CN104804152A - Preparation method and application of kaempferol imprinted microsphere based on nanometer titanium dioxide - Google Patents
Preparation method and application of kaempferol imprinted microsphere based on nanometer titanium dioxide Download PDFInfo
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- CN104804152A CN104804152A CN201410038126.8A CN201410038126A CN104804152A CN 104804152 A CN104804152 A CN 104804152A CN 201410038126 A CN201410038126 A CN 201410038126A CN 104804152 A CN104804152 A CN 104804152A
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Abstract
The invention provides a preparation method of a kaempferol surface molecularly imprinted polymer microsphere with TiO2 as a core by adopting a seed precipitation polymerization technology. The method solves the problems of severe embedding phenomenon and low separating treatment efficiency of polymer microspheres prepared through a precipitation polymerization technology and the problem of easy gelatinization of an initiator in a polymerization solution in the preparation process of imprinted microspheres prepared through a surface imprinting technology needing a surface grafting technology. An imprinted polymer microsphere prepared through adopting the method has the advantages of regular particle shape, uniform size, no agglomeration phenomenon and increased specific surface area, and makes binding sites of a polymer distributed on the surface of the microsphere in order to improve the adsorption performance of the kaempferol surface molecularly imprinted polymer microsphere. The above polymer prepared in the invention can realize effective separation and extraction of ginkgo flavone aglycone, and has a wide application prospect.
Description
Technical field
The invention belongs to surface molecule print technical field, specifically with TiO
2for the preparation of the kaempferide molecular imprinted polymer on surface microballoon of core, be namely a kind of preparation kaempferide to the parting material of higher selective recognition performance, and the application in pharmaceutical cpd separation and purification.
Background technology
Kaempferide is a kind of flavonoid compound, have hypotensive, reducing blood-fat, anticancer, strengthen the pharmaceutical uses such as capillary resistance, be activeconstituents important in herbal medicine.At present, traditional method for extracting Flavonoid substances mainly contains solvent method, microwave loss mechanisms, macroporous resin extraction method, supercritical extraction, capillary electrophoresis and enzyme process etc., but flavonoid compound type is various, and structural similitude, not only complete processing is loaded down with trivial details, energy consumption is high, selectivity is undesirable to adopt ordinary method, and these techniques have particular requirement to temperature and pressure, easily cause danger in operation, easily cause the waste of resource and the pollution of environment.
Molecular imprinting is development in recent years a kind of technology faster, and it is that analog antibody and antigen, enzyme-to-substrate etc. are present in natural Molecular Recognization, usually can be described as the technology manufacturing artificial " lock " that identify " molecule key ".Molecularly imprinted polymer (Molecular Imprinted Polymer, MIP) be a kind ofly there is fixing hole size and shape and specific molecular is had to the novel molecular identification material of specific selectivity, blank imprinted polymer (Nonimprinted Polymer, NIP) refers to does not add template molecule and the polymkeric substance that synthesizes.Because molecularly imprinted polymer has highly cross-linked structure, good stability, can use in severe environment, and it is cheap, simple to operate, template and polymkeric substance recoverable, possess the advantages such as strong specificity and highly selective, the effective ingredient of some low levelss directly can be screened from crude extract, have a good application prospect.
Traditional molecularly imprinted polymer adopts mass polymerization preparation, but polymkeric substance needs through processes such as grinding, sieve, and yield of wasting time and energy is not high, and particle shape is irregular thus cause microsphere to be difficult to enter adsorption site, and loading capacity is lower.By contrast, molecular blotting polymer microsphere Synthesis and applications facilitates, is convenient to functional design.The method preparing molecular engram microsphere at present mainly contains dispersion copolymerization method, multi-step swelling method, precipitation polymerization method and surface imprinted technology etc., but the perfluoro high polymers dispersion agent that use is sent out in dispersion polymerization is expensive; The operating process of multi-step swelling method is loaded down with trivial details; The recognition site that precipitation polymerization method prepares polymkeric substance is positioned at polymer microballoon inside mostly, microsphere and recognition site association rate low; Surface imprinted initiator easy gelation in polymeric solution when needing surface graft technology to prepare trace microballoon.So need a kind of preparation method of kaempferide molecular imprinted polymer on surface microballoon, this trace microballoon has particle shape rule on the one hand, and size is homogeneous, does not have agglomeration; Binding site is distributed in the surface of microballoon on the other hand, thus improves the absorption property of kaempferide molecular imprinted polymer on surface microballoon.Trace microballoon prepared by the present invention can effective separation and Extraction kaempferide, has broad application prospects.
