CN105295053A - Citrinin molecular imprinting material and preparation method thereof - Google Patents
Citrinin molecular imprinting material and preparation method thereof Download PDFInfo
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- CN105295053A CN105295053A CN201510820898.1A CN201510820898A CN105295053A CN 105295053 A CN105295053 A CN 105295053A CN 201510820898 A CN201510820898 A CN 201510820898A CN 105295053 A CN105295053 A CN 105295053A
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- notalin
- molecular engram
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Abstract
The invention provides a citrinin molecular imprinting material using a supported ionic liquid as a carrier The invention also discloses a preparation method of the molecular imprinting material. The method is as below: (1) adding a citrinin structural analogue 1,4-naphthalic acid as a template molecule into a DMF solution, stirring to fully dissolve, adding a functional monomer supported ionic liquid, stirring for 30 min, then adding tetraethoxysilane and a catalyst ammonia, and incubating at a water bath of 40 DEG C for 24 h; and (2) conducting pumping filtration. The present invention has the advantages that the supported ionic liquid is introduced as the carrier to provide a large surface area, and a surface by sol-gel method is employed for the synthesis of the molecular imprinting material. The invention has the advantages of low cost, simple synthesis process, easy control of the reaction conditions, particle size uniformity, and higher selectivity of citrinin. The molecular imprinting material can be used for joint application of solid phase extraction enrichment and high performance liquid chromatography, and the combination can be used in separation and enrichment of citrinin in various food samples, and has broad application prospects.
Description
Technical field
The invention belongs to technical field of polymer materials, especially relate to molecular engram material of a kind of notalin and preparation method thereof.
Background technology
Notalin contains 3 methyl, and 1 carboxyl, is dissolved in hot alcohol, methyl alcohol, ethyl acetate, benzene, acetone, chloroform, is slightly soluble in ethanol, be insoluble in water, but is dissolved in dilute sodium hydroxide, sodium carbonate and sodium acetate soln.Notalin can form inner complex, but all can pyrolysis in acidity or alkaline environment.In dehydrated alcohol or benzol-cyclohexane, present lemon yellow needle crystal, its fusing point is 178 DEG C-179 DEG C.As a kind of mycotoxins, notalin has microbiotic, anti-microbial activity, antimycotic and protozoacide multifrequency nature.Notalin is except very strong Nephrotoxicity, and research finds that notalin can cause the minimizing of Dopamine HCL in mouse brain, the increase of suprarenin and norepinephrine, suppresses central nervous system, also has carcinogenic, mutagenesis, teratogenesis.Toxicity, notalin and aflatoxin can be mentioned in the same breath.
At present for notalin, the limit standard that China is also ununified is just 50 μ g/kg to regulation limitation in monascorubin product, but to the national standard method as still not relevant in corn, rice etc. of other agricultural-food and limit standard.In developed country, Japan is unique country allowing to use food color and monascus product, its regulation look valency is 50 units (E10%, 1cm) is benchmark (being equivalent to five Ge Se valency units of China red koji), and the limitation of contained notalin is 0.2 below μ g/g.Require more strict to the notalin in food and feeds in American-European countries, when general provision adopts HPLC method to detect, require must not detect notalin in analyte.In order to reduce the harm of notalin to human body, a set of unified limit standard should be set up in countries in the world.Along with people are to the quick rising of food safety attention rate, the rapid detection of toxin has become the development trend of research both at home and abroad.But it is long that thin film chromatography, liquid phase chromatography, gold test strip method and immune affinity column method have sense cycle, and needed for program complexity, reagent is various, testing cost crosses the shortcomings such as high, can not meet modern measure requirement far away.Along with the development of molecular imprinting and improving constantly of mycotoxins testing requirement, the application of molecular imprinting in mycotoxins detects is more and more extensive.Be filled in by molecularly imprinted polymer in solid phase extraction column, can be used for the separation of sample, purifying and concentrated, compared with antibody, molecularly imprinted polymer preparation process is simple, good stability, long service life.
Summary of the invention
In view of this, the invention is intended to invent a kind of molecular engram material notalin to highly selective.
For achieving the above object, the technical scheme of the invention is achieved in that
Adopt function monomer load-type ion liquid as carrier, synthesize a kind of notalin molecular engram material.The present invention utilizes function monomer load-type ion liquid for carrier, and surface sol-gel method synthesizes a kind of sorbing material for selective enrichment trace notalin.This material can be used as Solid-Phase Extraction material, can overcome the preprocessing process of environmental sample system complexity, and for the enrichment of sample provides great convenience with being separated, compared with immune affinity column, cost is also low.Play an important role in the trace analysis of field of food, there is usability.
