CN105866301B - A kind of method of phthalic acid ester in ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies - Google Patents
A kind of method of phthalic acid ester in ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies Download PDFInfo
- Publication number
- CN105866301B CN105866301B CN201610434956.1A CN201610434956A CN105866301B CN 105866301 B CN105866301 B CN 105866301B CN 201610434956 A CN201610434956 A CN 201610434956A CN 105866301 B CN105866301 B CN 105866301B
- Authority
- CN
- China
- Prior art keywords
- extraction
- phthalic acid
- ionic liquid
- mass spectrometry
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
-
- 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
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
Landscapes
- Physics & Mathematics (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)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses the method for phthalic acid ester in a kind of ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies.Using the pretreatment mode of single drop micro-extraction, extractant is used as by the use of the methylimidazole hexafluorophosphate ionic liquid ionic liquid of 1 pi-allyl 3, using the detection means of gas-chromatography-mass spectrometry, the extraction of single drop microextraction method collection object, purifying, concentrate in a step, it is simple to operate, cost is low, bioaccumulation efficiency is high, solvent load is few, need not repeatedly it extract, amount of samples is few, solvent-oil ratio is few, selectivity to phthalic acid ester is good, the rate of recovery is between 98.3% to 106.3%, average relative standard's deviation of sample tests is between 1.2% to 3.8%.
Description
Technical field
The present invention relates to a kind of method for detecting phthalic acid ester, more particularly to one kind utilizes ionic liquid
As extractant, using the means of single drop micro-extraction combination gas-chromatography-mass spectrometry come qualitative and quantitative analysis aqueous-based food mould
Intend the method for phthalic acid ester in thing.
Background technology
Phthalic acid ester is a class environmental hormone class material, can influence the internal system of the mankind, causes reproduction, hair
Educate and abnormal behavior.Phthalic acid ester can increase the ductility and pliability of polymeric material, be a kind of more satisfactory increasing
Mould agent.Dress or liner is wrapped inside using plastic products in most of food, and phthalate compound may be from plastics
Migrated in packaging bag into food, the time that food is stored in plastic package material is longer, or the plastics for packaged food
Plasticizer loading is higher in material, can all increase the amount that plasticizer is migrated into food.In the world to the disabling of phthalic acid ester
Cry more and more higher, seems most important therefore, it is possible to carry out accurately analysis to the plasticizer contained in plastics packed product.
In the prior art to the big multiselect of sample pretreatment process of the measure of phthalic acid ester in aqueous-based food analogies
With organic solvent, it can be volatilized during using organic solvent along with solvent, and time-consuming for complex disposal process, for a long time
Pretreatment process in be easily introduced impurity in air, solvent and surrounding environment, sample is polluted, the quantitative knot of influence
The accuracy of fruit.Ionic liquid is that one kind is made up of specific cation and anion, in room temperature or close to being in a liquid state at room temperature
Organic salt.Its steam is forced down, not volatile；Stability is good, nonflammable；Solvability is strong；Designability is strong, can pass through structure
Change adjust its physicochemical property etc..The solvability of ionic liquid is very strong, and its solubility is often bigger than traditional organic solvent
Much, can be with the general organic matter such as extracting polyaromatic hydrocarbon.
Single drop micro-extraction utilizes the solvent droplet hung on microsyringe needle point on the basis of traditional liquid-liquid extraction
The liquid-phase extraction technology of the miniaturization extracted.Cumbersome, labor intensity that it overcomes traditional liquid-liquid extraction is big, extraction
Time length, extractant and amount of samples are big, the shortcomings of easily cause secondary environmental pollution, and can easily with follow-up chromatogram point
Analysis organically combines, and realizes the integrated process that sample pre-treatments and analysis are determined, is particularly suitable for trace in environmental sample
Amount, the measure of ultra trace pollutant.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide one kind enrichment and detection aqueous-based food simulation
The method of phthalic acid ester in thing, by the use of ionic liquid as extractant, the pretreatment mode of micro-extraction is dripped using list, with reference to
The detection means of gas-chromatography-mass spectrometry, carrys out phthalic acid ester in qualitative and quantitative analysis aqueous-based food analogies, easy to be high
Imitate, the good, sensitivity of selectivity is high, solvent-oil ratio is few.
