CN105413666B - A kind of solid phase extraction filler, solid phase extraction column and its preparation method and application - Google Patents
A kind of solid phase extraction filler, solid phase extraction column and its preparation method and application Download PDFInfo
- Publication number
- CN105413666B CN105413666B CN201510824253.5A CN201510824253A CN105413666B CN 105413666 B CN105413666 B CN 105413666B CN 201510824253 A CN201510824253 A CN 201510824253A CN 105413666 B CN105413666 B CN 105413666B
- Authority
- CN
- China
- Prior art keywords
- solid phase
- phase extraction
- hps
- filler
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses a kind of solid phase extraction filler and preparation method thereof, the filler is bonding beta cyclodextrin and the filler ODS CD HPS of octadecylsilane mixed function group；The invention also discloses the solid phase extraction column filled with filler ODS CD HPS.Described solid phase extraction column can be applied to the pre-treatment of biological sample, be particularly applicable to human body fluid and the middle polarity in tissue homogenate and the enrichment of low pole material and analysis detection.Compared with the existing common solid phase extraction column based on amorphous silica gel filler, the solid phase extraction column of the present invention need to only use the organic solvent of few volume to elute, there is high recovery of extraction, high reappearance, high extraction efficiency to middle polarity and low pole material, and during using the solid phase extraction column pre-treatment, elution is completed with one step of concentration, and the leacheate finally given the step such as blows without extra heating nitrogen and enrichment concentration can be achieved.
Description
Technical field
The invention belongs to instrument analysis technology field, and in particular to a kind of solid phase extraction filler, solid phase extraction column and its
Preparation method and application.
Background technology
The complicated component of biological sample, matrix interference is serious, and the endogenous material in biological sample is analyzed and detected, always
It is the focus of analysis worker.Existing biological sample pre-treating method includes organic solvent precipitation method (OSP), liquid liquid and extracted
Take (LLE), SPE (SPE), SPME (SPME) etc..Wherein SPE is most widely used.
Solid phase extraction, is the main selective absorption by solid phase filler to sample component and desorption process, realization pair
Separation, purifying and the enrichment of sample, its main purpose are to reduce sample substrate interference, raising detection sensitivity.For convenience,
SPE typically uses solid phase extraction column.But when specifically used, the existing solid phase extraction based on amorphous silica gel filler
Take pillar exist extraction functional group it is single, sample capacity is relatively low, elution with concentration can not a step complete technical problem.
The content of the invention
An object of the present invention is to provide a kind of solid phase extraction filler and preparation method thereof, its functional group being bonded
It is many.
To achieve the above object, solid phase extraction filler ODS-CD-HPS of the invention, it is bonded with beta-schardinger dextrin (β-CD)
With octadecylsilane (ODS) mixed function group.
The preparation method of the solid phase extraction filler ODS-CD-HPS, comprises the following steps：
(1) material C D-HPS synthesis：After vacuum dried (0.1~0.2mmHg, 110~120 DEG C, 12~14h)
22~25 grams of beta-schardinger dextrins are dissolved in 500~600 milliliters of anhydrous dimethyl formamides, are added after 24~26 milligrams of sodium hydrides,
It is stirred at room temperature under nitrogen protection transparent to reaction solution；Then to 3.5~4.2 milliliters of 3- (2,3- epoxies third of addition in the reaction solution
Oxygen) propyl trimethoxy silicane, under nitrogen protection in 70 DEG C reaction 5~6 hours after, add 20~22 grams it is vacuum dried
Activated silica gel afterwards, reacts 24~26 hours in 110~120 DEG C；Question response mixed liquor is cooled to after room temperature, uses G4 sand core funnels
Filtering, filter cake is washed with dimethylformamide, water, methanol successively；Finally filter cake is placed in soxhlet's extraction device, using acetone to be molten
Agent is extracted 12~14 hours, that is, bonded silica gel CD-HPS is made.
(2) filler ODS-CD-HPS synthesis：After vacuum dried (0.1~0.2mmHg, 80~90 DEG C, 12~14h)
20~22 grams of bonded silica gel CD-HPS be dispersed in 500~600 milliliters of nothings containing 0.2~0.3 milliliter of anhydrous triethylamine
In water-toluene, 15~18 milliliters of octadecyl trimethoxysilanes are subsequently added, 24~26 are heated to reflux under nitrogen protection small
When；Question response mixed liquor is cooled to after room temperature, is filtered with G4 sand core funnels, and filter cake uses toluene, isopropanol, methanol, water, third successively
Ketone is washed；Finally filter cake is placed in soxhlet's extraction device, using acetone as solvent extraction 12~14 hours, that is, product bonded silica is made
Glue ODS-CD-HPS.
