CN110204654A - Aflatoxin surface imprinted polymer and its application based on HKUST-1 - Google Patents

Aflatoxin surface imprinted polymer and its application based on HKUST-1 Download PDF

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CN110204654A
CN110204654A CN201910507513.4A CN201910507513A CN110204654A CN 110204654 A CN110204654 A CN 110204654A CN 201910507513 A CN201910507513 A CN 201910507513A CN 110204654 A CN110204654 A CN 110204654A
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hkust
mips
afs
aflatoxin
sample
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何娟
许红
宋立新
芮超凡
李媛媛
游利琴
黄志鹏
王慧格
张云霞
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Henan University of Technology
Henan Vocational College of Water Conservancy and Environment
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Henan University of Technology
Henan Vocational College of Water Conservancy and Environment
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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Abstract

The invention belongs to molecularly imprinted polymer field, a kind of aflatoxin surface imprinted polymer and its crops context of detection application are disclosed.Selection metal-organic framework materials HKUST-1 is carrier, and 7- acetoxyl group -4- methylcoumarin is the alternate template of aflatoxin, synthetic surface imprinted polymer HKUST-1@MIPs.The polymer of synthesis is used as adsorbent and prepares surface imprinted solid-phase extraction column, aflatoxin in food is extracted and separated, a kind of quick, efficient, cheap aflatoxin sample-pretreating method is obtained, in conjunction with high performance liquid chromatography, the detection method of aflatoxin in the food that one kind is cheap, easy to operate, detection limit is low is had developed.Be conducive to develop crops Mycotoxin identification sample pre-treatments, solving the problem of current pre-treating method, at high cost time-consuming.

Description

Aflatoxin surface imprinted polymer and its application based on HKUST-1
Technical field
The invention belongs to molecularly imprinted polymer field, it is related to a kind of aflatoxin surface imprinted polymer and its farming Application in terms of analyte detection.
Background technique
Crops are easy the infection by fungi during growth, harvest, storage and processing to generate aspergillus flavus Toxin (Aflatoxins, AFs), AFs belong to one kind of mycotoxin, are that Aspergillus flavus infects the toxic generation generated after crops Thank to product, in human body some biosystems and organ have serious murder by poisoning and carcinogenesis effect.Aspergillus flavus generation The AFs for thanking to generation can be left in agricultural product, if agricultural product are processed to food, can cause to damage to human body after the mankind are edible Evil；If agricultural product are processed to forage feed livestock, AFs can assemble in livestock body, when people still can be by using meat products To the harm of AFs.AFs type is more, and the structure of variety classes AFs has some difference, wherein aflatoxin G 2, G1, B2 and B1 (AFG2, AFG1, AFB2 and AFB1) structure is similar, is four kinds maximum to the murder by poisoning of human body in AFs.
AFs has good stability, cannot be decomposed the AFs in crops by the methods of common illumination.Due to AFs is big to the pollution range of crops, type is more, and distribution is wide, and the crops in the area of every country all can be by the dirt of AFs Dye, such as peanut, corn and soybean, wheat, agaric, various fruit.Therefore, AFs in food has been formulated in countries in the world and area Limit standard.
AFs is increasingly subject to the concern of people to the pollution problem of food.It is how quick, quasi- from complicated food samples Really, effectively extraction and separation AFs becomes research hotspot.For AFs detection there are many middle method, using chromatography, spectroscopic methodology, Immunization, biosensor etc. can detect AFs.But the pretreatment process of actual sample is the spirit for restricting detection An important factor for sensitivity.Pretreatment process should be enriched with target substance, also want the interference of despumation, prevent the presence pair of impurity The sensitivity of detection impacts.Therefore, the pre-treating method for how establishing a kind of fast and efficiently AFs sample becomes research One of hot spot.
When detecting four kinds of AFs, various samples pre-treating method has been used.The first, sample pre-treatments use immune parent And column；Second, sample pre-treatments use solid phase extraction；The third, sample pre-treatments use immune affinity column；4th kind is Enzyme-linked Immunosorbent Assay screening method；5th kind is thin-layered chromatography.And this five kinds of pretreatment technologies are also the more mature place of technology The method for managing AFs.
Liquid-liquid extraction method is the solvability extraction AFs different to AFs using organic reagent.Therefore, liquid-liquid extraction method needs A large amount of organic reagent, such as methanol, acetonitrile are used, leads to the higher cost of pre-treatment, and can cause damages to environment.And And AFs is extracted from sample using organic reagent and need to be taken a substantial amount of time by liquid-liquid extraction method.Simultaneously as practical sample Product mesostroma is more complicated, and the impurity that can be dissolved in organic reagent is more, while using liquid-liquid extraction method extraction AFs, It is possible that other impurities are extracted into organic reagent together with AFs, to influence the accuracy of testing result.
