CN103048400B - Solid-phase extraction column and preparation method thereof - Google Patents
Solid-phase extraction column and preparation method thereof Download PDFInfo
- Publication number
- CN103048400B CN103048400B CN201210525322.9A CN201210525322A CN103048400B CN 103048400 B CN103048400 B CN 103048400B CN 201210525322 A CN201210525322 A CN 201210525322A CN 103048400 B CN103048400 B CN 103048400B
- Authority
- CN
- China
- Prior art keywords
- sieve plate
- solid
- phase extraction
- pressed
- extraction column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a solid-phase extraction column and a preparation method thereof. At the bottom of a column tube, the following operations are carried out in sequence: an outlet sieve plate is pressed in, a graphitized carbon black layer is filled in, a layer of insulating sieve plate is pressed in, a multi-amination packing layer is filled in, a hydrophobic group bonded silica gel resin layer is filled in after being pressed into the insulating sieve plate, and an inlet sieve plate is finally pressed in; and an outlet of the extraction column is arranged at the bottom of the column tube. The solid-phase extraction column provided by the invention is a pesticide residue detection special column and is made of a three-layer adsorbing material. Impurities, such as amino acid microelements, and heavy metal, can be removed by selectively adsorbing and selectively eluting and purifying a matrix of a complex sample, so that the defect of poor purification effect of the conventional solid-phase extraction product can be avoided, the cleaning degree of the sample is greatly improved, an analyzer is effectively protected, the accuracy of sample detection is improved, the detection sensitivity is improved, the time is saved, and the working efficiency of detectors can be improved. Furthermore, the solid-phase extraction column has the advantages of generality, and low selectivity of a matrix of the sample to be detected, and can be applicable to detection of most food samples.
Description
Technical field
The invention provides a kind of solid-phase extraction column, the sample extraction detecting for Pesticide Residues purifies, and the invention also discloses the preparation method of solid-phase extraction column, belongs to analytical chemistry material technology field.
Background technology
In recent years, Pesticide Residues problem obtains common concern, and relevant research is also increasing.The kind of agricultural chemicals is numerous, and the conventional agricultural chemicals of China has organochlorine class, organic phosphates, carbamates, pyrethroid etc.Organochlorine class comprises benzene hexachloride, DDT etc., and China forbids such agricultural chemicals in nineteen eighty-three, but due to its long half time, still remaining in soil, underground water so far, they easily cause slow poisoning at people's body accumulation, serious harm human health.Organic phosphates and carbamates can suppress the activity of cholinesterase in biosome, cause passing to medium metabolic disorder, produce delayed neurotoxicity.Pyrethroid pesticide can affect cromoci and electron transport system, causes muscular tremor and tic.The purification of sample plays vital effect in the process of the residual detection of agriculture, the sample purification that Pesticide Residues detects has liquid-liquid extraction method, gel permeation chromatography, solid phase extraction conventionally, liquid-liquid extraction method is a kind of extraction and purification methods using the earliest, utilize the difference of agricultural chemicals to be measured solubleness (partition factor) in two kinds of inconsistent solvents and reach the object of separation, it is more that method expends solvent, and easily emulsification.Gel permeation chromatography is the mechanism of getting rid of based on volume, and by having the fixing phase of molecular sieve character, being used for the less material of isolated molecule quality can also analyzing molecules volume difference, have the macromolecule homolog of identical chemical property.Solid-Phase Extraction is paid attention to by people gradually as the important means of sample pre-treatments.Solid-Phase Extraction (Solid Phase Extraction is called for short SPE), also claims solid phase extractions, is an isolation technics that combines the process such as selective retention, selective elution.Its purification pattern is mainly divided into two kinds: first in the time that complicated sample solution passes through adsorbent (Sorbent), adsorbent can optionally retain target compound (Aimed Compound) and a small amount of chaff interference close with target compound character by acting forces such as polar interaction, hydrophobic interaction or ion-exchanges, other components see through adsorbent and flow out pillar, then with the stronger solvent system selection ground of another kind of eluting power, object is eluted, thereby realize separation, purifying and the enrichment to complex sample.The second refers to when sample solution passes through adsorbent, and main chaff interference is retained, and object and partial impurities flow out with solvent, adding appropriate solvent, object are washed out completely.This mechanism usually for fruit, vegetables, etc. remove fat-soluble chaff interference in the residual analysis of sample Multiple Pesticides and ion analysis.
