CN106317326A - Preparation method of phenolphthalein molecularly imprinted polymeric material as well as material and application thereof - Google Patents
Preparation method of phenolphthalein molecularly imprinted polymeric material as well as material and application thereof Download PDFInfo
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- CN106317326A CN106317326A CN201510388198.XA CN201510388198A CN106317326A CN 106317326 A CN106317326 A CN 106317326A CN 201510388198 A CN201510388198 A CN 201510388198A CN 106317326 A CN106317326 A CN 106317326A
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Abstract
The invention provides a nontoxic dummy template (phenolphthalein) molecularly imprinted polymeric material as well as a preparation and an application thereof. The nontoxic template molecule phenolphthalein, a functional monomer 4-vinylpyridine, a cross-linking agent ethylene dimethacrylate, and an initiator azodiisobutyronitrile are dissolved in a pore forming agent acetonitrile, and polymerization is carried out at 60 DEG C for 24 hours. Grinding, screening and settlement are carried out for products, and polymer particles whose particle sizes are in the range of 45-63 [mu]m are obtained. Methanol/glacial acetic acid is used as a solvent, soxhlet extraction is carried out for removing template molecule PP, and the PP imprinted polymeric material is obtained. The material has good adsorption capacity for bisphenol A (BPA), and appears good group selectivity for BPA and structural analogs thereof, such as bisphenol B, bisphenol E, bisphenol AF, bisphenol S, bisphenol AP and bisphenol Z. The material can be used as a solid phase extraction filling material at the same time, and is applied to selective separation experiments for the seven kinds of bisphenol substances in human urine samples, bovine serum samples, and beer samples with good selectivity and purifying capability.
Description
Technical field
The present invention relates to a kind of Selective Separation and purify bisphenol-A and the nontoxic replacement mould of analog thereof
The preparation of plate (phenolphthalein) molecularly imprinted polymer material and application, belong to biology and food analysis with new
Material Field.
Background technology
Bisphenol-A be acknowledged as a kind of incretion interferent (endocrine disrupting chemical,
EDC), it to reproduction and growth, nervous system, cardiovascular system, the metabolism of the mankind and is exempted from
The harm of epidemic disease system is the most extensively confirmed.In light of this situation, Environmental Protection Agency USA (USEPA)
With EFSA (EFSA) it has been specified that bisphenol-A maximum every day takes in the reference value of dosage,
Her Majesty the Queen in right of Canada as represented by the minister of Healt have also been made related work.European Union is to the plastic bisphenol-A for food production
Migration amount has done strict restriction.Limiting and regulation to tackle these, many manufacturers begin to use one
The analog raw material as an alternative of a little bisphenol-As.These analogs have Bisphenol F, bisphenol S,
Bisphenol b, bis-phenol E, bisphenol AF, bisphenol-ap and bisphenol Z etc..At present, some have been had to close
There is the report of endocrine disrupting in structure of bisphenol A analog.It has been reported that bisphenol S, bisphenol b,
Bisphenol F has the acute toxicity similar with bisphenol-A, genotoxicity and estrogen effect.There is research
Showing that bisphenol b and bisphenol AF can affect the activity of pregnane X receptor, this nuclear receptor can be directly
Affect the metabolism of exogenous material.In the nearest research about male adult Mus, bisphenol AF
Become Mus testicular function by impact and then cause the reduction of its internal testosterone concentration.Therefore these bisphenol-As
Analog also can constitute certain potential threat to human health.Along with these structure of bisphenol A are similar to
The increase year by year of thing industrial application amount, its discharge capacity in nature also can increase therewith, Jin Erjia
The big risk of Human body package.Hence set up method for separating and analyzing accurately and reliably, it is achieved to bisphenol-A
And there is the most cognitive in everyday exposure of situation in biological sample and food samples in analog
Extremely important meaning is had with health assessment aspect.
