CN102977334A - Molecularly imprinted polymer and preparation method and application thereof - Google Patents
Molecularly imprinted polymer and preparation method and application thereof Download PDFInfo
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- CN102977334A CN102977334A CN2012105885233A CN201210588523A CN102977334A CN 102977334 A CN102977334 A CN 102977334A CN 2012105885233 A CN2012105885233 A CN 2012105885233A CN 201210588523 A CN201210588523 A CN 201210588523A CN 102977334 A CN102977334 A CN 102977334A
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Abstract
The invention relates to a molecularly imprinted polymer which is an allyl isothiocyanate slow-release polymer synthesized by using allyl isothiocyanate as template molecule and beta-cyclodextrin as functional monomer. The obtained polymer is a new molecularly imprinted polymer having good slow-release properties, so as to provide a feasible preparation approach to the synthesis of allyl isothiocyanate molecularly imprinted polymers. Meanwhile, the prepared allyl isothiocyanate molecularly imprinted polymer is applied to the preservation field, and preservative paper made of the allyl isothiocyanate molecularly imprinted polymer has good preservative properties, which provides a feasible basis for the application of allyl isothiocyanate molecularly imprinted polymers in the preservation field.
Description
Technical field
A kind of molecularly imprinted polymer of the present invention and preparation method and application relate to a kind of allyl mustard oil slow-release preservative and preparation and application.Can utilize its slowly-releasing to allyl mustard oil to be applied to the food fresh keeping field.
Background technology
Molecularly imprinted polymer is the high molecular polymer that is complementary at binding site and chemical space structure and certain specific compound (template molecule)
[1]The method for preparing this polymkeric substance is molecular imprinting.Molecular imprinting is a kind of analysis, the isolation technique that the specific effect between manual simulation's Ag-Ab, vitamin H-antibiotin and the enzyme-to-substrate etc. grows up, and is mainly used in chiral material and separates
[2,3], Biomimic sensor
[4]Solid-Phase Extraction
[5,6]In the field.Along with the continuous maturation of molecular imprinting, in recent years, some research groups begin the drug delivery system that is applied to MIPs both at home and abroad
[7,8]This mainly is because the adsorptive power that MIPs has template molecule and template molecule can being slowly released after template molecule is by trace, can slowly discharge in vivo, thereby reaches the purpose of slowly-releasing.Therefore, will become another branch of MIP Application Areas for the slow releasing function of MIPs.At present, day by day abundant for the research of medicament slow release aspect, but the research that is applied to the food fresh keeping aspect also aquatic foods but rarely have report.
Allyl mustard oil is the product after the refining of black mustard oil enzymolysis, has good fungistatic effect
[9,10]But the volatility that it is stronger and irritating smell
[11]Be difficult to directly apply to the food fresh keeping field.At present, the someone studied the cavity that utilizes beta-cyclodextrin it was carried out embedding
[12]Thereby, cover its unpleasant odor and reach the purpose of slowly-releasing.But its slow-release time is shorter, and it is stable to reach slowly-releasing after 5 days, is unfavorable for long slowly-releasing.
Reference:
[1] Xiao Gong mountain true (day). Wu Shikang, Wang Pengfei translates. molecular imprinting-from the basis to using [M]. Beijing: Science Press, 2006.
[2] Kubo T, Matsumoto H, Shiraishi F, et al. Selective separation of hydroxy polychlorinated biphenyls (HO-PCBs) by the structural recognition on the molecularly imprinted polymers: Direct separation of the thyroid hormone active analogues from mixtures [J].
Anal Chim Acta, 2007, 589(2):180-185.
[3] Liu H M, Liu C H, Yang X J. Uniformly sized beta-cyclodextuin molecularly imprinted microspheres prepared by a novel surface imprinting technique for ursolic acid [J].
Anal Chim Acta, 2008, 628(1):87-94.
[4] Lad U, Khokhar S, Kale G M. Electrochemical creatinine biosensors [J].
Anal Chem. 2008,80(21):7910-7917.
