CN102527350A - Bisphenol A dummy template molecular imprinting stirring rod of and preparation method thereof - Google Patents
Bisphenol A dummy template molecular imprinting stirring rod of and preparation method thereof Download PDFInfo
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- CN102527350A CN102527350A CN2011104284441A CN201110428444A CN102527350A CN 102527350 A CN102527350 A CN 102527350A CN 2011104284441 A CN2011104284441 A CN 2011104284441A CN 201110428444 A CN201110428444 A CN 201110428444A CN 102527350 A CN102527350 A CN 102527350A
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Abstract
The invention relates to a bisphenol A dummy template molecular imprinting stirring rod of and a preparation method thereof, which is characterized in that an alkylated glass rod is used as a carrier, composite macromolecule coating is coated so as to obtain the stirring rod, and the macromolecule coating is bisphenol A dummy template molecular imprinted polymer. The composite process of the bisphenol A dummy template molecular imprinted polymer on the glass rod is as follows: the surface of the glass rod, on which silanol is exposed, is treated by silanization, then reacts with tetrabromobisphenol A, tetra-vinylpyridine, ethylene glycol dimethacrylate and azobisisobutyronitrile, and then the dummy template molecule tetrabromobisphenol A is eluted so as to obtain the bisphenol A dummy template imprinted polymer. The bisphenol A dummy template molecular imprinting stirring rod obtained by the invention is high in specific selectivity of bisphenol A, is good in interference resisting capacity, is high in sensitivity, is free from template leakage problem, and is high in the measurement accuracy of trace bisphenol A in water-bearing medium.
Description
Technical field
The present invention relates to a kind of method for preparing the pseudo-template molecular engram of bisphenol-A stirring rod, this stirring rod can be used for the bisphenol-A in Selective Separation, the water-enriched solution.
Background technology
(Stir Bar Sorptive Extraction is a kind of novel sample-pretreating method SBSE) to Stir Bar Sorptive Extraction, is to be proposed by Erik Baltussen etc. in 1999.(Solid Phase Microextraction SPME) grows up, and has inherited the advantage of SPME, and treasury is got, concentrated, desorb is in one from SPME for it.But extraction fixedly the volume ratio Fiber-SPME extraction stationary phase volume of phase big adsorption surface area is big more than 50 times, so have higher loading capacity and sensitivity than SPME.In addition, stirring rod is accomplished the absorption to determinand when self stirs, avoided the competitive Adsorption of stirrer in the SPME, so this device is very suitable for the analysis of trace components in the sample.
Unique commercial stirring rod coating material is nonpolar dimethyl silicone polymer (Polydimethylsiloxane at present; PDMS); To the non-constant of suction-operated of low pole such as bisphenol-A or polar substances, so go to toward needing the derivatization step at this type of enrichment material.This has increased the difficulty and the uncertainty of experimental implementation greatly, thereby has limited the application of SBSE.Therefore many new material new methods are introduced in the SBSE production of coatings, and the effect of SBSE enrichment phenols isopolarity material is made moderate progress.Molecular imprinting is wherein a kind of method just.This technology is simple to operate, and cost is lower, and the stirring rod coating of preparing simultaneously has good physical and chemical stability, possesses the recognition capability to specific molecular structure.But if with the target molecule bisphenol-A as template molecule, even behind wash-out repeatedly, still have the residual of template molecule in the coating, thereby in the test sample process, cause " template seepage " phenomenon, cause and measure the inaccurate of result.
Summary of the invention
To the problems referred to above; The purpose of this invention is to provide the pseudo-template molecular engram of a kind of bisphenol-A stirring rod; With tetrabromobisphenol A is pseudo-template molecule, processes pseudo-template molecularly imprinted polymer coating, and this coating has specific selectivity adsorption capacity preferably to bisphenol-A; Adsorption site on the coating is many simultaneously, greatly improves selectivity and the adsorption capacity of SBSE.
In order to realize the foregoing invention purpose, the technical scheme that the present invention adopts is:
The pseudo-template molecular engram of a kind of bisphenol-A stirring rod is to be carrier with alkylating glass bar, obtains after the composite high-molecular coating, and described polymeric coating layer is the pseudo-template molecularly imprinted polymer of bisphenol-A;
The pseudo-template molecularly imprinted polymer of bisphenol-A is following at the recombination process of glass bar: handle at the glass bar surface silicon alkanisation that exposes the silanol base; And then with tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate and azodiisobutyronitrile reaction; The pseudo-template molecule of flush away tetrabromobisphenol A can obtain the pseudo-template molecularly imprinted polymer of bisphenol-A again;
Tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate add according to 1: 2: 4 ratio of mol ratio; The addition of azodiisobutyronitrile is 2%～3% of tetrabromobisphenol A, tetrem thiazolinyl pyridine, an ethylene glycol dimethacrylate gross mass;
Described glass bar surface is adopted 3-(isobutene acyl-oxygen) propyl trimethoxy silicane to carry out silanization and is handled.