Bonded amount of the beta-schardinger dextrin in CD-HPS is 185~200 μm of ol/g, the octadecyl silicon
Bonded amount of the alkane in ODS-CD-HPS is 218~230 μm of ol/g.
The silica gel is porous spherical silica gel, and particle diameter is 10~20 μm, and aperture is
The second object of the present invention is to provide a kind of solid phase extraction column for filling above-mentioned filler, and its sample capacity is high.
To achieve the above object, a kind of solid phase extraction column of the invention, including empty tube column and filler, the filler is key
Close silica gel solid phase extraction filler ODS-CD-HPS.
Filler ODS-CD-HPS is directly filled inside the empty tube column of the solid phase extraction column, filler two ends are sealed by sieve plate
Firmly, prevent mixed fillers from leaking outside, pillar one end is sample or solvent inlet, the pillar other end is sample or solvent flow export.
The volume of the empty tube column is 1~6 milliliter, and the loading of the filler ODS-CD-HPS is 8~50 milligrams, filling
Post bed thickness is 2~3 millimeters.
The solid phase extraction filler that the present invention is provided be the porous spherical silica gel using high-purity as raw material, through be chemically bonded β-
Two kinds of functional groups of CD and ODS are prepared.Due to two kinds of mixed function groups β-CD and ODS being bonded on same silica gel particle
Synergy, and use the small spherical silica gel matrix of particle diameter so that filling the solid phase extraction column of the bonding filler has
Very high sample capacity.
The third object of the present invention is to provide application of the above-mentioned solid phase extraction pillar in biological sample pre-treating method, behaviour
Work is simple, and elution is completed with concentration one step of energy, can quickly be extracted and enriched biological sample.
To achieve the above object, the application during the solid phase extraction column of the invention provided is handled before biological sample, mainly
It is to play extraction and enrichment middle polarity and low pole material.
Described biological sample includes but are not limited to human body fluid and tissue is homogenized, and described body fluid is primarily referred to as serum
And urine.
Application in the biological sample pre-treating method that pillar is extracted based on above-mentioned solid phase of the present invention, including following step
Suddenly：
(1) activator is added in ODS-CD-HPS solid phase extraction columns, the volume of the activator is the empty tube column
1/3 times~1 times of volume；The activator is selected from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane
At least one of alkane, carbon tetrachloride, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane；
(2) with solid phase extraction column described in ultrapure water balance, the volume of the ultra-pure water and the volume phase of the activator
Together；
(3) by the solid phase extraction column after pending biological sample injection balance；The life for treating pre-treatment
The volume of thing sample is 1/3 times~1 times of the volume of the empty tube column；
(4) with the solid phase extraction column after milli-Q water loading, the volume of the ultra-pure water is the empty tube column
Volume 1/3~2/3；
(5) with solid phase extraction column described in nitrogen or air blow drying；
(6) solid phase extraction column is eluted with eluent, the volume of the eluent is the splitter
1/10~1/30 times of volume；The eluent is selected from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane
At least one of alkane, carbon tetrachloride, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane；
(7) the leacheate direct injected for obtaining step (6) analyzes steroid hormone and its generation into LC-MS/MS analyzers
Thank to thing.
Compared with the existing common solid phase extraction column based on amorphous silica gel filler, solid phase extraction column of the invention
Only the organic solvent of few volume need to be used to elute, there is high recovery of extraction, high reproduction to middle polarity and low pole material
Property, high extraction efficiency.And the solid phase extraction column is used, elution is completed with one step of concentration, and the leacheate finally given need not
Extra heating nitrogen the step such as blows and realizes enrichment concentration, it is adaptable to which automatic sample pre-treatment instrument is to all kinds of human body fluids and organizes even
The quick on-line extraction of multiclass compound in slurry and enrichment.
