CN102989416B - Aflatoxin adsorbent and method for removing aflatoxins in edible vegetable oil - Google Patents
Aflatoxin adsorbent and method for removing aflatoxins in edible vegetable oil Download PDFInfo
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Abstract
The invention relates to an aflatoxin adsorbent and a method for removing aflatoxins in edible vegetable oil. An aflatoxin adsorbent is prepared through the steps of: under the action of a coupling agent, stirring oxidized graphene and aminopropyl silicagel microspheres at a temperature of 20-30 DEG C in a faintly acid environment so as to carry out amide coupling reaction; carrying out post-processing so as to obtain an oxidized graphene/aminopropyl silicagel microsphere composite material; and under the action of the coupling agent, stirring the obtained composite material and aflatoxin antibodies at a temperature of 0-4 DEG C in a faintly acid phosphate buffer solution so as to carry out the amide coupling reaction, and then carrying out post-processing to obtain the aflatoxin adsorbent. The aflatoxin adsorbent is good in adsorption effect, and can be used for adsorbing various aflatoxins; the aflatoxin adsorbent is granular, thereby facilitating the separation of the aflatoxin adsorbent after being used; and the aflatoxin adsorbent is applied to the removal of the aflatoxins in the edible vegetable oil, and can effectively reduce the pollution level of the aflatoxins in the edible vegetable oil.
Description
Technical field
The invention belongs to the grain and oil quality security fields, be specifically related to remove in a kind of aflatoxin adsorbent and the edible vegetable oil method of aflatoxin.
Background technology
Aflatoxin is the compound that a class chemical constitution is made up of two furan nucleus and cumarin.Studies show that the edible food that is subjected to aflatoxin contamination has very big infringement to the liver organization of people and animal, show as liver cell nuclear swelling, steatosis, hemorrhage, necrosis and epithelial duct, proliferation of fibrous tissue, can cause liver cancer even death when serious.Aflatoxin also can reduce immunocompetence simultaneously, brings out the tumour at positions such as multiple cancer such as cancer of the stomach, kidney, the carcinoma of the rectum, breast cancer, ovary and small intestine.Therefore, just being delimited by cancer research mechanism of the World Health Organization as far back as aflatoxin in 1993 is 1 class carcinogenic substance.
The occurring in nature Aspergillus flavus is widely distributed, causes aflatoxin extensively to be present in the oil and foodstuffses such as rice, corn, peanut, sesame, soybean, vegetable seed the serious threat mankind's life and health.In addition, the aflatoxin structure is extremely stable, generally cook processing temperature and it can not be destroyed, and solubility is lower in water, is difficult for flush away; So the food security event that is caused by aflatoxin takes place repeatedly.After dairy industry was found aflatoxin, edible vegetable oil also repeatedly spread out of the message that aflatoxin exceeds standard; Keeping the necessity of its normal activities and grease is the mankind, therefore, to the research that removes of aflatoxin in the edible vegetable oil, is an important component part avoiding the food security event to take place again and strengthen foodsafety.
Existing removal methods at aflatoxin in the edible vegetable oil generally can be divided into physics method, chemical method and bioanalysis three classes at present.The removal methods of biological and chemical has strict demand, control reaction condition difficulty for the humiture of environment and the pH value etc. that is removed material.Radiation method in the physical method, simple to operate, removal effect is obvious, but equipment is required height, and the cost energy consumption is big, and may destroy nutriment, also is unfavorable for its popularization.The removal methods that is expected at present is to add the adsorbents adsorb aflatoxin to remove purpose to reach in edible vegetable oil.But found adsorbent at grease comprises atlapulgite at present, though removal effects such as diatomite, montmorillonite are better, because the viscosity of grease is big, filters the adsorbent difficulty with commonsense method, can not satisfy the demand that grease is produced fast well.Therefore, study a kind of method of efficiently removing aflatoxin in the edible vegetable oil fast, for ensureing that human edible oil consumption safety is of great significance and value.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for removing aflatoxin in a kind of aflatoxin adsorbent and the edible vegetable oil at the deficiency of above-mentioned prior art existence.This aflatoxin adsorbent preparation is simple, and advantages of good adsorption effect can be used for adsorbing multiple aflatoxin; Be used for the removal of edible vegetable oil aflatoxin, can effectively reduce the level of pollution of aflatoxin in the edible vegetable oil.