Solid-phase extraction column mostly is single-layer products in the market, and vegetables, the residual detection of fruit middle peasant are with mostly being double-layer product.For a long time, Detecting Pesticide mainly adopts double-deck Solid phase extraction sample, but the single adsorption character of complicated, the diversity of sample type and traditional adsorption stuffing makes testing person's work difficulty increasing, and the Chinese herbal medicine sample that this wherein receives much concern is particularly evident.Chinese herbal medicine sample composition complexity, mainly comprise amino acid, protein, fat, saponin class, polysaccharide, polypeptide compounds, contain other compositions such as volatile oil, fatty acid, vitamin, trace element and heavy metal simultaneously, testing has been proposed to stern challenge.Therefore, developing a kind of novel Solid-Phase Extraction product, to solve this demand be fundamental purpose of the present invention.
Summary of the invention
The present invention discloses a kind of solid-phase extraction column, solve the poor shortcoming of clean-up effect of traditional Solid-Phase Extraction product, improve the clean level of sample, increase the accuracy of sample detection, there is versatility, low for detected sample substrate selectivity, applicable to the detection of most food samples.
The present invention also provides the preparation method of solid-phase extraction column, is applicable to suitability for industrialized production.
solid-phase extraction column provided by the invention, its technical solution is as follows:
Bottom at column jecket is pressed into exit sieve plate, pack ketjenblack EC layer (adsorbent) into, be pressed into one deck isolation sieve plate, reinstall polyamino packing layer (adsorbent), after being pressed into isolation sieve plate, pack hydrophobic grouping bonded silica gel resin bed (adsorbent) into, be finally pressed into again import sieve plate; The bottom of column jecket is provided with extraction column outlet.
Import sieve plate is that esterphilic type macromolecular material sintering forms, and aperture is at 10-200um, thickness 5-10mm; Exit sieve plate is that hydrophobic type polymeric film material is made, aperture 5-100um, thickness 3-6mm.Isolation sieve plate is general sieve plate, aperture 5-100um, thickness 2-5mm; Material is tygon, polypropylene or teflon and makes.
The pore volume of ketjenblack EC is 0.8-1.2cm
3/ g, specific surface area is 250-400m
2/ g;
The material matrix of polyamino packing layer is high crosslinked polystyrene or polymethacrylate polymer, and material surface is primary amine, secondary amine or tertiary amine group, and polymeric matrix specific surface area is 1000 m
2/ g;
Hydrophobic grouping bonded silica gel is the golden nanometer particle of modification.
the preparation method of ketjenblack EC of the present invention, comprises the following steps:
Get sulfuric acid for carbon dust, hydrochloric acid, water, methyl alcohol, acetone and other organic solvent and wash away metal and other organic impurities; dry; quantitatively add 0.1mol/L NaOH to be placed in pyrolytic conversion stove; under high-purity helium protection; be warming up to 1000 DEG C with 10 DEG C/min; be incubated 12 hours, quantitatively add rapidly 0.1mol/L K after being down to room temperature
2hPO
4, be warming up to 2000 DEG C with 20 DEG C/min, be incubated 12 hours, after cooling, repeat to add K
2hPO
4step, product is after massive laundering, and acetone washing and drying, to obtain final product; For positive hexatomic ring lamellar structure, pore volume is 0.8-1.2cm
3/ g, specific surface area is 250-400m
2/ g.
In calcination process, add the inorganic salts such as Na salt, K salt, by occupying effect in space, organization material inner structure, generate pore volume rationally, even structure, novel stony desertification carbon black materials that specific surface area is large.Traditional Graphon material hole volume is 0.2-0.6cm
3/ g, specific surface area is 40-200m
2/ g, and material hole volume of the present invention is 0.8-1.2cm
3/ g, specific surface area is 250-400m
2/ g, material of the present invention has more positive hexatomic ring lamellar structure, and pigment planar molecule is had to stronger affinity, large molecular impurity is had to stronger stick effect simultaneously.
Because its typical case of the present invention is applied as the analysis of Residual Pesticides in Farm Produce.In plant sample, often contain a large amount of pigments, such as chlorophyll, xenthophylls, carotenoid etc., these compounds can exert an influence and energy hazard analysis instrument to pesticide residue analysis conventionally, so need to remove.Experiment shows that graphitized carbon black-materials of the present invention are best to the reservation of this class chaff interference, is requisite adsorbent during pesticide multi-residues is analyzed.
the preparation method of polyamino filler of the present invention, comprises the following steps:
In reactor, add expanded polystyrene microballoon, a large amount of concentrated hydrochloric acid, 2mol zinc chloride, 1mol paraformaldehyde, be heated to 70 DEG C, react 24 hours, product filters, and massive laundering, to neutral post-drying, is placed in strong aqua, ethylenediamine, trimethylamine aqueous solution that reactor adds mol ratio 3:2:1, the lower 60 DEG C of reactions of nitrogen protection 48 hours, product filters, and massive laundering, to neutral post-drying, both obtained; Specific surface area is 1000 m
2/ g.
