CN104785197A - Preparation method of mixed hemi-micelle solid phase extractant based on Fe3O4 magnetic nanoparticles - Google Patents
Preparation method of mixed hemi-micelle solid phase extractant based on Fe3O4 magnetic nanoparticles Download PDFInfo
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Abstract
The invention relates to a preparation method of a mixed hemi-micelle solid phase extractant based on Fe3O4 magnetic nanoparticles. The preparation process mainly comprises three steps: preparation of Fe3O4 magnetic nanoparticles; preparation of a mixed hemi-micelle solid phase extractant; and the process of solid phase extraction. A synthetic method provided by the invention is simple and easy to control. The prepared magnetic mixed hemi-micelle solid phase extractant has high extraction efficiency and is simple to operate. Pretreatment time of samples can be greatly shortened; a lot of poisonous and harmful solvents are not required; pollution is avoided; and loss of samples can be effectively reduced. The mixed hemi-micelle solid phase extractant is very suitable for rapid sample analysis requirements.
Description
Technical field
The invention belongs to new material scientific domain, particularly one is based on Fe
3o
4the preparation method of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle, and using it as sample pre-treatments material, extract and the compound in enriched biological sample.
Background technology
The SPE of mixing hemi-micelle is a kind of emerging solid phase extraction techniques.This technology is the effect by electrostatic attraction, hydrophobic force etc., the surface various ionic surfactant or ionic liquid being adsorbed in various metal oxide carrier forms mixing hemi-micelle, and in this, as the adsorbent of SPE, enrichment is carried out to the determinand in sample, purifies and concentrate.Compared with traditional environmental sample preprocess method, it is high that this novel Sample Pretreatment Technique Used has extraction efficiency, easy and simple to handle, greatly can shorten the pretreatment time of sample, do not need a large amount of poisonous and harmful solvent, avoid polluting, there is the feature that effect reduces sample loss simultaneously, be very suitable for the requirement of rapid sample analysis.
Although mixing hemi-micelle solid phase extraction techniques has various advantage, due to the Al that this adsorbent is used
2o
3and SiO
2the particle of carrier is relatively large, and specific area is little, and therefore in the analytic process of reality, the consumption of adsorbent is more.And this kind of technology many employing dresses column operation, in the application of reality, step is loaded down with trivial details, operates consuming time, particularly when the research being applied to complicated substrate sample measures, also needs more loaded down with trivial details time-consuming sample pretreatment process.
Magnetic nanoparticle has that specific area is large, surface is easy to the advantages such as modifications and magnetic nanoparticle has the characteristic that can be easy to separation when externally-applied magnetic field.People are applied to the trace even concentration and separation of trace analysis thing in chromatogram pretreatment process, particularly bulk sample.
Ionic liquid is made up of ion completely, be the salt of liquid condition in room temperature or near room temperature, therefore also referred to as ionic liquid at room temperature.Its design feature is that cation is larger and asymmetric, and anion is less.As a kind of novel green solvent, compared with traditional molecular solvent, ionic liquid has the advantage of many uniquenesses, forces down as surveyed steam at ambient temperature, not volatile; Liquid temperature wide ranges is from-100 DEG C to 300 DEG C, even higher; Good stability, nonflammable; Solvability is strong; Good conductivity; Change by structure regulates its physicochemical property; Can recycle.Current, ionic liquid has a very wide range of application in Synthetic Organic Chemistry, catalytic chemistry, electrochemistry, new material and analytical chemistry etc.Ionic surfactant refers to have fixing hydrophilic and oleophilic group, aligns, and can make the material that surface tension significantly declines in the surface energy of solution.It is a large class organic compound, and their character has characteristic, and application is very flexible, extensive, has very large practical value and theory significance.
In this invention, nano particle can by its larger specific area as a kind of excellent adsorbent, and ionic liquid and surfactant are due to its respective characteristic, and the solvent that can be used as a class green is applied in the sample treatment of different substrates.In order to verify that this extractant is applied to the feasibility of SPE, have selected three kinds of flavonoids medicines and carry out enrichment as object, flavonoids is by C
6-C
3-C
6the compound general name formed, its basic structure is a series of compounds that two phenyl ring (respectively called after A ring and B ring) are interconnected by 3 carbon atoms.Flavonoids medicine has multiple pharmacological action, such as, anti-oxidant, anti-inflammatory, anticancer etc.Cyanidenon, Quercetin and the Kaempferol in urine is measured in conjunction with HPLC/UV method.
