CN108452784A - Catecholamine Solid Phase Extraction functional composite material and its preparation method and application - Google Patents
Catecholamine Solid Phase Extraction functional composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of catecholamine Solid Phase Extraction functional composite materials, using magnetic 3D graphene nanos particle as core, surface by ethyl orthosilicate, mercaptopropyl trimethoxysilane, 2 phenylacrylic acids with mainly being synthesized and with special affinity site and have the functional polymer of cross-linked structure to Catecholamine matter.Accordingly, corresponding preparation method has been also set up.The absorption and dynamic extraction separation of the Catecholamine matters such as the trace adrenaline by Solid Phase Extraction functional composite material product of the present invention for illegally being added in the cosmetic sample analysis pre-treatment of matrix complexity, it can be achieved to detect the quick separating of Catecholamine matter, preparation method is simple, cost is relatively low, the method rate of recovery is high, relative standard deviation is small, has the characteristics that organic solvent using less, solid phase extraction manipulations are more convenient, quick, efficient.
Description
Technical field
The invention belongs to cosmetics safety detection technique field more particularly to a kind of catecholamine Solid Phase Extraction function and services
Material and its preparation method and application.
Background technology
Catecholamine is a kind of neural substance containing catechol and amido, adrenaline, norepinephrine, isopropyl
Adrenaline belongs to the Catecholamine matter of cosmetics disabling, these one or more kinds of substances are added in cosmetics,
Prevent skin aging, smoothing wrinkle from increasing the effects that skin elasticity to a certain extent, but central nervous system can be influenced by being excessively used
, there is each global ischemia symptom and functional lesion in the blood circulation of the main organs such as system and heart kidney.Therefore, European Union executes for 2008
New hygienic standards for cosmetics is, it is specified that such drug is banned substance.The Ministry of Public Health of China prints and distributes《Cosmetics health specification》
(version in 2007) has been revised cosmetics and has been limited with 1286 kinds of banned substance is shared in substance list, including this 3 kinds of chemical combination
Object.But driven in recent years by commercial interest, cosmetic industry abuse Catecholamine matter the phenomenon that in rise become
Gesture, this kind of drug that should strictly use by some bad producers and beauty parlor as skin wrinkle, increase the spy of skin elasticity
Ingredient abuse is imitated, the word that " quick smoothing wrinkle ", " light anti-aging " etc. exaggerate effect often appears in its exploitation.So
And consumer is using preceding and in and is not knowing about wherein " secret ", and hormone in vivo balance is caused to go to pot and cause a variety of
Disease.Therefore, Catecholamine matter is added into cosmetics, seriously endangers health.
Cosmetic sample is by the mixture of various material compositions mostly, and wherein detected harmful substance residual is often
It is micro even trace again, therefore parasexuality, reliability are most important really to analysis result for sample pretreatment process.Solid phase
Extraction (solid phase extraction, abbreviation SPE) be quickly grow in recent years it is a kind of based on the important of chromatographic isolation
Sample-pretreating method.Its essence of solid phase extraction techniques is exactly to be inhaled target substance from fluid sample using solid absorbent
Attached and matrix and chaff interferent with sample detaches, then with elution, to achieve the purpose that separation and enrichment target substance,
Enhance the Detection capability to target substance especially trace target substance, and then improves the rate of recovery of target substance.
3D graphenes are the three-dimensional nanometer materials that a kind of thickness is only a carbon atom, this structure by graphene
Special nature and three-dimensional porous structure are combined so that 3D graphenes have the specific surface area of bigger, more active sites,
Higher mechanical strength and the properties such as faster electronics and mass transfer, and make it in catalyst, sensor, super capacitor
Device, hydrogen storage, sorbing material etc., which have, to be more widely applied.3D graphenes are combined with magnetic separation technique,
A kind of novel functional composite material is made, is applied to sample pre-treatments, has shown to increasing adsorption capacity, improving trace group
Divide the huge advantages such as detection sensitivity, reinforcing material durability.
Click chemistry (Click chemistry) is by the Americanized scholar of Nobel chemistry Prize winner earliest
The organic synthesis concept that Sharpless was put forward for the first time in 2001, which is another, to be had after combinatorial chemistry to traditional
Chemical machine brings the Fast back-projection algorithm technology of significant innovation.The purport of click chemistry is exactly under mild reaction conditions, to pass through
The splicing of junior unit quickly and easily synthesizes various molecules with high selectivity to form carbon-heteroatom bond.Click chemistry reaction tool
It has many advantages：As reaction raw materials are easy to get；Reaction condition is mildly simple, insensitive to oxygen, water, need not be removed water, deoxygenation
Operation；Operation is simple and reaction speed is fast；Reaction product is selectively good, by-product is few and nontoxic byproduct, yield are high and
It is environmental-friendly；Reaction product is single, product postprocessing it is simple and it is easily separated purifying etc..Sulfydryl-alkene clicking chemistry reaction is a kind of
Novel click chemistry without metal as catalyst, under heating or ultraviolet irradiation condition, under initiator effect, alkenyl
Free radical polymerization can occur with the sulfydryl in function monomer, expand the alternative of function monomer, make composite material surface
Functional group more flexibleization and diversification.Sulfydryl-alkene clicking chemistry reaction has penetrated into life, drug, surface at present
Many research fields such as modification, macromolecule, functional material.
