CN114146690A - Carbonyl compound trapping agent, trapping device for carbonyl compound in exhaled smoke and detection method - Google Patents
Carbonyl compound trapping agent, trapping device for carbonyl compound in exhaled smoke and detection method Download PDFInfo
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- CN114146690A CN114146690A CN202111459658.5A CN202111459658A CN114146690A CN 114146690 A CN114146690 A CN 114146690A CN 202111459658 A CN202111459658 A CN 202111459658A CN 114146690 A CN114146690 A CN 114146690A
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- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 80
- 239000000779 smoke Substances 0.000 title claims abstract description 34
- 238000001514 detection method Methods 0.000 title abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 20
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 20
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 20
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 239000000126 substance Substances 0.000 abstract description 10
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 20
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- 150000001875 compounds Chemical class 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
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- 239000003571 electronic cigarette Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- -1 hydrazone compound Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- 210000000214 mouth Anatomy 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- 238000010812 external standard method Methods 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 210000004877 mucosa Anatomy 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- Biochemistry (AREA)
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Abstract
The invention relates to the technical field of flue gas component analysis, in particular to a carbonyl compound trapping agent, a trapping device and a detection method for carbonyl compounds in exhaled flue gas. The carbonyl compound trapping agent is prepared by the following steps: preparing first metal/SiO by using PS microspheres as cores and adopting a layer-by-layer self-assembly method2Composite hollow spheres; the first metal/SiO2The composite hollow ball is dipped in SiO2Taking out and drying the suspension; then plating a second metal on the second metal, and soaking the second metal in HF solution to remove SiO2Obtaining hollow spheres with open pores; mixing the ions of the first metal, the ions of the second metal, the hollow spheres and an organic ligandThe bodies together are made into a metal organic framework material; and (2) loading 2, 4-dinitrophenylhydrazine on the metal organic framework material. The application adopts the solid carrier to load the 2, 4-dinitrophenylhydrazine, and when the solid carrier is used for trapping carbonyl compounds in exhaled smoke, other chemical substances in the smoke cannot be trapped, so that the accuracy of analysis is improved.
Description
Technical Field
The invention relates to the technical field of flue gas component analysis, in particular to a carbonyl compound trapping agent, a trapping device for trapping carbonyl compounds in exhaled flue gas by using the trapping agent, and a method for detecting carbonyl compounds in exhaled flue gas by using the trapping agent.
Background
Cigarette smoke has been identified to contain 4850 chemical components, of which 0.6% are harmful components and 0.2% of the 0.6% are carcinogenic or potentially carcinogenic components. Smoking is not only a health hazard to smokers, but also pollution to the ambient air. Exhaled smoke is an important part of the environmental smoke of a traditional cigarette. However, neither new tobacco products such as e-cigarettes nor heated cigarettes produce sidestream smoke and the pollution to the surrounding environment may be significantly reduced compared to conventional cigarettes. However, in the use process of the electronic cigarette and the cigarette which is not heated and combusted, the smoke aerosol exhaled by the consumer still has certain influence on the quality of the ambient air.
The carbonyl compound is a main harmful component in cigarette smoke, has strong stimulation effect on respiratory system mucosa of a human body, and can generate great harm to the human body after being inhaled for a long time. Formaldehyde, acetaldehyde, acrolein, and crotonaldehyde are classified as group 1, group 2B, and group 3 carcinogens by the international agency for research on cancer (IARC), respectively. Therefore, the research on carbonyl compounds in the exhaled smoke has very important significance for researching the influence of smoking on the ambient air.
Patent document CN104267118A discloses a method for determining carbonyl compounds in mainstream smoke of cigarettes, which comprises the following steps: (1) filling an adsorption material for trapping carbonyl compounds into an adsorption tube of a cigarette machine trapping device with the adsorption tube, and trapping the carbonyl compounds in the mainstream smoke of the cigarettes; (2) transferring the adsorbing material trapping the carbonyl compound in the step (1) into an analyzing container, adding a desorption solution for desorption, adding a 2, 4-Dinitrophenylhydrazine (DNPH) solution for derivatization treatment, and obtaining a desorption solution containing the carbonyl compound; (3) detecting the desorption solution containing the carbonyl compound obtained in the step (2) by using liquid chromatography.
