CN106810638A - The preparation method and application of Sulfonamides hydrophilic magnetic molecular engram material - Google Patents

The preparation method and application of Sulfonamides hydrophilic magnetic molecular engram material Download PDF

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CN106810638A
CN106810638A CN201611206814.6A CN201611206814A CN106810638A CN 106810638 A CN106810638 A CN 106810638A CN 201611206814 A CN201611206814 A CN 201611206814A CN 106810638 A CN106810638 A CN 106810638A
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magnetic
imprinted polymer
added
molecularly imprinted
water
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何金兴
崔笑
崔一笑
梁金玲
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Qilu University of Technology
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Qilu University of Technology
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Abstract

The preparation method and application of Sulfonamides hydrophilic magnetic molecular engram material.The invention belongs to field of organic compound detection, and in particular to a kind of preparation method of Sulfa drugs molecule imprinted material, the application of above-mentioned Sulfa drugs molecule imprinted material polymer is further related to.The preparation method of Sulfonamides hydrophilic magnetic molecular engram material, its step is as follows：(1) Fe is prepared using coprecipitation3O4Particle；(2) Fe of silanization is prepared using stober methods3O4, obtaining Surface coating has SiO2Magnetic microsphere；(3) sulfamido molecularly imprinted polymer particle is synthesized.Using the magnetic molecularly imprinted material prepared by the method for the present invention have can in water phase quick adsorption capacity, powerful adsorption function, the stronger specific, rate of recovery preparation cost high and relatively low, while the big shortcoming of the required quantity of solvent for improving traditional Sample Pretreatment Technique.

Description

The preparation method and application of Sulfonamides hydrophilic magnetic molecular engram material
Technical field
The invention belongs to field of organic compound detection, and in particular to a kind of preparation side of Sulfa drugs molecule imprinted material Method, further relates to application of the above-mentioned Sulfa drugs molecule imprinted material polymer in Sulfonamides detection.
Background technology
Sulfa drugs is the antibiotics for being applied to whole body nervous system earliest, and its birth is antibiotic medicine Development place mat in field of medicaments road.Because sulfa drugs has cheap and efficient advantage, and then extensive It is applied to the fields such as medicine, animal husbandry, food.However, as sulfa drugs is in the extensive use in many fields, its abuse is existing As also occurring therewith, its potential carcinogenicity and the resistance to the action of a drug is also gradually displayed, and people increasingly worry the health of its own Can be compromised because of the abuse of sulfa drugs.At the same time, once sulfa drugs is flowed into environment, they will Into potable water system, and by soil absorption, trigger more serious problem.Therefore, in order to ensure safety and the people of food Health, many countries and tissue have done relevant regulations to the MRL of sulfa drugs.Such as, the state such as China and European Union The MRL of sulfanilamide (SN) total amount or single sulfa drugs is 100 μ g/kg in family's regulation, animal food and tissue.
At present, simple, quick, the economic method of sample pre-treatments and detection medicament residue has many kinds, such as solid phase Tandem Mass Spectrometry Analysis, high resolution mass spec detection, gas chromatography, the Capillary Electrophoresis of extraction, liquid chromatogram and low resolution Method etc..In physics and chemistry method, the most frequently used is high performance liquid chromatography, and it is primarily adapted for use in analysis volatility, half volatile and heat Unstability material, has become the effective ways of sulfa drugs qualitative and quantitative analysis at present.
Molecular imprinting technology be it is a kind of be effectively synthesized with high efficiency, compatibility, the method for specific polymer, synthesis Polymer can recognize entity, efficient adsorbed target product with natural imitation.Molecular imprinting technology is combined with solid phase extraction techniques, Make sample pretreatment process become simply, labour's loss reduce, solvent utilization rate is improved, and device reusable edible. But, common molecularly imprinted polymer material, surface-active is low, it is difficult to be separated with sample.
Magnetic-particle is applied in Dispersive solid phase extraction technology, they because being provided with magnetic, for close There is fast and efficiently feature into separation of the material in sample is detected.With magnetic-particle and the knot of molecularly imprinted polymer Close, new technology " magnetic molecularly imprinted " technology has obtained the attention and utilization of height.However, due to material shortage parent It is aqueous, it is limited in water content milk high, the application in the sample detection such as honey.So, research one kind can be in water phase In the magnetic molecularly imprinted materials of quick, the convenient various Sulfonamides of enrichment have compared with profound significance.
The A of CN 105085843 disclose the preparation method and molecular engram material prepared therefrom of a kind of molecular engram material Material, in preparation method, deposits Fe using coprecipitation on class graphite phase carbon nitride surface first3O4Obtain Fe3O4-g-C3N4Receive Rice material, and then obtain surface modification and have the magnetic silica class graphite phase carbon nitride nano material of acrylic, then with it It is carrier, by optimizing function monomer, being prepared using surface imprinted technology can be while quickly recognizes seven kinds of environment incretions The molecular engram material of chaff interference.The molecular engram material adsorption capacity is big, selectivity is good, response is fast, chemical stability is good, just It is high in operation, repeatable utilization rate, can simultaneously realize the identification of various trace steroids and phenols environment incretion interferent And separation and concentration, extend existing magnetic Nano material, class graphite phase carbon nitride material, the range of application of molecular engram material.