Solid phase extraction, to the difference of the reserve capability of object in sample and impurity, can separate target by adsorbent Object and impurity.Usually the stationary phases such as silica gel, C18 are fitted into solid phase extraction column, solid-phase extraction column is made, utilize column packing AFs is enriched on column packing by the adsorption capacity of AFs, the poor solvent for choosing AFs washes away impurity, finally good molten with AFs Agent elutes AFs.The enrichment and purification of sample can be completed with a step by carrying out pre-treatment to AFs using solid-phase extraction column.Use solid phase Extraction column carries out pre-treatment to actual sample and has the advantage that easy to operate, saves reagent, favorable reproducibility, price is lower.But Stationary phase does not have specific adsorption ability to AFs, is easy for other impurities to be adsorbed onto stationary phase, will affect containing AFs sample Testing result.
Affine in immunity extraction is the principle for capableing of specific recognition using antigen in biology and antibody, with antigen-antibody In a side as the affine absorption AFs of aglucon.But the storage condition of immune affinity column is more stringent, and low temperature is needed to be protected It deposits, and the use of immune affinity column is being to need to use at normal temperature, which limits the uses of immune affinity column.And use is exempted from Epidemic disease is affine, and the cost of post detection actual sample is larger.
Enzyme-linked Immunosorbent Assay screening method is to carry out screening to AFs using the color reaction of enzyme.But Enzyme-linked Immunosorbent Assay sieves Accurate quantitative analysis can not be accomplished by looking into method detection AFs, if it is detected that containing AFs in sample, it is accurately fixed also to need to carry out using other methods Amount.
Existing AFs sample-pretreating method have the shortcomings that it is respective, it is a kind of cheap, applicable therefore, it is necessary to research and develop The pre-treating method of wide, high sensitivity the AFs of range.
Currently, using molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) MIPs conduct Adsorbent, prepare molecular engram solid phase extraction (Molecularly Imprinted Solid Phase Extraction, MIPSE) column is concerned by people for the technology of sample pre-treatments.It is not only easy to operate using MIPSE column, and extract and divide From can a step complete, also have to target substance carry out specific adsorption ability.Therefore molecular engram and Solid Phase Extraction phase In conjunction with can a step complete to the extraction of target molecule, enrichment, it is easy to operate and can be with automatic processing batch sample, before saving The time is handled, the error that operation generates is reduced, saves a large amount of organic reagents, it is beneficial to environmental protection and economic and practical, it saves Testing cost, can large-scale application in many aspects such as food safety, environmental protection, pesticide residue and explosive detections.
Although the method that molecular engram is combined with Solid Phase Extraction can effectively extract target molecule, traditional molecule There is also some disadvantages for imprinted polymer: being not easy completely to elute template molecule；Mass transfer rate is lower；Polymer form is not advised Then；More low (Wang Y, Yang Y, Lan X, the et al.Bisphenol A sensing based on of adsorbance surface molecularly imprinted,ordered mesoporous silica[J],Electrochimica Acta,2011,56(5):2105-2109.；Hongliang H,Xiaoli G,Liying S,et al.Molecularly imprinted polymers based on SBA-15for selective solid-phase extraction of baicalein from plasma samples[J],Analytical and Bioanalytical Chemistry,2015, 407 (2): 509-519.), and surface imprinted technology can make up disadvantage mentioned above well.Surface molecule print technology is common Method is to be grafted or be coated on surfaces of carrier materials for the imprinted polymer with action site, so that action site exposure Near surface, surface in molecular imprinted polymer on surface increase mass transfer rate and efficiency.Compared to traditional blotting techniques, surface Trace polymerization reaction occurs to allow to more be exposed to suction to the binding site of target molecule specific recognition in carrier surface The surface of enclosure material has bigger specific surface area, and mass transfer rate is higher, is conducive to the elution of template and recombines.
