CN103111091A - Tea solid phase extraction column and sample pretreatment method for testing pesticide residues in tea leaves - Google Patents
Tea solid phase extraction column and sample pretreatment method for testing pesticide residues in tea leaves Download PDFInfo
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Abstract
The invention relates to a tea solid phase extraction column and a sample pretreatment method for testing pesticide residues in tea leaves. The tea solid phase extraction column comprises a column pipe and filler in the column pipe, wherein, the filler comprises the following components: 2 to 10 parts of carbon material, 2 to 10 parts of amino-group functionalized adsorbent material and 1 part of polar functional group modified high-polymer materials; the carbon filler is filled in the bottom layer of the column pipe; the amino-group functionalized adsorbent material and the polar functional group modified polymer materials are mixedly filled in the upper layer of the column pipe and a polypropylene sieve plate is provided between the two layers for separation. The invention also discloses a sample pretreatment method for testing pesticide residues in tea leaves. By utilizing the tea solid phase extraction column in sample pretreatment, the pesticide and the metabolite in hundreds of kinds of tea such as black tea, green tea, scented tea, puerh tea can be analyzed and detected, and 653 kinds of pesticide residues can be extracted and purified through sample treatment for once. Therefore, the tea solid phase extraction column and the sample pretreatment method for testing pesticide residues in tea leaves is speedy, economical and is high in universality.
Description
Technical field
The present invention relates to food hygiene, agricultural product security detection field, particularly the sample-pretreating method of a kind of tealeaves solid-phase extraction column and detection Pesticide Residues in Tea material.
Background technology
Tealeaves is not only a kind of main consumable beverage that China people like, and is traditional large agricultural exports of China.Relevant Pesticide Residues in Tea problem often is exposed by the media in recent years.For the needs of safeguarding domestic economy interests and protection health of people, countries in the world improve constantly maximum maximum permission quantity (MRL) requirement of Pesticides in Tea medicine.The agricultural chemicals that Japan implemented in 2006, veterinary drug reach relevant chemical substance " Positive List System ", wherein relate to 144 kinds that have of tealeaves, and the residues of pesticides beyond 144 kinds are adopted " uniform limit " (being that a reference value is set as 0.01ppm).Afterwards, the states such as European Union, the U.S., Australia have also implemented new Pesticide Residue standard, cause the export volume of China large province of a plurality of tea exports to descend rapidly, form the Trade technique barrier.
In order to tackle the Pesticide Residues in Tea that the improves constantly requirement of limiting the quantity of, countries in the world are all in the research of Efforts To Develop Pesticide Residues in Tea amount detection technique and relevant pretreatment technology.Multiple representational carbamate insecticides has appearred in the world, as the carbamate insecticides (can detect 200 kinds of agricultural chemicals) of the method (can detect 325 kinds of agricultural chemicals) of the how residual method (can detect 360 Multiple Pesticides) of U.S. FDA, German DFG, the Dutch Ministry of Public Health, Canadian many method for detecting residue (can detect 251 kinds of agricultural chemicals) etc.
Present existing SPE pre-treating method often needs 1-2 hours at least, with 2-3 kind solid-phase extraction column product, therefore exists and uses duration, the problem that cost is high.And because the SPE product that usually can buy layering is all to place carbon class material on the upper strata, and carbon class material is placed easily by water and the pollution of some matrix components in the upper strata, and the adsorpting pigment ability of contaminated rear carbon class material can decline to a great extent.
Patent 201010197943.X adopts colorimetric method for determining dithiocarbamate agricultural chemicals, for the dark colour crop, adds graphite powder and sodium chloride homogeneous, with adsorpting pigment; To have adopted absorption impurity to discharge the mode of Interference Detection equally on principle; Yet because colorimetric method is only more responsive to the pigment interference ratio, method has only added graphite powder removing pigment, and is not suitable for other detection means.