Although molecular engram material prepared by the above method has, attached capacity is big, selectivity is good, response is fast and chemically stable Property is good a little, but due to the characteristics of molecular engram material possesses biological antibody, so can only be (various to specific object Trace steroid and phenols environment incretion interferent) selective absorption property, and to other materials (such as sulfamido Veterinary drug) adsorptivity it is poor.Meanwhile, the method is prepared using the method for organic polymer with methacrylic acid and 2- vinylpyridines Molecularly imprinted polymer, limits its application in aqueous phase sample substrate (such as animal derived food).
The content of the invention
To solve above-mentioned technical problem, can quick in water phase, the convenient various sulphurs of enrichment the invention provides one kind The preparation method of the magnetic molecularly imprinted material of amine veterinary drug.
In addition, problem of the present invention for food middle peasant's residue of veterinary drug, by the imprinted material application obtained by above-mentioned preparation In Sulfonamides detection, rapid and convenient and accuracy rate detection method higher are established.
The imprinted material prepared using the method for the present invention, in animal derived food to sulfamethazine, The application of other Sulfonamides detection such as sulphadiazine, sulfamethyldiazine, sulphathiazole, is also the claimed present invention Scope.
The preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material, its step is as follows：
(1) Fe is prepared using coprecipitation3O4Particle；
(2) Fe of silanization is prepared using stober methods3O4, obtaining Surface coating has SiO2Fe3O4Magnetic microsphere；
(3) sulfamido molecularly imprinted polymer polymer is prepared：
A. template molecule is dissolved in acetonitrile, under nitrogen protection, is well mixed；
B. function monomer is added in a, is stirred；
C. crosslinking agent is added in b, is stirred；
D adds magnetic microsphere in c, stirs；
E. initiator is added in d, is stirred, thermal initiation obtains polymer.
Specifically, step (1) is：
By FeSO4.7H2O and FeCl3.6H2O mixes, and adds deionized water, and stirring is then protected to its dissolving in nitrogen Lower intensification, adds ammoniacal liquor, continues heating stirring reaction；
After reaction terminates, the black product of gained is separated with supernatant using externally-applied magnetic field, and with deionized water and nothing Water-ethanol cyclic washing black product is until black product is dried under vacuum to constant weight, gained black product by washing lotion in neutrality Fe3O4It is standby after particle grinding；
Step (2) is：
The Fe of synthesis in step (1)3O4Tetraethyl orthosilicate is added in particle, is stirred and evenly mixed, then under the protection of nitrogen Ammoniacal liquor is added, continues stirring reaction, and then water-bath, to Fe3O4Particle carries out surface and is modified；
Use magnet collecting reaction product, and with deionized water and absolute ethyl alcohol rinse product repeatedly until washing lotion is in Property, product is vacuum dried, prepared Surface coating has SiO2Fe3O4Magnetic microsphere.
More specifically, step (1) is：
By 2.5g FeSO4.7H2O and 4.0g FeCl3.6H2O is placed in conical flask, adds the deionized water of 200mL, is stirred Mix to its dissolving, 60 DEG C are then warming up under nitrogen protection, add 5mL ammoniacal liquor, continue heating stirring reaction 1h；
After reaction terminates, black product is separated with supernatant using the externally-applied magnetic field of super magnet, and use deionized water With absolute ethyl alcohol cyclic washing black product until be placed in vacuum drying chamber black product in dry at 60 DEG C in neutrality by washing lotion It is dry to constant weight, gained black product Fe3O4Particle is polished standby；
Step (2) is：
Take the Fe of synthesis in step (1)3O4Particle is poured into the round-bottomed flask for filling water and absolute ethyl alcohol, adds positive silicic acid Ethyl ester, stirs and evenly mixs 4min, and 5mL ammoniacal liquor is then added under the protection of nitrogen, continues stirring reaction 3h, and then in 50 DEG C of water Bath 1h, to Fe3O4Particle carries out surface and is modified；
Use magnet collecting reaction product, and with deionized water and absolute ethyl alcohol rinse product repeatedly until washing lotion is in Property, product is placed in vacuum drying chamber in being dried at 60 DEG C, prepared Surface coating has SiO2Magnetic microsphere；
Fe3O4The quality of particle is 1g with the volume ratio of tetraethyl orthosilicate：4mL, water is 1 with the volume ratio of absolute ethyl alcohol：4.
Step (3) is：
A. using sulfamethazine as template molecule, it is dissolved in acetonitrile, with nitrogen by the oxygen in system Cement out, and ultrasonication, it is well mixed；
B. function monomer is added in a, is stirred 4 hours；
C. crosslinking agent is added in b；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. Surface coating is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator, initiator are added in d has SiO with Surface coating2Magnetic microsphere mass ratio be 1:12, machinery Stirring, thermal initiation obtains magnetic pyrite amine molecule imprinted polymer.
More specifically, step (3) is：
A. using sulfamethazine as template molecule, it is dissolved in acetonitrile, with nitrogen by the oxygen in system Cement out, and ultrasonication 15min, it is well mixed；
B. it is 1 that mol ratio is added in a:1 function monomer methacrylic acid and hydroxyethyl methacrylate, stirring 4 is small When；
C. it is 1 that mol ratio is added in b:1 crosslinking agent ethylene glycol dimethacrylate and 3- (trimethyoxysilanes Base) propyl acrylate；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. Surface coating is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator azodiisobutyronitrile is added in d, azodiisobutyronitrile has SiO with Surface coating2Magnetic microsphere Mass ratio be 1:12, mechanical agitation, and in 50 DEG C of water-baths 5h, 60 DEG C of water-baths 24h, 85 DEG C of water-bath 2h；Obtain magnetic pyrite amine molecule Imprinted polymer.
