CN114146690B - Carbonyl compound trapping agent, trapping device and detection method for carbonyl compounds in exhaled smoke - Google Patents

Abstract

The present invention relates to the technical field of smoke component analysis, and in particular to a carbonyl compound trapping agent, a trapping device and a detection method for carbonyl compounds in exhaled smoke. This carbonyl compound collector is prepared through the following steps: using PS microspheres as the core, using a layer-by-layer self-assembly method to prepare the first metal/SiO ₂ composite hollow sphere; impregnating the first metal/SiO ₂ composite hollow sphere After being placed in the SiO ₂ suspension, take it out and dry it; then plate a second metal on it, and then soak it in an HF solution to remove SiO ₂ to obtain a hollow sphere with open holes; combine the ions of the first metal and the third The dimetallic ions, the hollow spheres and the organic ligands are used together to form a metal-organic framework material; 2,4-dinitrophenylhydrazine is loaded on the metal-organic framework material. This application uses a solid carrier to load 2,4-dinitrophenylhydrazine. When used to capture carbonyl compounds in exhaled smoke, it will not capture other chemical substances in the smoke, thus improving the accuracy of analysis.

Description

Carbonyl compound trapping agent, trapping device and detection device for carbonyl compounds in exhaled smoke Measurement method

Technical field

The invention relates to the technical field of smoke component analysis, and in particular to a carbonyl compound capture agent, a capture device that utilizes the capture agent to capture carbonyl compounds in exhaled smoke, and a capture device that utilizes the capture agent. Method for the detection of carbonyl compounds in exhaled smoke.

Background technique

Cigarette smoke has been confirmed to contain more than 4,850 chemical components, of which 0.6% are harmful components. Among these 0.6% harmful components, 0.2% are carcinogenic or possibly carcinogenic components. Smoking not only harms the smoker's health, but also pollutes the ambient air. Exhaled smoke is an important part of the environmental smoke of traditional cigarettes. However, new tobacco products such as e-cigarettes and heated cigarettes do not produce sidestream smoke and may significantly reduce pollution to the surrounding environment compared with traditional cigarettes. However, during the use of e-cigarettes and heat-not-burn cigarettes, the smoke aerosol exhaled by consumers will still have a certain impact on ambient air quality.

Carbonyl compounds are one of the main harmful components in cigarette smoke. They have a strong stimulating effect on the human respiratory system mucosa. Long-term inhalation will cause great harm to the human body. Formaldehyde, acetaldehyde, acrolein and crotonaldehyde are classified as Category 1, Category 2B and Category 3 carcinogens respectively by the International Agency for Research on Cancer (IARC). Therefore, studying the carbonyl compounds in exhaled smoke is of great significance for studying the impact of smoking on ambient air.

The patent document with publication number CN104267118A discloses such a method for measuring carbonyl compounds in mainstream cigarette smoke. The method includes the following steps: (1) Filling the smoking machine with an adsorption tube with an adsorbent material for capturing carbonyl compounds. In the adsorption tube of the capture device, capture the carbonyl compounds in the mainstream smoke of the cigarette; (2) transfer the adsorption material containing the carbonyl compounds captured in step (1) to the analysis container, and then add the desorption solution for desorption , add 2,4-dinitrophenylhydrazine (DNPH) solution for derivatization to obtain a desorption solution containing carbonyl compounds; (3) use liquid chromatography to desorb the carbonyl compounds obtained in step (2) The solution is tested.

In this application, after using adsorbent materials to capture the flue gas, the carbonyl compounds are captured by reacting the DNPH solution with the carbonyl compounds in the flue gas to form hydrazone compounds. The drawback is that it uses 2,4-dinitro. The phenylhydrazine (DNPH) solution is used for capture, and the 2,4-dinitrophenylhydrazine (DNPH) solution uses acid as the solvent. However, hydrazone derivatives of aldehydes (especially acrolein) are unstable under acidic conditions and are very prone to polymerization to form dimers, which will affect subsequent detection results. At the same time, there are also substances such as nicotine, alcohols, ammonia, and phenols in the flue gas. These substances may be dissolved in the acid solution or react with the acid solution, making the test solution impure and affecting subsequent test results.

