CN1803242A - Solid phase dispersion microwave extraction method of sample residues matrix and extraction stuffing and solvent - Google Patents
Solid phase dispersion microwave extraction method of sample residues matrix and extraction stuffing and solvent Download PDFInfo
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- CN1803242A CN1803242A CN 200510045459 CN200510045459A CN1803242A CN 1803242 A CN1803242 A CN 1803242A CN 200510045459 CN200510045459 CN 200510045459 CN 200510045459 A CN200510045459 A CN 200510045459A CN 1803242 A CN1803242 A CN 1803242A
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Abstract
The invention discloses a solid-phase dispersed microwave extraction method of residual sample base and solid-phase dispersed microwave extraction filler and extraction solvent, which comprises the following steps: 1) mixing the detected sample and solid-phase dispersed microwave extraction filler; grinding evenly; 2) adding the extraction solvent in the microwave generator to proceed the microwave radiation; 3) removing the solid impurity to obtain the extract with residue; removing the solid impurity through eccentric action; proceeding rotary evaporation condensation for the extract; dissolving fitful residue as solvent; purifying through the special right mixed purifying agent to analyze the sampling usage for instrument. The invention can extract object compound with different chemical properties effectively.
Description
Technical field
The present invention relates to the extraction and cleaning technology of sample residues in the analytical chemistry, specific design is used for the solid phase dispersion microwave extraction method of sample residues matrix of animal-derived food, plant source food and other biological sample residues of pesticides, residue of veterinary drug, biotoxin, organic pollution detection; The invention further relates to solid phase dispersion extraction filler, extractant that solid phase dispersion microwave extraction method of sample residues matrix adopts.
Background technology
The animal sources product, residues of pesticides in plant source product or the other biological sample, residue of veterinary drug, pollutant, biotoxin, and human body medicine, the analysis of poisonous substance, before adopting the rigorous analysis detection, as adopt gas-chromatography, liquid chromatogram, gas chromatography/mass spectrometry, liquid chromatography/mass spectrometry etc., must target compound to be measured be extracted from sample substrate and purify through numerous and diverse sample pre-treatments technology, just can carry out Instrumental Analysis, the effect of extraction and cleaning directly influences removes degree and the analytical accuracy that impurity disturbs, when particularly complicated sample matrix and multiple residuals being measured simultaneously, higher to the sample pre-treatments specification requirement.At present the extracting process to the sample that contains above-mentioned residuals has following several:
1, liquid-liquid extraction method: adopt the single organic solvent or the mixed solvent of opposed polarity that target compound is extracted;
2, solid phase extraction: adopt the pillar that has loaded different solid-phase adsorbents such as C18, C8, benzene sulfonic acid material etc., sample is added on the extraction pillar, then through steps such as appropriate solvent washing, wash-outs, with the method for evaluating objects compound extraction and cleaning;
3, matrix solid phase dispersion extraction method: adopt solid-phase adsorbents such as C18, C8, benzene sulfonic acid, grind simultaneously with animality sample or vegetalitas sample to be measured, form homogeneous granules shape mixture, add to then in the empty chromatographic column, make extraction column after compressing, wash and steps such as wash-out with suitable organic solvent, reach the purpose that the evaluating objects compound is extracted and purifies;
4, soxhlet extraction: analytic sample is loaded in the special-purpose solvent refluxing device, extracts testing sample repeatedly, reach the purpose of the evaluating objects compound being carried out extraction and cleaning with the organic solvent of heating evaporation condensation;
5, accelerated solvent extraction is followed the example of: testing sample is loaded in the special-purpose stainless steel extraction column, adopt special-purpose accelerated solvent extraction, under suitable pressure and temperature, extract with organic solvent, reach the purpose that the evaluating objects compound is extracted and purifies;
6, supercritical extraction: will treat that then sample is loaded in the special-purpose extraction column, be installed in the supercritical extract instrument, adopt carbon dioxide, under supercriticality, with suitable pressure and temperature sample is extracted, reach the purpose of the evaluating objects compound being carried out extraction and cleaning;
7, ultrasonic wave auxiliary extraction method: testing sample is packed in the appropriate containers, add extractant, carry out the ultrasonic cavitation auxiliary extraction, reach the effect of the evaluating objects compound being carried out extraction and cleaning by supersonic generator;
8, microwave auxiliary extraction method: testing sample is packed in the appropriate containers, add extractant, put into microwave generator,, reach the purpose of the evaluating objects compound being carried out extraction and cleaning by microwave radiation auxiliary extraction.