Surface imprinted polymer needs suitable carrier, and the selection of carrier affects the absorption property of surface imprinted polymer (Hu X,Xie L,Guo J,et al.Hydrophilic gallic acid–imprinted polymers over magnetic mesoporous silica microspheres with excellent molecular recognition ability in aqueous fruit juices[J],Food Chemistry,2015,179:206-212.).In order to reach Required morphosis, suitable partial size and aperture, the selection of carrier material are particularly important.Therefore novel, ratio is selected The carrier material that surface area is big, adsorption capacity is strong, and the analysis for being applied to toxin becomes more meaningful.Common carrier material Material has the features such as porosity, modified surface, and study more has graphene oxide, magnetic ferroferric oxide, carbon to receive at present Mitron and metal organic framework etc..Wherein metal-organic framework materials are as a kind of novel nano-material, because it is with high stable Property, that structure is easy to regulation, easy functionalization, synthesis condition is mild, cause extensive concern and research.It has no at present and utilizes metal Organic framework material prepares detection of the molecular imprinted polymer on surface for crops such as wheat toxin as carrier.
Summary of the invention
For the sample pre-treatments of mycotoxin in the crops such as wheat, present invention aims at develop it is a kind of quickly, Sensitive and cheap aflatoxin surface imprinted polymer substitutes immune affinity column, realizes that the crops such as wheat are yellow bent The detection of mould toxin.
Purpose to realize the present invention, technical solution are as follows:
The present invention with AFs to there is the compound 7- acetoxyl group -4- methylcoumarin of similar structures as template, selection gold Belong to the carrier that organic backbone (Metal-Organic Frameworks, MOFs) HKUST-1 is surface imprinted polymer.Metal has Machine framework material HKUST-1 has porous, large specific surface area, stable structure, the features such as being easily-synthesized.It is naked by the surface HKUST-1 The unsaturated action site Cu of dew2+With the coordination of the carbonyl and carboxyl of monomer and crosslinking agent, can be closed on the surface of HKUST-1 At one layer of molecularly imprinted polymer, to be prepared into AFs surface imprinted polymer HKUST-1@MIPs.
It is prepared especially by following method:
By HKUST-1 ultrasonic disperse in dehydrated alcohol, 7- acetoxyl group -4- methylcoumarin is weighed, monomer α-is added Methacrylic acid (α-MAA), ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate, EGDMA), Azodiisobutyronitrile (AIBN) is added, ultrasound is moved back into reaction flask, and ethyl alcohol is added, and heats magnetic agitation, the production that will be obtained Object is placed in dry object in baking oven.
Optimum condition: template molecule 7- acetoxyl group -4- methylcoumarin and α-MAA and EGDMA dosage ratio (mole Than) are as follows: 1:6:40,80 DEG C of reaction temperature.
By optimizing the ratio of α-MAA and EGDMA dosage, reaction temperature, template consumption etc. determines HKUST-1@MIPs table The polymer in face has maximal absorptive capacity to AFs.Again by adjusting addition HKUST-1 during synthesis HKUST-1@MIPs Amount, it is ensured that the polymeric layer on the surface HKUST-1@MIPs can be covered with the surface of HKUST-1, and thinner thickness.If synthesis The polymeric layer on the surface HKUST-1@MIPs is too thick, then adsorption site cannot be distributed in the surface of HKUST-1, influence HKUST-1@ The adsorbance and desorption rate of MIPs；If the polymeric layer on the surface HKUST-1@MIPs of synthesis cannot be covered with HKUST-1 completely Surface, expose HKUST-1, then will affect the adsorption capacity of HKUST-1@MIPs.
The surface imprinted polymer HKUST-1@MIPs that the present invention is synthesized is applied to sample and is poisoned as self-control column packing The separation and analysis of element carry out pre-treatment experiment to wheat samples, and analysis is found, the present invention makes column by oneself and good can select Property adsorption of aflatoxin, in terms of selectivity and adsorption capacity, the present invention makes column by oneself to the performance of the effect of aflatoxin more It is good.Adsorbance (6.0 μ g mgs of the HKUST-1@MIPs to aflatoxin-1)。
Comparison present invention self-control column, immune affinity column and commodity solid-phase extraction column imitate the processing of aflatoxin in wheat Fruit, the results showed that the present invention, which makes column by oneself, has better treatment effect to the actual sample containing aflatoxin.
The absorption property of surface imprinted polymer and imprinted polymer is compared, the measurement result of the rate of adsorption shows this hair The rate of adsorption of bright surface imprinted polymer can reach adsorption equilibrium in 5min, and faster mass transfer velocity is conducive to solid phase Processing of the extraction column to sample.
The extraction range of linearity of HKUST-1@MIPs column is 0.5 μ g kg-1-20μg kg-1, R2=0.9991-0.9996, it is yellow The detection limit of aspertoxin G2, G1, B2 and B1 are respectively 0.05 μ g kg-1, 0.02 μ g kg-1, 0.03 μ g kg-1With 0.05 μ g kg-1；Quantitative limit is respectively 0.2 μ g kg-1, 0.1 μ g kg-1, 0.15 μ g kg-1With 0.3 μ g kg-1.Aflatoxin G 2, G1, The recovery of standard addition of B2, B1 are 92.5%-118.4%, and relative standard deviation range is 3.14%-6.03%.This method is reliable With it is feasible, it is convenient and efficient and it is sensitive efficiently, can be used to substitute traditional immune affinity column processing analysis method.