Further, can by magnetic pyrite amine molecule imprinted polymer in vacuum drying oven 100 DEG C of aging 8h, grinding, Qualitative filter paper is wrapped up, and 50h-110h is extracted with apparatus,Soxhlet's, and extractant is methyl alcohol, and 80 DEG C of drying are obtained to constant weight Magnetic imprinted polymer particle.
The preparation method of Sulfonamides hydrophilic magnetic molecular engram material, including following steps：
(1) by 2.5g FeSO4.7H2O and 4.0g FeCl3.6H2O is placed in conical flask, adds the deionized water of 200mL, Stirring is then warming up to 60 DEG C under nitrogen protection to its dissolving, adds 5mL ammoniacal liquor, continues heating stirring reaction 1h；
After reaction terminates, black product is separated with supernatant using the externally-applied magnetic field of super magnet, and use deionized water With absolute ethyl alcohol cyclic washing black product until be placed in vacuum drying chamber black product in dry at 60 DEG C in neutrality by washing lotion It is dry to constant weight, gained black product Fe3O4Particle is polished standby；
(2) Fe of synthesis in step (1) is taken3O4Particle is poured into the round-bottomed flask for filling water and absolute ethyl alcohol, adds positive silicon Acetoacetic ester, stirs and evenly mixs 4min, and 5mL ammoniacal liquor is then added under the protection of nitrogen, continues stirring reaction 3h, and then at 50 DEG C Water-bath 1h, to Fe3O4Particle carries out surface and is modified；
Use magnet collecting reaction product, and with deionized water and absolute ethyl alcohol rinse product repeatedly until washing lotion is in Property, product is placed in vacuum drying chamber in being dried at 60 DEG C, prepared Surface coating has SiO2Magnetic microsphere；
Fe3O4The quality of particle is 1g with the volume ratio of tetraethyl orthosilicate：4mL, water is 1 with the volume ratio of absolute ethyl alcohol：4；
(3) a. is dissolved in acetonitrile using sulfamethazine as template molecule, with nitrogen by the oxygen in system Gas is cemented out, and ultrasonication 15min, is well mixed；
B. it is 1 that mol ratio is added in a:1 function monomer methacrylic acid and hydroxyethyl methacrylate, stirring 4 is small When；
C. it is 1 that mol ratio is added in b:1 crosslinking agent ethylene glycol dimethacrylate and 3- (trimethyoxysilanes Base) propyl acrylate；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. Surface coating is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator azodiisobutyronitrile is added in d, azodiisobutyronitrile has SiO with Surface coating2Magnetic microsphere Mass ratio be 1:12, mechanical agitation, and in 50 DEG C of water-baths 5h, 60 DEG C of water-baths 24h, 85 DEG C of water-bath 2h；Obtain magnetic pyrite amine molecule Imprinted polymer.
The experiment proves that, can directly be used using the magnetic molecularly imprinted polymer material obtained by present invention preparation Sulfamethazine, sulphadiazine, sulfamethyldiazine, sulphathiazole, sulfadoxine, sulfanilamide (SN) pair in animal derived food Sulfamonomethoxine, sinomin, ten kinds of detections of Sulfonamides of kynix NU-445 and cistosulfa point Analysis, it has high-selectivity adsorption and efficiently concentrating to sulfa drugs.
By application of the method imprinted material of the above in Sulfonamides are detected, including following steps：
(1) activate：The sulfanilamide (SN) magnetic molecularly imprinted polymer particle obtained by the preparation of the method according to claim 1 is taken to be added to In conical flask, activation process is carried out using methyl alcohol and deionized water successively, two-phase is separated using externally-applied magnetic field, outwell waste liquid, obtained To the magnetic molecularly imprinted polymer for having activated；
Wherein the quality of sulfanilamide (SN) magnetic molecularly imprinted polymer is with the quality volume of methyl alcohol and than being 1g：40mL, methyl alcohol with The volume ratio of deionized water is 1：1；
(2) extract：Sample solution to be detected or sample extraction solution are added in conical flask, with sulfanilamide (SN) magnetic molecule Trace polymerization composition granule is together placed in and mixing is vibrated on oscillator, and the trace object now deposited in the sample first turns from sample phase Solution is moved to, then is adsorbed to magnetic molecularly imprinted polymer surface, the wherein quality of sample and the volume ratio of solution is 1g： 15mL；
Sample extraction solution, using methyl alcohol or acetonitrile as extractant；
(3) separate：After the completion of extraction, magnet is placed in conical flask outer wall, using the effect of externally-applied magnetic field by sulfanilamide (SN) magnetic Molecularly imprinted polymer is separated with solution, outwells waste liquid；
(4) drip washing：To leacheate is added in the conical flask equipped with magnetic molecularly imprinted polymer, vibration mixing washes down miscellaneous Matter, reuses magnetic field and separates two-phase, outwells waste liquid, removes impurity, the wherein quality of magnetic molecularly imprinted polymer and drip washing The volume ratio of liquid is 1g：50mL；
Leacheate is deionized water or methyl alcohol；
(5) elute：To 2mL eluent sulfanilamide (SN) magnetic molecularly imprinted polymers are added in conical flask, fully vibration is mixed Close, the object to be measured adsorbed on magnetic molecularly imprinted polymer surface is eluted, then separate two using externally-applied magnetic field Phase, collects eluent；The eluent that will be separate is dried up under the conditions of 50 DEG C with nitrogen, and is dissolved again with 1.0mL methyl alcohol, is passed through High performance liquid chromatography detection analysis is injected after 0.45 μm of organic system membrane filtration.