Existing sample-pretreating method, the instrument and equipment of the needs complexity that has; The extraction effect to the biological sample of complexity that has is undesirable; Being difficult to of having extracted simultaneously to the multiple target compounds with different chemical character, particularly surpass more than 20 kinds, reach under the situation that hundreds of hundreds of kind residue measures simultaneously,, be difficult to the extraction effect that reaches balanced in the same pH scope at same polar solvent; Material or the metabolite extraction difficulty strong to protein combination are big, and the rate of recovery is low.
Summary of the invention
The method of the present invention's design, the biological sample of complexity can be remained in intracellular target compound disperses and microwave abstracting by matrix, the release of big limit and extracting, can the target compound of multiple different chemical character be extracted simultaneously, it is effective to carry thing, the extraction efficiency height, easy to be quick, use wide.
For achieving the above object, the present invention has adopted following technical proposals:
The invention discloses a kind of solid phase dispersion extraction filler that is used for solid phase dispersion microwave extraction method of sample residues matrix, comprise in the following solid phase components one or more at least, described solid phase components is: the silica type filler; Al
2O
3Filler; The Florisil filler; Graphitic carbon filler-no bonded carbon; Resin extender etc.Its preparation process is: according to the characteristic of sample substrate to be analyzed, select suitable solid phase components, mix by a certain percentage.
The invention discloses a kind of special-purpose extractant that is used for solid phase dispersion microwave extraction method of sample residues matrix, at least comprise one or more of following organic solvent or reagent, described organic solvent or reagent are: acetonitrile, acetone, methyl alcohol, ethyl acetate, carrene, n-hexane, acid, alkali, cushioning liquid.Its preparation process is that chemical property and polarity power according to target compound to be extracted mix by a certain percentage.
The present invention further discloses a kind of solid phase dispersion microwave extraction method of sample residues matrix, comprise the following order step:
1) will treat that the side sample mixes with corresponding solid phase dispersion extraction filler, grinding is uniformly dispersed, and forms matrix solid phase dispersed sample;
2) in matrix solid phase dispersed sample, add residue and extract solvent, place microwave generator to carry out the microwave radiation;
3) carry out shaking out, remove the extract that solid impurity must contain residue;
4) extract in the step 3) is purified, use for the Instrumental Analysis sample introduction;
Wherein said solid phase dispersion extraction filler is one or more in the following solid phase components: the silica type filler; Al
2O
3Filler; The Florisil filler; Graphitic carbon filler-no bonded carbon; Resin extender.
Preferably: described step 2) matrix solid phase dispersed sample mixture is put in and places microwave generator in the closed container.
In the described step 3) by the centrifugal solid impurity of removing.
The present invention preferably discloses the rapid extraction and the assay method of residue in the following sample:
One, the quickly extracting and determining of 24 kinds of sulfamido residues in animal tissue's sample:
1) takes by weighing animal sample, place in the mortar, add the C18 solid phase extraction filler, with the abundant mixed grinding of animal sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball/water mixed extract, jolting mixes, and puts into microwave generator then, the microwave radiation;
3) take out the test tube shaking out, centrifugation moves into supernatant in the conical flask;
4) rotary evaporation is extremely near does, and nitrogen stream dries up, and adds the phased soln that flows and also adds scavenging solution, and centrifugation after the jolting pipettes upper solution and crosses button-shaped filter membrane, gets sample feed flow phase chromatogram, tandem mass spectrum or liquid chromatogram measuring.
Two, the quickly extracting and determining of pesticide residue in the vegetable and fruit sample:
1) takes by weighing the vegetable and fruit sample, place in the mortar, add C18 and PSA and anhydrous sodium sulfate mixing solid phase extraction filler, fully mixed grinding;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball-acetone mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, the centrifugation heart moves into supernatant in the conical flask then;
4) rotary evaporation is done near, and nitrogen stream dries up, and adds the n-hexane dissolution residue, crosses button-shaped filter membrane in the sample introduction bottle, air feed phase chromatogram or mass spectroscopy.
