CN106475068A - The graphene oxide composite nano materials of phenylboric acid functionalization and its preparation and application - Google Patents
The graphene oxide composite nano materials of phenylboric 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 new phenylboric acid functionalization and its preparation and application.Described material is on the immobilized graphene oxide amine-modified to polyethyleneimine of magnetic nanoparticle wrapping up poly-dopamine, introduces the phenylboric acid monomer with carboxyl by the amino of polyethyleneimine further, is eventually used for glycoprotein enrichment.Detailed process is：First pass through solvent-thermal method and prepare ferroferric oxide magnetic nanoparticle, under alkalescence condition, dopamine can be in its surface auto polymerization.Interacted using hydrogen bond between poly-dopamine and graphene oxide and π-π and prepare magnetic oxygenated graphene composite nano material.Then, the polyethyleneimine of positively charged pass through electrostatic self-assembled immobilized on electronegative magnetic oxygenated graphenic surface.Finally, the magnetic oxygenated graphene composite nano material that phenylboric acid monomer obtains phenylboric acid functionalization is introduced by amidation process, and be used successfully to the enrichment of glycoprotein in bioanalysiss.
Description
Technical field
The present invention relates to a kind of graphene oxide composite nano materials of phenylboric acid functionalization and its preparation and
It is applied to the specific enrichment of glycoprotein.
Background technology
Boron is affine strategy is because it is simple to operate, no skewed popularity and the features such as do not destroy glycan structure, in sugar
Obtain more and more widely paying close attention in the enrichment of base Separation of Proteins.But traditional phenylboric acid monomer
(PBA) affinity is low and binding ability of cis vicinal diamines is weak leads to the selectivity to glycoprotein not
High.According to the literature, a kind of new phenylboric acid (2- methylol phenylboric acid ring-type monoesters and its derivant)
There are low pka values (pKa=7.3), higher than traditional phenylboric acid with the binding ability of cis vicinal diamines, because
This is the very potential novel monomeric of one kind, has been applied successfully to the enrichment (Chem. of glycoprotein
Commun.,2012,48,4115–4117；Small,2014,10,No.7,1379–1386).Boric acid functionalization material
The preparation methods adopting rear modification more, the host material that can be used for being bonded boric acid base group includes polymer
Microsphere, agarose gel, macro porous silica gel and magnetic nanoparticle etc..Nano material and polymer ratio
Finite surface area, supported quantity is limited；There is inevitable non-specific adsorption in silica matrix.Therefore send out
Open up new immobilization matrix material very necessary.
Graphene oxide (GO) contains oxygen-containing in a large number as a kind of important derivatives of Graphene, surface
Group, such as hydroxyl, epoxy and carboxyl.It is steady that substantial amounts of oxy radical improves graphene oxide chemistry
Qualitative and hydrophilic, also provides reaction site for preparing graphene oxide composite material.In recent years, receive
The nano-complex that rice corpuscles are bonded to surface of graphene oxide formation can play the excellent of the two simultaneously
Property and become a hot research, catalysis, photoelectron material, surface-enhanced Raman light scattering,
The fields such as bioanalysiss have good application prospect.Wherein, magnetic oxygenated Graphene is due to combining
The advantage of graphene oxide and magnetic nanoparticle and become a kind of new function material, successfully should
For dyestuff and pollutant absorption, medicine is immobilized and release, protein and DNA are immobilized, aptamers
Immobilized etc..Therefore, magnetic oxygenated graphene nanometer composite can be used as the immobilized reason of phenylboric acid monomer
Think substrate.
In sum, magnetic oxygenated graphene nanometer composite to be prepared one as immobilized substrate by us
Plant the new graphene oxide composite nano materials of phenylboric acid functionalization the enrichment for glycoprotein.
Content of the invention
It is an object of the invention to preparing a kind of graphene oxide composite Nano of new phenylboric acid functionalization
Material, and the specific enrichment for glycoprotein.
For realizing this purpose, the technical solution used in the present invention is：
The graphene oxide composite nano materials of phenylboric acid functionalization, are by ferroferric oxide magnetic nanoparticle
Or outer wrap has the ferroferric oxide magnetic nanoparticle of high molecular polymer immobilized to graphene oxide
On, modify after subsequently graphene oxide being carried out, be finally introducing phenylboric acid function monomer.
