CN105330782B - A kind of oleanolic acid molecularly imprinted polymer based on computer simulation and preparation method thereof, purposes - Google Patents
A kind of oleanolic acid molecularly imprinted polymer based on computer simulation and preparation method thereof, purposes Download PDFInfo
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Abstract
The invention discloses a kind of oleanolic acid molecularly imprinted polymer based on computer simulation and preparation method thereof, purposes, the preparation method of the oleanolic acid molecularly imprinted polymer based on computer simulation comprises the steps：Step 1：The pre-assembled system of computer simulation oleanolic acid molecularly imprinted polymer；Step 2：The preparation of imprinted polymer；Step 3：The elution of template molecule；Step 4：The drying of imprinted polymer.This hair is with the selection of theoretical direction MIP preparation conditions, part normal experiment is replaced to attempt by computer simulation, the experiment number for groping synthesis condition and unnecessary reagent and manpower consumption can be greatly reduced, trace operating efficiency and MIPs absorption property are improved, helps to disclose molecularly imprinted polymer recognition principle.And can simply, it is quick, specifically adsorb OA, realize Selective Separation and efficiently concentrating to OA.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of oleanolic acid molecularly imprinted polymer preparation method and
Purposes.
Background technology
Oleanolic acid（Oleanolic acid, OA) it is a kind of pentacyclic triterpenoid, it is distributed widely in about 60
In 190 kinds of plants of section.Pharmaceutical research proves that OA has liver protection, reducing blood lipid, inducing apoptosis of tumour cell, anti-oxidant, anti-inflammatory, drop
A variety of pharmacological activity such as sugar, with higher potential applicability in clinical practice.
Because oleanolic acid is complicated, it is difficult to obtained with synthetic method, so it is currently acquired neat pier to be extracted from plant
The conventional preparation method of tartaric acid.Traditional extraction（Organic solvent extraction, supercritical fluid extraction, microwave radiation exaraction and ultrasound
Assisted extraction）And isolation and purification method（Silica gel column chromatography, acid-base precipitation and chloroform extraction）Exist consumption of organic solvent it is big, point
The deficiencies such as, dissolvent residual low from efficiency is serious, pollution environment, the low and high labor intensity of product purity.
Molecularly imprinted polymer (molecularly imprinted polymers, MIPs) is by molecular engram skill
The polymeric material to specific target molecules with Selective recognition prepared by art.MIPs has mutual with target molecule space structure
Mend, functional group's interaction（Hydrogen bond, ion or Van der Waals force etc.）Polymerization hole, there is specific identification to target molecule
Ability.Have the advantages that to prepare that simple, physicochemical properties are stable due to MIPs, easily preserve, can Reusability, in solid phase extraction
Field is taken to show good application prospect.
Retrieval through prior art literature finds that Zhang etc. exists《Electroanalysis》2011, 23, 2446–
Article " the A Polypyrrole-Imprinted Electrochemical Sensor Based on delivered on 2455
Nano-SnO2/Multiwalled Carbon Nanotubes Film Modified Carbon Electrode for the
Oleanolic acid molecular engram sensor is prepared in Determination of Oleanolic Acid ", to detect actual sample
Oleanolic acid in product, but the method is only suitable for detection, it is impossible to meet extraction and the purifying demand of oleanolic acid in sample.