To achieve the above object, the invention provides following technical scheme：A kind of ionic liquid list drop micro-extraction-makings connection
With the method for phthalic acid ester in detection aqueous-based food analogies, it is characterised in that：Comprise the following steps：
1) testing sample is extracted：Sample 10-50mL is weighed in extraction flask, stirring magneton is added, will be extracted with extraction bottle cap
Take bottle to seal, with microsyringe extract 1-5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids, make it is micro enter
Sample device syringe needle is inserted in bottle after penetrating extraction bottle cap, microsyringe needle point is inserted below liquid level, is then delayed ionic liquid
Slow extrusion makes it be suspended on syringe needle, is extracted, starts agitator, mixing speed is 100-200r/min, control extraction temperature
Spend for 40-60 DEG C, after extraction 30-45min, then again suck back ionic liquid in microsyringe, by the extraction containing testing sample
Take liquid to be transferred in sample bottle, repeat 3-5 times, for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphates
Ionic liquid cleans microsyringe, and cleaning fluid is transferred in sample bottle；
2) prepared by testing sample：The extract containing testing sample is drawn with micro syringe to be transferred in ml headspace bottle；
3) prepared by standard liquid：The standard items of a variety of phthalic acid esters are taken, constant volume after diluting step by step is configured to multiple dense
The phthalic acid ester mixed standard solution of gradient is spent, the internal standard compound of same concentration is added in the mixed standard solution of every kind of concentration；
4) gas chromatography-mass spectrometry analysis：Using head-space sampler-gas chromatograph-mass spectrometer (GC-MS) is to standard liquid and contains
Testing sample extract is tested and analyzed：Head space condition：Head space equilibrium temperature：80℃；Equilibration time is 30-50min；Transmission
Temperature：100-120℃；GC conditions：Chromatographic column：Using DB-5MS chromatographic columns；Specification：30m×0.25mm×0.25μm；
Carrier gas：High-pure helium, purity >=99.999%；Injector temperature：250℃；Sample size：1μL；Split sampling, inertia shunting bushing pipe,
Split ratio：20:1；Constant current mode, flow velocity：1.0mL/min；Lining pipe, which is shunted, from inertia reduces absorption of the bushing pipe to sample；Matter
Spectral condition：Ionization mode：Electron bombardment ionization source (EI)；Ionizing energy：70eV；Transmission line temperature：280℃；Ion source temperature：230
℃；Quadrupole rod temperature：150℃；Grab type：Select ion scan+full scan (SIM+Scan)；Solvent delay：10min；Rise
Warm program：80 DEG C of initial temperature, keeps 0.5min, with 30 DEG C/min speed to 160 DEG C, keeps 3min, then with 5 DEG C/min's
Speed keeps 5min to 300 DEG C；
5) standard curve is drawn, is as a result calculated.
As a further improvement on the present invention, microsyringe needle point insertion liquid level lower section 0.5-1cm in the step 1.
As a further improvement on the present invention, microsyringe needle point is in fluid eddies in the step 1.
As a further improvement on the present invention, in the step 1 in extraction process every 2-3min, again by ionic liquid
Suck back in microsyringe, then extrude again.
As a further improvement on the present invention, phthalic acid ester standard items include phthalic acid two in the step 3
(2- ethylhexyls) (DEHP), dibutyl phthalate (DBP), O-phthalic acid butyl benzyl group ester (BBP), O-phthalic
Sour dinonyl (DINP), di-n-octyl phthalate (DNOP) and diisooctyl phthalate (DIDP).
As a further improvement on the present invention, the internal standard compound is Ergol.
As a further improvement on the present invention, in the step 4 Mass Spectrometry Conditions also include from following qualitative ion and
Quota ion：
As a further improvement on the present invention, scanning range 100-500 in gas chromatography-mass spectrometry analysis in the step 4
(m/z).Noise can be reduced.
The material consumption and proportioning of above steps of the present invention can be expanded or be reduced with equal proportion, without by specific weight
The limitation of value.
