CN111103277A - Chloropropanol sensitive gas sensor, preparation method thereof, detection device containing sensor and detection method - Google Patents
Chloropropanol sensitive gas sensor, preparation method thereof, detection device containing sensor and detection method Download PDFInfo
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- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000001514 detection method Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 58
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 25
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 23
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 23
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- MSYHGYDAVLDKCE-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluoro-1-imidazol-1-ylbutan-1-one Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)N1C=CN=C1 MSYHGYDAVLDKCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
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- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 10
- 230000005284 excitation Effects 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 85
- 239000010453 quartz Substances 0.000 claims description 84
- 238000005259 measurement Methods 0.000 claims description 31
- 238000012545 processing Methods 0.000 claims description 22
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- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000003595 spectral effect Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract description 2
- 239000012159 carrier gas Substances 0.000 abstract 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000008157 edible vegetable oil Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- PSJBSUHYCGQTHZ-UHFFFAOYSA-N 3-Methoxy-1,2-propanediol Chemical compound COCC(O)CO PSJBSUHYCGQTHZ-UHFFFAOYSA-N 0.000 description 1
- SIBFQOUHOCRXDL-UHFFFAOYSA-N 3-bromopropane-1,2-diol Chemical compound OCC(O)CBr SIBFQOUHOCRXDL-UHFFFAOYSA-N 0.000 description 1
- PQDNJBQKAXAXBQ-UHFFFAOYSA-N 3-fluoropropane-1,2-diol Chemical compound OCC(O)CF PQDNJBQKAXAXBQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
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- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000019100 sperm motility Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
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- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to the technical field of rapid detection of harmful substances in food, and particularly relates to a chloropropanol sensitive gas sensor, a preparation method, detection equipment containing the sensor and a detection method. According to the invention, chloropropanol sensitive molecule heptafluorobutyrylimidazole is embedded in chitosan, polyacrylic acid and polytetrafluoroethylene molecules in an embedding manner to form the chloropropanol detection sensor. The method comprises the steps of embedding a chloropropanol sensor in a measuring pool, enabling a chloropropanol gas sample to enter the measuring pool through nitrogen carrier gas, enabling blank nitrogen carrier gas to enter a reference pool, enabling a near-infrared light source and a fluorescence excitation light source to respectively enter the measuring pool and the reference pool through a light splitting system, subtracting a spectrum signal in the reference pool from a near-infrared signal and a fluorescence signal of the measuring pool to respectively obtain a near-infrared spectrum signal and a fluorescence spectrum signal which are related to the concentration of chloropropanol, and enabling the signals to be used for qualitative and quantitative analysis of chloropropanol in the sample.
Description
Technical Field
The invention belongs to the technical field of rapid detection of harmful substances in food, and particularly relates to a chloropropanol sensitive gas sensor, a preparation method, detection equipment containing the sensor and a detection method.
Background
Chloropropanol is mainly present in oils and fats represented by edible vegetable oils and related products, particularly in refined edible vegetable oils. The chloropropanol is various, mainly comprises 3-chloro-1, 2-propanediol (3-MCPD), and the 3-MCPD in the grease and related products is generated by various ways such as raw material storage, raw material natural existence, raw material cleaning and hot processing by water containing chloride ions, hot processing generation such as grease product cooking and the like. Researchers found that 3-MCPD is an carcinogenic substance through animal experiments, and 3-MCPD with the dosage of 30 mg/kg bw/d can cause dilation and necrosis of renal tubules of mice, affect sperm motility and fertility, and in severe cases can cause the possibility of canceration of kidney, testis, mammary gland and the like of the mice to increase.