Invention content
That the technical problem to be solved in the present invention is to provide a kind of preparation methods is simple, cost is relatively low, the catecholamine of function admirable
Solid Phase Extraction functional composite material and its preparation method and application, gained Solid Phase Extraction functional composite material is to catecholamines object
Matter has special affinity, can be applied to the catecholamines such as adrenaline in cosmetics, norepinephrine, isoprel
The safety detection of substance, to facilitate the Catecholamine matter progress fast selective extraction realized to illegally being added in cosmetics
It takes and detaches.
In order to solve the above technical problems, the present invention uses following technical scheme：
Catecholamine Solid Phase Extraction functional composite material, using magnetic 3D graphene nanos particle as core, surface has master
It to be synthesized by ethyl orthosilicate, mercaptopropyl trimethoxysilane, 2- phenylacrylic acids and to Catecholamine matter with special
Affinity site and the functional polymer for having cross-linked structure.
Above-mentioned catecholamine Solid Phase Extraction functional composite material is synergist to Fe using 3D graphenes3O4Magnetic nano-particle
It is modified, using ethyl orthosilicate as crosslinking agent, mercaptopropyl trimethoxysilane be mercapto reagent, 2- phenylacrylic acids are function
Molecule, azodiisobutyronitrile is initiator, to Fe3O4Magnetic nano-particle surface carries out modification layer by layer and prepares.
Modified Fe3O4Magnetic nano-particle, ethyl orthosilicate, mercaptopropyl trimethoxysilane, 2- phenylacrylic acids,
The rate of charge of azodiisobutyronitrile is 300~900mg: 2~6mmol: 2~6mmol: 3~9mmol: 0.0375~0.1125g.
The preparation method of above-mentioned catecholamine Solid Phase Extraction functional composite material, it is poly- using sulfydryl-alkene clicking chemistry surface
It is legal, with the Fe after 3D graphene modifieds3O4Magnetic nano-particle is core, then using ethyl orthosilicate as crosslinking agent, mercapto propyl three
Methoxy silane is mercapto reagent, and 2- phenylacrylic acids are functional molecular, and azodiisobutyronitrile is that polymerisation occurs for initiator,
Elute again remove impurity to get.
The preparation method of above-mentioned catecholamine Solid Phase Extraction functional composite material, according to the following steps operation carry out：
(1) 3D graphene modifieds Fe3O4Magnetic nano-particle
It takes 100~300mg 3D graphenes to be placed in three-neck flask, adds 50~150mL distilled water, ice-water bath ultrasound 10min
After mixing, 300rpm stirrings take 1000~3000mg Fe3O4Magnetic nano-particle, 50~150mL distilled water, ultrasonic 3min, by
It is added dropwise in three-neck flask, is filled with N210min reacts at room temperature 1h, is detached product with solution with strong magnet, absolute ethyl alcohol washing
3 times, adds 15mL absolute ethyl alcohols to disperse, obtain the 3D graphene magnetic fluids of black；
(2) preparation of sulfhydrylation 3D graphene magnetic nanos particle
It takes 300~900mg 3D graphene magnetic nano particles to be placed in three-neck flask, adds 50~150mL absolute ethyl alcohols, 2
~6mmol ethyl orthosilicates, ice-water bath ultrasonic disperse 3min, 360rpm stirring, are filled with N2, 2~6mL acetic acid is added；Take 2~
Three necks burning is added dropwise in 6mmol mercaptopropyl trimethoxysilanes, 50~150mL absolute ethyl alcohols, ice-water bath ultrasound 15min mixings
In bottle, 12h is reacted at 55 DEG C, is detached product with solution with strong magnet, absolute ethyl alcohol washs 3 times, adds 5mL absolute ethyl alcohols point
It dissipates, obtains sulfhydrylation 3D graphene magnetic fluids；
(3) catecholamine Solid Phase Extraction functional composite material is prepared using sulfydryl-alkene clicking chemistry surface aggregate method
It takes 300~900mg sulfhydrylation 3D graphene magnetic nano particles to be placed in three-neck flask, adds 50~150mL anhydrous
Ethyl alcohol, ultrasonic 3min dispersions, 360rpm stirrings are filled with N2, take 3~9mmol 2- phenylacrylic acids, 0.0375~0.1125g even
Nitrogen bis-isobutyronitrile, 50mL~150mL absolute ethyl alcohols, ultrasonic 10min dispersions are added dropwise in three-neck flask, 65 DEG C of reaction 2h,
75 DEG C of reaction 2h, are detached product with solution with strong magnet, and absolute ethyl alcohol washs 3 times, and products therefrom is fitted into filtration paper cylinder, with
The absolute ethyl alcohol of 100~300mL is eluant, eluent, and 2~6h of soxhlet extraction, after removing impurity, natural air drying is solid to get catecholamine
Mutually extraction functional composite material.
