CN107213879A - Hyperbranched chlorogenic acid molecular engram magnetic nano-balls of a kind of amino and its preparation method and application - Google Patents
Hyperbranched chlorogenic acid molecular engram magnetic nano-balls of a kind of amino and its preparation method and application Download PDFInfo
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Abstract
The invention discloses hyperbranched chlorogenic acid molecular engram magnetic nano-balls of a kind of amino and its preparation method and application.First synthesizing amino magnetic nano-balls；Then amino-magnetic nanosphere and methyl acrylate are added in ethanol, after stirring at normal temperature, add ethylenediamine heating stirring, obtain the magnetic nano-balls of the hyperbranched modification of amino；The magnetic nano-balls of the hyperbranched modification of amino, chlorogenic acid are added in ethanol, Dopamine hydrochloride is added and carries out polymerisation；The solid polymer for reacting generation is separated by externally-applied magnetic field, after elution, drying, that is, target product is obtained.It is hyperbranched that the present invention has carried out amino to carrier magnetic nano-balls, add the number of its surface amino groups active group, using dopamine as function monomer and crosslinking agent, preparation method is simple, mild condition, obtained target product uniform particle diameter, stability are strong, good water solubility, can quickly realize and the high selectivity of complex matrices Content of Chlorogenic Acid is removed and is enriched with.
Description
Technical field
The present invention relates to the technical fields such as molecular recognition, Magnetic Isolation, nano material and food analysis, and in particular to a kind of
Hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino and its preparation method and application.
Background technology
Chlorogenic acid (Chlorogenic acid, CGA) be it is a kind of found in a variety of meals plants and medicinal plant it is many
Phenolic compounds, makees with antioxidation activity, antiinflammatory action, antibiotic property, hypoglycemic, reducing blood lipid, antitumor action and anti-hypertension
With.
CGA is soluble in water, and the compound for generally having some similar functional groups coexists therewith, such as caffeic acid, gallic acid
Deng.Therefore, before CGA is quantified, it is necessary first to the selective extraction CGA from complex matrices.
At present, the conventional method of detection of complex matrix Content of Chlorogenic Acid mainly has chromatography (including gas chromatography (GC), high
Effect liquid phase chromatogram method (HPLC)), mass spectrography (MS) and GC-MS (GC-MS, HPLC-MS) etc..There is sample in these methods
Pretreatment process is complicated, the shortcomings of need time length, poor selectivity.
Molecular imprinting technology (Molecularly Imprinted Technique, MIT) is earliest by Wulff and Sarhan
Proposed, as an attractive technology, have to build with template molecule in size, shape and change in 1972
Learn function complete complementary specific position molecularly imprinted polymer (Molecularly Imprinted Polymers,
MIPs).MIPs has that precordainment, cost are low, it is simple to prepare, mechanically and chemically stability it is high, special suitable for adverse circumstances, selection
The advantages of opposite sex is high.Due to the advantage of its protrusion, MIPs has been widely used for chromatogram, biology sensor, drug delivery, solid phase
Extract fields such as (SPE).In such applications, polymer is as solid phase extraction adsorbentses, from various complex matrices to mesh
In marking analyte selective extraction or removing, there is very big application prospect.
The CGA molecularly imprinted polymers reported before are mostly prepared in organic media, polymer may be caused to know
Other ability, the non-specific adsorption height in water-based.Therefore, easy and effective preparation hydrophily CGA molecular engrams are developed
The method of polymer, to realizing that the efficiently concentrating of complex matrices Content of Chlorogenic Acid, effective detection, quick remove etc. have important grind
Study carefully meaning.
Dissaving polymer is that a class has the random multi-level branched polymer of the height of three-dimensional globular stereochemical structure, and it is unique
Three-dimensional molecular structure make it have the premium properties such as low viscosity, high reaction activity and good intermiscibility, while substantial amounts of end
End group can further functionalization.The concept of dissaving polymer is to be carried for the first time by E.I.Du Pont Company Kim and Webster for 1988
Go out, be hereafter just quickly become the focus of polymer science circle research.The synthesis of dissaving polymer has ABxMonomer polycondensation, AB*
The self condensing of monomer, vinyl polymerization and ABxA variety of methods such as the hyper-branched ring-opening polymerisation of monomer, synthesis step is simple and nothing
The separating-purifying for needing multistep complicated.Nano material is gradually expanded in recent years to the functionalization research of dissaving polymer, it is electroluminescent
The application aspect of the new function materials such as luminescent material, medicinal slow release agent, sensing material.