Due to the biological and complexity of food samples composition, it is achieved to the standard of bisphenols pollutant contained by it
Really analyze and need to rely on certain isolation of purified means.Solid-Phase Extraction material based on molecular imprinting
Just can realize the Selective Separation of target substance in complex matrices and purification, this be just to give birth to complexity
Thing sample and accurately analyzing of food samples provide reliable basis.Molecular imprinting (molecular
Imprinting technique) it is the new technique prepared and target compound is had specific identification ability material.
Different from function monomer Interaction Force according to template molecule during material preparation and identification, can
To be classified as covalent method, non-covalence method and half covalent method.Wherein being most widely used of non-covalence method.
Owing to having low cost, easily prepared, mechanical strength and chemical stability are good and can repeat
The advantage used, polymer is widely used in the preparation of molecular engram material.But preparing molecule
Need to use substantial amounts of template molecule during imprinted polymer, and generally use target analytes is template.
Generally cannot realize the removal completely to template molecule due to surname extraction, use prepared material
During there will be template reveal problem, quantitatively cause serious interference to the analysis of object.With
This if analyte is toxic pollutant, uses it can make environment as template molecule simultaneously in a large number
Become severe contamination.
In light of this situation, alternate template is used to prepare molecularly imprinted polymer gradually by research worker
Concern.The alternate template that research worker is generally selected is the homology similar to target substance molecular structure
Thing.It is prepared for Selective recognition Bisphenol F, bis-phenol E, double with bisphenol S for template than if any research worker
The molecularly imprinted polymer material of phenol A, bisphenol b and bisphenol AF.Although this research obtains well
Effect, but be template molecule owing to employing bisphenol S, the template leakage problem self produced makes material
Material cannot be applied to the analysis of bisphenol S.Bisphenol S also has the acute toxicity similar with bisphenol-A simultaneously,
Genotoxicity and estrogen effect, should not use in a large number.Therefore select beyond target substance homologue
Low toxicity or nontoxic material template molecule as an alternative have emphatically in molecular engram material preparation field
Big meaning.
Phenolphthalein is a kind of weak organic acid, and human body is not had toxic action, is often used as soda acid instruction
Agent.Additionally due to it has stimulation intestinal wall, the wriggling of intestinal is caused to promote effect of defecation, at medicine
Field is used to manufacture the medicine of the habitual Obstipation for the treatment of.Phenolphthalein molecular structure has two hydroxyls
Phenyl, has certain similarity with bisphenol structure, the bond angle between two hydroxyphenyl also with
Bisphenol is close, therefore as preparation, bisphenol can be had Selective recognition ability and divide
The preferable alternate template of sub-imprinted material.The most not by phenolphthalein template as an alternative, it is used for
Preparation has the relevant report of Selective recognition ability molecularly imprinted polymer material to bisphenol.
Summary of the invention
It is an object of the invention to provide a kind of to double in human urine sample, Ox blood serum sample and beer sample
Phenolic comp ' ds pollution has the nontoxic alternate template molecularly imprinted polymer of high selectivity and good detergent power
The methods for making and using same of material.
For achieving the above object, the technical solution used in the present invention is:
Selective Separation purifies the nontoxic alternate template molecularly imprinted polymer material of bisphenols pollutant,
Can prepare according to the following steps:
Template molecule phenolphthalein (PP), function monomer, cross-linking agent and initiator are dissolved in porogen,
Carry out bulk polymerization, product is carried out surname extraction, the most i.e. obtain nontoxic alternate template phenol
Phthalein molecularly imprinted polymer material.
Concretely comprise the following steps:
(1) template molecule PP, function monomer, cross-linking agent and initiator are dissolved in porogen, shape
Become pre-polymer solution；
(2) by ultrasonic for pre-polymer solution degassing, sealing after logical nitrogen deoxygenation, template molecule is placed in cold preservation
Bulk polymerization is carried out with function monomer after fully acting on；
(3) step (2) product is pulverized, grinds, sieves and settled；
(4) product is with methanol and glacial acetic acid mixed liquor as solvent, surname extraction, product drying to obtain
Nontoxic alternate template phenolphthalein molecularly imprinted polymer material.