Molecular engram material of the present invention has very strong recognition function to notalin.
The invention also discloses the preparation method of this molecular engram material:
A preparation method for notalin molecular engram material, comprises the steps:
(1) by the analog 1 of notalin, 4-naphthalic acid (KCB) joins in DMF solution as template molecule, stirring makes it fully dissolve, add function monomer load-type ion liquid, stir 30min, add tetraethoxysilane and catalyzer again, 40 DEG C of water-bath hatching 24h; Described catalyzer is ammoniacal liquor;
(2) suction filtration, first uses DMF drip washing, then is reactant with methyl alcohol drip washing, 50 DEG C of aging 8h of vacuum-drying; Above-mentioned polymkeric substance is placed in soxhlet's extractor, uses mixed solution that volume ratio is 8-10:1 methyl alcohol and glacial acetic acid as extraction solvent, repeatedly extract 48h, then use methanol extraction 12h, till detecting without KCB in extraction liquid.; 50 DEG C of vacuum-dryings, obtain the molecular engram material (MIP) notalin to highly selective.
Further, in step (1), the mass ratio of KCB and load-type ion liquid is 0.5-1:1; The volume ratio of tetraethoxysilane and catalyzer is 5-6:1.
Further, in step (2), methyl alcohol and glacial acetic acid volume ratio are after 48h carried by 8-10:1 rope, carry 12h with methyl alcohol rope, till detecting without KCB in extraction liquid.
Further, in step (1), the mass ratio of KCB and load-type ion liquid is 0.97:1; The volume ratio of tetraethoxysilane and catalyzer is 5.01:1.
Further, in step (2) methyl alcohol and glacial acetic acid volume ratio be this solution of 9:1 to after polymkeric substance surname extraction 48h, then with methyl alcohol to polymkeric substance surname extraction 12h, till detecting without KCB in extraction liquid.With function monomer load-type ion liquid for support, synthesize molecular engram material notalin to highly selective; The class material that the function monomer load-type ion liquid used is core is imidazole ring, structural formula be:
X
-＝Br
-、NTf
2 -、BF
4 -、PF
6 -
According to the method described above, but do not add template molecule KCB, the non-imprinted polymer (NIP) that preparation the present invention is corresponding.
Relative to prior art, the preparation method of the notalin molecular engram material described in the invention and be applied in during notalin detects there is following advantage:
The molecular engram material that the present invention utilizes surface sol-gel method to synthesize, has mass transfer velocity fast, and specific surface area is large, the advantage that grain diameter is homogeneous.This material can quick adsorption notalin, has strong selectivity to target compound; This material is chemically prepared, and has good stability, longer work-ing life.The present invention is with low cost, and experimental implementation is simple, easy control of reaction conditions, and obtained notalin molecularly imprinted polymer, as the filler of Solid-Phase Extraction and liquid chromatography coupling, is applicable to the separation and consentration of trace notalin in food.Compared with commercial immune affinity column, this material has easy to prepare, and selectivity is high, the advantage that cost is low.
Accompanying drawing explanation
The accompanying drawing of the part of formation the invention is used to provide the further understanding to the invention, and the schematic description and description of the invention, for explaining the invention, does not form the improper restriction to the invention.In the accompanying drawings:
Fig. 1 prepares schematic diagram for the molecularly imprinted polymer material described in the invention embodiment.
Fig. 2 is the FTIR spectrum figure of the load-type ion liquid described in the invention embodiment.
Fig. 3 is the FTIR spectrum figure described in the invention embodiment.
C load-type ion liquid, b molecularly imprinted polymer, the non-imprinted polymer of a.
Fig. 4 is the molecularly imprinted polymer described in the invention embodiment.
Fig. 5 is the scanning electron microscope (SEM) photograph of non-imprinted polymer.
Fig. 6 is for the molecularly imprinted polymer described in the invention embodiment and non-imprinted polymer are to the absorption property of the target compound KCB of different concns.
The curve of adsorption kinetics that Fig. 7 is the molecularly imprinted polymer described in the invention embodiment and non-imprinted polymer.
Fig. 8 is the specificity experiments of the molecularly imprinted polymer described in the invention embodiment.
Embodiment
In order to make the above-mentioned feature and advantage of the present invention clearly and easy understand, below in conjunction with accompanying drawing, embodiments of the present invention are described in further detail.
Load-type ion liquid described in following embodiment is oneself synthesis, and its synthetic method is as follows:
(1) three-necked bottle that 8.00g80-120 object silicon ball is placed in 250ml is taken, add 33% methanesulfonic aqueous solution 90ml, after carrying out back flow reaction 8h by induction stirring, solid matter is leached, the solid leached repeatedly is rinsed with distilled water, until the aqueous solution is in neutral, then be placed in vacuum drying oven, be adjusted to 70 DEG C of dry 8h.