It is the extraction of single drop microextraction method collection object, purifying, dense present invention employs the pretreatment mode of single drop micro-extraction
A step is shunk in, simple to operate, cost is low, bioaccumulation efficiency is high, solvent load is few.Utilize 1- pi-allyl -3- methylimidazole hexafluoro phosphorus
Hydrochlorate ionic liquid ionic liquid is used as extractant, it is not necessary to which repeatedly extraction, amount of samples is few, and solvent-oil ratio is few, to neighbour
The selectivity of phthalic acid ester is good, using the detection means of gas-chromatography-mass spectrometry, and easy to operate, sensitivity is high, uses
Chromatographic condition makes phthalic acid two (2- ethylhexyls) (DEHP), dibutyl phthalate (DBP), phthalic acid fourth
Base benzyl group ester (BBP), diisononyl phthalate (DINP), di-n-octyl phthalate (DNOP) and phthalic acid two
With impurity chromatographic peak separating effect preferably, the rate of recovery is between 98.3% to 106.3%, sample for the chromatographic peak of isodecyl ester (DIDP)
The relative standard deviation of test result is between 1.2% to 3.8%.
Brief description of the drawings
Fig. 1 is the chromatogram of hybrid standard sample of the present invention.
Embodiment
Following examples are given below to be described in further detail the present invention
1) instrument
Gas chromatograph-mass spectrometer (GC-MS) (U.S.'s Agilent 7890A-5975C types)；Head-space sampler (U.S. Agilent
7697A types)；Electronic balance (XS205, Mettler companies of Switzerland)；Microsyringe (50 μ L Town in Shanghai booth microsyringes factory).
2) reagent
Phthalic acid two (2- ethylhexyls) (DEHP, purity 99%), dibutyl phthalate (DBP, purity
99%), O-phthalic acid butyl benzyl group ester (BBP, purity 99%), diisononyl phthalate (DINP, purity 99%) is adjacent
Phthalic acid di-n-octyl (DNOP, purity 99%), diisooctyl phthalate (DIDP, purity 99%), 1- pi-allyls -3-
Methylimidazole hexafluorophosphate, n-hexane, methanol.3) gas chromatography-mass spectrometry analysis condition：Head space condition：Head space equilibrium temperature：
80℃；Equilibration time is 40min；Transmit temperature：110℃；GC conditions：Chromatographic column：Using DB-5MS chromatographic columns；Rule
Lattice：30m×0.25mm×0.25μm；Carrier gas：High-pure helium, purity >=99.999%；Injector temperature：250℃；Sample size：1μ
L；Split sampling, inertia shunting bushing pipe, split ratio：20:1；Constant current mode, flow velocity：1.0mL/min；Mass Spectrometry Conditions：Ionization side
Formula：Electron bombardment ionization source (EI)；Ionizing energy：70eV；Transmission line temperature：280℃；Ion source temperature：230℃；Quadrupole rod temperature：
150℃；Grab type：Select ion scan+full scan (SIM+Scan)；Scanning range 100-500m/z；Solvent delay：
10min；Heating schedule：80 DEG C of initial temperature, keeps 0.5min, with 30 DEG C/min speed to 160 DEG C, keeps 3min, then with 5
DEG C/min speed to 300 DEG C, keep 5min.
Qualitative ion and quota ion that table 1 is selected
4) preparation of standard liquid
By phthalic acid two (2- ethylhexyls) (DEHP), dibutyl phthalate (DBP), phthalic acid fourth
Base benzyl group ester (BBP), diisononyl phthalate (DINP), di-n-octyl phthalate (DNOP), phthalic acid two
Hybrid standard sample is obtained after isodecyl ester (DIDP) mixed in equal amounts, hybrid standard sample is prepared into the series standard of various concentrations
Sample, adds the Ergol internal standard compound of equivalent, with gas phase color in headspace sampling mode in the standard sample of every kind of concentration
Spectrum-GC-MS detected and draws standard curve,
The standard curve detection limit of table 2 and quantitative limit
| Sequence number | Title | Regression equation | Coefficient correlation | Detection limit μ g/g | Quantitative limit μ g/g |
| 1 | DEHP | Y=48.665x+2251.7 | 0.9990 | 0.02 | 0.06 |
| 2 | DBP | Y=55.786x+2254.8 | 0.9994 | 0.02 | 0.07 |
| 3 | BBP | Y=57.278x+2342.5 | 0.9993 | 0.01 | 0.04 |
| 4 | DINP | Y=46.494x+2437.9 | 0.9991 | 0.01 | 0.08 |
| 5 | DNOP | Y=48.235x+2439.6 | 0.9995 | 0.01 | 0.06 |
| 6 | DNOP | Y=55.602x+2349.8 | 0.9992 | 0.02 | 0.04 |
5) aqueous-based food analogies are prepared as testing sample according to GB/T23296.1-2009.