Traditional silica gel bonded SAX, its matrix of PSA material are Bio-sil, and specific surface area is 180-450 m
2/ g scope, the polymeric matrix specific surface area of new material can reach 1000 m
2/ g, can provide more adsorption site like this, and adopting a small amount of new material is the adsorbable 3 times of above compounds of traditional material that are greater than, simultaneously, material surface function group of the present invention be not single traditional primary amine or season amine groups, but two or three amino existence form mixed group be primary amine, secondary amine, tertiary amine group can exist simultaneously, can adsorb phenolic hydroxyl group compounds simultaneously, weak acid compounds and strong acid compounds, and material surface of the present invention also has the phenyl ring group of polymeric material matrix, adsorbable nonpolar and low pole compound, have polar adsorption concurrently, nonpolar suction-operated and anion exchange effect, can reach stick effect by anion exchange (aqueous solution) or polarity absorption (non-polar organic solutions).In the time being used in non-polar solution that (as normal hexane) carries out pre-service, can with-OH ,-NH or-molecule of SH functional group forms hydrogen bond.Anionic organic compounds (such as the compound that contains carboxyl, phenolic hydroxyl group) is had optionally and retained, also can produce huge legendary turtle cooperation use with metallic ion, for extracting metallic ion simultaneously.
the preparation method of hydrophobic grouping bonded silica gel of the present invention, comprises the following steps:
Obtain the golden nanometer particle of 10-15nm diameter by sodium citrate reduction gold chloride method, separately getting 50um full multi-hole blangel joins in reactor, add successively again dimethylbenzene 30ml, hydrosulphonyl silane reagent 20ml, pyridine 15ml heating reflux reaction to lower the temperature after 24 hours, with toluene, methylene chloride, methyl alcohol, acetone washed product post-drying, add in another reactor, add the originally golden nanometer particle of preparation, add again excessive positive stearylmercaptan, heating reflux reaction 48 hours, product filters and washes post-drying with methyl alcohol, acetone, to obtain final product.
Hydrophobic grouping comprises octadecyl, dodecyl, octyl, hexyl, phenyl, butane group, phenethyl, fat base, so-called modification refers to that Silica Surface contains golden nanometer particle as interval bridge, by bridge, hydrophobic grouping and silica gel are linked together, can increase the stability of hydrophobic grouping, the hydrophilic close ester character absorption impurity that can utilize golden nanometer particle surface to have simultaneously, makes sample purification obtain more desirable effect.Hydrophobic grouping of the present invention presents nonpolar or low pole, interact with the alkyl in sample, by the impurity in dispersion force adsorption sample, because most organic compound molecules all contain non-polar group more or less, apolar interaction can make these compounds be retained on the adsorbent that contains hydrophobic grouping.Due to the long-chain effect of hydrophobic grouping, the polarity effect of filler is all less than other Adsorption Phase, thus filler to salt without any reservation.Also can divide subsample desalination to some little molecules and median size with dewatering filling pillar.In addition, in ion analysis, can be by the aqueous solution that contains object ion by adsorbent, the low pole chaff interference thing (such as fat, palycyclic aromatic, phthalic ester) in solution is adsorbed agent and retains, thereby obtains pure solion.The effect being connected except having left and right as the nano Au particle of bridge, also has the function of adsorbing impurity.First nm of gold can, by nonpolar dispersion force absorbed portion middle polarity impurity, comprise hydrogen bond (Hydrogen by polar interaction simultaneously
bonding), dipole moment (Dipole/Dipole), induced dipole is apart from (Induced Dipole/Dipole), π-π (Pi-Pi) and other multiple interaction force, absorption is with the chaff interference of polar group, the larger atom of some electronegativity differences often on polar group, electron cloud has different density between these atoms, make functional group with polarity, this character and then the polar functional group that makes to have on chaff interference and the adsorbent of polar functional group interact.
good effect of the present invention is:solid-phase extraction column is that the residual detection dedicated columns of agriculture is three layers of sorbing material, purify complex sample matrix by selective adsorption, selective elution, remove the impurity such as amino acid, protein, fat, saponin class, polysaccharide, polypeptide compounds, volatile oil, fatty acid, vitamin, trace element and heavy metal, give clean samples of analytical instrument such as GC, HPLC, GC-MS, HPLC-MS, extend the serviceable life of analytical instrument, cost-saving, the accuracy of the residual detection of guarantee agriculture.Be mainly used in the sample pre-treatments step that food, Chinese herbal medicine and plant extracts Pesticide Residues detect; avoid the poor shortcoming of clean-up effect of traditional Solid-Phase Extraction product; greatly improve the clean level of sample; effectively protection analytical instrument; increase the accuracy of sample detection; improve the sensitivity detecting, saved the time, improved testing staff's work efficiency.And there is versatility, low for detected sample substrate selectivity, applicable to the detection of most food samples.
