CN104910339A - Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid - Google Patents

Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid Download PDF

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CN104910339A
CN104910339A CN201510354884.5A CN201510354884A CN104910339A CN 104910339 A CN104910339 A CN 104910339A CN 201510354884 A CN201510354884 A CN 201510354884A CN 104910339 A CN104910339 A CN 104910339A
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ion liquid
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molecularly imprinted
poly ion
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CN104910339B (en
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李蕾
曾延波
阮佳
张剑
曹红
徐启翔
肖平秀
陈金隆
王鑫
唐杰
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Jiaxing University
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Abstract

The invention discloses magnetic molecular imprinting polyion liquid for detecting ractopamine as well as a preparation method and an application of the magnetic molecular imprinting polyion liquid. The magnetic molecular imprinting polyion liquid is a granule material prepared in steps of polymerizing a carrier, a function monomer, a crosslinking agent and template molecules in the presence of an initiating agent and then eluting the template molecules, wherein the functional molecule is 1-ethyl-3-ethylimidazole hexafluorophosphate, the crosslinking agent is bromination 1,4-butane-3,3'-bis-1-vinyl imidazole, and the template molecule is ractopamine. According to the magnetic molecular imprinting polyion liquid, the ion liquid 1-ethyl-3-ethylimidazole hexafluorophosphate is adopted as the functional monomer, the ion liquid cross-linking agent is adopted as a cross-linking agent, the experiment shows that the magnetic molecular imprinting polyion liquid can rapidly reach an absorption balance state for the ractopamine and is high in adsorption capacity and good in selective adsorption capacity, and the maximum adsorption amount is 20.50 mu mol/g.

Description

For magnetic molecularly imprinted poly ion liquid detecting Ractopamine hydrochloride and its production and use
Technical field
The present invention relates to molecular imprinting field, particularly relate to a kind of for magnetic molecularly imprinted poly ion liquid detecting Ractopamine hydrochloride and its production and use.
Background technology
Clenbuterol hydrochloride is a kind of suprarenal gland class CNS stimulant of phenylethanol class medicine (phenethlamines), and Ractopamine hydrochloride, Clenbuterol hydrochloride belong to beta-stimulants, have larger harm to human body.In the state supervision department bulletin of 2002, do not allow to add clenbuterol hydrochloride in the feed, tap water of animal.Ractopamine hydrochloride (RAC) is the β of synthetic 2adrenergic receptor stimulant, can combine with the beta receptor on cytolemma, can act on suprarenin.It can make sympathetic activation thus be applied to bronchitic treatment.But when its heavy dose be used in feed or tap water as Animal feed-additive, can food utilization efficiency be improved, the metabolism of fat ability of animal body can be caused to strengthen, synthetic protein speed speeds, and changes the Nutrition and Metabolism of animal, reduces fat ratio, improve lean ratio, and animal is increased weight.But the residual meeting of RAC is accumulated in human body by the effect of food chain, cause human heart rate to overrun, heart disorder, diabetes, hypertension, hyperthyroidism, myalgia and the symptom such as dizzy, even can cause death.Therefore, set up fast effectively, simple and easy to do RAC detection method has become the vital task of China's meat food safety detection technique.
At present, the detection method of RAC mainly contain liquid phase chromatography (HPLC), High Performance Liquid Chromatography/Photodiode Array Detection (HPLC-PDA), sweep high performance liquid chromatography/fluorescence (HPLC/FLD), Liquid Chromatography/Mass Spectrometry (LC-MS), gas chromatography mass spectrometry method (GC-MS) [99]with capillary electrophoresis etc., but these methods often need comparatively complicated pre-treatment, and specific recognition cannot cause Sync enrichment interference component, also there is the shortcoming that adsorptive capacity is little.
Magnetic polymer particles has the advantages such as the good specific magnetising moment, chemical stability, dispersiveness, thermostability, hypotoxicity and easy functionalization.It a kind ofly has adsorbing functional polymer by what function monomer, linking agent, initiator etc. are obtained by polyreaction.This matrix material can realize sharp separation absorption by externally-applied magnetic field, also has stable physico-chemical property and mechanical property, has been widely used in Solid-Phase Extraction, chromatographic separation, electrochemical sensor etc. at present.
