CN105085765A - Preparation method for dimethyl phthalate molecularly imprinted microspheres - Google Patents
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Abstract
The invention relates to the field of molecularly imprinted polymers. In order to solve the problem that the adsorptivity of a recognition site is not excellent when dimethyl phthalate molecules are detected by adopting a molecular imprinting technique, the invention provides a preparation method for the dimethyl phthalate molecularly imprinted microspheres. The molecularly imprinted microspheres prepared by the method have structure-activity preordainment, specific recognition and environmental stability and can play a positive role in the field of enrichment and separation, detection and analysis and efficient deduction of phthalic acid ester (PAEs).
Description
Technical field
The present invention relates to molecularly imprinted polymer field, relate in particular to a kind of preparation method of dimethyl phthalate molecular engram microsphere.
Background technology
Phthalic ester (PAEs) is the organic compound that a class generally uses, and main softening agent and the tenderizer being used as plastics, is widely used.Dimethyl phthalate (DMP) is exactly a kind of common PAEs.Because PAEs compound and plastics and other goods itself are difficult to mortise, in unbound state in the goods such as plastics, As time goes on, be easy to dissociate out from the goods such as plastics, and PAEs itself is difficult to be decomposed into rapidly other materials, thus be extensively present in environment and organism, research shows that multiple PAEs has three and causes and (cause prominent, teratogenesis, carcinogenic) effect, and the endocrine biochemistry of multiple upset animal and group effect can be produced, biotic potential is caused to decline and genital malformation, there is serious harm, therefore, the great attention of people is caused to the detection of PAEs in ecotope.Conventional detection method mainly vapor-phase chromatography, liquid phase chromatography, gas chromatography-mass spectrography and liquid chromatograph mass spectrography, but as actual sample, in sample, the content of PAEs is often lower, and matrix is complicated, aforesaid method all needs to carry out enrichment and purifying to sample, and testing method is complicated.Therefore, prepare a kind ofly to have great importance to the separation and concentration material that PAEs has a height selective recognition ability, molecularly imprinted polymer prepared by molecular imprinting is the Perfected process of separation and concentration PAEs.
Molecular imprinting is the new technology of the model molecule specific recognition effect grown up in recent years, it utilizes crosslinking reaction that template molecule and function monomer are generated stable polymkeric substance by interacting, molecularly imprinted polymer (MolecularImprintingPolymer, MIP) is generated after eccysis template molecule.MIP leaves the hole with template molecule structure, functional group's complementation, it will show special selectivity and identity to template molecule and the molecule similar to template molecule.Molecularly imprinted polymer material has memory function, optionally can adsorb template molecule, completes the separated island form to target analytes.At present, the preparation method of MIP mainly contains mass polymerization, suspension polymerization, seed swelling method and precipitation polymerization method etc.But adopt molecularly imprinted polymer as the material of separation and concentration PAEs, the recognition site of gained imprinted polymer is mostly inner at polymer microballoon, and cause template molecule to be combined difficulty with recognition site, separation treatment efficiency is not high.In the recent period, the new trend of molecular imprinting is surface molecule print technology, and its advantage is, the recognition site of imprinted polymer, at microsphere surface, is easy to template molecule and is combined with recognition site, improves separation treatment efficiency.
Summary of the invention
The period of the day from 11 p.m. to 1 a.m is divided to there is the not good problem of recognition site adsorptivity for solving to employing molecular imprinting detection dimethyl phthalate, the present invention proposes a kind of preparation method of dimethyl phthalate molecular engram microsphere, molecular engram microsphere prepared by the method, there is structure effect precordainment, specific recognition and environmental stability, can play a positive role in the concentration and separation of PAEs, detection analysis and efficient subduction field.
The present invention is achieved by the following technical solutions: a kind of preparation method of dimethyl phthalate molecular engram microsphere is following steps:
(1) taking chitosan is dissolved in acetic acid solution, leave standstill and disappear to bubble end, then the acetic acid solution of chitosan dropwise to be joined in sodium hydroxide alcohol mixeding liquid and ageing 20 ~ 28h, chitosan microball (CS) is obtained after filtration, use distilled water wash several times, wash away sodium hydroxide alcohol mixeding liquid, then the chitosan microball after washing is joined in glutaraldehyde solution, magnetic agitation 1 ~ 3h, and then use distilled water wash several times, the glutaraldehyde solution that removing is residual, obtains the chitosan microball carrier (CS-CHO) after cross-link;
The relative molecular mass of chitosan is 3 × 10
5~ 7 × 10
5da.