Brief description of the drawings
Fig. 1 is the schematic diagram of solid-phase extraction column of the present invention;
1, import sieve plate; 2, isolation sieve plate; 3, exit sieve plate; 4, extraction column outlet; 5, column jecket; 6, ketjenblack EC layer; 7, polyamino packing layer; 8, hydrophobic grouping bonded silica gel resin bed;
Fig. 2 A is the fresh ginseng extract spectrogram before test example 1 Solid-Phase Extraction column purification of the present invention;
Fig. 2 B is the fresh ginseng extract spectrogram after test example 1 Solid-Phase Extraction column purification of the present invention;
Fig. 3 A is the tea extract spectrogram before test example 2 Solid-Phase Extraction column purification of the present invention;
Fig. 3 B is the tea extract spectrogram after test example 2 Solid-Phase Extraction column purification of the present invention;
Fig. 4 A is the American Ginseng sheet extract spectrogram before test example 3 Solid-Phase Extraction column purification of the present invention;
Fig. 4 B is the American Ginseng sheet extract spectrogram after test example 3 Solid-Phase Extraction column purification of the present invention.
Embodiment
embodiment 1
the preparation of ketjenblack EC
Get sulfuric acid for carbon dust, hydrochloric acid, water, methyl alcohol, acetone and other organic solvent and wash away metal and other organic impurities; dry; quantitatively add 0.1mol/L NaOH to be placed in pyrolytic conversion stove; under high-purity helium protection; be warming up to 1000 DEG C with 10 DEG C/min; be incubated 12 hours, quantitatively add rapidly 0.1mol/L K after being down to room temperature
2hPO
4, be warming up to 2000 DEG C with 20 DEG C/min, be incubated 12 hours, after cooling, repeat to add K
2hPO
4step, product is after massive laundering, and acetone washing and drying, to obtain final product; Through the test of specific surface area analysis instrument, pore volume is 0.8-1.2cm3/g, and specific surface area is 250-400m2/g.
the preparation of polyamino filler
In reactor, add expanded polystyrene microballoon, concentrated hydrochloric acid (50:1; mass ratio), 2mol zinc chloride, 1mol paraformaldehyde, be heated to 70 DEG C, react 24 hours; product filters; be washed to neutral post-drying, be placed in strong aqua, ethylenediamine, trimethylamine aqueous solution that reactor adds mol ratio 3:2:1, the lower 60 DEG C of reactions of nitrogen protection 48 hours; product filters; massive laundering, to neutral post-drying, both obtained: through the test of specific surface area analysis instrument, specific surface area is 1000 m
2/ g.
the preparation of hydrophobic grouping bonded silica gel
Obtain the golden nanometer particle of 10-15nm diameter by sodium citrate reduction gold chloride method, separately getting 50um full multi-hole blangel joins in reactor, add successively again dimethylbenzene 30ml, hydrosulphonyl silane reagent 20ml, pyridine 15ml heating reflux reaction to lower the temperature after 24 hours, with toluene, methylene chloride, methyl alcohol, acetone washed product post-drying, add in another reactor, add the originally golden nanometer particle of preparation, add again excessive positive stearylmercaptan, heating reflux reaction 48 hours, product filters and washes post-drying with methyl alcohol, acetone, to obtain final product.
embodiment 4
Shown in Fig. 1, solid-phase extraction column of the present invention is to be made up of hollow column jecket 1 and isolation sieve plate 2, exit sieve plate 3 and ketjenblack EC layer 6, polyamino packing layer 7, hydrophobic grouping bonded silica gel resin bed 8, wherein,
Be extraction column outlet 4 in the bottom of column jecket 5, made by macromolecular materials such as highdensity tygon or polypropylene, there is inertia feature can tolerate various polarity and non-polar organic solvent; The tube chamber bottom of column jecket 5 is provided with exit sieve plate 3; and ketjenblack EC layer 6(is housed referring to embodiment 1), on it, be pressed into one deck isolation sieve plate 2, reinstall polyamino packing layer 7(referring to embodiment 2: particle diameter 50um; aperture 60; specific surface area is 500 ㎡/g, shape: spherical, and carbon carrying capacity: 7%; pKa:10.1,10.9); be pressed into isolation and pack hydrophobic grouping bonded silica gel resin bed after sieve plate 2 into (referring to embodiment 3: particle diameter 50um, aperture 60, specific surface area; 500 ㎡/g, shape: spherical, carbon carrying capacity: 17%), be finally pressed into again import sieve plate 1;
Import sieve plate 1 forms for esterphilic type macromolecular material sintering, and aperture is at 10-200um, thickness 5-10mm; Exit sieve plate 3 is made for hydrophobic type polymeric film material, aperture 5-100um, thickness 3-6mm.Isolation sieve plate 2 is general sieve plate, aperture 5-100um, thickness 2-5mm; Material is tygon, polypropylene or teflon and makes.