Summary of the invention
The invention provides the molecular imprinting poly ion liquid for detecting Ractopamine hydrochloride of a kind of high-adsorption-capacity, good selectivity.
A kind of magnetic molecularly imprinted poly ion liquid, it is the granulate material that after being polymerized under initiator effect by carrier, function monomer, linking agent, template molecule, eluted template molecule is made, described function monomer is 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, described linking agent is bromination 1,4-butane-3,3 '-bis--1-vinyl imidazole, described template molecule is Ractopamine hydrochloride.
Preferably, the particle diameter of described magnetic molecularly imprinted poly ion liquid is 550 ~ 600nm.
Preferably, described carrier is the Fe that MAPS modifies 3o 4@SiO 2, Fe 3o 4@SiO 2represent SiO 2coated Fe 3o 4particle, for stating conveniently, is abbreviated as Fe 3o 4@SiO 2-MAPS.
Preferably, the Fe of described MAPS modification 3o 4@SiO 2particle diameter be 30 ~ 35nm.
Present invention also offers the preparation method of described magnetic molecularly imprinted poly ion liquid, comprise the following steps:
By the Fe that MAPS modifies 3o 4@SiO 2be scattered in solvent, add function monomer, linking agent, initiator and template molecule successively, carry out polyreaction under anaerobic, react rear collection product, remove the template molecule in product and carry out vacuum-drying, be i.e. obtained described magnetic molecularly imprinted poly ion liquid.
Preferably, the temperature of described polyreaction is 60 ~ 80 DEG C, and the time is 20 ~ 25h; More preferably, temperature is 60 DEG C, and the time is 24h.
Preferably, the mol ratio of described template molecule, function monomer, linking agent is 1: 4 ~ 6: 18 ~ 22; More preferably, mol ratio is 1: 5: 20.
Preferably, described carrier is 0.1 ~ 0.3g: 0.1mmol with the molal ratio of template molecule; More preferably, molal ratio is 0.1g: 0.1mmol.
Described initiator is Diisopropyl azodicarboxylate.Described function monomer is 0.1mmol: 5 ~ 8mg with the molal weight ratio of initiator; More preferably, molal weight ratio is 0.1mmol: 6mg.
Present invention also offers described magnetic molecularly imprinted poly ion liquid and detect the application in Ractopamine hydrochloride.
The magnetic molecularly imprinted poly ion liquid of the present invention take Ractopamine hydrochloride as template, with ionic liquid 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate ([C 7mim] [PF 6]) be function monomer, with ionic liquid linking agent bromination Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole ([C 4(mim) 2] [Br]) be polymerized for linking agent, experiment shows that this magnetic molecularly imprinted poly ion liquid can reach adsorption equilibrium state fast to Ractopamine hydrochloride, have higher loading capacity and good adsorption selection ability, maximal absorptive capacity is 20.50 μm of ol/g simultaneously.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the magnetic molecularly imprinted poly ion liquid of the present invention.
Fig. 2 is Fe 3o 4(A), Fe 3o 4@SiO 2the TEM figure of-MAPS (B), magnetic molecularly imprinted poly ion liquid (C).
Fig. 3 is Fe 3o 4(a), Fe 3o 4@SiO 2-MAPS (b) and [C 7mim] infrared spectrogram of-MMIP (c).
Fig. 4 is Fe 3o 4(a), Fe 3o 4@SiO 2-MAPS (b) and [C 7mim]-MMIP (c) thermogravimetric curve figure.
Fig. 5 (A) is magnetic absorption design sketch.
Fig. 5 (B) is Fe 3o 4(a), Fe 3o 4@SiO 2-MAPS (b) and [C 7mim] the magnetic hysteresis loop figure of-MMIP (c).
Fig. 6 is Fe 3o 4(a), Fe 3o 4@SiO 2-MAPS (b) and [C 7mim] XRD figure of-MMIP (c).
Fig. 7 is [C 7mim]-MMIP (a) and [C 7mim]-MNIP (b) is to the graph of a relation of the adsorptive capacity of RAC with adsorption time.
Fig. 8 is [C 7mim]-MMIP (a) and [C 7mim]-MNIP (b) is to the graph of a relation of the adsorptive capacity of Ractopamine hydrochloride with adsorption concentration.
