CN101565485A - Method for preparing molecularly imprinted polymers of ethinylestradiol analogue - Google Patents
Method for preparing molecularly imprinted polymers of ethinylestradiol analogue Download PDFInfo
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Abstract
The invention relates to a method for preparing molecularly imprinted polymers of ethinylestradiol analogue. The method comprises the following preparation steps: a, taking 17-ethenyl estradiol as a template, mixing template molecules, functional monomers, a crosslinking agent, a pore-foaming agent and an initiator, performing ultrasonic polymerization on the mixture for 12 to 24 hours at the temperature of 60 DEG C in the atmosphere of nitrogen, and obtaining polymers; b, performing centrifugation on the prepared polymers, discarding supernatant, using a methanol-acetic acid mixture for soak cleaning and removal of the template molecules, and obtaining the molecularly imprinted polymers; and c, performing vacuum drying on the polymers. Because the template is easy to separate from ethinylestradiol and estradiol on a chromatographic column, the prepared MIP cannot influence the accuracy of a result due to the leakage of the template when being used for solid-phase extractive materials. Moreover, the prepared MIP reveals obvious compatibility to the 17-ethenyl estradiol, the ethinylestradiol and the estradiol, and corresponding non-imprinted polymers (polymers prepared without the template in the same condition) reveal low compatibility.
Description
One, technical field
The invention belongs to the molecularly imprinted polymer technology of preparing, particularly a kind of have the concentration and separation preparation methods of highly selective, high-affinity to steroid hormone class medicines such as ethinylestradiol, estradiol.
Two, background technology
Steroid hormone that may be residual in environment or the animal food has potential harm to people healthy, becomes the important proposition that the food safety field relates to.As estradiol, ethinylestradiol (17 α-ethinylestradiol, EE2) etc., therefore their activity obviously is better than natural steroid hormone, medically is being widely used in the synthetic and treatment of diseases of contraceptive bian, also in livestock, aquaculture as the growth stimulant of animal.These hormonal substances often are discharged in the environment with movements such as ight soil, urines with the form of medicine original shape or meta-bolites, and most hormone medicines are discharged to still has activity, directly contaminated soil and water source in the environment.Contaminated water source and soil may cause secondary pollution to farm crop and wild plant.Steroid hormone has changed many character of plant plankton in the aquatic environment in the currently reported environment, for example reduces kind number in the unit environment, reduces biomass, cell density, increases diversity, average degree, and changes species structure.
At present, the steroid hormone detection technique of widespread usage has comprised fluorescent spectroscopy, mass spectroscopy, liquid chromatography, gas-chromatography, thin-layer chromatography, immunodetection and some combined interpretation technique, except immunization method, mostly need expensive investment among them, loaded down with trivial details sample pretreatment program and in a large number with an organic solvent.Although oneself is well-adapted endogenous hormones analysis means for an immunodetection, but the problem that also has specificity and susceptibility in actual applications, and depend on a large amount of experimentation on animalies, be subjected to condition restriction, as test the cost height, can not popularize in an all-round way, and time-consuming, take a lot of work, circulation ratio, accuracy are unsatisfactory.Therefore develop a kind of rapidly, seem very urgent of sensitive and economic analysis and detection technology.
Molecular imprinting (Molecular Imprinting) is a molecular recognition new technology that developed rapidly in recent years.It is the self-assembly (Self-assembling) by chemical molecular, the synthetic macromolecular compound that specific molecular is had specific adsorption.In the molecular imprinting reaction, at first (comprise covalent linkage by chemical bond between function monomer and the template molecule, ionic linkage, hydrogen bond, and Van der Waals force or the like) the formation mixture, carrying out in the polyreaction subsequently, the growth of polymeric chain and crosslinked with this compound action curing, the wash-out template molecule just forms the cave of energy specific adsorption template molecule in the polymer molecule, this polymkeric substance be called as molecularly imprinted polymer (Molecular Imprinting Polymer, MIP).This technology has been used for chiral chromatography and affinity chromatography now, Solid-Phase Extraction, a plurality of fields such as simulation biocatalysis.
Specific selectivity of MIP and affinity can be fixed on glass, pottery, the optical fiber easily, can simplify environmental sample system complicated pretreatment program as solid extracting agent, for sample collecting, enrichment and analysis provide great convenience.Mmole trace substance below horizontal after this method pre-concentration is handled, is reached more than the chromatographic detectability.Significantly reduce the time of sample pretreatment, really accomplish rapid detection.
