CN102432735B - Preparation method of magnetic molecularly imprinted polymer for separating/purifying sudan I - Google Patents
Preparation method of magnetic molecularly imprinted polymer for separating/purifying sudan I Download PDFInfo
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- CN102432735B CN102432735B CN 201110252472 CN201110252472A CN102432735B CN 102432735 B CN102432735 B CN 102432735B CN 201110252472 CN201110252472 CN 201110252472 CN 201110252472 A CN201110252472 A CN 201110252472A CN 102432735 B CN102432735 B CN 102432735B
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Abstract
The invention discloses a preparation method of a magnetic molecularly imprinted polymer for separating/purifying sudan I. The preparation method comprises the following steps of: dissolving the sudan I and methacrylic into acetonitrile; adding a cross-linking agent, an initiator and acetonitrile-based magnetic fluid; reacting in the absence of oxygen; separating microspheres generated by the reaction; and eluting the sudan I in the microspheres by adopting soxhlet extraction and drying. According to the preparation method disclosed by the invention, the magnetic fluid is added into the imprinted polymer; in the process of adsorbing and extracting a template molecule, the imprinted polymer can be directly added into a measured substance solution for adsorbing without being filled in a solid phase extraction column, and then imprinted polymer granules are gathered and separated by using a strong magnetic filed; and meanwhile, the imprinted polymer retains specific adsorption of the template molecule to the sudan, and thereby quick detection and analysis of the template molecule are realized.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic blotting polymkeric substance, relate in particular to a kind of preparation method of separation/purification Sudan red 1 magnetic molecularly imprinted polymer.
Background technology
Sudan red 1 is a kind of lipotropy azo industrial dye, the aspect of adding lustre to such as hyperchromic and footwear, floor that is usually used in solvent, oil, wax, gasoline, because it is bright-colored, with after fugitive color not, after being used for food dyeing, can cause the appetite that people are strong, so some illegal food enterprises use Sudan red 1 as foodstuff additive, common food has red chilly powder, paprika oleoresin, red bean corruption, red heart egg etc.Sudan red has carinogenicity. and international cancer research institution classifies Sudan red 1 as three class carcinogenss.
Molecular imprinting refers to that preparation has single-minded optionally aggregation technology to a certain specific target molecules, the hole of containing many specified shapes and size based on molecularly imprinted polymer (MIP) surface of this technology preparation, binding site with particular arrangement, therefore the structure to template molecule has certain selection recognition function.MIP is because its exclusive specific recognition ability, practicality and applied range obtain good application at aspects such as stratographic analysis, analogue enztme, liquid-solid extraction, Biomimic sensors in recent years.
At present, the preparation method of MIP has multiple, wherein traditional preparation method is mass polymerization, the synthetic Sudan red 1 MIP of this method of employings such as Francesco has realized the separation and concentration of Sudan red 1 in the red chilly powder (Francesco Puoci, Carmeol Garreffa, Francesca Iemma, et al.Molecularly imprinted solid phase extraction for sudan I in food matrices.Food Chemistry, 2005,93,349～353).Yet this method needs to grind in preparation process to sieve, and the space structure of destructible polymkeric substance descends selectivity, and the MIP particle shape that makes is irregular and productive rate is low.
Summary of the invention
The invention provides a kind of preparation method of separation/purification Sudan red 1 magnetic molecularly imprinted polymer, solved traditional method and need grind and sieve the space structure of destructible polymkeric substance, the problem that selectivity is low.
A kind of preparation method of separation/purification Sudan red 1 magnetic molecularly imprinted polymer comprises:
Sudan red 1, methacrylic acid are dissolved in acetonitrile, add linking agent, initiator and acetonitrile-base magnetic fluid, react under oxygen free condition, the microballoon that separating reaction generates adopts the Sudan red 1 in the soxhlet extraction wash-out microballoon, drying.