Summary of the invention
The invention provides a kind of seed precipitation polymerization method that adopts to prepare with TiO
2for the method for the kaempferide molecular imprinted polymer on surface microballoon of core, this method solve precipitation polymerization method and prepare the problems such as polymer microballoon embedding phenomenon is serious, separation treatment efficiency is low, the imprinted polymer prepared can be used for selective extraction, separation, enrichment Flavone aglycone material from ginkgolic flavone glycoside crude extract.
The present invention is achieved through the following technical solutions, and the steps include:
(1) by template molecule and function monomer 1:(2-10 in molar ratio): (5-50) is dissolved in appropriate pore-creating agent, after ultrasonic disperse 10-20min, adds proper amount of nano TiO
2, sealing, and at room temperature stir 2h-4h with the speed of 300rpm;
(2) mixed solution is placed in and reaction unit continues to stir and after leading to nitrogen deoxidation 10-20min, linking agent ethylene glycol dimethacrylate (EDMA) is added in mixed solution, continue to stir and after leading to nitrogen deoxidation 10-20min, add initiator Diisopropyl azodicarboxylate (AIBN) again, in 50 DEG C of-70 DEG C of constant temperature oil baths, react 24-48h under vacuum state, finally obtain polymer powder;
(3) polymkeric substance of synthesis is crossed 200 mesh sieves;
(4) with methyl alcohol: acetic acid (V/V, 9:1-5:5) is extracting solution, more than surname extraction 72h, wash-out removing template molecule, rear equilibrium methanol removes acetic acid;
(5) resulting polymers is placed in vacuum drying oven 60 DEG C of dry 24h, namely obtains with TiO
2for the molecular imprinted polymer on surface of core.
In step (1), template molecule is kaempferide, and preferred function monomer is the one in acrylamide (AM), 2-vinyl pyridine (2-VP), 4-vinylpridine (4-VP), methacrylic acid (MAA), and pore-creating agent selects acetonitrile.
In step (2), the amount of crosslinker species is 4-10 times of function monomer.
Adopt the inventive method obtain with TiO
2for the particle shape rule of the kaempferide molecular imprinted polymer on surface microballoon of core, size is homogeneous, there is no agglomeration, add the specific surface area of kaempferide molecular imprinted polymer on surface microballoon, and make the binding site of polymkeric substance be distributed in the surface of matrix, thus improve the absorption property of kaempferide molecular imprinted polymer on surface microballoon.Tested by adsorption equilibrium and Specific adsorption experiment show: this polymkeric substance contain match with template molecule space structure, the interactional three-dimensional cavity of functional group, there is significant molecule " memory " function.Polymkeric substance prepared by the present invention can reach the object of effective separation and Extraction ginkgo flavone aglycone, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 is obtained with TiO
2for the kaempferide molecular imprinted polymer on surface microballoon of core is at 2000 times of lower scanning electron microscope (SEM) photographs.
To be that embodiment 1 is obtained do not add TiO to Fig. 2
2kaempferide molecular blotting polymer microsphere at 5000 times of lower scanning electron microscope (SEM) photographs.
Fig. 3 is that embodiment 1 is obtained with TiO
2for core kaempferide molecular imprinted polymer on surface microballoon with do not add TiO
2the curve of adsorption kinetics of kaempferide molecular blotting polymer microsphere.
Fig. 4 is that embodiment 2 is obtained with TiO
2for the curve of adsorption kinetics of the kaempferide molecular imprinted polymer on surface microballoon of core.
Fig. 5 is that embodiment 2 is obtained with TiO
2for the adsorption isothermal line of the kaempferide molecular imprinted polymer on surface microballoon of core.