Molecular imprinting about estradiol is to detect template molecule with polymkeric substance at present, the whole wash-outs of template molecule can be able to not be caused " leakage " during owing to wash-out, makes the result be false positive.
Three, summary of the invention
Technical problem: the present invention is directed to above-mentioned technical problem, a kind of preparation method of molecular blotting polymer microsphere of ethinylestradiol analogue is provided.The MIP of this method preparation presents tangible affinity to ethinylestradiol, and can not influence result's accuracy when being used for the Solid-Phase Extraction material because of the leakage of template.
Technical scheme: a kind of preparation method of molecularly imprinted polymer of ethinylestradiol analogue, preparation process is: a. is a template with 17-ethyl estradiol, template molecule, function monomer, linking agent, pore-creating agent and initiator are mixed, ultrasonic, under nitrogen atmosphere, in 60 ℃ of polymerization 12～24h, get polymkeric substance; Described function monomer is a methacrylic acid, methyl methacrylate or acrylamide; Described linking agent is trimethylolpropane trimethacrylate or methacrylate glycol ester; Described pore-creating agent is acetonitrile or toluene.Described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide; Described template molecule and function monomer, its mol ratio are 1: 1～1: 5; Described template molecule and linking agent, its mol ratio are 1: 4～1: 8; The ratio of the volumetric usage of described pore-creating agent and template molecule molar weight is 60mL/mmol; The ratio of described initiator quality and template molecule molar weight is 80mg/mmol; B. the polymkeric substance of step a preparation is centrifugal, abandoning supernatant is embathed the removal template molecule with methyl alcohol-acetate mixed solution, till UV-detector detects less than template molecule, obtains molecularly imprinted polymer; C. with molecularly imprinted polymer, vacuum-drying obtains the ethinylestradiol analogue molecularly imprinted polymer.
Among the step a, described ultrasonic and logical nitrogen, its ultrasonic time is 5min, the logical nitrogen time is 10min.Ultrasonic is in order to be uniformly dispersed; Logical nitrogen is for deoxygenation, causes because this initiation reaction is a free radical, can not have oxygen to exist, and logical nitrogen can increase porosity.
Among the step b, described centrifugal, its centrifugal speed is 15000rpm.Guarantee that polymkeric substance can precipitate fully.
Among the step c, before vacuum-drying, the polymkeric substance washed with methanol is to remove residual acetate.
Beneficial effect:
1. template is not an ethinylestradiol, but ethinylestradiol analogue.Because template and ethinylestradiol, estradiol are easy to separate on chromatographic column, thereby make the MIP of preparation when being used for the Solid-Phase Extraction material, can not influence result's accuracy because of the leakage of template.
2. Zhi Bei MIP presents tangible affinity to 17-ethyl estradiol, ethinylestradiol, estradiol, and corresponding non-imprinted polymer (there is the polymkeric substance for preparing with similarity condition down in no template) shows low-down affinity.
Four, description of drawings
Fig. 1 is the transmission electron microscope figure that the present invention makes molecular blotting polymer microsphere, microscope JEM1010, and acceleration voltage 80kv, enlargement ratio 40000 *;
Fig. 2 is the Static Adsorption isothermal map that the present invention makes trace and non-imprinted polymer microballoon.
Five, embodiment
Embodiment 1
2.96g (1mmol) ethinylestradiol pressed powder is dissolved in the eggplant-shape bottle of the ethanolic soln that 15mL is housed, add a small amount of Pd/C, normal temperature feeds hydrogen down in the induction stirring, high performance liquid phase is followed the tracks of reaction process, and (the detection wavelength is 280nm, moving phase is that volume ratio is 8: 2 a methanol-water, flow velocity 1mL/min), until the peak that detects less than ethinylestradiol, the expression reaction finishes.Leach Pd/C, be spin-dried for ethanol, add an amount of ethyl alcohol recrystallization, obtain colourless needle crystal.
1H-NMR(CDCl
3)δ：0.92(s，3H，18-CH
3)，1.03(t，3H，CH
2CH
3)，2.82(m，2H，6-CH
2)，4.61(b，2H，OH-phenol)，6.56(d，1H，4-CH)，6.63(d，1H，2-CH)，7.15(d，1H，1-CH).M/z：283.2([M-H
2O]
+，100％).