In this application, after the flue gas is captured by using the adsorbing material, the DNPH solution reacts with the carbonyl compound in the flue gas to capture the carbonyl compound with the characteristic of generating a hydrazone compound, and the defects of the method are as follows: the method adopts a 2, 4-Dinitrophenylhydrazine (DNPH) solution for trapping, and the 2, 4-Dinitrophenylhydrazine (DNPH) solution takes acid liquor as a solvent. However, hydrazone derivatives of aldehydes (especially acrolein) are unstable under acidic conditions, and are very likely to undergo polymerization to form dimers, thereby affecting the subsequent detection results. Meanwhile, nicotine, alcohols, ammonia, phenols and other substances exist in the smoke, and the substances may be dissolved in the acid solution or react with the acid solution, so that the detection solution is impure, and the subsequent detection result is also affected.
Disclosure of Invention
The present invention is made to solve the above problems, and provides a carbonyl compound trapping agent, a device for trapping a carbonyl compound in exhaled breath, and a method for detecting a carbonyl compound in exhaled breath.
The technical scheme for solving the problems is to provide a carbonyl compound trapping agent, which is prepared by the following steps:
s1, preparing first metal/SiO by using PS microspheres as cores and adopting a layer-by-layer self-assembly method2Composite hollow spheres;
s2, enabling the first metal/SiO2The composite hollow ball is dipped in SiO2Taking out and drying the suspension; then plating a second metal on the second metal, and soaking the second metal in HF solution to remove SiO2Obtaining hollow spheres with open pores;
s3, preparing the ions of the first metal, the ions of the second metal, the hollow spheres and an organic ligand into a metal organic framework material;
s4, loading 2, 4-dinitrophenylhydrazine on the metal organic framework material.
In the present application, a carbonyl compound trapping agent and a method for producing the same are disclosed, in which a core of the carbonyl compound trapping agent is 2, 4-Dinitrophenylhydrazine (DNPH), but unlike the prior art, DBPH powder is supported on a solid support without using a DNPH solution, thereby avoiding the influence of a solvent on trapping.
Meanwhile, the solid carrier is not a conventional metal organic framework material or a metal hollow sphere: in a common metal organic framework material, DNPH is loaded on the surface of the metal organic framework material, but DNPH powder has the problems of easy oxidation and easy flammability, so that the contact between DNPH and air needs to be reduced. In a common metal hollow ball, DNPH can be filled in the hollow ball to reduce the contact with the outside air, but the DNPH is in an aggregation state in the metal hollow ball and is difficult to disperse, namely the DNPH has a small surface area, so that the problem of low trapping efficiency is caused. Aiming at the problems, the organic metal framework material and the organic metal framework material are innovatively combined to fix the organic metal framework material and the organic metal framework material inside the hollow metal ball, so that a novel solid carrier is obtained. When DNPH is loaded, DNPH enters the interior of the metal hollow sphere and is loaded on the metal organic framework in the metal hollow sphere.
It is to be noted that combining the two should not be understood as a method that the skilled person can easily think of, based on the idea that for metal organic framework materials, which need to be coated, is based on the characteristics of the DNPH material that it is to be loaded with, in the general field, the material to be loaded does not need to reduce the contact with the outside air and therefore does not create the idea of coating metal organic framework materials. In the case of a hollow metal sphere, if the loading area needs to be increased, the hollow metal sphere is generally prepared into a porous structure directly, but in the present application, DNPH is loaded, so that the compatibility between metal and DNPH is not good, and the problem of low loading rate is caused by loading DNPH only with the hollow metal sphere.
