CN109507330A - A kind of method of antibiotic in detection environmental sample - Google Patents
A kind of method of antibiotic in detection environmental sample Download PDFInfo
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- CN109507330A CN109507330A CN201811601749.6A CN201811601749A CN109507330A CN 109507330 A CN109507330 A CN 109507330A CN 201811601749 A CN201811601749 A CN 201811601749A CN 109507330 A CN109507330 A CN 109507330A
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- 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
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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
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- G—PHYSICS
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- 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
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- 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
- G01N30/16—Injection
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- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- 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
- G01N2030/042—Standards
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
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Abstract
A kind of method of antibiotic in detection environmental sample, specifically operates: the ion liquid abstraction of article to be measured according to the following steps;The doughnut liquid of extract liquor extracts: the preparation of standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the antibiotic solution of a variety of concentration；For use;Gas chromatographic analysis: standard solution and extraction detectable substance are analyzed using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)；And recorded, it is finally completed the detection process of antibiotic.The present invention finally makes detection accuracy good, causes to improve detection accuracy by conjunction with doughnut liquid-phase micro extraction technique, can effectively make up the deficiency of traditional organic extraction solvent, play its inherent advantages ionic liquid.
Description
Technical field
The invention belongs to detection method technical fields, are related to a kind of method for detecting antibiotic in environmental sample.
Background technique
Sulfa antibiotics are widely used in animal husbandry, culture fishery because of the effect of its prevention and control transmission
In, but such drug is difficult to degrade, the residence time is long, is eventually entered with various approach and is remained in environment water, influences ring
Border quality is simultaneously detrimental to health.The content of sulfa antibiotics is very low in environmental sample simultaneously, therefore detection accuracy is bad,
Cause final detection accuracy not high.
Therefore, how to solve the above problems, be the content that those skilled in the art are badly in need of research.
Summary of the invention
To overcome the deficiencies in the prior art described above, it is an object of that present invention to provide antibiotic in a kind of detection environmental sample
Method.
In order to achieve the above objects and other related objects, the present invention provides a kind of side for detecting antibiotic in environmental sample
Method specifically operates according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 60-80mL into extraction flask, and agitating device is added and carries out magnetic
Property stir process, extraction flask is sealed processing with extraction bottle cap, with microsyringe extraction ionic liquid at room temperature, and is used
Microsyringe syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on needle
On head, extracted, open agitating device, and be arranged extraction temperature be 45-50 DEG C, extract 20-35min after, then by room temperature from
Sub- liquid sucks back in microsyringe, by the extract liquor mobile example bottle containing detection product, is operated 4-6 times repeatedly by above-mentioned
Afterwards, pass through clean ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 55-65 DEG C of progress
Polymerization reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
It takes detectable substance and is moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
Further, head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition described in the step 4 is: top
Empty condition: head space equilibrium temperature: 80 DEG C；Equilibration time is 50-60min；Transmitting temperature is 112-115 degrees Celsius；Chromatographic condition:
DB-5MS capillary column；Injector temperature: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: the high-purity helium of > 99.999%, column
Flow: 1.5mL min-1；Sample introduction pressure 12psi；Sample introduction mode: Splitless injecting samples；1 μ L of sampling volume；Temperature program are as follows: 85 DEG C
1min is kept, rises to 230 DEG C with 25 DEG C of min-1, keeps 8min, the bulk analysis time is 15min；Mass Spectrometry Conditions: the source EI, energy
75eV, 220 DEG C of temperature；Quadrupole rod temperature: 150 DEG C；Solvent delay: 8min；Collision gas is high pure nitrogen.
Further, in step 2 the solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent,
Organic pore-foaming agent, azo initiator carry out mixing treatment, obtain mixed organic solvents.
Further, the azo initiator is from azodiisobutyronitrile.
Further, it is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
Further, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
Further, it needs to operate repeatedly 5 times in step 1.