By the structure of Sudan red 1 as can be known, alkaline azo group in its molecule and the hydroxyl on the naphthalene nucleus all can with MAA on carboxyl form intermolecular hydrogen bonding, therefore, Sudan red 1 and MAA carry out molecule by noncovalent interaction and assemble in advance, remove template molecule after the polymerization, form the netted hole with the Sudan red 1 complementary structure in MMIP, the binding site in these holes can identify the difference on the molecular structure, can be used for separating of Sudan red 1 and other materials.
Polarity of solvent can influence the combination of template molecule and function monomer, particularly disturbs the formation of hydrogen bond, so adopt the relatively low acetonitrile of polarity as solvent.And before polymerization with template molecule and function monomer ultrasonic half an hour in acetonitrile, can make the two form stabilized complex.
Described linking agent is preferably ethylene glycol dimethacrylate; The mol ratio of described Sudan red 1, methacrylic acid, ethylene glycol dimethacrylate is 1: 4: 8～16; More preferably 1: 4: 10, under this ratio, the trace factor maximum of imprinted polymer.
The temperature of described reaction is preferably 60～65 ℃, and the time is 20～30h.
Described acetonitrile-base magnetic fluid is the Fe through γ-methacryloxypropyl trimethoxy silane modification
3O
4The particle acetonitrile solution.
Fe in the described acetonitrile-base magnetic fluid
3O
4The concentration of particle is 1g/mL, and the red red I of every mmol adds 10mL acetonitrile-base magnetic fluid.
Described initiator is preferably Diisopropyl azodicarboxylate; The weight mol ratio of described Diisopropyl azodicarboxylate and methacrylic acid is 0.6～1.0g: 4 * 10
-3Mol.
Before the soxhlet extraction, microballoon is dissolved in the employed eluent of soxhlet extraction supersound process 20～60min, can shorten the soxhlet extraction time, and the template molecule wash-out is clean, the employed eluent of described soxhlet extraction is preferably methyl alcohol/acetic acid solution, and volume ratio is preferably 85: 15.
Traditional molecularly imprinted polymer need be filled into the polypropylene solid phase extraction column with the method that wet method is adorned post when the pre-treatment that is used for analyte, activated, application of sample, and drip washing, wash-out is finished the pre-treatment process of separation and concentration;
Imprinted polymer of the present invention has added magnetic fluid, in sorption extraction template molecule process, do not need to fill it in the solid-phase extraction column, adsorb but it directly can be added in the analyte solution, utilize high-intensity magnetic field that the imprinted polymer particle aggregation is separated then; This imprinted polymer has kept the specific adsorption to the template molecule Sudan red simultaneously, thereby has realized the rapid detection analysis of template molecule.
Description of drawings
Fig. 1 is Fe
3O
4The projection Electronic Speculum figure of particle;
Fig. 2 is the Fe before and after the modification
3O
4The magnetic hysteresis loop of particle;
Fig. 3 is nanometer Fe
3O
4And the XRD spectra of M-MIP;
Fig. 4 is Fe
3O
4The infrared spectrogram of granule modified front and back;
Fig. 5 is the curve of adsorption kinetics of magnetic blotting polymkeric substance (M-MIP) and the non-imprinted polymer of magnetic (M-NMIP);
Fig. 6 is the adsorption isothermal line of M-MIP and M-NMIP;
Fig. 7 is the Scatchard curve of imprinted polymer.
The concrete Fang Shi that implements
(1) gets 80mL H
2O joins in the there-necked flask, logical nitrogen deoxygenation half an hour, adds 9.56g FeCl then
36H
2O and 5.60g FeSO
47H
2O, there-necked flask place 65 ℃ of thermostatical oil baths, stir fast, drip strong aqua behind the 30min to pH=8-9, and visible color is blackening gradually, have namely generated Fe this moment
3O
4Precipitation.Entire reaction course is carried out under nitrogen protection.Behind the 1h, come sedimentation gained granular product with strong magnet, separate the upper strata stillness of night, use H successively
2O and absolute ethanol washing throw out are to neutral.