Magnetic Isolation is the magnetic contrast according to material, under the driving of magnetic force, magnetic component from non magnetic
A kind of isolation technics separated in component mixture.Traditionally, MIPs must be installed into solid-phase extraction column or carry out solid phase
Using centrifugation and filtering during extraction.Process is time-consuming, complexity, and generally extraction efficiency is relatively low.Magnetic Fe3O4Nano-particle (NPS) has
Have that biocompatibility is good, magnetic susceptibility is high, the low feature of toxicity.The molecularly imprinted polymer prepared by carrier of NPS is as admittedly
Mutually extraction adsorbent is except having the advantages that general nano material specific surface area is big, the rate of adsorption is fast, also with relatively low coercivity
And superparamagnetism, it can be directly dispersing in selective enrichment object in solution, using can be complete after the quick separating of magnetic field
Into extraction.
At present, also not on preparing and can divide to quick high-selectivity using magnetic nano-balls and hyperbranched polymerisation
From the relevant report of the chlorogenic acid molecularly imprinted polymer of enrichment complex matrices Content of Chlorogenic Acid.
The content of the invention
It is an object of the invention to provide a kind of hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino and its preparation
Methods and applications, this method using magnetic nano-balls as carrier, and carrier has been carried out it is hyperbranched, using fixed form method molecule print
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino, the hyperbranched green original of amino made from this method have been made in mark technology
Chlorogenic acid of the acid molecule trace magnetic nano-balls energy quick high-selectivity ground in separation and concentration complex matrices.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino, comprises the following steps：
Step one：Ag iron chloride, B g sodium acetates, C g hexamethylene diamines and D mL ethylene glycol are placed in reactor, 180~
7~9h is reacted at 210 DEG C, after reaction terminates, reaction product is washed, dried, that is, obtains amino-magnetic nanosphere；Wherein A:B:
C:D=(0.8~1.2):(3.4~4.8):(4.5~6.5):(20~30)；
Step 2：By amino-magnetic nanosphere, F mL absolute ethyl alcohols and G mL methyl acrylates made from E mg steps one
It is placed in reaction vessel, 5~7h is reacted under normal temperature, H mL ethylenediamines-ethanol solution, the stirring reaction at 40~60 DEG C is added
3~6h, after reaction terminates, reaction product is washed, dried, that is, obtains the magnetic nano-balls of the hyperbranched modification of amino；Wherein E:
F:G:H=(100~500):(20~30):(5~20):(15~25)；
Step 3：By the magnetic nano-balls of the hyperbranched modification of amino, J mg Dopamine hydrochlorides and K made from I g step 2
Mg chlorogenic acids are added in M mL Tris-HCl buffer solutions, at room temperature 6~8h of polymerisation, generate solid polymer；Wherein I:
J:K:M=(0.1~0.2):(45~65):(20~30):(20~30)；
Step 4：After the polymerisation in step 3 terminates, the solid-state generated in reaction solution is gathered by externally-applied magnetic field
Compound is separated；The solid polymer isolated is eluted again, dried, that is, obtains the hyperbranched chlorogenic acid molecule of amino
Trace magnetic nano-balls.
Reaction product is washed to neutrality, then at 40~50 DEG C and 0.05 with ultra-pure water in the step one and step 2
~0.09MPa vacuum under pressure dries 4~7h.
Ethylenediamine-ethanol solution in the step 2 be by volume ratio be 1:The ethylenediamine and absolute ethyl alcohol of (1~3) are mixed
Conjunction is formulated.
The pH value of Tris-HCl buffer solutions in the step 3 is 7~8.5.
The eluent used in the step 4 is that volume ratio is (92~99):The absolute ethyl alcohol of (8~1) and mixing for acetic acid
Close solution.
Drying temperature in the step 4 is 40~50 DEG C, and drying time is 4~7h.
Amino made from the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of described amino is hyperbranched
Chlorogenic acid molecular engram magnetic nano-balls, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of the amino are to chlorogenic acid
Adsorbance is 5.98~6.27mg/g.