Zhang Hui（Shandong Agricultural University's Master's thesis, 2014）OA molecularly imprinted polymers are prepared for using bulk polymerization, are used for
The OA in pawpaw is extracted, but there is numerous and diverse last handling process, low yield, template and remove difficult, product shape not in mass polymerization
Regular the shortcomings of；And influence Polymer adsorption performance, the MIPs of preparation is only 1.19 mg/g to OA adsorption capacity.Zhou Ling（In
Mountain university Master's thesis, 2014）OA-MIPs is prepared for using surface aggregate method, is applied to extract as solid-phase adsorbent
OA in glossy privet leaf, although improve adsorbance, but there is high non-specific adsorption（12.5 mg/g）.Chen etc. exists
《Talanta, 2012,99,959-965》" the Molecularly imprinted polymers based on of middle announcement
multi-walled carbon nanotubes for selective solid-phase extraction of
In the texts of oleanolic acid from the roots of kiwi fruit samples " one, multi-wall carbon nano-tube control is utilized
For OA-MIPs, and applied to the OA extracted in Kiwi berry, the shortcomings of equally existing high non-specific adsorption（15.9 mg/
g）.Zhang etc. exists《Sep. Purif. Technolo., 2011, 81, 411-417》Disclose by template of OA, acryloyl
Amine is that monomer, EGDMA are crosslinking agent, and OA-MIPs, MIPs and NIPs adsorbance is prepared for respectively about using precipitation polymerization process
For 8.61 mg/g and 1.78mg/g, but chloroform and methanol are employed in OA-MIPs preparations（3:1, v/v）It is used as pore
Agent, causes the in irregular shape of product, is not suitable as using as filler dress post.In addition, above method was prepared in MIPs
Many in journey to remove selection monomer, solvent and consumption using traditional experimental method, experiment specific aim and foresight are poor, workload greatly,
Preparation efficiency is low, and lacks the understanding to mechanism of polymerization.
The conventional experiment in part is replaced by computer simulation, the experiment number of synthesis condition can be greatly reduced, reduced not
Necessary reagent and manpower consumption, the efficiency of research and development for improving MIP, and MIP compatibility and selectivity, which all have, to be instructed
Effect.At present report prepared by the OA molecularly imprinted polymers based on computer simulation is related to through retrieval.As Li Min it is graceful《Meter
Calculation machine and applied chemistry》Article " the computer mould of oleanolic acid molecularly imprinted polymer delivered in 2014,31,541-546
Intend, prepare and Study on adsorption properties ", but he has screened function monomer merely with computer modeling technique, and template and function
The mol ratio of monomer and the selection of pore-foaming agent without reference to.
The content of the invention
The technical problem to be solved：Existing oleanolic acid（OA）Specific aim and prediction in the preparation method of imprinted polymer
The poor, workload of property is big, preparation efficiency is low, it is an object of the invention to provide a kind of OA molecularly imprinted polymers of computer simulation and
Its preparation method, purposes, so that the screening of theoretical direction MIP preparation conditions, improves trace operating efficiency and MIPs adsorptivity
Energy.
It is a further object to provide one kind prepare simply, monodispersity is good, uniform particle diameter imprinted polymer is micro-
The preparation method of ball, overcomes the shortcomings of existing separating and purifying technology, can simply, it is quick, specifically adsorb OA, realize
To OA Selective Separation and efficiently concentrating.
Technical scheme：In view of the above-mentioned problems, the invention discloses a kind of oleanolic acid molecule print based on computer simulation
Mark polymer and preparation method thereof, purposes, the preparation of the oleanolic acid molecularly imprinted polymer based on computer simulation
Method comprises the steps：
Step 1：The pre-assembled system of computer simulation oleanolic acid molecularly imprinted polymer：
With oleanolic acid（OA）For template molecule, it is with α-methacrylic acid (MAA), 4-vinylpridine (4-VP) respectively
Function monomer, acetonitrile, chloroform and tetrahydrofuran are pore-foaming agent, with quantum chemical methods simulated templates molecule and difference in functionality list
The combination energy Δ of the configuration of the pre-assembled system of molecularly imprinted polymer of body, energy and recombination reactionE, and monomer and template point
Solvation energy of the son in different solvents；
Step 2：The preparation of imprinted polymer
With reference to the result of calculation of step 1, oleanolic acid and function monomer are dissolved in pore-foaming agent and are sufficiently mixed, it is quiet at room temperature
4~8h is put, prepolymer is obtained；Crosslinking agent and initiator are added into prepolymer, nitrogen blows 5~10min after mixing, sealing, in
It polymerize 20~30h at 60~70 DEG C, obtains polymer microballoon；
Step 3：The elution of template molecule：
Imprinted polymer prepared by step 2 is placed in Soxhlet extraction device, with mixing for the methanol and acetic acid that volume ratio is 8: 2
Close solution and elute 12~24h, untill not having oleanolic acid in eluent, again with methanol washing removes the acetic acid of residual；
Step 4：The drying of imprinted polymer：
Elution post-consumer polymer obtained by step 3 is dried in vacuo at 40~50 DEG C, the polymerization of oleanolic acid molecular engram is obtained
Thing.