Embodiment
Embodiment 1
1mmol template molecule kaempferide and 4mmol function monomer 4-VP are dissolved in 40ml pore-creating agent acetonitrile, after ultrasonic disperse 10min, add 20mg TiO
2, mechanical stirring 2h, after logical nitrogen deoxidation 20min, adds linking agent EDMA20mmol, and logical nitrogen deoxidation 20min, adds initiator A IBN50mg, vacuum state lower seal, react 24h and obtain solid polymer in 63 DEG C of oil baths.The imprinted polymer of synthesis is crossed 200 order sub-sieves, with methyl alcohol: acetic acid (V/V, 9:1) is extracting solution, to polymer beads surname extraction 72h, after again with pure methyl alcohol surname extraction 24h, balance removing acetic acid.Resulting polymers is placed in vacuum drying oven 60 DEG C of dry 24h, namely obtains kaempferide molecular imprinted polymer on surface.Preparation does not add TiO
2kaempferide molecularly imprinted polymer test as blank, other preparation conditions are consistent.
Fig. 1 is the stereoscan photograph that kaempferide molecular imprinted polymer on surface microballoon that the present embodiment obtains amplifies 2000 times.To be that the present embodiment is obtained do not add TiO to Fig. 2
2kaempferide molecular blotting polymer microsphere at 5000 times of lower scanning electron microscope (SEM) photographs.The kaempferide molecular imprinted polymer on surface microballoon adopting the inventive method to obtain as seen from Figure 1 has good sphericity, even particle size distribution, its particle diameter is at about 1 μm, there is no agglomeration, add the specific surface area of kaempferide molecular imprinted polymer on surface microballoon, thus improve the adsorptivity of kaempferide surface molecule print aggregation microballoon.Fig. 2 can find out and not add TiO
2kaempferide molecular blotting polymer microsphere out-of-shape, particle diameter is uneven, and its particle diameter is significantly less than with TiO
2for the particle diameter of the kaempferide molecular imprinted polymer on surface microballoon of core, and between microballoon, there is no obvious agglomeration.
Take respectively with TiO
2for core kaempferide molecular imprinted polymer on surface microballoon and do not add TiO
2kaempferide molecular blotting polymer microsphere 50mg, then two Erlenmeyer flasks are placed in respectively, the kaempferide ethanolic soln that 50mL concentration is 100mg/L is added again in Erlenmeyer flask, from timing during starting of oscillation, filtrate is extracted respectively when 1min, 3min, 5min, 15min, 30min, 1h, 2h, 3h, 5h, 8h, 10h, then by 0.45 μm of organic system filter membrane, measured the Cf of kaempferide in equilibrium adsorption liquid by ultraviolet spectrophotometer, investigate the time dependent rule of the absorption of polymkeric substance to kaempferide molecule.
Fig. 3 is with TiO
2for core kaempferide molecular imprinted polymer on surface microballoon with do not add TiO
2the curve of adsorption kinetics of kaempferide molecular blotting polymer microsphere.As can be seen from Figure with TiO
2for the adsorption rate of the kaempferide molecular imprinted polymer on surface microballoon of core does not add TiO
2kaempferide molecular blotting polymer microsphere fast, and it is shorter to reach time of equilibrium adsorption, and adsorptive capacity when reaching adsorption equilibrium is larger, illustrate prepared by the inventive method with TiO
2binding site for the kaempferide molecular imprinted polymer on surface microballoon of core is distributed in the surface of matrix, is more conducive to the absorption to template molecule, thus improves the absorption property of kaempferide molecular imprinted polymer on surface microballoon.
Embodiment 2
1mmol template molecule kaempferide and 6mmol function monomer AM are dissolved in 30ml pore-creating agent acetonitrile, after ultrasonic disperse 10min, add 30mg TiO
2, mechanical stirring 2h, after logical nitrogen deoxidation 20min, adds linking agent EDMA30mmol, and logical nitrogen deoxidation 20min, adds initiator A IBN100mg, vacuum state lower seal, react 24h and obtain solid polymer in 63 DEG C of oil baths.The imprinted polymer of synthesis is crossed 200 order sub-sieves, with methyl alcohol: acetic acid (V/V, 9:1) is extracting solution, to polymer beads surname extraction 72h, after again with pure methyl alcohol surname extraction 24h, balance removing acetic acid.Resulting polymers is placed in vacuum drying oven 60 DEG C of dry 24h, namely obtains kaempferide molecular imprinted polymer on surface.
