CN106475068B - The graphene oxide composite nano materials of phenyl boric acid functionalization and its preparation and application - Google Patents
The graphene oxide composite nano materials of phenyl boric acid functionalization and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of graphene oxide composite nano materials of novel phenyl boric acid functionalization and its preparations and application.The material is further to introduce the phenyl boric acid monomer with carboxyl by the amino of polyethyleneimine on the immobilized graphene oxide amine-modified to polyethyleneimine of magnetic nanoparticle of poly-dopamine package, is eventually used for glycoprotein enrichment.Detailed process is：Ferroferric oxide magnetic nanoparticle is prepared by solvent-thermal method first, dopamine can be in its surface auto polymerization under alkaline condition.Magnetic oxygenated graphene composite nano material is prepared using hydrogen bond between poly-dopamine and graphene oxide and π-π interaction.Then, positively charged polyethyleneimine is immobilized on electronegative magnetic oxygenated graphene surface by electrostatic self-assembled.Finally, introducing phenyl boric acid monomer by amidation process obtains the magnetic oxygenated graphene composite nano material of phenyl boric acid functionalization, and it is used successfully to the enrichment of glycoprotein in bioanalysis.
Description
Technical field
The present invention relates to a kind of graphene oxide composite nano materials of phenyl boric acid functionalization and its preparation and it is applied to sugar
The specific enrichment of albumen.
Background technique
Boron is affine strategy because its is easy to operate, without skewed popularity and the features such as do not destroy glycan structure, in glycosylated protein
More and more extensive concern is obtained in separation and concentration.But traditional phenyl boric acid monomer (PBA) affinity it is low, with cis- vicinal diamines
Binding ability weak cause the selectivity to glycoprotein not high.According to the literature, a kind of novel phenyl boric acid (2- methylol benzene boron
Sour ring-type monoesters and its derivative) there is low pka values (pKa=7.3), the binding ability with cis- vicinal diamines is than traditional phenyl boric acid
It is higher, therefore be a kind of very potential novel monomeric, be applied successfully to glycoprotein enrichment (Chem.Commun.,
2012,48,4115–4117；Small,2014,10,No.7,1379–1386).After the preparation of boric acid functionalization material mostly uses
The method of modification, can be used for being bonded boric acid base group host material include polymer microballoon, Ago-Gel, macro porous silica gel and
Magnetic nanoparticle etc..Nano material and polymer specific surface area are limited, and supported quantity is limited；Silica matrix exists inevitable
Non-specific adsorption.Therefore Development of Novel immobilization matrix material is very necessary.
A kind of important derivatives of the graphene oxide (GO) as graphene, a large amount of oxygen-containing groups, such as hydroxyl are contained in surface
Base, epoxy and carboxyl.A large amount of oxygen-containing group improves graphene oxide chemical stability and hydrophily, also aoxidizes stone for preparation
Black alkene composite material provides reaction site.In recent years, nanoparticle is bonded to the nano-complex of surface of graphene oxide formation
The excellent properties of the two can be played simultaneously and become a hot research, in catalysis, photoelectron material, surface-enhanced Raman light
The fields such as scattering, bioanalysis have a good application prospect.Wherein, magnetic oxygenated graphene is due to combining graphene oxide
And the advantages of magnetic nanoparticle and become a kind of new function material, be successfully applied to dyestuff and pollutant absorption, medicine
Object is immobilized and release, protein and DNA are immobilized, aptamers immobilized etc..Therefore, magnetic oxygenated graphene nanometer composite can be made
For the ideal matrix of phenyl boric acid monomer immobilization.
In conclusion magnetic oxygenated graphene nanometer composite is prepared a kind of novel benzene as immobilized matrix by us
The graphene oxide composite nano materials of boric acid functionalization and the enrichment for being used for glycoprotein.
Summary of the invention
It is an object of the invention to prepare a kind of graphene oxide composite nano materials of novel phenyl boric acid functionalization, it is used in combination
In the specific enrichment of glycoprotein.
To realize that the purpose, the technical solution adopted by the present invention be：
The graphene oxide composite nano materials of phenyl boric acid functionalization are by ferroferric oxide magnetic nanoparticle or outside
The ferroferric oxide magnetic nanoparticle for being enclosed with high molecular polymer is immobilized on graphene oxide, then to graphene oxide
It is modified after progress, is finally introducing phenyl boric acid function monomer.