Embodiment 1
3 parts of 30mL blank samples are weighed respectively in extraction flask, and 10,30,50 μ g hybrid standard sample is added respectively, plus
Enter to stir magneton, extraction flask is sealed with extraction bottle cap, 2 μ L1- pi-allyl -3- methylimidazole hexafluoros are extracted with microsyringe
Phosphate ion liquid, makes microsyringe syringe needle be inserted after penetrating extraction bottle cap in bottle, microsyringe needle point is inserted liquid
1cm below face, then slowly extruding ionic liquid makes it be suspended on syringe needle, is extracted, and starts agitator, make it is micro enter
Sample device needle point is in fluid eddies, and mixing speed is 100r/min, and it is 55 DEG C to control extraction temperature, every 3min, again will
Ionic liquid is sucked back in microsyringe, is then extruded again, after extraction 45min, then ionic liquid is sucked back into micro-sampling again
In device, the extract containing testing sample is transferred in sample bottle, repeated 4 times, for the last time with clean 1- pi-allyls -3-
Methylimidazole hexafluorophosphoric acid ionic liquid cleans microsyringe, and cleaning fluid is transferred in sample bottle, uses micro-injection
Device is drawn the extract containing testing sample and is transferred in ml headspace bottle；Upper gas chromatograph-mass spectrometer (GC-MS) is detected.
The rate of recovery and RSD of 3 three kinds of mark-on samples of table
Embodiment 2
Sample a 30mL are weighed in extraction flask, add stirring magneton, with extraction bottle cap extraction flask is sealed, with it is micro enter
Sample device extracts 1.5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids, microsyringe syringe needle is penetrated extraction
Inserted after bottle cap in bottle, microsyringe needle point is inserted 1cm below liquid level, then slowly extruding ionic liquid hangs it
On syringe needle, extracted, start agitator, microsyringe needle point is in fluid eddies, mixing speed is 200r/
Min, it is 60 DEG C to control extraction temperature, every 3min, again sucks back in microsyringe ionic liquid, then extrudes again, is extracted
Take after 30min, then again suck back ionic liquid in microsyringe, the extract containing testing sample is transferred to sample bottle
In, repeat 3 times, cleaned for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphoric acid ionic liquids it is micro enter
Sample device, and cleaning fluid is transferred in sample bottle；The extract containing testing sample, which is drawn, with micro syringe is transferred to ml headspace bottle
In；Upper gas chromatograph-mass spectrometer (GC-MS) is detected.
Embodiment 3
Sample b 50mL are weighed in extraction flask, add stirring magneton, with extraction bottle cap extraction flask is sealed, with it is micro enter
Sample device extracts 2.5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids, microsyringe syringe needle is penetrated extraction
Inserted after bottle cap in bottle, microsyringe needle point is inserted 0.5cm below liquid level, then slowly extruding ionic liquid hangs it
Hang on syringe needle, extracted, start agitator, microsyringe needle point is in fluid eddies, mixing speed is 100r/
Min, it is 60 DEG C to control extraction temperature, every 3min, again sucks back in microsyringe ionic liquid, then extrudes again, is extracted
Take after 45min, then again suck back ionic liquid in microsyringe, the extract containing testing sample is transferred to sample bottle
In, repeat 3 times, cleaned for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphoric acid ionic liquids it is micro enter
Sample device, and cleaning fluid is transferred in sample bottle；The extract containing testing sample, which is drawn, with micro syringe is transferred to ml headspace bottle
In；Upper gas chromatograph-mass spectrometer (GC-MS) is detected.