The method for detecting chloropropanol in food mainly comprises two methods, namely gas chromatography and gas mass spectrometry. Firstly, adopting the steps of salt saturation, diatomite adsorption, ether or ethyl acetate elution, anhydrous sodium sulfate dehydration and the like to separate chloropropanol from a tested sample. Derivatization is usually carried out using a compound reagent such as heptafluorobutyryl reagent, phenylboronic acid, acetone, or heptanone to produce a chloropropanol derivative. 3-fluoro-1, 2-propylene glycol, 3-methoxy-1, 2-propylene glycol or 3-bromo-1, 2-propylene glycol and the like are selected as internal standard substances, and the problem of chloropropanol loss in a sample in the pretreatment process is corrected. The non-derivatized chloropropanol has higher polarity, and is separated by directly adopting a weak polarity or medium polarity capillary column, and the derivatized chloropropanol is separated by usually adopting a weak polarity column or a non-polar column. Usually, a temperature programming mode is adopted to separate a derivatized or underivatized chloropropanol substance, and finally, detection and analysis are carried out by methods such as flame ionization, electron capture or gas chromatography-mass spectrometry.
Although the chloropropanol separation and detection method has better accuracy and sensitivity, a series of adverse factors such as higher requirement on professional degree of operators, longer detection period, higher cost and the like exist, and a novel rapid detection method is urgently needed to solve the problem of chloropropanol detection.
Disclosure of Invention
The invention aims to provide a chloropropanol sensitive gas sensor, a preparation method, detection equipment containing the sensor and a detection method, which are used for realizing the safe and rapid detection and intelligent judgment of food in the production, processing, sale and other links of grease food. In order to solve the technical problem, the gas-sensitive fluorescent sensor is applied to the quality and safety intelligent detection of food markets represented by edible vegetable oil, and the specific implementation technical scheme is as follows:
a chloropropanol sensitive gas sensor comprises a polytetrafluoroethylene substrate, polyacrylic acid, heptafluorobutyrylimidazole and chitosan, wherein one end of the polyacrylic acid is combined on the polytetrafluoroethylene substrate, the other end of the polyacrylic acid is connected with the heptafluorobutyrylimidazole, and the chitosan covers the heptafluorobutyrylimidazole.
A preparation method of the chloropropanol sensitive gas sensor comprises the following steps:
(1) placing a polytetrafluoroethylene substrate in an acrylic acid solution, adding 0.005-0.05mol/L benzophenone serving as a catalyst into the solution at 25 ℃, placing the solution under an ultraviolet lamp for irradiation, sequentially washing the solution by using a strong alkali solution and deionized water to remove unpolymerized acrylic acid residues, and drying the solution in a vacuum state to obtain the polytetrafluoroethylene substrate with the surface covered with polyacrylic acid;
(2) uniformly coating a heptafluorobutyrylimidazole solution on a polytetrafluoroethylene substrate covered with polyacrylic acid, standing at 25 ℃, blowing the redundant liquid to dry by using inert gas, and placing the liquid in a closed device filled with the inert gas to obtain a heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene substrate;
(3) covering a chitosan solution on a heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene substrate, placing the substrate under an ultraviolet lamp for irradiation, cleaning the obtained sensor by using deionized water, and then drying the sensor by using inert gas to obtain the chitosan-heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene sensor.
Preferably, the concentration of the olefine acid solution in the step (1) is 30-60wt%, the ultraviolet lamp irradiation time is 8-12 h, and the pH value of the strong alkali solution is 7-10.
Preferably, the concentration of the heptafluorobutyrylimidazole solution in the step (2) is 0.005-0.05mol/L, and the standing time is 2-6 h.
Preferably, the concentration of the chitosan solution in the step (3) is 0.02-0.08 mol/L, and the irradiation time of an ultraviolet lamp is 4-8 h.
A detection device containing the chloropropanol sensitive gas sensor comprises a near-infrared halogen tungsten lamp 1, a near-infrared fixed grating 2, a measurement pool near-infrared light incidence quartz window 3, a measurement pool fluorescence incidence quartz window 4, a measurement pool 5, a near-infrared light emergence quartz window 6 containing the chloropropanol sensitive gas sensor, a fluorescence emergence quartz window 7 containing the chloropropanol sensitive gas sensor, a measurement pool near-infrared detector 8, a measurement pool fluorescence detector 9, a fluorescent LED lamp 10, a fluorescent grating 11, a reference pool near-infrared light incidence quartz window 12, a reference pool fluorescence incidence quartz window 13, a reference pool 14, a reference pool near-infrared light emergence quartz window 15, a reference pool fluorescence emergence quartz window 16, a reference pool near-infrared detector 17, a reference pool fluorescence detector 18 and a data processing unit 19.