The present invention solves the problems of the technologies described above the technical scheme that adopts to be:
A kind of aflatoxin adsorbent is characterized in that: it adopts following method to prepare:
(1) with graphene oxide and aminopropyl silica gel microball under action of coupling agents, in weak acid environment, the acid amides coupling reaction is carried out in 20-30 ℃ of stirring, obtain graphene oxide/aminopropyl silica gel microball composite through post processing then, wherein: mass ratio 1:400~500 of described graphene oxide and aminopropyl silica gel microball;
(2) with graphene oxide/aminopropyl silica gel microball composite and aflatoxin antibody under action of coupling agents, in the faintly acid phosphate buffer solution, the acid amides coupling reaction is carried out in 0-4 ℃ of stirring, obtain the aflatoxin adsorbent through post processing then, wherein: the mass ratio of described graphene oxide/aminopropyl silica gel microball composite and aflatoxin antibody is 450~550:1.
Press such scheme, the weak acid environment in the described step (1) refers to that pH is 5.5-6.5; Described coupling agent is 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, and the mass ratio of described coupling agent and graphene oxide is 10-12.5:1, and the described reaction time is 6-8h.
Press such scheme, graphene oxide in the described step (1) is to adopt chemical oxidization method to prepare graphite oxide crystalline flake graphite earlier, be dissociated into mono-layer graphite oxide alkene by high strength supersonic then, again through the centrifugal 1000rpm of choosing not sedimentation in centrifugal 2 minutes and the centrifugal 20min sedimentation of 8000rpm with remove do not have oxidation completely the graphene oxide fragment of graphite and little lamella obtain; The concentration of graphene oxide is 0.8-1g/L in described step (1) reaction system.Preferred 1000rpm not sedimentation in centrifugal 2 minutes and screen in the centrifugal 20min sedimentation of 8000rpm, can avoid centrifugation rate to cross low and may screen obtaining not oxidation graphite completely, and then cause the aflatoxin adsorbents adsorb efficient that finally makes not good, can avoid centrifugation rate too high and to cause screening the graphene oxide lamella that obtains too small again, and then cause its coupling effect difference and make the aflatoxin adsorbents adsorb poor effect for preparing for the preparation of the aflatoxin adsorbent time.
Described chemical oxidization method can adopt following method: as add nitration mixture and the potassium permanganate that sulfuric acid and phosphoric acid are formed in crystalline flake graphite, carry out preliminary oxidation reaction, form the graphite oxide that expands by hydrolysis then, the back is repeatedly washed purifying successively with hydrogen peroxide, hydrochloric acid and deionized water and is got final product.The mass ratio of potassium permanganate and crystalline flake graphite is preferably 6:1 when wherein adopting this method; The volume ratio of sulfuric acid and phosphoric acid is preferably 9:1; The mass fraction of described graphite in preliminary oxidizing process is preferably 0.70% ~ 0.75%, and the mass fraction in the end reaction system after hydrolysis is preferably 0.3% ~ 0.375%; Described preliminary oxidation reaction condition is preferably 50 ℃ of stirring reaction 12-48 hours.
Press such scheme, the ultrasonic power in the described step (1) be 800W or more than, ultrasonic time be 1h or more than.
Press such scheme, the pH of the faintly acid phosphate buffer solution in the described step (2) is 5.5-6.5, and concentration is 2-6mmol/L, and the described reaction time is 18-20h; Coupling agent in the described step (2) is 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, and the mass ratio of described coupling agent and aflatoxin antibody is 10-12.5:1.
Press such scheme, the concentration of coupling agent is 8-10 g/L in the reaction system of described step (2).
Press such scheme, the aflatoxin antibody in the described step (2) is aflatoxin universal antibody or aflatoxin b1 antibody.
Press such scheme, the post processing of described step (1) or (2) is centrifugal, carrying out washing treatment, and described cleaning solution is preferably the faintly acid phosphate buffer solution that pH is 5.5-6.5.
Take out the method for aflatoxin in a kind of food vegetable oil, it is characterized in that: it is that aflatoxin adsorbent with above-mentioned preparation is dispersed in the water, fully contacts to adsorb with edible vegetable oil then, leaves standstill to separate to the profit layering to get final product again.
Press such scheme, the aqueous dispersions of described aflatoxin adsorbent and the volume ratio of edible vegetable oil are greater than 1:5, described abundant contact is that the aqueous dispersions with the aflatoxin adsorbent mixed back room temperature gentle agitation at least 4 hours with edible vegetable oil, and described time of repose is 12~24 hours; Aflatoxin in the described edible vegetable oil can remove by the aflatoxin adsorbent that drops into respective amount fully according to the adsorption capacity of aflatoxin adsorbent.
Press such scheme, described edible vegetable oil is peanut oil, corn oil or peanut ready-mixed oil.