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 0.25mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 12h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 0.25mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 16h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
Embodiment 4
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 0.25mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 20h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 0.25mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 24h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
Embodiment 6
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 0.5mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 24h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
Embodiment 7
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 0.75mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 24h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
Embodiment 8
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 1mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 24h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.The used condition of present embodiment is the optimal conditions of preparation ethinylestradiol analogue molecularly imprinted polymer, and Electronic Speculum figure sees Fig. 1.
Embodiment 9
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 1.25mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 1mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 24h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
Embodiment 10
The nominal template 17-ethyl estradiol of 0.25mmol and the function monomer methacrylic acid of 1mmol are dissolved into the linking agent trimethylolpropane trimethacrylate that 15mL contains 2mmol, in the acetonitrile solution of the initiator Diisopropyl azodicarboxylate of 20mg, ultrasonic, logical nitrogen 10min, sealing, generate the white powder shaped polymer in 60 ℃ of oil bath precipitation polymerization 24h, with volume ratio is that methyl alcohol-acetic acid solution of 9: 1 is that extracting solution is removed template molecule, till UV-detector detects less than template molecule, use methanol wash centrifugal then, centrifugal speed is 15000rpm, abandoning supernatant, place 40 ℃ of vacuum drying ovens to be dried to weight in polymkeric substance, promptly get the ethinylestradiol analogue molecularly imprinted polymer.
In order to verify the trace effect of molecularly imprinted polymer, done following experiment:
Accurate title is decided the above-mentioned polymkeric substance of 20mg and is placed the 15mL Erlenmeyer flask respectively, add in the 17-ethyl estradiol, ethinylestradiol, estradiol acetonitrile solution of 10mL different concns (0.1,0.5,1,2,3,4,5mmol/L), sealing, jolting 24h under the room temperature moves into suspension liquid in the 10mL plastic centrifuge tube, with the 10000 centrifugal 10min of rotating speed that change, getting supernatant liquor quantitatively dilutes, 200～400nm scanning detects in ultraviolet-visible spectrophotometer, asks adsorptive capacity, sees Fig. 2.Calculation formula is as follows:
Q, adsorptive capacity, μ mol; A, absorbancy; A
f, absorption back solution absorbance; C, strength of solution, μ mol/mL; V, adsorbent solution volume, mL.
From Fig. 2 as seen, apparently higher than non-imprinted polymer, and adsorption effect is relevant with the structural similarity of ethinylestradiol and analogue thereof to the adsorptive capacity of 17-ethyl estradiol, ethinylestradiol and estradiol for the molecularly imprinted polymer of the ethinylestradiol analogue of gained.
Claims (5)
1. the preparation method of the molecularly imprinted polymer of an ethinylestradiol analogue is characterized in that preparation process is:
A. be template with 17-ethyl estradiol, template molecule, function monomer, linking agent, pore-creating agent and initiator are mixed, ultrasonic, under nitrogen atmosphere,, get polymkeric substance in 60 ℃ of polymerization 12～24h; Described function monomer is a methacrylic acid, methyl methacrylate or acrylamide; Described linking agent is trimethylolpropane trimethacrylate or methacrylate glycol ester; Described pore-creating agent is acetonitrile or toluene; Described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide; Described template molecule and function monomer, its mol ratio are 1: 1～1: 5; Described template molecule and linking agent, its mol ratio are 1: 4～1: 8; The ratio of the volumetric usage of described pore-creating agent and template molecule molar weight is 60mL/mmol; The ratio of described initiator quality and template molecule molar weight is 80mg/mmol;
B. the polymkeric substance of step a preparation is centrifugal, abandoning supernatant is embathed the removal template molecule with methyl alcohol-acetate mixed solution, till UV-detector detects less than template molecule, obtains molecularly imprinted polymer;
C. with molecularly imprinted polymer, vacuum-drying obtains the ethinylestradiol analogue molecularly imprinted polymer.
2. the preparation method of ethinylestradiol analogue molecular blotting polymer microsphere as claimed in claim 1 is characterized in that, among the step a, described ultrasonic time is 5min.
3. the preparation method of ethinylestradiol analogue molecular blotting polymer microsphere as claimed in claim 1 is characterized in that, among the step a, described nitrogen atmosphere is kept by logical nitrogen 10min.
4. the preparation method of ethinylestradiol analogue molecular blotting polymer microsphere as claimed in claim 1 is characterized in that, and is described centrifugal among the step b, and its centrifugal speed is 15000rpm.
5. the preparation method of ethinylestradiol analogue molecular blotting polymer microsphere as claimed in claim 1 is characterized in that, among the step c, before vacuum-drying, the polymkeric substance washed with methanol is to remove residual acetate.
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