CN114019019A - Quartz crystal microbalance sensor and detection of mustard gas and mustard gas simulants by quartz crystal microbalance sensor - Google Patents
Quartz crystal microbalance sensor and detection of mustard gas and mustard gas simulants by quartz crystal microbalance sensor Download PDFInfo
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- CN114019019A CN114019019A CN202111323203.0A CN202111323203A CN114019019A CN 114019019 A CN114019019 A CN 114019019A CN 202111323203 A CN202111323203 A CN 202111323203A CN 114019019 A CN114019019 A CN 114019019A
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- 238000003380 quartz crystal microbalance Methods 0.000 title claims abstract description 42
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000001514 detection method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000010453 quartz Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000004044 response Effects 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- GBNVXYXIRHSYEG-UHFFFAOYSA-N 1-chloro-2-ethylsulfanylethane Chemical group CCSCCCl GBNVXYXIRHSYEG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- GPTVQTPMFOLLOA-UHFFFAOYSA-N 1-chloro-2-ethoxyethane Chemical compound CCOCCCl GPTVQTPMFOLLOA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
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- 238000004440 column chromatography Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
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- 125000004122 cyclic group Chemical group 0.000 claims description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 6
- -1 arene macrocyclic compound Chemical class 0.000 abstract description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 231100000167 toxic agent Toxicity 0.000 description 4
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- SDOAWHDQUPUKBI-UHFFFAOYSA-N 1,4-dimethoxy-2-(2-phenylphenyl)benzene Chemical group COC1=C(C=C(C=C1)OC)C=1C(=CC=CC=1)C1=CC=CC=C1 SDOAWHDQUPUKBI-UHFFFAOYSA-N 0.000 description 2
- CXSAUYSENLOMSC-UHFFFAOYSA-N 2-[3-(2,5-dimethoxyphenyl)phenyl]-1,4-dimethoxybenzene Chemical compound COC1=CC=C(OC)C(C=2C=C(C=CC=2)C=2C(=CC=C(OC)C=2)OC)=C1 CXSAUYSENLOMSC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/02—Analysing fluids
- G01N29/022—Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/02—Analysing fluids
- G01N29/036—Analysing fluids by measuring frequency or resonance of acoustic waves
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2291/00—Indexing codes associated with group G01N29/00
- G01N2291/01—Indexing codes associated with the measuring variable
- G01N2291/014—Resonance or resonant frequency
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2291/00—Indexing codes associated with group G01N29/00
- G01N2291/02—Indexing codes associated with the analysed material
- G01N2291/021—Gases
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- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a quartz crystal microbalance sensor and detection of mustard gas and mustard gas simulant gas by the quartz crystal microbalance sensor, wherein the mustard gas simulant is 2-chloroethyl ethyl sulfide and 2-chloroethyl ethyl ether. The method comprises the following steps: under the ultrasonic condition, terphenyl [3] arene macrocyclic compound is added into ethanol solution to obtain uniform dispersion liquid, and then the dispersion liquid is coated on the surface of a quartz crystal electrode to form a sensitive material, and the sensor can be obtained after drying. The quartz crystal microbalance sensor based on the large ring has the advantages of simple preparation, high specificity, high sensitivity, quick response, low cost and the like, can be used for continuous real-time online detection of ppm-level mustard gas or a stimulant thereof, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of toxic substance detection, and particularly relates to a quartz crystal microbalance sensor and detection of mustard gas and mustard gas simulant gas by the quartz crystal microbalance sensor.
Background
Mustard gas (HD), which is a chemical name of 2, 2' -dichlorodiethyl sulfide, is a difficult-to-control erosive toxicant in chemical weapons, has the characteristics of strong toxicity, large storage capacity, strong penetrability, multi-target and multi-site poisoning and injury, lasting effect, no specific curative and the like, and is also called as the king of toxicants. Compared with other chemical warfare agents, the mustard gas is easy to cause panic due to simple synthesis and convenient storage.
The traditional mustard gas detection method is to utilize the property of hydrocarbon or the property of forming a compound to react with a chemical reagent and adopt a colorimetric method for detection. With the development of modern instrument analysis technology, methods such as a gas chromatography-mass spectrometry (GC-MS), a liquid chromatography method, a radioactive labeling method and the like are successfully used for detecting mustard gas. However, most of these methods require expensive large-scale instruments and equipment, and are complicated to operate, and lack specific identification for detecting a certain toxic agent. Therefore, the development of a new technology for detecting mustard gas with high selectivity, high specificity and high sensitivity is urgently needed.