Fe3O4Magnetic nano-particle is prepared according to the following steps using chemical coprecipitation：By 10.6g FeCl3·6H2O,
4.0g FeCl2·4H2O is placed in the three-neck flask equipped with 200mL deionized waters, ultrasonic dissolution, opens stirring, leads to N2Deoxygenation,
80 DEG C are heated to, 25mL concentrated ammonia liquors are added, 6h is reacted, product is detached with solution with strong magnet, Fe is cleaned with deionized water3O4
To neutrality, add 15mL water-dispersed, obtains the Fe of black3O4Magnetic fluid；
3D graphenes are prepared according to the following steps：It takes the graphene oxide ultrasonic disperse of 10mL 2mg/mL uniform, is sealed in
12h is reacted at 180 DEG C in the pyroreaction kettle of 20mL polytetrafluoroethyllining linings, is cooled to room temperature, 3D graphenes are taken out, with filter
Paper blots surface moisture, preserves；
Above-mentioned catecholamine Solid Phase Extraction functional composite material Catecholamine matter in separation, enrichment and purification of samples
Remaining application.
Above-mentioned catecholamine Solid Phase Extraction functional composite material is before the cosmetic sample analysis containing Catecholamine matter
Application in processing.
Above application, according to the following steps operation carry out：
(1) it activates
Catecholamine Solid Phase Extraction functional composite material 25mg is taken, is placed in conical flask with cover, is activated, is abandoned with 3mL methanol
Waste liquid is removed, is eluted with 3mL acetonitriles, the methanol on functional composite material surface is removed, waste liquid is discarded；It uses 3mL acetonitriles to balance again, abandons
Remove waste liquid；Obtain activated functional composite material；
(2) it extracts
Precision weighs cosmetic sample 0.5g, is placed in tool plug centrifuge tube, accurately pipettes saturated nacl aqueous solution 2mL, second
Nitrile 10mL, ice-water bath ultrasonic extraction 10min, 10000rpm centrifuges 10min at 4 DEG C, accurately pipettes upper layer acetonitrile extracting solution 5mL,
It is added in the conical flask with cover in step (1), is mixed with activated functional composite material；80min is extracted under oscillation action,
After the completion of extraction, magnetic field separation discards waste liquid；
(3) it elutes
The functional composite material handled through step (2) is eluted with 3mL acetonitriles, discards waste liquid；
(4) it elutes
Using the 0.1% aqueous formic acid-methanol of 2~6mL volume ratios 98: 2 as eluant, eluent, functional composite material is washed
It is de-, collect eluent；It is dried up with nitrogen at 35 DEG C, obtains residue, residue is re-dissolved with 1mL eluant, eluents, filtered through 0.45 μm
Efficient liquid phase chromatographic analysis is carried out after head filtering.
The problem of being abused for existing Catecholamine matter and being difficult to detect, inventor designs and is prepared for a kind of catechu
Phenol amine Solid Phase Extraction functional composite material, using magnetic 3D graphene nanos particle as core, surface has mainly by positive silicic acid second
Ester, mercaptopropyl trimethoxysilane, 2- phenylacrylic acids synthesize and have special affinity site to Catecholamine matter and have
The functional polymer of cross-linked structure.Accordingly, corresponding preparation method has been also set up, i.e., with the Fe after 3D graphene modifieds3O4Magnetic
Property nano-particle (magnetic material) be core, then by Silanization reaction, sulfydryl-alkene clicking chemistry polymerization reaction on the solid surface respectively will
Ethyl orthosilicate, mercaptopropyl trimethoxysilane, 2- phenylacrylic acids are successively bonded in magnetic core surface and form nonmagnetic polymerization
Object.Gained Solid Phase Extraction functional composite material of the invention has the feature of magnetic material Dynamic Separation, completes to target substance
After Catecholamine matter extraction, conveniently and efficiently it can be separated from sample substrate outside plus under magnetic fields, because
This separation and concentration particularly suitable for target substance in complex system.
Experimental study shows that compared with the existing technology, the present invention has the advantages that following prominent：
1. being prepared based on sulfydryl-alkene clicking chemistry and the catecholamine Solid Phase Extraction functional composite material of 3D graphene synergy
Method is easy to operate, and applicability is wide.
2. before polymerisation, with 3D graphenes to Fe3O4Magnetic nano-particle surface is modified, and enhances that its is fat-soluble,
It solves the problems, such as metal oxide and organic polymer compatibility, becomes the magnetic core of functional polymer.Due to 3 D stereo knot
The graphene of structure has 3D cavernous structures, this make the graphene of three-dimensional structure not only and have the distinctive physics of graphene and
Chemical property, and there are electrochemical properties more superior than the grapheme material of two dimensional surface, the specific surface area of bigger is stronger
Engineering properties has huge advantage to increasing adsorption capacity, raising trace components detection sensitivity, reinforcing material durability etc..