(2) Fe of non-modified
3O
4Particle surface has great amount of hydroxy group, is difficult for being dispersed in the organic solvent, is distributed in polymer surfaces when the preparation molecularly imprinted polymer more, leaks easily and handles, and therefore adopts the Fe of KH-570
3O
4Particle carries out surface modification.
Operate as follows: the Fe that gets above-mentioned preparation
3O
4Particle 2g places there-necked flask, adds dehydrated alcohol 38mL and water 2mL, adds 0.4mLKH-570 again, and ultrasonic half an hour to be to be uniformly dispersed, then stirring reaction 3h under reflux temperature.Gained particle water and absolute ethanol washing add in the 20mL acetonitrile afterwards, make it fully be dispersed into the acetonitrile-base magnetic fluid.
As shown in Figure 1, the Fe of preparation
3O
4Granular size is comparatively even, the about 20nm of median size, because particle has magnetic, so nano particle reunites easily, and dispersiveness is not fine.
As shown in Figure 2, by curve a as can be known, the Fe that makes
3O
4Particle is along with the increase of externally-applied magnetic field intensity, and the specific magnetising moment increases, and when externally-applied magnetic field increased to certain value, specific magnetising moment value growth trend eased up, and reached capacity gradually, and its saturation magnetization (Bs) is 92.5emu/g.Simultaneously as can be seen from the figure, magnetzation curve is a single curve of crossing initial point, illustrate when externally-applied magnetic field is 0, sample does not almost have remanent magnetism, has good superparamagnetism, and it is needed that this prepares M-MIP just: namely M-MIP has stronger magnetic response under externally-applied magnetic field, the motion of being convenient to particle is assembled, and after removing externally-applied magnetic field, because it has only very little remanent magnetism and coercive force, particle can scatter again very soon.Know that by curve b the particle after the modification presents superparamagnetism equally, just saturation magnetization reduces to some extent.
As shown in Figure 3, Fe
3O
4Nanoparticle diffraction spectra peak appears at 2 θ=30.33 °, and 35.73 °, 43.40 °, 53.96 °, locate for 57.37 ° and 63.13 °, (220) of respectively corresponding cube phase Fe3O4, (311), (400), (422), (511) and (440) crystal face is with the Fe of standard
3O
4Characteristic diffraction peak match, show particle composition Fe really
3O
4By Scherrer equation D=k λ/(β cos θ), k=0.89 wherein, λ=0.15418, β is peak width at half height, the mean sizes of calculating particle is 16.7nm, conforms to the median size of electromicroscopic photograph statistics.
587cm among Fig. 4
-1The place is the charateristic avsorption band of Fe-O key, 2923cm after the modification
-1New absorption peak appears in the place, and this is the C-H stretching vibration peak in the KH-570 molecule, simultaneously, and at 1700cm
-1The peak that the place occurs is that the peak is shunk in the vibration of C=O among the KH-570, because in fully washing back test, the Fe after the surface modification is described
3O
4Particle surface is to connect to have gone up coupling agent really.
Take by weighing 1mmol Sudan red 1 and 4mmol methacrylic acid (MAA), place the 250mL Erlenmeyer flask, add the 180mL acetonitrile, ultrasonic half an hour is to mix.Add acetonitrile-base magnetic fluid and the 1.0g initiator Diisopropyl azodicarboxylate (AIBN) of 3.00mL linking agent ethylene glycol dimethacrylate (EGDMA), 10mL embodiment 1 preparation then, continue ultrasonic.Oxygen in the logical nitrogen 1h venting system reacts 24h in 60 ℃ of air concussion devices.Taking-up is cooled to room temperature, and adding methyl alcohol/acetic acid (85: 15, V/V) the ultrasonic 30min of solution, through the B suction filtration, use again with solution and carry out soxhlet extraction 48h to detecting less than the Sudan red 1 molecule, then with acetone repeatedly sedimentation remove fine powder, at last in 60 ℃ of vacuum-drying 24h.