Wherein, the near-infrared halogen tungsten lamp 1 is connected with the near-infrared fixed grating 2, the near-infrared fixed grating 2 is respectively connected with the measuring cell 5 and the reference cell 14 through the measuring cell near-infrared light incidence quartz window 3 and the reference cell near-infrared light incidence quartz window 12, the fluorescence LED lamp 10 is connected with the fluorescence grating 11, the fluorescence grating 11 is respectively connected with the measuring cell 5 and the reference cell 14 through the measuring cell fluorescence incidence quartz window 4 and the reference cell fluorescence incidence quartz window 13, the measuring cell 5 is respectively connected with the measuring cell near-infrared detector 8 and the measuring cell fluorescence detector 9 through the near-infrared light emergent quartz window 6 containing the chloropropanol sensitive gas sensor and the fluorescence emergent quartz window 7 containing the chloropropanol sensitive gas sensor, the reference cell 14 is respectively connected with the near-infrared detector 17 through the reference cell near-infrared light emergent quartz window 15 and the reference cell fluorescence emergent quartz window 16, The reference cell fluorescence detector 18 is connected, and the signal output ends of the measurement cell near-infrared detector 8, the measurement cell fluorescence detector 9, the reference cell near-infrared detector 17 and the reference cell fluorescence detector 18 are respectively connected with the signal input end of the data processing unit 19.
A detection method of detection equipment using the chloropropanol sensitive gas sensor comprises the following steps:
(1) introducing a chloropropanol gas sample to be measured into the measurement cell 5, and introducing a reference gas into the reference cell 14;
(2) controlling a near-infrared halogen tungsten lamp 1 to emit near infrared, splitting the near-infrared composite light into monochromatic light by a near-infrared fixed grating 2, allowing the monochromatic near-infrared light to enter a measurement cell 5 and a reference cell 14 through a measurement cell near-infrared light incidence quartz window 3 and a reference cell near-infrared light incidence quartz window 12 respectively, allowing the monochromatic near-infrared light passing through the measurement cell 5 to be received by a measurement cell near-infrared detector 8 through a near-infrared light emergence quartz window 6 containing a chloropropanol sensitive gas sensor, and outputting V through a data processing unit 19Proximity measurementThe signal of (a); and the monochromatic near infrared light passing through the reference cell 14 is detected by the reference cell near infrared light outgoing quartz window 15 through the reference cell near infrared light outgoing quartz window 17 and then output V through the data processing unit 19Near referenceThe signal of (a);
(3) the fluorescent LED lamp 10 is controlled to emit fluorescence exciting light, the fluorescence grating 11 decomposes the fluorescence exciting composite light into fluorescence exciting monochromatic light, and the monochromatic fluorescence exciting light passes through the detectionThe measuring cell fluorescence incidence quartz window 4 and the reference cell fluorescence incidence quartz window 13 enter the measuring cell 5 and the reference cell 14, the fluorescence emission light passing through the measuring cell 5 is received by the measuring cell fluorescence detector 9 through the fluorescence emission quartz window 7 containing the chloropropanol sensitive gas sensor, and V is output through the data processing unit 19Fluorescence measurementThe signal of (a); and the fluorescence emission light passing through the reference cell 14 is detected by the reference cell fluorescence detector 18 via the reference cell fluorescence emission quartz window 16 and then output V by the data processing unit 19Near referenceThe signal of (a);
(4) respectively calculating the difference X of the spectral signals measured by the near infrared spectrum and the fluorescence1And X2:X1=ΔVNear to=VProximity measurement-VNear reference,X2=ΔVFluorescent lamp=VFluorescence measurement-VFluorescent referenceAnd substituting the chloropropanol concentration values into chloropropanol standard curves of a near infrared spectrum and a fluorescence spectrum respectively to obtain related information of the chloropropanol concentration of an unknown sample, and taking the average chloropropanol concentration value obtained by a near infrared algorithm and a fluorescence spectrum algorithm as a concentration value of the sample to be detected.