Three, the quickly extracting and determining of biological blood sample toxicity residue
1) takes by weighing the biological blood sample, place in the mortar, add C18 and the special-purpose solid phase extraction filler that mixes of PSA, fully mixed grinding;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add carrene, benzene mixed extract, screw the test tube lid, jolting mixes, and puts into microwave generator then, the microwave radiation;
3) take out the test tube jolting, centrifugation then moves into supernatant in the round-bottomed flask;
4) commentaries on classics is evaporated near doing, and nitrogen stream dries up, and adds the methyl alcohol dissolved residue, crosses button-shaped filter membrane in the sample introduction bottle, air feed phase chromatogram, mass spectrum PTV sample introduction mensuration.
Four, the quickly extracting and determining of quinolones residue in animal tissue's sample:
1) takes by weighing animal tissue's sample, place in the mortar, add the C18 solid phase extraction filler, with the abundant mixed grinding of animal sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball, 1% formic acid mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, centrifugation then moves into supernatant in the conical flask;
4) rotary evaporation is done near, and nitrogen stream dries up, and adds the phased soln residue that flows, lysate is moved in the teat glass, add and mix scavenging solution shaking out, centrifugation, pipette upper solution and cross button-shaped filter membrane in the sample introduction bottle, feed flow phase chromatogram, tandem mass spectrum or liquid chromatogram measuring.
Five, the quickly extracting and determining of malachite green residue in the aquatic products sample:
1) takes by weighing tissue sample, place in the mortar, add the mixed fillers of neutral alumina and C18 solid phase extraction filler, with the abundant mixed grinding of tissue sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball-perchloric acid mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, centrifugation moves into supernatant in another test tube bottle;
4) add carrene, shaking out, centrifugation, draw organic layer to flask, rotary evaporation is done near, and nitrogen stream dries up, add the phased soln residue that flows, the vibration dissolving moves into lysate in the teat glass on the vortex oscillation device, adds to mix scavenging solution, shaking out, centrifugation pipettes upper solution and crosses button-shaped filter membrane in the sample introduction bottle, feed flow phase chromatogram, tandem mass spectrum or liquid chromatogram measuring.
Six, the quickly extracting and determining of red that azoles and metabolite thereof in the blood serum sample
1) gets human serum in mortar, add in the mixed fillers and tool plug test tube of neutral alumina and C18 solid phase extraction filler, be uniformly dispersed with the abundant mixed grinding of tissue sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add cyclohexane-isopropyl alcohol-10.8 buffer solution mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, the centrifugation heart moves to supernatant in another test tube;
4) nitrogen stream dries up, and residue dissolves with methyl alcohol, is provided with liquid chromatogram, tandem mass spectrum mensuration.
Seven, the quickly extracting and determining of multiple poisonous substance (comprising the sedative of sleeping peacefully, drugs) and metabolite thereof in biological material (blood, urine, the liver) sample
1) get human body blood, urine, liver sample in mortar, the mixed fillers that adds diatomite and C18, anhydrous sodium sulfate solid phase extraction filler is uniformly dispersed with the abundant mixed grinding of tissue sample in tool plug test tube;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add benzene, chloroform, ethyl acetate mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, the centrifugation heart moves to supernatant in another test tube;
4) nitrogen stream dries up, and residue dissolves with methyl alcohol, air feed phase chromatogram/mass spectroscopy.
Residue to be measured in the sample, because its physicochemical properties difference, in the solid-phase grinding adsorption process, matrix is different with the object residue compound per sample, it is an amount of to add special-purpose solid phase dispersion extraction filler, common dispersion extraction filler comprises with silica gel being the positive of matrix, anti-phase, ion-exchange, mixed fillers by a certain percentage is (as ODS (C18), ODS-N (C18), C8, amino filler, carboxyl filler and mixed fillers thereof etc.), or non-silica type product is (as the porous polymer adsorbent, active carbon, PSA etc.), careful ground and mixed is even, and main character and content according to the impurity component that contains in (1) matrix of object residue compound and solid phase dispersion extraction filler selection proportion relation in the matrix sample is as protein, fat, pigment etc.; (2) polarity of target compound to be measured, ionic strength, subtracting property of acid are selected and proportioning the solid phase filler.