Described function monomer is 4-vinylpridine i.e. 4-VP, and cross-linking agent is ethylene glycol dimethacrylate
Ester i.e. EGDMA, described initiator is azodiisobutyronitrile i.e. AIBN, and described porogen is acetonitrile；
PP:4-VP:EGDMA:AIBN mol ratio is 1～2:2～8:10～40:0.00025～0.001；Its
Middle EGDMA is 1～2:1～4 with the volume ratio of acetonitrile；
Described in step (2), ultrasonic degassing operation is carried out in ice bath, and the time is 5-15min；Described
The logical nitrogen time is 5-15min；The temperature that described cold preservation is placed is 0-10 DEG C, and the time is 1-4h；Institute
Stating bulk polymerization to carry out under water bath condition, reaction temperature is 50-70 DEG C, and the response time is 12-48
h；
In screening operation described in step (3), it is 45-63 μm that screening retains granularity；Described sedimentation behaviour
Making with acetone as solvent, consumption is 10-40mL；
In methanol described in step (4) and glacial acetic acid mixed liquor, methanol with the volume ratio of glacial acetic acid is
9:1-9, the temperature that surname extraction uses is 80-120 DEG C, and extraction time is 12-48；Described dry behaviour
As vacuum drying, baking temperature is 50-70 DEG C, and drying time is 6-24h.
Phenolphthalein molecularly imprinted polymer material prepared by the preparation method provided according to the present invention can conduct
Adsorbent, applies the bisphenol-A in Selective Separation biological sample or food samples and structure thereof to be similar to
One or both in thing bisphenol b, bis-phenol E, bisphenol AF, bisphenol S, bisphenol-ap and bisphenol Z
In above.
In above-mentioned application, phenolphthalein molecularly imprinted polymer material uses as the filler of solid-phase extraction column；Institute
Belonging to biological sample behaviour urine sample and Ox blood serum sample, food samples is medicated beer.
Described nontoxic alternate template (phenolphthalein) molecularly imprinted polymer is as the filler of solid-phase extraction column.
Described nontoxic alternate template (phenolphthalein) molecularly imprinted polymer for isolated and purified human urine sample,
Bisphenols pollutant in Ox blood serum sample and beer sample.
The invention have the advantage that nontoxic alternate template (phenolphthalein) the molecularly imprinted polymer material of preparation
The template phenolphthalein used is nontoxic, environmental protection, in use will not cause dry to the analysis of target substance
Disturb.Meanwhile, it is to bisphenol-A and analog bisphenol b thereof, bis-phenol E, bisphenol AF, double
Phenol S, bisphenol-ap and bisphenol Z have the strongest class selectivity.The molecularly imprinted polymer material of the present invention
Material has superelevation specific selectivity to bisphenol in complex matrices, it is possible to the effective substrate that reduces is done
Disturb, it is possible to quick, sensitive, accurately and efficiently to human urine sample, Ox blood serum sample and medicated beer sample
Product are analyzed.
Accompanying drawing explanation
Fig. 1 is nontoxic alternate template (phenolphthalein) the molecularly imprinted polymer material (a, PP-MIP) of the present invention
With non-imprinted polymer material (b, NIP) and difference the most corresponding (c, PP-MIP；D, NIP)
The stereoscan photograph of material microporous structure.
Fig. 2 be the present invention nontoxic alternate template (phenolphthalein) molecularly imprinted polymer (PP-MIP) and
The corresponding non-imprinted polymer (NIP) adsorption isothermal curve to bisphenol-A (BPA).
Fig. 3 be the present invention nontoxic alternate template (phenolphthalein) molecularly imprinted polymer (PP-MIP) and
The Scatchard modal analysis results of corresponding non-imprinted polymer (NIP) isotherm adsorption data accorded.