Contents of the invention

The present invention aims to solve the above problems by providing a carbonyl compound trapping agent, a trapping device and a detection method for carbonyl compounds in exhaled smoke.

The technical solution of the present invention to solve the problem is to first provide a carbonyl compound trapping agent, which is prepared through the following steps:

S1. Using PS microspheres as cores, the first metal/SiO ₂ composite hollow spheres are prepared using a layer-by-layer self-assembly method;

S2. Dip the first metal/SiO ₂ composite hollow sphere into the SiO ₂ suspension, then take it out and dry it; then plate the second metal on it, and then soak it in the HF solution to remove SiO ₂ to obtain a hollow sphere with open pores. hollow ball;

S3. Make the ions of the first metal, the ions of the second metal, the hollow spheres and organic ligands together to form a metal-organic framework material;

S4. Load 2,4-dinitrophenylhydrazine on the metal organic framework material.

In this application, a carbonyl compound collector and its preparation method are first disclosed. Although the core of this carbonyl compound collector is also 2,4-dinitrophenylhydrazine (DNPH), it is different from the existing technology. Yes, instead of using a DNPH solution, the DBPH powder is loaded on a solid carrier to avoid the impact of the solvent on the capture.

At the same time, this solid carrier is not a conventional metal-organic framework material or metal hollow sphere: in ordinary metal-organic framework materials, when DNPH is loaded on it, it is loaded on its surface, but DNPH powder is easy to oxidize and easily Therefore, it is necessary to reduce the contact between DNPH and air. The metal organic framework material has a large surface area. Although it can increase the load rate, it also results in a large contact area between DNPH and air. There is a problem that DNPH is easily oxidized and flammable. . In ordinary metal hollow spheres, although DNPH can be filled inside the hollow sphere to reduce its contact with the outside air, DNPH is aggregated inside the metal hollow sphere and is difficult to disperse. That is, the surface area of DNPH is small, which will cause trapping. The problem of low collection efficiency. In response to these problems, this application innovatively combines the two and fixes the metal-organic framework material inside the metal hollow sphere, thus obtaining a new type of solid carrier. When loading DNPH, DNPH enters the inside of the metal hollow ball and is loaded on the metal-organic framework inside the metal hollow ball.

It is worth noting that combining the two should not be understood as a method that can be easily thought of by those skilled in the art. Based on the concept, for metal organic framework materials, they need to be coated based on their intended load. Due to the characteristics of DNPH materials, in general fields, the materials to be loaded do not need to reduce contact with the outside air, so there is no idea of coating metal organic framework materials. For metal hollow spheres, if the load area needs to be increased, the usual method is to directly prepare them into a porous structure. However, in this application, since DNPH is to be loaded, the compatibility between metal and DNPH is not good. Only porous metal hollow balls are used to load DNPH, which has the problem of low loading rate.

At the same time, based on the technical solution, how to fix the metal organic framework material inside the metal hollow sphere is also a technical problem. In order to achieve this fixation effect, in this application, the first metal/SiO ₂ composite hollow sphere is first prepared. At this time, the spherical shell of the hollow sphere is composed of the first metal and silica as the inner shell, and is impregnated with the SiO ₂ suspension. Then the middle shell is formed, and the second metal is plated to form the outer shell. At this time, when the silica in the inner shell and the middle shell is removed through chemical action, the inner shell presents a porous structure. At the same time, the outer shell needs to help the entry of HF and the removal of the reaction product of HF and silica. With openings, the silica between the inner shell and the outer shell is removed to form a void. When this hollow sphere is immersed in a mixture of the first metal ion solution, the second metal ion solution and the organic ligand, the first metal ion and the second metal ion lead the organic ligands that are coordinated with it (for convenience Note, denoted as material The linear material X in the opening of the inner shell is combined so that the overall material

Among them, the preparation of hollow spheres through layer-by-layer self-assembly method in step S1 is an existing technology, which uses negatively charged colloidal particles as a template, deposits a layer of positively charged polyelectrolyte on the template, and then adds the negatively charged material to the template. After being adsorbed on the colloid surface, the colloid can be calcined to remove it.