The ferroferric oxide magnetic nanoparticle partial size is in 100-300nm；Or in ferroferric oxide magnetic nano
Extra-granular is enclosed with high molecular polymer, and package shell thickness forms four oxidations three with core-shell structure in 5-20nm
Ferromagnetic nanoparticle；
By the ferroferric oxide magnetic nanoparticle of 1-20 mass parts or external four oxidations for being enclosed with high molecular polymer
Three ferromagnetic nanoparticles pass through in noncovalent interaction physical absorption to the surface of graphene oxide of 1 mass parts；
The high molecular polymer of 1-50 mass parts is introduced on 1 mass parts graphene oxide；
The graphene oxide of the high molecular polymer modification of 1 mass parts introduces 1-10 mass parts phenyl boric acid function monomer.
(1) ferroferric oxide magnetic nanoparticle of the synthesis partial size in 100-300nm；Or it is received in Fe 3 O 4 magnetic
High molecular polymer is enclosed with outside rice grain, package shell thickness forms four oxidations with core-shell structure in 5-20nm
Three ferromagnetic nanoparticles；The shell of package is in high molecular polymer, that is, poly-dopamine or poly- 3,4- dihydroxyphenylalanine
It is one or two or more kinds of.
(2) by the ferroferric oxide magnetic nanoparticle of 1-20 mass parts or external four oxygen for being enclosed with high molecular polymer
Change three ferromagnetic nanoparticles and passes through noncovalent interaction (one of π-π interaction, hydrogen bond or ionic bond or two kinds or more)
In physical absorption to the surface of graphene oxide of 1 mass parts.
(3) 1 mass parts graphene oxide is passed through into chemical covalent effect or noncovalent interaction (π-π interaction, hydrogen bond
Or one of ionic bond or two kinds or more) introduce 1-50 mass parts dendroid or hyper-branched polymer polymer；Macromolecule
Polymer includes one of polyethyleneimine, polypropyleneimine or daiamid or two kinds or more
1-10 mass parts are introduced by covalent bonding on the graphene oxide of the high molecular polymer modification of (4) 1 mass parts
Phenyl boric acid function monomer.The covalent bonding of phenyl boric acid function monomer specifically includes one of following or two kinds or more：Pass through ammonia
The amidation process of base and carboxyl introduces one of 2- Carboxybenzeneboronic acid (CPBA), 5- carboxyl -2- methylol phenyl boric acid (CBX)
Or two kinds or more；The nucleophilic addition of amino and aldehyde radical introduces 4- formylphenylboronic acid (FPBA)；Glutaraldehyde is as coupling agent
Introduce one of amino phenyl boric acid (APBA), 5- amino -2- methylol phenyl boric acid (ABX) or two kinds or more.
(5) the graphene oxide composite nano materials of the phenyl boric acid functionalization are used for bioanalysis, biotechnology
The enrichment of the specific recognition of glycoprotein, glycoprotein in field.
The invention has the advantages that：
(1) preparation simplicity, mild condition；Its preparation process is environmental-friendly using water as solvent.
(2) dendroid or hyperbranched high molecular polymer are introduced, can be mentioned for the bonding of subsequent phenyl boric acid function monomer
For more reaction sites, the selectivity of material is improved.
(3) graphene oxide composite nano materials have specific surface area is high, non-specific adsorption is few etc. as immobilized matrix
Advantage.
(4) non-covalent bonding method preparation has magnetic graphene oxide, does not destroy graphene oxide property.
Detailed description of the invention
Fig. 1 is Fe3O4/ PDA transmission electron microscope picture.
Fig. 2 is Fe3O4/ PDA/GO/BPEI transmission electron microscope picture.
Fig. 3 is that Fig. 2 is Fe3O4/ PDA/GO/BPEI/CBX transmission electron microscope picture.
Fig. 4 is Fe3O4The x-ray photoelectron spectroscopy figure of/PDA/GO/BPEI/CBX.
Fig. 5 is that glycoprotein horseradish peroxidase (HRP) and non-saccharide proteins Bovine Serum Albumin (BSA) passes through Fe3O4/
MALDI-TOF map after PDA/GO/BPEI/CBX enrichment.