Described ferroferric oxide magnetic nanoparticle particle diameter is in 100-300nm；Or in ferroso-ferric oxide magnetic
Property nano-particle outer wrap have high molecular polymer, its parcel shell thickness in 5-20nm, forms tool
There is the ferroferric oxide magnetic nanoparticle of nucleocapsid structure；
The ferroferric oxide magnetic nanoparticle of 1-20 mass parts or outer wrap are had the four of high molecular polymer
Fe 3 O magnetic nanoparticle passes through noncovalent interaction physical absorption to the graphene oxide of 1 mass parts
On surface；
The high molecular polymer of 1-50 mass parts is introduced on 1 mass parts graphene oxide；
The graphene oxide that the high molecular polymer of 1 mass parts is modified introduces 1-10 mass parts phenylboric acid function list
Body.
(1) synthesis particle diameter is in the ferroferric oxide magnetic nanoparticle of 100-300nm；Or aoxidize three four
Ferromagnetic nanoparticle outer wrap has high molecular polymer, and its parcel shell thickness is in 5-20nm, shape
Become there is the ferroferric oxide magnetic nanoparticle of nucleocapsid structure；The shell of parcel is high molecular polymer
I.e. one of poly-dopamine or poly- 3,4- dihydroxyphenylalanine or more than two kinds.
(2) ferroferric oxide magnetic nanoparticle of 1-20 mass parts or outer wrap there is high molecular polymer
Ferroferric oxide magnetic nanoparticle pass through noncovalent interaction (π-π interact, hydrogen bond or ion
One of key or more than two kinds) physical absorption is in the surface of graphene oxide of 1 mass parts.
(3) 1 mass parts graphene oxide is acted on by chemical covalent or noncovalent interaction (π-π is mutual
One of effect, hydrogen bond or ionic bond or more than two kinds) introduce 1-50 mass parts dendroid or super
Branched polymer；High molecular polymer includes polyethyleneimine, PPI or polyamide
One of amine or more than two kinds
On the graphene oxide that the high molecular polymer of (4) 1 mass parts is modified, 1-10 is introduced by covalent bonding
Mass parts phenylboric acid function monomer.The covalent bonding of phenylboric acid function monomer specifically include following in one
Plant or more than two kinds：By the amidation process of amino and carboxyl introduce 2- Carboxybenzeneboronic acid (CPBA),
One of 5- carboxyl -2- methylol phenylboric acid (CBX) or more than two kinds；Amino and the nucleophilic of aldehyde radical
Additive reaction introduces 4- formylphenylboronic acid (FPBA)；Glutaraldehyde introduces amino phenylboric acid as coupling agent
(APBA), one of 5- amino -2- methylol phenylboric acid (ABX) or more than two kinds.
(5) the graphene oxide composite nano materials of described phenylboric acid functionalization are used for bioanalysiss, life
The enrichment of the specific recognition of glycoprotein, glycoprotein in thing technical field.
The invention has the advantages that：
(1) prepare easy, mild condition；Its preparation process is using water as solvent, environmental friendliness.
(2) introduce dendroid or hyperbranched high molecular polymer, can be follow-up phenylboric acid function monomer
Bonding provides more reaction site, improves the selectivity of material.
(3) graphene oxide composite nano materials have specific surface area height, non-specific suction as immobilized substrate
Attached few the advantages of.
(4) non-covalent bonding method preparation has magnetic graphene oxide, not disruptive oxidation Graphene
Matter.
Brief description
Fig. 1 is Fe3O4/ PDA transmission electron microscope picture.
Fig. 2 is Fe3O4/ PDA/GO/BPEI transmission electron microscope picture.
Fig. 3 is Fe for Fig. 23O4/ PDA/GO/BPEI/CBX transmission electron microscope picture.
Fig. 4 is Fe3O4The x-ray photoelectron energy spectrum diagram of/PDA/GO/BPEI/CBX.
Fig. 5 is glycoprotein horseradish peroxidase (HRP) and non-saccharide proteins Bovine Serum Albumin (BSA) warp
Cross Fe3O4MALDI-TOF collection of illustrative plates after/PDA/GO/BPEI/CBX enrichment.
Specific embodiment
Embodiment 1
1.Fe3O4The preparation of/PDA/GO/BPEI/CBX：(1) weigh the FeCl of 1.08g3·6H2O and
The trisodium citrate of 0.2g, adds the ethylene glycol of 20ml, and ultrasonic disperse is uniform.Add the nothing of 1.2g
Water sodium acetate, magnetic agitation at least 30min.It is finally transferred to reactor, 200 DEG C of reaction 10h.Instead
Should finish, deionized water and each three times of washes of absolute alcohol product, vacuum drying, obtain Fe3O4.(2)
Take the Fe of 100mg3O4, add the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5, surpass
Sound is uniformly dispersed.Rapidly join the dopamine hydrochloride (DA) of 100mg, 25 DEG C of water-bath 2h, obtain
Fe3O4/PDA.Reaction finishes, deionized water and each three times of washes of absolute alcohol product, vacuum drying.