As a preferred method of the present invention, step S1 includes the following steps:

S1a. Mix the silica sol and the ion solution of the first metal to obtain solution C;

S1b. Add PS microspheres to the sodium dodecyl sulfate aqueous solution, wash and dry after ultrasonic to obtain microspheres A;

S1c. Add microsphere A to solution C, raise the temperature to 30-50°C and react for 2-3 hours; then add polyvinylpyrrolidone solution, raise the temperature to 40-85°C and react for 25-60 minutes, wash and dry;

S1d. Calculate the dried microspheres at 400-500°C for 1-2 hours.

As a preferred method of the present invention, steps S1b and S1c can be repeated several times on the dried microspheres obtained in S1c, and then S1d is performed.

In step S2, the first metal/SiO ₂ composite hollow sphere is immersed in the SiO ₂ suspension and then taken out and dried. The purpose of drying is to remove the dispersant in the SiO ₂ suspension. As the preferred method of the present invention, the SiO ₂ suspension Use water as dispersant. In step S2, before plating the second metal, sensitization needs to be performed first. As the preferred method of the present invention, a hydrochloric acid solution of SnCl ₂ is selected as the sensitizing liquid, and the sensitization treatment is performed for 10-12 hours. When plating the second metal, electroless plating is preferably used in the present invention.

The above-mentioned first metal and second metal can be any metal, but considering that there is a danger of DNPH powder being heated and flammable, when loading it, the solid carrier should have good heat dissipation. The first metal and the second metal are Metals with high thermal conductivity. Preferably, the first metal is one or more of Au and Ag. Preferably, the second metal is one or more of Cu and Al.

In step S3, the method of preparing a metal-organic framework material by combining ions of the first metal, ions of the second metal, hollow spheres and organic ligands is basically consistent with the method of preparing metal-organic framework materials in the prior art. As the present invention The optimization includes the following steps:

S3a. Mix the ionic solution of the first metal and the ionic solution of the second metal evenly to obtain solution A;

S3b. Dissolve 1,3,5-benzenetricarboxylic acid in a mixed solution of ethanol and N,N-dimethylformamide to obtain solution B;

S3c. Add the hollow sphere into the mixed solution of solution A and solution B, and keep it at a constant temperature of 100-200r/min and 85-100°C for 12-24h. After the obtained reaction product is purified with ethanol, it is filtered, washed and dried. The metal organic framework material is obtained.

In step S4, when loading DNPH, the DNPH powder can be directly mixed with the metal organic framework material obtained above at a low temperature of 0-10°C. In order to improve the loading uniformity, it is preferred to make DNPH into a solution and then load it, and then remove it. solution. As a preferred method of the present invention, step S4 includes the following steps: dissolve 2,4-dinitrophenylhydrazine in a solvent to obtain a 2,4-dinitrophenylhydrazine solution, and add the metal organic framework material to 2,4-dinitrophenylhydrazine. -In the dinitrophenylhydrazine solution, stir at 100-200r/min for 3-5h, take out the solid matter, and heat to remove the solvent under an inert atmosphere. As a preferred method of the present invention, ethanol is used as the solvent.

Another object of the present invention is to provide a method for detecting carbonyl compounds in exhaled smoke. This detection method uses the carbonyl compound prepared above to capture the carbonyl compounds in exhaled smoke.

As a preferred method of the present invention, this detection method includes the following steps: after letting the exhaled smoke pass through the carbonyl compound trapping agent, use acetonitrile to elute the carbonyl compound trapping agent and collect the eluent; and then use liquid Phase chromatography-ultraviolet detector analysis method is used to analyze and determine the eluent.

As preferred in the present invention, the carbonyl compounds in exhaled smoke include formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, crotonaldehyde, butanone, and butyraldehyde.