(1) the adsorption kinetic data
Take the ground Erlenmeyer flask that the kaempferide molecular imprinted polymer on surface after 50mg wash-out is placed in 150mL, then to add concentration be 50molL
-1kaempferide ethanolic soln, the timing when starting of oscillation, respectively 1,3,5,15,30,60,120,180,240,300min time, solution is extracted with syringe, cross 0.45 μm of organic system filter membrane, record absorbancy by uv-spectrophotometric again, investigate the time dependent rule of the absorption of polymkeric substance to kaempferide molecule.
The method of calculation of adsorptive capacity are as follows:
In formula: Q-loading capacity, mgg
-1;
Cr-quality initial concentration, mgml
-1;
Ce-quality of balance concentration, mgml
-1;
V-liquor capacity, ml;
The quality of m-sorbent material, g.
The kinetics of adsorption result of kaempferide molecular imprinted polymer on surface as shown in Figure 4.As shown in Figure 4, kaempferide molecular imprinted polymer on surface increases very fast at short notice to the adsorptive capacity of kaempferide, but along with duration of oscillation prolongation, adsorption rate reduces, and final adsorptive capacity is close to saturated.This is because template molecule defines the trace " hole " with solid form and size by trace and elution process at polymer surfaces and inside, it has the functional group with template molecule complementary structure, spatially stationary arrangement.Due to seed precipitation polymerization method synthetic polymer microballoon, in the absorption initial stage, template molecule is caught by molecular imprinted polymer on surface " hole ", more shallow " hole " is conducive to the quick adsorption of polymkeric substance to kaempferide, have an effect with functional group, adsorption rate is very fast, when surface " hole " reach absorption saturated after, substrate is subject to certain resistance to the mass transfer of polymeric inner " hole ", and adsorption rate is slack-off.
(2) adsorption equilibrium experiment:
Take the kaempferide molecular imprinted polymer on surface after 50mg wash-out respectively and be placed in 150ml ground Erlenmeyer flask, add respectively 100ml concentration be 1,3,5,7,9,11,14,16,18,20molL
-1kaempferide ethanolic soln, constant-temperature table airtight vibration 48h(molecularly imprinted polymer absorption reach balance), then extract solution with syringe, cross 0.45 μm of organic system filter membrane, measure solution absorbance with ultraviolet spectrophotometer, adsorptive capacity method of calculation are as above.
Kaempferide molecular imprinted polymer on surface to the isothermal adsorption result of the kaempferide solution of different concns as shown in Figure 5.As shown in Figure 5, along with the rising of kaempferide concentration, adsorptive capacity also increases thereupon and reaches adsorption equilibrium.This is because the adsorptive capacity of molecular imprinted polymer on surface is made up of specific adsorption, it determines primarily of the acting in conjunction of imprinted cavity and binding site, and the power that function monomer is combined with template molecule decides the power of binding site effect, impact is formed on the efficiency of specific adsorption.
(3) adsorption selectivity experiment:
1. 50mg/L Quercetin, kaempferide, rutin ethanolic soln is prepared respectively;
2. kaempferide molecularly imprinted polymer 50mg is added respectively in 3 kinds of different solutions;
3. be placed in shaking table 25 DEG C vibration 24h, rear centrifugal settling, gets supernatant liquor, and be the filtering with microporous membrane of 0.45 μm with aperture, gained solution ultraviolet-visible pectrophotometer measures its absorbancy respectively.
4. binding site equilibrium dissociation constant K is adopted
dand separation factor alpha evaluates selective adsorption.
K
D=C
p/C
e
K
d---binding site equilibrium dissociation constant, ml/g;
C
p---the concentration of Polymer adsorption substrate, namely polymkeric substance is to the adsorptive capacity Q of substrate, mg/g;
C
e---the concentration of substrate in solution during adsorption equilibrium, mg/ml.
α=K
Di/KD
j
α---separation factor, during general α >1, just represents that polymkeric substance has selective adsorption to template molecule;
K
di---the binding site equilibrium dissociation constant of template molecule, ml/g;
KD
j---the binding site equilibrium dissociation constant of disturbing molecule, ml/g.