The particle diameter of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of the amino is 20~25nm.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of described amino are in the enrichment to matrix Content of Chlorogenic Acid, inspection
Application in terms of survey, separation and removal.
Application of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of described amino in terms of chlorogenic acid is adsorbed.
Relative to prior art, beneficial effects of the present invention are：
The preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino that the present invention is provided, first uses hydro-thermal method
Synthesizing amino magnetic nano-balls；Then amino-magnetic nanosphere and methyl acrylate are added in ethanol, after stirring at normal temperature, then
Ethylenediamine heating stirring is added, the magnetic nano-balls of the hyperbranched modification of amino are obtained；The magnetic by the hyperbranched modification of amino is received again
Rice ball, chlorogenic acid are added in ethanol, obtain the compound of template-carrier；Dopamine hydrochloride is added to be polymerize, consolidate
State polymer；Solid polymer is separated finally by externally-applied magnetic field, solid polymer is eluted, dry after, that is, obtain
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino.Preparation method of the present invention is simple, mild condition, using magnetic Nano
Ball both may be implemented in the quick separating of solid-liquid under externally-applied magnetic field as carrier, ensure that the good dispersion of carrier, while right
Carrier magnetic nano-balls have carried out that amino is hyperbranched, add the number of its surface amino groups active group.And the present invention is with salt
Sour dopamine is function monomer and crosslinking agent, can fully be acted on template molecule, and reaction is simple easily operated；Using stent
Plate method molecular imprinting technology, makes gained solid polymer both have single-minded selectivity to specific template molecule, has again good
Water solubility.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls uniform particle diameter of amino produced by the present invention, stability are strong, water
Dissolubility is good, and the high adsorption capacity, adsorbance to chlorogenic acid are big, easy, efficiently, rapidly can realize to complex matrices Content of Chlorogenic Acid
High selectivity remove, separation and be enriched with, to matrix, the especially enrichment of complex matrices Content of Chlorogenic Acid, detect, separate and go
Had a good application prospect in terms of removing.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture for the amino-magnetic nanosphere that the step one of the embodiment of the present invention 1 is synthesized.
Fig. 2 is the transmission electricity of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from the embodiment of the present invention 1
Mirror figure.
Embodiment
Below in conjunction with the accompanying drawings and preferably embodiment of the invention is described in further details to the present invention.
Embodiment 1
Step 1: 0.98g iron chloride, 3.46g sodium acetates, 6.03g hexamethylene diamines and 30mL ethylene glycol are placed in reactor,
200 DEG C of reaction 9h, after reaction terminates, are washed to neutrality with ultrapure by reaction product, 4h are dried in vacuo under 45 DEG C, 0.06MPa,
Obtain amino-magnetic nanosphere.As shown in figure 1, the particle diameter of obtained amino-magnetic nanosphere is about 20nm.
Step 2: take amino-magnetic nanosphere made from 100mg steps one, then by 30mL absolute ethyl alcohols, 5mL acrylic acid first
Ester is placed in there-necked flask together, and 5h is reacted under normal temperature, adds stirring reaction 3h at 20mL ethylenediamines-ethanol solution, 50 DEG C, instead
After should terminating, reaction product is washed to neutrality with ultrapure, 4h is dried in vacuo under 45 DEG C, 0.06MPa, produces amino hyperbranched
The magnetic nano-balls of modification；Wherein ethylenediamine-ethanol solution be by volume ratio be 1:1 ethylenediamine and absolute ethyl alcohol mixed preparing
Form；
Step 3: by the magnetic nano-balls of the hyperbranched modification of amino made from 0.1g step 2,45mg function monomer hydrochloric acid
Dopamine (this function monomer can also play a part of crosslinking agent) and 20mg chlorogenic acids are added to the Tris- that 30mL pH value is 8.5
In HCl buffer solutions, polymerisation 8h, generates solid polymer at room temperature；
Step 4: after polymerisation terminates, the solid polymer generated in step 3 reaction solution is divided by externally-applied magnetic field
Separate out and；
Step 5: being 92 with volume ratio:The solid-state isolated in 8 absolute ethyl alcohol and the mixed liquor elution step four of acetic acid
Polymer, then 4h is dried at 45 DEG C, produce the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino.As shown in Fig. 2 system
The particle diameters of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino be about 22nm.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from embodiment 1 are subjected to absorption property detection,
It is specific as follows：
(1) the hyperbranched chlorogenic acid molecular engram magnetic nano-balls 10mg of amino is added to 10mL concentration for 35 μ g/mL
CGA the aqueous solution in, at room temperature shake 10min after, supernatant is separated by externally-applied magnetic field；
(2) concentration of CGA in gained supernatant in (1) is determined with high performance liquid chromatography, then to calculate amino hyperbranched
Adsorbance of the chlorogenic acid molecular engram magnetic nano-balls to CGA；
CGA concentration is 28.86 μ g/mL in measured supernatant；
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of described amino are to the calculation formula of CGA adsorbance：
C in formulaeFor the concentration of CGA in above-mentioned supernatant；
By calculating, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino are to CGA adsorbance：6.14mg/
g。
Embodiment 2
Step 1: by 1.05g iron chloride, 3.98g sodium acetates, 5.14g hexamethylene diamines and 25mL ethylene glycol are placed in reactor,
180 DEG C of reaction 8h, after reaction terminates, are washed to neutrality with ultrapure by reaction product, 5h are dried in vacuo under 40 DEG C, 0.07MPa,
Produce amino-magnetic nanosphere.
