CN108627380B - Method for removing or reducing toxic substance and method for detecting toxic substance - Google Patents
Method for removing or reducing toxic substance and method for detecting toxic substance Download PDFInfo
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Abstract
The invention belongs to the technical field of toxic substance removal/detection, and particularly relates to a method for removing or reducing toxic substances in an environment or a sample, wherein the toxic substances are one or more selected from mustard gas, bis (2-chloroethyl) ether, chloroethyl ethyl sulfide and chloroethyl ethyl ether; the method comprises the following steps: contacting the compound shown in the formula I with a toxic substance in a molar ratio of (1-10) to 1; wherein R is C1‑12An alkoxy group. Also relates to a quartz crystal microbalance sensor and a preparation method thereof. The compound shown in the formula I or the quartz crystal microbalance sensor can effectively remove, reduce and/or detect toxic substances in an environment or a sample, wherein the toxic substances are one or more selected from mustard gas, bis (2-chloroethyl) ether, chloroethyl ethyl sulfide and chloroethyl ethyl ether.
Description
Technical Field
The invention belongs to the technical field of toxic substance removal/detection, relates to a method for removing or reducing toxic substances, in particular to a method for removing or reducing toxic substances in an environment or a sample, a method for detecting toxic substances, and further relates to a quartz crystal microbalance sensor, a preparation method and application thereof.
Background
Mustard gas (sulfurr Mustard), chemically known as bis (2-chloroethyl) sulfide, has the following structural formula:
mustard gas is generally a colorless or light yellow liquid, volatile, having a garlic, mustard-like taste. Mustard gas is a chemical agent with great toxic effect, namely a liquid blister agent, and is used for manufacturing a toxic gas bomb; mustard gas contacts skin, eyes, respiratory tract and digestive tract of human body to cause damage to different degrees, after the skin is infected with liquid drops or vapor mustard gas, about 10% of mustard gas can be combined with the skin, and the rest 90% of free mustard gas can be distributed to organs such as kidney, liver, gastrointestinal tract and lung through blood circulation. The mustard original shape has short in vivo retention time, one part is metabolized in vivo to become nontoxic or low poison, and the other part reacts with DNA, RNA, certain proteins, enzyme, etc. in vivo to form hydrocarbonylation product, which can make cell metabolism and function generate disorder, such as degeneration, inflammation, necrosis, etc.
Mustard gas has gained widespread use in the first world war and the second world war since its synthesis in the early 19 th century, and has resulted in a significant loss of membership. During the second war, Japan leaves a large number of chemical weapons in China, and many inevitable casualties are continuously caused due to lack of relevant knowledge; for example, the china, the warrior, has buried a large amount of poison gas bomb underground, resulting in the occurrence of the daily loss of poison gas in recent years in many provinces such as Heilongjiang and Jilin. According to incomplete statistics, China has found that about 200 ten thousand of each daily residual gas bomb and about 100 ten thousand tons of toxic agent are distributed in more than ten provinces of China, and more than 2000 persons suffer from direct injury. In addition, mustard gas poisoning is not treatable by medicines at present, and the international agency for research on cancer (IARC) has also confirmed that mustard gas is a carcinogen, so that the research significance on removal, detection and detoxification of mustard gas is great. At present, the detection methods of mustard gas mainly comprise a colorimetric method, a gas chromatography-mass spectrometry (GC-MS), a liquid chromatography method, a radioactive labeling method and the like, and most of the methods need large-scale instruments and equipment, so that the operation is complex.