3. 3D graphenes are surface modified using sulfydryl-alkene clicking chemistry, it will be with Catecholamine matter shape
Magnetic 3D graphene surfaces are connected at the functional molecular of hydrogen bond action, ion association, π-π interactions, it is special to be formed
Affinity site and the polymer for having cross-linked structure are conducive to the selective adsorption for improving function and service fiber material.
4. gained Solid Phase Extraction functional composite material is due to magnetic core, during sorption extraction target substance, nothing
Dress column need to be filled, but directly adds it to and carries out adsorption and enrichment in the extracting solution of sample, you can is rapidly completed to mesh
Mark the extraction of substance；After extraction, it is not necessarily to high speed centrifugation, functional composite material can be assembled merely with externally-applied magnetic field, it is real
Now with the separation of sample matrices, the matrix in sample and impurity interference are quickly removed, analytical procedure is enormously simplified, saves analysis
Time reduces the consumption of organic solvent, to realize that the quick separating to target substance detects.
Specific implementation mode
Embodiment 1
One, the preparation of catecholamine Solid Phase Extraction functional composite material
(1) chemical coprecipitation is used to prepare Fe3O4Magnetic nano-particle
By 10.6g FeCl3·6H2O, 4.0g FeCl2·4H20 is placed in the three-neck flask equipped with 200mL deionized waters,
Ultrasonic dissolution opens stirring, leads to N2Deoxygenation, is heated to 80 DEG C, and 25mL concentrated ammonia liquors are added, and reacts 6h, with strong magnet by product with
Solution detaches, and Fe is cleaned with deionized water304To neutrality, add 15mL water-dispersed, obtains the Fe of black304Magnetic fluid (i.e. Fe3O4Magnetic
Property nano-particle)；
(2) preparation of 3D graphenes
It takes the graphene oxide ultrasonic disperse of 10mL 2mg/mL uniform, is sealed in the high temperature of 20mL polytetrafluoroethyllining linings
12h is reacted at 180 DEG C in reaction kettle, is cooled to room temperature, 3D graphenes are taken out, surface moisture is blotted with filter paper, is preserved；
(3) 3D graphene modifieds Fe304Magnetic nano-particle
It takes 100mg3D graphenes to be placed in three-neck flask, adds 50mL distilled water, after ice-water bath ultrasound 10min mixings,
300rpm is stirred, and takes 1000mgFe3O4Magnetic nano-particle, 50mL distilled water, ultrasonic 3min are added dropwise in three-neck flask, fill
Enter N210min reacts at room temperature 1h, is detached product with solution with strong magnet, and absolute ethyl alcohol washs 3 times, adds 15mL absolute ethyl alcohols
Dispersion, obtains the 3D graphene magnetic fluids (Fe of black3O4@3DG)；
(4) preparation of sulfhydrylation 3D graphene magnetic nanos particle
It takes 300mg 3D graphene magnetic nano particles to be placed in three-neck flask, adds 50mL absolute ethyl alcohols, the positive silicic acid of 2mmol
Ethyl ester, ice-water bath ultrasonic disperse 3min, 360rpm stirring, is filled with N2, 2mL acetic acid is added.Take 2mmol mercapto propyl trimethoxy silicon
Alkane, 50mL absolute ethyl alcohols, ice-water bath ultrasound 15min mixings are added dropwise in three-neck flask, react 12h at 55 DEG C, use strong magnet
Product is detached with solution, absolute ethyl alcohol washs 3 times, adds 5mL absolute ethyl alcohols to disperse, obtains sulfhydrylation 3D graphene magnetic fluids
(Fe3O4@3DG@SiO2-SH)；
(5) catecholamine Solid Phase Extraction functional composite material is prepared using sulfydryl-alkene clicking chemistry surface aggregate method
It takes 300mg sulfhydrylation 3D graphene magnetic nano particles to be placed in three-neck flask, adds 50mL absolute ethyl alcohols, ultrasound
3min disperses, and 360rpm stirrings are filled with N2, take 3mmol 2- phenylacrylic acids, 0.0375g azodiisobutyronitriles, 50mL is anhydrous
Ethyl alcohol, ultrasonic 10min dispersion, is added dropwise in three-neck flask, 65 DEG C of reactions 2h, 75 DEG C of reaction 2h, with strong magnet by product
It being detached with solution, absolute ethyl alcohol washs 3 times, and products therefrom is fitted into filtration paper cylinder, using the absolute ethyl alcohol of 100mL as eluant, eluent,
Soxhlet extraction 2h, after removing impurity, natural air drying is to get catecholamine Solid Phase Extraction functional composite material (Fe3O4@3DG@
SiO2-SH@Ph-COOH)。
Vibrating specimen magnetometer (VSM), FTIR spectrum (FT-IR), scanning electron microscope (SEM), power spectrum is respectively adopted
A variety of Instrumental Analysis means such as (EDS), particle diameter distribution (DLS), thermogravimetric analysis (TGA) are analyzed to Fe3O4、Fe3O4@3DG、Fe3O4@
3DG@SiO2-SH、Fe3O4@3DG@SiO2Four kinds of magnetic nano-particles such as-SH@Ph-COOH have carried out magnetization property, structure, shape
Looks and thermal stability etc. are characterized.The result shows that in magnetic core Fe3O4The 3D graphene modifieds that surface layer-by-layer carries out, sulfydryl
The click synthesis of silylating reagent, 2- phenylacrylic acids is successful, illustrates that synthesized functional polymer has core-shell type knot
Structure.