Embodiment 4
Sample c 40mL are weighed in extraction flask, add stirring magneton, with extraction bottle cap extraction flask is sealed, with it is micro enter
Sample device extracts 3.5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids, microsyringe syringe needle is penetrated extraction
Inserted after bottle cap in bottle, microsyringe needle point is inserted 0.5cm below liquid level, then slowly extruding ionic liquid hangs it
Hang on syringe needle, extracted, start agitator, microsyringe needle point is in fluid eddies, mixing speed is 100r/
Min, it is 50 DEG C to control extraction temperature, every 2min, again sucks back in microsyringe ionic liquid, then extrudes again, is extracted
Take after 36min, then again suck back ionic liquid in microsyringe, the extract containing testing sample is transferred to sample bottle
In, repeat 4 times, cleaned for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphoric acid ionic liquids it is micro enter
Sample device, and cleaning fluid is transferred in sample bottle；The extract containing testing sample, which is drawn, with micro syringe is transferred to ml headspace bottle
In；Upper gas chromatograph-mass spectrometer (GC-MS) is detected.
Embodiment 5
Sample d 10mL are weighed in extraction flask, add stirring magneton, with extraction bottle cap extraction flask is sealed, with it is micro enter
Sample device extracts 1.5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids, microsyringe syringe needle is penetrated extraction
Inserted after bottle cap in bottle, microsyringe needle point is inserted 0.8cm below liquid level, then slowly extruding ionic liquid hangs it
Hang on syringe needle, extracted, start agitator, microsyringe needle point is in fluid eddies, mixing speed is 200r/
Min, it is 40 DEG C to control extraction temperature, every 2min, again sucks back in microsyringe ionic liquid, then extrudes again, is extracted
Take after 30min, then again suck back ionic liquid in microsyringe, the extract containing testing sample is transferred to sample bottle
In, repeat 5 times, cleaned for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphoric acid ionic liquids it is micro enter
Sample device, and cleaning fluid is transferred in sample bottle；The extract containing testing sample, which is drawn, with micro syringe is transferred to ml headspace bottle
In；Upper gas chromatograph-mass spectrometer (GC-MS) is detected.
Embodiment 6
Sample e 20mL are weighed in extraction flask, add stirring magneton, with extraction bottle cap extraction flask is sealed, with it is micro enter
Sample device extracts 1.5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids, microsyringe syringe needle is penetrated extraction
Inserted after bottle cap in bottle, microsyringe needle point is inserted 0.5cm below liquid level, then slowly extruding ionic liquid hangs it
Hang on syringe needle, extracted, start agitator, microsyringe needle point is in fluid eddies, mixing speed is 100r/
Min, it is 45 DEG C to control extraction temperature, every 2min, again sucks back in microsyringe ionic liquid, then extrudes again, is extracted
Take after 44min, then again suck back ionic liquid in microsyringe, the extract containing testing sample is transferred to sample bottle
In, repeat 3 times, cleaned for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphoric acid ionic liquids it is micro enter
Sample device, and cleaning fluid is transferred in sample bottle；The extract containing testing sample, which is drawn, with micro syringe is transferred to ml headspace bottle
In；Upper gas chromatograph-mass spectrometer (GC-MS) is detected.
The testing result of the not be the same as Example of table 4
Note：ND is the implication for not detecting corresponding phthalate compound.