The beneficial effects of the present invention are using the hydrophilic magnetic molecularly imprinted material prepared by the method for the present invention With can to 10 kinds of Sulfonamides, (sulfamethazine, sulfanilamide (SN) be phonetic in animal derived food in aqueous phase food samples Pyridine, sulfamethyldiazine, sulphathiazole, sulfadoxine, 5-methoxysulfadiazine, sinomin, kynix sulfanilamide (SN) Isoxazole and cistosulfa) quickly adsorption capacity, powerful adsorption function, stronger specificity, the rate of recovery are high and relatively low Preparation cost, while the big and time-consuming shortcoming of the required quantity of solvent for improving conventional solid extraction Sample Pretreatment Technique.It is logical Cross and compare hydrophily and non-hydrophilic magnetic material in the solvent of different water cut ratio to the absorption property discovery of template molecule, Non-hydrophilic polymer is 0 to the adsorbance of the template molecule aqueous solution in water content solvent higher (more than 60%), in second Adsorbance in nitrile solution is 0.22mg/g.Adsorbance of the hydrophilic polymer in aqueous environment is 0.98mg/g, in acetonitrile In adsorbance be 0.10.Illustrate adsorbance of the hydrophilic polymer in aqueous environment more than non-hydrophilic polymer in second Adsorbance in nitrile solution.
The method is accurate, and sensitivity is high, and detection speed is fast, efficiency high, low cost, and magnetic material can be circulated repeatedly to be made With solving the problems, such as that sample pre-treatments are complicated and price high and the problem of single use of commercialization solid-phase extraction column Deng while the method also has certain economic benefit and social benefit.
Brief description of the drawings
Fig. 1：Suction of the methanol solution of the sulfamethazine of 5mL 30mg/L in 50mg magnetic molecularly imprinted materials Attached dynamic curve diagram；
Fig. 2：The quasi- pseudo-second-order kinetic equation fitted figure of magnetic molecularly imprinted polymer；
Fig. 3：The Particle diffusion equation model figure of magnetic molecularly imprinted polymer；
Fig. 4：The fitted figure of the Elovich equations of magnetic molecularly imprinted polymer；
Fig. 5：The adsorption isothermal curve of magnetic imprinted polymer and the non-imprinted polymer of magnetic to sulfamethazine；
Fig. 6：The Scatchard analyses of magnetic imprinted polymer and the non-imprinted polymer of magnetic；
Fig. 7：Magnetic molecularly imprinted polymer composite diagram.
Specific embodiment
The present invention is further illustrated with specific embodiment below in conjunction with the accompanying drawings, but with this does not limit the present invention.
Embodiment 1
The preparation of hydrophilic magnetic sulfanilamide (SN) molecularly imprinted polymer
1) using Co deposited synthesis Fe3O4Particle
By 2.5g FeSO4.7H2O and 4.0g FeCl3.6H2O is placed in conical flask, adds the deionization of 200mL, machinery Stirring is allowed to dissolve, and 60 DEG C are then warming up under nitrogen protection, disposable to add 5mL ammoniacal liquor, continues heating stirring reaction 1h； Reaction is separated black product with supernatant using the externally-applied magnetic field of super magnet after terminating, and with deionized water and absolute ethyl alcohol Cyclic washing is to washing lotion in neutrality；Synthetic is placed in vacuum drying chamber in dry to constant weight, gained black product at 60 DEG C It is standby after grinding；
2) Fe of silanization is prepared using stober methods3O4
Accurately weigh step 1) obtained in Fe3O4Particle 0.625g pours into the round bottom equipped with 2.5mL water and 8mL absolute ethyl alcohols In flask, 2mL TEOS, mechanical agitation 5min, mixing are added；1.5mL ammoniacal liquor is subsequently adding, continues stirring reaction 2h, and then 60 DEG C of water-bath 1h, to Fe3O4Particle carries out surface and is modified.Magnet collecting reaction product is used, and it is anti-with absolute ethyl alcohol with deionized water Sediment being rinsed again up to washing lotion is in neutrality, being placed in vacuum drying chamber in being dried at 60 DEG C, prepared Surface coating has SiO2's Magnetic microsphere；
3) using sulfamethazine as template molecule, it is dissolved in acetonitrile, with nitrogen by the oxygen in system Cement out, and ultrasonication 15min, it is well mixed；
B. it is 1 that mol ratio is added in a:1 function monomer methacrylic acid and hydroxyethyl methacrylate, stirring 4 is small When；
C. it is 1 that mol ratio is added in b:1 crosslinking agent ethylene glycol dimethacrylate and 3- (trimethyoxysilanes Base) propyl acrylate；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. Surface coating is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator azodiisobutyronitrile is added in d, azodiisobutyronitrile has SiO with Surface coating2Magnetic microsphere Mass ratio be 1:12, mechanical agitation, and in 50 DEG C of water-baths 5h, 60 DEG C of water-baths 24h, 85 DEG C of water-bath 2h；Obtain magnetic pyrite amine molecule Imprinted polymer.