test example 1:
Experiment purpose solid-phase extraction column clean-up effect of the present invention
Sample title fresh ginseng
Test duration 2012.9.10
Experimental procedure 1, get claim 2 grams of samples, add acetone 20 mL, after high-speed homogenization 1 min, with centrifugal 5 min of 8000 rpm, get supernatant, move in concentrated bottle, then add 20 mL acetone in residue, repeat to extract once, merge supernatant, at 35 DEG C, rotation is concentrated near doing, and adds acetonitrile-methylbenzene (3+1) 5 mL dissolved residues, to be clean.
2, with the pre-drip washing solid-phase extraction column of the present invention of 10 mL acetonitrile-methylbenzenes (3+1), efflux discards.By in 5 mL extract impouring solid-phase extraction columns, carry out wash-out with 20 mL acetonitrile-methylbenzenes (3+1).Collect whole eluents in the concentrated bottle of 250mL, in 35 DEG C of water-baths, rotation is concentrated near dry.With acetonitrile dissolving, and be settled to 1 mL, after 0.22 μ m membrane filtration, supply liquid chromatography-mass spectrography/mass spectroscopy.
3, the fresh ginseng extract that does not pass through Solid-Phase Extraction column purification of the present invention is directly carried out to liquid chromatography-mass spectrography/mass spectroscopy.
Experimental result: see spectrogram 2A and Fig. 2 B
Experiment conclusion: after Solid-Phase Extraction column purification of the present invention, disturb obviously and reduce.
test example 2:
Experiment purpose solid-phase extraction column clean-up effect of the present invention
Sample title tealeaves
Test duration 2012.9.10
Experimental procedure 1, get claim 2 grams of samples, add acetone 20 mL, after high-speed homogenization 1 min, with centrifugal 5 min of 8000 rpm, get supernatant, move in concentrated bottle, then add 20 mL acetone in residue, repeat to extract once, merge supernatant, at 35 DEG C, rotation is concentrated near doing, and adds acetonitrile-methylbenzene (3+1) 5 mL dissolved residues, to be clean.
2, with the pre-drip washing solid-phase extraction column of the present invention of 10 mL acetonitrile-methylbenzenes (3+1), efflux discards.By in 5 mL extract impouring solid-phase extraction columns, carry out wash-out with 20 mL acetonitrile-methylbenzenes (3+1).Collect whole eluents in the concentrated bottle of 250mL, in 35 DEG C of water-baths, rotation is concentrated near dry.With acetonitrile dissolving, and be settled to 1 mL, after 0.22 μ m membrane filtration, supply liquid chromatography-mass spectrography/mass spectroscopy.
3, the tea extract that does not pass through Solid-Phase Extraction column purification of the present invention is directly carried out to liquid chromatography-mass spectrography/mass spectroscopy.
Experimental result: see spectrogram 3A and Fig. 3 B.
Experiment conclusion: after Solid-Phase Extraction column purification of the present invention, disturb obviously and reduce
.
test example 3:
Experiment purpose solid-phase extraction column clean-up effect of the present invention
Sample title American Ginseng sheet
Test duration 2012.9.10
Experimental procedure 1, get claim 2 grams of samples, add acetone 20 mL, after high-speed homogenization 1 min, with centrifugal 5 min of 8000 rpm, get supernatant, move in concentrated bottle, then add 20 mL acetone in residue, repeat to extract once, merge supernatant, at 35 DEG C, rotation is concentrated near doing, and adds acetonitrile-methylbenzene (3+1) 5 mL dissolved residues, to be clean.