(3) prepare the GO aqueous solution of 1mg/ml, with finely dispersed Fe3O4/ PDA aqueous solution,
The two mass ratio is 1：1, room temperature reaction 8h.Reaction finishes, deionized water wash products 6 times,
Vacuum drying.(4) prepare the Fe of 1mg/ml3O4/ PDA/GO aqueous solution, ultrasonic disperse is uniform.So
Add BPEI aqueous solution afterwards, its quality is Fe3O410 times of/PDA/GO, room temperature reaction 10h.
Reaction finishes, deionized water wash products 6 times, vacuum drying.(5) weigh CBX monomer 15mg,
Add 0.1M pH=5.6MES (morpholino b acid) 15ml, ultrasonic so that it is dissolved.Add 64mg's
EDC (1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride), 19.8mg NHS (N- hydroxyl amber
Amber acid imide) form stable succinamide ester, 40 DEG C of activation 45min.Add the 0.1M of 30ml
Na2HPO4 adjusts pH to neutral, now adds the Fe of 15mg3O4/ PDA/GO/BPEI, room
Temperature reaction 4h.Reaction finishes, deionized water wash products 6 times, vacuum drying, stand-by.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDA/GO/BPEI/CBX is scattered in 200ul 50
MM pH=9.0NH4HCO3In, add the mixture (mass ratio 1 of HRP and BSA:5), room temperature
Concussion 2h.After reaction terminates, externally-applied magnetic field separation supernatant discarded, the non-glycoprotein of three buffer salt drip washing.
Then use 20ul eluent ACN/H2O/TFA(50:49:1) room temperature concussion 1h eluting HPR, eluting evaporates
Divide for MALDI-TOF analysis.
Embodiment 2
1.Fe3O4The preparation of/PDOPA/GO/PAMAM/CBX：(1) weigh the FeCl of 1.08g3·6H2O
With the trisodium citrate of 0.2g, add the ethylene glycol of 20ml, ultrasonic disperse is uniform.Add 1.2g
Anhydrous sodium acetate, magnetic agitation at least 30min.It is finally transferred to reactor, 200 DEG C of reaction 10h.
Reaction finishes, deionized water and each three times of washes of absolute alcohol product, vacuum drying, obtains Fe3O4.
(2) take the Fe of 100mg3O4, add the Tris-HCl buffer salt of 50ml 10mM pH=8.5 molten
Liquid, ultrasonic disperse is uniform.Rapidly join the 3,4-dihydroxyphenyl-L-alanine (DOPA) of 100mg, 25 DEG C
Water-bath 2h, obtains Fe3O4/PDOPA.Reaction finishes, deionized water and washes of absolute alcohol product
Each three times, vacuum drying.(3) prepare the GO aqueous solution of 1mg/ml, and finely dispersed
Fe3O4/ PDOPA aqueous solution, the two mass ratio is 1：1, room temperature reaction 8h.Reaction finishes,
Deionized water wash products 6 times, vacuum drying.(4) prepare the Fe of 1mg/ml3O4/PDOPA/GO
Aqueous solution, ultrasonic disperse is uniform.It is subsequently adding PAMAM solution, its quality is Fe3O4/PDOPA/GO
10 times, room temperature reaction 10h.Reaction finishes, deionized water wash products 6 times, vacuum drying.
(5) weigh CBX monomer 15mg, add 0.1M pH=5.6MES 15ml, ultrasonic so that it is dissolved.
The EDC of 64mg, 19.8mg NHS is added to form stable succinamide ester, 40 DEG C of activation 45min.
Add the 0.1M Na of 30ml2HPO4 adjusts pH to neutral, now adds 15mg's
Fe3O4/ PDOPA/GO/PAMAM, room temperature reaction 4h.Reaction finishes, and deionized water cleaning is produced
Thing 6 times, vacuum drying, stand-by.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDOPA/GO/PAMAM/CBX is scattered in
200ul 50mM pH=9.0NH4HCO3In, add the mixture (mass ratio 1 of HRP and BSA:5),
Room temperature shakes 2h.After reaction terminates, externally-applied magnetic field separation supernatant discarded, three buffer salt drip washing non-saccharide
Albumen.Then use 20ul eluent ACN/H2O/TFA(50:49:1) room temperature concussion 1h eluting HPR,
Eluting fraction is used for MALDI-TOF and analyzes.
Embodiment expands.