Preferably, the chloropropanol standard curve of the near infrared spectrum and the fluorescence spectrum of step (4) is obtained by: configuring a plurality of chloropropanol standard products with concentration gradients, respectively collecting the near infrared spectrum and fluorescence spectrum values of the chloropropanol standard products by utilizing detection equipment of a chloropropanol sensitive gas sensor, and calculating according to a difference formula to obtain corresponding X1And X2A numerical value; and respectively establishing a chloropropanol standard curve algorithm based on the near infrared spectrum and the fluorescence spectrum by using the spectral signal difference values measured by the near infrared spectrum and the fluorescence spectrum, and simultaneously determining a linear detection range and a nonlinear detection range of the standard curve.
The invention has the beneficial effects that:
the product of the invention is simple, has lower requirement on the professional degree of operators, short detection period, low cost, quick and accurate detection method, high sensitivity and is suitable for popularization.
Drawings
FIG. 1 is a molecular structure diagram of a chloropropanol sensitive molecule heptafluorobutyrylimidazole;
FIG. 2 is a schematic diagram of a process for manufacturing a chloropropanol sensitive gas sensor;
FIG. 3 is a schematic flow chart of a detection method of a chloropropanol sensitive gas sensor.
In the figure: 1. the system comprises a near infrared halogen tungsten lamp, 2 a near infrared fixed grating, 3 a measuring cell near infrared light incidence quartz window, 4 a measuring cell fluorescence incidence quartz window, 5 a measuring cell, 6 a near infrared light emergence quartz window containing a chloropropanol sensitive gas sensor, 7 a fluorescence emergence quartz window containing a chloropropanol sensitive gas sensor, 8 a measuring cell near infrared detector, 9 a measuring cell fluorescence detector, 10 a fluorescent LED lamp, 11 a fluorescent grating, 12 a reference cell near infrared light incidence quartz window, 13 a reference cell fluorescence incidence quartz window, 14 a reference cell, 15 a reference cell near infrared light emergence quartz window, 16 a reference cell fluorescence emergence quartz window, 17 a reference cell near infrared detector, 18 a reference cell fluorescence detector and 19 a data processing unit.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following examples and the accompanying drawings, which are illustrative of the present invention and are not to be construed as limiting thereof.
The method comprises the following steps: sensor manufacturing method (fig. 2)
(1) Placing polytetrafluoroethylene serving as a sensor substrate which is combined and reacted with chloropropanol in an acrylic acid solution with the concentration of 30-60wt%, adding 0.01 mol/L benzophenone serving as a catalyst into the solution at 25 ℃, placing the solution under an ultraviolet lamp for irradiating for 8-12 h, washing the solution by adopting KOH solution with the pH of 7-10 and deionized water in sequence to remove unpolymerized acrylic acid residues, and drying the solution in a vacuum state to obtain the polytetrafluoroethylene substrate with the surface covered with polyacrylic acid.
(2) Uniformly smearing heptafluorobutyrylimidazole (figure 1) with the concentration of 0.1 mol/L on a polytetrafluoroethylene substrate of polyacrylic acid, standing for 2-6 h at 25 ℃, blowing off the redundant liquid by using nitrogen gas and putting the liquid into a bottle filled with nitrogen gas to obtain the heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene substrate.
(3) Covering a chitosan solution with the concentration of 0.02-0.08 mol/L on a heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene substrate, placing the substrate under an ultraviolet lamp for irradiating for 4-8 h, cleaning the obtained sensor by deionized water, and then drying the sensor by using nitrogen to obtain the chitosan-heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene sensor.
The sensor prepared by the steps can be used for a gas chloropropanol detection sensor, and can be used for qualitatively and quantitatively detecting chloropropanol by mainly carrying out interaction on heptafluorobutyrylimidazole embedded on the sensor and chloropropanol, acquiring signal changes before and after the sensor and chloropropanol react through a near infrared spectrum or a fluorescence spectrum, and finally carrying out the qualitative and quantitative detection on the chloropropanol through the signal changes of the near infrared spectrum or the fluorescence spectrum.