It is preferred that, in described step 1, simulation software used is Gaussian 09, template and function monomer molecule
Gas phase geometric hash, solvation energy, which are calculated, uses Density functional b3lyp2, is carried out under the base groups of 6-31G (d) 3；Template
And the combination of function monomer interaction can be using Density functional b3lyp in 6-311++g (d, p) base group level calculation.
It is preferred that, in described step 2, described function monomer is α-methacrylic acid（MAA）, template and function monomer
Mol ratio be 1:4~1:5；Crosslinking agent is mol ratio 4:1 divinylbenzene（DVB）And GDMA
（EGDMA）, the mol ratio of monomer and crosslinking agent is 1:4~1:6；Initiator is azodiisobutyronitrile（AIBN）, the amount of initiator
For the 2%~4% of monomer and crosslinking agent gross mass；Pore-foaming agent is acetonitrile+ethanol, and its volume ratio is 3:1, the volume of the pore-foaming agent
For 16~24 times of overall reaction system volume.
A kind of preparation side of oleanolic acid molecularly imprinted polymer based on computer simulation according to any of the above
The oleanolic acid molecularly imprinted polymer that method is prepared.
Purposes of the oleanolic acid molecularly imprinted polymer in oleanolic acid preparation process in accordance with the above.
Beneficial effect：Replace the conventional experiment in part to attempt by computer simulation, can greatly reduce and grope to synthesize bar
The experiment number of part and unnecessary reagent and manpower consumption, improve the efficiency of research and development and absorption property of molecularly imprinted polymer,
And help to disclose molecularly imprinted polymer recognition principle.
Brief description of the drawings
The schematic diagram for the oleanolic acid molecularly imprinted polymer that Fig. 1 is prepared for the present invention；
Fig. 2 is the template that embodiment 1 is obtained using calculating simulation（OA）With function monomer molecule（MAA, 4-VP）Optimization
Configuration picture；
Fig. 3 is template and the NBO charge patterns of function monomer molecule；
Fig. 4 is that embodiment 1 calculates obtained template using calculating simulation（OA）With monomer（MA、4-VP）With 1:1 mol ratio
The compound configuration of formation；
Fig. 5 is the OA obtained in embodiment 1 using computer Simulation calculation and the 1 of 4-VP:2 compound OA-2VP structures
（a）；MA self-association structures： 2MA-1（b）, 2MA-2（c）；
Fig. 6 is the imprinted polymer infrared spectrogram for preparing in embodiment 1（a）Oleanolic acid infrared spectrogram；(b)
MIP infrared spectrograms；（c）Infrared spectrogram after MIP eluted templates；（d）NIP infrared spectrograms；
Fig. 7 is the mode of appearance scanning electron microscope (SEM) photograph of molecularly imprinted polymer prepared by embodiment 1；
Fig. 8 is the grain size distribution of molecularly imprinted polymer prepared by embodiment 1.
Embodiment
Technical solution of the present invention is not limited to cited specific implementation case, includes times of each specific implementation case
Meaning combination.