Further, the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
Since above-mentioned technical proposal is used, compared with the prior art, the invention has the beneficial effects that:
The method of antibiotic in a kind of detection environmental sample that the present invention obtains, by the way that ionic liquid and doughnut liquid phase is micro-
Abstraction technique combines, and can effectively make up the deficiency of traditional organic extraction solvent, play its inherent advantages, finally makes detection quasi-
True property is good, causes to improve detection accuracy.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily.
Embodiment:
The method of antibiotic in a kind of detection environmental sample provided in this embodiment, specifically operates according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 60-80mL into extraction flask, and agitating device is added and carries out magnetic
Property stir process, extraction flask is sealed processing with extraction bottle cap, with microsyringe extraction ionic liquid at room temperature, and is used
Microsyringe syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on needle
On head, extracted, open agitating device, and be arranged extraction temperature be 45-50 DEG C, extract 20-35min after, then by room temperature from
Sub- liquid sucks back in microsyringe, by the extract liquor mobile example bottle containing detection product, is operated 4-6 times repeatedly by above-mentioned
Afterwards, pass through clean ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 55-65 DEG C of progress
Polymerization reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
It takes detectable substance and is moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
Further, head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition described in the step 4 is: top
Empty condition: head space equilibrium temperature: 80 DEG C；Equilibration time is 50-60min；Transmitting temperature is 112-115 degrees Celsius；Chromatographic condition:
DB-5MS capillary column (30m × 0.25mm × 0.25 μm)；Injector temperature: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: high
Pure helium (> 99.999%), column flow: 1.5mL min-1；Sample introduction pressure 12psi (constant voltage mode)；Sample introduction mode: it does not shunt
Sample introduction；1 μ L of sampling volume；Temperature program are as follows: 85 DEG C of holding 1min rise to 230 DEG C with 25 DEG C of min-1, keep 8min, total score
The analysis time is 15min；Mass Spectrometry Conditions: the source EI, energy 75eV, 220 DEG C of temperature；Quadrupole rod temperature: 150 DEG C；Solvent delay:
8min；Collision gas is high pure nitrogen.
Further, in step 2 the solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent,
Organic pore-foaming agent, azo initiator carry out mixing treatment, obtain mixed organic solvents.
Further, the azo initiator is from azodiisobutyronitrile.
Further, it is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
Further, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
Further, it needs to operate repeatedly 5 times in step 1.
Further, the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
Embodiment 2:
The method of antibiotic in a kind of detection environmental sample provided in this embodiment, specifically operates according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 60mL into extraction flask, and agitating device is added and carries out magnetism
Extraction flask is sealed processing with extraction bottle cap, extracts ionic liquid at room temperature with microsyringe, and using micro- by stir process
Amount sample injector syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on syringe needle
On, it is extracted, opens agitating device, and it is 45 DEG C that extraction temperature, which is arranged, after extracting 20min, then ionic liquid at room temperature is inhaled
Return in microsyringe, by the extract liquor mobile example bottle containing detection product, by it is above-mentioned operate 4 times repeatedly after, by dry
Net ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 55-65 DEG C of progress
Polymerization reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
It takes detectable substance and is moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
Further, head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition described in the step 4 is: top
Empty condition: head space equilibrium temperature: 80 DEG C；Equilibration time is 50min；Transmitting temperature is 112 degrees Celsius；Chromatographic condition: DB-5MS
Capillary column (30m × 0.25mm × 0.25 μm)；Injector temperature: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: high-purity helium
(> 99.999%), column flow: 1.5mL min-1；Sample introduction pressure 12psi (constant voltage mode)；Sample introduction mode: Splitless injecting samples；
1 μ L of sampling volume；Temperature program are as follows: 85 DEG C of holding 1min rise to 230 DEG C with 25 DEG C of min-1, kept for 8min, bulk analysis time
For 15min；Mass Spectrometry Conditions: the source EI, energy 75eV, 220 DEG C of temperature；Quadrupole rod temperature: 150 DEG C；Solvent delay: 8min；Collision
Gas is high pure nitrogen.
Further, in step 2 the solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent,
Organic pore-foaming agent, azo initiator carry out mixing treatment, obtain mixed organic solvents.
Further, the azo initiator is from azodiisobutyronitrile.