Embodiment 3
1.Fe3O4The preparation of/PDA/GO/BPEI/CPBA：(1) weigh the FeCl of 1.08g3·6H2O and
The trisodium citrate of 0.2g, adds the ethylene glycol of 20ml, and ultrasonic disperse is uniform.Add the nothing of 1.2g
Water sodium acetate, magnetic agitation at least 30min.It is finally transferred to reactor, 200 DEG C of reaction 10h.Instead
Should finish, deionized water and each three times of washes of absolute alcohol product, vacuum drying, obtain Fe3O4.(2)
Take the Fe of 100mg3O4, add the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5, surpass
Sound is uniformly dispersed.Rapidly join the dopamine hydrochloride of 100mg, 25 DEG C of water-bath 2h, obtain
Fe3O4/PDA.Reaction finishes, deionized water and each three times of washes of absolute alcohol product, vacuum drying.
(3) prepare the GO aqueous solution of 1mg/ml, with finely dispersed Fe3O4/ PDA aqueous solution,
The two mass ratio is 1：1, room temperature reaction 8h.Reaction finishes, deionized water wash products 6 times,
Vacuum drying.(4) prepare the Fe of 1mg/ml3O4/ PDA/GO aqueous solution, ultrasonic disperse is uniform.So
Add BPEI aqueous solution afterwards, its quality is Fe3O410 times of/PDA/GO, room temperature reaction 10h.
Reaction finishes, deionized water wash products 6 times, vacuum drying.(5) weigh CPBA monomer 15mg,
Add 0.1M pH=5.6MES 15ml, ultrasonic so that it is dissolved.Add the EDC, 19.8mg of 64mg
NHS forms stable succinamide ester, 40 DEG C of activation 45min.Add the 0.1M Na of 30ml2HPO4
Adjust pH to neutral, now add the Fe of 15mg3O4/ PDA/GO/BPEI, room temperature reaction 4h.
Reaction finishes, deionized water wash products 6 times, vacuum drying, stand-by.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDA/GO/BPEI/CPBA is scattered in 200ul
50mM pH=9.0NH4HCO3In, add the mixture (mass ratio 1 of HRP and BSA:5), room
Temperature concussion 2h.After reaction terminates, externally-applied magnetic field separation supernatant discarded, three buffer salt drip washing non-saccharide eggs
In vain.Then use 20ul eluent ACN/H2O/TFA(50:49:1) room temperature concussion 1h eluting HPR, washes
De- fraction is used for MALDI-TOF and analyzes.
Embodiment 4
1.Fe3O4The preparation of/PDA/GO/PAMAM/FPBA：(1) weigh the FeCl of 1.08g3·6H2O and
The trisodium citrate of 0.2g, adds the ethylene glycol of 20ml, and ultrasonic disperse is uniform.Add the nothing of 1.2g
Water sodium acetate, magnetic agitation at least 30min.It is finally transferred to reactor, 200 DEG C of reaction 10h.Instead
Should finish, deionized water and each three times of washes of absolute alcohol product, vacuum drying, obtain Fe3O4.(2)
Take the Fe of 100mg3O4, add the Tris-HCl buffer salt solution of 50ml 10mM pH=8.5, surpass
Sound is uniformly dispersed.Rapidly join the dopamine hydrochloride of 100mg, 25 DEG C of water-bath 2h, obtain
Fe3O4/PDA.Reaction finishes, deionized water and each three times of washes of absolute alcohol product, vacuum drying.
(3) prepare the GO aqueous solution of 1mg/ml, with finely dispersed Fe3O4/ PDA aqueous solution,
The two mass ratio is 1：1, room temperature reaction 8h.Reaction finishes, deionized water wash products 6 times,
Vacuum drying.(4) prepare the Fe of 1mg/ml3O4/ PDA/GO aqueous solution, ultrasonic disperse is uniform.So
Add PAMAM aqueous solution afterwards, its quality is Fe3O410 times of/PDA/GO, room temperature reaction 10h.
Reaction finishes, deionized water wash products 6 times, vacuum drying.(5) weigh 200mg
Fe3O4/ PDA/GO/PAMAM is scattered in the absolute methanol of 40ml, adds 400mg FPBA
Monomer, mechanical agitation 24h.Add the cyano group hydroboration of 100mg every four hours in course of reaction
Sodium.Reaction finishes, deionized water wash products 6 times, vacuum drying, stand-by.