The present invention can realize that by the acid amides reaction bonding of graphene oxide and aminopropyl silica gel microball makes graphene oxide/aminopropyl silica gel microball composite earlier under imposing a condition down by the effect at coupling agent with graphene oxide and aminopropyl silica gel microball, and then adding aflatoxin antibody, then its COOH that contains and NH under the effect of coupling agent
2Group can be corresponding and graphene oxide or aminopropyl silica gel microball coupling bonding, and the three prepares the aflatoxin adsorbent with covalent bonds the most at last, the aflatoxin adsorbent that obtains thus has high-specific surface area and adsorption activity preferably because of graphene oxide on the one hand, direct adsorption of aflatoxin, the aflatoxin antibody that the while key is connected on the graphene oxide also can orientation be caught aflatoxin, finally by both synergies, in the limitation adsorption space of its structure, reach the removal effect of aflatoxin absorption preferably.Concrete experiment is also in conjunction with proof: the adsorption capacity of aflatoxin adsorbent provided by the invention (the aminopropyl silica gel microball of coupled oxidation Graphene and aflatoxin antibody simultaneously) obviously be better than single coupled oxidation Graphene and single coupling aflatoxin antibody aminopropyl silica gel microball adsorption capacity add and.
In addition on the one hand, the water-wet behavior that graphene oxide has in the aflatoxin adsorbent also is convenient to this adsorbent dissolving and is scattered in the suitable quantity of water, thereby reach with water be medium with pending edible vegetable oil contact to finish absorption, remove adsorbent by water oil content layer at last.And meanwhile, the graphite oxide ethylene linkage is connected on the aminopropyl silica gel microball, be combined with the aminopropyl silica gel microball, the use that can be convenient to this adsorbent especially uses the separation of back adsorbent to remove, be that the adsorbent that key connects behind the aminopropyl silica gel microball is graininess, after absorption is finished, can directly fall to the bottom of water layer behind the water oil content layer and be convenient to remove.
Beneficial effect of the present invention is:
(1) aflatoxin adsorbents adsorb provided by the invention is effective, can be used for adsorbing multiple aflatoxin, and actual application value is big; Be graininess, separate after easy to use;
(2) the method removal effect of taking-up aflatoxin is good in the food vegetable oil provided by the invention, can effectively reduce the level of pollution of aflatoxin in the edible vegetable oil, cost is low, and every 100mg aflatoxin adsorbent maximum can be adsorbed 70ng AFB1 and 10ng AFB 2; Simple to operate; The aflatoxin adsorbent is convenient to remove, and only needs leave standstill after finishing dealing with to separate to the water oil content layer to get final product.
The specific embodiment
Embodiment 1:
(1) aflatoxin preparation of adsorbent
The 3.0g crystalline flake graphite crossed join 400 mL sulfuric acid behind 325 mesh sieves and the phosphoric acid volume ratio is in the mixed solution of 9:1, stirred 10 minutes; Slowly add 18.0g potassium permanganate then in mixture, each addition is too much unsuitable, avoids reaction temperature to surpass 20 ℃.After treating that potassium permanganate all adds, be heated to 50 ℃ of stirring reactions 12 hours.After reaction finishes, allow mixture naturally cool to room temperature, be poured into ~ frozen water of 400mL in, continue stirring at room 0.5 hour, at last the 30wt% hydrogen peroxide is dropwise added reaction system and changes glassy yellow into to solution and stop.Standing over night, outwell supernatant, be the salt pickling 3 times of 5%-10% with the 1L mass fraction, then with 1L deionization washing 5 times, to remove metal ion, sulfate ion and chlorion with the solid freeze drying that obtains, place deionized water at last then, be made into the aqueous solution of 1 mg/mL, use ultrasonic echography 1h, ultrasonic power is 800W, treats that graphene oxide is dissociated into mono-layer graphite oxide alkene, with centrifuge 1000 rpm centrifugal 2 minutes, remove the i.e. oxidation graphene oxide completely not of sediment, 8000 rpm centrifugal 20 minutes then, and removing supernatant is little graphene oxide fragment, finally precipitate through 50 ℃ of dryings, be graphene oxide.
In the phosphate buffer that graphene oxide 20mg and the aminopropyl silica gel microball 10g of above-mentioned preparation joined 25ml 6mmol/L (PH=6.0), add 250mg 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride again, stirring at room 6-8h, the centrifugal supernatant that removes is unreacted graphene oxide lamella completely, clean 3 times with phosphate buffer, namely obtain graphene oxide/aminopropyl silica gel microball composite.
With synthetic graphene oxide/aminopropyl silica gel microball composite and 20mg aflatoxin b1 antibody and 250mg 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, (PH=6.0) 4 ℃ stirs 20h in the phosphate buffer of 25ml 6mmol/L, clean 3 times with phosphate buffer equally again, finally obtain the aflatoxin adsorbent.