Summary of the invention
Technical problem:
The object of the invention is to overcome the shortcoming in traditional Sample Pretreatment Technique, provide a kind of based on Fe
3o
4the preparation method of magnetic nanoparticle mixing hemi-micelle solid extracting agent, the Magnetic solid phases extractant utilizing the method to prepare is applied to the extraction of flavonoids medicine in biological sample, and this extractant has the following advantages: Solvent quantity is few, and extraction efficiency is high; Environmental friendliness, with low cost; Simple to operate, rate of extraction is fast; Good stability, renewable and recycling.In addition, this extracting process is simply accurate, and method choice is good, does not have the interference of protein and other endogenous material in urine.
Technical scheme:
1. technical solution of the present invention is:
A. based on Fe
3o
4the preparation of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle: one, solvent-thermal method prepares Fe
3o
4magnetic nanoparticle: ferric trichloride, sodium acetate and PAA join in the mixed solvent be made up of ethylene glycol and diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace to react, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use; Two, preparation mixing hemi-micelle solid extracting agent: the Fe that step one is prepared
3o
4magnetic nanoparticle joins in the cushioning liquid of certain pH value, then adds a certain amount of surfactant or ionic liquid, and ultrasonic rear standing, magnetic field is separated removing supernatant, obtains solid extracting agent.
B. based on Fe
3o
4@SiO
2the preparation of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle: one, solvent-thermal method prepares Fe
3o
4magnetic nanoparticle: ferric trichloride, sodium acetate and PAA join in the mixed solvent be made up of ethylene glycol and diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace to react, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use; Two, Fe
3o
4@SiO
2the preparation of magnetic nanoparticle: by the Fe prepared in step 2
3o
4magnetic nanoparticle joins in ethanol and deionized water, ultrasonic, then adds a certain amount of ammoniacal liquor and ethyl orthosilicate successively, stir lower reaction, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use.Three, preparation mixing hemi-micelle solid extracting agent: the Fe that step 2 is prepared
3o
4@SiO
2magnetic nanoparticle joins in the cushioning liquid of certain pH value, then adds a certain amount of surfactant or ionic liquid, and ultrasonic rear standing, magnetic field is separated removing supernatant, obtains solid extracting agent.
2. devise a simple Magnetic Isolation flow process, and the enrichment being applied to flavonoids medicine in biological sample be separated.The urine sample containing finite concentration medicine is added to the plastic tube being placed with magnetic mixing hemi-micelle solid extracting agent, ultrasonic rear standing, magnetic field is separated removing urine, the analysis thing organic solvent of enrichment is from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyzes after filtration by liquid chromatogram.
3. in step a described in () and b (), the molar concentration of ferric trichloride is 0.05 ~ 0.5mol/L, and the ratio of ethylene glycol and diethylene glycol is 1: 5 ~ 5: 1, and the reaction time is 4 ~ 24h.
4. in step b described in (two), Fe
3o
4the consumption of magnetic nanoparticle is 0.5 ~ 1.5g, and the volume of ethanol is 100 ~ 200mL, and the volume of deionized water is 25 ~ 35mL, ultrasonic time is 5 ~ 30min, the volume of ammoniacal liquor is 1 ~ 5mL, and the volume of ethyl orthosilicate is 2 ~ 10mL, and the reaction time is 4 ~ 12h.
5., in step a described in (two) and b (three), surfactant is lauryl sodium sulfate (SDS), halogenated phosphates (CPC), Cetyltrimethylammonium bromide (OTMABr), softex kw (CTAB); Ionic liquid is chlorination 1-hexyl-3-methylimidazole (C
6mimCl), bromination 1-hexyl-3-methylimidazole (C
6mimBr), chlorination 1-dodecyl-3-methylimidazole (C
12mimCl), bromination 1-dodecyl-3-methylimidazole (C
12mimBr), chlorination 1-cetyl-3-methylimidazole (C
16mimCl), bromination 1-cetyl-3-methylimidazole (C
16mimBr).The consumption of magnetic carbon nano-tube is 2 ~ 10mg, and the consumption of surfactant is 1 ~ 20mg, and cushioning liquid is buffer solution of sodium phosphate, buffer solution of potassium phosphate, Tris-HCl cushioning liquid; The pH of cushioning liquid is respectively 2.0 ~ 10.0,2.0 ~ 10.0,6.8 ~ 9.0; The concentration of cushioning liquid is 0.02 ~ 0.5M, and the volume of cushioning liquid is 1.0 ~ 10.0mL.