Brief description of the drawings
Fig. 1 is LC-MS/MS analysis of spectra after three kinds of typical steroid hormone A4, T, DHT extractions.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Solid phase extraction filler ODS-CD-HPS preparation method, comprises the following steps：
(1) material C D-HPS synthesis：22 grams of beta-schardinger dextrins after vacuum dried (0.1mmHg, 110 DEG C, 14h) are molten
In 500 milliliters of anhydrous dimethyl formamides, add after 24 milligrams of sodium hydrides, cause reaction solution shape is stirred at room temperature under nitrogen protection
Into clear solution；Then to 3.5 milliliters of 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicanes are added in the reaction solution, in nitrogen
Under protection in 70 DEG C reaction 5 hours after, add 20 grams it is vacuum dried after activated silica gel (particle diameter be 10~20 μm, aperture
For), reacted 24 hours in 120 DEG C；Question response mixed liquor is cooled to after room temperature, is filtered with G4 sand core funnels, filter cake is successively
Washed with dimethylformamide, water, methanol；Finally filter cake is placed in soxhlet's extraction device, using acetone as solvent extraction 12 hours,
Bonded silica gel CD-HPS is made.
(2) filler ODS-CD-HPS synthesis：By 20 grams of CD-HPS after vacuum dried (0.1mmHg, 80 DEG C, 14h)
Silica gel is dispersed in 500 milliliters of dry toluenes containing 0.2 milliliter of anhydrous triethylamine, is subsequently added 15 milliliters of octadecyls
Trimethoxy silane, is heated to reflux 24 hours under nitrogen protection；Question response mixed liquor is cooled to after room temperature, uses G4 sand core funnels
Filtering, filter cake is washed with toluene, isopropanol, methanol, water, acetone successively；Finally filter cake is placed in soxhlet's extraction device, with acetone
For solvent extraction 12 hours, that is, product bonded silica gel ODS-CD-HPS is made.Its chemical synthesis route is as follows：
Material C D-HPS carries out elementary analysis, as a result containing C 8.9%, containing H 1.9%, to disclose beta-schardinger dextrin in CD-
Bonded amount in HPS is 185 μm of ol/g.
Filler ODS-CD-HPS carries out elementary analysis, as a result containing C 14.6%, containing H 3.2%, to disclose ODS in ODS-
Bonded amount in CD-HPS is 218 μm of ol/g.
Embodiment 2
Solid phase extraction filler ODS-CD-HPS preparation method, comprises the following steps：
(1) material C D-HPS synthesis：25 grams of beta-schardinger dextrins after vacuum dried (0.2mmHg, 120 DEG C, 12h) are molten
In 600 milliliters of anhydrous dimethyl formamides, add after 26 milligrams of sodium hydrides, be stirred at room temperature under nitrogen protection saturating to reaction solution
It is bright；Then in the reaction solution add 4.2 milliliters of 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicanes, under nitrogen protection in
70 DEG C reaction 6 hours after, add 22 grams it is vacuum dried after activated silica gel (particle diameter be 10~20 μm, aperture is),
Reacted 26 hours in 110 DEG C；Question response mixed liquor is cooled to after room temperature, is filtered with G4 sand core funnels, and filter cake uses dimethyl successively
Formamide, water, methanol washing；Finally filter cake is placed in soxhlet's extraction device, using acetone as solvent extraction 14 hours, that is, key is made
Close silica gel CD-HPS.
(2) filler ODS-CD-HPS synthesis：By 22 grams of bonded silicas after vacuum dried (0.2mmHg, 90 DEG C, 12h)
Glue CD-HPS is dispersed in 600 milliliters of dry toluenes containing 0.3 milliliter of anhydrous triethylamine, is subsequently added 18 milliliter 18
Alkyl trimethoxysilane (ODS), is heated to reflux 26 hours under nitrogen protection；Question response mixed liquor is cooled to after room temperature, is used
G4 sand core funnels are filtered, and filter cake is washed with toluene, isopropanol, methanol, water, acetone successively；Filter cake is finally placed in soxhlet's extraction
In device, using acetone as solvent extraction 14 hours, that is, product bonded silica gel ODS-CD-HPS is made.
Material C D-HPS carries out elementary analysis, as a result containing C 9.6%, containing H 2.0%, to disclose beta-schardinger dextrin in CD-
Bonded amount in HPS is 200 μm of ol/g.
Filler ODS-CD-HPS carries out elementary analysis, as a result containing C 15.4%, containing H 3.4%, to disclose ODS in ODS-
Bonded amount in CD-HPS is 230 μm of ol/g.