Patent 03153725.1 residual pesticide purifying column and purification method thereof have been protected a kind of residual pesticide purifying column, utilize the suction-operated principle of adsorbent filler to remove impurity, adopted active carbon, diatomite, the filter aid mixed packing is used for the decontaminating column that the food farming residual analysis is used; Wherein diatomite and filter aid have all played the effect of filtering and support absorbent charcoal material, main or the impurity such as protein and pigment are removed, be suitable for the foodstuff sample, and it is abundant to be not suitable for the marennin such as tealeaves, be rich in natural tea folic acid, the sample of theophylline.
Patent 201010108788.X, carry out matrix effect compensation with the form of adding the matrix analogies in standard items, its purifying step has added C18, to remove a part of fatty character interference base matter, avoid the serious matrix interference to gas chromatographic detection, but its principle based on matrix effect compensation is more suitable for the mensuration to organophosphorus multi-pesticide residue in tealeaves, is not suitable for for the residual mensuration of other kind agricultures.
At last, in above-mentioned existing patented method, any one all can not be applicable to surpass extraction and the purification of 600 kinds of residues of pesticides.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of tealeaves solid-phase extraction column.Tealeaves solid-phase extraction column of the present invention is applied in sample pretreatment, can detects hundreds of Pesticides in Tea medicines and the metabolites such as black tea, green tea, jasmine tea, Pu'er tea, oolong tea, have fast, the characteristics of economy, highly versatile.
Another technical problem to be solved by this invention is to provide a kind of sample-pretreating method for detection of the Pesticide Residues in Tea material.
For solving above-mentioned first technical problem, the technical solution used in the present invention is to provide a kind of tealeaves solid-phase extraction column, this tealeaves solid-phase extraction column comprises the filler in column jecket and column jecket, described filler is comprised of following component, sorbing material 2-10 part of material with carbon element 2-10 part, aminofunctional, 1 part of the high polymer material of modifying with polar functional group, described material with carbon element fills in the column jecket bottom, the high polymer material mixed packing that the sorbing material of described aminofunctional and polar functional group are modified uses the polypropylene sieve plate as separation therebetween on the column jecket upper strata.
Preferably, described material with carbon element is one or both the mixture in graphitized carbon, active carbon, and described material with carbon element particle size range is 80 orders～400 orders, and specific area is 100～300m
2/ g.
Preferably, the sorbing material of described aminofunctional is one or more the mixture in amination silica gel NH2, polyamino SiClx glue PSA, amination polyethylene divinylbenzene, the particle size range of the sorbing material of described aminofunctional is 30 microns～80 microns, specific area is 300～800 meters squared per gram, and average pore size is 40～150 dusts.
Preferably, the particle size range of the high polymer material that described polar functional group is modified is 30 microns～80 microns, and specific area is 300～800 meters squared per gram, and average pore size is 40～150 dusts, degree of cross linking 15-80%.
Preferably, described material with carbon element is graphitized carbon, and its micropore ratio is not higher than 2%; Degree of graphitization is not less than 50%, and the sorbing material of described aminofunctional is polyamino SiClx glue PSA, and the high polymer material that described polar functional group is modified is amidatioon polyethylene divinylbenzene.
Preferably, described column jecket is high-density polyethylene material or glass material.
For solving above-mentioned second technical problem, a kind of sample-pretreating method that detects the Pesticide Residues in Tea material is characterized in that: comprise the steps:
1) Tea Samples smashed or pulverized;
2) to step 1) add in gained broken tea sample and extract solvent and buffer salt extracts, get supernatant after centrifugal; Repeat leaching process, repeat to need not to add again buffer salt in leaching process, merge supernatant concentration, get concentrate, treat loading;
3) with step 2) in the concentrate that obtains add in tealeaves solid-phase extraction column claimed in claim 6, receive efflux,
4) add eluting solvent, the residues of pesticides that remain on the tealeaves solid-phase extraction column eluted, get eluent, merge eluent and step 3) efflux that obtains;
5) eluent that merges and efflux are carried out Instrumental Analysis after concentrated, accurately qualitative, quantitative agricultural chemicals and metabolite thereof.
Preferably, broken tea sample step 2): extract solvent: buffer salt=1g:3-8mL:0.2-1g.