Embodiment 3
Take by weighing 1mmol Sudan red 1 and 4mmol methacrylic acid (MAA), place the 250mL Erlenmeyer flask, add the 180mL acetonitrile, ultrasonic half an hour is to mix.Add acetonitrile-base magnetic fluid and the 1.0g initiator Diisopropyl azodicarboxylate (AIBN) of 1.5mL linking agent ethylene glycol dimethacrylate (EGDMA), 10mL embodiment 1 preparation then, continue ultrasonic.Oxygen in the logical nitrogen 1h venting system reacts 24h in 65 ℃ of air concussion devices.Taking-up is cooled to room temperature, and adding methyl alcohol/acetic acid (85: 15, V/V) the ultrasonic 20min of solution, through the B suction filtration, use again with solution and carry out soxhlet extraction 48h to detecting less than the Sudan red 1 molecule, then with acetone repeatedly sedimentation remove fine powder, at last in 60 ℃ of vacuum-drying 24h.
Take by weighing 1mmol Sudan red 1 and 4mmol methacrylic acid (MAA), place the 250mL Erlenmeyer flask, add the 180mL acetonitrile, ultrasonic half an hour is to mix.Add acetonitrile-base magnetic fluid and the 0.6g initiator Diisopropyl azodicarboxylate (AIBN) of 1.88mL linking agent ethylene glycol dimethacrylate (EGDMA), 10mL embodiment 1 preparation then, continue ultrasonic.Oxygen in the logical nitrogen 1h venting system reacts 24h in 65 ℃ of air concussion devices.Taking-up is cooled to room temperature, and adding methyl alcohol/acetic acid (85: 15, V/V) the ultrasonic 60min of solution, through the B suction filtration, use again with solution and carry out soxhlet extraction 48h to detecting less than the Sudan red 1 molecule, then with acetone repeatedly sedimentation remove fine powder, at last in 60 ℃ of vacuum-drying 24h.
In order to estimate the absorption property of prepared Sudan red 1 magnetic molecularly imprinted polymer (M-MIP), as a comparison, we have prepared the blank imprinted polymer (M-NMIP) of magnetic simultaneously, and the same substantially M-MIP of its preparation method does not only add template molecule.
The mensuration of adsorptive capacity Q: take by weighing 20mg M-MIP and M-NMIP respectively, place 10mL ground Erlenmeyer flask, Sudan red 1-the acetonitrile solution that adds the 5mL different concns, put under the water bath with thermostatic control vibrator room temperature and shake 5h, through the organic membrane filtration of 0.45 μ m tetrafluoroethylene, get 0.5mL filtrate and be diluted to 5mL, shake up, with the Cf of Sudan red 1 in the uv-spectrophotometric instrument mensuration equilibrium adsorption liquid, according to formula Q=(C
0-C
1) V/m, by strength of solution change calculations polymkeric substance adsorptive capacity Q before and after the absorption, replicate(determination) is averaged for 3 times.In the formula, Q is equilibrium adsorption capacity (μ mol/g); C
0Initial concentration (mmol/L) for Sudan red 1; C
1The concentration of Sudan red 1 (mmol/L) during for adsorption equilibrium; V is the volume (mL) of solution; M is the quality (g) of M-MIP or M-NMIP.
5.1 the comparison of the M-MIP adsorption effect of different mol ratio preparation
Trace factor-alpha=the Q of MIP absorption property is described
MIP/ Q
NIP, Q in the formula
MIPAnd Q
NIPIt is respectively the saturated extent of adsorption of MIP and the template molecule of NIP.α is more big, and the trace effect is more good.Optimize by experiment, as Sudan red 1: MAA: EGDMA=1: when 4: 10 (mol ratio), α=1.97 are maximum, measure so following test is the M-MIP of this proportioning preparation.