Acetic acid is as solvent, and usage quantity is the amount making solute dissolves.Acetic acid is preferably the acetic acid solution that mass percent is 2%.
As preferably, in sodium hydroxide alcohol mixeding liquid, the volume ratio of NaOH solution and ethanolic soln is 4: 1, and wherein, the mass percent of NaOH solution is 10%, and the mass percent of ethanolic soln is 95%.Sodium hydroxide alcohol mixeding liquid is as solvent, and the amount of use is for making the amount of solute dissolves.
In glutaraldehyde solution, the amount of substance of glutaraldehyde is more than or equal to chitosan microball amount of substance.As preferably, in chitosan microball amount of substance and glutaraldehyde solution, the mol ratio of glutaraldehyde is 1: 1 ~ 2.The preferred mass percentage concentration of glutaraldehyde solution is 1%.
(2) chitosan microball carrier and 4-aminophthalic acid dimethyl ester are joined in acetonitrile, add methacrylic acid (MAA) again as function monomer, stirred at ambient temperature 12 ~ 36h makes template molecule and function monomer fully act on, then linking agent is added, initiator and acetonitrile, sonic oscillation 5 ~ 10min, frequency is 20KHz ~ 60KHz, logical nitrogen 15 ~ 30min, sealing, put into more than 60 DEG C water bath with thermostatic control reactions 1 ~ 2 day, take out, be cooled to room temperature, suction filtration obtains polymer microballoon, dry rear extracting solution extracts 24h ~ 48h in apparatus,Soxhlet's, wash away template molecule, with methyl alcohol, polymer microballoon is washed till neutrality, dry, obtain dimethyl phthalate molecular engram microsphere.
As preferably, 4-aminophthalic acid dimethyl ester is 1: 1 ~ 2 with the amount of substance ratio of chitosan microball carrier.Methacrylic acid is 4 ~ 8: 1 with the amount of substance ratio of 4-aminophthalic acid dimethyl ester.
As preferably, linking agent is selected from ethylene glycol dimethacrylate (EGDMA), linking agent is 10 ~ 30: 1 with the amount of substance ratio of 4-aminophthalic acid dimethyl ester, initiator is selected from Potassium Persulphate or ammonium persulphate, and 4-aminophthalic acid dimethyl ester is 5 ~ 10: 1 with the amount of substance ratio of initiator.
Acetonitrile is as solvent, and usage quantity is the amount making solute dissolves.
In described extracting solution, the volume ratio of acetic acid and methyl alcohol is 1: 3 ~ 5.
The present invention adopts surface molecule print technology to prepare PAEs nucleocapsid structure molecular engram microsphere, and described reaction equation is as follows:
In aforesaid equation, n is positive integer.
The present invention adopts surface imprinted method to prepare MIP, because its recognition site is based upon polymer surfaces, template molecule can be very fast near recognition site, there is higher association rate and dissociation efficiency, greatly can reduce non-specific adsorption to optionally affecting, and reduce embedding phenomenon, be a kind of immunoblot method efficiently.
Compared with prior art, the invention has the beneficial effects as follows:
(1) improve adsorptivity and the selectivity of recognition site in imprinted polymer, template molecule is combined comparatively easy with recognition site, separation treatment efficiency is high;
(2) generation of gel phenomenon and embedding phenomenon is avoided;
(3) synthesize cheap, cost is low;
Accompanying drawing explanation
Fig. 1 is chitosan microball (a), crosslinked chitosan microsphere (b) and dimethyl phthalate molecular engram microsphere (c) infrared spectrogram;
Fig. 2 is the 13C-NMR spectrogram of crosslinked chitosan microsphere (CS);
Fig. 3 is dimethyl phthalate molecular engram microsphere (MIP)
13c-NMR spectrogram;
Fig. 4 is the SEM figure of crosslinked chitosan microsphere (CS-CHO);
Fig. 5 is the SEM figure of dimethyl phthalate molecular engram microsphere (MIP);
Fig. 6 is the SEM figure of non-imprinted polymer (NIP);
Fig. 7 is the curve of adsorption kinetics of dimethyl phthalate molecular engram microsphere.