Embodiment 1
（1）The simulation of the pre-assembled system of molecularly imprinted polymer
（a）Using Gaussian softwares, using DFT method b3lyp, to template molecule under 6-31G (d) ranks
With the gas phase geometric hash of function monomer, it is determined that the structure each optimized is minimal point, the molecular structure of calculating is carried out
Frequency analysis, all molecules are without empty frequency；The optimization structure of three molecules is as shown in Figure 2；
（b）Under same level, the NBO distribution of charges of molecule is calculated, the possibility for analyzing template and function monomer
Binding site, the distribution of charges of three molecules is shown in Fig. 3.Contain two H in a carboxyl and a hydroxyl, two groups in OA
Atom and three O atoms can be respectively as proton donors and acceptor with forming hydrogen bond in function monomer.Function monomer MAA contains one
Individual carboxylic group, carboxyl H electric charges are that the electric charge of two oxygen atoms on 0.5, and carboxyl is respectively -0.60 and -0.71, show the work(
Energy monomer acts not only as hydrogen bond donor or hydrogen bond receptor and template molecule formation hydrogen bond, and the functional molecular can pass through
Effect forms hydrogen bond between self-molecules present；N atomic charges number on 4-VP molecule pyridine rings is -0.45, can as hydrogen bond receptor with
Template combines to form hydrogen bond.
（c）Structure and calculating of the template with the compound system of function monomer interaction composition are optimized using ONIOM methods
Its energy, by combining energyΔECompare template and function monomer interaction is strong and weak, selection function monomer；Model uses density
Functional b3lyp methods are in 6-311++g (d, p) base group level calculation；Handled using semi-empirical approach PM3；With reference to energyΔE's
Calculate such as formula（2）It is shown：
ΔE = E complex – E template – nE monomer（2）
In formula,E complexFor compound energy,E templateFor template energy,E monomerFor function monomer energy；
Oleanolic acid is with each function monomer with 1:The compound configuration of 1 mol ratio formation is shown in that Fig. 4, OA can have four kinds with MAA
Hydrogen bond action, so as to generate four kinds of compounds, wherein MAA carboxyls have 2 hydrogen bond works with OA carboxyls formation OA/-MAA-1 compounds
With site, therefore the Hyarogen-bonding formed is most strong, with reference to can highest, compound is most stable.4-VP and OA is 1:Can at 1 mole
Form two kinds of bond complexes.When 4-VP and OA are with 2:During 1 molar ratio reaction, a kind of conformation can be formed（See Fig. 5）, this is answered
The combination of compound can be -68.93 kJ/mol（It is shown in Table 1）, it is stable in conformation theory to illustrate compound.And MAA and OA with
2:During 1 molar ratio reaction, 2 MAA molecules can be combined together by intermolecular hydrogen bonding effect, easily occurred self-molecules present and formed
Close.（See Fig. 5）.
Table 1.ONIOM (b3lyp/6-311++g (d, p):Pm3 the energy of the template, monomer and the two compound that) calculateE
With combine energyΔE
| Compound | E(a.u.) | ΔE(a.u.) | ΔE (kJ/mol) |
| OA | -345.0083 | ||
| VP | -325.7714 | ||
| MA | -306.5815 | ||
| OA-MA-1 | -651.6151 | -0.0253 | -66.3958 |
| OA-MA-2 | -651.6019 | -0.0121 | -31.7567 |
| OA-MA-3 | -651.6009 | -0.0111 | -29.2255 |
| OA-MA-4 | -651.5993 | -0.0096 | -25.1453 |
| OA-VP-1 | -670.7972 | -0.0175 | -45.8866 |
| OA-VP-2 | -670.7887 | -0.0090 | -23.5536 |
| OA-2VP | -996.5774 | -0.0263 | -68.9311 |
| 2MA-1 | -613.1744 | -0.0115 | -30.2615 |
| 2MA-2 | -613.1890 | -0.0261 | -68.6198 |
（d）Using SCRF (SCRF) polarizable continuum model (CPCM) to template and the geometry knot of function monomer molecule
Structure is optimized, and solvation energy of these molecules in acetonitrile, tetrahydrofuran and chloroform solvent is calculated with this.It is all to calculate
Carried out under b3lyp/6-31g* levels, the initial configuration of molecule is using the structural stability after gas phase optimization.Solvation energy
（E solvation）Calculation formula is as follows：
E solvation = E gas – E solvent（1）
In formula,E gasFor the energy of molecule in the gas phase,E solventFor the energy of molecule in a solvent.