Bis (2-chloroethyl) ether (BCEE) is typically a colorless oily liquid with a chloroform-like odor. BCEE vapor is toxic, easily absorbed by the skin, and belongs to the high toxicity category due to its strong irritation. Human briefly contacts 3.2g/m3The BCEE vapor with the above concentration has obvious irritation to eyes and nasal cavity, intolerable feeling, cough, nausea and emesis, slowly damages lung, and has allowable maximum concentration of 90mg/m at workplace3. Pulmonary edema can occur after hours or days of inhalation of high concentrations of BCEE vapor. The structural formula of bis (2-chloroethyl) ether is as follows:
chloroethyl ethyl sulfide (CEES) has an irritant effect on eyes, respiratory system and skin, is toxic to swallow, and has a carcinogenic effect reported to a few, and has a structural formula:
chloroethyl ethyl ether (CEEE) is generally a colorless liquid, highly flammable, toxic to inhale and swallow, irritating to the eyes, respiratory system and skin, and especially severely damaging to the eyes. The structural formula of chloroethyl ethyl ether is as follows:
at present, there is a need for new methods for removing the above four toxic substances and methods for detecting the above four toxic substances.
Pillar arenes, as new generation supramolecular macrocyclic hosts, were first reported in 2008 by Ogoshi and Nakamoto et al in the journal of the american chemical society (j.am.chem.soc.), a class of cyclic oligomers formed by hydroquinone or hydroquinone ethers linked in the para position of the benzene ring through methylene bridges. The pillared aromatic hydrocarbon is a cylindrical structure in a spatial structure rather than a calixarene basket structure, so that the pillared aromatic hydrocarbon is superior to the calixarene when an interpenetrating complex and a tubular assembly are constructed, and the pillared aromatic hydrocarbon has a more rigid framework. At present, the research on derivatization, molecular recognition and assembly of the novel column arene becomes a focus of attention of chemists, and the utilization of the column arene for removing the four toxic substances is never reported.
Quartz Crystal Microbalance (QCM) is a sensitive sensor based on mass change, and has the advantages of very high sensitivity, specificity, simple operation, etc. The principle of the QCM is that by utilizing the inverse piezoelectric effect of a quartz crystal, the quartz crystal can generate vibration with a certain frequency under an alternating electric field, the frequency of the vibration is related to the mass of the crystal, and if substances are adsorbed on the surface of the crystal, the change of the mass can change the vibration frequency to generate frequency shift. This frequency shift and the quality increment have an equation called sauerbrey. In 1959, Sauerbrey derived the Sauerbrey equation for the relationship between the mass loaded on the surface of the piezoelectric crystal in the gas phase and the resonance frequency shift:
ΔF＝-2.26×10-6F2ΔM/A
wherein, Δ F represents the frequency change (Hz) of the piezoelectric crystal, F represents the original vibration frequency (Hz) of the piezoelectric crystal, Δ M represents the mass change value (g) of the substance loaded on the crystal surface, and A represents the area (cm) covered by the adsorbed substance2). The change in surface mass of the QCM can be calculated from the change in Δ F, and the concentration of the gas can be inferred.
Disclosure of Invention
It is an object of the present invention to provide a method for removing or reducing toxic substances in an environment or sample, wherein the toxic substances are one or more selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulfide and chloroethylethyl ether. One of the objects of the present invention is to provide a novel quartz crystal microbalance sensor. One of the objects of the present invention is to provide a novel method for manufacturing a quartz crystal microbalance sensor. It is another object of the present invention to provide a method for detecting one or more toxic substances selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulfide and chloroethylethyl ether. It is also an object of the present invention to provide the use of an alkoxy column [5] arene or a quartz crystal microbalance sensor of the present invention for removing, reducing and/or detecting toxic substances in an environment or sample, said toxic substances being one or more selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulfide and chloroethylethyl ether.
The present invention relates in a first aspect to a method of removing or reducing toxic substances in an environment or sample, the toxic substances being one or more selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulphide and chloroethylethyl ether;
the method comprises the following steps:
contacting the compound shown in the formula I with toxic substances in the environment or a sample in a molar ratio of (1-10) to 1;
wherein R is C1-12An alkoxy group.
In one embodiment of the invention, the molar ratio of the compound of formula I to the toxic substances in the environment or sample is (1-6):1, preferably 1: 1.