2. the enrichment of standard glycoprotein：Take 100 μ g Fe3O4/ PDA/GO/PAMAM/FPBA is scattered in 200
Ul 50mM pH=9.0NH4HCO3In, add the mixture (mass ratio 1 of HRP and BSA:5),
Room temperature shakes 2h.After reaction terminates, externally-applied magnetic field separation supernatant discarded, three buffer salt drip washing non-saccharide
Albumen.Then use 20ul eluent ACN/H2O/TFA(50:49:1) room temperature concussion 1h eluting HPR,
Eluting fraction is used for MALDI-TOF and analyzes.
Claims (8)
1. phenylboric acid functionalization graphene oxide composite nano materials it is characterised in that：
It is the ferroso-ferric oxide magnetic that ferroferric oxide magnetic nanoparticle or outer wrap are had high molecular polymer
Property nano-particle immobilized on graphene oxide, after subsequently graphene oxide being carried out modify, finally draw
Enter phenylboric acid function monomer.
2. nano material as claimed in claim 1 it is characterised in that：
Described ferroferric oxide magnetic nanoparticle particle diameter is in 100-300nm；Or in ferroso-ferric oxide magnetic
Property nano-particle outer wrap have high molecular polymer, its parcel shell thickness in 5-20nm, forms tool
There is the ferroferric oxide magnetic nanoparticle of nucleocapsid structure；
The ferroferric oxide magnetic nanoparticle of 1-20 mass parts or outer wrap are had the four of high molecular polymer
Fe 3 O magnetic nanoparticle passes through noncovalent interaction physical absorption to the graphene oxide of 1 mass parts
On surface；
The high molecular polymer of 1-50 mass parts is introduced on 1 mass parts graphene oxide；
The graphene oxide that the high molecular polymer of 1 mass parts is modified introduces 1-10 mass parts phenylboric acid function list
Body.
3. nano material described in a kind of claim 1 or 2 preparation method it is characterised in that：Four are aoxidized
Three ferromagnetic nanoparticle or outer wrap have the ferroferric oxide magnetic nanoparticle of high molecular polymer
Immobilized on graphene oxide, after subsequently graphene oxide being carried out modify, be finally introducing phenylboric acid work(
Can monomer.
4. nano material as claimed in claim 3 preparation method it is characterised in that：
Described ferroferric oxide magnetic nanoparticle particle diameter is in 100-300nm；Or in ferroso-ferric oxide magnetic
Property nano-particle outer wrap have high molecular polymer, its parcel shell thickness in 5-20nm, forms tool
There is the ferroferric oxide magnetic nanoparticle of nucleocapsid structure；The shell of parcel gathers for high molecular polymer
One of dopamine or poly- 3,4- dihydroxyphenylalanine or more than two kinds.
5. as described in claim 3 or 4 nano material preparation method it is characterised in that：
The immobilized process on graphene oxide of described ferroferric oxide magnetic nanoparticle is：By 1-20 matter
Measure the ferroferric oxide magnetic nanoparticle of part or outer wrap has the ferroso-ferric oxide of high molecular polymer
Magnetic nanoparticle pass through noncovalent interaction (π-π interacts, one of hydrogen bond or ionic bond or
More than two kinds) physical absorption is in the surface of graphene oxide of 1 mass parts.
6. nano material as claimed in claim 3 preparation method it is characterised in that：
Described graphene oxide is carried out after modify process be：1 mass parts graphene oxide is passed through chemistry altogether
Valency effect or noncovalent interaction (π-π interacts, one of hydrogen bond or ionic bond or two kinds with
On) introduce 1-50 mass parts dendroid or hyper-branched polymer polymer；High molecular polymer includes gathering
One of aziridine, PPI or daiamid or more than two kinds.
7. the nano material as described in claim 3 or 6 it is characterised in that：
The process of described introducing phenylboric acid function monomer is：After graphene oxide is modified, 1 mass parts
High molecular polymer modify graphene oxide on by covalent bonding introducing 1-10 mass parts phenylboric acid
Function monomer；
The covalent bonding of phenylboric acid function monomer specifically includes one of following or more than two kinds：Amidatioon is anti-
One of 2- Carboxybenzeneboronic acid or 5- carboxyl -2- methylol phenylboric acid or more than two kinds should be introduced；Nucleophilic adds
Reaction is become to introduce 4- formylphenylboronic acid；Glutaraldehyde introduces amino phenylboric acid or 5- amino -2- as coupling agent
One of methylol phenylboric acid or more than two kinds.
8. a kind of graphene oxide composite nano materials of the phenylboric acid functionalization described in claim 1 or 2 are used for
The specific recognition of glycoprotein, the enrichment of glycoprotein, the spy of glycopeptide in bioanalysiss, biological technical field
One of different identification, the enrichment of glycopeptide or more than two kinds.
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