Embodiment
Be described in further details the present invention below by embodiment, raw materials used all commercially available in embodiment, wherein the relative molecular mass of chitosan is 3 × 10
5~ 7 × 10
5da, 4-aminophthalic acid dimethyl ester is also prepared by following methods:
A () puts into 20g4-nitrophthalic acid acid anhydride and 25mL methyl alcohol in three-necked bottle, after 4-nitrophthalic acid acid anhydride dissolves, add the 1mL vitriol oil, condensing reflux 7h at 120 DEG C.Steam remaining methyl alcohol, concentrated solution is poured in mixture of ice and water, obtain light yellow solid.Filter, the sodium carbonate solution with 10% washs 3 times, is being washed with distilled water to pH6.5 ~ 7.0, ethyl alcohol recrystallization, obtains 4-nitrophthalic acid dimethyl ester light yellow crystal;
B () puts into 4-nitrophthalic acid dimethyl ester, 200mL benzene and the 10mL concentrated hydrochloric acid that 4.5g above-mentioned steps (a) obtains in three-necked bottle, add 5g zinc powder under stirring, reaction 15min, then adds 5g zinc powder, room temperature reaction 15h.Add 400mL distilled water, and be adjusted to pH=7.0 with 1mol/LNaOH, static separatory.Steamed by benzene in organic layer, cooling obtains light yellow solid, recrystallization in ethanol, obtains 4-aminophthalic acid dimethyl ester light yellow crystal.
Embodiment 1
(1) acetic acid solution that 1.0g chitosan is dissolved in 25mL2% is taken, leave standstill and within 12 hours, make its froth breaking, with syringe, chitosan solution is dropwise joined (10%NaOH and 95% ethanol in sodium hydroxide alcohol mixeding liquid, volume ratio is 4: 1), obtain regular, the even-grained chitosan microball of shape, obtained Chitosan Beads is placed on ageing 24h in mixed solution.Filtration obtains chitosan microball (CS), with distilled water wash 5 times, remove unnecessary sodium hydroxide alcohol mixeding liquid, then chitosan microball is joined 50mL glutaraldehyde solution (mass percent is 1%) (being equivalent to 0.005mol glutaraldehyde), magnetic agitation 2h.Then use a large amount of distilled water repetitive scrubbing, to remove residual glutaraldehyde solution, obtain the chitosan microball carrier (CS-CHO) after cross-link;
(2) crosslinked chitosan microsphere 0.5g above-mentioned steps (1) obtained and 1mmol4-aminophthalic acid dimethyl ester join in 25mL acetonitrile, add 6mmol methacrylic acid (MAA) again as function monomer, stirred at ambient temperature 24h, template molecule and function monomer are fully acted on, add 20mmol linking agent ethylene glycol dimethacrylate (EGDMA), 7mmol initiator potassium persulfate and 50mL acetonitrile, be 20KHz sonic oscillation 5min by frequency, logical nitrogen 15min, sealing, puts into 60 DEG C of waters bath with thermostatic control and reacts 48h.Take out, be cooled to room temperature, suction filtration obtains polymer microballoon, vacuum-drying, with the extracting solution of 250mL, wherein V (acetic acid): V (methyl alcohol)=1: 4 extracts 24h in apparatus,Soxhlet's, wash away template molecule, with methyl alcohol, polymkeric substance is washed till neutrality, vacuum-drying, obtains dimethyl phthalate molecular engram microsphere 1.
Embodiment 2
(1) acetic acid solution of the molten 40mL2% of 2.0g chitosan is taken, leave standstill and within 8 hours, make its froth breaking, with syringe, chitosan solution is dropwise joined (10%NaOH and 95% ethanol in sodium hydroxide alcohol mixeding liquid, volume ratio is 4: 1), obtain regular, the even-grained chitosan microball of shape, obtained Chitosan Beads is placed on ageing 20h in mixed solution.Filtration obtains chitosan microball (CS), with distilled water wash 7 times, remove unnecessary sodium hydroxide ethanolic soln, chitosan microball is joined 50mL glutaraldehyde solution (mass percent 1%) (being equivalent to 0.005mol glutaraldehyde), magnetic agitation 3h.Then use a large amount of distilled water repetitive scrubbing, to remove residual glutaraldehyde solution, obtain the chitosan microball carrier (CS-CHO) after cross-link.