Preferably, the extraction solvent step 2) is one or more mixtures that mix with arbitrary proportion in methyl alcohol, acetonitrile, n-hexane, acetone, carrene, ethyl acetate, benzinum, toluene, oxolane or isopropyl alcohol.
Preferably, the buffer salt step 2) is one or more the mixture in sodium chloride, sodium acetate, natrium citricum.
Preferably, the eluting solvent described in step 4) is one or more the mixture in methyl alcohol, acetonitrile, acetone, n-hexane, carrene or toluene.
Preferably, described extraction solvent is acetonitrile.
Effect of the present invention is the tealeaves solid-phase extraction column of research and development, has the single treatment sample, and the outstanding feature of 653 kinds of residues of pesticides in extraction and cleaning tealeaves has surpassed the developed country such as American-European-Japanese to the level of Pesticides in Tea medicine multi-residue analysis.Simultaneously the tealeaves solid-phase extraction column in the present invention, by having optimized the performance of tens kinds of sorbing materials, optimized three kinds of materials, again by optimizing consumption and the proportioning of three kinds of materials, reached purification requirement to several large class tealeaves in conjunction with application process.The selection of sorbing material should be considered can not have strong absorption affinity to the agricultural chemicals determinand, thereby affected its elute effect; Also to consider the clean-up effect of sorbing material, need farthest to remove the sample substrate chaff interference.For our preferred graphitized carbon of material with carbon element, it is carried out surface area, and the control of microporosity is to guarantee the absorption to matrix interference things such as pigments, also will guarantee does not simultaneously have excessive absorption to agricultural chemicals, effectively avoid some many lopps agricultural chemicals carbon material surface adsorbed by force can't wash-out problem.The high polymer material that adopts polar functional group to modify, for nonpolar chaff interference, Tea Polyphenols, theophylline, good Adsorption effect is arranged all, bonded silica gel or metal oxide have been avoided simultaneously, the absorption for organophosphor isopolarity agricultural chemicals as magnesium silicate, aluminium oxide etc. causes reduces the absorption to object when strengthening the absorption of matrix interference thing.
The tealeaves solid-phase extraction column that relates in the present invention mixes use by the material to different physicochemical properties, reached the effect that to remove simultaneously the interference matrix in multiple Tea Samples pesticide residue quality inspection survey process, SPE pre-treating method commonly used has been saved the experimental implementation time of half at least, and only use a solid phase extraction column, reduced economy and manually-operated cost.
The present invention is at the material of tealeaves SPE dedicated columns, filling, all innovations to some extent of selection aspect of detection method and detecting instrument, abundant for marennins such as tealeaves, be rich in natural tea folic acid, the sample of theophylline has not only used the mode of mixed packing, also adopted the layering filling, realized the mode that two kinds of pillars are connected in series in a supporting tube.And the material that adopts in decontaminating column not only contains carbon class material, also added the material of silica gel material (being the sorbing material of aminofunctional) with the basic functionality of ion exchange, novelties such as high polymer material that polar functional group is modified; Utilized different absorption principle absorption impurity.Application process in the present invention combines the characteristics of tealeaves solid-phase extraction column, disposable purification by novelty, the grouping detection method, realized in tealeaves class complex matrices sample detecting in the residual and metabolin of Multiple Pesticides, be a present unique detection method of 653 kinds of agricultural chemicals and chemical pollutant in extraction and cleaning tealeaves simultaneously, filled up domestic blank.
At present in the carbamate insecticides of fruit, greengrocery agricultural product, the main purification means that adopt have SPE column purification, liquid liquid to distribute purification and gel permeation chromatography (GPC) to purify, it is traditional purification method that liquid liquid distributes purification, it requires tested agricultural chemicals and related chemicals to have similar dissolution characteristics, so it adapted to for how residual being difficult to more than 300 kinds.Gel permeation chromatography purifies and is more suitable for rich grease-contained sample.The SPE column purification is the purification method that generally adopts in modern retention analysis, therefore, on the basis of GB/T19648-2006 " the mensuration gas chromatography-mass spectrography of 500 kinds of agricultural chemicals and related chemicals residual quantity in fruits and vegetables " research work, the inventor has consulted a large amount of many residue detection of tealeaves documents, has selected the SPE post of 18 kinds of different fillers to carry out the contrast experiment for depigmentation, removal of impurities and precision, degree of accuracy effect.