Step two: detection equipment for detecting chloropropanol gas sample by using chloropropanol-containing sensitive gas sensor
As shown in fig. 3, the detecting device includes a near infrared spectrum detecting section and a fluorescence spectrum detecting section, the device comprises a near-infrared halogen tungsten lamp 1, a near-infrared fixed grating 2, a measuring cell near-infrared light incidence quartz window 3, a measuring cell fluorescence incidence quartz window 4, a measuring cell 5, a near-infrared light emergence quartz window 6 containing a chloropropanol sensitive gas sensor, a fluorescence emergence quartz window 7 containing a chloropropanol sensitive gas sensor, a measuring cell near-infrared detector 8, a measuring cell fluorescence detector 9, a fluorescent LED lamp 10, a fluorescent grating 11, a reference cell near-infrared light incidence quartz window 12, a reference cell fluorescence incidence quartz window 13, a reference cell 14, a reference cell near-infrared light emergence quartz window 15, a reference cell fluorescence emergence quartz window 16, a reference cell near-infrared detector 17, a reference cell fluorescence detector 18 and a data processing unit 19.
Wherein, the near-infrared halogen tungsten lamp 1 is connected with the near-infrared fixed grating 2, the near-infrared fixed grating 2 is respectively connected with the measuring cell 5 and the reference cell 14 through the measuring cell near-infrared light incidence quartz window 3 and the reference cell near-infrared light incidence quartz window 12, the fluorescence LED lamp 10 is connected with the fluorescence grating 11, the fluorescence grating 11 is respectively connected with the measuring cell 5 and the reference cell 14 through the measuring cell fluorescence incidence quartz window 4 and the reference cell fluorescence incidence quartz window 13, the measuring cell 5 is respectively connected with the measuring cell near-infrared detector 8 and the measuring cell fluorescence detector 9 through the near-infrared light emergent quartz window 6 containing the chloropropanol sensitive gas sensor and the fluorescence emergent quartz window 7 containing the chloropropanol sensitive gas sensor, the reference cell 14 is respectively connected with the near-infrared detector 17 through the reference cell near-infrared light emergent quartz window 15 and the reference cell fluorescence emergent quartz window 16, The reference cell fluorescence detector 18 is connected, and the signal output ends of the measurement cell near-infrared detector 8, the measurement cell fluorescence detector 9, the reference cell near-infrared detector 17 and the reference cell fluorescence detector 18 are respectively connected with the signal input end of the data processing unit 19.
As shown in fig. 3, a chloropropanol gas sample to be measured is introduced into the measurement cell 5, a reference gas (such as nitrogen) is introduced into the reference cell 14, the chloropropanol gas sample can adsorb chloropropanol by a solid-phase microextraction technique, and the chloropropanol gas sample is introduced into the measurement cell 5 by nitrogen in a heating desorption manner. Near-infrared halogen tungsten lamp 1 is controlled by software to emit near infrared, near-infrared fixed grating 2 divides the near-infrared composite light into monochromatic light, the monochromatic near-infrared light enters measuring cell 5 and reference cell 14 through measuring cell near-infrared light incidence quartz window 3 and reference cell near-infrared light incidence quartz window 12 respectively, the monochromatic near-infrared light passing through measuring cell 5 is received by measuring cell near-infrared detector 8 through near-infrared light emergence quartz window 6 containing chloropropanol sensitive gas sensor, and V is output by data processing unit 19Proximity measurementThe signal of (a); and the monochromatic near infrared light passing through the reference cell 14 is detected by the reference cell near infrared light outgoing quartz window 15 through the reference cell near infrared light outgoing quartz window 17 and then output V through the data processing unit 19Near referenceOf the signal of (1). Meanwhile, the operation software controls the fluorescent LED lamp 10 to emit fluorescence excitation light, the fluorescence grating 11 decomposes the fluorescence excitation composite light into fluorescence excitation monochromatic light, the monochromatic fluorescence excitation light enters the measuring cell 5 and the reference cell 14 through the fluorescence incidence quartz window 4 and the fluorescence incidence quartz window 13 of the measuring cell and respectively, and the fluorescence emission light passing through the measuring cell 5 is emitted through the fluorescence emergence quartz window 7 containing the chloropropanol sensitive gas sensorThe fluorescence detector 9 of the measuring cell receives the signal and outputs V through the data processing unit 19Fluorescence measurementThe signal of (a); and the fluorescence emission light passing through the reference cell 14 is detected by the reference cell fluorescence detector 18 via the reference cell fluorescence emission quartz window 16 and then output V by the data processing unit 19Near referenceOf the signal of (1).