Common solid phase dispersion extraction filler applicability
(1) silica type filler
LC-18:: be connected to octadecyl on the silica gel, the key end was handled, and reversed phase extraction is suitable for nonpolar compound to middle polarity.
ENVI
TM-18: be connected to octadecyl on the silica gel, the key end was handled, and phase coverage rate and carbon content are higher than
LC-18 has very strong resistance to acids and bases, and non-polarization and thing are had higher capacity, and reversed phase extraction is suitable for nonpolar compound to middle polarity.
LC-8: be connected to octane on the silica gel, the key end was handled, and reversed phase extraction is suitable for nonpolar to the middle polarity compound.
ENVI-8: be connected to octane on the silica gel, the key end was handled, and phase coverage rate and carbon content are higher than LC-8, had very strong resistance to acids and bases, and reversed phase extraction has higher capacity to non-polar compound.
LC-4: be connected to dimethylbutane on the silica gel, the key end was handled, and with respect to LC-8 or LC-18, hydrophobicity is weak, reversed phase extraction, and reversed phase extraction is suitable for the extraction of polypeptide and protein.
LC-ph: be connected to phenyl on the silica gel, to for LC-8 or LC-18, its reservation is short slightly, and reversed phase extraction is suitable for nonpolar to the middle polarity compound.
HISEP
TM: key and hydrophilic radical network on the hydrophobic surface, the albumen in the biological sample is excluded, and the little molecule of medicine is retained.
LC-CN: be connected to the third cyano group alkane on the silica gel, the key end was handled, and reversed phase extraction is suitable for the compound of middle polarity; The positive extraction is suitable for polar compound.
LC-Diol: be connected to glycol-based on the silica gel, the positive extraction is suitable for polar compound.
LC-NH2: be connected to Propylamino on the silica gel, the positive extraction is suitable for polar compound.Weak anionic exchange extraction, weak anionic and organic acid compound.
LC-SAX: be connected to the chlorination doped quaternary ammonium salt on the silica gel: reinforcing yin essence ion-exchange is suitable for anion, organic acid, nucleic acid, nucleotides etc.
LC-SCX: connect sulfonate sodium on the silica gel, the strong cation exchange extraction is suitable for cation, antibiotic, and medicine, amino acid, etc.
LC-WCX: connect sodium carbonate salt on the silica gel, weak cation exchange extraction is suitable for cation, ammonia, antibiotic, medicine, organic base, amino acid etc.
LC-Si: no bonded silica gel is suitable for the polar compound extraction, as ethanol, aldehyde, amine, medicine, dyestuff, agricultural chemicals, ketone, nitrogen-containing compound, organic acid, phenol, steroids etc.
(2) Al
2O
3Filler
LC-Alumina-A, acid pH 5, polar compound ion-exchange and sorption extraction are as vitamin.
LC-Alumina-B, alkaline pH 8.5, sorption extraction and cation exchange.
LC-Alumina-N, neutral pH 6.5, polar compound sorption extraction, regulate pH, sun and anion exchange are suitable for vitamin, antibiotic, glucosides, steroids etc.
(3) Florisil filler
LC-Florisil: be used for the sorption extraction of polar compound, as ethanol, aldehyde, amine, medicine, dyestuff, agricultural chemicals, ketone, nitrogen-containing compound, organic acid, phenol, steroids, organochlorine etc.ENVI-Florisil: be used for the sorption extraction of polar compound, as ethanol, aldehyde, amine, medicine, dyestuff, agricultural chemicals, ketone, nitrogen-containing compound, organic acid, phenol, steroids, organochlorine etc.
(4) graphitic carbon filler-no bonded carbon
ENVI-Carb: the sorption extraction that is used for polarity and non-polar compound.
ENVI-Carb C: the sorption extraction that is used for polarity and non-polar compound.
(5) resin extender
ENVI-ChromP: be used for the extraction of polar orientation compound, as extracting phenols from the aqueous solution.Also can be used for nonpolar sorption extraction to the middle polarity aromatic.