Innovative point of the present invention: it using 7- acetoxyl group -4- methylcoumarin as alternate template, can reduce cost, exclude mould Plate leakage problem improves the accuracy of testing result；Using metal organic framework HKUST-1 as carrier, carrier material specific surface area Height, loose porous, stable structure, polymer can be grafted on carrier surface；Using surface imprinted technology, using coordination and Polymer is grafted on carrier surface, rather than is simply wrapped in carrier surface by covalent bond effect, and the method for grafting can make Carrier and the stronger combination of polymer, are not easy that polymeric layer is made to fall off from carrier surface, can preferably be used for actual sample Enrichment；Synthetic surface imprinted polymer specific surface area is high, mass transfer rate is fast, and elution rate is very fast, reusability is good；By this side Method combination HPLC-fluorescence detection device, in wheat aflatoxin separate, analyze provided with detection it is a kind of new low When cost, low consumption and highly sensitive detection method.
Detailed description of the invention
The SEM that Fig. 1 is HKUST-1 and HKUST-1@MIPs schemes；Wherein, the SEM figure of A, B:HKUST-1；C, D:HKUST- The SEM of 1@MIPs schemes；
Fig. 2 is the XRD diagram of HKUST-1 and HKUST-1@MIPs；
Fig. 3 is HKUST-1, the ATR-FT-IR of HKUST-1@NIPs and HKUST-1@MIPs schemes；
The absorption property that Fig. 4 is HKUST-1@MIPs compares；The isothermal of A:HKUST-1@MIPs and HKUST-1@NIPs is inhaled Attached curve；The adsorpting rate curve of B:HKUST-1@MIPs and MIPs；C: Lang Gemiaoer Tellurium determination matched curve；D: pseudo- Second-order kinetic equation matched curve；
Fig. 5 is the reusability histogram of HKUST-1@MIPs solid-phase extraction column；
Fig. 6 is actual sample testing result comparison diagram；A: non-mark-on soybean；B: mark-on soybean；C: non-mark-on rice；D: add Mark rice；E: non-mark-on peanut；F: mark-on peanut；G: non-mark-on wheat；H: mark-on wheat；I: non-mark-on corn；J: mark-on is beautiful Rice；
Fig. 7 is self-control column and immune affinity column testing result comparison diagram；The high-efficient liquid phase chromatogram of A:AFs standard specimen；B: warp The high-efficient liquid phase chromatogram of the processed mark-on sample of AFs immune affinity column；C:HKUST-1@MIPs solid-phase extraction column is processed Mark-on sample high-efficient liquid phase chromatogram.
Specific embodiment
It is as follows for embodiment for the present invention is better described:
Embodiment 1
(1) synthesis of HKUST-1
3.15g (15mmol) two (trichloromethyl) carbonic ester (BTC) is taken, 75mL ethyl alcohol, ultrasound, until BTC is completely molten is added Solution.Accurately weigh 6.05g (25mmol) Cu (NO3)2·3H275mL H is added in another beaker in O2O, ultrasound, until Cu (NO3)2·3H2O is completely dissolved.Mix the solution in two beakers, magnetic agitation 20min pours into hydrothermal reaction kettle, at 120 DEG C 12h is reacted, filtering three times using ethanol washing, removes unreacted BTC, is washed with water and washs three times, removes unreacted Cu (NO3)2·3H2O is filtered, and is dried at 150 DEG C, is obtained violet solid, as dewatered HKUST-1.
(2) synthesis of HKUST-1@MIPs
0.0654g (0.3mmol) 7- acetoxyl group -4- methylcoumarin is accurately weighed, is added 0.1518mL (1.8mmol) α-MAA, 2.2656mL (12mmol) EGDMA, add 0.04g AIBN, and ultrasonic 10min is moved back into there-necked flask, and second is added Obtained product is placed in baking oven dry by alcohol, the magnetic agitation 5h at 80 DEG C.
The synthesis process such as HKUST-1@MIPs (template is not added) of the non-imprinted polymer in surface (HKUST-1@NIPs).