2, with the pre-drip washing solid-phase extraction column of the present invention of 10 mL acetonitrile-methylbenzenes (3+1), efflux discards.By in 5 mL extract impouring solid-phase extraction columns, carry out wash-out with 20 mL acetonitrile-methylbenzenes (3+1).Collect whole eluents in the concentrated bottle of 250mL, in 35 DEG C of water-baths, rotation is concentrated near dry.With acetonitrile dissolving, and be settled to 1 mL, after 0.22 μ m membrane filtration, supply liquid chromatography-mass spectrography/mass spectroscopy.
3, the American Ginseng sheet extract that does not pass through Solid-Phase Extraction column purification of the present invention is directly carried out to liquid chromatography-mass spectrography/mass spectroscopy.
Experimental result: see spectrogram 4A and Fig. 4 B
Experiment conclusion: after Solid-Phase Extraction column purification of the present invention, disturb obviously and reduce.
test example 4
The clean-up effect of solid-phase extraction column of the present invention is as follows:
SPE :ProElut GPR 1.5g/12ml;
(1) activation: 10 mL acetonitriles: toluene (3:1), efflux discards;
(2) loading: liquid to be clean is added to pillar, collect efflux;
(3) wash-out: 5mL acetonitrile: pour in pillar after toluene (3:1) is washed rotary evaporation bottle, then add 20mL acetonitrile: toluene (3:1), collect efflux;
(4) again dissolve: at 40-45 DEG C, with decompression distillation, collections liquid is concentrated into closely dry, then dries up with nitrogen, then add after 1mL n-hexane dissolution residue for GC-MS analysis.
Conclusion: through the product of appeal treatment and purification, product matrix interference obviously reduces, detects lower bound and greatly reduces, and detects and all can reach <0.01mg/kg for multi-pesticide residue.The recovery reaches >=and 80.00%.Avoid the poor shortcoming of clean-up effect of traditional Solid-Phase Extraction product, greatly improved the clean level of sample, effectively protected analytical instrument; increase the accuracy of sample detection; improve the sensitivity detecting, saved the time, improved testing staff's work efficiency.And there is versatility, low for detected sample substrate selectivity, applicable to the detection of most food samples.
Claims (1)
1. a solid-phase extraction column, comprise void column pipe, sieve plate, adsorbent, it is characterized in that: the bottom at column jecket is pressed into exit sieve plate, pack ketjenblack EC layer into, be pressed into one deck isolation sieve plate, reinstall polyamino packing layer, be pressed into isolation and pack hydrophobic grouping bonded silica glue-line into after sieve plate, be finally pressed into again import sieve plate; The bottom of column jecket is provided with extraction column outlet;
Described import sieve plate is that esterphilic type macromolecular material sintering forms, and aperture is at 10-200 μ m, thickness 5-10mm;
Described exit sieve plate is that hydrophobic type polymeric film material is made, aperture 5-100 μ m, thickness 3-6mm;
Described isolation sieve plate is general sieve plate, aperture 5-100 μ m, thickness 2-5mm; Material is tygon, polypropylene or teflon and makes;
The material of described ketjenblack EC is positive hexatomic ring lamellar structure, and pore volume is 0.8-1.2cm
3/ g, specific surface area is 250-400m
2/ g;
The material matrix of described polyamino packing layer is high crosslinked polystyrene or polymethacrylate polymer, and material surface is primary amine, secondary amine or tertiary amine group, and polymeric matrix specific surface area is 1000 m
2/ g;
The golden nanometer particle that described hydrophobic grouping bonded silica gel is modification.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210525322.9A CN103048400B (en) | 2012-12-10 | 2012-12-10 | Solid-phase extraction column and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210525322.9A CN103048400B (en) | 2012-12-10 | 2012-12-10 | Solid-phase extraction column and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103048400A CN103048400A (en) | 2013-04-17 |
CN103048400B true CN103048400B (en) | 2014-06-18 |
Family
ID=48061115
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210525322.9A Expired - Fee Related CN103048400B (en) | 2012-12-10 | 2012-12-10 | Solid-phase extraction column and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103048400B (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103611334B (en) * | 2013-10-22 | 2016-07-06 | 上海安谱实验科技股份有限公司 | A kind of packing method of siliceous earth column |