Grind uniform mixture and place polytetrafluoroethylene (PTFE) test tube or other containers usually, different according to the sample substrate type of extracting with the object residue compound, add the special-purpose solvent that extracts, as single organic solvent, mixed organic solvents, cushioning liquid, cushioning liquid-organic solution mixed liquor etc., different according to the sample substrate type of extracting with the object residue compound, add the special-purpose solvent that extracts.Matrix sample and object residue compound are determined according to polarity, the ionic strength polarity of target compound with the special-purpose apolegamy relation of extracting solvent, according to the similar principle that mixes, and distribution, the adsorption-desorption of target compound between solid phase and liquid phase is attached, by chemical force and microwave power target compound is extracted to greatest extent, the impurity chaff interference is attracted on the solid dispersed phase to greatest extent and is removed.
Extract solvent as using always:
To polarity, anti-phase a little less than being inverted to by force according to nonpolar, weak positive mainly contains n-hexane to the order of strong positive; Isooctane; Carbon tetrachloride; Chloroform; Carrene; Oxolane; Ether; Ethyl acetate; Acetone; Acetonitrile; Isopropyl alcohol; Methyl alcohol; Water; Acid etc.As required, select two or more, after optimizing test, mix by a certain percentage, be mixed with and special-purpose mixing of matrix solid phase dispersion microwave extraction extract solvent.
Among the present invention, adopted " microwave auxiliary extraction method " step in the prior art simultaneously, to take out through the container of microwave auxiliary extraction, jolting is extracted, character according to object residue compounds and solvent, jolting extraction time can be done suitable adjustment, places centrifuge, and is centrifugal limpid to extract with suitable rotating speed, shift out extract, as required or do further and purify, in Instrumental Analysis the present invention, adopt common purification method in the chemical analysis, being about to extract carries out dissolving extraction again behind the concentrate drying, select organic solvent commonly used, be used for the preceding purification degreasing of sample introduction, meet the sample that analytical instrument requires to obtain purity.
Among the present invention, residues of pesticides, residue of veterinary drug, pollutant, biotoxin and human body medicine in existing animal sources product, plant source product or the other biological sample, the analytical method of poisonous substance are made up and improve, the biological sample of complexity can be remained in intracellular target compound disperses and microwave abstracting by matrix, the release of big limit and extracting, can the target compound of multiple different chemical character be extracted simultaneously, it is effective to carry thing, the extraction efficiency height, easy to be quick, use wide.Before adopting the rigorous analysis detection, to have in to animal tissue in 24 kinds of sulfamidos, 10 kinds of quinolones, 11 kinds of aminoglycosides, 3 kinds of chloromycetins, 3 kinds of polyethers, the plant sample that aflatoxin carries out sample pre-treatments by described method in (fruit, vegetables) 250 kinds of residues of pesticides, the plant sample (peanut) now, extraction effect obviously is better than original method.
The specific embodiment
The specific embodiment one:
24 kinds of quickly extracting and determinings that sulfamido is residual in the animal tissue
Take by weighing animal sample 1g, place in the mortar, add 3g C18 solid phase extraction filler, with the abundant mixed grinding of animal sample, pack into then in the 50mL polytetrafluoroethylene (PTFE) test tube, add 30mL second eyeball, screw the test tube lid, jolting mixed 2 minutes, put into microwave generator then, select suitable energy, microwave radiation 30 seconds was taken out the test tube jolting 5 minutes, centrifugal 5 minutes with 3000 rev/mins then, supernatant is moved in the conical flask, and rotation is evaporated near doing under 40 ℃ of temperature, and nitrogen stream dries up, add the mobile phased soln residue of 1mL, the vibration dissolving is 1 minute on the vortex oscillation device, and lysate is moved in the 5mL teat glass, adds 1mL mixing scavenging solution, jolting 2 minutes, with 3000 rev/mins centrifugal 3 minutes, pipette upper solution and cross button-shaped filter membrane in 2mL sample introduction bottle, feed flow phase chromatogram/tandem mass spectrum or liquid chromatogram measuring.