Fig. 4 is that the PP-MIP of the present invention is to BPA, bisphenol b (BPB), bis-phenol E (BPE), double
Phenol AF (BPAF), bisphenol S (BPS), bisphenol-ap (BPAP), bisphenol Z (BPZ), 17 β-
Estradiol (E2) and the imprinting factor evaluation result of diethylstilbestrol (DES).
Detailed description of the invention
This nontoxic alternate template (phenolphthalein) molecularly imprinted polymer material is to BPA and six kinds of structure classes thereof
Like thing, there is the strongest specific selectivity and detergent power.This material can be used for bisphenols in complex matrices
Pollutant isolated and purified.
Embodiment 1
Selective Separation purifies nontoxic alternate template (phenolphthalein) the molecular engram polymerization of bisphenols pollutant
Thing material and the preparation of corresponding non-marking material:
(1) by 0.318g (1mmol) template molecule phenolphthalein (PP), 0.42mL (4mmol)
Function monomer 4-vinylpridine (4-VP), 3.8mL (20mmol) cross-linking agent dimethacrylate
Glycol ester (EGDMA) and 40mg initiator azodiisobutyronitrile (AIBN) are dissolved in 5.6mL
Porogen acetonitrile in, formed pre-polymer solution；
(2) pre-polymer solution is placed in ice bath, ultrasonic degassing 10min, this backward pre-polymer solution
In seal after logical nitrogen 10min deoxygenation, at 5 DEG C, 2h is placed in cold preservation；
(3) pre-polymer solution after sealing cold preservation is put in 60 DEG C of water-baths, carries out polymerisation in bulk anti-
Answer 24h, generate the bulk polymer of white；
(4) white chunks polymer being pulverized, grind, sieves and settled, the screen cloth of sieve used is
200-250 mesh, obtains the granularity white powder shaped polymer in 45-63 μm；
(5) with methanol and glacial acetic acid mixed liquor as solvent, volume ratio is 9:1, the temperature of 150 DEG C
Lower soxhlet type 24h is to remove the template molecule phenolphthalein in powdered polymer materials；
(6), after soxhlet type terminates, polymer is placed in vacuum drying oven in 60 DEG C of dry 12h,
I.e. obtain nontoxic alternate template (phenolphthalein) molecularly imprinted polymer material.
The condition preparing the non-imprinted material corresponding with imprinted material is: use and aforesaid operations step
(1) preparation condition similar in, by 0.42mL (4mmol) function monomer 4-vinylpridine
(4-VP), 3.8mL (20mmol) cross-linking agent Ethylene glycol dimethacrylate (EGDMA) and
40mg initiator azodiisobutyronitrile (AIBN) is dissolved in the porogen acetonitrile of 5.6mL, is formed
Pre-polymer solution；Use the operational approach identical with aforesaid operations step (2), by pre-polymer solution
It is placed in ice bath, ultrasonic degassing 10min, in this backward pre-polymer solution after logical nitrogen 10min deoxygenation
Sealing, at 5 DEG C, 2h is placed in cold preservation；Use the reaction bar identical with aforesaid operations step (3)
Part, the pre-polymer solution after sealing cold preservation is put in 60 DEG C of water-baths, carries out bulk polymerization 24h,
Generate the bulk polymer of white；Aforesaid operations step (4) is used to process non-imprinted material, sieve used
The screen cloth of son is 200-250 mesh, obtains the granularity white powder shaped polymer in 45-63 μm；Do not adopt
Non-imprinted material is processed by above-mentioned operating procedure (5)；The method using aforesaid operations step (6) is done
Dry obtain non-imprinted material.