By Fig. 1 it can be seen that the microstructure and surface feelings of the AFs surface imprinted polymer HKUST-1@MIPs of synthesis Condition, figure A and B are the SEM figures of HKUST-1, and figure C and D is the SEM figure of HKUST-1@MIPs.Compare HKUST-1@MIPs and The SEM of HKUST-1 schemes it can be seen that the surface texture of HKUST-1@MIPs and HKUST-1 have larger difference, in SEM camera lens Under, HKUST-1 structure is neat, and be positive octahedral structure, and for granular size at 20 μm or so, surface is smooth；HKUST-1@MIPs's Granular size is identical as HKUST-1, and surface can clearly be seen that polymeric layer, the thinner thickness of polymeric layer do not influence to carry The monnolithic case of body, identical as HKUST-1 shape, after graft polymers, HKUST-1@MIPs is also positive octahedral structure, still Surface has polymeric layer, short texture.If using the method for simple physically encapsulation by polymer wrapped in carrier HKUST-1 Surface, the polymer of carrier surface are easy falling off.And utilize MAA and EGDMA and HKUST-1 central ion Cu2+Coordination make With the surface that polymer is grafted to HKUST-1, polymer is more secured in conjunction with HKUST-1, and structure is more stable, Bu Hui Polymer is caused to separate with HKUST-1 in operating process.After polymer is grafted on the surface of HKUST-1, appearance becomes Change, causes HKUST-1@MIPs and HKUST-1 that different appearances is presented under scanning electron microscope.It can illustrate that MIPs is grafted to The surface of HKUST-1 successfully synthesizes AFs surface imprinted polymer HKUST-1@MIPs.
(3) characterization of HKUST-1@MIPs
HKUST-1 the and HKUST-1@MIPs synthesized on a small quantity is taken, is characterized using XRD, analysis of spectra, comparison MIPs connects The difference of branch polymer before and after HKUST-1.See Fig. 2.As seen from the figure, the characteristic diffraction peak and HKUST-1 of HKUST-1@MIPs Diffraction maximum it is identical, illustrate HKUST-1 with HKUST-1@MIPs have the identical structure in part, synthesize HKUST-1@MIPs after, The crystal structure of HKUST-1 is not destroyed.The peak height of the XRD spectra of HKUST-1 is higher than the XRD spectrum of HKUST-1@MIPs The peak height of figure.The reason of causing this phenomenon may be after being aggregated on the surface HKUST-1 due to MIPs, to affect X-ray Diffraction, to keep the X-ray diffraction luminous intensity of HKUST-1 with HKUST-1@MIPs different, it was demonstrated that the surface imprinted polymerization of AFs The successful synthesis of object HKUST-1@MIPs.
The HKUST-1 synthesized on a small quantity, HKUST-1@NIPs and HKUST-1@MIPs are taken, is characterized using ATR-FT-IR, Analysis of spectra, comparison MIPs are grafted on the difference of functional group contained by the polymer of the front and back HKUST-1.Determine that MIPs has been grafted on The surface HKUST-1.See Fig. 3.As seen from the figure, the ATR-FT-IR spectrum of HKUST-1, HKUST-1@NIPs and HKUST-1@MIPs: HKUST-1 is in 3350cm-1Hydroxyl group of the absorption peak at place from BTC, 1370cm-1And 1453cm-1The absorption peak at place comes from The C-O and C=O of BTC.The characteristic peak of the ATR-FT-IR figure of HKUST-1@NIPs and HKUST-1@MIPs is identical, HKUST-1@ MIPs has not contained 7- acetoxyl group -4- methylcoumarin.HKUST-1@MIPs and HKUST-1@NIPs is in 1739cm-1With 1150cm-1This has absorption peak at two, the C-O-C of stretching vibration and EGDMA respectively from the C=O double bond of MAA and EGDMA Asymmetric stretching vibration, and HKUST-1 does not have absorption peak at two at this, illustrates that MAA and EGDMA are carried out on the surface HKUST-1 Polymerization reaction.Moreover, the characteristic absorption peak of HKUST-1 and HKUST-1@MPS also appears in the ATR-FT- of HKUST-1@MIPs In IR spectrogram.The result shows that monomer α-MAA and crosslinking agent EGDMA are carried out on the surface HKUST-1 under the action of initiator Polymerization reaction, MIPs have been grafted to the surface of HKUST-1, successfully synthesize AFs surface imprinted polymer HKUST-1@MIPs.
Application examples 1
(1) preparation of actual sample
Rice, peanut, wheat, soybean and corn sample are all bought from local supermarket.Sample is broken into powder using pulverizer End is sieved (< 80 mesh).The sample for taking 5.0 ± 0.1g adds acetonitrile/water (84:16, v/v) solution of 20mL, shakes 20min, glass The filtering of glass fiber filter paper.The filtered solution of 4mL is taken, and the Tween-20PBS buffer solution of 46mL 1% is added, AFs is marked The load solution that can configure various concentration is added in sample in quasi- solution.