Claims (8)
1. the method for phthalic acid ester in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies,
It is characterized in that：Comprise the following steps：
1) testing sample is extracted：Sample 10-50mL is weighed in extraction flask, stirring magneton is added, with extraction bottle cap by extraction flask
Sealing, extracts 1-5 μ L 1- pi-allyl -3- methylimidazole hexafluorophosphoric acid ionic liquids with microsyringe, makes microsyringe
Syringe needle is inserted in bottle after penetrating extraction bottle cap, microsyringe needle point is inserted below liquid level, is then slowly squeezed ionic liquid
Sening as an envoy to, it is suspended on syringe needle, is extracted, and starts agitator, and mixing speed is 100-200r/min, controls the extraction temperature to be
40-60 DEG C, after extraction 30-45min, then ionic liquid sucked back in microsyringe again, by the extract containing testing sample
It is transferred in sample bottle, repeats 3-5 times, for the last time with clean 1- pi-allyls -3- methylimidazole hexafluorophosphoric acid salt ions
Liquid rinse microsyringe, and cleaning fluid is transferred in sample bottle；
2) prepared by testing sample：The extract containing testing sample is drawn with micro syringe to be transferred in ml headspace bottle；
3) prepared by standard liquid：The standard items of a variety of phthalic acid esters are taken, constant volume after diluting step by step is configured to multiple concentration ladders
The phthalic acid ester mixed standard solution of degree, adds the internal standard compound of same concentration in the mixed standard solution of every kind of concentration；
4) gas chromatography-mass spectrometry analysis：Using head-space sampler-gas chromatograph-mass spectrometer (GC-MS) to standard liquid and containing to be measured
Sample extraction liquid is tested and analyzed：Head space condition：Head space equilibrium temperature：80℃；Equilibration time is 30-40min；Transmission temperature
Degree：100-110℃；GC conditions：Chromatographic column：Using DB-5MS chromatographic columns；Specification：30m×0.25mm×0.25μm；Carry
Gas：High-pure helium, purity >=99.999%；Injector temperature：250℃；Sample size：1μL；Split sampling, inertia shunting bushing pipe, point
Stream ratio：20:1；Constant current mode, flow velocity：1.0mL/min；Mass Spectrometry Conditions：Ionization mode：Electron bombardment ionization source (EI)；Ionizing energy：
70eV；Transmission line temperature：280℃；Ion source temperature：230℃；Quadrupole rod temperature：150℃；Grab type：Select ion scan
+ full scan (SIM+Scan)；Solvent delay：10min；Heating schedule：80 DEG C of initial temperature, keeps 0.5min, with 30 DEG C/min
Speed to 160 DEG C, keep 3min, then with 5 DEG C/min speed to 300 DEG C, keep 5min；
5) standard curve is drawn, is as a result calculated.
2. in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies according to claim 1
The method of phthalic acid ester, it is characterised in that：The step 1）0.5-1cm below middle microsyringe needle point insertion liquid level.
3. in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies according to claim 2
The method of phthalic acid ester, it is characterised in that：The step 1）Middle microsyringe needle point is in fluid eddies.
4. in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies according to claim 3
The method of phthalic acid ester, it is characterised in that：The step 1）Every 2-3min in middle extraction process, again by ionic liquid
Suck back in microsyringe, then extrude again.
5. a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food according to claim any one of 1-4
The method of phthalic acid ester in analogies, it is characterised in that：The step 3）Middle phthalic acid ester standard items include adjacent benzene
Dioctyl phthalate two (2- ethylhexyls) (DEHP), dibutyl phthalate (DBP), O-phthalic acid butyl benzyl group ester (BBP),
Diisononyl phthalate (DINP), di-n-octyl phthalate (DNOP) and diisooctyl phthalate
(DIDP)。
6. in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies according to claim 5
The method of phthalic acid ester, it is characterised in that：The internal standard compound is Ergol.