Embodiment 2
Material is carried out static adsorption evaluation:
Precise embodiment 1 preparation nontoxic alternate template (phenolphthalein) molecularly imprinted polymer material and with
The non-each 40mg of imprinted polymer material of correspondence, be distributed to be contained in 10mL sealing respectively good
The a series of concentration of 2mL of glass sample bottle (0.02mmol/L, 0.05mmol/L, 0.1mmol/L,
0.2mmol/L, 0.5mmol/L, 1.0mmol/L, 2.0mmol/L, 4.0mmol/L) BPA
In acetonitrile solution.Sample bottle is shaken continuously with the speed of 150 revs/min in the water bath with thermostatic control of 25 DEG C
After 24h respectively by solidliquid mixture with 0.22 μm membrane filtration.High performance liquid chromatography is utilized to divide respectively
Analysis filtrate remains the concentration of BPA.Analysis result is depicted as adsorption isothermal curve, and result is shown in Fig. 2.
It is very easy to find the imprinted material absorbability to BPA apparently higher than non-imprinted material.Again by trace material
Material and the isotherm adsorption data accorded Scatchard model of non-imprinted material are analyzed, result such as Fig. 3 institute
Show.Two different straight lines are obtained after the adsorpting data of imprinted material is analyzed, it was demonstrated that this
There are high affine and low affine two kinds of different adsorption sites in bright material, as shown in Figure 3.Utilization is passed through
Scatchard analysis obtains slope and the intercept of two straight lines, calculates high affine and low affine adsorption potential
Point is respectively 4.661 μm ol g to the maximal absorptive capacity of BPA-1With 65.64 μm ol g-1。
BPA is had very well by nontoxic alternate template (phenolphthalein) the molecularly imprinted polymer material of this invention
Selectivity and higher adsorption capacity.
Embodiment 3
Evaluate nontoxic alternate template (phenolphthalein) the molecularly imprinted polymer material invented to BPA, BPB,
The imprinting factor of BPE, BPAF, BPS, BPAP, BPZ, E2, DES:
Imprinted material embodiment 1 prepared and non-imprinted material, with methanol for dispersion solvent, fill respectively
Enter rustless steel chromatographic column (100mm × 4.6mm i.d.), obtain marking post and non-trace post.Pass through
Liquid chromatograph obtains above-mentioned substance retention time on trace post and non-trace post, and then obtains trace
The evaluation result of the factor.Specifically comprise the following steps that the concentration being respectively configured above-mentioned analyte is 20ppm's
Acetonitrile solution, chromatograph is with acetonitrile for flowing phase, and flow rate of mobile phase is 1mL/min, and column temperature is 25 DEG C,
Detection wavelength is 220nm, and the one in each 20 above-mentioned acetonitrile solutions of μ L of each hand sampling is to trace
Post and non-trace post, obtain analyte guarantor on trace post and non-trace post respectively by chromatographic evaluation
Stay time (tR), utilize acetone to replace the bisphenols pollutant acetonitrile solution in above-mentioned chromatographic step,
To trace post and the dead time t of non-trace post0By capacity factor measure computing formula k=(tR-t0)/t0Calculate
Analyte is at trace post (kPP-MIP) and non-trace post (kNIPCapacity factor measure on).Utilize trace because of
Sub-computing formula IF=kPP-MIP/kNIPCalculate the phenolphthalein molecularly imprinted polymer print to above-mentioned 9 kinds of analytes
The mark factor, result is as shown in Figure 4.
Found by evaluation, institute's invention imprinted material to seven kinds of bisphenols pollutant (BPA, BPB,
BPE, BPAF, BPS, BPAP, BPZ) imprinting factor be significantly higher than it to E2's and DES
Imprinting factor.The above results shows nontoxic alternate template (phenolphthalein) molecularly imprinted polymer invented
Material has good class selectivity to seven kinds of bisphenols pollutant.
Claims (9)
1. the preparation method of a phenolphthalein molecularly imprinted polymer material, it is characterised in that:
Template molecule phenolphthalein (PP), function monomer, cross-linking agent and initiator are dissolved in porogen,
Carry out bulk polymerization, product is carried out surname extraction, the most i.e. obtain nontoxic alternate template phenol
Phthalein molecularly imprinted polymer material.