TWI500915B (en) * | 2014-07-18 | 2015-09-21 | Agricultural Chemicals And Toxic Substances Res Inst Council Of Agriculture | A quick extraction kit for a procedure of detecting pesticide residues in agricultural products and a method of taking primary test liquid from agricultural sample by the quick extraction kit |
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 |
CN106621464B (en) * | 2016-09-21 | 2019-11-19 | 北京市饲料监察所 | The molecular blotting column of Clenbuterol, salbutamol and Ractopamine is separated simultaneously |
CN107389815A (en) * | 2017-07-12 | 2017-11-24 | 云南中烟工业有限责任公司 | The method and feed liquid dehydration device of lactic acid and butyric acid in a kind of detection tobacco sauce |
CN107748099B (en) * | 2017-10-20 | 2020-09-01 | 西北大学 | Preparation method of self-heating solid-phase saponification extraction column for pretreatment of blood sample |
CN107831229A (en) * | 2017-10-30 | 2018-03-23 | 诺安实力可商品检验(青岛)有限公司 | The assay method that a kind of Pesticides in Tea medicine remains more |
WO2019196023A1 (en) * | 2018-04-11 | 2019-10-17 | 巨研科技股份有限公司 | Rapid screening tubular column |
CN110813266A (en) * | 2018-08-07 | 2020-02-21 | 中国科学院大连化学物理研究所 | Graphitized carbon chromatographic stationary phase and preparation method thereof |
CN109342584A (en) * | 2018-09-29 | 2019-02-15 | 景宁畲族自治县食品药品检验检测中心 | Pesticide residue detection method in a kind of Liu Yazi fruit |
WO2020087209A1 (en) * | 2018-10-29 | 2020-05-07 | 深圳逗点生物技术有限公司 | Porous modified adsorbent for solid-phase extraction, preparation method therefor and solid-phase extraction device |
CN109772878B (en) * | 2019-02-21 | 2021-11-09 | 曲阜师范大学 | Plant extraction device for lead in peripheral soil of heavy metal enterprise |
CN111617514A (en) * | 2019-02-27 | 2020-09-04 | 中国水产科学研究院 | Solid phase extraction column with adjustable sample loading volume |
CN111110712B (en) * | 2019-12-27 | 2022-04-19 | 深圳太太药业有限公司 | Method for reducing pesticide residue in American ginseng extract |
CN111855869A (en) * | 2020-07-28 | 2020-10-30 | 江西省食品检验检测研究院(江西国家果蔬产品及加工食品质量监督检验中心) | Solid phase extraction column for diazepam residue detection |
CN112033786B (en) * | 2020-08-19 | 2021-03-09 | 深圳市环境科学研究院 | Solid-phase extraction method for perfluorinated compounds in environmental water |
CN112098553B (en) * | 2020-09-11 | 2023-06-09 | 安徽中创食品检测有限公司 | Method for detecting capsaicin compounds in duck necks |
CN113274987A (en) * | 2021-05-18 | 2021-08-20 | 贵州金之键高科技材料有限公司 | Functional coordination material and application thereof in natural extract |
WO2023060622A1 (en) * | 2021-10-17 | 2023-04-20 | 南通市台盈新材料科技有限公司 | Enrichment tube for enriching total flavones in epimedium brevicomu maxim leaf extracting solution |
CN114414713A (en) * | 2022-01-19 | 2022-04-29 | 中国计量大学 | Response surface method optimization-based method for extracting and detecting main PAEs (polycyclic aromatic hydrocarbons) in tea |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6541273B1 (en) * | 1999-11-12 | 2003-04-01 | Aventis Cropscience, S.A. | Multiple sorbent cartridges for solid phase extraction |
US20070102358A1 (en) * | 2005-11-09 | 2007-05-10 | Cera Inc. | Solid phase extraction column |
CA2737638A1 (en) * | 2008-09-22 | 2010-03-25 | Brigham Young University | Functionalized graphitic stationary phase and methods for making and using same |
CN101492432A (en) * | 2008-12-01 | 2009-07-29 | 南开大学 | Paclitaxel produced by separation purification of epiphyte with high-efficiency solid phase abstraction-HPLC method |
CN201840909U (en) * | 2010-10-27 | 2011-05-25 | 天津市富集科技有限公司 | Plate-like extractor |
CN102671428A (en) * | 2011-03-18 | 2012-09-19 | 上海市食品药品检验所 | Mixed solid phase extraction column, and preparation method and application thereof |
CN102500134B (en) * | 2011-09-30 | 2015-01-21 | 宁波大学 | Preparation method and application of molecularly imprinted solid phase extraction small column for separating pyrethroid pesticide |
CN102489249A (en) * | 2011-11-25 | 2012-06-13 | 中国检验检疫科学研究院 | Composite solid-phase extraction column used in vegetable pesticide removing, and preparation method thereof |
CN102600811A (en) * | 2012-03-31 | 2012-07-25 | 天津博纳艾杰尔科技有限公司 | Sample pretreatment method for tea leaf pesticide residue detection and tea leaf purification column |
-
2012
- 2012-12-10 CN CN201210525322.9A patent/CN103048400B/en not_active Expired - Fee Related