At first, selected magnesium silicate (FS), graphitized carbon (PC), neutral alumina (Al-N), graphitized carbon/amination silica gel (PC/NH2), graphitized carbon/magnesium silicate (PC/FS), six kinds of solid-phase extraction columns of graphitized carbon/neutral alumina/magnesium silicate (PC/Al-N/FS) to carry out the depigmentation contrast experiment, from the experimental results, graphitized carbon/amination silica gel (PC/NH2) solid-phase extraction column depigmentation best results.
according to the previous step experimental result, choice for use solid-phase extraction column, graphitized carbon and amination silica gel are carried out different filling mixture ratio researchs, be graphitized carbon/amination silica gel (1g), graphitized carbon/amination silica gel (1.6g), graphitized carbon/amination silica gel (2g) and different filling order, be that graphitized carbon is in lower floor, amination silica gel is on the upper strata, amination silica gel/graphitized carbon (1g), amination silica gel/graphitized carbon (2g) and PSA(have the adsorbent of two amino)/graphitized carbon (1g) and PSA(have the adsorbent of two amino)/solid-phase extraction column of graphitized carbon (2g) carried out the contrast experiment, because the tealeaves pigment is very heavy, from the experimental results, filler is that the solid-phase extraction column depigmentation effect of 2g and rate of recovery result are better than that other are several, and graphitized carbon is in lower floor, amination silica gel is better in the pillar depigmentation effect of upper strata 2g.The rate of recovery the results are shown in Table 1.
the tealeaves matrix components is very complicated, pigment content is very high, also contain a large amount of theophyllines and caffeine, in order to obtain desirable purification and impurity-eliminating effect, experimental result according to the front, our development and Design the special solid-phase extraction column that is fit to many residue detection in tealeaves, decontaminating column amination silica gel/propane sulfonic acid (PRS) that we mix three kinds of fillers/graphitized carbon (1g), amination silica gel/propane sulfonic acid (PRS)/graphitized carbon (2g), amination silica gel/octadecyl silane/graphitized carbon (1g), amination silica gel/octadecyl silane/graphitized carbon (2g) and tealeaves solid-phase extraction column have carried out the contrast experiment.The tealeaves solid phase extraction column stuffing is by A, B, and three kinds of compositions of C form according to certain proportional layered filling.Wherein A is graphitized carbon, and its effect is to remove the pigment in tealeaves and can not adsorb the target agricultural chemicals simultaneously; B is polyamines base SiClx glue, mainly removes the impurity such as theophylline in tealeaves and caffeine; C is a kind of amidatioon polyethylene divinylbenzene material, and its Main Function is the impurity of removing outside pigment and theophylline thereof.The SPE post that these three kinds of fillers mix can play better clean-up effect, and its depigmentation, removal of impurities and rate of recovery result are best, and the rate of recovery the results are shown in Table 2.
Experimental results show that, 653 kinds of agricultural chemicals and the residual tealeaves SPE column purification through optimal design of related chemicals in green tea, black tea, oolong tea and Pu'er tea, can obtain clean-up effect preferably, and can obtain the desirable rate of recovery, method is simple and efficient, and the agricultural chemicals of mensuration and related chemicals kind number reach 653 kinds.
Table one or two kind of filler mixing SPE post rate of recovery experimental result
Three kinds of filler mixing SPE post rate of recovery experimental results of table two
This tealeaves solid-phase extraction column is applied in sample pretreatment, can be used for black tea, green tea, jasmine tea,
Pu'er tea, etc. the analyzing and testing of hundreds of Pesticides in Tea medicines and metabolite, have the single treatment sample,
In extraction and cleaning tealeaves 653 kinds of residues of pesticides and fast, the characteristics of economy, highly versatile.