OA, MA and VP solvation energy are as shown in table 2, the solvation energy of template molecule and function monomer in three kinds of solvents
Less, wherein solvation energy is minimum in chloroform, the effect of pattern of descriptive parts molecule and function monomer and chloroform is smaller, theoretical for difference
Result of calculation shows that chloroform may be more suitable for pore-foaming agent.But during actual experiment, the selection of pore-foaming agent is also with polymerizeing
Method is relevant.
Solvation energies of table 2 OA, MA and the VP in acetonitrile, tetrahydrofuran and chloroform
（2）0.1mmol OA are dissolved in 2.0 mL ethanol, 6.0mL acetonitriles and 0.4 mmol MAA is then added, makes mould
After plate molecule and monomer are sufficiently mixed, 4 h are stood at room temperature, prepolymer is obtained；Mixed cross-linker is added into prepolymer
2.0 mmol（DVB/EGDMA, mol/mol, 4:1）With the mg of initiator azodiisobutyronitrile 6.44, it is well mixed, leads to nitrogen
5min, sealing, polymerize 24h at a temperature of 65 DEG C, obtains polymer microballoon；100mL methanol/acetic acid is added to polymer microballoon
Mixed solution（V/V, 8:2）, Soxhlet extraction 24h, untill there is no oleanolic acid in eluent, last again with methanol washing
The acetic acid of residual is removed, untill eluent is neutrality.Then the imprinted polymer for removing template is dried in vacuo in 50 DEG C,
The final MIPs for obtaining OA.Non- imprinted polymer（NIP）Preparation in addition to template molecule is not added with, prepare and locate as stated above
Reason.The MIPs is 17.5 mg/g to OA saturated extent of adsorption, and NIPs non-specific adsorption amount is 4.36 mg/g.
Fig. 6 is MIPs the and NIPs infrared absorpting light spectras prepared by the present embodiment, and wherein a is MIPs, 3448cm-1For OA
O-H stretching vibrations in molecule, 2940cm-1、2863cm-1 For C-H stretching vibrations, 1733cm in polymerization system-1Crosslinking agent EGDMA
Ester group C=O stretching vibrations, 1701cm-1For C=O stretching vibrations of OA carboxyls, 1460cm-1、1384cm-1For methylene in polymerization system
Base and methyl C-H deformation vibrations, 1170 cm-1、1104 cm-1For crosslinking agent EGDMA C-O-C stretching vibrations, 834 cm-1、
797 cm-1、713 cm-1For crosslinking agent DVB=vibration of C-H out-of-plane deformation and aromatic ring frame δ vibrations, show template, monomer
And the full cross-linked polymerization of crosslinking agent；B is NIPs in figure, is compared with a, 3448cm-1Absorb and disappear, 2940cm-1、2863cm-1For
C-H stretching vibrations substantially weaken in polymerization system, show that template molecule is not present, other infrared absorption peaks and MIPs infrared absorptions
Peak is basically identical.
Fig. 7 is the scanning electron microscope (SEM) photograph of the MIPs prepared by the present embodiment, and the OA molecularly imprinted polymers of preparation are in more to advise
Microballoon shape then, uniform particle diameter.
Fig. 8 is the grain size distribution of the MIPs prepared by the present embodiment, MIPs number average diameter（Number-average
diameter, D n）For 3.15 μm, polydispersity index（Polydispersity index, PDI）For 1.027.