Two, catecholamine Solid Phase Extraction functional composite material is applied to the detaching of Catecholamine matter in moisture retention water, rich
Collection and purifying
(1) catecholamine Solid Phase Extraction functional composite material 25mg obtained by this example is taken to be placed in conical flask with cover, with 3mL first
Alcohol activates, and discards waste liquid, is eluted with 3mL acetonitriles, and the methanol on functional composite material surface is removed, waste liquid is discarded；3mL second is used again
Nitrile balances, and discards waste liquid；Obtain activated functional composite material；
(2) commercially available cosmetics (moisture retention water) are accurately weighed in right amount, the accurate catecholamine mixed standard solution that is added is appropriate, system
At the sample of four kinds (1 μ g/g, 5 μ g/g, 10 μ g/g, 20 μ g/g) different mark-on levels.Mark-on sample 0.5g accurately is weighed, is placed in
In tool plug centrifuge tube, saturated nacl aqueous solution 2mL is accurately pipetted, acetonitrile 10mL, ice-water bath ultrasonic extraction 10min, at 4 DEG C
10000rpm centrifuges 10min, accurately pipettes upper layer acetonitrile extracting solution 5mL, is added in the conical flask with cover in step (1), with work
The functional composite material mixing changed；80min is extracted under oscillation action, after the completion of extraction, it is useless to discard sample for magnetic field separation
Liquid；Functional composite material is eluted with 3mL acetonitriles, discards waste liquid；
(3) volume ratio 98 is used：2 0.1% aqueous formic acid-methanol elutes for eluant, eluent (2mL × 3 time), collects elution
Liquid；It is dried up with nitrogen at 35 DEG C, obtains residue, residue is re-dissolved with 1mL eluant, eluents, carried out after 0.45 μm of filter filters
Efficient liquid phase chromatographic analysis.
As a result：1 gained catecholamine Solid Phase Extraction functional composite material of embodiment is to the catecholamines object in moisture retention water
Matter has separation and concentration and purification capacity, to adrenaline, norepinephrine, isoprel mark-on reclaims in moisture retention water
Rate is respectively 92.11-98.09%, 94.19-100.2%, 94.66-105.4%, and relative standard deviation is respectively 0.24-
0.87%, 0.28-0.82%, 0.64-1.30%.
Embodiment 2
One, the preparation of catecholamine Solid Phase Extraction functional composite material
Step (1) (2) is the same as embodiment 1.
(3) 3D graphene modifieds Fe3O4Magnetic nano-particle
It takes 200mg 3D graphenes to be placed in three-neck flask, adds 100mL distilled water, after ice-water bath ultrasound 10min mixings,
300rpm is stirred, and takes 2000mg Fe3O4Magnetic nano-particle, 100mL distilled water, ultrasonic 3min are added dropwise in three-neck flask,
It is filled with N210min reacts at room temperature 1h, is detached product with solution with strong magnet, and absolute ethyl alcohol washs 3 times, adds the anhydrous second of 15mL
Alcohol disperses, and obtains the 3D graphene magnetic fluids of black.
(4) preparation of sulfhydrylation 3D graphene magnetic nanos particle
It takes 600mg 3D graphene magnetic nano particles to be placed in three-neck flask, adds 100mL absolute ethyl alcohols, the positive silicon of 4mmol
Acetoacetic ester, ice-water bath ultrasonic disperse 3min, 360rpm stirring, is filled with N2, 4mL acetic acid is added.Take 4mmol mercapto propyl trimethoxies
Silane, 100mL absolute ethyl alcohols, ice-water bath ultrasound 15min mixings are added dropwise in three-neck flask, react 12h at 55 DEG C, with strong
Magnet detaches product with solution, and absolute ethyl alcohol washs 3 times, adds 5mL absolute ethyl alcohols to disperse, obtains sulfhydrylation 3D graphene magnetic currents
Body；
(5) catecholamine Solid Phase Extraction functional composite material is prepared using sulfydryl-alkene clicking chemistry surface aggregate method
It takes 600mg sulfhydrylation 3D graphene magnetic nano particles to be placed in three-neck flask, adds 100mL absolute ethyl alcohols, ultrasound
3min disperses, and 360rpm stirrings are filled with N2, take 6mmol 2- phenylacrylic acids, 0.075g azodiisobutyronitriles, 100mL is anhydrous
Ethyl alcohol, ultrasonic 10min dispersion, is added dropwise in three-neck flask, 65 DEG C of reactions 2h, 75 DEG C of reaction 2h, with strong magnet by product
It being detached with solution, absolute ethyl alcohol washs 3 times, and products therefrom is fitted into filtration paper cylinder, using the absolute ethyl alcohol of 200mL as eluant, eluent,
Soxhlet extraction 4h, after removing impurity, natural air drying is to get functional composite material.