Meanwhile, on the basis of the technical scheme, how to fix the metal organic framework material inside the metal hollow sphere is also a technical problem. To achieve this anchoring effect, in the present application, first a first metal/SiO is prepared2The composite hollow sphere has an inner shell made of first metal and silicon dioxide and impregnated with SiO2Forming an intermediate shell after the suspension, and forming an outer shell after plating a second metal. At this time, when the silica is removed from the inner shell and the intermediate shell by chemical action, the inner shell has a porous structure, and the outer shell has open pores due to the need to facilitate the entry of HF and the removal of the reaction product of HF and silica, and the silica between the inner shell and the outer shell is removed to form voids. When the hollow sphere is immersed in a mixed solution of a first metal ion solution, a second metal ion solution and an organic ligand, the organic ligand (for convenience of explanation, denoted as material X) which is coordinated and connected with the first metal ion and the second metal ion simultaneously enters the inner shell of the hollow sphere and the gap between the inner shell and the outer shell, and the block material X positioned in the inner shell is combined with the block material X positioned in the gap and the linear material X positioned in a plurality of openings of the inner shell, so that the integral material X covers the inner shell, and the fixation of the material X on the hollow metal sphere is realized.
The step S1 is to prepare the hollow sphere by a layer-by-layer self-assembly method, which is a prior art, and is to deposit a layer of positively charged polyelectrolyte on a template, and then to remove the colloid by calcining after the negatively charged material is adsorbed on the surface of the colloid.
Preferably, step S1 includes the steps of:
s1a, mixing the silica sol and the ionic solution of the first metal to obtain a solution C;
s1b, adding the PS microspheres into a sodium dodecyl sulfate aqueous solution, and washing and drying after ultrasonic treatment to obtain microspheres A;
s1c, adding the microspheres A into the solution C, heating to 30-50 ℃, and reacting for 2-3 h; then adding polyvinylpyrrolidone solution, heating to 40-85 ℃, reacting for 25-60min, washing and drying;
s1d, calcining the dried microspheres at the temperature of 400-500 ℃ for 1-2 h.
In a preferred embodiment of the present invention, the dried microspheres obtained in S1c are subjected to steps S1b and S1c several times, and then to S1d.
In step S2, the first metal/SiO2The composite hollow ball is dipped in SiO2Taking out and drying the suspension to remove SiO2Dispersing agents in suspension, preferred for the present invention, SiO2The suspension takes water as a dispersing agent. In step S2, sensitization is required before plating the second metal, and as a preferred option of the present invention, SnCl is used as the sensitizing solution2And (5) carrying out sensitization treatment for 10-12h by using a hydrochloric acid solution. In the case of plating the second metal, electroless plating is preferably used in the present invention.
The first metal and the second metal may be any metals, but the first metal and the second metal are metals having high thermal conductivity, considering that the solid support should have good heat dissipation when it is loaded because DNPH powder is liable to be thermally flammable. 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 for preparing the metal-organic framework material by combining the ions of the first metal, the ions of the second metal, the hollow spheres and the organic ligand is substantially the same as the method for preparing the metal-organic framework material in the prior art, and preferably includes the following steps:
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;
and S3c, adding the hollow spheres into a mixed solution of the solution A and the solution B, keeping the temperature at the rotation speed of 100-200r/min and the temperature of 85-100 ℃ for 12-24h, purifying the obtained reaction product by using ethanol, and then performing suction filtration, washing and drying to obtain the metal organic framework material.
In step S4, when DNPH is loaded, DNPH powder may be directly mixed with the metal organic framework material obtained as described above at a low temperature of 0 to 10 ℃, and in order to improve the uniformity of loading, it is preferable to load DNPH after making it into a solution, and then remove the solution. Preferably, step S4 includes the following steps: dissolving 2, 4-dinitrophenylhydrazine in a solvent to obtain a 2, 4-dinitrophenylhydrazine solution, adding the metal organic framework material into the 2, 4-dinitrophenylhydrazine solution, stirring for 3-5h at the speed of 100-200r/min, taking out a solid, and heating to remove the solvent in an inert atmosphere. Preferably, the solvent is ethanol.
It is still another object of the present invention to provide a method for detecting carbonyl compounds in exhaled breath, which uses the carbonyl compounds prepared as described above to trap carbonyl compounds in exhaled breath.
Preferably, the detection method comprises the following steps: after the exhaled smoke passes through the carbonyl compound trapping agent, leaching the carbonyl compound trapping agent by using acetonitrile, and collecting eluent; and then analyzing and measuring the eluent by adopting a liquid chromatography-ultraviolet detector analysis method.