(2) crosslinked chitosan microsphere 1.0g above-mentioned steps (1) obtained and 1mmol4-aminophthalic acid dimethyl ester join in 25mL acetonitrile, add 4mmol methacrylic acid (MAA) again as function monomer, stirred at ambient temperature 12h, makes template molecule and function monomer fully act on.Adding 10mmol linking agent ethylene glycol dimethacrylate (EGDMA), 5mmol initiator ammonium persulfate and 50mL acetonitrile, is 60KHz sonic oscillation 10min by frequency, and logical nitrogen 20min, sealing, puts into 70 DEG C of waters bath with thermostatic control and react 36h.Take out, be cooled to room temperature, suction filtration obtains polymer microballoon, vacuum-drying.With the extracting solution of 250mL, wherein V (acetic acid): V (methyl alcohol)=1: 3 extracts 24h in apparatus,Soxhlet's, washes away template molecule, with methyl alcohol, polymkeric substance is washed till neutrality, vacuum-drying, obtains dimethyl phthalate molecular engram microsphere 2.
Embodiment 3
(1) acetic acid solution that 1.5g chitosan is dissolved in 20mL2% is taken, leave standstill and within 15 hours, make its froth breaking, with syringe, chitosan solution is dropwise joined (10%NaOH and 95% ethanol in sodium hydroxide alcohol mixeding liquid, volume ratio is 4: 1), obtain regular, the even-grained chitosan microball of shape, obtained Chitosan Beads is placed on ageing 28h in mixed solution, filtration obtains chitosan microball (CS), with distilled water wash 4 times, remove unnecessary sodium hydroxide ethanolic soln.Chitosan microball is joined 50mL glutaraldehyde solution (mass percent 1%) (being equivalent to 0.005mol glutaraldehyde), magnetic agitation 1h.Then use a large amount of distilled water repetitive scrubbing, to remove residual glutaraldehyde solution, obtain the chitosan microball carrier (CS-CHO) after cross-link.
(2) crosslinked chitosan microsphere 0.75g above-mentioned steps (1) obtained and 1mmol4-aminophthalic acid dimethyl ester join in 25mL acetonitrile, add 8mmol methacrylic acid (MAA) again as function monomer, stirred at ambient temperature 36h, makes template molecule and function monomer fully act on.Adding 30mmol linking agent ethylene glycol dimethacrylate (EGDMA), 10mmol initiator potassium persulfate and 50mL acetonitrile, is 40KHz sonic oscillation 7min by frequency, and logical nitrogen 20min, sealing, puts into 80 DEG C of waters bath with thermostatic control and react 24h.Take out, be cooled to room temperature, suction filtration obtains polymer microballoon, vacuum-drying.With the extracting solution of 250mL, wherein V (hydrochloric acid): V (methyl alcohol)=1: 5 extracts 24h in apparatus,Soxhlet's, washes away template molecule, with methyl alcohol, polymkeric substance is washed till neutrality, vacuum-drying, obtains dimethyl phthalate molecular engram microsphere 3.
Test case 1
The crosslinked chitosan microsphere (CS), chitosan microball carrier (CS-CHO) and the dimethyl phthalate molecular engram microsphere (MIP) that obtain above-described embodiment 1 test on IRPrestige-21 type Fourier transformation infrared spectrometer that (KBr pressed disc method, sweep limit is at 400-4000cm
-1), obtain infrared spectra as shown in Figure 1.
Test case 2
The crosslinked chitosan microsphere (CS) obtained above-described embodiment 2, dimethyl phthalate molecular engram microsphere utilize ADVANCEII/400MHZ type nuclear magnetic resonance analyser to carry out sign and measure.Obtain chitosan microball as shown in Figure 2 and dimethyl phthalate molecular engram microsphere as shown in Figure 3
13c-NMR wave spectrum.
Test case 3
Get the crosslinked chitosan microsphere, molecular blotting polymer microsphere and the non-imprinted polymer that obtain in above-described embodiment 3 respectively to be evenly fixed in sample table, observing samples pattern and mode of appearance (voltage sets of SEM is 5kV) under SS-550 type scanning electronic microscope, obtain the SEM figure of crosslinked chitosan microsphere (CS-CHO) as shown in Figure 4, the SEM figure of the SEM figure of dimethyl phthalate molecular engram microsphere (MIP) as shown in Figure 5 and non-imprinted polymer (NIP) as shown in Figure 6.