Specific embodiment
Embodiment 1
1.Fe3O4The preparation of/PDA/GO/BPEI/CBX：(1) FeCl of 1.08g is weighed3·6H2The citric acid of O and 0.2g
Trisodium, is added the ethylene glycol of 20ml, and ultrasonic disperse is uniform.The anhydrous sodium acetate of 1.2g, magnetic agitation at least 30min is added.Most
After be transferred to reaction kettle, 200 DEG C of reaction 10h.End of reaction, respectively three times with deionized water and washes of absolute alcohol product, vacuum
It is dry, obtain Fe3O4.(2) Fe of 100mg is taken3O4, the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5, ultrasound is added
It is uniformly dispersed.The dopamine hydrochloride (DA) of 100mg is rapidly joined, 25 DEG C of water-bath 2h obtain Fe3O4/PDA.End of reaction is used
Deionized water and washes of absolute alcohol product respectively three times, vacuum drying.(3) the GO aqueous solution for preparing 1mg/ml, and is uniformly dispersed
Fe3O4The mixing of/PDA aqueous solution, the two mass ratio are 1：1, react at room temperature 8h.End of reaction, with deionized water wash products 6
It is secondary, vacuum drying.(4) Fe of 1mg/ml is prepared3O4/ PDA/GO aqueous solution, ultrasonic disperse are uniform.Then BPEI aqueous solution is added,
Its quality is Fe3O410 times of/PDA/GO react at room temperature 10h.End of reaction, with deionized water wash products 6 times, vacuum is dry
It is dry.(5) CBX monomer 15mg is weighed, 0.1M pH=5.6MES (morpholino b acid) 15ml is added, ultrasound makes it dissolve.It is added
(N- hydroxysuccinimidyl acyl is sub- by the EDC (1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride) of 64mg, 19.8mg NHS
Amine) form stable succinamide ester, 40 DEG C of activation 45min.The 0.1M Na of 30ml is added2HPO4 adjusts pH to neutrality, at this time
Add the Fe of 15mg3O4/ PDA/GO/BPEI reacts at room temperature 4h.End of reaction, with deionized water wash products 6 times, vacuum is dry
It is dry, for use.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDA/GO/BPEI/CBX is scattered in 200ul 50mM pH=
9.0NH4HCO3In, the mixture (mass ratio 1 of HRP and BSA is added:5), room temperature shakes 2h.After reaction, externally-applied magnetic field point
From discarding supernatant, buffer salt elutes non-glycoprotein three times.Then 20ul eluent ACN/H is used2O/TFA(50:49:1) room temperature is shaken
1h elution HPR is swung, eluting fraction is analyzed for MALDI-TOF.
Embodiment 2
1.Fe3O4The preparation of/PDOPA/GO/PAMAM/CBX：(1) FeCl of 1.08g is weighed3·6H2The lemon of O and 0.2g
Sour trisodium, is added the ethylene glycol of 20ml, and ultrasonic disperse is uniform.The anhydrous sodium acetate of 1.2g, magnetic agitation at least 30min is added.
It is finally transferred to reaction kettle, 200 DEG C of reaction 10h.End of reaction, respectively three times with deionized water and washes of absolute alcohol product, very
Sky is dry, obtains Fe3O4.(2) Fe of 100mg is taken3O4, the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5 is added, surpasses
Sound is uniformly dispersed.The 3,4-dihydroxyphenyl-L-alanine (DOPA) of 100mg is rapidly joined, 25 DEG C of water-bath 2h obtain Fe3O4/PDOPA。
End of reaction, respectively three times with deionized water and washes of absolute alcohol product, vacuum drying.(3) the GO aqueous solution of 1mg/ml is prepared,
With finely dispersed Fe3O4The mixing of/PDOPA aqueous solution, the two mass ratio are 1：1, react at room temperature 8h.End of reaction uses deionization
Water wash products 6 times, vacuum drying.(4) Fe of 1mg/ml is prepared3O4/ PDOPA/GO aqueous solution, ultrasonic disperse are uniform.Then plus
Enter PAMAM solution, quality is Fe3O410 times of/PDOPA/GO react at room temperature 10h.End of reaction cleans production with deionized water
Object 6 times, vacuum drying.(5) CBX monomer 15mg is weighed, 0.1M pH=5.6MES 15ml is added, ultrasound makes it dissolve.It is added
The EDC of 64mg, 19.8mg NHS form stable succinamide ester, 40 DEG C of activation 45min.The 0.1M Na of 30ml is added2HPO4
PH is adjusted to neutrality, adds the Fe of 15mg at this time3O4/ PDOPA/GO/PAMAM reacts at room temperature 4h.End of reaction uses deionization
Water wash products 6 times, vacuum drying, for use.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDOPA/GO/PAMAM/CBX is scattered in 200ul 50mM pH
=9.0NH4HCO3In, the mixture (mass ratio 1 of HRP and BSA is added:5), room temperature shakes 2h.After reaction, externally-applied magnetic field
Separation discards supernatant, and buffer salt elutes non-glycoprotein three times.Then 20ul eluent ACN/H is used2O/TFA(50:49:1) room temperature
It shakes 1h and elutes HPR, eluting fraction is analyzed for MALDI-TOF.