Preferred carbonyl compounds in exhaled breath include formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, crotonaldehyde, butanone, butyraldehyde.
Preferably, the conditions for instrumental analysis are as follows: the liquid chromatography column was Dionex Acclaim explicit E2 (250 mm. times.4.6 mm, 120A, 5 μm). Flow rate: 1 mL/min; sample introduction volume: 10 mu L of the solution; a detector: DAD, detection wavelength: 365 nm. The analysis time was 45 min. The gradient elution conditions are shown in table 1 below.
Table 1.
The invention also aims to provide a device for trapping carbonyl compounds in exhaled smoke, which comprises a trapping pipe, wherein two ends of the trapping pipe are respectively communicated with a blowing nozzle and a gas sampling pump; the collecting pipe is provided with a collecting filler made of the carbonyl compound collecting agent.
Preferably, a three-way valve is arranged between the collecting pipe and the gas sampling pump. And three ports of the three-way valve are respectively communicated with the collecting pipe, the gas sampling pump and the outside air.
Preferably, at least two parts of the trapping filler are arranged in the trapping pipe, and the interval between two adjacent parts of the trapping filler is at least 10 cm. The trapping filler close to the gas sampling pump is used for absorbing carbonyl compounds in the outside air, and the influence of the carbonyl compounds in the outside air on the detection result of the carbonyl compounds in the exhaled smoke is avoided.
Preferably, a smoking behavior recorder is arranged between the blowing nozzle and the collecting pipe. The smoking behavior recorder is commercially available in the prior art, the suction nozzle end of the smoking behavior recorder is connected with the blowing nozzle, the inserting port is connected with the collecting pipe, parameters of smoke exhaled by a volunteer can be recorded, and the volume of the smoke exhaled by the volunteer is calculated. In order to enable the smoking behavior recorder to realize sensing and data recording, the outer diameter of the rubber hose connected with the insertion port needs to be about 5-8 cm.
The invention has the beneficial effects that:
according to the method, the solid carrier is adopted to load the 2, 4-dinitrophenylhydrazine, so that the carbonyl compound trapping agent is obtained, when the carbonyl compound trapping agent is used for trapping the carbonyl compound in the exhaled smoke, other chemical substances in the smoke cannot be trapped, when the trapped substances are analyzed subsequently, the other chemical substances cannot influence the analysis result, and the accuracy of analysis is improved.
Drawings
FIG. 1 is a schematic diagram of a device for trapping carbonyl compounds in exhaled breath;
in the figure: the smoking behavior monitoring device comprises a blowing nozzle 1, a smoking behavior recorder 2, a collecting pipe 3, a three-way valve 4 and a gas sampling pump 5.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
Preparation of carbonyl compound trapping agent:
s1, dissolving 0.48g of PVP in 100mL of ethanol solution, pouring the solution into a 250mL four-mouth bottle provided with a thermometer, a stirrer and a condensing device, stirring for 30min at 70 ℃, adding 16g of monomer St and 0.16g of initiator AIBN, reacting for 8h at 70 ℃, washing and drying to obtain the PS microspheres. Adding the PS microspheres into a sodium dodecyl sulfate aqueous solution with the concentration of 6mmol/L, and washing and drying after 15min of ultrasonic treatment for later use.
Mixing 1g TEOS and 3.8g EtOH, dropwise adding 6.4g deionized water and 0.1g nitric acid under magnetic stirring, stirring and refluxing for 3h at 50 ℃ after dropwise adding, and cooling to obtain the silica sol. Mixing 1g of AgNO3Adding into 100mL distilled water, adding 5mL ammonia water with concentration of 25%, and stirring to obtain AgNO3And (3) solution.
Mixing the above silica sol with AgNO3After the solutions are uniformly mixed, the PS microspheres processed by the sodium dodecyl sulfate are added into the solution, the system is placed in a water bath at 40 ℃ for reaction for 2.5 hours, then 4mL of polyvinylpyrrolidone solution is dropwise added, the temperature is raised to 65 ℃, the reaction is carried out for 40min, and then the washing and the drying are carried out. .