(2) application of this aflatoxin adsorbent during AFB1 and B2 remove in peanut oil
Get 5.0g peanut oil and add 2 mL and contain in the aqueous solution of 500mg aflatoxin adsorbent, gentle agitation 4 hours, room temperature left standstill 12 hours.After treating water oil content layer, get upper strata peanut oil 2.0g, detect standby.According to the aflatoxin in GB/T 18979-2003 standard detection peanut oil,: the content of handling AFB1 in the preceding peanut oil is 110.33 μ g/kg, AFB 2 content are 26.57 μ g/kg, the content of handling AFB1 in the peanut oil of back is 40.09 μ g/kg, and AFB 2 content are 16.05 μ g/kg.The result shows thus: 500mg aflatoxin adsorbent can adsorb AFB1 and the 52.6ng AFB 2 of 351.2ng in the peanut oil.
(3) application during AFB1 is removed in corn oil is got 5.0g corn oil and is added the aqueous solution that 2 mL contain 100mg aflatoxin adsorbent, and gentle agitation 4 hours, room temperature left standstill 12 hours.After treating water oil content layer, get upper strata corn oil 1.6g, detect standby.Detect according to GB/T 18979-2003 standard, detection obtains: AFB1 content is 20.59 μ g/kg in the preceding corn oil of processing, and the content of handling AFB1 in the corn oil of back is 6.59 μ g/kg.(namely do not carry out after step (2) handles respectively, the AFB1 content of detection is respectively 12.59 μ g/kg and 18.59 μ g/kg to same corn oil with containing the aminopropyl silica gel microball (being that the aminopropyl silica gel microball directly adopts step (2) coupling aflatoxin b1 antibody) of 100mg coupling aflatoxin b1 antibody and the aminopropyl silica gel microball of coupled oxidation Graphene.The result shows thus: 100mg aspergillus flavus adsorbent can adsorb the AFB1 of 70ng in the peanut oil, and concrete analysis can get: its adsorption capacity obviously be better than single coupled oxidation Graphene and single coupling aflatoxin antibody aminopropyl silica gel microball adsorption capacity add and.
(4) application during AFB1 is removed in the peanut ready-mixed oil
Get 5.0g peanut ready-mixed oil and add the aqueous solution that 2mL contains 500mg aspergillus flavus adsorbent, gentle agitation 4 hours, room temperature left standstill 12 hours.After treating water oil content layer, get upper strata peanut ready-mixed oil 1.4g, detect standby.Detect according to GB/T 18979-2003 standard, detection obtains: AFB1 content is 53.37 μ g/kg in the preceding peanut ready-mixed oil of processing, and AFB1 does not detect in the peanut ready-mixed oil of processing back.
Embodiment 2
(1) aflatoxin preparation of adsorbent
Join in the mixed solution of sulfuric acid and phosphoric acid after crystalline flake graphite crossed 325 mesh sieves, stir; Slowly add a small amount of potassium permanganate then in mixture, each addition is too much unsuitable, avoids reaction temperature to surpass 20 ℃.After treating that potassium permanganate all adds, be heated to 50 ℃ of stirring reactions 12 hours.After reaction finishes, allow mixture naturally cool to room temperature, be poured into ~ frozen water of 400mL in, continue stirring at room, at last hydrogen peroxide is dropwise added reaction system and changes glassy yellow into to solution and stop.Standing over night, outwell supernatant, with salt pickling 3 times, wash 5 times with deionized water then, to remove metal ion, sulfate ion and chlorion, at last with the solid oxidation graphite freeze drying that obtains, place deionized water to be made into the aqueous solution then, treat that with ultrasonic echography graphene oxide is dissociated into mono-layer graphite oxide alkene, with centrifugal 2 minutes of centrifuge 1000 rpm, remove the i.e. oxidation graphene oxide completely not of sediment, 8000 rpm centrifugal 20 minutes then, removing supernatant is little graphene oxide fragment, finally precipitates drying, is graphene oxide.
Graphene oxide 20mg and the aminopropyl silica gel microball 8g of above-mentioned preparation are joined in the phosphate buffer of pH 6.5, add 200mg 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride again, stirring at room 6-8h, the centrifugal supernatant that removes is unreacted graphene oxide lamella completely, and washing obtains graphene oxide/aminopropyl silica gel microball composite.