The near infrared spectrum and the fluorescence spectrum both follow the Lambert beer law, when the near infrared spectrum or the fluorescence spectrum passes through a measuring pool or a reference pool with a certain optical path, the near infrared or fluorescence intensity attenuation amplitude of the near infrared spectrum or the fluorescence spectrum is related to the properties of a sample in the measuring pool or the reference pool, and the near infrared spectrum or the fluorescence spectrum of a measured sample and a reference substance can directly or indirectly detect and react chemical components and concentrations in the measured sample, so that qualitative and quantitative analysis of the measured substance is achieved.
The near infrared light emergent quartz window 6 of the measuring cell 5 containing the chloropropanol sensitive gas sensor interacts with the near infrared light source generated by the near infrared halogen tungsten lamp 1 which is subjected to the near infrared fixed grating 2 light splitting treatment, the generated spectrum is received by the measuring cell near infrared detector 8, and V related to the oil quality in the measuring cell 5 is generated and outputProximity measurement(ii) a The near-infrared light source generated by the near-infrared halogen tungsten lamp 1 is split by the near-infrared fixed grating 2 to generate a light source which enters the reference cell 14 through the optical fiber, and the generated near-infrared spectrum signal related to the reference gas is detected by the reference cell near-infrared detector 17 to generate VNear referenceThe data of the signal and reference chamber mainly eliminate the influence of background noise on the detection result of the measuring cell.
The fluorescence emergent quartz window 7 of the measuring cell 5 containing the chloropropanol sensitive gas sensor interacts with exciting light generated by a fluorescence LED lamp 10 subjected to light splitting treatment by a fluorescence grating 11, the generated emission spectrum is received by a cell fluorescence detector 9, and V related to the quality of oil in the measuring cell 5 is generated and outputFluorescence measurement(ii) a The fluorescence excitation light source generated by the fluorescence grating 11 of the fluorescence LED lamp 10 enters the reference cell 14 through the optical fiber, and the generated fluorescence spectrum signal related to the reference gas is detected by the reference cell fluorescence detector 18 and generates VFluorescent referenceSignal, VFluorescent referenceSignal ownerThe method is used for removing the influence of background noise on the detection result of the chloropropanol sample.
The method comprises the following specific steps:
1. preparing chloropropanol standard substances with the concentrations of 0.001mg/kg, 0.010 mg/kg, 0.100 mg/kg, 1.000 mg/kg and 10.000 mg/kg, respectively collecting the near infrared spectrum and fluorescence spectrum values of the five concentration gradient standard substances, and calculating according to a difference formula to obtain corresponding X1And X2Numerical values. Wherein, X1And X2The difference between the measured spectral signals of the near infrared spectrum and the fluorescence in the measurement cell 5 and the reference cell 14, respectively, is as follows: x1=ΔVNear to=VProximity measurement-VNear reference,X2=ΔVFluorescent lamp=VFluorescence measurement-VFluorescent reference。
2. And respectively establishing a chloropropanol standard curve algorithm based on the near infrared spectrum and the fluorescence spectrum, and simultaneously determining a linear detection range and a nonlinear detection range of the standard curve.