Calcining the dried microspheres at 450 ℃ for 1.5h to obtain Ag/SiO2A composite hollow sphere.
S2, adding 1g of silicon dioxide into 50mL of deionized water, and performing ultrasonic dispersion for 10min to obtain SiO2And (3) suspension. Then the Ag/SiO2Adding SiO into the composite hollow sphere2And (4) ultrasonically dispersing the suspension for 5min, standing for 2h, and taking out the solid to dry.
Adding 5g of SnCl2·2H2And mixing O, 80mL of deionized water and 50mL of hydrochloric acid with the concentration of 30% to obtain the sensitizing solution. And adding the dried composite hollow spheres into the sensitizing solution, sensitizing for 11 hours at 500min/r, and taking out for washing. Taking 12g/L copper sulfate 50mL, 13g/L potassium sodium tartrate 80mL and 30% formaldehydeAnd mixing 20mL of the solution, adding the washed composite hollow sphere into the mixed solution, and reacting for 2h under the magnetic stirring of 500min/r to complete the chemical copper plating.
And (3) adding the chemically plated copper composite hollow sphere into a 30% HF solution for soaking for 24h, taking out the solid, washing and drying to obtain the hollow sphere with the open pore.
S3, uniformly mixing 10mL of 0.05g/mL silver nitrate solution and 10mL of 0.05g/mL copper nitrate solution, dissolving 1g of 1,3, 5-benzene tricarboxylic acid in 30mL of mixed solution of ethanol and N, N-dimethylformamide in equal volume ratio, and uniformly mixing the two mixed solutions. And then adding the hollow spheres into the mixed solution, keeping the temperature at 90 ℃ for 18h at the rotating speed of 150/min, purifying the obtained reaction product with ethanol, and performing suction filtration, washing and drying to obtain the metal organic framework material.
S4, dissolving 0.05g of 2, 4-dinitrophenylhydrazine in 5mL of ethanol, adding 5g of the obtained metal organic framework material after DNPH is completely dissolved, stirring for 4 hours at 150r/min, taking out solids, stirring the solids in a closed manner for 0.5 hour at 50 ℃ under the protection of nitrogen, and then blowing nitrogen to be dry to obtain the carbonyl compound trapping agent.
Trapping of carbonyl compounds in exhaled smoke:
a trap device was prepared, and as shown in FIG. 1, this trap device was composed of a mouthpiece 1, a smoking behavior recorder 2, a trap tube 3, a three-way valve 4, and a gas sampling pump 5 in this order, which were connected through a rubber hose having an outer diameter of 7.5 cm. The collection pipe 3 is provided with a collection filler which comprises two sieve plates and a carbonyl compound collection agent filled between the two sieve plates, and the filling amount of the carbonyl compound collection agent is 1000 mg.
When the device is used, the three-way valve 4 is rotated to the c path and the b path to be communicated, and the gas sampling pump 5 is started (the flow rate is set to 5000 mL/min). When a volunteer starts to suck, the smoke stays in the oral cavity for 20s after each suction, then the mouth is aligned with the mouthpiece 1 (the face is required to be attached to the mouthpiece), the three-way valve 4 is screwed to the path a and the path b to be communicated, the volunteer slowly spits the smoke, and carbonyl compounds in the exhaled smoke are trapped by the trapping filler in the trapping tube 3. When no obvious smoke exists in the pipeline, the volunteer stops blowing, and simultaneously the three-way valve 4 is turned to the c path to be communicated with the b path, and the air is discharged. And (5) continuing sucking by the volunteer, trapping the exhaled smoke by the second port, collecting 9 exhaled smoke in total, and finishing sampling.
Detection of carbonyl compounds in exhaled smoke:
and taking down the trapping filler in the trapping tube 3, leaching the trapping filler with acetonitrile, collecting eluent, placing a small amount of eluent in a 2mL chromatographic bottle, and performing HPLC-DAD analysis.
The instrument analysis conditions were as follows: the liquid chromatography column was Dionex Acclaim explicit E2 (250 mm. times.4.6 mm, 120A, 5 μm). Flow rate: 1 mL/min; sample introduction volume: 10 mu L of the solution; a detector: DAD, detection wavelength: 365 nm. Analysis time 45min, gradient elution conditions as in table 1 above.