With synthetic graphene oxide/aminopropyl silica gel microball composite and 18mg aflatoxin b1 antibody and 180mg 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, (PH=6.5) 0 ℃ stirs 18h in the phosphate buffer of 2mmol/L, clean 3 times with phosphate buffer equally again, finally obtain the aflatoxin adsorbent.
(2) application during AFB1 is removed in the peanut ready-mixed oil
Get 5.0g peanut ready-mixed oil and add the aqueous solution that 2mL contains 500mg aspergillus flavus adsorbent, gentle agitation 4 hours, room temperature left standstill 12 hours.After treating water oil content layer, get upper strata peanut ready-mixed oil 1.4g, detect standby.Detect according to GB/T 18979-2003 standard, detection obtains: AFB1 content is 53.37 μ g/kg in the preceding peanut ready-mixed oil of processing, and AFB1 does not detect in the peanut ready-mixed oil of processing back.
Aminopropyl silica gel microball described above can be buied or adopted and reported that at present literature method makes functionalized reagent with aminopropyl triethoxysilane and silica gel microball is carried out amino functional and get by Wuhan Hua Kewei section science and technology limited Company.
Claims (10)
1. aflatoxin adsorbent is characterized in that: it adopts following method to prepare:
(1) with graphene oxide and aminopropyl silica gel microball under action of coupling agents, in weak acid environment, the acid amides coupling reaction is carried out in 20-30 ℃ of stirring, obtain graphene oxide/aminopropyl silica gel microball composite through post processing then, wherein: mass ratio 1:400~500 of described graphene oxide and aminopropyl silica gel microball;
(2) with graphene oxide/aminopropyl silica gel microball composite and aflatoxin antibody under action of coupling agents, in the faintly acid phosphate buffer solution, the acid amides coupling reaction is carried out in 0-4 ℃ of stirring, obtain the aflatoxin adsorbent through post processing then, wherein: the mass ratio of described graphene oxide/aminopropyl silica gel microball composite and aflatoxin antibody is 450~550:1.
2. aflatoxin adsorbent according to claim 1, it is characterized in that: the weak acid environment in the described step (1) refers to that pH is 5.5-6.5; Described coupling agent is 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, and the mass ratio of described coupling agent and graphene oxide is 10-12.5:1, and the described reaction time is 6-8h.
3. aflatoxin adsorbent according to claim 1, it is characterized in that: the graphene oxide in the described step (1) is to adopt chemical oxidization method to prepare graphite oxide crystalline flake graphite earlier, be dissociated into mono-layer graphite oxide alkene by high strength supersonic then, again through the centrifugal 1000rpm of choosing not sedimentation in centrifugal 2 minutes and the centrifugal 20min sedimentation of 8000rpm with remove do not have oxidation completely the graphene oxide fragment of graphite and little lamella obtain; The concentration of graphene oxide is 0.8-1g/L in described step (1) reaction system.
4. aflatoxin adsorbent according to claim 3 is characterized in that: the ultrasonic power in the described step (1) be 800W or more than, ultrasonic time be 1h or more than.
5. aflatoxin adsorbent according to claim 1, it is characterized in that: the pH of the faintly acid phosphate buffer solution in the described step (2) is 5.5-6.5, and concentration is 2-6mmol/L, and the described reaction time is 18-20h; Coupling agent in the described step (2) is 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, and the mass ratio of described coupling agent and aflatoxin antibody is 10-12.5:1.
6. aflatoxin adsorbent according to claim 1, it is characterized in that: the concentration of coupling agent is 8-10 g/L in the reaction system of described step (2).
7. aflatoxin adsorbent according to claim 1, it is characterized in that: the aflatoxin antibody in the described step (2) is aflatoxin universal antibody or aflatoxin b1 antibody.
8. remove the method for aflatoxin in the food vegetable oil, it is characterized in that: it is that the described aflatoxin adsorbent of each claim among the claim 1-7 is dispersed in the water, fully contact to adsorb with edible vegetable oil then, leave standstill again to separate to the profit layering and get final product.
9. remove the method for aflatoxin in the food vegetable oil according to claim 8, it is characterized in that: the aqueous dispersions of described aflatoxin adsorbent and the volume ratio of edible vegetable oil are greater than 1:5, described abundant contact is that the aqueous dispersions with the aflatoxin adsorbent mixed back room temperature gentle agitation at least 4 hours with edible vegetable oil, and described time of repose is 12~24 hours; Aflatoxin in the described edible vegetable oil can remove by the aflatoxin adsorbent that drops into respective amount fully according to the adsorption capacity of aflatoxin adsorbent.
10. remove the method for aflatoxin in the food vegetable oil according to claim 8, it is characterized in that: described edible vegetable oil is peanut oil, corn oil or peanut ready-mixed oil.
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