As the preferred method of the present invention, the instrument analysis conditions are as follows: the liquid chromatography column is Dionex Acclaim® Explosive E2 (250 mm × 4.6 mm, 120 Å, 5 μm). Flow rate: 1mL/min; injection volume: 10μL; detector: DAD, detection wavelength: 365nm. Analysis time is 45 minutes. Gradient elution conditions are shown in Table 1 below.

Table 1.

Another object of the present invention is to provide a capture device for carbonyl compounds in exhaled smoke, which includes a capture tube. Both ends of the capture tube are connected to a mouthpiece and a gas sampling pump respectively; There is a collection filler made of the carbonyl compound collector prepared above.

Preferably, a three-way valve is provided between the collection tube and the gas sampling pump. The three ports of the three-way valve are connected to the collection pipe, the gas sampling pump and the outside air respectively.

As a preferred method of the present invention, at least two portions of the collection filler are provided in the collection tube, and the distance between two adjacent portions of the collection filler is at least 10 cm. The collection filler close to the gas sampling pump is used to absorb carbonyl compounds in the external air to prevent the carbonyl compounds in the external air from affecting the detection results of the carbonyl compounds in the exhaled smoke.

As a preferred option of the present invention, a smoking behavior recorder is also provided between the mouthpiece and the collection tube. The smoking behavior recorder is an existing technology available on the market. The nozzle end is connected to the mouthpiece, and the plug port is connected to the collection tube. It can record the parameters of the smoke exhaled by volunteers and calculate the volume of the smoke exhaled. In order for the smoking behavior recorder to sense and record data, the outer diameter of the rubber hose connected to the plug interface needs to be about 5~8cm.

Beneficial effects of the present invention:

This application uses a solid carrier to load 2,4-dinitrophenylhydrazine, and obtains a carbonyl compound capturing agent. When used to capture carbonyl compounds in exhaled smoke, it will not capture other carbonyl compounds in the smoke. Chemical substances, when the captured substances are subsequently analyzed, no other chemical substances will affect the analysis results, which improves the accuracy of the analysis.

Description of the drawings

Figure 1 is a schematic structural diagram of a capture device for carbonyl compounds in exhaled smoke;

In the picture: mouthpiece 1, smoking behavior recorder 2, collection tube 3, three-way valve 4, gas sampling pump 5.

Detailed ways

The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the accompanying drawings, but the present invention is not limited to these embodiments.

Example 1

Preparation of carbonyl compound collector:

S1. Dissolve 0.48g of PVP in 100mL of ethanol solution, then pour the solution into a 250mL four-neck bottle equipped with a thermometer, stirrer and condensation device, stir at 70°C for 30min, add 16g of monomer St and 0.16g The initiator AIBN was reacted at 70°C for 8 hours, and PS microspheres were obtained after washing and drying. Add the PS microspheres to a sodium dodecyl sulfate aqueous solution with a concentration of 6 mmol/L, sonicate for 15 minutes, wash and dry, and set aside.

Mix 1g TEOS and 3.8g EtOH, then add 6.4g deionized water and 0.1g nitric acid dropwise under magnetic stirring. After the addition is completed, stir and reflux at 50°C for 3 hours. After cooling, a silica sol is obtained. Add 1gAgNO ₃ to 100 mL of distilled water, then add 5 mL of 25% ammonia water, stir evenly, and obtain an AgNO ₃ solution.

After the above-mentioned silica sol and AgNO ₃ solution are mixed evenly, add the above-mentioned PS microspheres treated with sodium dodecyl sulfate into them, place the system in a 40°C water bath to react for 2.5 hours, and then add it dropwise Add 4 mL of polyvinylpyrrolidone solution, raise the temperature to 65°C, react for 40 minutes, and then wash and dry. .

The dried microspheres were calcined at 450°C for 1.5 hours to obtain Ag/SiO ₂ composite hollow spheres.

S2. Add 1g of silica to 50mL of deionized water and disperse it ultrasonically for 10 minutes to obtain a _SiO2 suspension. Then add the above-mentioned Ag/SiO ₂ composite hollow spheres into the SiO ₂ suspension, disperse it ultrasonically for 5 minutes, let it stand for 2 hours, and then take out the solid material and dry it.