100 DEG C of aging 8h, grinding in vacuum drying oven by magnetic pyrite amine molecule imprinted polymer, qualitative filter paper wrapped Wrap up in, 50h-110h is extracted with apparatus,Soxhlet's, extractant is methyl alcohol, and 80 DEG C of drying obtain magnetic imprinted polymer to constant weight Particle.
Non- imprinted polymer in addition to template is not added with, other steps with imprinted polymer preparation process.In order to than more hydrophilic The hydrophily of property polymeric material, the process of experiment is prepared for the magnetic molecularly imprinted polymerization of the Sulfonamides of non-hydrophilic Thing, its preparation process is in addition to hydrophily function monomer is not added with, and other steps are identical.
Embodiment 2
Imprinted polymer to gained in embodiment 1 is characterized, and determines the presence of trace binding site；
Described characterizing method includes Dynamic Adsorption, Static Adsorption and selectivity experiment.
The sign of magnetic molecularly imprinted polymer
(1) the adsorption kinetic data
50mg magnetic molecularly imprinted polymers accurately are weighed, is placed in 25mL volumetric flasks, 5mL is accurately pipetted with pipette In the SMZ- aqueous solution of 30mg/L, 5min, 10min, 20min, 40min, 80min are vibrated at room temperature respectively, after 120min, Material is separated under the absorption of applied magnet；
Sulfamethazine in determining supernatant using ultraviolet-visible spectrophotometer under the conditions of wavelength 270nm Concentration；The adsorption kinetic data is that, in order to determine the adsorption efficiency of the magnetic molecularly imprinted polymer of synthesis, this patent is determined Different adsorption times, adsorption capacity of the sorbing material to object.Result figure 1.As seen from the figure, after adsorbing 5 minutes, adsorption capacity 88.2%, the 25min for basically reaching maximum adsorption capacity is that can reach adsorption equilibrium.
Through measuring, it is known that, the concentration of initial sulfamethazine is lower, and the time for reaching adsorption equilibrium can be more It is short.This may be relevant with the structural property of synthetic material, due to Macroscopic single crystal after, may cause to gather by milled processed The hole that compound surface produces is deep mixed, and shallower hole is conducive to the quick adsorption of object, so the initial rank of experiment The adsorption efficiency of section can be very high.After shallower hole is adsorbed completely, the hole of depths can exist necessarily in adsorbed target thing Steric hindrance, the speed of absorption can be made slack-off, be finally reached adsorption equilibrium.
The polymer for being prepared with mass polymerization in the past, the time for reaching adsorption equilibrium is more long, and what is had will even adsorb 24h, and use the molecular imprinted polymer on surface of the preparation very fast to the adsorption dynamics adsorption kinetics of template molecule, the mass transfer speed of polymer Degree is quickly, it is possible to which this material is used as into SPE-detection of the high performance liquid chromatography combination to sulfa drugs.
In order to determine the characterization of adsorption and kinetic parameter of material in adsorption process, pseudo-first-order absorption is carried out to experimental result The fitting of dynamics, quasi- secondary absorption dynamics, Particle diffusion and Elovich equations.Fitting result such as Fig. 1 and as shown in table 1. R2As the important parameter of model of fit and experimental data degree of being consistent, R2Closer to 1, the degree of being consistent of experimental data and model of fit It is higher.As shown in Table 2, the dynamic (dynamical) linearly dependent coefficient R of quasi- secondary absorption2It is 0.999, linear relationship is good, is presented aobvious Write related levels.Quasi- secondary absorption dynamics can reflect two reactions occurred in adsorption process, and one is whole control The long response time in reaction time, a reaction for being to be rapidly achieved balance.Being mainly of the step of rate of adsorption is limited in this experiment Learn absorption
The adsorption dynamics adsorption kinetics fitting result contrast of 1 four kinds of equations of table
2) Binding experiment is balanced
It is real in order to investigate adsorption capacity of the prepared hydrophilic magnetic molecularly imprinted polymer to sulfamethazine Test and accurately weigh the sorbing material of 50mg in 25mL volumetric flasks, be separately added into the SMZ- aqueous solution of 5mL various concentrations (20mg/L, 30mg/L, 40mg/L, 70mg/L, 80mg/L), shaking table fully vibrates 30min.Under the conditions of wavelength 270nm, use Ultraviolet-visible spectrophotometer determines the absorbance of supernatant, and calculates adsorption capacity.Non- trace is done under the same conditions to gather Balance Binding experiment of the compound to sulfamethazine.
Adsorption capacity is to evaluate the magnetic molecularly imprinted polymer important parameter strong and weak to template molecule binding ability.By scheming 5 understand that magnetic imprinted polymer and the non-imprinted polymer of magnetic have different degrees of to the adsorbance of sulfamethazine Increase.When the initial concentration of sulfamethazine is 70mg/L, imprinted polymer and non-imprinted polymer are to template molecule The adsorption capacity of sulfamethazine is respectively 4.1mg/g and 0.27mg/g, and imprinted polymer is to sulfamethazine Adsorbance is about 15 times of non-imprinted polymer adsorbance, illustrates that imprinted polymer is to template compared to non-imprinted polymer The adsorptivity of molecule is preferable.