6. require described in 2, the volume adding urine is 1 ~ 10mL; Ultrasonic time is 2 ~ 10min; Time of repose is 2 ~ 10min; The kind of organic solvent is methyl alcohol, and containing the methyl alcohol of 1% acetic acid, containing the methyl alcohol of 2% acetic acid, acetonitrile, containing the acetonitrile of 1% acetic acid, containing the acetonitrile of 2% acetic acid; The volume of organic solvent used is 0.5 ~ 3mL; Wash number is 1 ~ 5 time.
Accompanying drawing explanation
Fig. 1 be the present invention prepare based on Fe
3o
4@SiO
2the formation of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle and be applied to the schematic flow sheet of solid phase extraction concentration medicine.
Fig. 2 is the Fe that the present invention obtains
3o
4@SiO
2surface sweeping Electronic Speculum (a) of magnetic nanoparticle and transmission electron microscope (b) spectrogram.
Fig. 3 is C under pH=10.0 condition
16mimBr is at Fe
3o
4@SiO
2the adsorption curve on magnetic nanoparticle surface.
Fig. 4 is Fe
3o
4@SiO
2the consumption of magnetic nanoparticle is for the impact of three kinds of flavonoids medicine rate of recovery in urine.
Fig. 5 is that urine sample obtains through the present invention the chromatogram obtained after magnetic extractant enrichment, and (a) is the urine sample containing 5.0ng/mL tri-kinds of flavonoids medicines; B () is the urine sample containing 10.0ng/mL tri-kinds of flavonoids medicines.
Specific embodiments
One, example is prepared
Following examples are citings more of the present invention, should not be seen as limitation of the invention.
Embodiment 1
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By above-mentioned for 4.0mg obtained Fe
3o
4magnetic nanoparticle, the buffer solution of sodium phosphate of 1.0mg softex kw (CTAB) and 2ml0.02M pH=7.0 joins in plastic tube successively, mixed liquor ultrasonic disperse 5min, balance leaves standstill 10min again, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 2s, then add 2mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 2min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the methyl alcohol of 1% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 2
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By above-mentioned for 4.0mg obtained Fe
3o
4magnetic nanoparticle, 3.0mg chlorination 1-dodecyl-3-methylimidazole (C
12mimCl) and the buffer solution of potassium phosphate of 2m10.02M pH=7.0 join successively in plastic tube, mixed liquor ultrasonic disperse 5min, balance leaves standstill 10min again, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 2s, then add 2mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 2min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the methyl alcohol of 1% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 3
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By 1.0g Fe
3o
4magnetic nanoparticle joins in 150mL ethanol and 25mL deionized water, and then ultrasonic 5min adds 2mL ammoniacal liquor and 5mL ethyl orthosilicate successively, react 6h under stirring, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use.
By above-mentioned for 4.0mg obtained Fe
3o
4@SiO
2magnetic nanoparticle, the buffer solution of sodium phosphate of 4.0mg lauryl sodium sulfate (SDS) and 2ml0.02M pH=2.0 joins in plastic tube successively, mixed liquor ultrasonic disperse 5min, balance leaves standstill 10min again, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 5s, then add 4mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 5min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the methyl alcohol of 2% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 4
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By 1.0g Fe
3o
4magnetic nanoparticle joins in 150mL ethanol and 25mL deionized water, and then ultrasonic 5min adds 2mL ammoniacal liquor and 5mL ethyl orthosilicate successively, react 6h under stirring, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use.
By above-mentioned for 4.0mg obtained Fe
3o
4@SiO
2magnetic nanoparticle, the Tris-HCl cushioning liquid of 4.0mg Cetyltrimethylammonium bromide (OTMABr) and 4ml0.02M pH=9.0 joins in plastic tube successively, mixed liquor ultrasonic disperse 5min, balance leaves standstill 10min again, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 3s, then add 3mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 10min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the acetonitrile of 2% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 5
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 50.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By 1.0g Fe
3o
4magnetic nanoparticle joins in 150mL ethanol and 25mL deionized water, and then ultrasonic 5min adds 2mL ammoniacal liquor and 5mL ethyl orthosilicate successively, react 6h under stirring, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use.
By above-mentioned for 4.0mg obtained Fe
3o
4@SiO
2magnetic nanoparticle, 10.0mg chlorination 1-cetyl-3-methylimidazole (C
16mimCl) and the Tris-HCl cushioning liquid of 4ml0.02M pH=7.0 join successively in plastic tube, mixed liquor ultrasonic disperse 5min, balance leaves standstill 10min again, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 3s, then add 3mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 10min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the acetonitrile of 2% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 6
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 50.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By 1.0g Fe
3o
4magnetic nanoparticle joins in 150mL ethanol and 25mL deionized water, and then ultrasonic 5min adds 2mL ammoniacal liquor and 5mL ethyl orthosilicate successively, react 6h under stirring, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use.