Fig. 9 is [C 7mim]-MMIP (a) and [C 7mim]-MNIP (b) is to the absorption spirogram of RAC and 3 kind of analog.
Figure 10 is [C 7mim]-MMIP adsorbs the First order dynamic model of RAC.
Figure 11 is [C 7mim]-MMIP adsorbs the second-order kinetics model of RAC.
Figure 12 is the liquid phase spectrogram of pork sample after extraction: a: for not adding the pork sample of Ractopamine hydrochloride through [C 7mim]-MMIP extraction after HPLC; B: add the pork sample of the Ractopamine hydrochloride of 5 μ g/kg phenolic compounds through [C 7mim]-MNIP; C: for adding the pork sample of the Ractopamine hydrochloride of 5 μ g/kg phenolic compounds through [C 7mim]-MMIP.
Embodiment
The preparation of carrier:
By 0.01mol FeCl 24H 2o and 0.02mol FeCl 36H 2o is dissolved in 80mL deionized water, uses constant pressure funnel slowly to drip 10mL NH 3h 2o, react 30min at 80 DEG C, be cooled to room temperature, magnetic field separation goes out Fe 3o 4, be washed with water to neutrality, 60 DEG C of vacuum-drying 12h, obtain Fe 3o 4.
Get 300mg Fe 3o 4be scattered in 40mL ethanol and 10mL water, add 5mL strong aqua, 2mL tetraethoxy TEOS, stirring at room temperature 12h after ultrasonic 15min, magnetic field separation, use 0.1mol/L dilute hydrochloric acid, water washing solid successively, 60 DEG C of vacuum-drying 12h, obtain Fe 3o 4@SiO 2.
Get 250mg Fe 3o 4@SiO 2, be scattered in 50mL dry toluene and 5mL 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (MAPS), N 2reflux at lower 70 DEG C of environment 12h, and externally-applied magnetic field is separated and washes solid with water, obtained Fe 3o 4@SiO 2-MAPS.
The preparation of function monomer:
Get 0.05mol 1-vinyl imidazole, 0.05mol monobromethane is scattered in 15 ml methanol, stir 15h at 60 DEG C, after cooling, mixture is added in 500mL ether, leaches precipitation, at room temperature dry, obtained bromination 1-vinyl-3-ethyl imidazol(e).
Get 0.05mol bromination 1-vinyl-3-ethyl imidazol(e), 0.05mol NH 4pF 6be scattered in 50mL water, stirring at room temperature 12h, filters out solid, washes rear drying at room temperature with water, obtained 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate ([C 7mim] [PF 6]). 1H NMR(400MHz，DMSO，ppm)：9.78(s，1H)，8.38(s，1H)，7.93(s，1H)，7.28(dd，1H)，5.94(dd，1H)，5.42(dd，2H)，4.32(q，2H)，1.45(t，3H)； 13C NMR(400MHz，DMSO，ppm)：135.24，129.04，123.29，119.32，108.88，44.80，16.56)
The preparation of linking agent:
Get 0.1mol 1-vinyl imidazole, 0.05mol Isosorbide-5-Nitrae-dibromobutane is scattered in 30mL methyl alcohol, stirs 15h at 60 DEG C, pours in 1L ether, drying at room temperature after cooling, obtained bromination Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole ([C 4(mim) 2] [Br]). 1H NMR(400MHz，DMSO，ppm)：9.74(s，1H)，8.27(s，1H)，8.00(s，1H)，6.00(dd，1H)，5.37(dd，1H)，5.32(dd，1H)，4.25(q，2H)，1.41(t，3H)； 13C NMR(400MHz，DMSO，ppm)：135.04，128.85，123.09，119.31，108.87，44.83，15.06
The preparation of magnetic molecularly imprinted poly ion liquid:
By 0.1g Fe 3o 4@SiO 2-MAPS is scattered in 30mL (toluene+acetonitrile=1: 1), add 0.5mmol 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, 2.0mmol bromination 1 successively, 4-butane-3,3 '-bis--1-vinyl imidazole, 30mg Diisopropyl azodicarboxylate (AIBN) and 0.1mmol Ractopamine hydrochloride, logical nitrogen 15min deoxygenation, sealing, 24h is stirred at 60 DEG C, magnetic field separation product, template molecule is removed with methanol-acetic acid solution (volume ratio 9: 1) washing, 20 DEG C of vacuum-drying 24h, obtained magnetic molecularly imprinted poly ion liquid [C 7mim]-MMIP.Preparation process as shown in Figure 1.