Prepare the method for the pseudo-template molecular engram of described bisphenol-A stirring rod, step is following:
The activation of step (1) glass bar: the glass bar of establishing iron core in inciting somebody to action soaks activation 5h～10h with NaOH solution and hydrochloric acid solution respectively, uses distilled water flushing then, and vacuum drying is subsequent use; Described baking temperature is 100 ℃～150 ℃.The NaOH solution concentration is 0.5～1.5mol L
-1, be preferably 1mol L
-1Concentration of hydrochloric acid solution is 0.05～0.15mol L
-1, be preferably 0.1mol L
-1
The alkylation of step (2) glass bar: the glass bar of step (1) activation is soaked in 2h～4h in the alkylating reagent, washed with methanol, nitrogen dries up;
Solution before step (3) the preparation polymerization: successively tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate and azodiisobutyronitrile are added in the organic solvent, ultrasonic, mix, subsequent use; Tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate add according to 1: 2: 4 ratio of mol ratio.The addition of azodiisobutyronitrile be above-mentioned three kinds of polymerisation amounts and 2%～3%.The mass ratio of organic solvent and polymerization reactant is 2: 1; Said organic solvent is a methyl alcohol.
The pseudo-template molecularly imprinted polymer of the compound bisphenol-A of the alkylating glass bar of step (4): the alkylating glass bar of step (2) is immersed in the preceding solution of polymerization of step (3) preparation, under nitrogen stream protective condition, 60 ℃～65 ℃ are carried out polymerisation 4h～8h;
The stirring rod that it is good that step (5) will be coated with stain is taken out from polymeric block, uses washed with methanol, and drying obtains the pseudo-template molecular engram of bisphenol-A stirring rod.
Beneficial effect:
1. the present invention is the synthetic carrier of imprinted polymer with the glass bar, and material is simple and easy to, and alkylation process is simple.
2. the present invention is pseudo-template molecule with structure of bisphenol A analog tetrabromobisphenol A; And do not use bisphenol-A to be template molecule; In the high selectivity that obtains bisphenol-A, thoroughly avoided the template leakage problems, improved the degree of accuracy of measuring trace amount of bisphenol A in the water-bearing media effectively.
3. to adopt radical polymerization preparation be the stirring rod of coating with the pseudo-template molecularly imprinted polymer of bisphenol-A in the present invention, and the preparation method is simple.
4. the trace stirring rod of the present invention preparation combines efficient liquid phase fluorescence detector, need not additional other pre-treatment step, the direct bisphenol-A in the enriched sample, and the specific selectivity height, antijamming capability is good, and is highly sensitive, obviously is superior to the stirring rod of commercialization coating.
Description of drawings
Fig. 1 is the photo figure and the sem photograph thereof of pseudo-template molecular engram stirring rod, wherein:
Fig. 1 (A) is the photo figure of pseudo-template molecular engram stirring rod and blank glass rod;
Fig. 1 (B) is the sem photograph of pseudo-template molecular engram stirring rod, and multiplication factor is 5000;
Fig. 1 (C) is the sem photograph of pseudo-template molecular engram stirring rod cross section, and multiplication factor is 10000.
Fig. 2 be bisphenol-A in the milk through the chromatogram of enrichment, wherein:
A is 100nmol L
-1The chromatographic curve of the water quality standard solution of bisphenol-A;
B is the chromatographic curve of milk without enrichment;
C is the chromatographic curve of milk through the enrichment of PDMS stirring rod;
D is the chromatographic curve of milk through the enrichment of pseudo-template molecular engram stirring rod.
The specific embodiment
Agents useful for same is all commercially available.
Tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate and 3-(isobutene acyl-oxygen) propyl trimethoxy silicane reagent are all available from Sigma-Aldrich company (U.S.); Azodiisobutyronitrile is available from the brilliant pure reagent in Shanghai Co., Ltd.
Embodiment 1
The preparation method of the pseudo-template molecular engram of bisphenol-A stirring rod may further comprise the steps:
1) in glass bar (30mm * 5mm i.d.), puts into iron core, two ends sintering (shown in Figure 1A).Glass bar was used 1mol L successively before alkylation is handled
-1NaOH solution and 0.1mol L
-1Hydrochloric acid solution soaks 6h, fully washes with distilled water again, and is last, the glass rod of activation is placed in the vacuum drying chamber, and dry 1h under 120 ℃ of conditions, subsequent use.
2) glass bar of step 1) being handled is soaked in 2h in the acetone soln of 3-(isobutene acyl-oxygen) propyl trimethoxy silicane of 10% (v/v), washed with methanol, and nitrogen dries up, as the carrier that is coated with stain.