By above-mentioned for 4.0mg obtained Fe
3o
4@SiO
2magnetic nanoparticle, 10.0mg bromination 1-cetyl-3-methylimidazole (C
16mimBr) and the buffer solution of sodium phosphate of 5ml0.02M pH=10.0 join successively in plastic tube, mixed liquor ultrasonic disperse 5min, leaving standstill 10min again makes it balance, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 3s, then add 3mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 10min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing acetonitrile of enrichment is from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 7
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By 1.0g Fe
3o
4magnetic nanoparticle joins in 150m wing ethanol and 25mL deionized water, and then ultrasonic 5min adds 2mL ammoniacal liquor and 5mL ethyl orthosilicate successively, react 6h under stirring, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use.
By above-mentioned for 0.4mg obtained Fe
3o
4@SiO
2magnetic nanoparticle, the buffer solution of potassium phosphate of 4.0mg Cetyltrimethylammonium bromide (OTMABr) and 4ml0.02M pH=8.0 joins in plastic tube successively, mixed liquor ultrasonic disperse 5min, leaving standstill 10min again makes it balance, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 3s, then add 3mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 10min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the acetonitrile of 2% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 8
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 12h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By above-mentioned for 5.0mg obtained Fe
3o
4magnetic nanoparticle, the buffer solution of sodium phosphate of 20.0mg halogenated phosphates (CPC) and 2ml0.02M pH=7.0 joins in plastic tube successively, mixed liquor ultrasonic disperse 5min, balance leaves standstill 10min again, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 2s, then add 2mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 2min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the methyl alcohol of 1% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 9
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 10h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By above-mentioned for 4.0mg obtained Fe
3o
4magnetic nanoparticle, 3.0mg chlorination 1-dodecyl-3-methylimidazole (C
12mimCl) and the buffer solution of potassium phosphate of 2ml0.02M pH=8.8 join successively in plastic tube, mixed liquor ultrasonic disperse 10min, leaving standstill 2min again makes it balance, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 2s, then add 2mL and contain 20.0ng/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 2min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the methyl alcohol of 2% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Embodiment 10
2.4g ferric trichloride, 3.4g sodium acetate and 3.4g PAA are joined in the mixed solvent be made up of 33.75ml ethylene glycol and 11.25ml diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace and react 4h, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use;
By above-mentioned for 4.0mg obtained Fe
3o
4magnetic nanoparticle, 3.0mg chlorination 1-dodecyl-3-methylimidazole (C
12mimCl) and the buffer solution of potassium phosphate of 2ml0.02M pH=7.0 join successively in plastic tube, mixed liquor ultrasonic disperse 5min, leaving standstill 10min again makes it balance, be placed in plastic tube sidewall with externally-applied magnetic field afterwards magnetic-particle is separated, abandoning supernatant after 2s, then add 2mL and contain 20.0nf/mL flavonoids medicine (cyanidenon, Quercetin, Kaempferol) urine sample, shake 10min, add externally-applied magnetic field, supernatant discarded urine, the analysis thing of enrichment is with containing the acetonitrile of 2% acetic acid from wash-out magnetic extractant, eluent nitrogen dries up and redissolves with methyl alcohol, analyze by liquid chromatogram after filtration.
Claims (6)
1. one kind based on Fe
3o
4the preparation method of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle, is characterized in that preparation process is:
A. based on Fe
3o
4the preparation of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle: one, solvent-thermal method prepares Fe
3o
4magnetic nanoparticle: ferric trichloride, sodium acetate and PAA join in the mixed solvent be made up of ethylene glycol and diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace to react, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use; Two, preparation mixing hemi-micelle solid extracting agent: the Fe that step one is prepared
3o
4magnetic nanoparticle joins in the cushioning liquid of certain pH value, then adds a certain amount of surfactant or ionic liquid, and ultrasonic rear standing, magnetic field is separated removing supernatant, obtains solid extracting agent.