Embodiment expands.
Embodiment 3
1.Fe3O4The preparation of/PDA/GO/BPEI/CPBA：(1) FeCl of 1.08g is weighed3·6H2The citric acid of O and 0.2g
Trisodium, is added the ethylene glycol of 20ml, and ultrasonic disperse is uniform.The anhydrous sodium acetate of 1.2g, magnetic agitation at least 30min is added.Most
After be transferred to reaction kettle, 200 DEG C of reaction 10h.End of reaction, respectively three times with deionized water and washes of absolute alcohol product, vacuum
It is dry, obtain Fe3O4.(2) Fe of 100mg is taken3O4, the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5, ultrasound is added
It is uniformly dispersed.The dopamine hydrochloride of 100mg is rapidly joined, 25 DEG C of water-bath 2h obtain Fe3O4/PDA.End of reaction, spend from
Sub- water and washes of absolute alcohol product respectively three times, vacuum drying.(3) the GO aqueous solution of 1mg/ml is prepared, and it is finely dispersed
Fe3O4The mixing of/PDA aqueous solution, the two mass ratio are 1：1, react at room temperature 8h.End of reaction, with deionized water wash products 6 times,
Vacuum drying.(4) Fe of 1mg/ml is prepared3O4/ PDA/GO aqueous solution, ultrasonic disperse are uniform.Then BPEI aqueous solution is added,
Quality is Fe3O410 times of/PDA/GO react at room temperature 10h.End of reaction, with deionized water wash products 6 times, vacuum drying.
(5) CPBA monomer 15mg is weighed, 0.1M pH=5.6MES 15ml is added, ultrasound makes it dissolve.The EDC of 64mg is added,
19.8mg NHS forms stable succinamide ester, 40 DEG C of activation 45min.The 0.1M Na of 30ml is added2HPO4 adjusts pH into
Property, the Fe of 15mg is added at this time3O4/ PDA/GO/BPEI reacts at room temperature 4h.End of reaction, with deionized water wash products 6
It is secondary, vacuum drying, for use.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDA/GO/BPEI/CPBA is scattered in 200ul50mM pH=
9.0NH4HCO3In, the mixture (mass ratio 1 of HRP and BSA is added:5), room temperature shakes 2h.After reaction, externally-applied magnetic field point
From discarding supernatant, buffer salt elutes non-glycoprotein three times.Then 20ul eluent ACN/H is used2O/TFA(50:49:1) room temperature is shaken
1h elution HPR is swung, eluting fraction is analyzed for MALDI-TOF.
Embodiment 4
1.Fe3O4The preparation of/PDA/GO/PAMAM/FPBA：(1) FeCl of 1.08g is weighed3·6H2The lemon of O and 0.2g
Sour trisodium, is added the ethylene glycol of 20ml, and ultrasonic disperse is uniform.The anhydrous sodium acetate of 1.2g, magnetic agitation at least 30min is added.
It is finally transferred to reaction kettle, 200 DEG C of reaction 10h.End of reaction, respectively three times with deionized water and washes of absolute alcohol product, very
Sky is dry, obtains Fe3O4.(2) Fe of 100mg is taken3O4, the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5 is added, surpasses
Sound is uniformly dispersed.The dopamine hydrochloride of 100mg is rapidly joined, 25 DEG C of water-bath 2h obtain Fe3O4/PDA.End of reaction is spent
Ionized water and washes of absolute alcohol product respectively three times, vacuum drying.(3) the GO aqueous solution of 1mg/ml is prepared, and it is finely dispersed
Fe3O4The mixing of/PDA aqueous solution, the two mass ratio are 1：1, react at room temperature 8h.End of reaction, with deionized water wash products 6 times,
Vacuum drying.(4) Fe of 1mg/ml is prepared3O4/ PDA/GO aqueous solution, ultrasonic disperse are uniform.Then PAMAM aqueous solution is added,
Quality is Fe3O410 times of/PDA/GO react at room temperature 10h.End of reaction, with deionized water wash products 6 times, vacuum drying.