Step 2: take amino-magnetic nanosphere made from 200mg steps one, then by 25mL absolute ethyl alcohols, 15mL acrylic acid
Methyl esters is placed in there-necked flask together, and 5h is reacted under normal temperature.Stirring reaction 4h at 18mL ethylenediamines-ethanol solution, 60 DEG C is added,
After reaction terminates, reaction product is washed to neutrality with ultrapure, 5h is dried in vacuo under 40 DEG C, 0.07MPa, produce amino over-expense
Change the magnetic nano-balls of modification；Wherein ethylenediamine-ethanol solution be by volume ratio be 1:1.5 ethylenediamine and absolute ethyl alcohol mixing
It is formulated；
Step 3: by the magnetic nano-balls of the hyperbranched modification of amino made from 0.15g step 2,50mg function monomer hydrochloric acid
Dopamine (this function monomer can also play a part of crosslinking agent) and 20mg chlorogenic acids are added to the Tris- that 25mL pH value is 7.5
In HCl buffer solutions, polymerisation 7h, generates solid polymer at room temperature；
Step 4: after polymerisation terminates, the solid polymer generated in step 3 reaction solution is divided by externally-applied magnetic field
Separate out and；
Step 5: the solid polymer isolated in elution step four, then 5h is dried at 40 DEG C, produce amino hyperbranched
Chlorogenic acid molecular engram magnetic nano-balls.Wherein eluent is that volume ratio is 93:7 absolute ethyl alcohol and the mixed liquor of acetic acid.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from embodiment 2 are subjected to absorption property detection,
It is specific as follows：
(1) the hyperbranched chlorogenic acid molecular engram magnetic nano-balls 10mg of amino is added to 10mL concentration for 35 μ g/mL
CGA the aqueous solution in, at room temperature shake 10min after, supernatant is separated by externally-applied magnetic field；
(2) concentration of CGA in gained supernatant in (1) is determined with high performance liquid chromatography, then to calculate amino hyperbranched
Adsorbance of the chlorogenic acid molecular engram magnetic nano-balls to CGA；
CGA concentration is 28.77 μ g/mL in measured supernatant；
By calculating, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino are to CGA adsorbance：6.23mg/
g。
Embodiment 3
Step 1: by 1.15g iron chloride, 4.06g sodium acetates, 5.29g hexamethylene diamines and 28mL ethylene glycol are placed in reactor,
190 DEG C of reaction 8h, after reaction terminates, are washed to neutrality with ultrapure by reaction product, 6h are dried in vacuo under 48 DEG C, 0.06MPa,
Produce amino-magnetic nanosphere.