The structural characterization of functional composite material is the same as embodiment 1.
Two, catecholamine Solid Phase Extraction functional composite material is applied to the detaching of Catecholamine matter in moisturiser, rich
Collection and purifying concrete operations are with reference to processing of the catecholamine Solid Phase Extraction functional composite material to moisture retention water in embodiment 1.
As a result：2 gained catecholamine Solid Phase Extraction functional composite material of embodiment is to the catecholamines object in moisturiser
Matter has separation and concentration and purification capacity, to adrenaline, norepinephrine, isoprel mark-on in moisturiser sample
The rate of recovery is respectively 94.90-98.98%, 94.41-105.4%, 97.04-107.8%, and relative standard deviation is respectively 0.21-
1.09%, 0.11-0.74%, 0.36-1.34%.
Embodiment 3
One, the preparation of catecholamine Solid Phase Extraction functional composite material
Step (1) (2) is the same as embodiment 1.
(3) 3D graphene modifieds Fe3O4Magnetic nano-particle
It takes 300mg 3D graphenes to be placed in three-neck flask, adds 150mL distilled water, after ice-water bath ultrasound 10min mixings,
300rpm is stirred, and takes 3000mgFe3O4Magnetic nano-particle, 150mL distilled water, ultrasonic 3min are added dropwise in three-neck flask,
It is filled with N210min reacts at room temperature 1h, is detached product with solution with strong magnet, and absolute ethyl alcohol washs 3 times, adds the anhydrous second of 15mL
Alcohol disperses, and obtains the 3D graphene magnetic fluids of black.
(4) preparation of sulfhydrylation 3D graphene magnetic nanos particle
It takes 900mg 3D graphene magnetic nano particles to be placed in three-neck flask, adds 150mL absolute ethyl alcohols, the positive silicon of 6mmol
Acetoacetic ester, ice-water bath ultrasonic disperse 3min, 360rpm stirring, is filled with N2, 6mL acetic acid is added.Take 6mmol mercapto propyl trimethoxies
Silane, 150mL absolute ethyl alcohols, ice-water bath ultrasound 15min mixings are added dropwise in three-neck flask, react 12h at 55 DEG C, with strong
Magnet detaches product with solution, and absolute ethyl alcohol washs 3 times, adds 5mL absolute ethyl alcohols to disperse, obtains sulfhydrylation 3D graphene magnetic currents
Body；
(5) catecholamine Solid Phase Extraction functional composite material is prepared using sulfydryl-alkene clicking chemistry surface aggregate method
It takes 900mg sulfhydrylation 3D graphene magnetic nano particles to be placed in three-neck flask, adds 150mL absolute ethyl alcohols, ultrasound
3min disperses, and 360rpm stirrings are filled with N2, take 9mmol 2- phenylacrylic acids, 0.1125g azodiisobutyronitriles, 150mL is anhydrous
Ethyl alcohol, ultrasonic 10min dispersion, is added dropwise in three-neck flask, 65 DEG C of reactions 2h, 75 DEG C of reaction 2h, with strong magnet by product
It being detached with solution, absolute ethyl alcohol washs 3 times, and products therefrom is fitted into filtration paper cylinder, using the absolute ethyl alcohol of 300mL as eluant, eluent,
Soxhlet extraction 6h, after removing impurity, natural air drying is to get functional composite material.
The structural characterization of functional composite material is the same as embodiment 1.
Two, catecholamine Solid Phase Extraction functional composite material be applied to light sensation face cream in Catecholamine matter separation,
Enrichment and purifying
Concrete operations are with reference to processing of the catecholamine Solid Phase Extraction functional composite material to moisture retention water in embodiment 1.
As a result：3 gained catecholamine Solid Phase Extraction functional composite material of embodiment is to the catecholamines in light sensation face cream
Substance has separation and concentration and purification capacity, to adrenaline, norepinephrine, isoprel in light sensation face cream sample
Recovery of standard addition is respectively 94.70-98.05%, 93.40-103.6%, 92.74-109.6%, and relative standard deviation is respectively
0.12-1.10%, 0.35-1.13%, 0.38-0.78%.