Test case 4
The mensuration of dimethyl phthalate molecular engram microsphere adsorption curve.The dimethyl phthalate molecular engram microsphere (every part of 0.03g) that the embodiment 1 ~ 3 taking 10 parts of equivalent respectively obtains is placed in test tube, add in the solution of the 2mL different concns DMP prepared respectively, in isothermal vibration 24h, absorption is made to reach balance, remove supernatant liquor, its absorbancy is surveyed with ultraviolet spectrophotometer, and the concentration of DMP in calculated equilibrium adsorption liquid.The adsorptive capacity of polymkeric substance to substrate is gone out according to concentration of substrate change calculations in solution before and after combination.Result obtains adsorption curve as shown in Figure 7.
Adsorption curve illustrates that loading capacity only has smaller increase after substantially reaching capacity, embody than kinetics of adsorption and stable adsorption equilibrium faster, illustrate that dimethyl phthalate molecular engram microsphere dimethyl terephthalate molecule prepared by the present invention has good detectivity.
Claims (9)
1. a preparation method for dimethyl phthalate molecular engram microsphere, is characterized in that, described preparation method is following steps:
(1) taking chitosan is dissolved in acetic acid solution, leave standstill and disappear to bubble end, then the acetic acid solution of chitosan dropwise to be joined in sodium hydroxide alcohol mixeding liquid and ageing 20 ~ 28h, chitosan microball is obtained after filtration, use distilled water wash several times, the chitosan microball after washing is joined in glutaraldehyde solution, magnetic agitation 1 ~ 3h, and then use distilled water wash several times, obtain chitosan microball carrier;
(2) chitosan microball carrier and 4-aminophthalic acid dimethyl ester are joined in acetonitrile, add methacrylic acid again, linking agent, initiator and acetonitrile is added after stirred at ambient temperature 12 ~ 36h, sonic oscillation 5 ~ 10min, logical nitrogen 15 ~ 30min, sealing, put into more than 60 DEG C water bath with thermostatic control reactions 1 ~ 2 day, take out, be cooled to room temperature, suction filtration obtains polymer microballoon, 24h ~ 48h is extracted with extracting solution after drying, with methyl alcohol, polymer microballoon is washed till neutrality again, vacuum-drying, obtains dimethyl phthalate molecular engram microsphere.
2. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, is characterized in that, the relative molecular mass of chitosan is 3 × 10
5~ 7 × 10
5da.
3. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, it is characterized in that, in the sodium hydroxide alcohol mixeding liquid of step (1), the volume ratio of NaOH solution and ethanolic soln is 4:1, wherein, the mass percent of NaOH solution is 10%, and the mass percent of ethanolic soln is 95%.
4., according to the preparation method of a kind of dimethyl phthalate molecular engram microsphere of claim 1 or 2, it is characterized in that, in glutaraldehyde solution, the amount of substance of glutaraldehyde is more than or equal to chitosan microball amount of substance.
5. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, is characterized in that, the 4-aminophthalic acid dimethyl ester in step (2) is 1:1 ~ 2 with the amount of substance ratio of chitosan microball carrier.
6. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, is characterized in that, methacrylic acid is 4 ~ 8:1 with the amount of substance ratio of 4-aminophthalic acid dimethyl ester.
7. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, it is characterized in that, linking agent is selected from ethylene glycol dimethacrylate, and linking agent is 10 ~ 30:1 with the amount of substance ratio of 4-aminophthalic acid dimethyl ester.
8. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, it is characterized in that, initiator is selected from Potassium Persulphate or ammonium persulphate, and 4-aminophthalic acid dimethyl ester is 5 ~ 10:1 with the amount of substance ratio of initiator.