Preparation method the most according to claim 1, it is characterised in that: concretely comprise the following steps:
(1) template molecule phenolphthalein PP, function monomer, cross-linking agent and initiator are dissolved in porogen,
Form pre-polymer solution；
(2) by ultrasonic for pre-polymer solution degassing, sealing after logical nitrogen deoxygenation, cold preservation carries out this after placing
Body polyreaction；
(3) product of step (2) is pulverized, grinds, sieves and settled；
(4) product is with methanol and glacial acetic acid mixed liquor as solvent, and surname extraction, product after drying and get final product
To nontoxic alternate template phenolphthalein molecularly imprinted polymer material.
Preparation method the most according to claim 1 and 2, it is characterised in that:
Described function monomer is 4-vinylpridine i.e. 4-VP, and cross-linking agent is ethylene glycol dimethacrylate
Ester i.e. EGDMA, described initiator is azodiisobutyronitrile i.e. AIBN, and described porogen is acetonitrile；
Please herein to the proportionate relationship between each material in full step (1).
Preparation method the most according to claim 2, it is characterised in that: super described in step (2)
Sound degassing operation is carried out in ice bath, and the time is 5-15min；The described logical nitrogen time is 5-15min；
The temperature that described cold preservation is placed is 0-10 DEG C, and the time is 1-4h；Described bulk polymerization is at water-bath bar
Carrying out under part, reaction temperature is 50-70 DEG C, and the response time is 12-48h.
Preparation method the most according to claim 2, it is characterised in that: sieve described in step (3)
Dividing in operation, it is 45-63 μm that screening retains granularity；Described settling operation with acetone as solvent, consumption
For material volume 2-4 times.
Preparation method the most according to claim 2, it is characterised in that: first described in step (4)
In alcohol and glacial acetic acid mixed liquor, methanol is 9:1-9 with the volume ratio of glacial acetic acid, the temperature that surname extraction uses
Degree is for 80-120 DEG C, and extraction time is 12-48；Described drying process is vacuum drying, baking temperature
For 50-70 DEG C, drying time is 6-24h.
7. the phenolphthalein molecularly imprinted polymer prepared according to the arbitrary described preparation method of claim 1-6
Material.
8. the phenolphthalein molecularly imprinted polymer material described in claim 7 is as an adsorbent, is selecting
Bisphenol-A in property separation biological sample or food samples and analog bisphenol b thereof, bis-phenol E,
Application in one or more in bisphenol AF, bisphenol S, bisphenol-ap and bisphenol Z.
9. according to the application described in claim 8, it is characterised in that:
Described phenolphthalein molecularly imprinted polymer material uses as the filler of solid-phase extraction column；Affiliated biological
Sample behaviour urine sample and Ox blood serum sample, food samples is medicated beer.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341553A (en) * | 2013-08-02 | 2015-02-11 | 中国科学院大连化学物理研究所 | Ultra-high-selectivity bisphenol substitute template molecularly imprinted polymer and application thereof |
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2015
- 2015-07-01 CN CN201510388198.XA patent/CN106317326A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341553A (en) * | 2013-08-02 | 2015-02-11 | 中国科学院大连化学物理研究所 | Ultra-high-selectivity bisphenol substitute template molecularly imprinted polymer and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| XIAOLI SUN，ET AL: "Highly class-selective solid-phase extraction of bisphenols in milk，sediment and human urine samples using well-designed dummy molecularly imprinted polymers", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| XIAOLI SUN，ET AL: "Highly selective dummy molecularly imprinted polymer as a solid-phase extraction sorbent for five bisphenols in tap and river water", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| ZHIYONG GUO，ET AL: "A highly sensitive electrochemiluminescence method combined with molecularly imprinted solid phase extraction for the determination of phenolphthalein in drug，slimming food and human plasma", 《FOOD CHEMISTRY》 * |
| 杨甲甲等: "替代模板分子印迹聚合物的制备及其用于人尿、牛血清和啤酒中7种双酚类物质的选择性固相萃取", 《色谱》 * |
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Application publication date: 20170111 |