In one embodiment of the invention, the sample is a liquid sample or a gaseous sample.
In one embodiment of the invention, R is C1-6Alkoxy, preferably methoxy, ethoxy, propoxyButoxy or pentyloxy, more preferably methoxy, ethoxy or butoxy.
The second aspect of the invention relates to a quartz crystal microbalance sensor, which comprises a quartz crystal microbalance and a thin film loaded on the surface of an electrode of the quartz crystal microbalance; wherein the film comprises a compound of formula I;
wherein R is C1-12An alkoxy group.
The quartz crystal microbalance sensor according to the second aspect of the present invention, wherein the thin film has a thickness of 0.1 to 2 μm, preferably 0.2 to 1 μm, and more preferably 0.5 μm.
According to a second aspect of the invention, a quartz crystal microbalance sensor is provided, wherein R is C1-6The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentoxy group, and more preferably a methoxy group, an ethoxy group or a butoxy group.
The third aspect of the present invention relates to a method for manufacturing the quartz crystal microbalance sensor according to the second aspect, comprising the steps of:
(1) mixing a compound shown as a formula I with a solvent to obtain a suspension;
(2) coating the suspension on the surface of an electrode of a quartz crystal microbalance, and drying to obtain a quartz crystal microbalance sensor;
wherein R is C1-12An alkoxy group.
The production method according to the third aspect of the present invention, wherein, in the step (1), the solvent is one or more selected from the group consisting of water, acetone and ethanol.
The production method according to the third aspect of the present invention, wherein, in the step (2), the coating is a drop coating or spin coating, preferably a drop coating; more preferably, the dropping speed of the suspension during the dropping is 6 to 130. mu.L/min, and still more preferably 10. mu.L/min, 30. mu.L/min, 50. mu.L/min, 70. mu.L/min, 90. mu.L/min, 100. mu.L/min, 110. mu.L/min, 120. mu.L/min or 123. mu.L/min.
The production method according to the third aspect of the invention, wherein, in the step (1), the mixing is performed under ultrasonic conditions; preferably, the ultrasonic frequency is 10-70kHz, more preferably 20-40 kHz.
The production method according to the third aspect of the invention, wherein, in the step (2), the drying is performed under vacuum conditions;
preferably, the drying temperature is 33 to 69 ℃, more preferably 40 to 60 ℃, and further preferably 50 ℃;
preferably, the drying time is 16 to 50 minutes, more preferably 20 to 40 minutes, and further preferably 30 minutes.
Preferably, the relative degree of vacuum is from-0.05 MPa to-0.1 MPa.
The production process according to the third aspect of the invention, wherein R is C1-6The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentoxy group, and more preferably a methoxy group, an ethoxy group or a butoxy group.
The fourth aspect of the present invention relates to a method for detecting a toxic substance, which is one or more selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulfide and chloroethylethyl ether;
the detection method comprises the following steps:
the quartz crystal microbalance sensor according to the second aspect of the present invention is configured such that the electrode loaded with the thin film is placed in an environment or a sample, and the content of the toxic substance in the environment or the sample is calculated from the change value of the vibration frequency of the quartz crystal before and after the placement of the electrode in the sensor.
The detection method according to the fourth aspect of the present invention, wherein the sample is a gaseous sample or a liquid sample.
The fifth aspect of the invention relates to the use of a compound of formula i or a quartz crystal microbalance sensor according to any of the second aspects of the invention for removing, reducing and/or detecting toxic substances in an environment or sample; wherein the toxic substance is one or more selected from mustard gas, bis (2-chloroethyl) ether, chloroethyl ethyl sulfide and chloroethyl ethyl ether;
wherein R is C1-12An alkoxy group.
Use according to a fifth aspect of the invention, wherein R is C1-6The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentoxy group, and more preferably a methoxy group, an ethoxy group or a butoxy group.
The use according to the fifth aspect of the invention, wherein the sample is a gaseous sample or a liquid sample.