5.2 the kinetics of adsorption of Sudan red 1 M-MIP
Growth along with adsorption time, the adsorptive capacity of the template molecule of M-MIP also has increase, in order to study this increase trend of adsorptive capacity, M-MIP and M-NMIP that employing makes by embodiment 4 methods, under different adsorption times, measure both adsorptive capacitys, draw curve of adsorption kinetics, as shown in Figure 5.In the initial stage of absorption, Sudan red 1 solution and polymer scale sum velocity are very fast, and adsorptive capacity increases sharply, and reaches balance very soon.This is because in the initial stage, and the hole of polymer surfaces catches the Sudan red 1 molecule rapidly, when surface void be adsorbed saturated after, Sudan red 1 has certain steric hindrance to the mass transfer of the binding site of deep layer, adsorption rate reduces, and tends towards stability.
5.3 the adsorption isothermal line of Sudan red 1 M-MIP
Under the room temperature, adsorption isothermal curve is that adsorption time is the change curve that the adsorptive capacity of the M-MIP of 5h and the Sudan red 1 of M-NMIP increases with its concentration, M-MIP and M-NMIP that employing makes by embodiment 4 methods, measure the adsorptive capacity behind the absorption 5h under both different concns, draw adsorption isothermal curve, as shown in Figure 6.The equilibrium adsorption capacity of M-MIP and the Sudan red 1 of M-NMIP is respectively 68.81 μ mol/g and 39.37 μ mol/g.The equilibrium adsorption capacity of the Sudan red 1 of M-MIP illustrates that apparently higher than M-NMIP the synthetic Sudan red 1 of M-MIP has specific adsorption.
5.4Scatchard analyze
In the research of molecular imprinting, often use the evident characteristics of Scatchard model evaluation molecularly imprinted polymer.The Scatchard equation is as follows: Q/Ce=(Qmax-Q)/Kd, among the family name, Q be polymkeric substance to the equilibrium adsorption capacity (μ mol/g) of Sudan red 1, Ce is equilibrium concentration in the solution (μ mol/ml), Qmax represents the Bmax of binding site, and Kd is the balance dissociation constant of binding site.According to following formula, adopt the M-MIP and the M-NMIP that make by embodiment 4 methods, namely get the Scatchard curve with the Q mapping of Q/Ce, as shown in Figure 7.
The Q of the Q/Ce of M-MIP obviously is nonlinear relationship among the figure, but two parts of curve have good linear relationship, show in the concentration range of studying, the adsorption of the Sudan red 1 of M-MIP is not of equal value fully, the different binding site of M-MIP last existence two classes, reason may be to have multiple interaction between function monomer and the microsphere, can form the title complex of two class different componentss, can form two kinds of differences in conjunction with the hole of character in polymkeric substance after crosslinked.
Two sections linearities among the figure are obviously partly carried out match respectively preferably, can obtain match linear equation: Q/Ce=-1.127Q+95.33 (r=0..9778) and Q/Ce=-0.308Q+64.83 (r=0.9988) respectively.Slope and intercept by linear equation can be in the hope of Kd1=0.89mmol/L, Kd2=3.25mmol/L, Qmax1=84.59 μ mol/g, Qmax2=210.49 μ mol/g.And the Scatchard curve of M-NMIP is a linear correlation curve, shows the binding site isotropy of M-NMIP, and this is owing to there not being the trace process, so can only form a kind of nonselective binding site.