The magnetic molecularly imprinted polymer of preparation has selective absorption to sulfamethazine, and reason is by titanium dioxide The magnetic ball of silicon parcel shows that have chemical bond to generate is connected with polymer, in polymerization process, with sulfamethazine Used as template molecule, sulfamethazine forms part with methacrylic acid, and polymeric inner has phonetic with sulfanilamide (SN) dimethyl The active group that pyridine matches, after sulfamethazine is eluted, position originally has specific hole presence, this Specific hole causes that magnetic molecularly imprinted polymer has good binding ability to sulfamethazine.
Scatchard is analyzed：
The data that will be obtained are used for the Scatchard analyses of imprinted polymer and non-imprinted polymer.Analysis result is shown in Fig. 6
Scatchard equations：Q/C=Q/b+Qmax/b
C refers to the initial concentration of solution in equation, and Q refers to adsorption capacity when reaching adsorption equilibrium, and Qmax refers to maximum saturation The flourish amount of absorption, Scatchard equations are obtained final product with Q/C to Q mappings.Polymer can be obtained by Scatchard slope of a curves and intercept Qmax and Kd.
As seen from the figure, the Scatchard equations of sulfamethazine magnetic molecularly imprinted polymer are a lines The good straight line of property, its R20.99 is can reach, regression equation is y=-0.0014x+0.0624.Illustrate the magnetic of the method synthesis Molecularly imprinted polymer is a kind of combination to object sulfamethazine.And the non-imprinted polymer of magnetic can not be simulated Linear equation, in scatterplot state, shows that non-imprinted polymer does not have specific binding site from side.
3) selectivity experiment
This experimental selection plasticiser similar to template molecule structure (BBP, DCHP) and MTMC, at the same with ten kinds of sulfanilamide (SN) Class medicine is at war with, and determines selection implementations of the magnetic molecularly imprinted polymer to this 13 kinds of solution.The results are shown in Table 2.
From Table 2, it can be seen that magnetic imprinted polymer will be far longer than non-trace to the adsorbance of sulfa drugs gathering Adsorption capacity of the compound to sulfa drugs.The non-imprinted polymer of magnetic can reach it to the adsorbance of plasticiser and MTMC To more than 10 times of sulfa drugs adsorbance, and magnetic imprinted polymer, the adsorbance to BBP, DCHP and MTMC is only 20.58μg/g、0μg/g、0μg/g.From result, magnetic blotting Molecularly Imprinted Polymer has special absorption to sulfa drugs Property, and the non-microsphere polymer of magnetic is then without specificity.
Magnetic molecularly imprinted polymer has and has absorption specificity to sulfa drugs, because in the mistake of Macroscopic single crystal Cheng Zhong, template molecule sulfamethazine is bonded with function monomer, forms certain inside stereochemical structure.Work as template After molecule is eluted, its region for existing forms specific hole, and the hole can be with specific adsorption object, Er Feiyin Mark polymer does not exist this species specific hole, simply by physics or chemically adsorbs, so its absorption is special Property is very low.
The magnetic molecularly imprinted polymer of table 2 is to 13 kinds of selection implementations of solution
From Table 2, it can be seen that magnetic imprinted polymer will be far longer than non-trace to the adsorbance of sulfa drugs gathering Adsorption capacity of the compound to sulfa drugs.The non-imprinted polymer of magnetic can reach it to the adsorbance of plasticiser and MTMC To more than 10 times of sulfa drugs adsorbance, and magnetic imprinted polymer, the adsorbance to BBP, DCHP and MTMC is only 20.58μg/g、0μg/g、0μg/g.From result, magnetic blotting Molecularly Imprinted Polymer has special absorption to sulfa drugs Property, and the non-microsphere polymer of magnetic is then without specificity.
Magnetic molecularly imprinted polymer has and has absorption specificity to sulfa drugs, because in the mistake of Macroscopic single crystal Cheng Zhong, template molecule sulfamethazine is bonded with function monomer, forms certain inside stereochemical structure.Work as template After molecule is eluted, its region for existing forms specific hole, and the hole can be with specific adsorption object, Er Feiyin Mark polymer does not exist this species specific hole, simply by physics or chemically adsorbs, so its absorption is special Property is very low.
Embodiment 3
The application of hydrophilic magnetic sulfamido molecularly imprinted polymer
For the applicability of evaluation method, with chicken, goat milk and milk sample are raw material, with the hydrophily sulfamido for preparing Veterinary drug magnetic molecularly imprinted polymer is Dispersive solid phase extraction material, under the extraction conditions of optimization, sample is added Mark recovery experiment, the concentration of the sulfa drugs of sample is tri- levels of 5ug/kg, 10ug/kg and 20ug/kg, sample after addition Through absorption, enrichment and purification after after, as a result the rate of recovery and relative standard deviation of determination sample see the table below (a) respectively, (b) and (c).As seen from table, three kinds of TIANZHU XINGNAO Capsuls of sample are in addition to the TIANZHU XINGNAO Capsul of milk sample is relatively low, other two kinds The rate of recovery scope of 10 kinds of sulfa drugs of sample is more than 65%.