Description of drawings
Fig. 1 is the schematic diagram of tealeaves solid-phase extraction column
The specific embodiment
The present invention is described further below in conjunction with drawings and Examples.
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 8:8:1, wherein graphitized carbon fills in the column jecket bottom.
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 6:4:1, wherein graphitized carbon fills in the column jecket bottom.
use volume capacity to be the glass column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 5:4:1, wherein graphitized carbon fills in the column jecket bottom.
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 4:4:1, wherein graphitized carbon fills in the column jecket bottom.
use volume capacity to be the glass column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 2:2:1, wherein graphitized carbon fills in the column jecket bottom.
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 2:2:1, wherein graphitized carbon fills in the column jecket bottom.Wherein the graphitized carbon material particle size range is 80 orders, and specific area is 100m
2/ g, its micropore ratio 1.5%, degree of graphitization 50%; The particle size range of silicon amide glue material is 30 microns, and specific area is 800 meters squared per gram, and average pore size is 40 dusts; Amidatioon polyethylene divinylbenzene material particle size scope is 30 microns, and specific area is 800 meters squared per gram, and average pore size is 40 dusts, the degree of cross linking 15%.
Embodiment 7
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 6:4:1, wherein graphitized carbon fills in the column jecket bottom.Wherein the graphitized carbon material particle size range is 400 orders, and specific area is 300m
2/ g, its micropore ratio 2%, degree of graphitization 60%; The particle size range of silicon amide glue material is 80 microns, and specific area is 300 meters squared per gram, and average pore size is 150 dusts; Amidatioon polyethylene divinylbenzene material particle size scope is 80 microns, and specific area is 300 meters squared per gram, and average pore size is 150 dusts, the degree of cross linking 50%.
Embodiment 8
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 2:2:1, wherein graphitized carbon fills in the column jecket bottom.Wherein the graphitized carbon material particle size range is 200 orders, and specific area is 200m
2/ g, its micropore ratio 1%, degree of graphitization 80%; The particle size range of silicon amide glue material is 60 microns, and specific area is 500 meters squared per gram, and average pore size is 80 dusts; Amidatioon polyethylene divinylbenzene material particle size scope is 60 microns, and specific area is 500 meters squared per gram, and average pore size is 80 dusts, the degree of cross linking 80%
Embodiment 9
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 8:8:1, wherein graphitized carbon fills in the column jecket bottom.Wherein the graphitized carbon material particle size range is 300 orders, and specific area is 150m
2/ g, its micropore ratio 1%, degree of graphitization 50%; The particle size range of silicon amide glue material is 70 microns, and specific area is 600 meters squared per gram, and average pore size is 120 dusts; Amidatioon polyethylene divinylbenzene material particle size scope is 70 microns, and specific area is 700 meters squared per gram, and average pore size is 120 dusts, the degree of cross linking 60%
Embodiment 10
use volume capacity to be the high density polyethylene (HDPE) column jecket of 6mL or 12mL, one end of column jecket 1 is the inlet 4 of sample or solvent, the other end is the flow export 5 of sample or solvent, wherein fill graphitized carbon, amination silica gel NH2, three kinds of materials of amidatioon polyethylene divinylbenzene, wherein amination silica gel NH2 mixes as one deck 2 with amidatioon polyethylene divinylbenzene, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 conduct separations in 20um aperture therebetween, the two ends of filler are sealed by sieve plate, be filled to three kinds of two-layer material mixing decontaminating columns, graphitized carbon in this tealeaves solid-phase extraction column, the mass ratio of amination silica gel NH2 and three kinds of materials of amidatioon polyethylene divinylbenzene is 6:4:1, wherein graphitized carbon fills in the column jecket bottom.Wherein the graphitized carbon material particle size range is 100 orders, and specific area is 150m
2/ g, its micropore ratio 2%, degree of graphitization 50%; The particle size range of silicon amide glue material is 40 microns, and specific area is 450 meters squared per gram, and average pore size is 80 dusts; Amidatioon polyethylene divinylbenzene material particle size scope is 40 microns, and specific area is 450 meters squared per gram, and average pore size is 80 dusts, the degree of cross linking 30%.
Embodiment 11
Use the tealeaves solid-phase extraction column in embodiment 2 to detect several agricultural chemicals and chemical contamination in tealeaves: concrete steps are as follows:
1) Tea Samples is pulverized through pulverizer, crossed 20 mesh sieves, mixing, sealing as sample, is indicated mark;
2) take 5g step 1) gained Tea Samples (being accurate to 0.01g), in the 80mL centrifuge tube, add the 15mL acetonitrile, the 15000r/min homogeneous extracts 1min, and the centrifugal 5min of 4200r/min gets supernatant in 200mL heart bottle.Residue repeats to extract once with the 15mL acetonitrile, and is centrifugal, merges secondary raffinate, and 40 ℃ of water-bath rotary evaporations are to the 1mL left and right, and are to be clean;
3) the tealeaves solid-phase extraction column to embodiment 2 adds the approximately high anhydrous sodium sulfate of 2cm, with 10mL acetonitrile-methylbenzene prewashing tealeaves solid-phase extraction column, discards efflux.Under connect the heart bottle, put on fixed mount.With step 2) in the concentrate that obtains be transferred in the tealeaves solid-phase extraction column, with 2mL acetonitrile-methylbenzene washing sample liquid bottle, triplicate, and cleaning solution is moved in post, add the 50mL liquid reservoir on post, with 25mL acetonitrile-methylbenzene washing pillar, collect above-mentioned all effluxes in the heart bottle again, in 40 ℃ of water-baths, rotation is concentrated into approximately 0.5mL.Add the 5mL n-hexane to carry out exchange of solvent, repeat twice, make at last the long-pending 1mL that is about of sample liquid, be used for gaschromatographic mass spectrometry and measure.
Embodiment 12
In the tealeaves solid-phase extraction column detection tealeaves of use embodiment 1, several agricultural chemicals and chemical pollutant concrete steps are as follows:
1) Tea Samples is pulverized through pulverizer, crossed 20 mesh sieves, mixing, sealing as sample, is indicated mark;
2) take 5g step 1) gained Tea Samples (being accurate to 0.01g), in the 80mL centrifuge tube, add the 15mL acetonitrile, the 15000r/min homogeneous extracts 1min, and the centrifugal 5min of 4200r/min gets supernatant in 200mL heart bottle.Residue repeats to extract once with the 15mL acetonitrile, and is centrifugal, merges secondary raffinate, and 40 ℃ of water-bath rotary evaporations are to the 1mL left and right, and are to be clean;
3) the tealeaves solid-phase extraction column in the embodiment 1 adds the approximately high anhydrous sodium sulfate of 2cm, with 10mL acetonitrile-methylbenzene prewashing tealeaves solid-phase extraction column, discards efflux.Under connect the heart bottle, put on fixed mount.With step 2) in the concentrate that obtains be transferred in the tealeaves solid-phase extraction column, with 2mL acetonitrile-methylbenzene washing sample liquid bottle, triplicate, and cleaning solution is moved in post, add the 50mL liquid reservoir on post, with 25mL acetonitrile-methylbenzene washing pillar, collect above-mentioned all effluxes in the heart bottle again, in 40 ℃ of water-baths, rotation is concentrated into approximately 0.5mL.Add the 5mL n-hexane to carry out exchange of solvent, repeat twice, sample liquid is amassed be about 1mL, then dry up in 35 ℃ of lower nitrogen, 1mL acetonitrile+water (3+2) dissolved residue after 0.2 μ m filtering with microporous membrane, is measured for liquid chromatography-tandem mass spectrometry.
The use of filler in above-described embodiment 1-11, be not limited only to use by the mode of special purification post, can also disperse the form of SPE to use by the sorbing material of absorption different substrates, the high polymer material of modifying as sorbing material and the polar functional group of material with carbon element, aminofunctional be placed in centrifuge tube with the form of disperseing SPE and uses.
The above, it is only preferred embodiment of the present invention, be not that technical scheme of the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment does.