Embodiment 3
The making of solid phase extraction column, comprises the following steps：One 1 milliliter of empty tube column is taken, 8~10 milligrams are directly filled
ODS-CD-HPS fillers form close uniform post bed, and filler two ends are sealed by sieve plate, prevent filler from leaking outside, pillar one end is sample
Product or solvent inlet, the pillar other end are sample or solvent flow export, and sample or solvent inject from pillar one end.
Embodiment 4
The making of solid phase extraction column, comprises the following steps：One 3 milliliters of empty tube column is taken, 20~25 millis are directly filled
Gram ODS-CD-HPS fillers form close uniform post bed, and filler two ends are sealed by sieve plate, prevent filler from leaking outside, pillar one end is
Sample or solvent inlet, the pillar other end are sample or solvent flow export, and sample or solvent inject from pillar one end.
Embodiment 5
The making of solid phase extraction column, comprises the following steps：One 6 milliliters of empty tube column is taken, 40~50 millis are directly filled
Gram ODS-CD-HPS fillers form close uniform post bed, and filler two ends are sealed by sieve plate, prevent filler from leaking outside, pillar one end is
Sample or solvent inlet, the pillar other end are sample or solvent flow export, and sample or solvent inject from pillar one end.
Embodiment 6
Based on the application in the human body fluid of solid phase extraction column made from embodiment 4 or tissue homogenate pre-treating method,
Comprise the following steps：
(1) 3 ml methanols are added in ODS-CD-HPS solid phase extraction columns；
(2) with solid phase extraction column described in 3 milliliters of ultrapure water balances；
(3) by the solid phase extraction column after 1~3 milliliter of pending human body fluid or tissue homogenate injection balance
In；
(4) with the solid phase extraction column after 1~2 milliliter of milli-Q water loading；
(5) with solid phase extraction column described in nitrogen or air blow drying；
(6) solid phase extraction column is eluted with 0.1 ml methanol of exact volume,
(7) the leacheate direct injected for obtaining step (6) analyzes steroid hormone and its generation into LC-MS/MS analyzers
Thank to thing.
It can be seen that, being blown etc. without extra heating nitrogen can be straight with 0.1 milliliter of eluent solvent after step, 1~3 milliliter of sample extraction
Connect by 10~30 times of enrichment.The analyses of the LC-MS/MS after three kinds of typical steroid hormones are extracted through the above method are shown in Fig. 1
Spectrogram.As seen from the figure, determinand steroid hormone A4, T, DHT mass spectrum response are obvious in leacheate increases, and interference matrix substantially subtracts
Few, test limit scope is significantly increased, and easy to operate, and leacheate concentration is quick.
Claims (8)
1. a kind of solid phase extraction filler, it is characterised in that it is bonded with beta-schardinger dextrin and octadecylsilane mixed function group；
It is prepared by following steps：
（1）Material C D-HPS synthesis：22~25 grams of beta-schardinger dextrins after will be vacuum dried be dissolved in 500~600 milliliters it is anhydrous
In dimethylformamide, add after 24~26 milligrams of sodium hydrides, be stirred at room temperature under nitrogen protection transparent to reaction solution；Then to
3.5~4.2 milliliters of 3- are added in the reaction solution（The oxygen of 2,3- epoxies third）Propyl trimethoxy silicane, under nitrogen protection in 70oC
Reaction 5~6 hours after, add 20~22 grams it is vacuum dried after activated silica gel, in 110~120oC reactions 24~26 are small
When；Question response mixed liquor is cooled to after room temperature, is filtered with G4 sand core funnels, and filter cake is washed with dimethylformamide, water, methanol successively
Wash；Finally filter cake is placed in soxhlet's extraction device, using acetone as solvent extraction 12~14 hours, that is, bonded silica gel CD- is made
HPS；
（2）Filler ODS-CD-HPS synthesis：20~22 grams of bonded silica gel CD-HPS after will be vacuum dried are dispersed in
In 500~600 milliliters of dry toluenes containing 0.2~0.3 milliliter of anhydrous triethylamine, 15~18 milliliters of octadecyls are subsequently added
Trimethoxy silane, is heated to reflux 24~26 hours under nitrogen protection；Question response mixed liquor is cooled to after room temperature, uses G4 cores
Funnel is filtered, and filter cake is washed with toluene, isopropanol, methanol, water, acetone successively；Finally filter cake is placed in soxhlet's extraction device, with
Acetone is solvent extraction 12~14 hours, that is, product bonded silica gel ODS-CD-HPS is made.
