8.3Hz,1H),7.49(t,J＝7.4Hz,1H).13C-NMR(150MHz,DMSO-d6),:192.77,173.27,154.71,143.54,140.41,136.25,134.16,129.54,128.10,124.78,121.29,118.57。MS(HR ESI-TOF):m/z calcd for C16H10O4:266.0652，found[M+H]+:267.0647。
(2) HOFA (4mmol) and hydroxylamine hydrochloride (20mmol) are refluxed and reacted in dichloromethane for 24 hours, the solvent is removed under reduced pressure after cooling, the obtained product is recrystallized in THF to obtain the fluorescent probe 4- (3-hydroxy-4-oxo-4H-chromen-2-yl) benzaldehyde oxime (HOFO for short), the yield is 89%, and the structural formula of the fluorescent probe is shown in the specification
1H-NMR(600MHz,DMSO-d6),:9.62(s,1H),8.18(d,J＝8.3Hz,2H),8.09(d,J＝8.0Hz,1H),7.79–7.73(m,2H),7.71(s,1H),7.61(d,J＝8.4Hz,2H),7.44(t,J＝7.4Hz,1H),7.05(br s,1H).13C-NMR(150MHz,DMSO-d6),:172.86,154.57,145.16,139.05,137.98,136.76,133.75,129.81,127.87,125.00,124.82,124.60,121.36,118.44.MS(HR ESI-TOF):m/z calcd forC16H11O4N:281.0761,found[M+H]+:282.0754。
(3) The fluorescent response of HOFO in solution to halophosphate neurotoxic gases was tested using Diethyl Chlorophosphate (DCP) as a mimic of halophosphate neurotoxic gases.
Dissolving HOFO in methanol to prepare 4 parts of HOFO solution with the same concentration (0.01 mM); adding different amounts of DCP into 4 parts of HOFO solution to obtain 4 parts of DCP solution to be tested with different concentrations, wherein the concentration of DCP is 0.05mM, 0.2mM, 0.4mM and 0.8 mM; and then respectively carrying out fluorescence spectrum tests on the solutions to be tested, wherein the change of the fluorescence response of the HOFO to the solutions to be tested containing DCP with different concentrations along with time is shown in figure 1, and the results show that the response of the HOFO to the DCP tends to be complete after 60s, which indicates that the HOFO has a very fast response rate to the DCP. Exciting HOFO solution (0.01mM) by 365nm light, wherein when the concentration of DCP in the HOFO solution is increased from 0 to 0.8mM, the fluorescence response of the HOFO to DCP with different concentrations is shown in figure 2, the fluorescence emission peak of the HOFO at 560nm is continuously enhanced along with the increase of the concentration of the DCP, and the detection limit of the HOFO to the DCP can reach 1.3ppb (namely 7.8 nmol/L); diethyl Chloroacetate (DCP), Diethyl Cyanophosphate (DCNP), dimethyl methylphosphonate (DMMP), Triethyl phosphate (TEP) and Acetic acid (AcOH) were added to 5 parts of the HOFO solution (0.01mM) to obtain 5 different solutions to be tested (each of the 5 compounds was 0.8mM in concentration), the solutions to be tested were excited with 365nm light, and the fluorescent response of the HOFO to the 5 compounds was shown in fig. 3, which was found to show a specific response to DCP in the solution.
(4) And (4) preparing the fluorescent test paper.
PEG (Mw: 10000) was used as a base material, 1g of PEG was dissolved in 300mL of ethyl acetate, 50mg of HOFO was added, the mixture was heated and mixed uniformly, and the mixture was poured onto a glass slide, dried at 60 ℃ to form a film, and cut into a fluorescent test paper loaded with HOFO in an appropriate shape (for example, a rectangle) according to the experimental requirements.
(5) And (3) testing the detection performance of the HOFO-loaded fluorescent test paper on the DCP steam.
Placing the fluorescent test paper loaded with the HOFO in a gas atmosphere with different DCP steam concentrations for 10-600 s (for example, 60s), wherein the spectral response of the solid HOFO in the fluorescent test paper to the DCP steam is shown in FIG. 4, so that the fluorescent intensity of the solid HOFO is still increased progressively along with the change of the DCP steam concentration, the insertional graph is a fluorescent comparison result of the fluorescent test paper before testing and the fluorescent test paper after testing under a portable ultraviolet lamp, and the detection limit of the solid HOFO in the fluorescent test paper to the DCP steam can reach 2.6 ppb; the comparison of the fluorescence response of the solid-state HOFO in the fluorescence test paper to different compound vapors (the concentration of the compound vapors is 120ppm) is shown in FIG. 5, which shows that the solid-state HOFO in the fluorescence test paper still has specific response to DCP.