Mix 5gSnCl ₂ ·2H ₂ O, 80mL deionized water, and 50mL hydrochloric acid with a concentration of 30% to obtain a sensitizing solution. The dried composite hollow spheres were added to the sensitizing solution, sensitized at 500 min/r for 11 hours, and then taken out and washed. Take 50 mL of 12 g/L copper sulfate, 80 mL of 13 g/L potassium sodium tartrate, and 20 mL of formaldehyde solution with a concentration of 30%. Mix the washed composite hollow spheres into the mixed solution and react under magnetic stirring at 500 min/r. 2h, complete electroless copper plating.

The composite hollow spheres after electroless copper plating were soaked in a HF solution with a concentration of 30% for 24 hours, and then the solids were taken out, washed and dried to obtain hollow spheres with openings.

S3. Take 10 mL of 0.05 g/mL silver nitrate solution and 10 mL of 0.05 g/mL copper nitrate solution, mix them evenly, and dissolve 1 g of 1,3,5-benzenetricarboxylic acid in 30 mL of ethanol and N,N-dimethylformamide. In a mixed solution with equal volume ratio, mix the above two mixed solutions evenly. Then the hollow spheres were added to the mixture, and the reaction was rotated at 150/min and kept at a constant temperature of 90°C for 18 hours. The obtained reaction product was purified by ethanol, washed and dried by suction filtration to obtain a metal-organic framework material.

S4. Dissolve 0.05g 2,4-dinitrophenylhydrazine in 5mL ethanol. After DNPH is completely dissolved, add 5g of the metal organic framework material obtained above, stir at 150r/min for 4h, take out the solid, and remove the solid The mixture was sealed and stirred under nitrogen protection at 50°C for 0.5 h, and then nitrogen was blown to dryness to obtain a carbonyl compound collector.

Capture of carbonyl compounds in exhaled smoke:

Prepare a collection device, as shown in Figure 1. This collection device includes a mouthpiece 1, a smoking behavior recorder 2, a collection tube 3, a three-way valve 4 and a gas sampling pump 5. The five components are connected by an external A rubber hose with a diameter of 7.5cm is connected. A collection filler is installed in the collection tube 3. The collection filler includes two sieve plates and a carbonyl compound collector filled between the two sieve plates. The filling amount of the carbonyl compound collector is 1000 mg.

When in use, turn the knob of the three-way valve 4 until road c and road b are connected, and turn on the gas sampling pump 5 (the flow rate is set to 5000mL/min). Traditional cigarettes are used for smoking. When the volunteer starts smoking, after each puff, the smoke stays in the mouth for 20 seconds, and then aligns the mouth with the mouthpiece 1 (the face is required to fit the mouthpiece), and at the same time, the three-way Turn the knob of valve 4 until road a and road b are connected. The volunteer slowly exhales the smoke, and the carbonyl compounds in the exhaled smoke are captured by the collection filler in the collection tube 3. When there is no obvious smoke in the pipeline, the volunteer stops blowing, and at the same time, turn the 4-way button of the three-way valve to connect the c and b routes to vent. The volunteer continued to smoke and collected the second puff of exhaled smoke. A total of 9 puffs of exhaled smoke were collected, and the sampling was completed.

Detection of carbonyl compounds in exhaled smoke:

Remove the trapping packing in the trapping tube 3, elute the trapping packing with acetonitrile, collect the eluate, and place a small amount of the eluate into a 2 mL chromatography bottle for HPLC-DAD analysis.

The instrument analysis conditions are as follows: the liquid chromatography column is Dionex Acclaim® Explosive E2 (250mm×4.6mm, 120Å, 5μm). Flow rate: 1mL/min; injection volume: 10μL; detector: DAD, detection wavelength: 365nm. The analysis time is 45 minutes, and the gradient elution conditions are as shown in Table 1 above.

A series of standard working solutions were prepared using formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, crotonaldehyde, 2-butanone, butyraldehyde 2,4-dinitrophenylhydrazone derivatives, and HPLC-DAD analysis under the above conditions was also performed. A standard curve was prepared and each carbonyl compound in the eluate was quantified by external standard method.