(2) column purification is made by oneself
It accurately weighs 200mg HKUST-1@MIPs and is used to prepare molecularly imprinted solid phase extraction column.With 10mL methanol to molecule Trace solid-phase extraction column is activated, then is washed away methanol with 10mL distilled water and taken target toxin out of to avoid methanol and cause pair The influence of target toxin concentration.Take 10mL corn actual sample extracting solution loading.It is eluted later with 10mL water to wash away impurity.Most It is eluted afterwards with 2mL hplc grade methanol, collects eluent, N2Lower drying, 2mL flow phased soln and use HPLC- with membrane filtration FD detects solution concentration.
(3) affine in immunity column purification
Immune affinity column is taken, is waited after liquid flow is complete in columns, with 50mL 1ng mL-1Actual sample extracting solution loading, 10mL Water elution, the elution of 2mL methanol.With membrane filtration, solution concentration is detected using HPLC-FD.
(4) absorption property of HKUST-1@MIPs
The absorption property of HKUST-1@MIPs is detected by adsorption isotherm experiment and rate of adsorption experiment, and is used The adsorption mechanism of Lang Gemiaoer Tellurium determination and pseudo second order kinetics equation research HKUST-1 MIPs.As the A of Fig. 4 schemes institute Show, uses 1 μ g mL-1To 100 μ g mL-1Various concentration AFs solution measure HKUST-1@MIPs and HKUST-1@NIPs couple The adsorption capacity of AFs.The result shows that two kinds of polymer all increases the adsorbance of AFs with the increase of AFs concentration.In 100 μ g mL-1Concentration under, HKUST-1@MIPs and HKUST-1@NIPs is to the maximal absorptive capacity of AFs respectively more than 42.11 μ g mg-1 With 17.94 μ g mg-1.Obviously, almost impossible containing the AFs for being higher than this concentration in actual sample, illustrate HKUST-1@MIPs It is completely suitable for the enrichment of AFs in actual sample.HKUST-1@MIPs is much bigger to the adsorbance ratio HKUST-1@NIPs of AFs, Showing that HKUST-1@MIPs has preferable adsorption capacity to AFs, HKUST-1@NIPs is weaker to the adsorption capacity of AFs, because HKUST-1@NIPs only has non-specific physical absorption to AFs, and adsorbance is smaller.Different from HKUST-1@NIPs to the non-of AFs Specific physical absorption, HKUST-1@MIPs is to the specific recognition site that the absorption of AFs is by the surface HKUST-1@MIPs It generates, the ability with specific adsorption AFs.The size and geometry of the specific recognition site on the surface HKUST-1@MIPs It is complementary with the size of AFs and geometry, and specific recognition site surface can form hydrogen bond with the functional group of AFs and make With to AFs with stronger adsorption capacity.Therefore, HKUST-1@MIPs is higher than HKUST-1@NIPs to the adsorbance of AFs.
As shown in the B figure of Fig. 4, with 10 μ g mL-1The rate of adsorption of AFs solution detection HKUST-1@MIPs and MIPs. HKUST-1 MIPs reaches adsorption equilibrium to the absorption of AFs in 5 minutes, and adsorbance is 6.0 μ g mg-1, it is shown that it is surface imprinted Quick adsorption ability of the polymer to AFs.It is and the HKUST-1@MIPs couple since the specific surface area of HKUST-1@MIPs is larger The specific recognition site of AFs is located at surface or the near surface of HKUST-1@MIPs mostly, therefore contacts HKUST-1@in AFs The surface MIPs is adsorbed, and reaches quick adsorption effect.And MIPs is adsorbed on that just to reach within 10 minutes or so absorption flat to AFs Weighing apparatus is suction of the specific recognition site to AFs inside MIPs since its most of recognition site is located at polymeric inner It is attached to need the longer time.Therefore, MIPs, which will reach adsorption equilibrium to the absorption of AFs, needs longer time, HKUST-1@MIPs With the rate of adsorption more higher than MIPs.In the preprocessing process to the actual sample containing AFs, HKUST-1@MIPs is used The more time can be saved, sample pretreatment efficiency is helped to improve, reduces experimental error.