(2) the activation silicon ball taking 1.5g is placed in the round-bottomed flask of 100ml, adds 50ml dry toluene, dropwise adds the two hydrogen imidazoles of 4600ulN-[3-(three ethoxy silylation) propyl group]-4,5-.At N
2under protection, 90 DEG C of backflow 14h.By the solid product washing with acetone be obtained by reacting, under vacuum dry 12h, obtain product A.
(3) product A taking 1.4g is placed in the round-bottomed flask of 100ml, adds 40ml dehydrated alcohol, adds the 3-propantheline bromide hydrobromide of 4g, at N
2under protection, 90 DEG C of backflow 14h, by the solid product washing with alcohol be obtained by reacting, dry 12h, obtains product B under vacuum.
(4) product B taking 0.8g is placed in the round-bottomed flask of 100ml, adds 30ml ethanol and 20mlKHCO
3the aqueous solution (0.25M), stirring at room temperature 30min.By the solid product washing with alcohol be obtained by reacting.Dry 12h, obtains load-type ion liquid under vacuum.
Other (KCB, notalin, tetraethoxysilane, ammoniacal liquor, DMF, methyl alcohol, acetic acid) are commercially available, without any process before using.
Embodiment 1
The invention provides a kind of preparation method of notalin molecular engram material, concrete syntheti c route as shown in Figure 1:
(1) by 0.6mmol1,4-naphthalic acid (KCB) joins in 1.7mlDMF, stir 15min to dissolving completely, add 100mg load-type ion liquid, continue to stir 30min, add 9mmol tetraethoxysilane subsequently, stirring reaction 30min, add 0.4ml ammoniacal liquor (3.0mol/L) again, stirring reaction 20min, 40 DEG C of water-bath hatching 24h;
(2) suction filtration, first uses DMF drip washing, then washes away unreacted reactant further with methyl alcohol, and 50 DEG C of aging 8h in vacuum drying oven, repeatedly extract 48h by the methanol acetic acid that volume ratio is 9:1, then use methanol extraction 12h, till detecting without KCB in extraction liquid.50 DEG C of vacuum-dryings, obtain the molecular engram material (MIP) notalin to highly selective.
According to the method described above, do not add KCB, the non-imprinted polymer (NIP) that preparation the present invention is corresponding.
In order to understand the performance of molecular engram material provided by the invention better, to synthesis, used base mateiral---load-type ion liquid has carried out FTIR spectrum sign.
Fig. 2 is the FTIR spectrum figure of load-type ion liquid.From the infrared colour spectrogram of load-type ion liquid, occur that aliphatic C-H vibrates (2943cm
-1and 2891cm
-1), the vibration (694cm of C-Si
-1), remain the vibration (800cm of Si-O
-1and 469cm
-1).And at 1658cm
-1there is the vibration peak of N-H in place, at 1554cm
-1and 1461cm
-1there is the vibration peak of imidazole ring in place.In sum, load-type ion liquid successfully synthesizes.
The FTIR spectrum figure of Fig. 3 load-type ion liquid, molecularly imprinted polymer and non-imprinted polymer.From infrared spectrogram, MIP with NIP has similar infrared spectrogram.The infrared spectrogram analyzing MIP is known, at 1094cm
-1there is the stretching vibration of Si-O-Si, at 800cm
-1and 465cm
-1there is the vibration of Si-0 in place.The infrared spectrogram of MIP compared with load-type ion liquid, at 1554cm
-1and 1461cm
-1place remains the vibration of imidazole ring, and the vibration peak of N-H in load-type ion liquid is by 1658cm
-1transfer to 1631cm
-1place.These results illustrate, load-type ion liquid, as a kind of function monomer, has successfully synthesized KCB molecularly imprinted polymer.
Fig. 4, Fig. 5 are the scanning electron microscope (SEM) photograph of molecularly imprinted polymer and non-imprinted polymer respectively.As can be seen from the figure molecularly imprinted polymer all becomes irregular spongy with the surface of non-imprinted polymer, and granular size is comparatively homogeneous, and there is a lot of holes on surface.