3) solution before the preparation polymerization: in 3mL methyl alcohol, add 1mmol tetrabromobisphenol A, 2mmol tetrem thiazolinyl pyridine, 4mmol ethylene glycol dimethacrylate and 30mg azodiisobutyronitrile successively, ultrasonic 3min mixes.
4) with step 2) the alkylation glass bar handled immerses in the methanol solution of step 3) preparation, and under nitrogen stream protective condition, 60 ℃ are carried out polymerisation 6h.
5) stirring rod that it is good that step 4) is coated with stain is taken out from polymeric block, with methyl alcohol soaking and washing stirring rod 5～10 times.Final stirring rod places vacuum drying chamber dry, obtains the pseudo-template molecular engram stirring rod (Figure 1B, Fig. 1 C) of bisphenol-A.
Embodiment 2 adsorption experiment reference examples
With commercially available non-molecular engram stirring rod--the pseudo-template molecular engram of the bisphenol-A stirring rod of-PDMS stirring rod (available from Viscotek Corporation), embodiment 1 preparation is carried out adsorption test respectively under the same conditions; Adsorption test condition: 6mL milk is diluted to 30mL, and regulates pH value to 6～7.In solution, put into stirring rod, adsorb 1～2h with the 300rpm rotating speed under 20 ℃～25 ℃ conditions.After absorption finishes, with 1mL methyl alcohol desorption stirring rod.After stripping liquid nitrogen dries up, redissolve with 150 μ L methyl alcohol, the liquid that redissolves is used for Liquid Detection.
The result is as shown in Figure 2, before extraction, can't see the chromatographic peak (shown in the chromatographic curve B) of bisphenol-A in the chromatogram of milk.Milk is (shown in the chromatographic curve C) after the enrichment of PDMS stirring rod, and going out Feng Chu at bisphenol-A has a small peak, but the peak value of this chromatographic peak is not enough to quantitatively, goes out Feng Chu at bisphenol-A simultaneously, also has the matrix interference phenomenon.But after the enrichment of pseudo-template molecular engram stirring rod (shown in the chromatographic curve D), the bisphenol-A in the milk can be by accurate mensuration.Pseudo-template molecular engram stirring rod has shown the good selection absorption property to bisphenol-A.
Embodiment 3
The preparation method of the pseudo-template molecular engram of bisphenol-A stirring rod, 0.5mol L is adopted in the glass bar activation
-1NaOH solution and 0.05mol L
-1Hydrochloric acid solution soaks 10h; Glass bar is soaked in the acetone soln 4h of 3-(isobutene acyl-oxygen) propyl trimethoxy silicane of 15 volume %, the quality of azodiisobutyronitrile be tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate quality and 3%.All the other are all with embodiment 1.
Embodiment 4
The preparation method of the pseudo-template molecular engram of bisphenol-A stirring rod, 1.5mol L is adopted in the glass bar activation
-1NaOH solution and 0.15mol L
-1Hydrochloric acid solution soaks 5h; Glass bar is soaked in the acetone soln 3h of 3-(isobutene acyl-oxygen) propyl trimethoxy silicane of 5 volume %, the quality of azodiisobutyronitrile be tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate quality and 2.5%.All the other are all with embodiment 1.
Claims (7)
1. the pseudo-template molecular engram of bisphenol-A stirring rod is characterized in that being is carrier with alkylating glass bar, obtains after the composite high-molecular coating, and described polymeric coating layer is the pseudo-template molecularly imprinted polymer of bisphenol-A.
2. the pseudo-template molecular engram of bisphenol-A according to claim 1 stirring rod; It is characterized in that the pseudo-template molecularly imprinted polymer of described bisphenol-A is following at the recombination process of glass bar: carry out silanization on the glass bar surface that exposes the silanol base and handle; And then and tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate and azodiisobutyronitrile reaction, the pseudo-template molecule of flush away tetrabromobisphenol A again.
3. the pseudo-template molecular engram of bisphenol-A according to claim 2 stirring rod is characterized in that tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate add according to the ratio of mol ratio 1:2:4; The addition of azodiisobutyronitrile is 2%～3% of tetrabromobisphenol A, tetrem thiazolinyl pyridine, an ethylene glycol dimethacrylate gross mass; The silanization processing is carried out on described glass bar surface, and silylating reagent is 3-(isobutene acyl-oxygen) propyl trimethoxy silicane, and catalyst is a pyridine, and catalyst volume is 1%～2% of 3-(isobutene acyl-oxygen) propyl trimethoxy silicane volume.