(a) chicken meat sample recovery of standard addition (Mean ± RSD)
(b) goat milk sample recovery of standard addition (Mean ± RSD)
(c) milk sample recovery of standard addition (Mean ± RSD)

Claims (9)

1. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material, its step is as follows：
(1) Fe is prepared using coprecipitation3O4Particle；
(2) Fe of silanization is prepared using stober methods3O4, obtaining Surface coating has SiO2Fe3O4Magnetic microsphere；
(3) sulfamido molecularly imprinted polymer is prepared：
A. template molecule is dissolved in acetonitrile, under nitrogen protection, is well mixed；
B. function monomer is added in a, is stirred；
C. crosslinking agent is added in b, is stirred；
D adds the magnetic microsphere obtained by step (2) in c, stirs；
E. initiator is added in d, is stirred, thermal initiation obtains polymer.
2. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material as claimed in claim 1, it is special Levy and be, described step (1) is：
By FeSO4.7H2O and FeCl3.6H2O mixes, and adds deionized water, and stirring then rises under nitrogen protection to its dissolving Temperature, adds ammoniacal liquor, continues heating stirring reaction；
After reaction terminates, the black product of gained is separated with supernatant using externally-applied magnetic field, and with deionized water and anhydrous second Alcohol cyclic washing black product is until black product is dried under vacuum to constant weight, gained black product Fe by washing lotion in neutrality3O4Grain It is standby after son grinding；
Described step (2) is：
The Fe of synthesis in step (1)3O4Tetraethyl orthosilicate is added in particle, is stirred and evenly mixed, then added under the protection of nitrogen Ammoniacal liquor, continues stirring reaction, and then water-bath, to Fe3O4Particle carries out surface and is modified；
Magnet collecting reaction product is used, and product is rinsed repeatedly up to washing lotion is in neutrality with deionized water and absolute ethyl alcohol, Product is vacuum dried, prepared Surface coating has SiO2Fe3O4Magnetic microsphere.
3. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material as claimed in claim 1, it is special Levy and be, described step (1) is specially：
By 2.5g FeSO4.7H2O and 4.0g FeCl3.6H2O is placed in conical flask, adds the deionized water of 200mL, is stirred to it Dissolving, is then warming up to 60 DEG C under nitrogen protection, adds 5mL ammoniacal liquor, continues heating stirring reaction 1h；
After reaction terminates, black product is separated with supernatant using externally-applied magnetic field, and with deionized water and absolute ethyl alcohol repeatedly Washing black product is until be placed in vacuum drying chamber black product in dry to constant weight, gained at 60 DEG C in neutrality by washing lotion Black product Fe3O4Particle is polished standby；
Described step (2) is specially：
Take the Fe of synthesis in step (1)3O4Particle is poured into the round-bottomed flask for filling water and absolute ethyl alcohol, adds tetraethyl orthosilicate, 4min is stirred and evenly mixed, 5mL ammoniacal liquor is then added under the protection of nitrogen, continue stirring reaction 3h, and then in 50 DEG C of water-bath 1h, To Fe3O4Particle carries out surface and is modified；
Magnet collecting reaction product is used, and product is rinsed repeatedly up to washing lotion is in neutrality with deionized water and absolute ethyl alcohol, Product is placed in vacuum drying chamber in being dried at 60 DEG C, prepared Surface coating has SiO2Magnetic microsphere；
Described Fe3O4The quality of particle is 1g with the volume ratio of tetraethyl orthosilicate：4mL, water is 1 with the volume ratio of absolute ethyl alcohol： 4。
4. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material as claimed in claim 1, it is special Levy and be, described step (3) is：
A. using sulfamethazine as template molecule, it is dissolved in acetonitrile, with nitrogen by the replacement of oxygen in system Out, and ultrasonication, it is well mixed；
B. function monomer is added in a, is stirred 4 hours；
C. crosslinking agent is added in b；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. the Surface coating obtained by step (2) is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator, initiator are added in d has SiO with Surface coating2Magnetic microsphere mass ratio be 1:12, mechanical agitation, Thermal initiation, obtains magnetic pyrite amine molecule imprinted polymer.
5. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material as claimed in claim 1, it is special Levy and be, described step (3) is：
A. using sulfamethazine as template molecule, it is dissolved in acetonitrile, with nitrogen by the replacement of oxygen in system Out, and ultrasonication 15min, it is well mixed；
B. it is 1 that mol ratio is added in a:1 function monomer methacrylic acid and hydroxyethyl methacrylate, stirs 4 hours；
C. it is 1 that mol ratio is added in b:1 crosslinking agent ethylene glycol dimethacrylate and 3- (trimethoxysilyl) Propyl acrylate；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. Surface coating is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator azodiisobutyronitrile is added in d, azodiisobutyronitrile has SiO with Surface coating2Magnetic microsphere quality Than being 1:12, mechanical agitation, and in 50 DEG C of water-baths 5h, 60 DEG C of water-baths 24h, 85 DEG C of water-bath 2h；Magnetic pyrite amine molecule trace is obtained to gather Compound.
6. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material as claimed in claim 5, it is special Levy and be,
100 DEG C of aging 8h, grinding in vacuum drying oven by magnetic pyrite amine molecule imprinted polymer, qualitative filter paper wrapped up, and is used Apparatus,Soxhlet's extracts 50h-110h, and extractant is methyl alcohol, and 80 DEG C of drying obtain magnetic imprinted polymer particle to constant weight.