Step 2: take amino-magnetic nanosphere made from 250mg steps one, then by 28mL absolute ethyl alcohols, 18mL acrylic acid
Methyl esters is placed in there-necked flask together, and 6.5h is reacted under normal temperature.Add stirring reaction at 22mL ethylenediamines-ethanol solution, 48 DEG C
5.6h, after reaction terminates, is washed to neutrality with ultrapure by reaction product, is dried in vacuo 6h under 48 DEG C, 0.06MPa, produces ammonia
The magnetic nano-balls of the hyperbranched modification of base.Wherein ethylenediamine-ethanol solution be by volume ratio be 1:2 ethylenediamine and absolute ethyl alcohol
Mixed preparing is formed；
Step 3: by the magnetic nano-balls of the hyperbranched modification of amino made from 0.13g step 2,60mg function monomer hydrochloric acid
Dopamine (this function monomer can also play a part of crosslinking agent) and 20mg chlorogenic acids are added to the Tris- that 26mL pH value is 8.0
In HCl buffer solutions, polymerisation 7.4h, generates solid polymer at room temperature；
Step 4: after polymerisation terminates, the solid polymer generated in step 3 reaction solution is divided by externally-applied magnetic field
Separate out and；
Step 5: the solid polymer isolated in elution step four, then 6h is dried at 48 DEG C, produce amino hyperbranched
Chlorogenic acid molecular engram magnetic nano-balls.Wherein eluent is that volume ratio is 94:6 absolute ethyl alcohol and the mixed liquor of acetic acid.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from embodiment 3 are subjected to absorption property detection,
It is specific as follows：
(1) the hyperbranched chlorogenic acid molecular engram magnetic nano-balls 10mg of amino is added to 10mL concentration for 35 μ g/mL
CGA the aqueous solution in, at room temperature shake 10min after, supernatant is separated by externally-applied magnetic field；
(2) concentration of CGA in gained supernatant in (1) is determined with high performance liquid chromatography, then to calculate amino hyperbranched
Adsorbance of the chlorogenic acid molecular engram magnetic nano-balls to CGA；
CGA concentration is 28.73 μ g/mL in measured supernatant；
By calculating, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino are to CGA adsorbance：6.27mg/
g。
Embodiment 4
Step 1: by 0.85g iron chloride, 4.52g sodium acetates, 4.86g hexamethylene diamines and 24mL ethylene glycol are placed in reactor,
195 DEG C of reaction 7.8h, after reaction terminates, neutrality is washed to ultrapure by reaction product, is dried in vacuo under 46 DEG C, 0.08MPa
4.5h, produces amino-magnetic nanosphere.
Step 2: take amino-magnetic nanosphere made from 350mg steps one, then by 27mL absolute ethyl alcohols, 5mL acrylic acid first
Ester is placed in there-necked flask together, and 5.5h is reacted under normal temperature.Add stirring reaction at 20mL ethylenediamines-ethanol solution, 55 DEG C
5.8h, after reaction terminates, is washed to neutrality with ultrapure by reaction product, is dried in vacuo 4.5h under 46 DEG C, 0.08MPa, produces
The magnetic nano-balls of the hyperbranched modification of amino；Wherein ethylenediamine-ethanol solution be by volume ratio be 1:3 ethylenediamine and anhydrous second
Alcohol mixed preparing is formed；
Step 3: by the magnetic nano-balls of the hyperbranched modification of amino made from 0.16g step 2,65mg function monomer hydrochloric acid
Dopamine (this function monomer can also play a part of crosslinking agent) and 20mg chlorogenic acids are added to the Tris- that 30mL pH value is 8.0
In HCl buffer solutions, polymerisation 6.9h, generates solid polymer at room temperature；
Step 4: after polymerisation terminates, the solid polymer generated in step 3 reaction solution is divided by externally-applied magnetic field
Separate out and；
Step 5: the solid polymer isolated in elution step four, then 4.5h is dried at 46 DEG C, produce amino over-expense
The chlorogenic acid molecular engram magnetic nano-balls of change.Wherein eluent is that volume ratio is 95:The mixing of 5 absolute ethyl alcohol and acetic acid
Liquid.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from embodiment 4 are subjected to absorption property detection,
It is specific as follows：
(1) the hyperbranched chlorogenic acid molecular engram magnetic nano-balls 10mg of amino is added to 10mL concentration for 35 μ g/mL
CGA the aqueous solution in, at room temperature shake 10min after, supernatant is separated by externally-applied magnetic field；
(2) concentration of CGA in gained supernatant in (1) is determined with high performance liquid chromatography, then to calculate amino hyperbranched
Adsorbance of the chlorogenic acid molecular engram magnetic nano-balls to CGA；
CGA concentration is 28.87 μ g/mL in measured supernatant；
By calculating, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino are to CGA adsorbance：6.13mg/
g。
Embodiment 5
Step 1: by 0.8g iron chloride, 3.4g sodium acetates, 4.5g hexamethylene diamines and 20mL ethylene glycol are placed in reactor, 205
DEG C reaction 7h, reaction terminate after, reaction product is washed to neutrality with ultrapure, 4h is dried in vacuo under 40 DEG C, 0.05MPa, i.e.,
Obtain amino-magnetic nanosphere.