In summary, the fluorescent probe, the fluorescent test paper and the preparation method thereof for detecting the nerve gas simulant provided by the invention have the advantages that the fluorescent probe is novel in structure, takes the flavone dye with high fluorescence quantum yield, good light stability, definite light-emitting mechanism, simple and convenient synthesis and low toxicity as the fluorescent probe matrix, takes the oxime group with high reaction activity as the identification group of the halophosphate nerve gas, and realizes the fluorescent lighting type fluorescent sensing of the halophosphate nerve gas, thereby realizing the detection of the halophosphate nerve gas; the fluorescent probe has fluorescence specificity for the halophosphate nerve gas, can be directly used for qualitatively and quantitatively detecting the halophosphate nerve gas in a solution, and has high sensitivity and low detection limit; the prepared fluorescent test paper can be used for detecting halophosphate nervotoxic gas in the gas atmosphere, and has the advantages of simple detection method, low preparation cost and convenient carrying.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A fluorescent probe for detecting nerve gas simulant is characterized in that the structural formula of the fluorescent probe is shown as
2. A method of preparing a fluorescent probe for nerve gas simulant detection according to claim 1, comprising the steps of:
A. placing 2-hydroxyacetophenone, 4- (diethoxymethyl) benzaldehyde and inorganic base in a polar solvent, and heating and refluxing for 12-36 h; cooling to room temperature, adding hydrogen peroxide, stirring at room temperature for 12-36 h, adding excessive hydrochloric acid, stirring, concentrating, and performing column chromatography to obtain a fluorescent probe intermediate;
B. fluorescent probe intermediate and hydroxylamine hydrochloride in CH2Cl2And carrying out medium reflux reaction for 4-36 h, and concentrating and recrystallizing to obtain the fluorescent probe.
3. The method of claim 2, wherein in step A, the inorganic base is KOH or NaOH; the polar solvent is methanol, ethanol or ethylene glycol.
4. The method for preparing a fluorescent probe for detecting a nerve gas simulant according to claim 2, wherein in the step A, the molar ratio of the 2-hydroxyacetophenone, the 4- (diethoxymethyl) benzaldehyde, the inorganic base and the hydrogen peroxide is 1: 3-5: 5-40: 10-50.
5. The method for preparing a fluorescent probe for detecting a nerve gas mimic according to claim 2, wherein in the step B, the molar ratio of the fluorescent probe intermediate to hydroxylamine hydrochloride is 1: 2-10.
6. A preparation method of fluorescent test paper for detecting nerve gas simulants is characterized by comprising the following steps:
C. placing the fluorescent probe for detecting nerve gas simulant according to claim 1 and a matrix material in an organic solvent, and uniformly mixing;
D. and then spreading the mixed solution on a substrate, drying to form a film, and cutting to obtain the film.
7. The method for preparing the fluorescence test paper for detecting the nerve gas simulant according to claim 6, wherein in the step C, the weight ratio of the fluorescence probe for detecting the nerve gas simulant to the matrix material is 1: 10-1000; the matrix material is PEG, PP or PB; the boiling point of the organic solvent is less than 100 ℃.
8. The method of claim 7, wherein in step D, the substrate is a glass or quartz plate.
9. A fluorescent test paper for detecting nerve gas simulant, which is characterized by being prepared by the preparation method of the fluorescent test paper for detecting nerve gas simulant according to any one of claims 6 to 8.
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| CN112300202B (en) * | 2020-11-03 | 2022-08-09 | 中国人民解放军61699部队 | Fluorescent probe, nerve toxin detection element, preparation method and application |
| CN115403514B (en) * | 2022-09-29 | 2024-01-30 | 中国科学院上海微系统与信息技术研究所 | Compound and application thereof in detection of organic phosphate nerve agent simulator product |
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| CN103969208A (en) * | 2014-05-30 | 2014-08-06 | 中国人民解放军军事医学科学院毒物药物研究所 | Use of o-carbonyl oxime compound and preparation method thereof |
| CN106279162A (en) * | 2016-07-19 | 2017-01-04 | 中国科学院化学研究所 | One-dimensional organic semiconductor nanowires/band that organophosphorus compound toxic gas is had fluorescence response and its preparation method and application |
| CN107445885A (en) * | 2017-07-20 | 2017-12-08 | 中国科学院化学研究所 | Organic fluorescence sensing material of alternative detection nerve toxicant and its preparation method and application |
| CN109283167A (en) * | 2018-11-02 | 2019-01-29 | 陕西师范大学 | Sensor array based on monolayer fluorescence sense film and its pattern-recognition to toxic gas |
| CN109358029A (en) * | 2018-11-15 | 2019-02-19 | 东北林业大学 | It is a kind of for nerve gas similar to the acridine fluorescent material of analyte detection |
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