[5] Yang T, Li H Y, Wei S, et al. Development of a selective molecularly imprinted polymer-based solid-phase extraction for indomethacin from water samples [J].
Talanta, 2009, 78(2):442-447.
[6] Li Yahui, Wang Yueqiu, Zhang Shuoyao, etc. the preparation of malachite green molecular imprinting thing and the application in Solid-Phase Extraction [J] thereof. chemical research and application, 2008,20 (9): 1163-1165.
[7] Alvarez-Lorenzo C, Concheiro A. Molecularly imprinted polymers for drug delivery [J]. J Chromatogr B, 2004, 804(1): 231.
[8] Sellergren B, Allender C J.Molecularly imprinted polymers: A bridge to advanced drug delivery, Adv. Drug Del. Rev., 2005; 57, 1733-1741.
[9] Mari M, Guizzardi M. The Postharvest Phase: Emerging technologlies for the control of fungal diseases [J]. Phytoparasitica, 1998, 26(1):59-66.
[10] Suhr K I, Nielsen P V, Inhibition of rungal growth on wheat and rye bread by modified armosphere packaging and active packaging using volatile mustard essential oil [J]. Food Microbiology and Safety, 2005, 70:37-44.
[11] Ling Guanting, Tao Minqiang compiles. foodstuff additive handbook (second edition) [M].Beijing: Chemical Industry Press, 1997,306.
[12] Li Xuehong, Jin Zhengyu. the control of the molecule embedding thing of allyl mustard oil under differing temps discharges [J]. Food science, 2007,28(3): 139-142.
Summary of the invention
The object of the invention is to prepare a kind of new molecularly imprinted polymer with good slowly-releasing template molecule function, the research its preparation method, and with in product application and the Perserving materials preparation, show good fresh keeping property.
A kind of molecularly imprinted polymer of the present invention, as template molecule take allyl mustard oil, take beta-cyclodextrin as function monomer, form host-guest coordination compound, add linking agent 2, the 4-tolylene diisocyanate occurs free-radical polymerized, thereby the crosslinked rigid polymer of height of formation around allyl mustard oil, with solvent acetone polymkeric substance is precipitated out from solvent at last, obtaining molecularly imprinted polymer is the allyl mustard oil release polymer, claims again the allyl mustard oil molecularly imprinted polymer.
The preparation method of a kind of molecularly imprinted polymer of the present invention follows these steps to be prepared successively:
(1) function monomer beta-cyclodextrin, template molecule allyl mustard oil are dissolved in the dimethyl sulfoxide (DMSO), ultrasonication is evenly mixed, carries out the reaction of one-phase heat of stirring; The mol ratio of beta-cyclodextrin and allyl mustard oil is 0.6-1:1; Heating temperature is 40 ℃-45 ℃, and be 6h-12h heat-up time; Every 5g function monomer adds dimethyl sulfoxide (DMSO) 50 mL-150mL.
(2) said mixture is added the linking agent 2,4 toluene diisocyanate, linking agent and function monomer mol ratio are 3-10:1.Mix rear nitrogen filled protection, carry out two-stage heat of stirring reaction and obtain the molecularly imprinted polymer reaction solution; Heating temperature is 60 ℃-65 ℃, and be 20h-24h heat-up time.
(3) the molecularly imprinted polymer reaction solution that polyreaction in the step (2) is synthetic slowly adds in the acetone, with the cotton-shaped molecularly imprinted polymer vacuum filtration that generates, in filtrate, continue to add acetone, till generating without precipitation, again with acetone and hot water repetitive scrubbing precipitation, with unreacted monomer molecule and linking agent wash-out; Obtain pure allyl mustard oil molecularly imprinted polymer, drying for standby behind the porphyrize through vacuum-drying.
Above-mentioned raw materials for production and related reagent are anhydrous raw material and anhydrous reagent.