Further, it is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
Further, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
Further, it needs to operate repeatedly 5 times in step 1.
Further, the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
Embodiment 3:
The method of antibiotic in a kind of detection environmental sample provided in this embodiment, specifically operates according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 75mL into extraction flask, and agitating device is added and carries out magnetism
Extraction flask is sealed processing with extraction bottle cap, extracts ionic liquid at room temperature with microsyringe, and using micro- by stir process
Amount sample injector syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on syringe needle
On, it is extracted, opens agitating device, and it is 45 DEG C that extraction temperature, which is arranged, after extracting 20min, then ionic liquid at room temperature is inhaled
Return in microsyringe, by the extract liquor mobile example bottle containing detection product, by it is above-mentioned operate 4 times repeatedly after, by dry
Net ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 60 DEG C and gather
Close reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
Detectable substance is simultaneously moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
Further, head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition described in the step 4 is: top
Empty condition: head space equilibrium temperature: 80 DEG C；Equilibration time is 55min；Transmitting temperature is 113 degrees Celsius；Chromatographic condition: DB-5MS
Capillary column (30m × 0.25mm × 0.25 μm)；Injector temperature: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: high-purity helium
(> 99.999%), column flow: 1.5mL min-1；Sample introduction pressure 12psi (constant voltage mode)；Sample introduction mode: Splitless injecting samples；
1 μ L of sampling volume；Temperature program are as follows: 85 DEG C of holding 1min rise to 230 DEG C with 25 DEG C of min-1, kept for 8min, bulk analysis time
For 15min；Mass Spectrometry Conditions: the source EI, energy 75eV, 220 DEG C of temperature；Quadrupole rod temperature: 150 DEG C；Solvent delay: 8min；Collision
Gas is high pure nitrogen.
Further, in step 2 the solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent,
Organic pore-foaming agent, azo initiator carry out mixing treatment, obtain mixed organic solvents.
Further, the azo initiator is from azodiisobutyronitrile.
Further, it is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
Further, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
Further, it needs to operate repeatedly 5 times in step 1.
Further, the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
Embodiment 4:
The method of antibiotic in a kind of detection environmental sample provided in this embodiment, specifically operates according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 70mL into extraction flask, and agitating device is added and carries out magnetism
Extraction flask is sealed processing with extraction bottle cap, extracts ionic liquid at room temperature with microsyringe, and using micro- by stir process
Amount sample injector syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on syringe needle
On, it is extracted, opens agitating device, and it is 48 DEG C that extraction temperature, which is arranged, after extracting 25min, then ionic liquid at room temperature is inhaled
Return in microsyringe, by the extract liquor mobile example bottle containing detection product, by it is above-mentioned operate 5 times repeatedly after, by dry
Net ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 60 DEG C and gather
Close reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
Detectable substance is simultaneously moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
Further, head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition described in the step 4 is: top
Empty condition: head space equilibrium temperature: 80 DEG C；Equilibration time is 55min；Transmitting temperature is 114 degrees Celsius；Chromatographic condition: DB-5MS
Capillary column (30m × 0.25mm × 0.25 μm)；Injector temperature: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: high-purity helium
(> 99.999%), column flow: 1.5mL min-1；Sample introduction pressure 12psi (constant voltage mode)；Sample introduction mode: Splitless injecting samples；
1 μ L of sampling volume；Temperature program are as follows: 85 DEG C of holding 1min rise to 230 DEG C with 25 DEG C of min-1, kept for 8min, bulk analysis time
For 15min；Mass Spectrometry Conditions: the source EI, energy 75eV, 220 DEG C of temperature；Quadrupole rod temperature: 150 DEG C；Solvent delay: 8min；Collision
Gas is high pure nitrogen.
Further, in step 2 the solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent,
Organic pore-foaming agent, azo initiator carry out mixing treatment, obtain mixed organic solvents.
Further, the azo initiator is from azodiisobutyronitrile.
Further, it is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
Further, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
Further, it needs to operate repeatedly 5 times in step 1.