4. the preparation method of the pseudo-template molecular engram of bisphenol-A stirring rod is characterized in that step is following:
The activation of step (1) glass bar: the glass bar of establishing iron core in inciting somebody to action is used NaOH solution and salt soak activation 5h～10h respectively, uses distilled water flushing then, and vacuum drying is subsequent use;
The alkylation of step (2) glass bar: the glass bar of step (1) activation is soaked in 2h～4h in the alkylating reagent, washed with methanol, nitrogen dries up;
Solution before step (3) the preparation polymerization: successively tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate and azodiisobutyronitrile are added in the organic solvent, ultrasonic, mix, subsequent use;
The pseudo-template molecularly imprinted polymer of the compound bisphenol-A of the alkylating glass bar of step (4): the alkylating glass bar of step (2) is immersed in the preceding solution of polymerization of step (3) preparation; Under nitrogen stream protective condition, 60 ℃～65 ℃ are carried out polymerisation 4h～8h;
Step (5), good stirring rod is taken out from polymeric block with being coated with stain, uses washed with methanol, and drying obtains the pseudo-template molecular engram of bisphenol-A stirring rod.
5. the preparation method of the pseudo-template molecular engram of bisphenol-A according to claim 4 stirring rod is characterized in that the described vacuum drying temperature of step (1) is 100 ℃～150 ℃; Described alkylating reagent is the solution of 3-(isobutene acyl-oxygen) propyl trimethoxy silicane, and concentration is 5～15 volume %; Described NaOH solution concentration is 0.5～1.5 mol L
-1, concentration of hydrochloric acid is 0.05～0.15 mol L
-1
6. the preparation method of the pseudo-template molecular engram of bisphenol-A according to claim 4 stirring rod is characterized in that the described alkylating reagent of step (2) is the solution of 3-(isobutene acyl-oxygen) propyl trimethoxy silicane, and concentration is 10 volume %; Described NaOH solution concentration is 1 mol L
-1, concentration of hydrochloric acid is 0.1 mol L
-1
7. the preparation method of the pseudo-template molecular engram of bisphenol-A according to claim 4 stirring rod is characterized in that step (3) tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate add according to the ratio of mol ratio 1:2:4; The addition of azodiisobutyronitrile be tetrabromobisphenol A, tetrem thiazolinyl pyridine, ethylene glycol dimethacrylate quality and 2%～3%; The mass ratio of organic solvent and reactant is 2:1, and described organic solvent is a methyl alcohol.
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| CN104128207A (en) * | 2014-07-15 | 2014-11-05 | 武汉纺织大学 | Preparation method of core-shell pseudo template imprinted magnetic nano-catalyst for use in degradation of Congo red |
| CN104250349A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method and application of dummy template molecularly imprinted polymer |
| CN104772127A (en) * | 2015-03-25 | 2015-07-15 | 南开大学 | Production method of carbon fiber cloth surface molecular imprinting passive sampling membrane for organic pollutants in water environment |
| CN104119536B (en) * | 2014-07-15 | 2016-08-24 | 武汉纺织大学 | The preparation method of bisphenol-A solid extracting agent based on pseudo-template covalency imprinted silica gel |
| CN106268712A (en) * | 2015-06-11 | 2017-01-04 | 南开大学 | A kind of method of preparation and use of micro-extraction carbon-point based on surface molecule print |
| CN111318264A (en) * | 2020-02-15 | 2020-06-23 | 江苏大学 | Preparation method of boron affinity molecular imprinting stirring rod and application of stirring rod in adsorption separation of catechol |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250349A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method and application of dummy template molecularly imprinted polymer |
| CN104128207A (en) * | 2014-07-15 | 2014-11-05 | 武汉纺织大学 | Preparation method of core-shell pseudo template imprinted magnetic nano-catalyst for use in degradation of Congo red |
| CN104119536B (en) * | 2014-07-15 | 2016-08-24 | 武汉纺织大学 | The preparation method of bisphenol-A solid extracting agent based on pseudo-template covalency imprinted silica gel |
| CN104772127A (en) * | 2015-03-25 | 2015-07-15 | 南开大学 | Production method of carbon fiber cloth surface molecular imprinting passive sampling membrane for organic pollutants in water environment |
| CN106268712A (en) * | 2015-06-11 | 2017-01-04 | 南开大学 | A kind of method of preparation and use of micro-extraction carbon-point based on surface molecule print |
| CN106268712B (en) * | 2015-06-11 | 2018-12-18 | 南开大学 | A kind of method of preparation and use of the micro-extraction carbon-point based on surface molecule print |
| CN111318264A (en) * | 2020-02-15 | 2020-06-23 | 江苏大学 | Preparation method of boron affinity molecular imprinting stirring rod and application of stirring rod in adsorption separation of catechol |
| CN111318264B (en) * | 2020-02-15 | 2021-11-23 | 江苏大学 | Preparation method of boron affinity molecular imprinting stirring rod and application of stirring rod in adsorption separation of catechol |
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Application publication date: 20120704 |