The application of a kind of molecularly imprinted polymer of the present invention refers to the application of allyl mustard oil molecularly imprinted polymer aspect Perserving materials, is mainly used in the preparation of tin foil.The preparation method of tin foil is as follows:
(6-1) chitosan is dissolved in 1% acetic acid aqueous solution fully is mixed with coating liquid, chitosan-containing 1-4g in every 100mL coating liquid, under room temperature, slowly add the allyl mustard oil molecularly imprinted polymer, contain allyl mustard oil molecularly imprinted polymer 0.1-0.4g in every 100mL coating liquid.Add glycerine, glycerine and coating liquid volume ratio are 0.1%-0.4%, and constant temperature stirs.
(6-2) with evenly coating on the paper of certain area with casting method after the vacuum outgas of step (6-1) mixed solution, just obtain having the tin foil of slow-release function.
Beneficial effect of the present invention
A kind of molecularly imprinted polymer of the present invention, as template molecule take allyl mustard oil, take beta-cyclodextrin as function monomer, form host-guest coordination compound, add the linking agent 2,4 toluene diisocyanate occur free-radical polymerized, thereby around allyl mustard oil the crosslinked rigid polymer of height of formation, with solvent acetone polymkeric substance is precipitated out from solvent at last, obtains the allyl mustard oil release polymer.The polymkeric substance of gained is a kind of new molecularly imprinted polymer with good sustained release performance, for allyl mustard oil molecularly imprinted polymer synthetic provides a kind of feasible preparation scheme.Simultaneously, the allyl mustard oil molecularly imprinted polymer of preparation is applied to fresh-keeping field, prepared tin foil has good fresh keeping property, for the allyl mustard oil molecularly imprinted polymer is applied to fresh-keepingly, provides feasible foundation.
Below just embodiment and Figure of description the invention will be further described:
Description of drawings
Fig. 1 be under the different humidity condition on the impact of AITC slow release effect, illustrate that under certain ambient relative humidity, MIP shows certain release characteristics, and along with the corresponding increase of increasing release rate of ambient relative humidity.The speed that MIP discharges behind placement 168h under RH98%, RH75% and the RH50% condition eases up gradually.
Fig. 2 is on the impact of AITC slow release effect under the condition of different temperatures, illustrate that it is not very large that molecularly imprinted polymer discharges temperature influence, but along with the rate of release of the rising molecularly imprinted polymer of temperature also slightly rises, the thermally-stabilised fine of molecularly imprinted polymer is described, and low temperature is conducive to the stable of molecularly imprinted polymer.
Fig. 3 is that the different treatment group is on the impact of cold fresh meat pH value; Fig. 4 is that the different treatment group is to cold fresh meat Influences of MDA Content; Fig. 5 is that the different treatment group is on the impact of cold fresh meat TVB-N content; Fig. 6 is that the different treatment group affects cold fresh meat total plate count.These four figure illustrate that the tin foil that has added the allyl mustard oil molecularly imprinted polymer shows good fresh keeping property.The tin foil that adds the allyl mustard oil molecularly imprinted polymer can better suppress the rising of cold fresh meat pH value, slow down the growth of mda and TVB-N content, the growth of anti-bacteria, can better keep cold fresh meat to be in and fresh state, the extended period shelf-lives improves its commodity value.
Embodiment
Take by weighing the 5g beta-cyclodextrin and be dissolved in the 50mL dimethyl sulphoxide solution, add the 0.2mL allyl mustard oil in 45 ℃ of magnetic agitation 6h.Ultrasonic oscillation 10min mix and after get rid of liquid hollow gas, pass into nitrogen protection, and add the 3mL 2,4 toluene diisocyanate, constant temperature stirs 24h in 65 ℃ of nitrogen protection situations.Be cooled to room temperature, in the acetone that adding is stirred molecularly imprinted polymer be precipitated out from solution, precipitate with acetone and 50 ℃ of hot water repetitive scrubbings respectively behind the vacuum filtration, with unreacted linking agent and monomer molecule wash-out.Porphyrize after the vacuum-drying, dry storage.
Obtaining the polymkeric substance yield is that 53.13%, AITC content is 40.45 μ l/g.