Further, the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
Embodiment 5:
The method of antibiotic in a kind of detection environmental sample provided in this embodiment, specifically operates according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 80mL into extraction flask, and agitating device is added and carries out magnetism
Extraction flask is sealed processing with extraction bottle cap, extracts ionic liquid at room temperature with microsyringe, and using micro- by stir process
Amount sample injector syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on syringe needle
On, it is extracted, opens agitating device, and it is 50 DEG C that extraction temperature, which is arranged, after extracting 35min, then ionic liquid at room temperature is inhaled
Return in microsyringe, by the extract liquor mobile example bottle containing detection product, by it is above-mentioned operate 6 times repeatedly after, by dry
Net ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 65 DEG C and gather
Close reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
Detectable substance is simultaneously moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
Further, head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition described in the step 4 is: top
Empty condition: head space equilibrium temperature: 80 DEG C；Equilibration time is 60min；Transmitting temperature is 115 degrees Celsius；Chromatographic condition: DB-5MS
Capillary column (30m × 0.25mm × 0.25 μm)；Injector temperature: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: high-purity helium
(> 99.999%), column flow: 1.5mL min-1；Sample introduction pressure 12psi (constant voltage mode)；Sample introduction mode: Splitless injecting samples；
1 μ L of sampling volume；Temperature program are as follows: 85 DEG C of holding 1min rise to 230 DEG C with 25 DEG C of min-1, kept for 8min, bulk analysis time
For 15min；Mass Spectrometry Conditions: the source EI, energy 75eV, 220 DEG C of temperature；Quadrupole rod temperature: 150 DEG C；Solvent delay: 8min；Collision
Gas is high pure nitrogen.
Further, in step 2 the solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent,
Organic pore-foaming agent, azo initiator carry out mixing treatment, obtain mixed organic solvents.
Further, the azo initiator is from azodiisobutyronitrile.
Further, it is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
Further, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
Further, it needs to operate repeatedly 5 times in step 1.
Further, the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
Ionic liquid by conjunction with doughnut liquid-phase micro extraction technique, can effectively be made up the organic extraction of tradition by the present invention
The deficiency for taking solvent, plays its inherent advantages, finally makes detection accuracy good, causes to improve detection accuracy.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of method of antibiotic in detection environmental sample, which is characterized in that specifically operate according to the following steps:
The ion liquid abstraction of step 1, article to be measured: weighing sample 60-80mL into extraction flask, and agitating device is added and carries out magnetic
Property stir process, extraction flask is sealed processing with extraction bottle cap, with microsyringe extraction ionic liquid at room temperature, and is used
Microsyringe syringe needle passes through to be placed in liquid in bottle cap injection bottle, is then slowly squeezed out ionic liquid at room temperature and is suspended on needle
On head, extracted, open agitating device, and be arranged extraction temperature be 45-50 DEG C, extract 20-35min after, then by room temperature from
Sub- liquid sucks back in microsyringe, by the extract liquor mobile example bottle containing detection product, is operated 4-6 times repeatedly by above-mentioned
Afterwards, pass through clean ionic liquid at room temperature high pressure washing microsyringe；
The doughnut liquid extraction of step 2, extract liquor: and then that the extract liquor that step 1 obtains further is put into both ends is close
The hollow fiber conduit of envelope, and be loaded with organic extract liquid in the closed cavity of the hollow fiber conduit and be provided with the micro- extraction of solid phase
Fiber is taken, the solid-phase micro-extraction fibre submerges in the organic extract liquid；And the mixed solution is placed in oxygen-free environment
In after, capillary is launched in Xiang Suoshu mixed organic solvents, and the mixed organic solvents are filled to the capillary
In cavity；Continue in oxygen-free environment, the mixed organic solvents for having the capillary will be launched and be heated to 55-65 DEG C of progress
Polymerization reaction, to the polymerization reaction after to capillary washing, aging process and remove the capillary and extracted
It takes detectable substance and is moved in empty bottle；
The preparation of step 3, standard solution: taking the standard article of Multiple Classes of Antibiotics, after gradually diluting, is prepared into the anti-of a variety of concentration
Raw element solution；For use；
Step 4, gas chromatographic analysis: standard solution and extraction are detected using head-space sampler-gas chromatograph-mass spectrometer (GC-MS)
Object is analyzed；And recorded, it is finally completed the detection process of antibiotic.