As shown in the C figure of Fig. 4, HKUST-1 MIPs meets Lang Gemiaoer Deng Wenxifumoxing to the absorption of AFs, have compared with High R2It is worth (0.9970).It can be shown that HKUST-1@MIPs is to be similar to mono layer adsorption to the absorption of AFs, the suction to AFs Attached process occurs to illustrate the polymerization on the surface HKUST-1@MIPs on the surface@MIPs HKUST-1 or internal specific uniformly point Nitride layer is relatively thin, almost occurs on the surface of polymeric layer to the absorption of AFs, rather than is deep into inside.Therefore, HKUST-1@ The rate of adsorption of MIPs is higher than MIPs, and the polymeric layer on HKUST-1@MIPs is distributed in the surface of HKUST-1, polymerization Nitride layer can be entirely used for absorption AFs, and MIPs ball interior is not used to absorption AFs or adsorbance is very low, so MIPs will be weaker than HKUST-1@MIPs to the adsorption capacity of AFs.
As shown in the D figure of Fig. 4, HKUST-1@MIPs more meets The pseudo-second-order dynamic model to the absorption of AFs, have compared with High R2It is worth (0.9997).It can be shown that HKUST-1@MIPs is to there may be chemical actions in the adsorption process of AFs, without list It is physical absorption, it is similar with AFs structure, size by the α-MAA containing hydroxyl and EGDMA group illustrates that HKUST-1@MIPs has At adsorption site, when AFs enters the polymeric layer of HKUST-1@MIPs, the carbonyl shape of hydroxyl and AFs on adsorption site At hydrogen bond, AFs is firmly retained in the polymeric layer on the surface HKUST-1@MIPs.With the physical absorption phase of HKUST-1@NIPs Than the chemisorption of HKUST-1@MIPs has better adsorption capacity to AFs: faster, adsorbance is bigger for the rate of adsorption.
(4) reusability
The reusability of HKUST-1@MIPs is one of the key factor for influencing its application value.To detect HKUST-1@ The reusability of MIPs repeats six activation, loading, elution and elution on same branch HKUST-1@MIPs solid-phase extraction column Step.As shown in figure 5, with the increase for repeating washing steps, HKUST-1@MIPs solid-phase extraction column to the rate of recovery of AFs gradually It reduces, but reduced rate is slower, and the rate of recovery recycled at the 6th is still greater than 95%.The result shows that HKUST-1@ MIPs solid-phase extraction column is to the absorption/elution stability with higher and reusability of AFs, if by HKUST-1@MIPs Solid-phase extraction column can save testing cost for the pre-treatment containing AFs sample, have preferable practical value.
The evaluation of 2 method of application examples
With reference to national standard to the limitation of AFs in food, using sample substrate liquid as solvent, AFs is solute, is configured a series of The solution of concentration crosses HKUST-1@MIPs solid-phase extraction column, collects eluent and is detected into high performance liquid chromatograph.Such as table 1 Shown, the standard curve range of linearity of four kinds of toxin is 0.5 μ g kg-1-20μg kg-1, R2=0.9991-0.9996, it is linear good It is good, it can be used for carrying out the content of AFs quantitative calculating.The detection limit of AFG2, AFG1, AFB2 and AFB1 are respectively 0.05 μ g kg-1, 0.02 μ g kg-1, 0.03 μ g kg-1With 0.05 μ g kg-1；Quantitative limit is respectively 0.2 μ g kg-1, 0.1 μ g kg-1, 0.15 μ g kg-1With 0.3 μ g kg-1.Detection limit and quantitative limit are all far below country to the limitation of AFs in food, HKUST-1@MIPs column knot The method for closing high performance liquid chromatography-fluorescence device can be used for the detection of AFs in food.
Detection limit, quantitative limit and the range of linearity of 1 four kinds of AFs detection methods of table
For the reliability of verification method, recovery testu is carried out to four kinds of AFs.According to the HKUST-1@MIPs optimized The SPE condition of solid-phase extraction column sets 1 μ g kg-1、5μg kg-1With 10 μ g kg-1Three spiked levels carry out mark-on Recovery experiment, and calculate RSD.
The recovery of standard addition of 2 four kinds of AFs of table
The precision of 3 method of table
It can be learnt by table 2 and table 3: in 1 μ g kg-1、5μg kg-1With 10 μ g kg-1Under spiked levels, four kinds of AFs' plus The mark rate of recovery is 92.5%-118.4%, and RSD range is 3.14%-6.03%.To four kinds of AFs three concentration levels mark-on The relative standard deviation of the rate of recovery is respectively less than 15% specified in national standard method, illustrates HKUST-1@MIPs solid-phase extraction column For four kinds of AFs in food detection have the preferable rate of recovery and accuracy, can be used for AFG2, AFG1 in actual sample, The analysis detection of AFB2 and AFB1.The detection of 3 actual sample of application examples
It can be applied to the analysis detection of actual sample further to verify HKUST-1@MIPs solid-phase extraction column, take in room Lower wheat, rice, corn, peanut and the soybean sample for placing one month of temperature crosses HKUST-1 MIPs solid phase as actual sample Extraction column is detected into HPLC-FD.