Adopt same procedure, under not adding template molecule condition, prepare non magnetic molecular imprinting poly ion liquid ([C 7mim]-MNIP).
Morphology characterization
The pattern of transmission electron microscope to magnetic microsphere is adopted to observe, shown in Fig. 2 (A), naked Fe 3o 4magnetic nanoparticles size is homogeneous, spherical in shape, and particle diameter is about 15nm, as can be seen from Fig. 2 (B), and SiO 2coated Fe 3o 4and after bonding 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (MAPS), Fe 3o 4@SiO 2-MAPS particle diameter is increased to about 30 ~ 35nm, shown in Fig. 2 (C), the spheroid of slightly adhesion close sized by the magnetic Nano microsphere after modifying, and outer casing thickness increases, it is 550 ~ 600nm that the median size of final product reaches, and illustrates and has successfully prepared [C 7mim]-MNIP.
Infrared spectroscopy
562cm in Fig. 3 spectral line a -1for Fe 3o 4the absorption peak of the stretching vibration of Fe-O key in nano particle.Fe 3o 4@SiO 21095cm in the infrared spectrogram of-MAPS -1there is a strong absorption band at place, the stretching vibration peak of Si-O, 948cm -1for the stretching vibration peak of Si-OH, illustrate by the polyreaction of TEOS successful at Fe 3o 4microsphere surface is coated SiO 2, and 1725cm -1, 1630cm -1the stretching vibration peak of what the absorption peak at place was corresponding is C=O, C=C on MAPS, shows that MAPS modifies Fe 3o 4@SiO 2surface.Fig. 3 spectral line c is [C 7mim] infrared spectrogram of-MMIP, 1550cm -1, 1165cm -1the absorption peak at place, belongs to the stretching vibration peak of C=N, the C-N on MIP, 840cm respectively -1belong to PF on ionic liquid 6stretching vibration peak, also there is Fe simultaneously 3o 4@SiO 2the characteristic peak of-MAPS is (as 1095cm -1), illustrate and successfully prepared [C 7mim]-MMIP.
Thermogravimetric analysis
Fig. 4 is Fe 3o 4, Fe 3o 4@SiO 2-MAPS and [C 7mim] thermal gravimetric analysis curve of-MMIP. as can be seen from Fig. 4, Fe 3o 4without obvious weightless peak, only weightlessness 4.2%, illustrates its good thermal stability.Relatively Fe 3o 4@SiO 2-MAPS and [C 7mim] thermal gravimetric analysis curve of-MMIP, Fe 3o 4@SiO 2-MAPS weightlessness is less, is about 23.7%, and major cause is SiO 2have the stability to heat, the weightless peak at 550 DEG C of places is caused by the MAPS due to grafting.And [C 7mim] weight loss of-MMIP is comparatively large, is about 78.3%, [C 7mim] weightlessness of-MMIP is decomposition due to MIP, surplus materials is difficult nanometer Fe of decomposing 3o 4.
Magnetometric analysis
Utilize vibrating sample magnetometer (VSM) to Fe 3o 4, Fe 3o 4@SiO 2-MAPS and [C 7mim]-MMIP carries out magnetic property analysis.As shown in Figure 5 B, under room temperature, Fe 3o 4, Fe 3o 4@SiO 2-MAPS and [C 7mim] the maximum magnetic flux saturation ratio of-MMIP is respectively 71.340emu/g, 17.983emu/g and 4.572emu/g.These three kinds of magnetic Nano microspheres all do not have hysteresis, and have this interpret sample of hard magnetization intensity and have superparamagnetism.Fe 3o 4@SiO 2-MAPS and [C 7mim] the saturated magnetic intensity of-MMIP declines to some extent, is due to its surface coated nonmagnetic layer.