Embodiment 2
（1）The simulation be the same as Example 1 of the pre-assembled system of molecularly imprinted polymer；
（2）0.08mmol OA are dissolved in 2.0 mL ethanol, 6.0 mL acetonitriles and 0.4 mmol MAA is then added, makes
After template molecule and monomer are sufficiently mixed, 4 h are stood at room temperature, prepolymer is obtained；Mixing crosslinking is added into prepolymer
The mmol of agent 2.0（DVB/EGDMA, mol/mol, 4:1）With the mg of initiator azodiisobutyronitrile 6.44, it is well mixed, leads to nitrogen
The min of gas 5, sealing, in polymerizeing 24 h at 65 DEG C, obtains imprinted polymer；100 mL methanol/acetic acid is added to this polymer
Mixed solution（8:2, V/V）, the h of Soxhlet extraction 24, untill there is no oleanolic acid in eluent, last again with methanol washing
To remove the acetic acid of residual, untill eluent is neutrality.Then the imprinted polymer for removing template is done in 50 DEG C of vacuum
It is dry, the final MIPs for obtaining OA.Non- imprinted polymer（NIPs）Preparation in addition to template molecule is not added with, prepare as stated above
And processing.The MIPs is 18.8 mg/g to OA static saturated adsorption capacity, and NIPs non-specific adsorption amount is 7.04 mg/
g。
Embodiment 3
（1）The simulation be the same as Example 1 of the pre-assembled system of molecularly imprinted polymer；
（2）0.1 mmol OA are dissolved in 2.0 mL ethanol, 6.0mL acetonitriles and 0.4 mmol MAA is then added, makes mould
After plate molecule and monomer are sufficiently mixed, 4 h are stood at room temperature, prepolymer is obtained；Mixed cross-linker is added into prepolymer
2.0 mmol（DVB/EGDMA, mol/mol, 4:1）With the mg of initiator A IBN 12.88, it is well mixed, leads to the min of nitrogen 10,
Sealing, in polymerizeing 24 h at 70 DEG C, obtains polymer microballoon；Polymer is placed in Soxhlet extraction device, 100 mL first is added
Alcohol/acetic acid mixed solution（8:2, V/V）24 h are eluted, untill not having oleanolic acid in eluent, last again with methanol is washed
The acetic acid of residual is washed away, untill eluent is neutrality.Then the imprinted polymer for removing template is done in 50 DEG C of vacuum
It is dry, the final MIPs for obtaining OA.Non- imprinted polymer（NIPs）Preparation in addition to template molecule is not added with, prepare as stated above
And processing.The MIPs is 16.3 mg/g to OA static saturated adsorption capacity, and NIPs non-specific adsorption amount is 4.57 mg/g.
Comparative example 1
Existed using Zhang etc.《Sep. Purif. Technolo., 2011,81,411-417》The method of announcement.Will
0.1mmol template molecule OA and 0.4 mmol function monomer acrylamides are dissolved in 40 mL chloroform+methanol mixed solvent
（V/v, 3:1）, 6 h are placed at 4 DEG C in refrigerator, template molecule and monomer is sufficiently mixed；Then 2.0 mmol friendship is added
Join agent EGDMA and 0.1mmol initiator A IBN, ultrasonic 5min, lead to nitrogen 10min, sealing polymerize 48h at a temperature of 60 DEG C,
Obtain polymer microballoon；The obtained rpm of polymer 1000 is centrifuged into 10 min, supernatant is abandoned, methanol/acetic acid mixed solution is added
（9:1, V/V）Soxhlet extraction, untill not having oleanolic acid in eluent；Last polymer is settled repeatedly with acetone, then is used
Methanol washing removes the acetone of residual.Then the imprinted polymer for removing template is finally obtained into OA- in 40 DEG C of vacuum drying
MIPs.NIPs preparation is prepared and handled as stated above in addition to template molecule is not added with.The MIPs is to OA adsorbance
8.96 mg/g, NIPs non-specific adsorption amount are 2.32 mg/g.
Comparative example 2
Using Zhang Hui（Shandong Agricultural University's Master's thesis, 2014）The bulk polymerization of report is prepared for OA-MIPs.