Take by weighing the 5g beta-cyclodextrin and be dissolved in the 150mL dimethyl sulphoxide solution, add the 0.3mL allyl mustard oil in 45 ℃ of magnetic agitation 6h.Ultrasonic oscillation 10min mix and after get rid of liquid hollow gas, pass into nitrogen protection, and add the 4mL 2,4 toluene diisocyanate, constant temperature stirs 24h in 65 ℃ of nitrogen protection situations.Be cooled to room temperature, in the acetone that adding is stirred molecularly imprinted polymer be precipitated out from solution, precipitate with acetone and 50 ℃ of hot water repetitive scrubbings respectively behind the vacuum filtration, with unreacted linking agent and monomer molecule wash-out.Porphyrize after the vacuum-drying, dry storage.
Obtaining the polymkeric substance yield is that 53.97%, AITC content is 49.14 μ l/g.
Under the different humidity condition, allyl mustard oil molecularly imprinted polymer slow release effect
Take by weighing the 5g beta-cyclodextrin and be dissolved in the 100mL dimethyl sulphoxide solution, add the 0.4mL allyl mustard oil in 45 ℃ of magnetic agitation 6h.Ultrasonic oscillation 10min mix and after get rid of liquid hollow gas, pass into nitrogen protection, and add the 5mL 2,4 toluene diisocyanate, constant temperature stirs 24h in 65 ℃ of nitrogen protection situations.Be cooled to room temperature, in the acetone that adding is stirred molecularly imprinted polymer be precipitated out from solution, precipitate with acetone and 50 ℃ of hot water repetitive scrubbings respectively behind the vacuum filtration, with unreacted linking agent and monomer molecule wash-out.Porphyrize after the vacuum-drying, dry storage.
Obtaining the polymkeric substance yield is that 65.02%, AITC content is 53.66 μ l/g.
Take by weighing about the molecularly imprinted polymer 2.0g that makes, evenly on tiling and the glass surface ware, do two groups parallel.Watch-glass is positioned over drying wherein to be sealed.Wherein be added with the saturated salt solution (bag and magnesium nitrate RH=50%, saturated sodium-chloride RH=75%, saturated vitriolate of tartar RH=98%) of certain volume, afterwards every 12h ventilation 5min, every 24h taking sample determination inclusion compound residual quantity.As shown in Figure 1.
Under the condition of different temperatures, allyl mustard oil molecularly imprinted polymer slow release effect
Take by weighing the 5g beta-cyclodextrin and be dissolved in the 100mL dimethyl sulphoxide solution, add the 0.4mL allyl mustard oil in 45 ℃ of magnetic agitation 6h.Ultrasonic oscillation 10min mix and after get rid of liquid hollow gas, pass into nitrogen protection, and add the 5mL 2,4 toluene diisocyanate, constant temperature stirs 24h in 65 ℃ of nitrogen protection situations.Be cooled to room temperature, in the acetone that adding is stirred molecularly imprinted polymer be precipitated out from solution, precipitate with acetone and 50 ℃ of hot water repetitive scrubbings respectively behind the vacuum filtration, with unreacted linking agent and monomer molecule wash-out.Porphyrize after the vacuum-drying, dry storage.
Obtaining the polymkeric substance yield is that 65.02%, AITC content is 53.66 μ l/g.
Take by weighing about the molecularly imprinted polymer 2.0g that makes, evenly on tiling and the glass surface ware, do two groups parallel.Watch-glass is positioned over drying wherein to be sealed.Wherein be added with the saturated vitriolate of tartar RH=98% solution of certain volume.Moisture eliminator is placed respectively 10 ℃, in 25 ℃ and the 40 ℃ of constant incubators.Afterwards every 12h ventilation 5min, every 24h taking sample determination inclusion compound residual quantity.As shown in Figure 2.
The chitosan that takes by weighing 0.5g deacetylation 95% is dissolved in the 50mL1% strength acetic acid solution fully, slowly adds 0.1g allyl mustard oil molecularly imprinted polymer under certain temperature, and the adding volume fraction is 0.1% glycerine, and constant temperature stirs.Mixed solution is cooled to room temperature, evenly coats on the paper of 35cm * 35cm with casting method after the vacuum outgas, just obtain having the tin foil of slow-release function.