5.5 adsorption selectivity research
In order to study the selection adsorptivity of M-MIP, so selected for use the Sudan red III similar to the Sudan red 1 molecular structure to compare.Be solvent with the acetonitrile, studied the M-MIP that makes by embodiment 4 methods and M-NMIP respectively to the adsorptive capacity of above-mentioned two kinds of materials by static equilibrium absorption, the results are shown in Table 1.As shown in Table 1, the adsorptive capacity of the Sudan red 1 of M-MIP has showed good selectivity apparently higher than M-NMIP, illustrates that there is evident difference in their space structures.The adsorptive capacity of M-MIP and the Sudan red III of M-NMIP is all smaller, and does not have obvious selectivity, and reason is that two phenyl on the Sudan red III molecule and methyl have increased the spatial volume than Sudan red 1.The effect that imprinted polymer and microsphere are described thus is the interactional synergy between space size, shape and the functional group.
The adsorption selectivity of table 1 Sudan red 1 and Sudan red III
Claims (9)
1. the preparation method of a separation/purification Sudan red 1 magnetic molecularly imprinted polymer comprises:
Sudan red 1, methacrylic acid are dissolved in acetonitrile, add linking agent, initiator and acetonitrile-base magnetic fluid, react under oxygen free condition, the microballoon that separating reaction generates adopts the Sudan red 1 in the soxhlet extraction wash-out microballoon, drying;
Described acetonitrile-base magnetic fluid is the Fe through γ-methacryloxypropyl trimethoxy silane modification
3O
4The particle acetonitrile solution.
2. preparation method according to claim 1 is characterized in that, described linking agent is ethylene glycol dimethacrylate.
3. preparation method according to claim 2 is characterized in that, the mol ratio of described Sudan red 1, methacrylic acid, ethylene glycol dimethacrylate is 1: 4: 8～16.
4. preparation method according to claim 3 is characterized in that, the mol ratio of described Sudan red 1, methacrylic acid, ethylene glycol dimethacrylate is 1: 4: 10.
5. preparation method according to claim 1 is characterized in that, the temperature of described reaction is 60～65 ℃, and the time is 20～30h.
6. preparation method according to claim 1 is characterized in that, described initiator is Diisopropyl azodicarboxylate.
7. preparation method according to claim 1 is characterized in that, the weight mol ratio of described Diisopropyl azodicarboxylate and methacrylic acid is 0.6～1.0g: 4 * 10
-3Mol.
8. preparation method according to claim 1 is characterized in that, before the soxhlet extraction, microballoon is dissolved in the employed eluent of soxhlet extraction supersound process 20～60min.
9. according to claim 1 or 8 described preparation methods, it is characterized in that the employed eluent of described soxhlet extraction is methyl alcohol/acetic acid solution.
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| CN103301820B (en) * | 2013-07-04 | 2015-06-10 | 广西民族大学 | Core-shell type Rhodamine B molecular imprinting solid-phase extraction magnetic material, and preparation method and application thereof |
| CN103551125A (en) * | 2013-10-23 | 2014-02-05 | 邵秋荣 | Preparation method of Sudan red II molecular imprinting solid-phase extraction column filling material |
| CN104262192A (en) * | 2014-10-21 | 2015-01-07 | 中国计量科学研究院 | Sudan red I crystal A and preparation method thereof |
| CN105622824B (en) * | 2014-11-07 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN109679014A (en) * | 2018-12-12 | 2019-04-26 | 武汉轻工大学 | A kind of porous magnetic molecular engram material and preparation method thereof |
| CN110256629A (en) * | 2019-05-09 | 2019-09-20 | 重庆大学 | A kind of preparation method of Bravo magnetic molecularly imprinted polymer |
| CN110982022B (en) * | 2019-12-20 | 2021-07-09 | 中国药科大学 | Magnetic capsaicin molecularly imprinted polymer and preparation method thereof |
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| CN100478679C (en) * | 2006-12-13 | 2009-04-15 | 西南大学 | Method for detecting sudan red in foods |
| CN101091911B (en) * | 2007-04-16 | 2010-12-15 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
| CN101339170A (en) * | 2008-04-25 | 2009-01-07 | 浙江树人大学 | Ion liquid extraction high efficiency liquid phase chromatography ultraviolet detection for sudan red analog compound |
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