7. in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies according to claim 6
The method of phthalic acid ester, it is characterised in that：The step 4）Middle Mass Spectrometry Conditions also include from following qualitative ion and
Quota ion：
。
8. in a kind of ionic liquid list drop micro-extraction-gas chromatography mass spectrometry detection aqueous-based food analogies according to claim 7
The method of phthalic acid ester, it is characterised in that：The step 4）Scanning range 100- in middle gas chromatography-mass spectrometry analysis
500m/z。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610434956.1A CN105866301B (en) | 2016-06-17 | 2016-06-17 | A kind of method of phthalic acid ester in ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610434956.1A CN105866301B (en) | 2016-06-17 | 2016-06-17 | A kind of method of phthalic acid ester in ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105866301A CN105866301A (en) | 2016-08-17 |
| CN105866301B true CN105866301B (en) | 2017-11-07 |
Family
ID=56650709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610434956.1A Active CN105866301B (en) | 2016-06-17 | 2016-06-17 | A kind of method of phthalic acid ester in ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105866301B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109946249B (en) * | 2019-03-18 | 2021-06-01 | 江苏科技大学 | Method for colorimetric determination of hydrogen sulfide by using headspace single-drop liquid phase microextraction method and intelligent equipment |
| CN113933432B (en) * | 2021-10-22 | 2023-08-25 | 中国烟草总公司郑州烟草研究院 | High-sensitivity and high-precision analysis method suitable for detecting alkaloid in tobacco leaves |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102520091B (en) * | 2011-12-20 | 2014-07-23 | 中国科学院上海有机化学研究所 | Method for detecting plasticizer content in solid sample by headspace solid phase microextraction gas chromatography-tandem mass spectrometry |
| CN103822982B (en) * | 2014-02-25 | 2015-12-09 | 浙江大学宁波理工学院 | A kind of ionic liquid-dispersive liquid-liquid microextraction method enrichment and the method detecting phthalate compound in wine sample |
| CN105203661A (en) * | 2015-09-18 | 2015-12-30 | 上海市农业科学院 | Method for detecting various phthalic acid ester plasticizers in vegetables, fruits and edible mushrooms at same time |
-
2016
- 2016-06-17 CN CN201610434956.1A patent/CN105866301B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105866301A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Recent advances in analysis of phthalate esters in foods | |
| Rios et al. | Headspace solid-phase microextraction of oil matrices heated at high temperature and phthalate esters determination by gas chromatography multistage mass spectrometry | |
| CN102353742B (en) | Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum | |
| Ghasemi et al. | Headspace hollow fiber protected liquid-phase microextraction combined with gas chromatography–mass spectroscopy for speciation and determination of volatile organic compounds of selenium in environmental and biological samples | |
| Márquez-Sillero et al. | Direct determination of 2, 4, 6-tricholoroanisole in wines by single-drop ionic liquid microextraction coupled with multicapillary column separation and ion mobility spectrometry detection | |
| CN102175785B (en) | Method for detecting VOC (Volatile Organic Compound) matters in toy paint | |
| CN105974039B (en) | A kind of method for being enriched with and detecting phthalic acid ester in food packaging plastic products | |
| CN105021754A (en) | Liquid chromatography-tandem mass spectrometry method for simultaneous determination of specific migration of 18 phenols or phenol derivatives in five plastic food simulants | |
| CN105866301B (en) | A kind of method of phthalic acid ester in ionic liquid list drop micro-extraction gas chromatography mass spectrometry detection aqueous-based food analogies | |
| CN103969368B (en) | A kind of method of ethyl acetate and seven kinds of residual monomers in Rapid Simultaneous Determination tackifier | |
| Ramezani et al. | A novel ultrasound-assisted back extraction reverse micelles method coupled with gas chromatography–flame ionization detection for determination of aldehydes in heated edibles oils | |
| Demirhan et al. | Overview of green sample preparation techniques in food analysis | |
| JP2016200531A (en) | Analytic method | |
| CN103808814B (en) | A kind of method for detecting Phthalic Acid Esters in Food | |
| CN104634899B (en) | The method that a kind of supertension auxiliary liquid-liquid micro-extraction measures plasticizer | |
| CN104713962B (en) | For detecting the pre-treating method of benzo (a) pyrene in oil product and detecting the method for benzo (a) pyrene in oil product | |
| CN104792906A (en) | Method for determining squalene content of baijiu | |
| CN103033583A (en) | Method for enriching and measuring ester components in natural perfume by using ionic liquid | |
| CN112557564B (en) | Method for determining content of benzene solvent in solvent type acrylate adhesive | |
| Uansiri et al. | Ultrasound-assisted low density solvent based dispersive liquid-liquid microextraction for determination of phthalate esters in bottled water samples | |
| CN103837615B (en) | Method applying HPLC and simultaneously determining phytoecdysone substance | |
| Keriene et al. | Solid phase extraction and gas chromatographic-mass spectrometric analysis of phthalates in surface water: Method development and validation | |
| CN106018610B (en) | A kind of method of phthalic acid ester in ionic liquid microwave abstracting-food packaging plastic products of high performance liquid chromatography detection | |
| CN106362692A (en) | Magnetic graphene oxide and application thereof | |
| Guerra et al. | Analysis of citrates and benzoates used in poly (vinyl chloride) by supercritical fluid extraction and gas chromatography |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |