CN104324521B - The sample-pretreating method of Chinese herbal medicine solid-phase extraction column and detection pesticide made of Chinese medicinal herbs residue - Google Patents
The sample-pretreating method of Chinese herbal medicine solid-phase extraction column and detection pesticide made of Chinese medicinal herbs residue Download PDFInfo
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Abstract
The invention discloses a kind of Chinese herbal medicine solid-phase extraction column, this Chinese herbal medicine solid-phase extraction column comprises the filler in column jecket and column jecket, described filler is made up of following component, the silica gel material 1 part that sorbing material 2-10 part of material with carbon element 2-10 part, aminofunctional and non-polar functional group modify, described material with carbon element fills in column jecket bottom, and the silica gel material mixed packing that the sorbing material of described aminofunctional and non-polar functional group modify is on column jecket upper strata.There is disclosed herein and use Chinese herbal medicine solid-phase extraction column to detect the residual sample-pretreating method of Chinese herbal medicine middle peasant.This Chinese herbal medicine solid-phase extraction column is applied in sample pretreatment, can be used for ramulus mori, honeysuckle, the fruit of Chinese wolfberry and lotus leaf four kinds of Chinese herbal medicine Pesticides and metabolite analysis detect, there is single treatment sample, in extraction and cleaning Chinese herbal medicine 400 Multiple Pesticides remain and fast, the feature of economy, highly versatile.
Description
Technical field
The present invention relates to medicine, agricultural product security detection field.More specifically, the sample-pretreating method of a kind of Chinese herbal medicine solid-phase extraction column and detection pesticide made of Chinese medicinal herbs residue is related to.
Background technology
In recent years, countries in the world, to the demand expanding day of natural drug, are especially particularly paid close attention to green medicine.And Chinese herbal medicine is the rarity of our Chinese nation, there is the long history of several thousand.China has abundant natural medicine resource, and these resources are that the Chinese medicine production of China provides abundant raw material, but the quality security problem occurred in Chinese medicine is produced constrains the development of China's Chinese medicine.Residues of pesticides are outstanding problems in traditional Chinese medicine quality safety.From customs statistics in recent years, outlet Chinese medicine is frequently detained because the Harmful Residue exceeds standard and is moved back fortune, has become the obstacle of China's Chinese medicine outlet and Chinese medicine development.
Residues of pesticides refer in plant growth, agricultural production process, and applying pesticides rear portion agricultural chemicals directly or indirectly residues in the phenomenon in cereal, vegetables, fruit, Chinese medicine, livestock products, aquatic products and in soil and water.Height poison, persistent pesticide kind that China defines operable low pesticide variety and prohibits the use in Producing medicinal herbs.But because medicinal material grower can not cultivate the mechanism of action of plant population and the influence factor to ecological environment thereof according to the physicochemical properties of agricultural chemicals itself to Chinese medicine, use some height poison, persistent pesticide control medicinal material disease and pests, cause some high poison, persistent pesticide remaining in Chinese medicine thus.
Analysis for harmful chemicals such as Chinese medicinal herbs Pesticides detects, no matter use which kind of analyzing detecting method, usually all need analyzed microchemistry composition to be separated preferably with Chinese herbal medicine sample main matrix (as pigment, organic acid, organic base, sugar, oil-soluble impurities etc.) and other impurity, to avoid matrix for detection sensitivity, the interference of accuracy.Normally used sample treatment comprises liquid-liquid extraction method, solid phase extraction, sulfonation method and low-temperature freezing etc.But current process and detection method have the defect of complicated operation, poor universality.
Patent 201010597201.6, describes a kind of containing the processing method before the Chinese herbal medicine sample determination of several residues of pesticides.Method And Principle is by the impurity in the suction-operated absorption Chinese medicine of solid phase extraction filler, to get rid of the interference to detecting.Adsorption stuffing used is PSA, can remove the organic acid impurities in Chinese medicine.But the method is only applicable to the detection of 15 kinds of carbamate pesticide residues, and single due to filler, cannot for the treatment of the Chinese medicine of complex matrices.
Patent 201010197943.X adopts colorimetric method for determining dithiocarbamate agricultural chemicals, for dark colour crop, adds graphite powder and sodium chloride homogeneous, with adsorpting pigment; It principle is equally the mode that have employed the detection of adsorbing contaminant exclusive PCR; But because colorimetric method is only more responsive to pigment interference ratio, method only adds graphite powder to remove pigment, and is not suitable for other detection means.
Patent 03153725.1 residual pesticide purifying column and purification method thereof, protect a kind of residual pesticide purifying column, utilize the suction-operated principle of adsorbent filler to remove impurity, have employed active carbon, diatomite, filter aid mixed packing is used for the decontaminating column of farming residual analysis in food; Wherein diatomite and filter aid all serve the effect of filtering and supporting absorbent charcoal material, mainly still remove the impurity such as protein and pigment, are suitable for foodstuff sample, are not suitable for the Chinese herbal medicine sample being rich in organic acid, organic base, sugar.
Finally, in above-mentioned existing patented method, any one be not all suitable for extract from Chinese herbal medicine simultaneously and purification more than 400 kinds of residues of pesticides.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of Chinese herbal medicine solid-phase extraction column, and the present invention's extraction column used not only used the mode of mixed packing, additionally uses layering filling, realizes the mode that two kinds of pillars are connected in series in a supporting tube.And the material adopted in decontaminating column is not only containing carbon class material, also add the material such as silica gel material of the silica gel material (i.e. the sorbing material of aminofunctional) of the basic functionality with ion exchange, non-polar functional group's modification; Make use of different absorption principle adsorbing contaminant.
Second technical problem that the present invention will solve is to provide a kind of sample-pretreating method using above-mentioned extraction column to detect pesticide residues in Chinese herbal medicines material, the method combines the feature of Chinese herbal medicine solid-phase extraction column, by the disposable purification of novelty, interblock interference method, achieve Multiple Pesticides in Chinese herbal medicine class complex matrices sample to remain and detect while metabolin, be a unique detection method simultaneously can planting agricultural chemicals and chemical pollutant in extraction and cleaning Chinese herbal medicine more than more than 400 at present, filled up domestic blank.
For solving above-mentioned first technical problem, the present invention adopts following technical proposals:
A kind of Chinese herbal medicine solid-phase extraction column, comprises the filler in column jecket and column jecket, and the present invention's filler used is made up of the sorbing material of 2-10 part material with carbon element, 2-10 part aminofunctional and the silica gel material of 1 part of non-polar functional group's modification; In extraction column, material with carbon element fills in column jecket bottom, and the silica gel material mixed packing that the sorbing material of aminofunctional and non-polar functional group modify is on column jecket upper strata.
The performance of several conventional sample pre-treatments sorbing material is compared in the present invention, three kinds of materials are optimized, again by consumption and the proportioning of optimization three kinds of materials, connected applications method reaches the catharsis to this four classes Chinese herbal medicine mesostroma interfering material of ramulus mori, honeysuckle, the fruit of Chinese wolfberry and lotus leaf.Selected sorbing material should consider can not there be strong absorption affinity to agricultural chemicals determinand, thus affects its elute effect; Also to consider the clean-up effect of sorbing material, make it farthest can remove sample substrate chaff interference.
Material with carbon element used be selected from graphitized carbon and active carbon one or both, the particle size of material with carbon element is 80 order-500 orders, and specific area is 100-300m
2/ g; The material with carbon element preferably used is graphitized carbon, micropore ratio≤2% of graphitized carbon used, degree of graphitization>=50%.For the preferred graphitized carbon of material with carbon element, surface area is carried out to it, the control of microporosity, to ensure the absorption to matrix interference things such as pigments, also will ensure do not have excessive absorption to agricultural chemicals, effectively avoiding some many lopps agricultural chemicals to adsorb at carbon material surface by force cannot the problem of wash-out simultaneously.
The sorbing material of aminofunctional used is selected from one or more in amino bonded silica gel, polyamino bonded silica gel PSA and amination polyethylene divinylbenzene; The particle size of the sorbing material of aminofunctional used is 30 μm-80 μm, and specific area is 300-800m
2/ g, average pore size is
; The sorbing material of aminofunctional preferably used is polyamino bonded silica gel PSA.
The silica gel material that non-polar functional group used modifies is selected from one or more in octadecyl functional group bonded silica gel, phenyl functional group's bonded silica gel, octyl group functional group bonded silica gel and hexyl functional group bonded silica gel; The particle size of the silica gel material that non-polar functional group used modifies is 30 μm-80 μm, and specific area is 300m
2/ g-800m
2/ g, average pore size is
, phosphorus content is 11%-20%; The silica gel material that the non-polar functional group of preferred use modifies is octadecyl functional group bonded silica gel.Adopt the silica gel material that non-polar functional group modifies, good Adsorption effect is all had for oil-soluble impurities, sugar etc., avoid the metal oxide being usually used in Chinese herbal medicine sample Pesticide Residues at present and detecting simultaneously, as the absorption for organophosphor isopolarity agricultural chemicals that magnesium silicate, aluminium oxide etc. cause, while strengthening the absorption of matrix interference thing, reduce the absorption to object.
The column jecket inside of the Chinese herbal medicine solid-phase extraction column that the present invention is used is provided with sieve plate, and column jecket material therefor is high-density polyethylene material or glass, and the material that sieve plate uses is polypropylene.
For solving above-mentioned second technical problem, the technical solution used in the present invention is as follows:
Use above-mentioned Chinese herbal medicine solid-phase extraction column to detect a sample-pretreating method for pesticide residues in Chinese herbal medicines material, comprise the steps:
1) Chinese herbal medicine sample is prepared;
2) by step 1) gained Chinese herbal medicine sample carries out extracting, centrifugal, concentrated, obtain concentrate;
3) on Chinese herbal medicine solid-phase extraction column, add the high anhydrous sodium sulfate of about 2cm, then Chinese herbal medicine solid-phase extraction column is activated;
4) by step 2) concentrate that obtains adds in Chinese herbal medicine solid-phase extraction column, receives efflux;
5) in Chinese herbal medicine solid-phase extraction column, adding eluting solvent, obtain eluent, by eluent and step 4) efflux that obtains merges;
6) by step 5) amalgamation liquid that obtains concentrates, analyzes and draw quantitative and qualitative analysis agricultural chemicals and metabolite thereof.
Preferably, step 1) Chinese herbal medicine be selected from ramulus mori, honeysuckle, lotus leaf or the fruit of Chinese wolfberry, before detection starts, ramulus mori, honeysuckle and lotus leaf three kinds of Chinese herbal medicine medicines need smash or pulverize into fine powder, and the fruit of Chinese wolfberry can directly use.
Preferably, step 2) described extraction comprises homogeneous extraction and heterogeneous body extracts, described homogeneous first adds Extraction solvent when extracting and carries out homogeneous in the container containing Chinese herbal medicine sample, then in container, add buffer salt again carry out homogeneous extraction, obtain extract, container is carried out centrifugally operated and gets supernatant; It is in remaining residue after taking supernatant, add Extraction solvent carry out infiltrations extraction and obtain extract for the second time that described heterogeneous body extracts, after gained second time extract is carried out centrifugally operated, get supernatant, merge twice centrifugal supernatant obtained, the supernatant of merging is concentrated; Described Extraction solvent is selected from one or more in methyl alcohol, acetonitrile, n-hexane, acetone, carrene, ethyl acetate, benzinum, toluene, oxolane and isopropyl alcohol, and preferably, described Extraction solvent is selected from acetonitrile; Described buffer salt is selected from one or more in sodium chloride, sodium acetate and natrium citricum, and preferably, described buffer salt is selected from sodium chloride.This experiment is by contrast, and to reach a conclusion be acetonitrile, acetone and n-hexane are compared to methyl alcohol, carrene, ethyl acetate, benzinum, toluene, oxolane and isopropyl alcohol and have good extraction efficiency to agricultural chemicals; And further comparative study acetonitrile, n-hexane+acetone (volume ratio of n-hexane and acetone is 4:6), the extraction efficiency of n-hexane+acetone (volume ratio of n-hexane and acetone is 9:1) three kinds of Extraction solvent, n-hexane+acetone (the volume ratio 9:1 of n-hexane and acetone) due to polarity weak, be more suitable for extracting pigment and containing the few sample of grease, but recovery rate is low, the remains of pesticide in plant tissue can not be extracted completely.In n-hexane+acetone (the volume ratio 4:6 of n-hexane and acetone), content of acetone is larger, polarity is also stronger, and can be molten with aqueous phase, most of agricultural chemicals can be dissolved, and filtration and dissolving are all easy to, but acetone can extract again grease in plant tissue and pigment in a large number, for next step purification brings difficulty.Acetonitrile extracts less as Extraction solvent to grease and pigment, in the analysis of the agricultural chemicals such as organophosphor, organochlorine, pyrethroid, carbamates, adopt by AOAC method, the Extraction solvent that Ye Shi China commonly uses at present.Acetonitrile compared with acetone, although price some, can extract Multiple Pesticides simultaneously remain, and the chaff interference of coextraction is few, simple to operate, therefore this method have selected acetonitrile as Extraction solvent.
During extraction agricultural chemicals except considering the characteristic of agricultural chemicals, also must consider feature and the state of sample, for the high sample of sugar content as matrimony vine, to first add appropriate water, its sugar is fully dissolved, extract with solvent acetonitrile that can be miscible with it again, in experiment, 15mL acetonitrile is added to the water of matrimony vine sample interpolation 5mL again and extract.
Preferably, step 1) described in Chinese herbal medicine sample and step 2) described in Extraction solvent and the amount ratio of buffer salt be: 1g:3-20mL:0.1-1.5g.
The present invention has carried out great many of experiments for the sample size of Chinese herbal medicine solid-phase extraction column, have found the sample size of suitable solid-phase extraction column of the present invention, under the extraction conditions of this standard setting, 5g matrimony vine and honeysuckle are while extracting agricultural chemicals substantially completely, and the interference matrix extracted altogether is less, and lotus leaf is then because pigment is darker, there is larger interference, ramulus mori, because its matrix is complicated, if sample size is excessive also can cause the incomplete of purification, causes the pollution of instrument and the drift of baseline.So have finally chosen honeysuckle and matrimony vine sample size is 5g, and lotus leaf and ramulus mori sample size are 2.5g.Determine sample size, the amount of the Extraction solvent that subsequent operation uses and buffer salt is according to the ratio-dependent of text description above.
Step 3) in when Chinese herbal medicine solid-phase extraction column is activated, add organic solvent to Chinese herbal medicine solid-phase extraction column to activate, the organic solvent that activation uses is selected from one or more in methyl alcohol, acetonitrile, n-hexane, acetone, carrene, ethyl acetate, benzinum, toluene, oxolane and isopropyl alcohol.Chinese herbal medicine solid-phase extraction column in the present invention is impurity absorption pattern solid-phase extraction column, and the object of this extraction pattern is the impurity in removing sample, and in this extraction pattern, target compound is retained in sample substrate, and impurity is then retained by solid-phase extraction column.The selection of activating reagent, the present invention devises several activating solvent, acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene), n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone), n-hexane+acetone (n-hexane: the volume ratio 9:1 of acetone) carries out contrast experiment, result shows, and acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene) and n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone) all can remove the impurity in Chinese herbal medicine solid-phase extraction column and create the solvent environment being applicable to adsorption sample impurity.Final selected activating reagent is respectively: acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene) and n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone), and concrete selection need be consistent with eluting solvent.
Step 5) in eluting solvent be selected from methyl alcohol, acetonitrile, acetone, n-hexane, carrene and toluene one or more, preferably, eluting solvent is n-hexane and the acetone mixed solvent that formed of 4:6 by volume.The selection of eluting solvent, the present invention devises several eluting solvent, acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene), n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone), n-hexane+acetone (n-hexane: the volume ratio 9:1 of acetone) carries out contrast experiment, result display acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene) and n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone) can realize the complete wash-out of most of agricultural chemicals all substantially, and there is the problem little with Extraction solvent intersolubility in n-hexane+acetone (n-hexane: the volume ratio 9:1 of acetone).In addition, n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone) is as eluent, because not containing acetonitrile, can not impact gas chromatographic column, save the step of exchange of solvent, and concentration time comparatively acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene) system shortening 50%, simplify experimentation, greatly save experimental period, and do not use highly toxic toluene in this dicyandiamide solution, be conducive to the health of experimenter, when sample testing instrument is gas chromatograph-mass spectrometer (GC-MS), eluting solvent is finally chosen to be n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone), highly sensitive in gas chromatograph-mass spectrometer (GC-MS) due to Liquid Chromatography-tandem Mass instrument, n-hexane+acetone (n-hexane: the volume ratio 4:6 of acetone) polarity is slightly stronger than acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene), the pigment impurity extracted from sample is also more, this sample can produce baseline drift on liquid chromatography-tandem mass spectrometry instrument, easily cause instrumental pollution etc., and acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene) is while guarantee agricultural chemicals object good recovery, above problem can also be eliminated, when sample testing instrument is liquid chromatography-tandem mass spectrometry instrument, eluting solvent is finally chosen to be acetonitrile+toluene (acetonitrile: the volume ratio 3:1 of toluene).
Beneficial effect of the present invention is as follows:
The Chinese herbal medicine solid-phase extraction column related in the present invention is by used in combination to the material of different physicochemical properties, reach the effect of the interference matrix removed in ramulus mori, honeysuckle, the fruit of Chinese wolfberry and lotus leaf four kinds of Chinese herbal medicine sample pesticide residue quality detection processes, comparatively conventional SPE pre-treating method saves the experimental implementation time of at least half, and only use a solid-phase extraction column, reduce economy and manual operation cost.
In ramulus mori, honeysuckle, the fruit of Chinese wolfberry and lotus leaf, Multiple Pesticides and related chemicals remain the Chinese herbal medicine SPE column purification through optimal design, good clean-up effect can be obtained, and the desirable rate of recovery can be obtained, method is simple and efficient, can meet the mensuration demand of above-mentioned Chinese medicine Pesticides and related chemicals.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates the schematic diagram of Chinese herbal medicine solid-phase extraction column.
In figure, 1-column jecket, 2-filler mixed layer, 3-material with carbon element layer, 4-inlet, 5-flow export, 6-sieve plate.
Detailed description of the invention
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 6:3:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size range is 80 order-200 orders, and specific area is 110m
2/ g, its micropore ratio 2%, degree of graphitization 55%; The particle size range of amino bonded silica gel material is 50 μm-60 μm, and specific area is 430m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 50 μm-60 μm, and specific area is 430m
2/ g, average pore size is
, phosphorus content is 13%-15%.
Embodiment 2
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 8:5:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size range is 80 order-300 orders, and specific area is 250m
2/ g, its micropore ratio 2%, degree of graphitization 60%; The particle size range of amino bonded silica gel material is 50 μm-70 μm, and specific area is 470m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 50 μm-70 μm, and specific area is 470m
2/ g, average pore size is
, phosphorus content is 13%-17%.
Embodiment 3
Use the glass column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 3:8:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size distribution range is 120 order-400 orders, and specific area is 150m
2/ g, its micropore ratio 2%, degree of graphitization 70%; The particle size range of amino bonded silica gel material is 60 μm-70 μm, and specific area is 600m
2/ g, average pore size is
octadecyl silane material particle size scope is 60 μm-70 μm, and specific area is 600m
2/ g, average pore size is
phosphorus content is 14%-17%.
Embodiment 4
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 4:5:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size distribution range is 200 order-300 orders, and specific area is 130m
2/ g, its micropore ratio 2%, degree of graphitization 65%; The particle size range of amino bonded silica gel material is 50 μm-70 μm, and specific area is 510m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 50 μm-70 μm, and specific area is 510m
2/ g, average pore size is
, phosphorus content is 15%-17%.
Embodiment 5
Use the glass column jecket that volume capacity is 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, polyamino bonded silica gel, octadecyl silane three kinds of materials, wherein polyamino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of polyamino bonded silica gel and octadecyl silane three kinds of materials is 6:6:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size distribution range is 100 order-400 orders, and specific area is 180m
2/ g, its micropore ratio 2%, degree of graphitization 70%; The particle size range of polyamino bonded silica gel material is 60 μm-80 μm, and specific area is 480m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 60 μm-80 μm, and specific area is 480m
2/ g, average pore size is
, phosphorus content is 13%-17%.
Embodiment 6
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 6:6:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size distribution range is 80 order-200 orders, and specific area is 140m
2/ g, its micropore ratio 1.5%, degree of graphitization 50%; The particle size range of amino bonded silica gel material is 30 μm-40 μm, and specific area is 650m
2/ g, average pore size is
octadecyl silane material particle size scope is 30 μm-40 μm, and specific area is 650m
2/ g, average pore size is
phosphorus content is 11%-14%.
Embodiment 7
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 3:8:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size range is 120 order-400 orders, and specific area is 170m
2/ g, its micropore ratio 2%, degree of graphitization 60%; The particle size range of amino bonded silica gel material is 50 μm-80 μm, and specific area is 470m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 50 μm-80 μm, and specific area is 350m
2/ g, average pore size is
, phosphorus content is 14%-17%.
Embodiment 8
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 8:5:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size range is 200 order-400 orders, and specific area is 280m
2/ g, its micropore ratio 1%, degree of graphitization 80%; The particle size range of amino bonded silica gel material 40 μm-60 μm, specific area is 600m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 40 μm-60 μm, and specific area is 580m
2/ g, average pore size is
, phosphorus content is 17%-20%.
Embodiment 9
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 6:6:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size range is 120 order-200 orders, and specific area is 170m
2/ g, its micropore ratio 1%, degree of graphitization 50%; The particle size range of amino bonded silica gel material is 50 μm-70 μm, and specific area is 430m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 50 μm-70 μm, and specific area is 430m
2/ g, average pore size is
, phosphorus content is 16%-18%.
Embodiment 10
Use the high density polyethylene (HDPE) column jecket that volume capacity is 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, amino bonded silica gel, octadecyl silane three kinds of materials, wherein amino bonded silica gel mixes with octadecyl silane as one deck 2, graphitized carbon is as one deck 3, use the polypropylene sieve plate 6 in 20 μm of apertures as separation 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 Chinese herbal medicine solid-phase extraction column, the mass ratio of amino bonded silica gel and octadecyl silane three kinds of materials is 8:5:1, wherein graphitized carbon fills in column jecket bottom.Wherein graphitized carbon material particle size range is 400 order-500 orders, and specific area is 210m
2/ g, its micropore ratio 2%, degree of graphitization 50%; The particle size range of amino bonded silica gel material is 40 μm-50 μm, and specific area is 530m
2/ g, average pore size is
; Octadecyl silane material particle size scope is 40 μm-50 μm, and specific area is 530m
2/ g, average pore size is
, phosphorus content is 18%-20%.
Embodiment 11
The Chinese herbal medicine solid-phase extraction column CleanertTPH in embodiment 2 is used to detect several agricultural chemicals and chemical contamination in Chinese herbal medicine: concrete steps are as follows:
1) pulverized through pulverizer by Chinese herbal medicine sample, cross 20 mesh sieves, mixing, sealing, as sample, indicates mark;
2) take step 1) in gained Chinese herbal medicine sample honeysuckle, fruit of Chinese wolfberry sample 5g or lotus leaf, ramulus mori sample 2.5g (being accurate to 0.01g), in 50mL centrifuge tube, add 15mL acetonitrile, 1min is extracted with the rotating speed homogeneous of 15000r/min, 2g sodium chloride is added again in centrifuge tube, homogeneous extracts 1min again, by extract with the centrifugal 5min of the rotating speed of 4200r/min, gets supernatant in 150mL heart bottle.Residue 15mL acetonitrile repeats to extract once, by extract with the centrifugal 5min of the rotating speed of 4200r/min, gets supernatant, and merge the supernatant that secondary centrifuging obtains, 40 DEG C of water-bath rotary evaporations are concentrated into 1mL-2mL, to be clean;
3) in the Chinese herbal medicine solid-phase extraction column of embodiment 2, add about 2cm height anhydrous sodium sulfate, with 10mL n-hexane-acetone prewashing Chinese herbal medicine solid-phase extraction column, discard efflux.Under connect heart bottle, be positioned on fixed mount.By step 2) in the concentrate that obtains be transferred in Chinese herbal medicine solid-phase extraction column, with 2mL n-hexane-acetone washing sample liquid bottle, repeat twice, and cleaning solution is moved in post, post adds 25mL liquid reservoir, again with 25mL n-hexane-acetone washing pillar, collect above-mentioned all effluxes in heart bottle, in 40 DEG C of water-baths, concentrated by rotary evaporation is near dry.Add 1mL n-hexane and carry out constant volume, 0.2 μm of membrane filtration, for Gas Chromatography-Mass Spectrometry.75% is greater than to the mensuration rate of recovery of the agricultural chemicals such as the organophosphor in Chinese herbal medicine, organochlorine, meets detection requirement.
Comparative example
The filler of Chinese herbal medicine dedicated columns is the silica gel material modified by the sorbing material of 2-10 part material with carbon element, 2-10 part aminofunctional and 1 part of polar functional group; Described material with carbon element fills in column jecket bottom, and the silica gel material mixed packing that the sorbing material of described aminofunctional and polar functional group are modified is on column jecket upper strata.Then test on contrast post according to the step described in embodiment 11, the mensuration rate of recovery result of the agricultural chemicals such as part organophosphor, organochlorine obtained is less than 75%, does not meet detection requirement.
Embodiment 12
The Chinese herbal medicine solid-phase extraction column Chinese herbal medicine solid-phase extraction column of embodiment 1 is used to detect several agricultural chemicals and chemical pollutant concrete steps in Chinese herbal medicine as follows:
1) pulverized through pulverizer by Chinese herbal medicine sample, cross 20 mesh sieves, mixing, sealing, as sample, indicates mark;
2) 2g step 1 is taken) gained Chinese herbal medicine sample (being accurate to 0.01g), in 50mL centrifuge tube, add 15mL acetonitrile (fruit of Chinese wolfberry sample need add 5mL water again), 1min is extracted with the rotating speed homogeneous of 15000r/min, 2g sodium chloride is added again in centrifuge tube, homogeneous extracts 1min again, by extract with the centrifugal 5min of the rotating speed of 4200r/min, gets supernatant in 150mL heart bottle.Residue 15mL acetonitrile repeats to extract once, and by extract with the centrifugal 5min of the rotating speed of 4200r/min, merge the supernatant of secondary centrifuging, 40 DEG C of water-bath rotary evaporations are concentrated into 1mL-2mL, to be clean;
3) add about 2cm height anhydrous sodium sulfate to the Chinese herbal medicine solid-phase extraction column in embodiment 1, with 10mL acetonitrile-methylbenzene prewashing Chinese herbal medicine solid-phase extraction column, discard efflux.Under connect heart bottle, be positioned on fixed mount.By step 2) in the concentrate that obtains be transferred in Chinese herbal medicine solid-phase extraction column, with 2mL acetonitrile-methylbenzene washing sample liquid bottle, repeat twice, and cleaning solution is moved in post, post adds 25mL liquid reservoir, again with 25mL acetonitrile-methylbenzene washing pillar, collect above-mentioned all effluxes in heart bottle, in 40 DEG C of water-baths, concentrated by rotary evaporation is to 1mL-2mL, concentrate is placed in nitrogen and dries up on instrument and dry up, add 1mL acetonitrile-water (1:1, volume ratio), mixing, after 0.2 μm of filtering with microporous membrane, measures for liquid chromatography-tandem mass spectrometry.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (14)
1. a Chinese herbal medicine solid-phase extraction column, it is characterized in that: described Chinese herbal medicine solid-phase extraction column comprises the filler in column jecket and column jecket, described filler is made up of the sorbing material of 2-10 part material with carbon element, 2-10 part aminofunctional and the silica gel material of 1 part of non-polar functional group's modification; Described material with carbon element fills in column jecket bottom, and the silica gel material mixed packing that the sorbing material of described aminofunctional and non-polar functional group modify is on column jecket upper strata;
Described material with carbon element be selected from graphitized carbon and active carbon one or both;
The sorbing material of described aminofunctional is selected from one or more in amino bonded silica gel, polyamino bonded silica gel and amination polyethylene divinylbenzene;
The silica gel material that described non-polar functional group modifies is selected from one or more in octadecyl functional group bonded silica gel, phenyl functional group's bonded silica gel, octyl group functional group bonded silica gel and hexyl functional group bonded silica gel.
2. Chinese herbal medicine solid-phase extraction column according to claim 1, is characterized in that: described material with carbon element particle size is 80 order-500 orders, and specific area is 100-300m
2/ g.
3. Chinese herbal medicine solid-phase extraction column according to claim 1, is characterized in that: the particle size of the sorbing material of described aminofunctional is 30 μm-80 μm, and specific area is 300-800m
2/ g, average pore size is
4. Chinese herbal medicine solid-phase extraction column according to claim 1, is characterized in that: the particle size of the silica gel material that described non-polar functional group modifies is 30 μm-80 μm, and specific area is 300m
2/ g-800m
2/ g, average pore size is
phosphorus content is 11%-20%.
5. the Chinese herbal medicine solid-phase extraction column according to any one of claim 1-4, is characterized in that: described material with carbon element is graphitized carbon, and its micropore ratio is not higher than 2%, and degree of graphitization is not less than 50%; The sorbing material of described aminofunctional is polyamino bonded silica gel; The silica gel material that described non-polar functional group modifies is octadecyl functional group bonded silica gel; Described column jecket inside is provided with sieve plate, and described column jecket is high-density polyethylene material or glass material, and described sieve plate is polypropylene material.
6. use Chinese herbal medicine solid-phase extraction column as claimed in claim 1 to detect a sample-pretreating method for pesticide residues in Chinese herbal medicines material, it is characterized in that, comprise the steps:
1) Chinese herbal medicine sample is prepared;
2) by step 1) gained Chinese herbal medicine sample carries out extracting, centrifugal, concentrated, obtain concentrate;
3) on Chinese herbal medicine solid-phase extraction column, add the high anhydrous sodium sulfate of 2cm, then Chinese herbal medicine solid-phase extraction column is activated;
4) by step 2) concentrate that obtains all adds in Chinese herbal medicine solid-phase extraction column, receives efflux;
5) in Chinese herbal medicine solid-phase extraction column, adding eluting solvent, obtain eluent, by eluent and step 4) efflux that obtains merges;
6) by step 5) amalgamation liquid that obtains concentrates, analyzes and draw quantitative and qualitative analysis agricultural chemicals and metabolite thereof.
7. sample-pretreating method according to claim 6, is characterized in that: step 1) described Chinese herbal medicine is selected from ramulus mori, honeysuckle, lotus leaf or the fruit of Chinese wolfberry.
8. sample-pretreating method according to claim 6, it is characterized in that: step 2) described extraction comprises homogeneous extraction and heterogeneous body extracts, described homogeneous first adds Extraction solvent when extracting and carries out homogeneous in the container containing Chinese herbal medicine sample, then in container, add buffer salt again carry out homogeneous extraction, obtain extract, container is carried out centrifugally operated and gets supernatant; It is in remaining residue after taking supernatant, add Extraction solvent carry out infiltrations extraction and obtain extract for the second time that described heterogeneous body extracts, after gained second time extract is carried out centrifugally operated, get supernatant, merge twice centrifugal supernatant obtained, the supernatant of merging is concentrated; Described Extraction solvent is selected from one or more in methyl alcohol, acetonitrile, n-hexane, acetone, carrene, ethyl acetate, benzinum, toluene, oxolane and isopropyl alcohol; Described buffer salt is selected from one or more in sodium chloride, sodium acetate and natrium citricum.
9. sample-pretreating method according to claim 8, is characterized in that: described Extraction solvent is selected from acetonitrile.
10. sample-pretreating method according to claim 8, is characterized in that: described buffer salt is sodium chloride.
11. sample-pretreating methods according to claim 6, is characterized in that: step 1) described in Chinese herbal medicine sample and step 2) described in Extraction solvent and the amount ratio of buffer salt be: 1g:3-20ml:0.1-1.5g.
12. sample-pretreating methods according to claim 6, it is characterized in that: step 3) described activation with an organic solvent, the organic solvent of described activation is selected from one or more in methyl alcohol, acetonitrile, n-hexane, acetone, carrene, ethyl acetate, benzinum, toluene, oxolane and isopropyl alcohol; Step 5) described eluting solvent be selected from methyl alcohol, acetonitrile, acetone, n-hexane, carrene and toluene one or more.
13. sample-pretreating methods according to claim 6 or 12, it is characterized in that: step 3) described activation with an organic solvent, the organic solvent of described activation is selected from n-hexane and the acetone mixed solvent that formed of 4:6 or acetonitrile and the toluene mixed solvent that formed of 3:1 by volume by volume.
14. sample-pretreating methods according to claim 6 or 12, is characterized in that: step 5) described eluting solvent is selected from n-hexane and the acetone mixed solvent that formed of 4:6 or acetonitrile and the toluene mixed solvent that formed of 3:1 by volume by volume.
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| CN105032381B (en) * | 2015-06-05 | 2017-12-29 | 中国农业科学院农业质量标准与检测技术研究所 | Compound molecule trace solid-phase extraction column and preparation method and application |
| CN106289895B (en) * | 2015-06-05 | 2019-05-07 | 吉林出入境检验检疫局检验检疫技术中心 | A kind of ecological textile venomous injurant quality detection decontaminating column and preparation method thereof |
| CN105628840A (en) * | 2015-12-28 | 2016-06-01 | 中国检验检疫科学研究院 | GC-Q-TOF/MS technology for detecting 708 kinds of pesticide residues in pome fruits |
| CN106383192B (en) * | 2016-11-09 | 2018-05-11 | 无锡艾科瑞思产品设计与研究有限公司 | A kind of detection method of Mobucin |
| CN107632079B (en) * | 2017-08-18 | 2020-05-29 | 浙江省农业科学院 | Special purifying column for fumonisins and application thereof |
| CN107727781B (en) * | 2017-09-30 | 2021-01-05 | 北京农业质量标准与检测技术研究中心 | Solid-phase extraction column capable of simultaneously purifying various mycotoxins and application thereof |
| CN108107135A (en) * | 2017-12-12 | 2018-06-01 | 广州广电计量检测股份有限公司 | Measure the pre-treating method of persticide residue and its quantitative approach and kit in edible flowers |
| CN110514764A (en) * | 2019-09-05 | 2019-11-29 | 山东陆桥检测技术股份有限公司 | It is a kind of to measure the remaining detection method of Multiple Pesticides in non-fat property fruits and vegetables |
| CN112326821B (en) * | 2020-10-27 | 2021-06-04 | 青岛大学附属医院 | Method for detecting lipid content of biological liver tissue |
| CN113311095B (en) * | 2021-05-08 | 2022-11-08 | 珠海市公安局刑事警察支队 | Water body pesticide pretreatment enrichment method and water body pesticide content detection method |
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| DE112010000810T5 (en) * | 2009-01-29 | 2012-06-21 | Hitachi High-Technologies Corporation | Apparatus for the pretreatment of biological samples and mass spectrometers equipped therewith |
| CN101852699A (en) * | 2009-04-02 | 2010-10-06 | 天津市农业科学院中心实验室 | Method for treating organochlorine pesticide residue sample in Chinese medicinal material before measurement |
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