2. solid phase extraction filler according to claim 1, it is characterised in that bonding of the beta-schardinger dextrin in CD-HPS
Measure as 185~200 μm of ol/g, bonded amount of the octadecyl trimethoxysilane in ODS-CD-HPS is 218~230 μ
mol/g。
3. solid phase extraction filler according to claim 1 or 2, it is characterised in that the activated silica gel is porous spherical silicon
Glue, particle diameter is 10~20 μm, and aperture is 100~120.
4. a kind of solid phase extraction column, including empty tube column and filler, it is characterised in that the filler is described in claim 1 or 2
Solid phase extraction filler ODS-CD-HPS.
5. solid phase extraction column according to claim 4, it is characterised in that inside the empty tube column of the solid phase extraction column
Filler ODS-CD-HPS is directly filled, filler ODS-CD-HPS two ends are sealed by sieve plate, pillar one end is that sample or solvent inject
Mouthful, the pillar other end is sample or solvent flow export.
6. solid phase extraction column according to claim 5, it is characterised in that the volume of the empty tube column is 1~6 milliliter,
The loading of the filler ODS-CD-HPS is 8~50 milligrams, and packed column bed thickness is 2~3 millimeters.
7. the application based on the solid phase extraction column described in any one of claim 4 to 6 in biological sample pre-treating method.
8. application of the solid phase extraction column according to claim 7 in biological sample pre-treating method, it is characterised in that
Comprise the following steps：
（1）Activator is added in ODS-CD-HPS solid phase extraction columns, the volume of the activator is the appearance of the empty tube column
Long-pending 1/3 times~1 times；The activator is selected from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, four
At least one of chlorination carbon, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane；
（2）With solid phase extraction column described in ultrapure water balance, the volume of the ultra-pure water is identical with the volume of the activator；
（3）By after in the solid phase extraction column after the biological sample injection balance of pre-treatment；Treat the biological sample of pre-treatment
Volume be 1/3 times~1 times of volume of the empty tube column；
（4）With the solid phase extraction column after milli-Q water loading, the volume of the ultra-pure water is the appearance of the empty tube column
Long-pending 1/3~2/3；
（5）With solid phase extraction column described in nitrogen or air blow drying；
（6）The solid phase extraction column is eluted with eluent, the volume of the eluent is the volume of the empty tube column
1/10~1/30 times；The eluent is selected from methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, chloroform, dichloromethane, four
At least one of chlorination carbon, ether, toluene, benzene, hexamethylene, petroleum ether, hexane, pentane；
（7）By step（6）Obtained leacheate direct injected analyzes steroid hormone and its metabolin into LC-MS/MS analyzers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510824253.5A CN105413666B (en) | 2015-11-24 | 2015-11-24 | A kind of solid phase extraction filler, solid phase extraction column and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510824253.5A CN105413666B (en) | 2015-11-24 | 2015-11-24 | A kind of solid phase extraction filler, solid phase extraction column and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105413666A CN105413666A (en) | 2016-03-23 |
| CN105413666B true CN105413666B (en) | 2017-10-24 |
Family
ID=55492468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510824253.5A Expired - Fee Related CN105413666B (en) | 2015-11-24 | 2015-11-24 | A kind of solid phase extraction filler, solid phase extraction column and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105413666B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018574A (en) * | 2016-05-05 | 2016-10-12 | 同济大学 | Fractionation device for carrying out simple and rapid ion exchange on peptide or protein mixture |
| CN110938053B (en) * | 2019-12-23 | 2022-08-05 | 南京中医药大学翰林学院 | Extraction method of ginkgo element |
| CN111175422A (en) * | 2020-03-30 | 2020-05-19 | 南通市疾病预防控制中心 | Cyclodextrin polymer for polycyclic aromatic hydrocarbon solid phase extraction, solid phase extraction column and solid phase extraction method thereof |
| CN112611828B (en) * | 2020-12-29 | 2021-10-08 | 大连润生康泰医学检验实验室有限公司 | Method for purifying, enriching and detecting steroid hormone in blood |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394673A (en) * | 2002-07-18 | 2003-02-05 | 武汉大学 | Application of beta-cyclodextrin bonded silicone gel as solid phase extraction adsorption medium |