Preparing a series of standard working solutions by using formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, crotonaldehyde, 2-butanone and butyraldehyde 2, 4-dinitrophenylhydrazone derivative compounds, performing HPLC-DAD analysis under the conditions, making a standard curve, and quantifying each carbonyl compound in the eluent by an external standard method.
Example 2
This embodiment is substantially the same as embodiment 1, except that:
in the trapping of carbonyl compounds in the exhaled smoke, the cigarette is heated and does not burn for smoking.
Example 3
This embodiment is substantially the same as embodiment 1, except that:
in the trapping of carbonyl compounds in the exhaled smoke, electronic cigarettes are adopted for suction.
Example 4
This embodiment is substantially the same as embodiment 1, except that:
two parts of trapping fillers are arranged in the trapping pipe 3, the interval between the two parts of trapping fillers is 10cm, and the trapping fillers far away from the gas sampling pump 5 are used for carrying out acetonitrile leaching and collection and analysis of eluent.
Example 5
This embodiment is substantially the same as embodiment 1, except that: au was selected as the first metal.
In step S1, 1g of chloroauric acid was added to 100mL of distilled water, and then 0.1g of hydroxylamine hydrochloride was added thereto and stirred uniformly to obtain a chloroauric acid solution.
And (2) uniformly mixing the silica sol and a chloroauric acid solution, adding the PS microspheres treated by the sodium dodecyl sulfate into the mixture, placing the system in a water bath at 40 ℃ for reaction for 2.5 hours, then dropwise adding 4mL of polyvinylpyrrolidone solution, heating to 65 ℃, reacting for 40min, washing and drying. .
Calcining the dried microspheres at 450 ℃ for 1.5h to obtain Au/SiO2A composite hollow sphere.
In step S3, 10mL of a 0.05g/mL chloroauric acid solution and 10mL of a 0.05g/mL copper nitrate solution were mixed uniformly.
Example 6
This embodiment is substantially the same as embodiment 1, except that: al is selected as the second metal.
In step S2, 50mL of 12g/L aluminum chloride, 80mL of 13g/L potassium sodium tartrate and 20mL of 30% formaldehyde solution are mixed, the washed composite hollow spheres are added into the mixed solution, and the mixture is reacted for 2 hours under the magnetic stirring of 500min/r, so that the chemical aluminum plating is completed.
In step S3, 10mL of 0.05g/mL silver nitrate solution and 10mL of 0.05g/mL aluminum nitrate solution were mixed well.
Example 7
This embodiment is substantially the same as embodiment 1, except that: the conditions of the parameters for the preparation of the carbonyl compound trapping agent are different.
S1, mixing the silica sol and AgNO3After the solution is uniformly mixed, the PS microspheres treated by the sodium dodecyl sulfate are added into the solution, the system is placed in a water bath at the temperature of 30 ℃ for reaction for 4 hours, then 4mL of polyvinylpyrrolidone solution is dropwise added, the temperature is raised to 40 ℃, the reaction is carried out for 60min, and then the washing and the drying are carried out. Calcining the dried microspheres at 400 ℃ for 2h to obtain Ag/SiO2A composite hollow sphere.
S3, uniformly mixing 10mL of 0.05g/mL silver nitrate solution and 10mL of 0.05g/mL copper nitrate solution, dissolving 1g of 1,3, 5-benzene tricarboxylic acid in 30mL of mixed solution of ethanol and N, N-dimethylformamide in equal volume ratio, and uniformly mixing the two mixed solutions. And then adding the hollow spheres into the mixed solution, keeping the temperature at 100 ℃ for 24 hours at a rotating speed of 100/min, purifying the obtained reaction product with ethanol, and performing suction filtration, washing and drying to obtain the metal organic framework material.
S4, dissolving 0.05g of 2, 4-dinitrophenylhydrazine in 5mL of ethanol, adding 5g of the obtained metal organic framework material after DNPH is completely dissolved, stirring for 5h at 100r/min, taking out the solid, stirring the solid in a closed manner for 1h at 50 ℃ under the protection of nitrogen, and then blowing the nitrogen to be dry to obtain the carbonyl compound trapping agent.