As seen from Figure 6: wheat, rice, corn, peanut and soybean sample are stored under optimum conditions, it is possible to create AFs, type, the content for the AFs that different samples generate be not also identical.Soybean sample detects AFG1, AFB2, AFB1；Rice Sample detection goes out AFG2, AFG1, AFB2；Peanut sample detects AFG2, AFG1；Wheat samples detect AFG1, AFB2；Corn Sample detection goes out AFG1, AFB2.Before and after mark-on, the corresponding chromatography peak heights of different types of AFs are significantly different, AFs after mark-on Chromatographic peak increase.In the chromatogram for illustrating non-mark-on sample, AFs chromatographic peak corresponding with mark-on sample chromatogram figure is not miscellaneous Mass peak, but non-mark-on sample itself just contains AFs, by the enrichment of HKUST-1@MIPs column, in high-efficient liquid phase chromatogram It shows, it was demonstrated that HKUST-1@MIPs solid-phase extraction column can effectively extract the AFs in actual sample, can not only extract The higher AFs of content in mark-on sample is taken, the lower AFs of content in non-mark-on sample can be also extracted, can be used for variety classes AFs, difference AFs content actual sample detection.
Comparative example 1 makes column by oneself and immune affinity column compares
Further to verify practical application valence of the HKUST-1@MIPs solid-phase extraction column in food in the analysis detection of AFs Value, from the C of Fig. 7: the chromatographic peak peak shape of corresponding four kinds of toxin is preferable in chromatogram, can be kept completely separate four kinds of AFs, can determine Property can also quantitative analysis.The B and figure C of comparison diagram 7 are can be found that: HKUST-1@MIPs solid-phase extraction column and AFs immune affinity column There is preferable extracting power to the AFs in actual sample, two kinds of extraction columns are very nearly the same to AFG2 and AFB2 extracting power, but Compared to AFs immune affinity column, HKUST-1@MIPs solid-phase extraction column has better effect of extracting to AFG1 and AFB1.And HKUST-1@MIPs solid-phase extraction column lower production costs, it is cheap, it can reuse, stable structure and easy to maintain is answered It is extensive with prospect.

Claims (2)

1. a kind of aflatoxin surface imprinted polymer, which is characterized in that be prepared via a method which:
By HKUST-1 ultrasonic disperse in dehydrated alcohol, 7- acetoxyl group -4- methylcoumarin is weighed, monomer Alpha-Methyl is added Acrylic acid, ethylene glycol dimethacrylate add azodiisobutyronitrile, and ultrasound is moved back into reaction flask, and ethyl alcohol is added, adds Obtained product is placed in dry object in baking oven by pyromagnetic force stirring.
2. aflatoxin surface imprinted polymer as described in claim 1, which is characterized in that template molecule 7- acetyl oxygen The molar ratio of base -4- methylcoumarin and α-methacrylic acid and ethylene glycol dimethacrylate are as follows: 1:6:40, reaction temperature 80℃。
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CN111471147A (en) * 2020-05-19 2020-07-31 河南水利与环境职业学院 Double-template molecular amino functional metal organic framework imprinted polymer and synthetic method and application thereof
CN111499800A (en) * 2020-05-19 2020-08-07 河南水利与环境职业学院 Zearalenone surface imprinted polymer, synthesis method thereof and application thereof in grain detection
CN111471147B (en) * 2020-05-19 2022-12-09 河南水利与环境职业学院 Double-template molecular amino functionalized metal organic framework imprinted polymer, and synthetic method and application thereof
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CN113262766A (en) * 2021-05-17 2021-08-17 河南水利与环境职业学院 Aflatoxin porous aromatic skeleton PAF-6 molecularly imprinted material and application thereof
CN113262766B (en) * 2021-05-17 2023-03-21 河南水利与环境职业学院 Aflatoxin porous aromatic skeleton PAF-6 molecularly imprinted material and application thereof
CN113698621A (en) * 2021-09-15 2021-11-26 中国农业大学 Application of aluminum metal organic framework material in aflatoxin B1 detection
CN116338054A (en) * 2023-04-19 2023-06-27 广东维安检测科技有限公司 Detection method of aflatoxin B1 in traditional Chinese medicine based on liquid chromatography

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