| CN102350327A (en) * | 2011-08-12 | 2012-02-15 | 天津博纳艾杰尔科技有限公司 | Novel hydrophilic C18 filling material and its solid phase extraction column |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1990310A1 (en) * | 2007-04-23 | 2008-11-12 | Trasis S.A. | Method for the preparation of reactive 18F fluoride, and for the labeling of radiotracers, using a modified non-ionic solid support and without any evaporation step |
-
2015
- 2015-11-24 CN CN201510824253.5A patent/CN105413666B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394673A (en) * | 2002-07-18 | 2003-02-05 | 武汉大学 | Application of beta-cyclodextrin bonded silicone gel as solid phase extraction adsorption medium |
| CN102350327A (en) * | 2011-08-12 | 2012-02-15 | 天津博纳艾杰尔科技有限公司 | Novel hydrophilic C18 filling material and its solid phase extraction column |
Non-Patent Citations (1)
| Title |
|---|
| Molecularly imprinted polymer prepared with bonded β-cyclodextrin and acrylamide on functionalized silica gel for selective recognition of tryptophan in aqueous media;Lei Qin et al.;《Journal of Chromatography A》;20080208;第1187卷;第94-102页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105413666A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105413666B (en) | A kind of solid phase extraction filler, solid phase extraction column and its preparation method and application | |
| Xu et al. | Magnetic solid-phase extraction of phthalate esters (PAEs) in apparel textile by core–shell structured Fe3O4@ silica@ triblock-copolymer magnetic microspheres | |
| CN109293938A (en) | Prepare the composite material of metallic framework compound binding molecule imprinted polymer | |
| CN207440022U (en) | A kind of device of the outer free drug of liposome and liposome in separated plasma | |
| Yuan et al. | Fe3O4/graphene molecularly imprinted composite for selective separation of catecholamine neurotransmitters and their analysis in rat brain tissues | |
| CN101864021B (en) | Preparation method of nanometer silicon gel surface gastrodin molecular engram polymers | |
| Xu et al. | Preparation and characterization of magnetic chitosan microsphere sorbent for separation and determination of environmental estrogens through SPE coupled with HPLC | |
| Chen et al. | The synthesis of a dual-template surface molecularly imprinted polymer based on silica gel and its application in the removal of pesticides from tea polyphenols | |
| CN109225171A (en) | A kind of preparation method and application of the modified organic inorganic hybridization integral post of surface ion imprinted polymer | |
| Zhu et al. | The preparation and the recognition property of molecularly imprinted polymer of podophyllotoxin | |
| Ji et al. | Water-compatible micron-sized monodisperse molecularly imprinted beads for selective extraction of five iridoid glycosides from Cornus officinalis fructus | |
| CN109092275A (en) | A kind of preparation method of the alkyl linked silica filler of novel hydrophilic | |
| CN103007905A (en) | Tetraazacalix [2] arene [2] triazine bonded silica gel solid phase extraction material, preparation method and application thereof | |
| Bagheri et al. | Role of precursors and coating polymers in sol–gel chemistry toward enhanced selectivity and efficiency in solid phase microextraction | |
| CN108872447A (en) | The detection method of thyroid imhibitor based on hydrophily Solid Phase Extraction | |
| US8043564B2 (en) | Copolymer, and adsorbent or concentrating medium and needle for solid phase microextraction prepared using the copolymer | |
| CN104910339B (en) | Magnetic molecularly imprinted poly ion liquid and its production and use for detecting Ractopamine | |
| Belenguer-Sapiña et al. | A poly (glycidyl-co-ethylene dimethacrylate) nanohybrid modified with β-cyclodextrin as a sorbent for solid-phase extraction of phenolic compounds | |
| CN105561958B (en) | Ionic liquid bonded silica gel for enrichment and purification of shellfish toxins and preparation method thereof | |
| Qin et al. | Magnetic molecularly-imprinted microspheres with a core-shell structure for the extraction of catalpol from both Rehmannia glutinosa Libosch and biological samples | |
| CN104208905B (en) | Silver ion-loaded solid-phase extraction column and preparation and application thereof | |
| Yu et al. | Novel polymeric monolith materials with a β‐cyclodextrin‐graphene composite for the highly selective extraction of methyl jasmonate | |
| Yılmaz et al. | Preconcentration of indapamide from human urine using molecularly imprinted solid‐phase extraction | |
| CN105801751A (en) | Preparation and application of MIP (molecularly imprinted polymer) with tropane alkaloid drug specificity | |
| CN103520955B (en) | Molecular-imprinting integral stirring and adsorbing bar and preparation 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171024 Termination date: 20191124 |