Example 8
This embodiment is substantially the same as embodiment 1, except that: the conditions of the parameters for the preparation of the carbonyl compound trapping agent are different.
S1, mixing the silica sol and AgNO3After the solution is uniformly mixed, the PS microspheres treated by the sodium dodecyl sulfate are added into the solution, the system is placed in a water bath at 50 ℃ for reaction for 2 hours, then 4mL of polyvinylpyrrolidone solution is dropwise added, the temperature is raised to 65 ℃, the reaction is carried out for 25min, and then the washing and the drying are carried out. Calcining the dried microspheres at 500 ℃ for 2h to obtain Ag/SiO2A composite hollow sphere.
S3, uniformly mixing 10mL of 0.05g/mL silver nitrate solution and 10mL of 0.05g/mL copper nitrate solution, dissolving 1g of 1,3, 5-benzene tricarboxylic acid in 30mL of mixed solution of ethanol and N, N-dimethylformamide in equal volume ratio, and uniformly mixing the two mixed solutions. And then adding the hollow spheres into the mixed solution, keeping the temperature at 85 ℃ for 12 hours at the rotating speed of 200/min, purifying the obtained reaction product with ethanol, and performing suction filtration, washing and drying to obtain the metal organic framework material.
S4, dissolving 0.05g of 2, 4-dinitrophenylhydrazine in 5mL of ethanol, adding 5g of the obtained metal organic framework material after DNPH is completely dissolved, stirring for 3h at 200r/min, taking out the solid, stirring the solid in a closed manner for 1.5h at 50 ℃ under the protection of nitrogen, and then blowing the nitrogen to be dry to obtain the carbonyl compound trapping agent.
Comparative example 1
This comparative example is substantially identical to example 1, except that: the carbonyl compound trapping agent is different.
Uniformly mixing 10mL of 0.05g/mL silver nitrate solution and 10mL of 0.05g/mL copper nitrate solution, dissolving 1g of 1,3, 5-benzene tricarbonic acid in 30mL of mixed solution of ethanol and N, N-dimethylformamide in the same volume ratio, uniformly mixing the two mixed solutions, purifying the obtained reaction product by using ethanol, and carrying out suction filtration, washing and drying to obtain the metal organic framework material.
Dissolving 0.05g of 2, 4-dinitrophenylhydrazine in 5mL of ethanol, adding 5g of the obtained metal organic framework material after DNPH is completely dissolved, stirring for 4h at 150r/min, taking out the solid, stirring the solid in a closed manner for 0.5h at 50 ℃ under the protection of nitrogen, and then blowing nitrogen to dryness to obtain the carbonyl compound trapping agent.
Comparative example 2
This comparative example is substantially identical to example 1, except that: the carbonyl compound trapping agent is different.
The hollow sphere having an open pore obtained in S2 was used as a carbonyl group-trapping agent.
Comparative example 3
The trapping device and trapping method disclosed in patent document No. CN104267118A were used to trap carbonyl compounds in exhaled breath, and the analysis was performed under the conditions of the apparatus of example 1 of the present application.
The results of the assay analysis in examples and comparative examples are shown in table 2 below.
Table 2.
As can be seen from table 2, the trapping agent of the present application is effective in trapping various carbonyl compounds in exhaled breath.
Detection accuracy detection
Preparing 1mg/mL formaldehyde solution of biochemical compound of 2, 4-dinitrophenylhydrazone derivative, 1mg/mL acetaldehyde solution of biochemical compound of 2, 4-dinitrophenylhydrazone derivative, 1mg/mL acetone solution of biochemical compound of 2, 4-dinitrophenylhydrazone derivative, 1mg/mL acrolein solution of biochemical compound of 2, 4-dinitrophenylhydrazone derivative, 1mg/mL propionaldehyde solution of 2, 4-dinitrophenylhydrazone derivative, 1mg/mL crotonaldehyde solution of biochemical compound of 2, 4-dinitrophenylhydrazone derivative, 1mg/mL 2-butanone solution of 2, 4-dinitrophenylhydrazone derivative and 1mg/mL butyraldehyde solution of 2, 4-dinitrophenylhydrazone derivative. Each solution was taken 1mL, and after mixing well, a sample solution was obtained. 8 portions of each sample solution were prepared.