Example 2

This embodiment is basically the same as Embodiment 1, and the only difference lies in:

To capture carbonyl compounds in exhaled smoke, heat-not-burn cigarettes are used for smoking.

Example 3

This embodiment is basically the same as Embodiment 1, and the only difference lies in:

To capture carbonyl compounds in exhaled smoke, e-cigarettes are used for smoking.

Example 4

This embodiment is basically the same as Embodiment 1, and the only difference lies in:

Two sets of trapping packings are installed in the trapping tube 3. The distance between the two trapping packings is 10cm. The trapping packing away from the gas sampling pump 5 is used for acetonitrile elution and collection and analysis of the eluate.

Example 5

This embodiment is basically the same as Embodiment 1, and the only difference is that Au is selected as the first metal.

In step S1, add 1g of chloroauric acid to 100 mL of distilled water, then add 0.1g of hydroxylamine hydrochloride, and stir evenly to obtain a chloroauric acid solution.

After the above-mentioned silica sol and chloroauric acid solution are mixed evenly, add the above-mentioned PS microspheres treated with sodium dodecyl sulfate into them, place the system in a 40°C water bath for reaction for 2.5 hours, and then gradually Add 4 mL of polyvinylpyrrolidone solution dropwise, raise the temperature to 65°C, react for 40 minutes, and then wash and dry. .

The dried microspheres were calcined at 450°C for 1.5h to obtain Au/SiO ₂ composite hollow spheres.

In step S3, take 10 mL of 0.05 g/mL chloroauric acid solution and 10 mL of 0.05 g/mL copper nitrate solution and mix them evenly.

Example 6

This embodiment is basically the same as Embodiment 1, and the only difference is that Al is selected as the second metal.

In step S2, mix 50 mL of 12 g/L aluminum chloride, 80 mL of 13 g/L potassium sodium tartrate, and 20 mL of formaldehyde solution with a concentration of 30%. Add the washed composite hollow spheres to the mixed solution, and stir at 500 min/r. The reaction was carried out for 2 hours under magnetic stirring to complete electroless aluminum plating.

In step S3, take 10 mL of 0.05 g/mL silver nitrate solution and 10 mL of 0.05 g/mL aluminum nitrate solution and mix them evenly.

Example 7

This example is basically the same as Example 1, and the only difference is that the parameter conditions for preparing the carbonyl compound trapping agent are different.

S1. After the above-mentioned silica sol and AgNO ₃ solution are mixed evenly, add the above-mentioned PS microspheres treated with sodium dodecyl sulfate into them, place the system in a 30°C water bath to react for 4 hours, and then gradually Add 4 mL of polyvinylpyrrolidone solution dropwise, raise the temperature to 40°C, react for 60 minutes, and then wash and dry. The dried microspheres were calcined at 400°C for 2 hours to obtain Ag/SiO ₂ composite hollow spheres.

S3. Take 10 mL of 0.05 g/mL silver nitrate solution and 10 mL of 0.05 g/mL copper nitrate solution, mix them evenly, and dissolve 1 g of 1,3,5-benzenetricarboxylic acid in 30 mL of ethanol and N,N-dimethylformamide. In a mixed solution with equal volume ratio, mix the above two mixed solutions evenly. Then, hollow spheres were added to the mixture, and the reaction product was kept at a constant temperature of 100°C and 100/min for 24 hours. The obtained reaction product was purified by ethanol, washed and dried by suction filtration to obtain a metal-organic framework material.

S4. Dissolve 0.05g 2,4-dinitrophenylhydrazine in 5mL ethanol. After DNPH is completely dissolved, add 5g of the metal organic framework material obtained above, stir at 100r/min for 5h, take out the solid, and remove the solid The mixture was sealed and stirred under nitrogen protection at 50°C for 1 hour, and then nitrogen was blown to dryness to obtain a carbonyl compound collector.

Example 8

This example is basically the same as Example 1, and the only difference is that the parameter conditions for preparing the carbonyl compound trapping agent are different.