The specific embodiment two:
The rapid extraction side of 250 kinds of residues of pesticides of vegetable and fruit kind is measured
Take by weighing sample 2g, place in the mortar, add C18 and the special-purpose solid phase extraction filler 5g that mixes of PSA, abundant mixed grinding, pack into then in the 50mL polytetrafluoroethylene (PTFE) test tube, add 30mL second eyeball-acetone mixed extract, screw the test tube lid, jolting mixed 2 minutes, put into microwave generator then, select suitable energy, microwave radiation 30 seconds was taken out the test tube jolting 5 minutes, centrifugal 5 minutes with 3000 rev/mins then, supernatant is moved in the conical flask, and rotation is evaporated near doing under 40 ℃ of temperature, and nitrogen stream dries up, add 1mL n-hexane dissolution residue, the vibration dissolving is 1 minute on the vortex oscillation device, crosses button-shaped filter membrane in 2mL sample introduction bottle, air feed phase chromatogram/mass spectroscopy.
The specific embodiment three:
(blood, urine, liver) poisonous substance (Tetramine, heroin, Ba Bituo, chlorpromazine etc.) quickly extracting and determining in the biological sample
Take by weighing blood sample 1g, place in the mortar, add C18 and the special-purpose solid phase extraction filler 3g that mixes of PSA (1: 3), abundant mixed grinding, pack into then in the 50mL polytetrafluoroethylene (PTFE) test tube, add 30mL carrene-benzene mixed extract (7: 3), screw the test tube lid, jolting mixed 2 minutes, put into microwave generator then, select suitable energy, microwave radiation 30 seconds was taken out the test tube jolting 5 minutes, centrifugal 5 minutes with 3000 rev/mins then, supernatant is moved in the round-bottomed flask, and rotation is evaporated near doing under 40 ℃ of temperature, and nitrogen stream dries up, add 1mL methyl alcohol dissolved residue, the vibration dissolving is 1 minute on the vortex oscillation device, crosses button-shaped filter membrane in 2mL sample introduction bottle, measures for gas chromatography/mass spectrometry PTV sample introduction.
The specific embodiment four:
The quickly extracting and determining of 10 kinds of quinolones residual quantities is planted by animal tissue
Take by weighing animal sample 1g, place in the mortar, add 3g C18 solid phase extraction filler, with the abundant mixed grinding of animal sample, pack into then in the 50mL polytetrafluoroethylene (PTFE) test tube, add 30mL second eyeball-1% formic acid (8: 2) mixed extract, screw the test tube lid, jolting mixed 2 minutes, put into microwave generator then, select suitable energy, microwave radiation 30 seconds was taken out the test tube jolting 5 minutes, centrifugal 5 minutes with 3000 rev/mins then, supernatant is moved in the conical flask, and rotation is evaporated near doing under 40 ℃ of temperature, and nitrogen stream dries up, add the mobile phased soln residue of 1mL, the vibration dissolving is 1 minute on the vortex oscillation device, and lysate is moved in the 5mL teat glass, adds 1mL mixing scavenging solution, jolting 2 minutes, with 3000 rev/mins centrifugal 3 minutes, pipette upper solution and cross button-shaped filter membrane in 2mL sample introduction bottle, feed flow phase chromatogram/tandem mass spectrum or liquid chromatogram measuring.
The specific embodiment five:
The quickly extracting and determining of malachite green residual quantity in the aquatic products
Take by weighing tissue sample 3g, place in the mortar, the mixed fillers (5: 5) that adds 10g neutral alumina and C18 solid phase extraction filler, with the abundant mixed grinding of tissue sample, pack into then in the 50mL polytetrafluoroethylene (PTFE) test tube, add 30mL second eyeball-perchloric acid (95: 5) mixed extract, screw the test tube lid, jolting mixed 2 minutes, put into microwave generator then, select suitable energy, microwave radiation 30 seconds, took out the test tube jolting 5 minutes, centrifugal 5 minutes with 3000 rev/mins then, supernatant is moved in another test tube bottle, add the 15mL carrene, jolting 5 minutes, 3000 rev/mins centrifugal 5 minutes, draw organic layer to flask, rotation is evaporated near doing under 40 ℃ of temperature, and nitrogen stream dries up, add the mobile phased soln residue of 1mL, the vibration dissolving is 1 minute on the vortex oscillation device, and lysate is moved in the 5mL teat glass, adds 1mL mixing scavenging solution, jolting 2 minutes, with 3000 rev/mins centrifugal 3 minutes, pipette upper solution and cross button-shaped filter membrane in 2mL sample introduction bottle, feed flow phase chromatogram/tandem mass spectrum or liquid chromatogram measuring.