9. the preparation method of a kind of dimethyl phthalate molecular engram microsphere according to claim 1, is characterized in that, in extracting solution, the volume ratio of acetic acid and methyl alcohol is 1:3 ~ 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434270A (en) * | 2017-08-08 | 2017-12-05 | 同济大学 | Iron carbon aerogels Fenton negative electrode and its preparation with contaminant molecule trace |
| CN110907425A (en) * | 2019-11-27 | 2020-03-24 | 上海应用技术大学 | Surface molecular imprinting SERS sensor based on core-shell structure poly-dopamine coated nano-gold particles and preparation and application thereof |
| CN111036299A (en) * | 2019-12-27 | 2020-04-21 | 华南理工大学 | Catalytic material for targeted removal of phthalate pollutants based on MIL-100 carbide and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007050333A (en) * | 2005-08-17 | 2007-03-01 | Univ Of Miyazaki | Adsorbent and its manufacturing method |
| CN101298039A (en) * | 2008-01-18 | 2008-11-05 | 清华大学 | Preparation of chitosan molecular imprinting adsorbing agent |
| CN101574645A (en) * | 2009-06-05 | 2009-11-11 | 中国科学院生态环境研究中心 | Magnetic nano-material extractant and preparation method thereof |
| CN101628228A (en) * | 2008-07-15 | 2010-01-20 | 周奇迪 | Filter medium for removing phthalic acid ester in water and preparation method thereof |
| CN101928404A (en) * | 2010-07-09 | 2010-12-29 | 广东海洋大学 | Preparation of imprinted crosslinked chitosan resin and application thereof in removal of cadmium from pinctada martensii homogenate |
| CN102372821A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) and preparation method thereof |
| CN102453213A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Molecular entram polymer for selectively separating phthalate ester metabolites and preparation and application thereof |
| CN102731684A (en) * | 2012-07-04 | 2012-10-17 | 浙江农林大学 | Preparation method of urethane molecularly imprinted polymer |
| CN102814172A (en) * | 2012-08-21 | 2012-12-12 | 华南师范大学 | Preparation method for molecular imprinting-type photocatalyst and application of molecular imprinting-type photocatalyst |
-
2015
- 2015-06-24 CN CN201510354912.3A patent/CN105085765B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007050333A (en) * | 2005-08-17 | 2007-03-01 | Univ Of Miyazaki | Adsorbent and its manufacturing method |
| CN101298039A (en) * | 2008-01-18 | 2008-11-05 | 清华大学 | Preparation of chitosan molecular imprinting adsorbing agent |
| CN101628228A (en) * | 2008-07-15 | 2010-01-20 | 周奇迪 | Filter medium for removing phthalic acid ester in water and preparation method thereof |
| CN101574645A (en) * | 2009-06-05 | 2009-11-11 | 中国科学院生态环境研究中心 | Magnetic nano-material extractant and preparation method thereof |
| CN101928404A (en) * | 2010-07-09 | 2010-12-29 | 广东海洋大学 | Preparation of imprinted crosslinked chitosan resin and application thereof in removal of cadmium from pinctada martensii homogenate |
| CN102372821A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) and preparation method thereof |
| CN102453213A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Molecular entram polymer for selectively separating phthalate ester metabolites and preparation and application thereof |
| CN102731684A (en) * | 2012-07-04 | 2012-10-17 | 浙江农林大学 | Preparation method of urethane molecularly imprinted polymer |
| CN102814172A (en) * | 2012-08-21 | 2012-12-12 | 华南师范大学 | Preparation method for molecular imprinting-type photocatalyst and application of molecular imprinting-type photocatalyst |
Non-Patent Citations (4)
| Title |
|---|
| HUMA SHAIKHA等: ""Preparation and characterization of molecularly imprinted polymer for di(2-ethylhexyl) phthalate: Application to sample clean-up prior to gas chromatographic determination"", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| M. MONIER等: ""Preparation of molecularly imprinted cross-linked chitosan/glutaraldehyde resin for enantioselective separation of l-glutamic acid"", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
| 王小祥等: ""改性壳聚糖的制备及其对水中酞酸酯的吸附"", 《环境科学与技术》 * |
| 许文龙: ""叠氮化壳聚糖及其离子凝胶微球制备与性能"", 《中国优秀硕士学位论文全文数据库·工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434270A (en) * | 2017-08-08 | 2017-12-05 | 同济大学 | Iron carbon aerogels Fenton negative electrode and its preparation with contaminant molecule trace |
| CN107434270B (en) * | 2017-08-08 | 2020-08-18 | 同济大学 | Iron-carbon aerogel electro-Fenton cathode with pollutant molecular imprinting and preparation method thereof |
| CN110907425A (en) * | 2019-11-27 | 2020-03-24 | 上海应用技术大学 | Surface molecular imprinting SERS sensor based on core-shell structure poly-dopamine coated nano-gold particles and preparation and application thereof |
| CN110907425B (en) * | 2019-11-27 | 2022-07-08 | 上海应用技术大学 | Surface molecular imprinting SERS sensor based on core-shell structure poly-dopamine coated nano-gold particles and preparation and application thereof |
| CN111036299A (en) * | 2019-12-27 | 2020-04-21 | 华南理工大学 | Catalytic material for targeted removal of phthalate pollutants based on MIL-100 carbide and preparation method and application thereof |
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