2. according to right want 1 described in a kind of detection environmental sample antibiotic method, which is characterized in that step 4 institute
Stating head-space sampler-gas chromatograph-mass spectrometer (GC-MS) specific works condition is: head space condition: head space equilibrium temperature: 80 DEG C；
Equilibration time is 50-60min；Transmitting temperature is 112-115 degrees Celsius；Chromatographic condition: DB-5MS capillary column；Injection port temperature
Degree: 280 DEG C；Transmission line temperature: 290 DEG C；Carrier gas: the high-purity helium of > 99.999%, column flow: 1.5mL min-1；Sample introduction pressure
Power 12psi (constant voltage mode)；Sample introduction mode: Splitless injecting samples；1 μ L of sampling volume；Temperature program are as follows: 85 DEG C of holding 1min, with
25 DEG C of min-1 rise to 230 DEG C, keep 8min, and the bulk analysis time is 15min；Mass Spectrometry Conditions: the source EI, energy 75eV, temperature 220
℃；Quadrupole rod temperature: 150 DEG C；Solvent delay: 8min；Collision gas is high pure nitrogen.
3. the method for antibiotic in a kind of detection environmental sample according to claim 2, which is characterized in that in step 2
The solid-phase micro-extraction fibre be by α-methacrylic acid, styrene, organic crosslinking agent, organic pore-foaming agent, azo initiator into
Row mixing treatment, obtains mixed organic solvents.
4. the method for antibiotic in a kind of detection environmental sample according to claim 3, which is characterized in that the azo draws
Sending out agent is from azodiisobutyronitrile.
5. the method for antibiotic in a kind of detection environmental sample according to claim 1 or 2 or 3 or 4, which is characterized in that
It is micron-sized hydrophobic hollow fiber conduit that the hollow fiber conduit, which selects tube wall aperture,.
6. the method for antibiotic in a kind of detection environmental sample according to claim 5, which is characterized in that the hollow fibre
Tieing up pipe and selecting tube wall aperture is micron-sized hydrophobic hollow fiber conduit.
7. the method for BPS in magnetic bamboo charcoal Solid Phase Extraction-liquid chromatographic detection water according to claim 1 or 2 or 3 or 4,
It is characterized in that, the organic extract liquid selects at least one of toluene, dimethylbenzene, chlorobenzene, benzene.
8. the method for BPS in magnetic bamboo charcoal Solid Phase Extraction-liquid chromatographic detection water according to claim 1 or 2 or 3 or 4,
It is characterized in that, needing to operate repeatedly in step 15 times.
9. the method for BPS, feature exist in magnetic bamboo charcoal Solid Phase Extraction-liquid chromatographic detection water according to claim 5
In needing to operate repeatedly in step 15 times.
10. the side of BPS in magnetic bamboo charcoal Solid Phase Extraction-liquid chromatographic detection water according to claim 1 or 2 or 3 or 4
Method, which is characterized in that the article to be measured is any one of water sample, soil, urine, extraction from biological material liquid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618209A (en) * | 2019-09-19 | 2019-12-27 | 浙江树人学院（浙江树人大学） | Method for measuring tetracycline antibiotics in surface water by ionic liquid extraction-high performance liquid chromatography |
| CN113861074A (en) * | 2021-09-23 | 2021-12-31 | 中国检验检疫科学研究院 | Preparation method and application of novel ionic liquid MALDI matrix |
-
2018
- 2018-12-26 CN CN201811601749.6A patent/CN109507330A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618209A (en) * | 2019-09-19 | 2019-12-27 | 浙江树人学院（浙江树人大学） | Method for measuring tetracycline antibiotics in surface water by ionic liquid extraction-high performance liquid chromatography |
| CN113861074A (en) * | 2021-09-23 | 2021-12-31 | 中国检验检疫科学研究院 | Preparation method and application of novel ionic liquid MALDI matrix |
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