In the present invention, unless otherwise specified:
the term "sensor" refers to a detecting device, which can sense the measured information and convert the sensed information into electrical signals or other information output in required form according to a certain rule, so as to meet the requirements of information transmission, processing, storage, display, recording, control and the like.
The term "quartz crystal microbalance" mainly comprises a quartz crystal sensor, signal collection, signal detection, data processing and the like. The quartz crystal sensor is a core component thereof, and the basic structure is as follows: a quartz crystal oscillation piece is obtained by cutting (AT-CUT) from a quartz crystal along the 35 degrees and 15' relative to the main optical axis of the quartz crystal. Gold layers are coated on two corresponding surfaces of the quartz crystal sandwich structure to serve as electrodes, and the quartz crystal sandwich structure is formed between the two electrodes. The quartz crystal microbalance utilizes the piezoelectric effect of quartz crystal to convert the surface quality change of quartz crystal electrode into the frequency change of the output electric signal of quartz crystal oscillation circuit, so as to obtain high-precision data through other auxiliary equipment such as computer.
The term "suspension" (suspension) means that solid particles are dispersed in a liquid and do not settle down quickly due to brownian motion, and a mixture of the solid dispersed phase and the liquid is called a suspension. The particle size of the solid particles in the suspension is 10-3～10- 4cmIs larger than the colloid.
The term "coating" refers to covering a substrate surface with a layer of material.
The term "dispensing" refers to covering the electrode surface with a layer of material by slow dispensing.
The term "spin coating" refers to contacting the electrode surface with a suspension of the material and spinning the electrode so that the electrode surface is coated with a layer of the material.
The term "bis (2-chloroethyl) ether" is abbreviated in english to BCEE and has the following structural formula:
the term "chloroethylethylthio" is abbreviated as CEES in english and has the following structural formula:
the term "chloroethyl ethyl ether" is abbreviated English to CEEE and has the following structural formula:
the invention has the following beneficial effects:
1. the method can effectively remove or reduce toxic substances in the environment or the sample, wherein the toxic substances are one or more selected from mustard gas, bis (2-chloroethyl) ether, chloroethyl ethyl sulfide and chloroethyl ethyl ether.
2. The method for preparing the quartz crystal microbalance sensor obtains a novel quartz crystal microbalance sensor.
3. The detection method has strong response capability to toxic substances, and can accurately determine the content of the toxic substances, wherein the toxic substances are one or more selected from mustard gas, bis (2-chloroethyl) ether, chloroethyl ethyl sulfide and chloroethyl ethyl ether.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 shows the results of example 1 before and after mixing BuP5A with mustard gas1H-NMR chart;
FIG. 2 shows BuP5A and BCEE before and after mixing in example 11H-NMR chart;
FIG. 3 shows BuP5A and CEES before and after mixing in example 11H-NMR chart;
FIG. 4 shows BuP5A and CEEE mixed before and after1H-NMR chart;
FIG. 5 is a time-frequency response curve of the quartz crystal microbalance sensor detecting CEES in example 3;
FIG. 6 shows the detection of CEES, water vapor and CO by a quartz crystal microbalance sensor2Comparative figures of results.
Detailed Description
Example 1: removing mustard gas (SM), bis (2-chloroethyl) ether (BCEE), chloroethyl ethyl sulfide (CEES), and chloroethyl
Ethyl Ether (CEEE)
Butyl oxygen column [5] is weighed accurately]15.22mg of aromatic hydrocarbon (BuP5A) was dissolved in 2.6mL of deuterated o-xylene to prepare a bulk solution having a concentration of 5 mmol/L. Then, taking multiple 0.5mL host solutions, and respectively absorbing guest molecules SM 0.313 mu L (5mmol/L), BCEE 0.293 mu L (5mmol/L), CEES 0.291 mu L (5mmol/L), CEEE 0.274 mu L (5mmol/L) and the host to prepare a mixture with the molar concentration of 1: 1. Finally, the single host, the single object and the mixed system are carried out1The results of H-NMR measurement are shown in FIGS. 1 to 4.