Embodiment 43D graphenes study the synergistic effect of functional composite material adsorption capacity
One, the preparation of functional composite material
The preparation of the functional composite material of 3D graphene synergy includes following three processes：3D graphenes are to Fe3O4Surface into
Row modification, forms 3D graphene magnetic nano particles (Fe3O4@3DG)；In Fe3O4The surfaces@3DG carry out hydrosulphonyl silane modification,
Form Fe3O4@3DG@SiO2-SH；Using sulfydryl-alkene clicking chemistry, olefin(e) acid functional molecular is connected to Fe3O4@3DG@SiO2-SH
Surface forms the functional polymer (Fe for having special affinity site to Catecholamine matter and having cross-linked structure3O4@
3DG@SiO2-SH@Ph-COOH)。
In order to evaluate synergistic effect of the 3D graphenes to functional composite material adsorption capacity, two kinds of function and service materials have been synthesized
Material.I.e. to Fe3O4When surface is modified, under same experimental conditions, 1 (Fe of material3O4@3DG@SiO2- SH@Ph-COOH) it uses
3D graphenes are modified, 2 (Fe of material3O4@SiO2- SH@Ph-COOH) then sulfydryl silicon is directly carried out without using 3D graphenes
Alkanisation is modified.
Two, functional composite material is to adrenergic adsorption experiment
The accurate composite material 1 and composite material 2 for weighing 25mg, is respectively placed in conical flask with cover, and 2 are activated with methanol
Secondary, acetonitrile balances 2 times, and the epinephrine solution 10mL of 1mg/mL is added, two conical flasks are placed in shaken at room temperature in oscillator
80min detaches supernatant and material outside plus under magnetic fields.It is appropriate that precision pipettes supernatant, with acetonitrile constant volume,
Absorbance is measured at 280nm, calculates adsorbance.
According to formula Q=(C0-Ce) V/W, composite material adsorbance is calculated by solution concentration variation before and after absorption.In formula,
Q is equilibrium adsorption capacity (mg/g)；C0It is respectively the initial concentration and adsorption equilibrium concentration (mg/mL) of epinephrine solution with Ce；V
For the volume (mL) of solution；W is the quality (g) of functional composite material.
Three, synergistic effect result of study of the 3D graphenes to functional composite material adsorption capacity
Material 1 and material 2 is used to carry out adsorption experiment to above-mentioned epinephrine solution respectively, the results are shown in Table 1.
Influence of the 1 3D graphenes of table to functional composite material absorption property
Using 3D graphenes to Fe3O4Surface is modified, and is significantly improved the adsorbance of functional composite material, is illustrated 3D
Graphene has apparent synergistic function.3D graphenes are by two-dimensional graphene multiple-layer stacked and what is formed have three-dimensional poroid knot
The material of structure makes the specific surface area of material greatly increase, so that the adsorbance of functional polymer significantly increases.
Claims (10)
1. a kind of catecholamine Solid Phase Extraction functional composite material, it is characterised in that using magnetic 3D graphene nanos particle as core,
Its surface, which has, mainly to be synthesized and by ethyl orthosilicate, mercaptopropyl trimethoxysilane, 2- phenylacrylic acids to catecholamines
Substance has special affinity site and has the functional polymer of cross-linked structure.
2. catecholamine Solid Phase Extraction functional composite material according to claim 1, it is characterised in that：It is with 3D graphenes
Synergist is to Fe3O4Magnetic nano-particle is modified, and is mercapto by crosslinking agent, mercaptopropyl trimethoxysilane of ethyl orthosilicate
Base reagent, 2- phenylacrylic acids are functional molecular, and azodiisobutyronitrile is initiator, to Fe3O4Magnetic nano-particle surface carries out
Layer by layer prepared by modification.
3. catecholamine Solid Phase Extraction functional composite material according to claim 1, it is characterised in that：It is described modified
Fe3O4The throwing of magnetic nano-particle, ethyl orthosilicate, mercaptopropyl trimethoxysilane, 2- phenylacrylic acids, azodiisobutyronitrile
Material is than being 300~900mg: 2~6mmol: 2~6mmol: 3~9mmol: 0.0375~0.1125g.
4. the preparation method of catecholamine Solid Phase Extraction functional composite material described in claim 3, it is characterised in that use sulfydryl-
Alkene clicking chemistry surface aggregate method, with the Fe after 3D graphene modifieds3O4Magnetic nano-particle is core, then with ethyl orthosilicate
For crosslinking agent, mercaptopropyl trimethoxysilane is mercapto reagent, and 2- phenylacrylic acids are functional molecular, and azodiisobutyronitrile is to draw
Send out agent occur polymerisation, then elute remove impurity to get.