S1. After the above-mentioned silica sol and AgNO ₃ solution are mixed evenly, add the above-mentioned PS microspheres treated with sodium dodecyl sulfate into them, place the system in a 50°C water bath to react for 2 hours, and then gradually Add 4 mL of polyvinylpyrrolidone solution dropwise, raise the temperature to 65°C, react for 25 minutes, and then wash and dry. The dried microspheres were calcined at 500°C for 2 hours to obtain Ag/SiO ₂ composite hollow spheres.

S3. Take 10 mL of 0.05 g/mL silver nitrate solution and 10 mL of 0.05 g/mL copper nitrate solution, mix them evenly, and dissolve 1 g of 1,3,5-benzenetricarboxylic acid in 30 mL of ethanol and N,N-dimethylformamide. In a mixed solution with equal volume ratio, mix the above two mixed solutions evenly. Then, the hollow spheres were added to the mixture, and the reaction product was kept at a constant temperature of 85°C and 200/min for 12 hours. The reaction product was purified by ethanol, filtered, washed and dried to obtain a metal-organic framework material.

S4. Dissolve 0.05g 2,4-dinitrophenylhydrazine in 5mL ethanol. After DNPH is completely dissolved, add 5g of the metal organic framework material obtained above, stir at 200r/min for 3h, take out the solid, and remove the solid The mixture was sealed and stirred under nitrogen protection at 50°C for 1.5 hours, and then nitrogen was blown to dryness to obtain a carbonyl compound collector.

Comparative example 1

This comparative example is basically the same as Example 1, and the only difference lies in that the carbonyl compound trapping agent is different.

Take 10 mL of 0.05 g/mL silver nitrate solution and 10 mL of 0.05 g/mL copper nitrate solution and mix them evenly. Dissolve 1 g of 1,3,5-benzenetricarboxylic acid in 30 mL of ethanol and N, N-dimethylformamide. In a mixed solution with a volume ratio, the above two mixed solutions are mixed evenly, and the obtained reaction product is purified by ethanol, filtered, washed and dried to obtain a metal organic framework material.

Dissolve 0.05g 2,4-dinitrophenylhydrazine in 5mL ethanol. After DNPH is completely dissolved, add 5g of the metal organic framework material obtained above, stir at 150r/min for 4h, take out the solid material, and place the solid material in Stir in a sealed manner under nitrogen protection at 50°C for 0.5 h, and then blow nitrogen to dryness to obtain a carbonyl compound collector.

Comparative example 2

This comparative example is basically the same as Example 1, and the only difference lies in that the carbonyl compound trapping agent is different.

The hollow spheres with open holes obtained in S2 were used as carbonyl collecting agents.

Comparative example 3

The carbonyl compounds in the exhaled smoke are captured using the capture device and capture method disclosed in the patent document with publication number CN104267118A, and analyzed using the instrumental analysis conditions of Example 1 of the present application.

The detection and analysis results in the examples and comparative examples are shown in Table 2 below.

Table 2.

As can be seen from Table 2, the collector in this application can effectively capture various carbonyl compounds in exhaled smoke.

Detection accuracy testing

Prepare a 2,4-dinitrophenylhydrazone derivative solution of 1 mg/mL formaldehyde, a 2,4-dinitrophenylhydrazone derivative solution of 1 mg/mL acetaldehyde, and a 2,4-dinitrophenylhydrazone derivative solution of 1 mg/mL acetone. -Dinitrophenylhydrazone derivative solution, 1 mg/mL acrolein 2,4-dinitrophenylhydrazone derivative solution, 1 mg/mL propionaldehyde 2,4-dinitrophenylhydrazone derivative solution Raw compound solution, 1 mg/mL crotonaldehyde 2,4-dinitrophenylhydrazone derivative solution Raw compound solution, 1 mg/mL 2-butanone 2,4-dinitrophenylhydrazone derivative solution Raw compound solution, 1 mg/ mL butyraldehyde 2,4-dinitrophenylhydrazone derivative compound solution. Take 1 mL of each solution and mix evenly to obtain a sample solution. Prepare 8 samples respectively.