Non-Patent Citations (6)
Title |
---|
Katherine C. Grabar et al..Preparation and Characterization of Au Colloid Monolayers.《Anal. Chem.》.1995,第67卷(第4期), |
Preparation and Characterization of Au Colloid Monolayers;Katherine C. Grabar et al.;《Anal. Chem.》;19950215;第67卷(第4期);第735-743页 * |
Qishu Qu et al..Silica spheres coated with C18-modified gold nanoparticles for capillary LC and pressurized CEC separations.《Electrophoresis》.2010,第31卷 |
Silica spheres coated with C18-modified gold nanoparticles for capillary LC and pressurized CEC separations;Qishu Qu et al.;《Electrophoresis》;20101231;第31卷;第556-562页 * |
叶芳贵 等.金纳米粒子修饰毛细管硅胶整体柱的制备及其电色谱性能研究.《分析化学》.2011,第39卷(第3期), |
金纳米粒子修饰毛细管硅胶整体柱的制备及其电色谱性能研究;叶芳贵 等;《分析化学》;20110331;第39卷(第3期);第341-345页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103048400A (en) | 2013-04-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103048400B (en) | Solid-phase extraction column and preparation method thereof | |
Badawy et al. | A review of the modern principles and applications of solid-phase extraction techniques in chromatographic analysis | |
Zhang et al. | Separation of chlorogenic acid from honeysuckle crude extracts by macroporous resins | |
Capriotti et al. | Recent advances and developments in matrix solid-phase dispersion | |
Liang et al. | Carbon-based sorbents: carbon nanotubes | |
CN102532390B (en) | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof | |
Duan et al. | Selective trace enrichment of acidic pharmaceuticals in real water and sediment samples based on solid-phase extraction using multi-templates molecularly imprinted polymers | |
Ma et al. | Preparative separation and purification of rosavin in Rhodiola rosea by macroporous adsorption resins | |
Ou et al. | Determination of DL-tetrahydropalmatine in Corydalis yanhusuo by L-tetrahydropalmatine imprinted monolithic column coupling with reversed-phase high performance liquid chromatography | |
EP3199233B1 (en) | Preparation method of a solid phase extraction column comprising graphene or modified graphene | |
Bi et al. | Selective extraction and separation of oxymatrine from Sophora flavescens Ait. extract by silica-confined ionic liquid | |
Lv et al. | Layer-by-layer fabrication of restricted access media-molecularly imprinted magnetic microspheres for magnetic dispersion microextraction of bisphenol A from milk samples | |
Li et al. | Imidazolium ionic-liquid-modified phenolic resin for solid-phase extraction of thidiazuron and forchlorfenuron from cucumbers | |
Sadegh et al. | Ultrasound-assisted solid phase microextraction-HPLC method based on Fe3O4@ SiO2-NH2-molecularly imprinted polymer magnetic nano-sorbent for rapid and efficient extraction of harmaline from Peganum harmala extract | |
Hou et al. | Graphene oxide reinforced ionic liquid-functionalized adsorbent for solid-phase extraction of phenolic acids | |
Zhang et al. | Graphene/polydopamine‐modified polytetrafluoroethylene microtube for the sensitive determination of three active components in Fructus Psoraleae by online solid‐phase microextraction with high‐performance liquid chromatography | |
Manousi et al. | Recent advances in the extraction of triazine herbicides from water samples | |
Wei et al. | Resin adsorption as a means to enrich rare stilbenes and coumarin from pigeon pea leaves extracts | |
CN104083904A (en) | Functionalized porous zinc sulfide nano microsphere solid-phase extraction column and preparation method thereof | |
Atlabachew et al. | A (−)‐norephedrine‐based molecularly imprinted polymer for the solid‐phase extraction of psychoactive phenylpropylamino alkaloids from Khat (Catha edulis Vahl. Endl.) chewing leaves | |
Zheng et al. | A novel metal-organic framework composite, MIL-101 (Cr)@ MIP, as an efficient sorbent in solid-phase extraction coupling with HPLC for tribenuron-methyl determination | |
Xie et al. | Separation of Panax notoginseng saponins on modified rosin ester-bonded silica stationary phase and its mechanism | |
Gutiérrez‐Serpa et al. | Application of MOFs and Their Derived Materials in Solid‐Phase Extraction | |
Wang et al. | Preparation of a nitro-substituted tris (indolyl) methane modified silica in deep eutectic solvents for solid-phase extraction of organic acids | |
CN103433009A (en) | Prometryn molecular imprinting solid phase extraction column and application method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140618 Termination date: 20141210 |
|
EXPY | Termination of patent right or utility model |