7. the preparation method of Sulfonamides hydrophilic magnetic molecularly imprinted polymer material as claimed in claim 1, including Following steps：
(1) by 2.5g FeSO4.7H2O and 4.0g FeCl3.6H2O is placed in conical flask, adds the deionized water of 200mL, stirring To its dissolving, 60 DEG C are then warming up under nitrogen protection, add 5mL ammoniacal liquor, continue heating stirring reaction 1h；
After reaction terminates, black product is separated with supernatant using the externally-applied magnetic field of super magnet, and with deionized water and nothing Water-ethanol cyclic washing black product is until be placed in vacuum drying chamber in drying at 60 DEG C black product extremely in neutrality by washing lotion Constant weight, gained black product Fe3O4Particle is polished standby；
(2) Fe of synthesis in step (1) is taken3O4Particle is poured into the round-bottomed flask for filling water and absolute ethyl alcohol, adds positive silicic acid second Ester, stirs and evenly mixs 4min, and 5mL ammoniacal liquor is then added under the protection of nitrogen, continues stirring reaction 3h, and then in 50 DEG C of water-baths 1h, to Fe3O4Particle carries out surface and is modified；
Magnet collecting reaction product is used, and product is rinsed repeatedly up to washing lotion is in neutrality with deionized water and absolute ethyl alcohol, Product is placed in vacuum drying chamber in being dried at 60 DEG C, prepared Surface coating has SiO2Magnetic microsphere；
Fe3O4The quality of particle is 1g with the volume ratio of tetraethyl orthosilicate：4mL, water is 1 with the volume ratio of absolute ethyl alcohol：4；
(3) a. is dissolved in acetonitrile using sulfamethazine as template molecule, is put the oxygen in system with nitrogen Swap out and, and ultrasonication 15min, it is well mixed；
B. it is 1 that mol ratio is added in a:1 function monomer methacrylic acid and hydroxyethyl methacrylate, stirs 4 hours；
C. it is 1 that mol ratio is added in b:1 crosslinking agent ethylene glycol dimethacrylate and 3- (trimethoxysilyl) Propyl acrylate；
Wherein template molecule and function monomer, the ratio of crosslinking agent be：0.1mmol：6mmol：6mmol；
Acetonitrile：Solvent=the 6ml of template molecule+function monomer+crosslinking agent composition:12.1mmol；
D. Surface coating is added in c SiO2Magnetic microsphere, stir；
Surface coating has SiO2Magnetic microsphere be with the mass volume ratio of acetonitrile：1g:20ml；
E. initiator azodiisobutyronitrile is added in d, azodiisobutyronitrile has SiO with Surface coating2Magnetic microsphere quality Than being 1:12, mechanical agitation, and in 50 DEG C of water-baths 5h, 60 DEG C of water-baths 24h, 85 DEG C of water-bath 2h；Magnetic pyrite amine molecule trace is obtained to gather Compound.
8. the Sulfonamides hydrophilic magnetic molecularly imprinted polymer material obtained by the preparation method according to claim 1 is in inspection Survey sulfamethazine, sulphadiazine, sulfamethyldiazine, sulphathiazole, sulfadoxine, 5-methoxysulfadiazine, sulfanilamide (SN) Application in methyl oxazole, kynix NU-445 and cistosulfa Sulfonamides.
9. application of the imprinted polymer material as claimed in claim 8 in Sulfonamides are detected, including following steps：
(1) activate：Take the sulfanilamide (SN) magnetic molecularly imprinted polymer particle obtained by the preparation of the method according to claim 1 and be added to taper In bottle, activation process is carried out using methyl alcohol and deionized water successively, two-phase is separated using externally-applied magnetic field, outwell waste liquid, lived The magnetic molecularly imprinted polymer changed；
Wherein the quality of sulfanilamide (SN) magnetic molecularly imprinted polymer is with the quality volume of methyl alcohol and than being 1g：40mL, methyl alcohol with go from The volume ratio of sub- water is 1：1；
(2) extract：Sample solution to be detected or sample extraction solution are added in conical flask, it is magnetic molecularly imprinted with sulfanilamide (SN) Polymer beads are together placed in and mixing are vibrated on oscillator, now deposit trace object in the sample first from sample phase transfer to Solution, then magnetic molecularly imprinted polymer surface is adsorbed to, the wherein quality of sample and the volume ratio of solution is 1g： 15mL；
Sample extraction solution, using methyl alcohol or acetonitrile as extractant；
(3) separate：After the completion of extraction, magnet is placed in conical flask outer wall, using the effect of externally-applied magnetic field by sulfanilamide (SN) magnetic molecule Imprinted polymer is separated with solution, outwells waste liquid；
(4) drip washing：To leacheate is added in the conical flask equipped with magnetic molecularly imprinted polymer, lower impurity is washed in vibration mixing, then Secondary utilization magnetic field separates two-phase, outwells waste liquid, removes impurity, the wherein body of the quality of magnetic molecularly imprinted polymer and leacheate Product is than being 1g：50mL；
Described leacheate is deionized water or methyl alcohol；
(5) elute：To 2mL eluent sulfanilamide (SN) magnetic molecularly imprinted polymers are added in conical flask, fully vibration mixing will Adsorb the object to be measured on magnetic molecularly imprinted polymer surface to elute, then separate two-phase using externally-applied magnetic field, receive Collection eluent；The eluent that will be separate is dried up under the conditions of 50 DEG C with nitrogen, and is dissolved again with 1.0mL methyl alcohol, through 0.45 μm High performance liquid chromatography detection analysis is injected after organic system membrane filtration.
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