Kaempferide molecularly imprinted polymer is to the K of different substrate
dand α, in table 1, table 2
Table 1 polymkeric substance is to the binding site equilibrium dissociation constant K of different substrate
d(ml/g)
Table 2 polymkeric substance is to the separation factor alpha of different substrate
Can be found out by table 1, table 2 data, kaempferide molecularly imprinted polymer is to the K of kaempferide
dobviously be greater than two kinds of interference substrates, illustrate that kaempferide molecularly imprinted polymer has significant selective adsorption to kaempferide, and separation factor be greater than 1, the effective separation to kaempferide can be realized under interference existence condition.
Claims (9)
1. the preparation method of a kaempferide molecular imprinted polymer on surface microballoon, it is characterized in that the moiety of its reactant is: template molecule, function monomer, carrier, linking agent, initiator, pore-creating agent, wherein template molecule, function monomer, the molar mass of linking agent is than being 1:(2-10): (5-50), template molecule and carrier addition are than being 1:(10-100) [n (mmol): m (mg)], template molecule is 1:(10-60 with the amount ratio of pore-creating agent) [n (mmol): V (ml)], the amount of crosslinker species is 4-10 times of function monomer, initiator amount is the 5%-20% of function monomer and linking agent quality sum.
2. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 1, is characterized in that in described method, template molecule is selected from flavonoid compound.
3. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 2, is characterized in that in described method, template molecule is kaempferide.
4. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 1, is characterized in that in described method, function monomer selects the one in acrylamide, 2-vinyl pyridine, 4-vinylpridine, methacrylic acid.
5. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 1, is characterized in that in described method, carrier selects nano-TiO
2.
6. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 1, it is characterized in that in described method, linking agent is the one in ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pore-creating agent is the one in acetonitrile, chloroform, acetone, and initiator is Diisopropyl azodicarboxylate.
7. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 1, its concrete steps are:
Be dissolved in appropriate pore-creating agent in molar ratio by template molecule and function monomer, ultrasonic disperse, adds proper amount of nano TiO
2, stir, be placed in logical nitrogen deoxidation on reaction unit, add linking agent and pore-creating agent, control temperature, 50-70 DEG C of reaction, obtains the polymer microballoon of particle diameter between 0.5-2 μm;
Polymkeric substance methyl alcohol/the acetic acid mixture obtained is carried out wash-out more than 72 hours in soxhlet extraction device, then with methanol solution washing balance removing acetic acid, by the polymkeric substance vacuum-drying after washing, namely obtains kaempferide molecularly imprinted polymer.
8. the preparation method of kaempferide molecular imprinted polymer on surface microballoon according to claim 7, is characterized in that the ultrasonic disperse time in step (1) is 10-20min, stirs 2-4 hour, and logical nitrogen deaeration time is 10-20min; Mixed solution methyl alcohol in step (2): the volume ratio of acetic acid is 9:1-5:5.
9. obtained kaempferide molecular imprinted polymer on surface microballoon according to claim 1 is used in the separation and purification of pharmaceutical cpd, and it is characterized in that: adsorption temp is 20-40 DEG C, adsorptive capacity is 2-4mg/g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801900A (en) * | 2016-03-26 | 2016-07-27 | 吉首大学 | Preparation method and application of imprinted polymer capable of selectively gathering F-ions |
| CN117089020A (en) * | 2023-08-30 | 2023-11-21 | 昆明理工大学 | Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material |
-
2014
- 2014-01-26 CN CN201410038126.8A patent/CN104804152A/en active Pending
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| ZHANG ZHIMIAO等: "Preparation and Adsorption Performance of Molecularly Imprinted Polymers for Kaempferol", 《DESALINATION AND WATER TREATMENT》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801900A (en) * | 2016-03-26 | 2016-07-27 | 吉首大学 | Preparation method and application of imprinted polymer capable of selectively gathering F-ions |
| CN105801900B (en) * | 2016-03-26 | 2018-06-01 | 吉首大学 | A kind of imprinted polymer preparation method and application of optional enrichment F- ions |
| CN117089020A (en) * | 2023-08-30 | 2023-11-21 | 昆明理工大学 | Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material |
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Application publication date: 20150729 |