Fig. 5 (A) is magnet adsorption photo.Can see from Fig. 5 A, [C 7mim]-MMIP Granular composite in solution by foreign field be separated before and after photo.When there is not foreign field, [C 7mim]-MMIP even particulate dispersion in bottle, in brown color suspension, when adding foreign field, brown yellow granule by rapid adsorption on the bottle wall of externally-applied magnetic field, within a short period of time solution went clear, this illustrates [C 7mim]-MMIP has good magnetic response, can reach the effect of sharp separation.
XRD analysis
This experiment X-ray diffraction (XRD) analyzes the structural performance of the magnetic-particle often walking synthesis.As shown in Figure 6, in (220), (311), (400), (440), (511) and (440) place, can see strong fignal center, this is Fe 3o 4characteristic peak, illustrate through to modify and the magneticsubstance of trace still has Fe 3o 4spinel structure.As can be seen from Fig. 6 also, at Fe 3o 4@SiO 2-MAPS (b) and [C 7mim] 2 θ=22 ° are unformed SiO in-MMIP (c) 2diffraction peak.
Absorption property is analyzed
Get 20mg [C 7mim]-MMIP and [C 7mim]-MNIP is scattered in 20mL Ractopamine hydrochloride methanol solution respectively, and under room temperature, temperature stirs 8min, with magnetic field separation magnetic poly ion liquid, gets supernatant liquor ultraviolet-visible pectrophotometer and detects, and adsorptive capacity is by following formulae discovery:
Q = ( C 0 - C e ) V m
In formula, Q is the adsorptive capacity (μm ol/g) of magnetic molecularly imprinted poly ion liquid, C 0, C ebe respectively the concentration (μm ol/L) of the starting point concentration of Ractopamine hydrochloride, the rear Ractopamine hydrochloride of magnetic molecularly imprinted poly ion liquid absorption, V is the volume (L) of solution, and m is the quality (g) of magnetic molecularly imprinted poly ion liquid.
As shown in Figure 7, [C 7mim]-MMIP (a line) to the adsorptive capacity of Ractopamine hydrochloride along with adsorption time increases gradually, 8min reaches capacity absorption, absorption reaches balance, illustrates that this magnetic molecularly imprinted poly ion liquid material absorption to Ractopamine hydrochloride has feature fast, [C 7mim] the maximum saturation adsorptive capacity of-MMIP reaches 20.50 μm of ol/g.From Fig. 7 also, magnetic molecularly imprinted poly ion liquid [C 7mim] adsorptive capacity of-MMIP is apparently higher than non magnetic molecular imprinting poly ion liquid [C 7mim]-MNIP.
Research [C 7mim]-MMIP and [C 7mim]-MNIP to the adsorptive capacity of 100 ~ 1000 μm of ol/L Ractopamine hydrochlorides, as shown in Figure 8, [C 7mim]-MMIP increases with the increase of its concentration the adsorptive capacity of Ractopamine hydrochloride, and after the starting point concentration of absorption is greater than 800 μm of ol/L, adsorptive capacity reaches balance.By [C 7mim]-MMIP and [C 7mim]-MNIP (b line) compares the adsorptive capacity of Ractopamine hydrochloride, [C 7mim]-MMIP has the adsorptive capacity larger to Ractopamine hydrochloride, and this is due to [C 7mim] there is special binding site to target molecule in-MMIP, has recognition capability to the absorption of Ractopamine hydrochloride.
Investigate [C 7mim]-MMIP is to the adsorption selectivity of target molecule Ractopamine hydrochloride, and thing is as shown in Figure 9 as a comparison to select 3 kinds of analogs such as salbutamol, Clenbuterol hydrochloride and Phenylethanolamine A.[C 7mim] adsorptive capacity of-MMIP to Ractopamine hydrochloride, salbutamol, Clenbuterol hydrochloride and Phenylethanolamine A be respectively 20.5,11.2,11.1,10.9, [C 7mim] adsorptive capacity of-MNIP to Ractopamine hydrochloride (Ractopamine), salbutamol (Sabutamol), Clenbuterol hydrochloride (Clenbuterol hydrochloride) and Phenylethanolamine A (Phenyle thanolamine A) be respectively 10.8,8.9,8.7,8.5, can be found out by adsorptive capacity, [C 7mim]-MMIP and [C 7mim]-MNIP has absorption to 4 kinds of clenbuterol hydrochloride, for they provide condition for extraction and detection.