3. Respectively bringing the near infrared spectrum data and the fluorescence spectrum data obtained from the sample to be detected into corresponding standard curves to obtain the related information of the chloropropanol concentration of the unknown sample, and taking the average chloropropanol concentration value obtained by the near infrared algorithm and the fluorescence spectrum algorithm as the concentration value of the sample to be detected.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (8)
1. A chloropropanol sensitive gas sensor is characterized in that: the composite material comprises a polytetrafluoroethylene substrate, polyacrylic acid, heptafluorobutyrylimidazole and chitosan, wherein one end of the polyacrylic acid is combined on the polytetrafluoroethylene substrate, the other end of the polyacrylic acid is connected with the heptafluorobutyrylimidazole, and the chitosan covers the heptafluorobutyrylimidazole.
2. A method for preparing a chloropropanol sensitive gas sensor according to claim 1, which comprises the following steps:
(1) placing a polytetrafluoroethylene substrate in an acrylic acid solution, adding 0.005-0.05mol/L benzophenone serving as a catalyst into the solution at 25 ℃, placing the solution under an ultraviolet lamp for irradiation, sequentially washing the solution by using a strong alkali solution and deionized water to remove unpolymerized acrylic acid residues, and drying the solution in a vacuum state to obtain the polytetrafluoroethylene substrate with the surface covered with polyacrylic acid;
(2) uniformly coating a heptafluorobutyrylimidazole solution on a polytetrafluoroethylene substrate covered with polyacrylic acid, standing at 25 ℃, blowing the redundant liquid to dry by using inert gas, and placing the liquid in a closed device filled with the inert gas to obtain a heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene substrate;
(3) covering a chitosan solution on a heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene substrate, placing the substrate under an ultraviolet lamp for irradiation, cleaning the obtained sensor by using deionized water, and then drying the sensor by using inert gas to obtain the chitosan-heptafluorobutyrylimidazole-polyacrylic acid-polytetrafluoroethylene sensor.
3. The method for preparing a chloropropanol sensitive gas sensor according to claim 2, characterized in that: the concentration of the olefine acid solution in the step (1) is 30-60wt%, the irradiation time of an ultraviolet lamp is 8-12 h, and the pH value of the strong alkali solution is 7-10.
4. The method for preparing a chloropropanol sensitive gas sensor according to claim 2, characterized in that: the concentration of the heptafluorobutyrylimidazole solution in the step (2) is 0.005-0.05mol/L, and the standing time is 2-6 h.
5. The method for preparing a chloropropanol sensitive gas sensor according to claim 2, characterized in that: the concentration of the chitosan solution in the step (3) is 0.02-0.08 mol/L, and the irradiation time of an ultraviolet lamp is 4-8 h.
6. A detection apparatus containing the chloropropanol-sensitive gas sensor according to claim 1, characterized in that: comprises a near-infrared halogen tungsten lamp (1), a near-infrared fixed grating (2), a measuring cell near-infrared light incidence quartz window (3), a measuring cell fluorescence incidence quartz window (4), a measuring cell (5), a near-infrared light emergent quartz window (6) containing a chloropropanol sensitive gas sensor, a fluorescence emergent quartz window (7) containing a chloropropanol sensitive gas sensor, a measuring cell near-infrared detector (8) and a measuring cell fluorescence detector (9), the device comprises a fluorescent LED lamp (10), a fluorescent grating (11), a reference cell near infrared light incidence quartz window (12), a reference cell fluorescent incidence quartz window (13), a reference cell (14), a reference cell near infrared light emergent quartz window (15), a reference cell fluorescent emergent quartz window (16), a reference cell near infrared detector (17), a reference cell fluorescent detector (18) and a data processing unit (19);
wherein, the near-infrared halogen tungsten lamp (1) is connected with the near-infrared fixed grating (2), the near-infrared fixed grating (2) is respectively connected with the measuring cell (5) and the reference cell (14) through the measuring cell near-infrared light incidence quartz window (3) and the reference cell near-infrared light incidence quartz window (12), the fluorescence LED lamp (10) is connected with the fluorescence grating (11), the fluorescence grating (11) is respectively connected with the measuring cell (5) and the reference cell (14) through the measuring cell fluorescence incidence quartz window (4) and the reference cell fluorescence incidence quartz window (13), the measuring cell (5) is respectively connected with the measuring cell near-infrared detector (8) and the measuring cell fluorescence detector (9) through the near-infrared light emergence quartz window (6) containing the chloropropanol sensitive gas sensor and the fluorescence emergence quartz window (7) containing the chloropropanol sensitive gas sensor, the reference cell (14) is respectively connected with the reference cell near infrared detector (17) and the reference cell fluorescence detector (18) through a reference cell near infrared light emergent quartz window (15) and a reference cell fluorescence emergent quartz window (16), and the signal output ends of the measurement cell near infrared detector (8), the measurement cell fluorescence detector (9), the reference cell near infrared detector (17) and the reference cell fluorescence detector (18) are respectively connected with the signal input end of the data processing unit (19).
