CN103599619B - Electron beam irradiation is utilized to improve the method for ochratoxin A degradation effect in solution - Google Patents
Electron beam irradiation is utilized to improve the method for ochratoxin A degradation effect in solution Download PDFInfo
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- CN103599619B CN103599619B CN201310575254.1A CN201310575254A CN103599619B CN 103599619 B CN103599619 B CN 103599619B CN 201310575254 A CN201310575254 A CN 201310575254A CN 103599619 B CN103599619 B CN 103599619B
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Abstract
The invention discloses the method utilizing electron beam irradiation to improve ochratoxin A degradation effect in solution, be characterized in the ochratoxin A in the electron beam irradiation process aqueous solution adopting electron accelerator to produce, after process, water can produce the extremely strong OH of oxidisability, the aqueous electron that reproducibility is extremely strong by radiolysis
with H free radical, wherein OH free radical can with the phenyl ring of OTA and unsaturated bond generation addition reaction, aqueous electron
the Cl element of easy attack OTA, and make its dehalogenation; H free radical, after its dechlorination, adds to rapidly on group, causes OTA to degrade.The pH value of the ochratoxin A aqueous solution is adjusted to 7 ~ 10 when being irradiation by the process conditions of raising degradation effect; The initial concentration of solution is not higher than 200ng/mL, and during the irradiation dose 1 ~ 12kGy of employing, OTA degradation rate is more than 98%.The present invention is easy and simple to handle, Be very effective, the OTA during the OTA that can effectively degrade is water-soluble.
Description
Technical field
The present invention relates to the method utilizing electron beam irradiation to improve ochratoxin A degradation effect in solution, belong to fungi poison toxin and environmental technology field in degraded food.
Background technology
The poisonous secondary metabolite of one that OTA (ochratoxin A) is produced by Penicillium and aspergillus.OTA comparatively stablizes, not easily degrades, and be extensively present in occurring in nature, crops and feed become its main contaminated object, the health of serious threat human and animal.Great mass of data shows, OTA has certain carcinogenic, teratogenesis and mutagenicity, and strong renal toxicity, hepatotoxicity, neurotoxicity and immunotoxicity, and its toxicity is only second to aflatoxin.Within 1993, OTA is classified as 2B class carcinogenic substance by international cancer research institution.The GB2701-2011 " in food fungi poison toxin limitation " of Chinese revised in 2011, the limit standard (see table 1) of OTA in clear stipulaties food.
The limit standard of OTA in table 1 food
The method of degraded OTA has a lot, comprises physical method, chemical method, biological method etc., but these method great majority degradeds are thorough, complicated operation, destruction nutritional labeling etc., make it be restricted in actual production process.Irradiation-induced degradation technology is widely used in food storage and manufacture field because of features such as its reaction is thorough, speed is fast, non-secondary pollutions, effectively improves the security of food and extends the shelf life of product.
Electron beam is a kind of high beam electrons stream, has very high energy, effectively can kill the bacterium in food, insect pest, virus and degradable organic pollutant etc., can be used for the preservation and freshness of fruit, vegetables, meat and cereal.In recent years, electron beam irradiation degradative fungi toxin is subject to the extensive concern of scholar, but its degradation effect is by the impact of the many factors such as initial concentration, environment.Therefore, the OTA how efficiently in degraded solutions is the technical problem to be solved in the present invention.
Summary of the invention
The object of the invention is for above-mentioned present situation, by contrasting ray type, and the optimization of the irradiation technique condition such as solvent, initial concentration solution and pH, propose to utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution, effectively improve its degradation effect, this method be easy and simple to handle, Be very effective.
Technical scheme provided by the invention is:
Utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution, comprising:
Step 1, preparation initial concentration are lower than the ochratoxin A solution of 200ng/mL;
Step 2, the pH value of ochratoxin A solution is adjusted to 7 ~ 10;
Step 3, the electron beam irradiation ochratoxin A solution produced with electron accelerator, ochratoxin A in degraded solutions.
Preferably, the described electron beam irradiation that utilizes improves in the method for ochratoxin A degradation effect in solution, and in described step 1, the initial concentration of ochratoxin A solution is 50ng/mL.
Preferably, the described electron beam irradiation that utilizes improves in the method for ochratoxin A degradation effect in solution, and in described step 1, the solvent of ochratoxin A solution is water.
Preferably, the described electron beam irradiation that utilizes improves in the method for ochratoxin A degradation effect in solution, in described step 2, regulates the pH of ochratoxin A solution to 8 ~ 9.
Preferably, the described electron beam irradiation that utilizes improves in the method for ochratoxin A degradation effect in solution, and in described step 3, the intensity of the electron beam of irradiation ochratoxin A solution is 1 ~ 12kGy.
Preferably, the described electron beam irradiation that utilizes improves in the method for ochratoxin A degradation effect in solution, and in described step 3, the intensity of the electron beam of irradiation ochratoxin A solution is 10kGy.
Of the present inventionly devise the method utilizing electron beam irradiation to improve ochratoxin A degradation effect in solution.The present invention adopts electron beam irradiation to the OTA aqueous solution (the ochratoxin A aqueous solution), and the OTA aqueous solution is after electron beam irradiation, and aqueous solvent can produce the extremely strong OH of oxidisability, the aqueous electron that reproducibility is extremely strong by radiolysis
with H free radical, wherein OH free radical can with the phenyl ring of OTA and unsaturated bond generation addition reaction, aqueous electron
the Cl element of easy attack OTA, and make its dehalogenation; H free radical, after its dechlorination, adds to rapidly on group, causes OTA to degrade.Meanwhile, the present invention, by changing initial concentration and the initial pH value of the OTA aqueous solution, adopts electron beam to carry out irradiation-induced degradation to OTA, to improve its degradation effect further, under different initial concentrations and pH condition, and OH, aqueous electron in the OTA aqueous solution
with H free radical, corresponding change can occur, affect OTA degraded, in the basic conditions, the degradation effect of the OTA aqueous solution of low concentration is best.The present invention is easy and simple to handle, Be very effective, and the OTA during the OTA that can effectively degrade is water-soluble, OTA degradation rate is more than 98%.