By OA and 2- butenoic acids with 1:3 mixed in molar ratio, add crosslinking agent（Styrene+divinylbenzene, 2:1；Monomer and crosslinking agent rub
You are than being 3:8）With 4 wt % initiator sodium peroxydisulfate, shake up, OA and 2- fourth diluted acids is completely dissolved in liquid mixed system
In.Mixed system inflated with nitrogen, sealing, stand and progress polymerisation 30 h are put into 85 DEG C of thermostat water baths after 12h.Polymerisation
After end, polymer is taken out, is placed in 30 DEG C of electric heating constant-temperature blowing drying boxes and dries, grind, 200 mesh sieves are crossed.It will obtain
Polymer rinsed with methanol after be placed in Soxhlet extraction device, add methanol/acetic acid mixed solution（9:1, V/V）, until elution
Untill there is no OA in liquid,（9:1, V/V）Elution, until there is no oleanolic acid in eluent untill, last again with methanol wash with
Remove the acetic acid of residual, freeze-day with constant temperature to constant weight, the final MIPs for obtaining OA.NIP preparation is pressed in addition to template molecule is not added with
The above method is prepared and handled.The MIPs is 1.48 mg/g to OA adsorbance, and NIPs non-specific adsorption amount is 0.87
mg/g。
Claims (2)
1. a kind of preparation method of the oleanolic acid molecularly imprinted polymer based on computer simulation, it is characterised in that described
Preparation method comprises the steps：
Step 1：The pre-assembled system of computer simulation oleanolic acid molecularly imprinted polymer：
Using oleanolic acid as template molecule, respectively using α-methacrylic acid, 4- vinylpyridines as function monomer, acetonitrile, chlorine
Imitative and tetrahydrofuran is pore-foaming agent, is polymerize with quantum chemical methods simulated templates molecule with the molecular engram of difference in functionality monomer
The Binding energy of the configuration of the pre-assembled system of thing, energy and recombination reaction, and monomer with template molecule in different solvents
Solvation energy；
Step 2：Oleanolic acid and function monomer are dissolved in pore by the preparation of imprinted polymer with reference to the result of calculation of step 1
It is sufficiently mixed in agent, 4~8h is stood at room temperature, prepolymer is obtained；Then crosslinking agent and initiator are added into prepolymer,
Nitrogen blows 5~10min after mixing, sealing, in polymerizeing 20~30h at 60~70 DEG C, obtains polymer microballoon；
Step 3：The elution of template molecule
Imprinted polymer prepared by step 2 is placed in Soxhlet extraction device, with mixing for the methanol and acetic acid that volume ratio is 8: 2
Close solution and elute 12~24h, untill not having oleanolic acid in eluent, again with methanol washing removes the acetic acid of residual；
Step 4：The drying of imprinted polymer：
Elution post-consumer polymer obtained by step 3 is dried in vacuo at 40~50 DEG C, the polymerization of oleanolic acid molecular engram is obtained
Thing；
In described step 1, simulation software used is Gaussian 09, template and function monomer molecule gas phase geometry structure
Type optimization, solvation energy, which are calculated, uses Density functional b3lyp2, is carried out under the base groups of 6-31G (d) 3；Template and function monomer
The combination of interaction can be using Density functional b3lyp in 6-311++g (d, p) base group level calculation；
In described step 2, described function monomer is α-methacrylic acid, and the mol ratio of template and function monomer is 1:4
~1:5 ；Crosslinking agent is mol ratio 4:1 divinylbenzene and GDMA, monomer and crosslinking agent rub
You are than being 1:4~1:6 ；Initiator is azodiisobutyronitrile, the amount of initiator for monomer and crosslinking agent gross mass 2%~
4% ；Pore-foaming agent is acetonitrile+ethanol, and its volume ratio is 3:1, the volume of the pore-foaming agent for overall reaction system volume 16~
24 times.
2. a kind of preparation of oleanolic acid molecularly imprinted polymer based on computer simulation according to above claim 1
The oleanolic acid molecularly imprinted polymer that method is prepared.
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