Relatively [C 7mim]-MNIP, [C 7mim]-MMIP to the adsorptive capacity of Ractopamine hydrochloride higher than [C 7mim]-MNIP.Relatively salbutamol, Clenbuterol hydrochloride and Phenylethanolamine A, [C 7mim]-MMIP to the adsorptive capacity of Ractopamine hydrochloride higher than [C 7mim]-MNIP, show [C 7mim]-MMIP has higher recognition performance to Ractopamine hydrochloride, and this is due to [C 7mim] there is the hole matched with Ractopamine hydrochloride in-MMIP, and can specifically in conjunction with Ractopamine hydrochloride.
Kinetics of adsorption is analyzed
In order to study [C further 7mim]-MNIP to the kinetics of adsorption of Ractopamine hydrochloride, respectively to [C 7mim] adsorptive capacity-time curve of-MNIP carries out kinetics of adsorption model analysis, adopts First order dynamic model and second-order kinetics model to characterize respectively.By the fitting coefficient R of two kinds of models, determine [C 7mim] which kind of kinetics of adsorption process-MMIP belong to.
One-level, second-order kinetic equation are as follows:
ln(Q e-Q t)＝lnQ 1-k 1t
t/Q t＝1/k 2Q 2 2+t/Q 2
In formula, Q efor [C 7mim]-MMIP to the equilibrium adsorption capacity (μm ol/g) of Ractopamine hydrochloride, Q tfor t [C 7mim]-MMIP to the adsorptive capacity (μm ol/g) of Ractopamine hydrochloride, k 1for first order rate constant (min -1), k 2for first order rate constant (min -1).
Table 1 [C 7mim]-MMIP adsorbs the kinetics first-order model of Ractopamine hydrochloride and second-level model parameter
Take matched curve that two kinds of dynamic adsorption models obtain as shown in FIG. 10 and 11, in the graph of a relation that the matching of pseudo-first-order kinetic model obtains, ln (Q e-Q t) linear with t, fitting coefficient is 0.9912.In the graph of a relation that pseudo-second order kinetic model-fitting obtains, t/Q twith the linear relationship that t is good, fitting coefficient is 0.9993.Meanwhile, theoretical adsorptive capacity (18.73 μm of ol g of obtaining of pseudo-second order kinetic Adsorption Model matching -1) and experimental value 20.50 μm of ol g -1) relatively.Can infer thus, should [C 7mim] adsorption process of-MMIP is pseudo-second order kinetic absorption.
Food samples detects to be analyzed
Adopt [C 7mim]-MMIP extracts and HPLC combines, and carries out detect delay to the Ractopamine hydrochloride in pork liver, pork. and concrete grammar is as follows:
Enzymolysis: the CH first preparing 0.2M (pH=5.2) 3cOONH 4buffered soln.The pork liver of accurate weighing 2g, pork, and put it in No. 1, centrifuge tube, get the CH of 8.0mL 3cOONH 4buffered soln, add β-hydrochloric acid glucal glycosides enzyme 40 μ L, mix it with vortex instrument, lucifuge is reacted in the shaking table of 37 DEG C.
Extract: pork, pork liver are cooled to room temperature, and are mixed with vortex instrument, centrifugal 20min under 5000rmp condition, the supernatant liquor obtained is transferred to No. 2, centrifuge tube.Add appropriate HClO 4, its pH is made to be 1.0 ± 0.2, under 5000rmp condition after centrifugal 20min, the supernatant liquor obtained is transferred to No. 3, centrifuge tube, getting appropriate 10M NaOH solution regulates pH to be 9.5 ± 0.2, add the ethyl acetate of 15mL, with vortex instrument, it is mixed, vibrate 15 rear min in shaking table, centrifugal 10min under 5000rpm condition, upper organic phase is transferred in No. 4, centrifuge tube, 10mL t-butyl methyl ether is added in No. 3, centrifuge tube, mixed with vortex instrument, centrifugal 10min under 5000rmp condition, the organic phase of the upper organic phase obtained and No. 3, centrifuge tube merges, N is used at 40 DEG C 2purging instrument blows near dry, with the 2% aqueous formic acid constant volume of 5mL to treat that next step reacts.