As can be seen from fig. 1-4, when the host molecule BuP5A is added to the guest, the chemical shifts of hydrogen on the guest molecules are shifted to high fields with different magnitudes, and the peak pattern is significantly broadened or even disappears. This is due to the fact that the shielding of the guest molecules penetrating into the cavities of BuP5A results in a shift of the chemical potential of the hydrogen protons to a high field. Meanwhile, since the host molecule BuP5A is affected by the unshielding effect, the chemical shift of the hydrogen atom on it will shift to the low field, and the change value of the chemical shift of the hydrogen on the host aromatic ring is shown in table 1.
TABLE 1
In table 1, as can be seen from the magnitude of the chemical shift change between the host and the guest, the host molecule BuP5A has certain interaction with mustard gas and 3 mustard gas mimics BCEE, CEES and CEEE. When the guest molecule changes by O → S in the middle, the host chemical shift becomes large, indicating that the host-guest interaction increases. The main body has strong removing ability to mustard gas and the like.
Example 2: preparation of quartz crystal microbalance sensor
Dissolving 1.5g of butoxy-based column [5] arene (BuP5A) material in 15g of water, treating for 30 minutes under 40kHz ultrasonic radiation, preparing stabilized water suspension, sucking 5-10 microliters of the suspension obtained by a micro-syringe, dripping the suspension into an electrode area of a quartz crystal vibrating piece of a quartz crystal microbalance at the speed of 120 microliter/min, and heating in a vacuum furnace at the temperature of 50 ℃ for 30 minutes to remove water, thus obtaining the quartz crystal microbalance sensor with a modified layer of BuP5A film with the thickness of 0.5 micrometer coated on the surface of the electrode area.
Example 3: detection of CEES by quartz crystal microbalance sensor
The electrode prepared in example 2, the surface of which was coated with the film modified with BuP5A, was placed in a detection chamber, then 100ppm CEES was introduced into the detection chamber using nitrogen as a carrier gas, and at the same time, frequency response data collected by a frequency meter, which was sensed by a quartz crystal microbalance crystal in the detection chamber, was recorded by a computer of a signal collection system, and the results are shown in fig. 5. Figure 5 shows that the sensor has a very fast response to CEES, and that the response of the sensor is balanced within 40s of the gas introduced.
2Comparative example: detection of water vapor and CO by quartz crystal microbalance sensor
Referring to the method of example 3, 100ppm of steam and 100ppm of CO were added, respectively2The results of the detection by passage into the detection chamber, compared with example 3, are shown in FIG. 6, which shows thatThe sensor of the present invention has very good selectivity for CEES, and its response capability to CEES is water vapor or CO2More than 5 times.
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 (36)
1. A method of removing or reducing toxic substances in an environment or sample, the toxic substances being one or more selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulfide and chloroethylethyl ether;
the method comprises the following steps:
contacting the compound shown in the formula I with toxic substances in the environment or a sample in a molar ratio of (1-10) to 1;
wherein R is C1-12An alkoxy group.
2. The method of claim 1, wherein the molar ratio of the compound of formula i to the toxic substance in the environment or sample is (1-6): 1.
3. The method of claim 1, wherein the molar ratio of the compound of formula i to the toxic substance in the environment or sample is 1: 1.
4. The method of claim 1, wherein the sample is a liquid sample or a gaseous sample.
5. The method of any one of claims 1 to 4Wherein R is C1-6An alkoxy group.
6. The method of any one of claims 1 to 4, wherein R is methoxy, ethoxy, propoxy, butoxy, or pentoxy.
7. The method of any one of claims 1 to 4, wherein R is methoxy, ethoxy, or butoxy.
8. A quartz crystal microbalance sensor comprises a quartz crystal microbalance and a thin film loaded on the surface of an electrode of the quartz crystal microbalance; wherein the film comprises a compound of formula I;
wherein R is C1-12An alkoxy group.