Step 2: take amino-magnetic nanosphere made from 400mg steps one, then by 20mL absolute ethyl alcohols, 10mL acrylic acid
Methyl esters is placed in there-necked flask together, and 6h is reacted under normal temperature.Stirring reaction 5h at 15mL ethylenediamines-ethanol solution, 40 DEG C is added,
After reaction terminates, reaction product is washed to neutrality with ultrapure, 4h is dried in vacuo under 40 DEG C, 0.05MPa, produce amino over-expense
Change the magnetic nano-balls of modification.Wherein ethylenediamine-ethanol solution be by volume ratio be 1:1.8 ethylenediamine and absolute ethyl alcohol mixing
It is formulated；
Step 3: by the magnetic nano-balls of the hyperbranched modification of amino made from 0.12g step 2,55mg function monomer hydrochloric acid
Dopamine (this function monomer can also play a part of crosslinking agent) and 25mg chlorogenic acids are added to the Tris- that 20mL pH value is 7.0
In HCl buffer solutions, polymerisation 6h, generates solid polymer at room temperature；
Step 4: after polymerisation terminates, the solid polymer generated in step 3 reaction solution is divided by externally-applied magnetic field
Separate out and；
Step 5: the solid polymer isolated in elution step four, then 4h is dried at 40 DEG C, produce amino hyperbranched
Chlorogenic acid molecular engram magnetic nano-balls.Wherein eluent is that volume ratio is 97:3 absolute ethyl alcohol and the mixed liquor of acetic acid.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from embodiment 5 are subjected to absorption property detection,
It is specific as follows：
(1) the hyperbranched chlorogenic acid molecular engram magnetic nano-balls 10mg of amino is added to 10mL concentration for 35 μ g/mL
CGA the aqueous solution in, at room temperature shake 10min after, supernatant is separated by externally-applied magnetic field；
(2) concentration of CGA in gained supernatant in (1) is determined with high performance liquid chromatography, then to calculate amino hyperbranched
Adsorbance of the chlorogenic acid molecular engram magnetic nano-balls to CGA；
CGA concentration is 29.02 μ g/mL in measured supernatant；
By calculating, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino are to CGA adsorbance：5.98mg/
g。
Embodiment 6
Step 1: by 1.2g iron chloride, 4.8g sodium acetates, 6.5g hexamethylene diamines and 26mL ethylene glycol are placed in reactor, 210
DEG C reaction 8.5h, reaction terminate after, reaction product is washed to neutrality with ultrapure, 7h is dried in vacuo under 50 DEG C, 0.09MPa,
Produce amino-magnetic nanosphere.
Step 2: take amino-magnetic nanosphere made from 500mg steps one, then by 23mL absolute ethyl alcohols, 20mL acrylic acid
Methyl esters is placed in there-necked flask together, and 7h is reacted under normal temperature.Stirring reaction 6h at 25mL ethylenediamines-ethanol solution, 45 DEG C is added,
After reaction terminates, reaction product is washed to neutrality with ultrapure, 7h is dried in vacuo under 50 DEG C, 0.09MPa, produce amino over-expense
Change the magnetic nano-balls of modification.Wherein ethylenediamine-ethanol solution be by volume ratio be 1:2.5 ethylenediamine and absolute ethyl alcohol mixing
It is formulated；
Step 3: by the magnetic nano-balls of the hyperbranched modification of amino made from 0.2g step 2,62mg function monomer hydrochloric acid
Dopamine (this function monomer can also play a part of crosslinking agent) and 30mg chlorogenic acids are added to the Tris- that 23mL pH value is 7.8
In HCl buffer solutions, polymerisation 6.5h, generates solid polymer at room temperature；
Step 4: after polymerisation terminates, the solid polymer generated in step 3 reaction solution is divided by externally-applied magnetic field
Separate out and；
Step 5: the solid polymer isolated in elution step four, then 7h is dried at 50 DEG C, produce amino hyperbranched
Chlorogenic acid molecular engram magnetic nano-balls.Wherein eluent is that volume ratio is 99:1 absolute ethyl alcohol and the mixed liquor of acetic acid.