The carbonyl compound trapping agents in examples 1, 5 to 8 and comparative examples 1 to 3 were placed in the sample solutions, respectively, left to stand for 10min, and then taken out, followed by rinsing with acetonitrile, collecting the eluate, placing the eluate in a 2mL chromatography bottle, and performing HPLC-DAD analysis using the analytical conditions of the apparatus in example 1, with the detection results shown in table 3 below.
TABLE 3 (the units in TABLE 3 are mg)
As can be seen from table 3, the amount of the trapped carbonyl compound trapping agent of the present invention was closer to the actual value, and the detection results were more accurate.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A carbonyl compound trapping agent, characterized by: is prepared by the following steps:
s1, preparing first metal/SiO by using PS microspheres as cores and adopting a layer-by-layer self-assembly method2Composite hollow spheres;
s2, enabling the first metal/SiO2The composite hollow ball is dipped in SiO2After in suspensionTaking out and drying; then plating a second metal on the second metal, and soaking the second metal in HF solution to remove SiO2Obtaining hollow spheres with open pores;
s3, preparing the ions of the first metal, the ions of the second metal, the hollow spheres and an organic ligand into a metal organic framework material;
s4, loading 2, 4-dinitrophenylhydrazine on the metal organic framework material.
2. A carbonyl compound trap as claimed in claim 1, characterized in that: the first metal is one or more of Au and Ag.
3. A carbonyl compound trap as claimed in claim 1, characterized in that: the second metal is one or more of Cu and Al.
4. A carbonyl compound trap as claimed in claim 1, characterized in that: step S3 includes the following steps:
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;
and S3c, adding the hollow spheres into a mixed solution of the solution A and the solution B, keeping the temperature at the rotation speed of 100-200r/min and the temperature of 85-100 ℃ for 12-24h, purifying the obtained reaction product by using ethanol, and then performing suction filtration, washing and drying to obtain the metal organic framework material.
5. A carbonyl compound trap as claimed in claim 1, characterized in that: the step S4 includes the following steps: dissolving 2, 4-dinitrophenylhydrazine in a solvent to obtain a 2, 4-dinitrophenylhydrazine solution, adding the metal organic framework material into the 2, 4-dinitrophenylhydrazine solution, stirring for 3-5h at the speed of 100-200r/min, taking out a solid, and heating to remove the solvent in an inert atmosphere.
6. A method for detecting carbonyl compounds in exhaled smoke is characterized by comprising the following steps: trapping carbonyl compounds in exhaled breath using a carbonyl compound trap according to any of claims 1-5.
7. The method of claim 6 for detecting carbonyl compounds in exhaled breath, wherein: the method comprises the following steps: after the exhaled smoke passes through the carbonyl compound trapping agent, leaching the carbonyl compound trapping agent by using acetonitrile, and collecting eluent; and then analyzing and measuring the eluent by adopting a liquid chromatography-ultraviolet detector analysis method.
8. A device for trapping carbonyl compounds in exhaled smoke comprises a trapping pipe (3), wherein two ends of the trapping pipe (3) are respectively communicated with a blowing nozzle (1) and a gas sampling pump (5); is characterized in that: the collection pipe (3) is provided with a collection packing made of the carbonyl compound collector according to any of claims 1-5.
9. The device for trapping carbonyl compounds in exhaled breath according to claim 8, wherein: at least two parts of the trapping fillers are arranged in the trapping pipe (3), and the interval between every two adjacent parts of the trapping fillers is at least 10 cm.
10. The device for trapping carbonyl compounds in exhaled breath according to claim 8, wherein: a three-way valve (4) is arranged between the collecting pipe (3) and the gas sampling pump (5).
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| CN114146690B (en) | 2023-10-10 |
| WO2023098632A1 (en) | 2023-06-08 |
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