The carbonyl compound trapping agents in Examples 1, 5-8 and Comparative Examples 1-3 were respectively placed in the sample solution and allowed to stand for 10 minutes, then taken out, and then rinsed with acetonitrile, and the eluate was collected. In a 2 mL chromatographic bottle, HPLC-DAD analysis was performed using the instrumental analysis conditions in Example 1. The detection results are shown in Table 3 below.

Table 3. (Units in Table 3 are mg)

It can be seen from Table 3 that by using the carbonyl compound trapping agent of the present application, the trapping amount is closer to the actual value, which can make the detection results more accurate.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which the present invention belongs can make various modifications or additions to the described specific embodiments or substitute them in similar ways, but this will not deviate from the spirit of the present invention or exceed the definition of the appended claims. range.

Claims (8)

1. A carbonyl compound trapping agent, characterized in that: the preparation method comprises the following steps:

s1, preparing a first metal/SiO (silicon dioxide) by taking PS microspheres as cores and adopting a layer-by-layer self-assembly method ₂ Composite hollow spheres;

s2, the first metal/SiO is processed ₂ The composite hollow sphere is immersed in SiO ₂ Taking out and drying the suspension; plating a second metal thereon, soaking in HF solution to remove SiO ₂ Obtaining a hollow sphere with an opening;

s3, preparing the ions of the first metal, the ions of the second metal, the hollow spheres and the organic ligand into a metal-organic framework material;

s4, loading the 2, 4-dinitrophenylhydrazine on the metal organic framework material;

the first metal is one or two of Au and Ag;

the second metal is one or two of Cu and Al.

2. A carbonyl compound trapping agent according to claim 1, wherein: step S3 comprises the steps of:

s3a, uniformly mixing the ionic solution of the first metal and the ionic solution of the second metal to obtain a solution A;

S3B, dissolving 1,3, 5-benzene tricarboxylic acid in a mixed solution of ethanol and N, N-dimethylformamide to obtain a solution B;

s3c, adding the hollow spheres into a mixed solution of the solution A and the solution B, keeping the temperature at the constant temperature of 85-100 ℃ for 12-24 hours at the rotating speed of 100-200r/min, purifying the obtained reaction product by ethanol, and performing suction filtration, washing and drying to obtain the metal organic framework material.

3. A carbonyl compound trapping agent according to claim 1, wherein: the step S4 includes the following steps: 2, 4-dinitrophenylhydrazine is dissolved in a solvent to obtain a 2, 4-dinitrophenylhydrazine solution, the metal organic framework material is added into the 2, 4-dinitrophenylhydrazine solution, the mixture is stirred for 3 to 5 hours at 100 to 200r/min, then the solid is taken out, and the solvent is removed by heating under an inert atmosphere.

4. A detection method of carbonyl compounds in exhaled smoke is characterized in that: a method for capturing carbonyl compounds in exhaled breath by using the carbonyl compound capturing agent as claimed in any one of claims 1 to 3.

5. The method for detecting carbonyl compounds in exhaled breath as claimed in claim 4, wherein: the method comprises the following steps: after the exhaled flue gas passes through the carbonyl compound trapping agent, eluting the carbonyl compound trapping agent by acetonitrile, and collecting eluent; the eluate is then analyzed using liquid chromatography-ultraviolet detector analysis.

6. The device for capturing carbonyl compounds in exhaled smoke comprises a capturing pipe (3), wherein two ends of the capturing pipe (3) are respectively communicated with a blowing nozzle (1) and a gas sampling pump (5); is characterized in that: the trapping pipe (3) is provided with a trapping filler made of the carbonyl compound trapping agent according to any one of claims 1 to 3.

7. The device for capturing carbonyl compounds in exhaled breath as claimed in claim 6, wherein: at least two trapping fillers are arranged in the trapping pipe (3), and at least 10cm of space is reserved between every two adjacent trapping fillers.

8. The device for capturing carbonyl compounds in exhaled breath as claimed in claim 6, wherein: a three-way valve (4) is arranged between the trapping pipe (3) and the gas sampling pump (5).