The specific embodiment six:
The quickly extracting and determining of red that azoles and metabolite thereof in the serum
Get human serum 1mL to placing in the mortar, add in mixed fillers (3: 2) the 10mL tool plug test tube of 5g neutral alumina and C18 solid phase extraction filler, with the abundant mixed grinding of tissue sample, pack into then in the 10mL polytetrafluoroethylene (PTFE) test tube, add 6mL cyclohexane-isopropyl alcohol-10.8 buffer solution (97: 2: 1) mixed extract, screw the test tube lid, jolting mixed 2 minutes, put into microwave generator then, select suitable energy, microwave radiation 30 seconds was taken out the test tube jolting 5 minutes, centrifugal 5 minutes with 3000 rev/mins then, supernatant is moved in another test tube, and nitrogen stream dries up, and residue dissolves with 100 μ L methyl alcohol, get 50 μ L sample introductions, measure with liquid chromatogram/tandem mass spectrum.
The quickly extracting and determining and the said method of multiple poisonous substance (comprising the sedative of sleeping peacefully, drugs) and metabolite thereof are similar in biological material (blood, urine, the liver) sample.
Before adopting the rigorous analysis detection, to have in to animal tissue in 24 kinds of sulfamidos, 10 kinds of quinolones, 11 kinds of aminoglycosides, 3 kinds of chloromycetins, 3 kinds of polyethers, the plant sample that aflatoxin carries out sample pre-treatments by the described method of the above-mentioned specific embodiment in (fruit, vegetables) 250 kinds of residues of pesticides, the plant sample (peanut) now, extraction effect obviously is better than original method.
Claims (12)
1, a kind of solid phase dispersion extraction filler that is used for solid phase dispersion microwave extraction method of sample residues matrix comprises in the following solid phase components one or more at least, and described solid phase components is: the silica type filler; Al
2O
3Filler; The Florisil filler; Graphitic carbon filler-no bonded carbon; Resin extender.
2, a kind of extractant that is used for solid phase dispersion microwave extraction method of sample residues matrix, at least comprise one or more of following organic solvent or reagent, described organic solvent or reagent are: acetonitrile, acetone, methyl alcohol, ethyl acetate, carrene, n-hexane, acid, alkali, cushioning liquid.
3, a kind of solid phase dispersion microwave extraction method of sample residues matrix comprises the following order step:
1) will treat that the side sample mixes with corresponding solid phase dispersion extraction filler, grinding is uniformly dispersed, and forms matrix solid phase dispersed sample;
2) in matrix solid phase dispersed sample, add residue and extract solvent, place microwave generator to carry out the microwave radiation;
3) carry out shaking out, remove the extract that solid impurity must contain residue;
4) extract in the step 3) is purified, use for the Instrumental Analysis sample introduction;
Wherein said solid phase dispersion extraction filler is one or more in the following solid phase components: the silica type filler; Al
2O
3Filler; The Florisil filler; Graphitic carbon filler-no bonded carbon; Resin extender.
4, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
Described step 2) in matrix solid phase dispersed sample mixture is put in and places microwave generator in the closed container.
5, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
In the described step 3) by the centrifugal solid impurity of removing.
6, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of 24 kinds of sulfamido residues in animal tissue's sample:
1) takes by weighing animal sample, place in the mortar, add the C18 solid phase extraction filler, with the abundant mixed grinding of animal sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball/water mixed extract, jolting mixes, and puts into microwave generator then, the microwave radiation;
3) take out the test tube shaking out, centrifugation moves into supernatant in the conical flask;
4) rotary evaporation is extremely near does, and nitrogen stream dries up, and adds the phased soln that flows and also adds scavenging solution, and centrifugation after the jolting pipettes upper solution and crosses button-shaped filter membrane, gets sample feed flow phase chromatogram, tandem mass spectrum or liquid chromatogram measuring.
7, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of pesticide residue in the vegetable and fruit sample:
1) takes by weighing the vegetable and fruit sample, place in the mortar, add C18 and PSA mixing solid phase extraction filler, fully mixed grinding;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball-acetone mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, the centrifugation heart moves into supernatant in the conical flask then;
4) rotary evaporation is done near, and nitrogen stream dries up, and adds the n-hexane dissolution residue, crosses button-shaped filter membrane in the sample introduction bottle, air feed phase chromatogram or mass spectroscopy.
8, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of biological blood sample toxicity residue:
1) takes by weighing the biological blood sample, place in the mortar, add C18 and PSA and the special-purpose solid phase extraction filler that mixes of anhydrous sodium sulfate, fully mixed grinding;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add carrene, benzene mixed extract, screw the test tube lid, jolting mixes, and puts into microwave generator then, the microwave radiation;
3) take out the test tube jolting, centrifugation then moves into supernatant in the round-bottomed flask;
4) commentaries on classics is evaporated near doing, and nitrogen stream dries up, and adds the methyl alcohol dissolved residue, crosses button-shaped filter membrane in the sample introduction bottle, air feed phase chromatogram, mass spectrum PTV sample introduction mensuration.
9, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of quinolones residue in animal tissue's sample:
1) takes by weighing animal tissue's sample, place in the mortar, add the C18 solid phase extraction filler, with the abundant mixed grinding of animal sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball, 1% formic acid mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, centrifugation then moves into supernatant in the conical flask;
4) rotary evaporation is done near, and nitrogen stream dries up, and adds the phased soln residue that flows, lysate is moved in the teat glass, add and mix scavenging solution shaking out, centrifugation, pipette upper solution and cross button-shaped filter membrane in the sample introduction bottle, feed flow phase chromatogram, tandem mass spectrum or liquid chromatogram measuring.
10, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of malachite green residue in the aquatic products sample:
1) takes by weighing tissue sample, place in the mortar, add the mixed fillers of neutral alumina and C18 solid phase extraction filler, with the abundant mixed grinding of tissue sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add second eyeball-perchloric acid mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, centrifugation moves into supernatant in another test tube bottle;
4) add carrene, shaking out, centrifugation, draw organic layer to flask, rotary evaporation is done near, and nitrogen stream dries up, add the phased soln residue that flows, the vibration dissolving moves into lysate in the teat glass on the vortex oscillation device, adds to mix scavenging solution, shaking out, centrifugation pipettes upper solution and crosses button-shaped filter membrane in the sample introduction bottle, feed flow phase chromatogram, tandem mass spectrum or liquid chromatogram measuring.
11, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of red that azoles and metabolite thereof in the blood serum sample:
1) gets human serum in mortar, add in the mixed fillers and tool plug test tube of neutral alumina and C18 solid phase extraction filler, be uniformly dispersed with the abundant mixed grinding of tissue sample;
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add cyclohexane-isopropyl alcohol-10.8 buffer solution mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, the centrifugation heart moves to supernatant in another test tube;
4) nitrogen stream dries up, and residue dissolves with methyl alcohol, is provided with liquid chromatogram, tandem mass spectrum mensuration.
12, the residual matrix solid phase dispersion microwave extraction method of sample according to claim 3 is characterized in that,
The quickly extracting and determining of multiple poisonous substance and metabolite thereof in the biological material sample:
1) get human body blood, urine, liver sample in mortar, the mixed fillers that adds diatomite and C18, anhydrous sodium sulfate solid phase extraction filler is uniformly dispersed with the abundant mixed grinding of tissue sample in tool plug test tube:
2) pack into then in the polytetrafluoroethylene (PTFE) test tube, add benzene, chloroform, ethyl acetate mixed extract, screw the test tube lid, jolting mixes, and puts into the radiation of microwave generator microwave then;
3) take out the test tube jolting, the centrifugation heart moves to supernatant in another test tube;
4) nitrogen stream dries up, and residue dissolves with methyl alcohol, air feed phase chromatogram/mass spectroscopy.
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