Extraction: 20mg [C 7mim]-MMIP and [C 7mim]-MNIP joins in 5mL reserve liquid respectively, stirring at room temperature 8min, magnetic poly ion liquid material magnet is adsorbed on bottom or wall, with 5mL acetonitrile/acetic acid mixture (volume ratio 9: 1) wash-out, collect elutriant, nitrogen blows elutriant to 0.5mL, and high performance liquid chromatography detects.
Liquid phase chromatogram condition: chromatographic column is Thermo Hypersil GOLD (150mm × 2.1mm, 5 μm), moving phase is methyl alcohol: water=50: 50 (v: v), flow velocity: 0.3mL/min, column temperature 25 DEG C, determined wavelength 278nm, sample size 20 μ L. Ractopamine hydrochloride retention time is 2.0min.
As shown in figure 12, curve a is [C 7mim]-MMIP to extract before non-mark-on Ractopamine hydrochloride color atlas in pork, all Ractopamine hydrochloride do not detected as seen from Figure 12 in pork.In order to investigate the feasibility of method, adopt using standard samples recovery, to adding 5 μ g/kg in sample water, the Ractopamine hydrochloride concentration of 10 μ g/kg tests, and the results are shown in Figure 12 and table 2, and curve b and c is for through [C 7mim]-MMIP, [C 7mim]-MNIP extracting and enriching pork in Ractopamine hydrochloride color atlas, [C is described 7mim]-MMIP, [C 7mim]-MNIP can adsorb Ractopamine hydrochloride, and the Ractopamine hydrochloride after absorption can well from [C 7mim] elute in-MMIP, visible [C simultaneously 7mim]-MMIP ratio [C 7mim] adsorptive power of-MNIP is eager to excel, and this is the reason due to molecular imprinting recognition site.
As seen from Table 2, [C 7mim] rate of recovery of-MMIP between 98.52% ~ 105.10%, RSD in 2.6% ~ 4.3% scope, [C 7mim] rate of recovery of-MNIP is in 65.91% ~ 70.59% scope, and RSD is in 2.9% ~ 4.2% scope.
Table 2 [C 7mim]-MMIP and [C 7mim]-MNIP extracts the mensuration (n=3) of pork, Ractopamine hydrochloride in pork liver
With this understanding, the linearity range and the detection limit (S/N=3) that obtain Ractopamine hydrochloride are as shown in table 3.Present method and other measure Ractopamine hydrochloride method and contrast, present method has wide linearity range and lower detectability.
Table 3 the inventive method and other chromatographys measuring Ractopamine hydrochloride contrast
a：microextraction by packed sorbent b：uniformly-sized molecularly imprinted polymers c：solid phase extraction
Visible, in conjunction with magnetic molecularly imprinted poly ion liquid extraction and high-efficient liquid phase chromatogram technology, the present invention successfully detects the Ractopamine hydrochloride in pork, pork liver, detects and is limited to 0.50 μ g/kg, and the rate of recovery is 98.52% ~ 105.10%.

Claims (9)

1. a magnetic molecularly imprinted poly ion liquid, it is the granulate material that after being polymerized under initiator effect by carrier, function monomer, linking agent, template molecule, eluted template molecule is made, it is characterized in that, described function monomer is 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, described linking agent is bromination 1, two-1-the vinyl imidazole of 4-butane-3,3'-, described template molecule is Ractopamine hydrochloride.
2. magnetic molecularly imprinted poly ion liquid as claimed in claim 1, is characterized in that, particle diameter is 550 ~ 600nm.
3. magnetic molecularly imprinted poly ion liquid as claimed in claim 1, is characterized in that, described carrier is the Fe that MAPS modifies 3o 4@SiO 2, Fe 3o 4@SiO 2represent SiO 2coated Fe 3o 4particle.
4. magnetic molecularly imprinted poly ion liquid as claimed in claim 1, is characterized in that, the Fe that described MAPS modifies 3o 4@SiO 2particle diameter be 30 ~ 35nm.