(5) 200mg Fe is weighed3O4/ PDA/GO/PAMAM is scattered in the anhydrous methanol of 40ml, and 400mg FPBA monomer is added, mechanical
Stirring is for 24 hours.The sodium cyanoborohydride of 100mg is added in reaction process every four hours.End of reaction is cleaned with deionized water
Product 6 times, vacuum drying, for use.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDA/GO/PAMAM/FPBA is scattered in 200ul 50mM pH
=9.0NH4HCO3In, the mixture (mass ratio 1 of HRP and BSA is added:5), room temperature shakes 2h.After reaction, externally-applied magnetic field
Separation discards supernatant, and buffer salt elutes non-glycoprotein three times.Then 20ul eluent ACN/H is used2O/TFA(50:49:1) room temperature
It shakes 1h and elutes HPR, eluting fraction is analyzed for MALDI-TOF.
Claims (8)
1. the graphene oxide composite nano materials of phenyl boric acid functionalization, it is characterised in that：
It is by ferroferric oxide magnetic nanoparticle or the external ferroferric oxide magnetic nano for being enclosed with high molecular polymer
Grain is immobilized on graphene oxide, modifies after then carrying out to graphene oxide, is finally introducing phenyl boric acid function monomer；
Wherein, it is in polyethyleneimine, polypropyleneimine or polyamide that high molecular polymer used is modified after graphene oxide
It is one or two or more kinds of；
The phenyl boric acid function monomer is 2- Carboxybenzeneboronic acid, 5- carboxyl -2- methylol phenyl boric acid, 4- formylphenylboronic acid, ammonia
One of base phenyl boric acid or 5- amino -2- methylol phenyl boric acid or two kinds or more.
2. nano material as described in claim 1, it is characterised in that：
The ferroferric oxide magnetic nanoparticle partial size is in 100-300 nm；Or in ferroferric oxide magnetic nanoparticle
Outside is enclosed with high molecular polymer, and package shell thickness forms the ferroso-ferric oxide magnetic with core-shell structure in 5-20 nm
Property nano particle；
By the ferroferric oxide magnetic nanoparticle of 1-20 mass parts or the external ferroso-ferric oxide for being enclosed with high molecular polymer
Magnetic nanoparticle passes through in noncovalent interaction physical absorption to the surface of graphene oxide of 1 mass parts；
The high molecular polymer of 1-50 mass parts is introduced on 1 mass parts graphene oxide；
The graphene oxide of the high molecular polymer modification of 1 mass parts introduces 1-10 mass parts phenyl boric acid function monomer.
3. a kind of preparation method of nano material as claimed in claim 1 or 2, it is characterised in that：By ferroferric oxide magnetic nano
Particle or the external ferroferric oxide magnetic nanoparticle for being enclosed with high molecular polymer are immobilized on graphene oxide, then right
Graphene oxide is modified after carrying out, and is finally introducing phenyl boric acid function monomer.
4. the preparation method of nano material as claimed in claim 3, it is characterised in that：
The ferroferric oxide magnetic nanoparticle partial size is in 100-300 nm；Or in ferroferric oxide magnetic nanoparticle
Outside is enclosed with high molecular polymer, and package shell thickness forms the ferroso-ferric oxide magnetic with core-shell structure in 5-20 nm
Property nano particle；The shell of package is one of high molecular polymer, that is, poly-dopamine or poly- 3,4- dihydroxyphenylalanine
Or two kinds.
5. the preparation method of nano material as described in claim 3 or 4, it is characterised in that：
The immobilized process on graphene oxide of the ferroferric oxide magnetic nanoparticle is：By four oxygen of 1-20 mass parts
Change three ferromagnetic nanoparticles or the external ferroferric oxide magnetic nanoparticle for being enclosed with high molecular polymer pass through it is non-covalent
One of π-π interaction, hydrogen bond or ionic bond or two kinds or more of effect physics are adsorbed onto the graphene oxide of 1 mass parts
On surface.
6. the preparation method of nano material as claimed in claim 3, it is characterised in that：
It is described graphene oxide is carried out after the process modified be：By 1 mass parts graphene oxide by chemical covalent act on or
One of the non-covalent π-π interaction of person, hydrogen bond or ionic bond or two kinds or more of effect introduce 1-50 mass parts dendroid
Or hyper-branched polymer polymer.
7. the preparation method of the nano material as described in claim 3 or 6, it is characterised in that：
The process of the introducing phenyl boric acid function monomer is：After modifying graphene oxide, the polyphosphazene polymer of 1 mass parts
It closes and 1-10 mass parts phenyl boric acid function monomer is introduced by covalent bonding on the graphene oxide of object modification.
8. a kind of graphene oxide composite nano materials of phenyl boric acid functionalization of any of claims 1 or 2 for bioanalysis,
One of the specific recognition of glycoprotein, the enrichment of glycoprotein, the specific recognition of glycopeptide, the enrichment of glycopeptide in field of biotechnology
Or two kinds or more.
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