7. A detection method using the detection device of the chloropropanol sensitive gas sensor as claimed in claim 6, characterized by comprising the following steps:
(1) introducing a chloropropanol gas sample to be detected into the measuring cell (5), and introducing a reference gas into the reference cell (14);
(2) the near-infrared halogen tungsten lamp (1) is controlled to emit near infrared, the near-infrared fixed grating (2) splits the near-infrared composite light into monochromatic light, the monochromatic near-infrared light enters the measuring cell (5) and the reference cell (14) through the measuring cell near-infrared light incidence quartz window (3) and the reference cell near-infrared light incidence quartz window (12) respectively, the monochromatic near-infrared light passing through the measuring cell (5) is received by the measuring cell near-infrared detector (8) through the near-infrared light emergence quartz window (6) containing the chloropropanol sensitive gas sensor, and V is output through the data processing unit (19)Proximity measurementThe signal of (a); the monochromatic near infrared light passing through the reference cell (14) is detected by a reference cell near infrared light outgoing quartz window (15) through a reference cell near infrared detector (17) and then output V through a data processing unit (19)Near referenceThe signal of (a);
(3) the fluorescence LED lamp (10) is controlled to emit fluorescence excitation light, the fluorescence grating (11) decomposes the fluorescence excitation composite light into fluorescence excitation monochromatic light, the monochromatic fluorescence excitation light enters the measurement cell (5) and the reference cell (14) through the fluorescence incidence quartz window (4) of the measurement cell and the fluorescence incidence quartz window (13) of the reference cell respectively, the fluorescence emission light passing through the measurement cell (5) is received by the fluorescence detector (9) of the measurement cell through the fluorescence emergence quartz window (7) containing the chloropropanol sensitive gas sensor, and V is output through the data processing unit (19)Fluorescence measurementThe signal of (a); and the fluorescence emission light passing through the reference cell (14) is detected by a reference cell fluorescence detector (18) through a reference cell fluorescence emission quartz window (16) and then output V through a data processing unit (19)Near referenceThe signal of (a);
(4) respectively calculating the difference X of the spectral signals measured by the near infrared spectrum and the fluorescence1And X2:X1=ΔVNear to=VProximity measurement-VNear reference,X2=ΔVFluorescent lamp=VFluorescence measurement-VFluorescent referenceAnd substituting the chloropropanol concentration values into chloropropanol standard curves of a near infrared spectrum and a fluorescence spectrum respectively to obtain related information of the chloropropanol concentration of an unknown sample, and taking the average chloropropanol concentration value obtained by a near infrared algorithm and a fluorescence spectrum algorithm as a concentration value of the sample to be detected.
8. The detection method of a detection apparatus using the chloropropanol sensitive gas sensor, according to claim 7, characterized in that the chloropropanol standard curve of the near infrared spectrum and fluorescence spectrum of step (4) is obtained by: configuring a plurality of chloropropanol standard products with concentration gradients, respectively collecting the near infrared spectrum and fluorescence spectrum values of the chloropropanol standard products by utilizing detection equipment of a chloropropanol sensitive gas sensor, and calculating according to a difference formula to obtain corresponding X1And X2A numerical value; and respectively establishing a chloropropanol standard curve algorithm based on the near infrared spectrum and the fluorescence spectrum by using the spectral signal difference values measured by the near infrared spectrum and the fluorescence spectrum, and simultaneously determining a linear detection range and a nonlinear detection range of the standard curve.
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