5. the preparation method of magnetic molecularly imprinted poly ion liquid as described in as arbitrary in claim 1-4, comprises the following steps:
By the Fe that MAPS modifies 3o 4@SiO 2be scattered in solvent, add function monomer, linking agent, initiator and template molecule successively, carry out polyreaction under anaerobic, react rear collection product, remove the template molecule in product and carry out vacuum-drying, be i.e. obtained described magnetic molecularly imprinted poly ion liquid.
6. preparation method as claimed in claim 5, it is characterized in that, the temperature of described polyreaction is 60 ~ 80 DEG C, and the time is 20 ~ 25h.
7. preparation method as claimed in claim 5, it is characterized in that, the mol ratio of described template molecule, function monomer, linking agent is 1: 4 ~ 6: 18 ~ 22.
8. preparation method as claimed in claim 5, it is characterized in that, described carrier is 0.1 ~ 0.3g: 0.1mmol with the molal ratio of template molecule.
9. the magnetic molecularly imprinted poly ion liquid as described in as arbitrary in claim 1-4 is detecting the application in Ractopamine hydrochloride.
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CN105784857A (en) * 2015-11-27 2016-07-20 佛山科学技术学院 Analysis test method for ractopamine
CN106215823A (en) * 2016-08-23 2016-12-14 华南理工大学 Polymeric ionic liquid wraps up silicon dioxide microparticle composite and preparation method thereof and the application of carboxymethyl-lysine in removal makes soy sauce
CN108927114A (en) * 2016-08-01 2018-12-04 福建出入境检验检疫局检验检疫技术中心 A kind of method of polycyclic aromatic hydrocarbon in efficient absorption spirulina
CN110387019A (en) * 2019-08-05 2019-10-29 河南师范大学 It is a kind of for removing the preparation method and applications of 2,4-D pesticide residue molecularly imprinted polymer
CN114644737A (en) * 2022-03-16 2022-06-21 陕西科技大学 Magnetic surface molecular imprinting electrochemical sensor and preparation method and application thereof

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CN103965419A (en) * 2014-05-19 2014-08-06 渤海大学 Preparation method of magnetic imprinted polymer for separating and purifying ractopamine

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CN105784857A (en) * 2015-11-27 2016-07-20 佛山科学技术学院 Analysis test method for ractopamine
CN105784857B (en) * 2015-11-27 2019-02-01 佛山科学技术学院 Analysis test method for Ractopamine
CN108927114A (en) * 2016-08-01 2018-12-04 福建出入境检验检疫局检验检疫技术中心 A kind of method of polycyclic aromatic hydrocarbon in efficient absorption spirulina
CN108940215A (en) * 2016-08-01 2018-12-07 福建出入境检验检疫局检验检疫技术中心 A kind of method of enriched removal polycyclic aromatic hydrocarbon
CN108940216A (en) * 2016-08-01 2018-12-07 福建出入境检验检疫局检验检疫技术中心 A kind of method of polycyclic aromatic hydrocarbon in removing spirulina
CN108927114B (en) * 2016-08-01 2020-10-30 福建出入境检验检疫局检验检疫技术中心 Method for efficiently adsorbing polycyclic aromatic hydrocarbon in spirulina
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CN108940215B (en) * 2016-08-01 2020-12-22 福州海关技术中心 Method for removing polycyclic aromatic hydrocarbon in enrichment manner
CN106215823B (en) * 2016-08-23 2018-10-09 华南理工大学 Polymeric ionic liquid wrap up silicon dioxide microparticle composite material and its preparation method and in removal makes soy sauce carboxymethyl-lysine application
CN106215823A (en) * 2016-08-23 2016-12-14 华南理工大学 Polymeric ionic liquid wraps up silicon dioxide microparticle composite and preparation method thereof and the application of carboxymethyl-lysine in removal makes soy sauce
CN110387019A (en) * 2019-08-05 2019-10-29 河南师范大学 It is a kind of for removing the preparation method and applications of 2,4-D pesticide residue molecularly imprinted polymer
CN114644737A (en) * 2022-03-16 2022-06-21 陕西科技大学 Magnetic surface molecular imprinting electrochemical sensor and preparation method and application thereof
CN114644737B (en) * 2022-03-16 2023-07-28 陕西科技大学 Magnetic surface molecular imprinting electrochemical sensor and preparation method and application thereof

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