Embodiment 2
Study the absorption property (as shown in Figure 6) of this molecular engram material.The molecularly imprinted polymer of 4mg is placed in 2ml centrifuge tube, add respectively 1.5ml different concns (10,20,30,40,50,60,80,100,120,150,200mg/L) DMC methyl alcohol standardized solution, at room temperature vibrate 4h, and under 15 DEG C and 4000r/min centrifugal 15min.The supernatant liquor accurately pipetting 400 μ l is diluted to 4ml, measures the absorbance of KCB, according to the concentration of typical curve calculating K CB, finally calculate loading capacity at ultraviolet-visible spectrophotometer (λ=327nm) place.Simultaneously parallelly do non-imprinted polymer and test the adsorption selectivity of KCB, wherein molecularly imprinted polymer and non-imprinted polymer all need to do blank assay.As can be seen from Figure 6, along with the rising of KCB concentration, loading capacity increases gradually, finally keeps balance gradually.Under same concentrations, the loading capacity of molecularly imprinted polymer is greater than the loading capacity of non-imprinted polymer.
Embodiment 3
Study the dynamic performance (as shown in Figure 8) of this molecular engram material.The molecularly imprinted polymer of 4mg is placed in 2ml centrifuge tube, add the DMC methyl alcohol standardized solution of 1.5ml100mg/L, at room temperature vibrate 10 respectively, 20,30,40,60,90,120,160,200,300,360min, centrifugal 15min under 15 DEG C and 4000r/min condition.The supernatant liquor accurately pipetting 400 μ l is diluted to 4ml, measures the absorbance of KCB, according to the concentration of typical curve calculating K CB, finally calculate loading capacity at ultraviolet-visible spectrophotometer (λ=327nm) place.Simultaneously parallelly do non-imprinted polymer and test the adsorption selectivity of KCB, wherein molecularly imprinted polymer and non-imprinted polymer all need to do blank assay.As shown in Figure 7, imprinted polymer to target compound be adsorbed on 60min time almost reach balance.
Embodiment 4
Select the competitor that ochratoxin A (OTA) is notalin, study the selectivity of this molecular engram material.Compound concentration is the OTA of 1.0 μ g/L and the list mark solution of notalin respectively.The solution prepared by 4mL, by solid phase extraction column, by methanol-eluted fractions, detects with high performance liquid chromatography.As shown in Figure 8, illustrate that molecularly imprinted polymer has selective recognition to notalin.
The foregoing is only the preferred embodiment of the invention; not in order to limit the invention; within all spirit in the invention and principle, any amendment done, equivalent replacement, improvement etc., within the protection domain that all should be included in the invention.
Claims (7)
1. a notalin molecular engram material, is characterized in that, using function monomer charge type ionic liquid is carrier.
2. the preparation method of a kind of notalin molecular engram material described in claim 1, is characterized in that, comprise the steps:
(1) the analog KCB of notalin is joined in DMF solution as template molecule, stir and make it fully dissolve, add function monomer load-type ion liquid, stir 30min, then add tetraethoxysilane and catalyzer, 40 DEG C of water-bath hatching 24h;
(2) step (1) products therefrom is first used DMF drip washing, then remove unreacted reactant with methyl alcohol drip washing, 50 DEG C of aging 8h of vacuum-drying; Reaction product after aging is put in soxhlet's extractor, washes away template molecule; 50 DEG C of vacuum-dryings, obtain molecular engram material notalin to highly selective.
3. the preparation method of a kind of notalin molecular engram material according to claim 2, is characterized in that: in step (1), the mass ratio of KCB and load-type ion liquid is 0.5-1:1; The volume ratio of tetraethoxysilane and catalyzer is 5-6:1.
4. according to the preparation method according to a kind of notalin molecular engram material according to claim 2, it is characterized in that: washing away template molecule in step (2) is use volume ratio for after 8-10:1 methyl alcohol and glacial acetic acid mixing solutions surname extraction 48h, use methyl alcohol surname extraction 12h again, till detecting without KCB in extraction liquid.
5. the preparation method of a kind of notalin molecular engram material according to claim 2, is characterized in that, step (1) described catalyzer is ammoniacal liquor.
6. the preparation method of a kind of notalin molecular engram material according to claim 2, is characterized in that: in step (1), the mass ratio of KCB and load-type ion liquid is 0.97:1; The volume ratio of tetraethoxysilane and catalyzer is 5.01:1.
7. a kind of notalin molecular engram material described in claim 1, is characterized in that, for the rapid detection of notalin in food.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109293938A (en) * | 2018-10-11 | 2019-02-01 | 河南工业大学 | Prepare the composite material of metallic framework compound binding molecule imprinted polymer |
| CN112174990A (en) * | 2020-09-16 | 2021-01-05 | 陕西科技大学 | Preparation method of imidazole ionic liquid modified phenylboronic acid material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293938A (en) * | 2018-10-11 | 2019-02-01 | 河南工业大学 | Prepare the composite material of metallic framework compound binding molecule imprinted polymer |
| CN112174990A (en) * | 2020-09-16 | 2021-01-05 | 陕西科技大学 | Preparation method of imidazole ionic liquid modified phenylboronic acid material |
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