B. based on Fe
3o
4@SiO
2the preparation of the mixing hemi-micelle solid extracting agent of magnetic nanoparticle: one, solvent-thermal method prepares Fe
3o
4magnetic nanoparticle: ferric trichloride, sodium acetate and PAA join in the mixed solvent be made up of ethylene glycol and diethylene glycol, ultrasonic 1h obtains the mixed solution of black, proceeded in the reactor of polytetrafluoroethylene (PTFE) material, sealing, be placed in Muffle furnace to react, after reaction terminates, be cooled to room temperature, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use; Two, Fe
3o
4@SiO
2the preparation of magnetic nanoparticle: by the Fe prepared in step 2
3o
4magnetic nanoparticle joins in ethanol and deionized water, ultrasonic, then adds a certain amount of ammoniacal liquor and ethyl orthosilicate successively, stir lower reaction, after reaction terminates, add external magnetic field separated product, by methyl alcohol and washed several times with water, in 60 DEG C of vacuum drying to constant weight, for subsequent use; Three, preparation mixing hemi-micelle solid extracting agent: the Fe that step 2 is prepared
3o
4@SiO
2magnetic nanoparticle joins in the cushioning liquid of certain pH value, then adds a certain amount of surfactant or ionic liquid, and ultrasonic rear standing, magnetic field is separated removing supernatant, obtains solid extracting agent.
2. devise a simple Magnetic Isolation flow process, and the enrichment being applied to flavonoids medicine in biological sample be separated, the urine sample containing finite concentration medicine is added to the plastic tube being placed with magnetic mixing hemi-micelle solid extracting agent, ultrasonic rear standing, magnetic field is separated removing urine, the analysis thing organic solvent of enrichment is from wash-out magnetic extractant, and eluent nitrogen dries up and redissolves with methyl alcohol, analyzes after filtration by liquid chromatogram.
3. preparation method according to claim 1, it is characterized in that: in described step a () and b (), the molar concentration of ferric trichloride is 0.05 ~ 0.5mol/L, and the ratio of ethylene glycol and diethylene glycol is 1: 5 ~ 5: 1, and the reaction time is 4 ~ 24h.
4. preparation method according to claim 1, is characterized in that: in described step b (two), Fe
3o
4the consumption of magnetic nanoparticle is 0.5 ~ 1.5g, and the volume of ethanol is 100 ~ 200mL, and the volume of deionized water is 25 ~ 35mL, ultrasonic time is 5 ~ 30min, the volume of ammoniacal liquor is 1 ~ 5mL, and the volume of ethyl orthosilicate is 2 ~ 10mL, and the reaction time is 4 ~ 12h.
5. preparation method according to claim 1, in described step a (two) and b (three), surfactant is lauryl sodium sulfate (SDS), halogenated phosphates (CPC), Cetyltrimethylammonium bromide (OTMABr), softex kw (CTAB); Ionic liquid is chlorination 1-hexyl-3-methylimidazole (C
6mimCl), bromination 1-hexyl-3-methylimidazole (C
6mimBr), chlorination 1-dodecyl-3-methylimidazole (C
12mimCl), bromination 1-dodecyl-3-methylimidazole (C
12mimBr), chlorination 1-cetyl-3-methylimidazole (C
16mimCl), bromination 1-cetyl-3-methylimidazole (C
16mimBr).The consumption of magnetic carbon nano-tube is 2 ~ 10mg, and the consumption of surfactant is 1 ~ 20mg, and cushioning liquid is buffer solution of sodium phosphate, buffer solution of potassium phosphate, Tris-HCl cushioning liquid; The pH of cushioning liquid is respectively 2.0 ~ 10.0,2.0 ~ 10.0,6.8 ~ 9.0; The concentration of cushioning liquid is 0.02 ~ 0.5M, and the volume of cushioning liquid is 1.0 ~ 10.0mL.
6. preparation method according to claim 2, the volume adding urine is 1 ~ 10mL; Ultrasonic time is 2 ~ 10min; Time of repose is 2 ~ 10min; The kind of organic solvent is methyl alcohol, and containing the methyl alcohol of 1% acetic acid, containing the methyl alcohol of 2% acetic acid, acetonitrile, containing the acetonitrile of 1% acetic acid, containing the acetonitrile of 2% acetic acid; The volume of organic solvent used is 0.5 ~ 3mL; Wash number is 1 ~ 5 time.
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| CN107029449A (en) * | 2017-03-24 | 2017-08-11 | 常州宏霖生化工程有限公司 | A kind of Fe3O4Magnetic liquid is combined the preparation method and applications of colloidal liquid aphrons |
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| CN105948134A (en) * | 2016-05-03 | 2016-09-21 | 上海交通大学 | Preparation method of magnetic accumulation body material |
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