Quartz Crystal Microbalance (QCM) sensors are sensitive analytical instruments based on small mass changes. A specific quartz crystal oscillator is used as a transducer, a layer of sensitive film material is attached to the surface of a quartz crystal electrode and used as a frequency sensitive element, and when a detected substance and the sensitive material are adsorbed due to interaction, the mass can be changed, so that vibration frequency change is generated under an alternating electric field, and detection of trace and trace substances is realized. The QCM sensor has the advantages of high measurement precision up to nanogram level, simple structure/use, low cost, quick response, good specificity and the like. Thus, QCM sensors may be an ideal detection means for potential chemical weapons.
Disclosure of Invention
The invention aims to solve the problems of low sensitivity, expensive instruments and equipment, complex operation and the like of the traditional mustard gas detection method, and provides a simple and portable sensor detection method with high sensitivity, good responsiveness and strong anti-interference capability for mustard gas. The invention relates to a novel quartz crystal microbalance sensor which is constructed by modifying a sensitive film material of a large ring shown in a formula I on a quartz crystal electrode. During detection, the mustard gas and the simulants thereof are identified and adsorbed by the macrocyclic ring of the formula I modified on the surface of the quartz crystal electrode, and are converted into corresponding frequency signals of the sensor through slight mass change, so that quantitative detection of the target object is achieved.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention relates to a quartz crystal microbalance sensor, which is characterized by comprising a quartz crystal microbalance and a sensitive film material modified on the surface of a quartz crystal electrode; the sensitive membrane material comprises a macrocyclic compound shown in a formula I; the thickness of the sensitive membrane material is 0.5 mu m;
wherein R is C1–8An alkyl group.
According to one embodiment of the invention, R is C1–4Alkyl groups, preferably methyl, ethyl and butyl.
The second aspect of the present invention relates to a method for preparing a sensitive film represented by formula i according to the first aspect, comprising the following steps:
(1) mixing and dissolving the compounds 1 and 2 in a molar ratio of 2: 1 in dioxane and water, adding 2 equivalents of potassium carbonate and 10% of catalytic amount of 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride, heating, stirring and refluxing for 12 hours under the protection of argon gas, cooling reaction liquid to room temperature after the reaction is finished, spin-drying the solvent, extracting for three times by using dichloromethane and water, mixing an organic phase with silica gel, and performing column chromatography to obtain a cyclic monomer 3; the solvent ratio of dioxane to water is 5: 1;
(2) mixing a monomer 3 and paraformaldehyde according to the molar weight of 1: 1, dissolving in a 1, 2-dichloroethane solution, adding 1 equivalent of boron trifluoride diethyl etherate catalyst, reacting for 20 minutes, quenching with a saturated sodium bicarbonate aqueous solution, washing an organic phase with saturated sodium chloride and water for three times, mixing the organic phase with silica gel, and separating by column chromatography to obtain a macrocyclic compound of the formula I;
（HCHO）nrefers to paraformaldehyde.
According to an embodiment of the inventionIn the embodiment, R is C1–4Alkyl groups, preferably methyl, ethyl and butyl.
The third aspect of the present invention relates to a method for manufacturing the quartz crystal microbalance sensor of the first aspect, comprising the steps of:
(1) ultrasonically cleaning a quartz crystal electrode by deionized water and ethanol for 5 minutes, and then drying for 2 hours at 50 ℃ for later use;
(2) adding the prepared macrocyclic compound shown in the formula I into a quantitative solvent, and obtaining a uniform dispersion liquid under the ultrasonic condition; the solvent is one or a mixture of water and ethanol;
(3) spin-coating the macrocyclic sensitive material dispersion liquid prepared in the step (2) on the surface of the quartz crystal electrode obtained in the step (1), drying the quartz crystal electrode surface in vacuum at 50 ℃ for 8-10 h to obtain the quartz crystal microbalance sensor coated with the macrocyclic sensitive material shown in the formula I,
according to one embodiment of the invention, R is C1–4Alkyl groups, preferably methyl, ethyl and butyl.