Claims (10)
1. tealeaves solid-phase extraction column, it is characterized in that, this tealeaves solid-phase extraction column comprises the filler in column jecket and column jecket, and described filler is comprised of following component: 1 part of the high polymer material that sorbing material 2-10 part of material with carbon element 2-10 part, aminofunctional and polar functional group are modified; Described material with carbon element fills in the column jecket bottom, and the high polymer material mixed packing that the sorbing material of described aminofunctional and polar functional group are modified uses the polypropylene sieve plate as separation therebetween on the column jecket upper strata.
2. tealeaves solid-phase extraction column according to claim 1 is characterized in that: preferably, described material with carbon element is one or both the mixture in graphitized carbon, active carbon, and described material with carbon element particle size range is 80 orders～400 orders, and specific area is 100～300m
2/ g.
3. tealeaves solid-phase extraction column according to claim 1 is characterized in that: preferably, the sorbing material of described aminofunctional is one or more the mixture in amination silica gel NH2, polyamino SiClx glue PSA, amination polyethylene divinylbenzene; The particle size range of the sorbing material of described aminofunctional is 30 microns～80 microns, and specific area is 300～800 meters squared per gram, and average pore size is 40～150 dusts.
4. tealeaves solid-phase extraction column according to claim 1, it is characterized in that: preferably, the particle size range of the high polymer material that described polar functional group is modified is 30 microns～80 microns, and specific area is 300～800 meters squared per gram, average pore size is 40～150 dusts, degree of cross linking 15-80%.
5. the described tealeaves solid-phase extraction column of any one according to claim 1-4, it is characterized in that: preferably, described material with carbon element is graphitized carbon, and its micropore ratio is not higher than 2%; Degree of graphitization is not less than 50%, and the sorbing material of described aminofunctional is polyamino SiClx glue PSA, and the high polymer material that described polar functional group is modified is amidatioon polyethylene divinylbenzene.
6. tealeaves solid-phase extraction column according to claim 5, it is characterized in that: preferably, described column jecket is high-density polyethylene material or glass material.
7. a sample-pretreating method that detects the Pesticide Residues in Tea material, is characterized in that: comprise the steps:
1) Tea Samples smashed or pulverized;
2) to step 1) add in gained broken tea sample and extract solvent and buffer salt extracts, get supernatant after centrifugal; Repeat leaching process, repeat to need not to add again buffer salt in leaching process, merge supernatant concentration, get concentrate, treat loading;
3) with step 2) in the concentrate that obtains add in tealeaves solid-phase extraction column claimed in claim 6, receive efflux;
4) add eluting solvent, the residues of pesticides that remain on the tealeaves solid-phase extraction column eluted, get eluent, merge eluent and step 3) efflux that obtains;
5) eluent that merges and efflux are carried out Instrumental Analysis after concentrated, accurately qualitative, quantitative agricultural chemicals and metabolite thereof.
8. a kind of sample-pretreating method for the detection of Pesticide Residues in Tea material according to claim 7, is characterized in that: step 2) middle broken tea sample: extract solvent: buffer salt=1g:3-8mL:0.2-1g.
9. according to claim 7 or 8 described a kind of sample-pretreating methods that detect for the Pesticide Residues in Tea material is characterized in that:
Step 2) the extraction solvent described in is one or more mixtures that mix with arbitrary proportion in methyl alcohol, acetonitrile, n-hexane, acetone, carrene, ethyl acetate, benzinum, toluene, oxolane or isopropyl alcohol;
Step 2) buffer salt described in is one or more the mixture in sodium chloride, sodium acetate, natrium citricum;
Eluting solvent described in step 4) is one or more the mixture in methyl alcohol, acetonitrile, acetone, n-hexane, carrene or toluene.
10. a kind of sample-pretreating method that detects for the Pesticide Residues in Tea material according to claim 9, it is characterized in that: described extraction solvent is acetonitrile.
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| CN201310056873.XA CN103111091B (en) | 2012-03-31 | 2013-02-22 | Tea solid phase extraction column and sample pretreatment method for testing pesticide residues in tea leaves |
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