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from embodiment 6 are subjected to absorption property detection,
It is specific as follows：
(1) the hyperbranched chlorogenic acid molecular engram magnetic nano-balls 10mg of amino is added to 10mL concentration for 35 μ g/mL
CGA the aqueous solution in, at room temperature shake 10min after, supernatant is separated by externally-applied magnetic field；
(2) concentration of CGA in gained supernatant in (1) is determined with high performance liquid chromatography, then to calculate amino hyperbranched
Adsorbance of the chlorogenic acid molecular engram magnetic nano-balls to CGA；
CGA concentration is 28.93 μ g/mL in measured supernatant；
By calculating, the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino are to CGA adsorbance：6.07mg/
g。
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent structure transformation that technical spirit is made to above example, still fall within skill of the present invention
In the protection domain of art scheme.
Claims (10)
1. the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of a kind of amino, it is characterised in that including following
Step：
Step one：A g iron chloride, B g sodium acetates, C g hexamethylene diamines and D mL ethylene glycol are placed in reactor, 180~210
7~9h is reacted at DEG C, after reaction terminates, reaction product is washed, dried, that is, obtains amino-magnetic nanosphere；Wherein A:B:C:D
=(0.8~1.2):(3.4~4.8):(4.5~6.5):(20~30)；
Step 2：Amino-magnetic nanosphere, F mL absolute ethyl alcohols and G mL methyl acrylates made from E mg steps one are placed in
In reaction vessel, under normal temperature react 5~7h, add H mL ethylenediamines-ethanol solution, at 40~60 DEG C stirring reaction 3~
6h, after reaction terminates, reaction product is washed, dried, that is, obtains the magnetic nano-balls of the hyperbranched modification of amino；Wherein E:F:G:
H=(100~500):(20~30):(5~20):(15~25)；
Step 3：The magnetic nano-balls of the hyperbranched modification of amino, J mg Dopamine hydrochlorides and K mg made from I g step 2 is green
Ortho acid is added in M mL Tris-HCl buffer solutions, at room temperature 6~8h of polymerisation, generates solid polymer；Wherein I:J:K:
M=(0.1~0.2):(45~65):(20~30):(20~30)；
Step 4：After the polymerisation in step 3 terminates, by externally-applied magnetic field by the solid polymer generated in reaction solution
Separate；The solid polymer isolated is eluted again, dried, that is, obtains the hyperbranched chlorogenic acid molecular engram of amino
Magnetic nano-balls.
2. the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino according to claim 1, it is special
Levy and be：Reaction product is washed to neutrality, then at 40~50 DEG C and 0.05 with ultra-pure water in the step one and step 2
~0.09MPa vacuum under pressure dries 4~7h.
3. the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino according to claim 1, it is special
Levy and be：Ethylenediamine-ethanol solution in the step 2 be by volume ratio be 1:The ethylenediamine and absolute ethyl alcohol of (1~3) are mixed
Conjunction is formulated.
4. the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino according to claim 1, it is special
Levy and be：The pH value of Tris-HCl buffer solutions in the step 3 is 7~8.5.
5. the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino according to claim 1, it is special
Levy and be：The eluent used in the step 4 is that volume ratio is (92~99):The absolute ethyl alcohol of (8~1) and mixing for acetic acid
Close solution.
6. the preparation method of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino according to claim 1, it is special
Levy and be：Drying temperature in the step 4 is 40~50 DEG C, and drying time is 4~7h.
7. the preparation side of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino in claim 1-6 described in any one
The hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino made from method, it is characterised in that：The hyperbranched green original of the amino
Acid molecule trace magnetic nano-balls are 5.98~6.27mg/g to the adsorbance of chlorogenic acid.
8. the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino according to claim 7, it is characterised in that：It is described
The particle diameter of the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino is 20~25nm.
9. the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino described in claim 7 or 8 are to matrix Content of Chlorogenic Acid
Enrichment, detection, separation and removal in terms of application.
10. the hyperbranched chlorogenic acid molecular engram magnetic nano-balls of amino described in claim 7 or 8 are in terms of chlorogenic acid is adsorbed
Application.
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