9. The quartz crystal microbalance sensor of claim 8, wherein the thin film has a thickness of 0.1-2 μm.
10. The quartz crystal microbalance sensor of claim 8, wherein the thin film has a thickness of 0.2-1 μm.
11. The quartz crystal microbalance sensor of claim 8, wherein the thin film has a thickness of 0.5 μm.
12. The quartz crystal microbalance sensor of any one of claims 8 to 11, wherein R is C1-6An alkoxy group.
13. The quartz crystal microbalance sensor of any one of claims 8 to 11, wherein R is methoxy, ethoxy, propoxy, butoxy or pentoxy.
14. The quartz crystal microbalance sensor of any one of claims 8 to 11, wherein R is methoxy, ethoxy or butoxy.
15. A method of making the quartz crystal microbalance sensor of any one of claims 8 to 14, comprising the steps of:
(1) mixing a compound shown as a formula I with a solvent to obtain a suspension;
(2) coating the suspension on the surface of an electrode of a quartz crystal microbalance, and drying to obtain a quartz crystal microbalance sensor;
wherein R is C1-12An alkoxy group.
16. The method according to claim 15, wherein in step (1), the solvent is selected from one or more of water, acetone and ethanol.
17. The method of claim 15, wherein in step (2), the coating is drop coating or spin coating.
18. The process according to any one of claims 15 to 17, wherein in step (1), the mixing is carried out under ultrasonic conditions.
19. The method according to any one of claims 15 to 17, wherein in step (2), the drying is performed under vacuum conditions.
20. The process according to any one of claims 15 to 17, wherein in step (2), the drying temperature is 33-69 ℃.
21. The method according to any one of claims 15 to 17, wherein in step (2), the drying temperature is 40-60 ℃.
22. The method according to any one of claims 15 to 17, wherein in step (2), the drying temperature is 50 ℃.
23. The method according to any one of claims 15 to 17, wherein in step (2), the drying time is 16-50 minutes.
24. The method according to any one of claims 15 to 17, wherein in step (2), the drying time is 20-40 minutes.
25. The method according to any one of claims 15 to 17, wherein in step (2), the drying time is 30 minutes.
26. The method according to claim 19, wherein in the step (2), the relative vacuum degree is from-0.05 MPa to-0.1 MPa.
27. The method of any one of claims 15-17, wherein R is C1-6An alkoxy group.
28. The method of any one of claims 15 to 17, wherein R is methoxy, ethoxy, propoxy, butoxy, or pentoxy.
29. The method of any one of claims 15 to 17, wherein R is methoxy, ethoxy, or butoxy.
30. A method for detecting a toxic substance, which is one or more selected from the group consisting of mustard gas, bis (2-chloroethyl) ether, chloroethylethyl sulfide and chloroethylethyl ether;
the detection method comprises the following steps:
placing the thin film-loaded electrode of the quartz crystal microbalance sensor according to any one of claims 8 to 14 in an environment or a sample, and calculating the content of the toxic substance in the environment or the sample based on the variation value of the vibration frequency of the quartz crystal before and after the placement in the sensor.
31. The method of claim 30, wherein the sample is a gaseous sample or a liquid sample.
32. Use of a compound of formula i or a quartz crystal microbalance sensor according to any one of claims 8 to 14 for removing, reducing and/or detecting toxic substances in an environment or sample; wherein the toxic substance is one or more selected from mustard gas, bis (2-chloroethyl) ether, chloroethyl ethyl sulfide and chloroethyl ethyl ether;
wherein R is C1-12An alkoxy group.
33. The use of claim 32, wherein R is C1-6An alkoxy group.
34. The use of claim 32, wherein R is methoxy, ethoxy, propoxy, butoxy, or pentoxy.
35. The use according to claim 32, wherein R is methoxy, ethoxy or butoxy.
36. The use of claim 32, wherein the sample is a gaseous sample or a liquid sample.
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