According to one embodiment of the invention, the spin coating method comprises the following steps: spin-coating at low speed for 35-45 s and spin-coating at high speed for 15-25 s;
the invention also discloses the application of the quartz crystal microbalance sensor in the aspect of quantitatively detecting mustard gas and mustard gas simulating agents, and the experimental result shows that: has quick response and high sensitivity to mustard gas simulator vapor with the concentration of 10-100 ppm, and has specificity and no interference from other gases.
The detection method comprises the following steps:
putting the quartz crystal electrode coated with the sensitive membrane of the macrocyclic compound into a sample chamber to be tested, and testing the response curve of the simulating agent according to the mass change of the membrane material adsorbed sample and the change value of the vibration frequency of the quartz crystal electrode; wherein the mustard gas simulant is 2-chloroethyl ethyl sulfide and 2-chloroethyl ethyl ether.
Compared with the prior art, the quartz crystal microbalance sensor and the detection of the mustard gas simulant thereof disclosed by the invention have the positive effects that:
1. the terphenyl aromatic hydrocarbon macrocycle can realize effective adsorption and recognition of mustard gas simulants through host-guest interaction, and the mustard gas simulants are 2-chloroethyl ethyl sulfide and 2-chloroethyl ethyl ether.
2. The novel quartz crystal microbalance sensor is prepared by the invention.
3. The quartz crystal microbalance sensor prepared by the invention has quick response and high sensitivity to mustard gas simulator vapor with the concentration of 10-100 ppm, has specificity and is not interfered by other gases. The mustard gas simulant is 2-chloroethyl ethyl sulfide and 2-chloroethyl ethyl ether.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2, 5-dimethoxyterphenyl [3] arene in example 1;
FIG. 2 is a time-frequency response curve of the quartz crystal microbalance sensor detecting CEES in example 3;
FIG. 3 is a time-frequency response curve of the quartz crystal microbalance sensor detection CEEE of example 4;
FIG. 4 shows the quartz crystal microbalance sensor pair of example 5 at a concentration of 100 ppm of CEES, CEEE, H2、CO、CO2、H2O、NO、NO2、NH3Detection selectivity for benzene and THF.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The raw materials and reagents used in the present invention are commercially available. Wherein the 1, 3-di (2, 5-dimethoxyphenyl) benzene monomer, paraformaldehyde, boron trifluoride diethyl etherate, quartz crystal electrode, etc. are all commercially available.
Example 1
Preparation of 2, 5-dimethoxyterphenyl [3] arene (2, 5-MeBP 3)
1.0 g of 1, 3-bis (2, 5-dimethoxyphenyl) benzene monomer and 0.1 g of paraformaldehyde were weighed and dissolved in 200 mL of 1, 2-dichloroethane solution, 0.36 mL of boron trifluoride diethyl etherate catalyst was added, the reaction was quenched with saturated aqueous sodium bicarbonate solution after 20 minutes, and then washed three times with saturated sodium chloride and water, and the organic phase was sampled with silica gel and separated by column chromatography to obtain 0.7 g of 2,5-MeBP3 macrocycle, melting point 256 ℃ and the results are shown in FIG. 1.
Example 2
Preparation of Quartz Crystal Microbalance (QCM) sensor
100 mg of 2,5-MeBP3 macrocyclic compound is weighed and added into 20 mL of ethanol solution with the concentration of 75 percent, and ultrasonic treatment is carried out for 30 minutes under the condition of 40KHz to obtain sensitive membrane material dispersion liquid with the concentration of 5 mg/mL. And then sucking 2 mL of sensitive material dispersion liquid by using a micro-injector, spin-coating for 35s at low speed on the center of the surface of the QCM electrode by using a spin-coating instrument, then spin-coating for 25s at high speed, and vacuum-drying for 8 h at 50 ℃ to obtain the quartz crystal microbalance sensor with the electrode coated and decorated with a layer of sensitive film material with the thickness of 0.5 mu m.
Example 3
QCM sensors detect 2-chloroethyl ethyl sulfide (CEES)
The QCM sensor electrode prepared in example 2 and coated with a 2,5-MeBP3 sensing film was placed in the detection chamber and CEES was loaded into the detection chamber at a concentration of 100 ppm by nitrogen, the 2,5-MeBP3 sensing film adsorbed CEES while the collected data was processed by the resonant circuit and sensor frequency response data using computer related software and plotted into a related response curve. The results are shown in FIG. 2, which shows that the sensor has a very fast response to CEES, with a 10 ppm concentration of sample being able to respond when gas 20 is introduced.