Obtaining the paper mean thickness is 0.337mm; Water vapour permeability is 240.11 g/m
2Oxygen-permeable is 2500cm
3/ m
2The right-angle tearing degree is 32.3 KN/m; Tensile strength is 20.3 MPa.
The chitosan that takes by weighing 1.5g deacetylation 95% is dissolved in the 50mL1% strength acetic acid solution fully, slowly adds 0.1g allyl mustard oil molecularly imprinted polymer under certain temperature, and the adding volume fraction is 0.1% glycerine, and constant temperature stirs.Mixed solution is cooled to room temperature, evenly coats on the paper of 35cm * 35cm with casting method after the vacuum outgas, just obtain having the tin foil of slow-release function.
Obtaining the paper mean thickness is 0.423mm; Water vapour permeability is 197.8g/m
2Oxygen-permeable is 0.5cm
3/ m
2The right-angle tearing degree is 21.4KN/m; Tensile strength is 40.3 MPa.
AITC molecularly imprinted polymer active fresh-keeping paper fresh keeping property
The chitosan that takes by weighing 1g deacetylation 95% is dissolved in the 50mL1% strength acetic acid solution fully, forms the base fluid of filming, and the chitosan film base fluid is uniformly coated on the tin foil of 35cm * 35cm, makes tin foil, is the chitosan group; With the preparation the AITC molecularly imprinted polymer take by weighing 0.2g, join gradually stir in the chitosan film base fluid after, vacuum outgas 30min prepares chitosan AITC inclusion compound complex liquid.It is uniformly coated on the tin foil of 35cm * 35cm, dries rear for subsequent usely, be the AITC group.The cold fresh meat of CK group for not packing with tin foil.
Each index is all take one-level green meat standard rating terminal point: pH judgement criteria: 5.6≤pH≤6.2 are as the one-level green meat; 6.3≤pH≤6.6 are secondary green meat; PH＞6.7 are rotten meat; Total volatile basic nitrogen judgement criteria: TVB-N≤15mg/100g is the one-level green meat; TVB-N≤20mg/100g is secondary green meat; TVB-N＞20mg/100g is rotten meat; The total plate count judgement criteria: the logarithmic value of total number of bacterial colony (log)＜4 is the one-level green meat; 4＜CUF＜6 are secondary green meat; CUF＞6 are rotten meat.Fresh-keeping effect such as Fig. 3, Fig. 4, Fig. 5, shown in Figure 6.
Claims (6)
1. molecularly imprinted polymer, it is characterized in that take allyl mustard oil as template molecule, take beta-cyclodextrin as function monomer, form host-guest coordination compound, add linking agent 2, the 4-tolylene diisocyanate occurs free-radical polymerized, thereby the crosslinked rigid polymer of height of formation around allyl mustard oil, with solvent acetone polymkeric substance is precipitated out from solvent at last, obtaining molecularly imprinted polymer is the allyl mustard oil release polymer, i.e. the allyl mustard oil molecularly imprinted polymer.
2. according to the preparation method of a kind of molecularly imprinted polymer claimed in claim 1, its feature follows these steps to be prepared the allyl mustard oil molecularly imprinted polymer successively:
(1) function monomer beta-cyclodextrin, template molecule allyl mustard oil are dissolved in the dimethyl sulfoxide (DMSO), ultrasonication is evenly mixed, carries out the reaction of one-phase heat of stirring and obtains mixing solutions; The mol ratio of beta-cyclodextrin and allyl mustard oil is 0.6-1:1; Heating temperature is 40 ℃-45 ℃, and be 6h-12h heat-up time; Every 5g function monomer adds dimethyl sulfoxide (DMSO) 50 mL-150mL;
(2) add the linking agent 2,4 toluene diisocyanate in step (1) mixing solutions, linking agent and function monomer mol ratio are 3-10:1;
Mix rear nitrogen filled protection, carry out two-stage heat of stirring reaction and obtain the molecularly imprinted polymer reaction solution; Heating temperature is 60 ℃-65 ℃, and be 20h-24h heat-up time;
(3) the molecularly imprinted polymer reaction solution that polyreaction in the step (2) is synthetic slowly adds in the acetone, with the cotton-shaped molecularly imprinted polymer vacuum filtration that generates, in filtrate, continue to add acetone, till generating without precipitation, again with acetone and hot water repetitive scrubbing precipitation, with unreacted monomer molecule and linking agent wash-out; Obtain the allyl mustard oil molecularly imprinted polymer through vacuum-drying, drying for standby behind the porphyrize.