5. the preparation method of catecholamine Solid Phase Extraction functional composite material according to claim 4, it is characterised in that by with
Lower step operation carries out：
(1) 3D graphene modifieds Fe3O4Magnetic nano-particle
It takes 100~300mg 3D graphenes to be placed in three-neck flask, adds 50~150mL distilled water, ice-water bath ultrasound 10min mixings
Afterwards, 300rpm is stirred, and takes 1000~3000mg Fe3O4Magnetic nano-particle, 50~150mL distilled water, ultrasonic 3min add dropwise
Enter in three-neck flask, is filled with N210min reacts at room temperature 1h, is detached product with solution with strong magnet, absolute ethyl alcohol washing 3
It is secondary, add 15mL absolute ethyl alcohols to disperse, obtains the 3D graphene magnetic fluids of black；
(2) preparation of sulfhydrylation 3D graphene magnetic nanos particle
It takes 300~900mg 3D graphene magnetic nano particles to be placed in three-neck flask, adds 50~150mL absolute ethyl alcohols, 2~
6mmol ethyl orthosilicates, ice-water bath ultrasonic disperse 3min, 360rpm stirring, are filled with N2, 2~6mL acetic acid is added；Take 2~
Three necks burning is added dropwise in 6mmol mercaptopropyl trimethoxysilanes, 50~150mL absolute ethyl alcohols, ice-water bath ultrasound 15min mixings
In bottle, 12h is reacted at 55 DEG C, is detached product with solution with strong magnet, absolute ethyl alcohol washs 3 times, adds 5mL absolute ethyl alcohols point
It dissipates, obtains sulfhydrylation 3D graphene magnetic fluids；
(3) catecholamine Solid Phase Extraction functional composite material is prepared using sulfydryl-alkene clicking chemistry surface aggregate method
It takes 300mg~900mg sulfhydrylation 3D graphene magnetic nano particles to be placed in three-neck flask, adds the anhydrous second of 50~150mL
Alcohol, ultrasonic 3min dispersions, 360rpm stirrings are filled with N2, take 3~9mmol 2- phenylacrylic acids, 0.0375~0.1125g azos
Bis-isobutyronitrile, 50mL~150mL absolute ethyl alcohols, ultrasonic 10min dispersion are added dropwise in three-neck flask, 65 DEG C of reaction 2h, and 75
DEG C reaction 2h, product is detached with solution with strong magnet, absolute ethyl alcohol washing 3 times, the product of gained is fitted into filtration paper cylinder, with
The absolute ethyl alcohol of 100~300mL is eluant, eluent, and 2~6h of soxhlet extraction, after removing impurity, natural air drying is solid to get catecholamine
Mutually extraction functional composite material.
6. the preparation method of catecholamine Solid Phase Extraction functional composite material according to claim 5, it is characterised in that described
Fe3O4Magnetic nano-particle is prepared according to the following steps using chemical coprecipitation：By 10.6g FeCl3·6H2O, 4.0gFeCl2·
4H2O is placed in the three-neck flask equipped with 200mL deionized waters, ultrasonic dissolution, opens stirring, leads to N2Deoxygenation is heated to 80 DEG C, adds
Enter 25mL concentrated ammonia liquors, reacts 6h, product is detached with solution with strong magnet, Fe is cleaned with deionized water3O4To neutrality, add 15mL
It is water-dispersed, obtain the Fe of black3O4Magnetic fluid.
7. the preparation method of catecholamine Solid Phase Extraction functional composite material according to claim 5, it is characterised in that described
3D graphenes are prepared according to the following steps：It takes the graphene oxide ultrasonic disperse of 10mL 2mg/mL uniform, is sealed in 20mL polytetrafluoros
12h is reacted at 180 DEG C in the pyroreaction kettle of ethylene liner, is cooled to room temperature, 3D graphenes are taken out, surface is blotted with filter paper
Moisture preserves.
8. catecholamine Solid Phase Extraction functional composite material catechu in separation, enrichment, purification of samples according to claim 1
The remaining application of phenol amine substance.
9. catecholamine Solid Phase Extraction functional composite material is in the cosmetic sample containing Catecholamine matter described in claim 1
Analyze the application in pre-treatment.
10. application according to claim 9, it is characterised in that operation carries out according to the following steps：
(1) it activates
Catecholamine Solid Phase Extraction functional composite material 25mg is taken, is placed in conical flask with cover, is activated, is discarded useless with 3mL methanol
Liquid is eluted with 3mL acetonitriles, and the methanol on functional composite material surface is removed, waste liquid is discarded；It uses 3mL acetonitriles to balance again, discards useless
Liquid；Obtain activated functional composite material；
(2) it extracts
Precision weighs cosmetic sample 0.5g, is placed in tool plug centrifuge tube, accurately pipettes saturated nacl aqueous solution 2mL, acetonitrile
10mL, ice-water bath ultrasonic extraction 10min, 10000rpm centrifuges 10min at 4 DEG C, accurately pipettes upper layer acetonitrile extracting solution 5mL, adds
Enter in the conical flask with cover in step (1), is mixed with activated functional composite material；80min is extracted under oscillation action, is extracted
After the completion of taking, magnetic field separation discards waste liquid；
(3) it elutes
The functional composite material handled through step (2) is eluted with 3mL acetonitriles, discards waste liquid；
(4) it elutes
Using the 0.1% aqueous formic acid-methanol of 2~6mL volume ratios 98: 2 as eluant, eluent, functional composite material is eluted,
Collect eluent；It is dried up with nitrogen at 35 DEG C, obtains residue, residue is re-dissolved with 1mL eluant, eluents, through 0.45 μm of filter mistake
Efficient liquid phase chromatographic analysis is carried out after filter.
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