Example 4
QCM sensor detection and 2-chloroethyl Ether (CEEE)
The QCM sensor electrode prepared in example 2, surface coated with 2,5-MeBP3 sensitive membrane material was placed in a detection chamber and then CEEE was loaded into the detection chamber at a concentration of 100 ppm by nitrogen, and the 2,5-MeBP3 crystal sensitive membrane material adsorbed the CEEE while the collected data was processed and plotted as a related response curve by a resonant circuit and sensor frequency response data using computer related software. The results are shown in FIG. 3.
Example 5
Specificity of QCM sensors for CEES and CEEE detection
Referring to the methods of examples 3 and 4, 100 ppm of hydrogen (H) was added, respectively2) Carbon monoxide (CO) and carbon dioxide (CO)2) Water (H)2O), Nitric Oxide (NO), carbon dioxide (NO)2) Ammonia (NH)3) Benzene (benzzene) and Tetrahydrofuran (THF) were passed into the detection chamber for detection, and the results are shown in fig. 4, indicating that the sensor of the present invention has very good specificity for CEES and CEEE.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The quartz crystal microbalance sensor is characterized by comprising a quartz crystal microbalance and a sensitive film material modified on the surface of a quartz crystal electrode; the sensitive membrane material comprises a macrocyclic compound shown in a formula I; the thickness of the sensitive membrane material is 0.5 mu m;
wherein R is C1–8An alkyl group.
2. The quartz crystal microbalance sensor of claim 1, wherein R is C1–4An alkyl group.
3. The method for preparing the sensitive film material modified on the quartz crystal microbalance electrode as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) mixing and dissolving the compounds 1 and 2 in a molar ratio of 2: 1 in dioxane and water, adding 2 equivalents of potassium carbonate and 10% of catalytic amount of 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride, heating, stirring and refluxing for 12 hours under the protection of argon gas, cooling reaction liquid to room temperature after the reaction is finished, spin-drying the solvent, extracting for three times by using dichloromethane and water, mixing an organic phase with silica gel, and performing column chromatography to obtain a cyclic monomer 3; the solvent ratio of dioxane to water is 5: 1;
(2) mixing a monomer 3 and paraformaldehyde according to the molar weight of 1: 1, dissolving in a 1, 2-dichloroethane solution, adding 1 equivalent of boron trifluoride diethyl etherate catalyst, reacting for 20 minutes, quenching with a saturated sodium bicarbonate aqueous solution, washing an organic phase with saturated sodium chloride and water for three times, mixing the organic phase with silica gel, and separating by column chromatography to obtain a macrocyclic compound of the formula I;
（HCHO）nrefers to paraformaldehyde.
4. The method of claim 3, wherein R is selected from the group consisting of methyl, ethyl, and butyl.
5. A preparation method of a quartz crystal microbalance sensor is characterized by comprising the following steps:
(1) ultrasonically cleaning a quartz crystal electrode by deionized water and ethanol for 5 minutes, and then drying for 2 hours at 50 ℃ for later use;
(2) adding the prepared macrocyclic compound shown in the formula I into a quantitative solvent, and obtaining a uniform dispersion liquid under the ultrasonic condition; the solvent is one or a mixture of water and ethanol;
(3) and (3) spin-coating the macrocyclic sensitive material dispersion liquid prepared in the step (2) on the surface of the quartz crystal electrode obtained in the step (1), wherein the thickness of the surface is 0.5 mu m, and performing vacuum drying for 8-10 h at 50 ℃ to obtain the quartz crystal microbalance sensor coated with the macrocyclic sensitive material shown in the formula I.
6. The method of claim 5, wherein R is C1–4Alkyl groups, preferably methyl, ethyl and butyl.
7. The method for preparing a quartz crystal microbalance sensor according to claim 5, wherein the spin coating is performed by: spin coating at low speed for 35-45 s, and spin coating at high speed for 15-25 s.
8. Use of the quartz crystal microbalance sensor according to claim 1 for the quantitative detection of mustard gas and mustard gas simulants, characterized in that the detection method is as follows:
putting the quartz crystal electrode coated with the sensitive membrane of the macrocyclic compound into a sample chamber to be tested, and testing the response curve of the simulating agent according to the mass change of the membrane material adsorbed sample and the change value of the vibration frequency of the quartz crystal electrode; wherein the mustard gas simulant is 2-chloroethyl ethyl sulfide and 2-chloroethyl ethyl ether.
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