3. the preparation method of a kind of molecularly imprinted polymer according to claim 2 is characterized in that raw materials for production and related reagent are anhydrous raw material and anhydrous reagent.
4. according to the application of a kind of molecularly imprinted polymer claimed in claim 1, it is characterized in that the application of allyl mustard oil molecularly imprinted polymer aspect Perserving materials.
5. the application of a kind of molecularly imprinted polymer according to claim 4 is characterized in that preparing tin foil.
6. according to claim 5 a kind of application of molecularly imprinted polymer is characterized in that the preparation method of tin foil is:
(6-1) chitosan is dissolved in 1% acetic acid aqueous solution fully is mixed with coating liquid, chitosan-containing 1-4g in every 100mL coating liquid, under room temperature, slowly add the allyl mustard oil molecularly imprinted polymer, contain allyl mustard oil molecularly imprinted polymer 0.1-0.4g in every 100mL coating liquid;
Add glycerine, glycerine and coating liquid volume ratio are 0.1%-0.4%, and constant temperature stirs;
(6-2) with evenly coating on the paper of certain area with casting method after the vacuum outgas of step (6-1) mixed solution, just obtain having the tin foil of slow-release function.
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Cited By (5)
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| CN105399915A (en) * | 2015-12-18 | 2016-03-16 | 天津医科大学 | Aesculin sustained and controlled release molecular imprinting skeletal material, and preparation method thereof |
| CN105601846A (en) * | 2015-09-10 | 2016-05-25 | 河北科技师范学院 | Chitosan surface molecularly imprinted rod-like material |
| CN108867190A (en) * | 2018-06-15 | 2018-11-23 | 上海海洋大学 | A kind of slow-release preserving fruit and vegetable utilizing paper membrane and its preparation method and application |
| CN110763539A (en) * | 2019-11-22 | 2020-02-07 | 福州大学 | Hydroxyl polychlorinated biphenyl detection method based on molecular imprinting column and weight system |
| CN114837017A (en) * | 2022-03-28 | 2022-08-02 | 常州太乙新材料有限公司 | Thermal sublimation coating coated on low-gram-weight base paper |
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| CN105601846A (en) * | 2015-09-10 | 2016-05-25 | 河北科技师范学院 | Chitosan surface molecularly imprinted rod-like material |
| CN105601846B (en) * | 2015-09-10 | 2018-01-12 | 河北科技师范学院 | Chitosan surface molecule print club-shaped material |
| CN105399915A (en) * | 2015-12-18 | 2016-03-16 | 天津医科大学 | Aesculin sustained and controlled release molecular imprinting skeletal material, and preparation method thereof |
| CN105399915B (en) * | 2015-12-18 | 2017-12-12 | 天津医科大学 | Aesculin delays controlled release molecular engram framework material and preparation method thereof |
| CN108867190A (en) * | 2018-06-15 | 2018-11-23 | 上海海洋大学 | A kind of slow-release preserving fruit and vegetable utilizing paper membrane and its preparation method and application |
| CN108867190B (en) * | 2018-06-15 | 2021-01-29 | 上海海洋大学 | Slow-release fruit and vegetable fresh-keeping paper film and preparation method and application thereof |
| CN110763539A (en) * | 2019-11-22 | 2020-02-07 | 福州大学 | Hydroxyl polychlorinated biphenyl detection method based on molecular imprinting column and weight system |
| CN114837017A (en) * | 2022-03-28 | 2022-08-02 | 常州太乙新材料有限公司 | Thermal sublimation coating coated on low-gram-weight base paper |
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