Accompanying drawing explanation
Fig. 1 is flow chart of the present invention.
Fig. 2 be in the embodiment of the present invention 1 different ray on the impact of OTA irradiation-induced degradation effect.
Fig. 3 be in the embodiment of the present invention 2 different solvents on the impact of OTA irradiation-induced degradation effect.
Fig. 4 is that the initial concentration of the OTA aqueous solution in the embodiment of the present invention 3 is on the impact of OTA irradiation-induced degradation effect.
Fig. 5 is that the initial pH value of the OTA aqueous solution in the embodiment of the present invention 4 is on the impact of OTA irradiation-induced degradation effect.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail, can implement according to this with reference to description word to make those skilled in the art.
Embodiment 1, different ray affect OTA degradation effect
At ambient temperature,
OTA standard reserving solution is diluted with water to 100ng/ml, adopt respectively 0 ~ 10kGy electron beam and
60co-gamma-rays carries out radiation treatment.
Interpretation of result:
As shown in Figure 2, x-axis represents irradiation intensity, the ratio of the concentration after y-axis represents the initial concentration of OTA solution and degrades, and ■ represents electron beam, ● represent
60co-gamma-rays.
Ray type is different, and in solution, the degradation effect of ochratoxin A is also different.When dosage is lower, electron beam to the irradiation-induced degradation effect outline of OTA higher than
60co-gamma-rays.When 1kGy, its degradation rate is respectively 70.98% and 61.92%.Along with the increase of dosage, the increase of degradation rate tends to be steady.When 7.5kGy, the OTA under two kinds of radiation parameters is almost degradable.Its reason is that gamma-rays belongs to uncharged electromagnetic radiation, and the electron beam produced by high-energy electron accelerator is the electronics with negative electrical charge.Long-term large quantity research finds gamma-rays meeting initiated oxidation effect, and may there is reduction effect in electron beam irradiation process, can reduce oxidation effect to a certain extent.
Embodiment 2, different solvents affect OTA degradation effect
At ambient temperature,
OTA standard reserving solution water, acetonitrile, 60% methyl alcohol and hydrogen peroxide solution are diluted to 100ng/mL; Employing intensity is that the electron beam of 0 ~ 25kGy carries out radiation treatment.
Interpretation of result:
As shown in Figure 3, x-axis represents irradiation intensity, the ratio of the concentration after y-axis represents the initial concentration of OTA solution and degrades, ■ represents that the solvent of OTA solution is water, ● the solvent of expression OTA solution is acetonitrile, the solvent of ▲ expression OTA solution is 60% methyl alcohol, and ▼ represents that the solvent of OTA solution is hydrogen peroxide.
After electron beam irradiation, OTA is effectively degraded, and in these four kinds of solvents, the degradation rate of OTA increases along with the increase of dosage.Its reason is that irradiation dose is higher, just can produce more free radical, brings out more free radical and addition, substitution reaction occur OTA, and degrade more thorough, its degradation rate is also higher.The irradiation-induced degradation rate of solvent on OTA has significant impact.The degradation rate of OTA is followed successively by water > methanol solution >=acetonitrile solution > hydrogen peroxide solution.Solvent in OTA solution produces chemical reaction through irradiation, produces the extremely strong H free radical of the extremely strong OH of oxidisability, reproducibility and aqueous electron
these free radicals and OTA react, and cause it to degrade.The free radical that water produces through electron beam irradiation is maximum, and degradation rate is also the fastest.Methyl alcohol can catch OH free radical and aqueous electron
number of free radical reduces, thus inhibits the degraded of OTA.In this experiment, hydrogen peroxide concentration is higher, too much H
2o
2active more weak HO can be formed with OH free radical
2, thus reduce the degradation rate of OTA.Because acetonitrile is more stable, higher dosage just can lure certain free radical that solution irradiation produces into, participates in the degradation reaction of OTA, so its degradation rate rises suddenly when 10kGy.Therefore the solvent that the present invention selects is the aqueous solution.
Embodiment 3, initial concentration are tested the degradation effect of OTA in the aqueous solution
At ambient temperature,
The OTA aqueous solution of preparation 50ng/mL, 100ng/mL and 200ng/mL tri-kinds of variable concentrations, employing intensity is that the electron beam of 0 ~ 25kGy carries out radiation treatment.
Interpretation of result
As shown in Figure 4, x-axis represents irradiation intensity, the ratio of the concentration after y-axis represents the initial concentration of the OTA aqueous solution and degrades, and ■ represents that concentration is the OTA aqueous solution of 50ng/mL, ● represent that concentration is the OTA aqueous solution of 100ng/mL, ▲ represent that concentration is the OTA aqueous solution of 200ng/mL.
The degraded of initial concentration to OTA of the OTA aqueous solution has a certain impact.In three kinds of OTA aqueous solution, the degradation rate of OTA is followed successively by 50ng/ml > 100ng/ml > 200ng/ml, and namely low initial concentration is conducive to the degraded of OTA.When 5kGy, the degradation rate of the OTA aqueous solution of 3 kinds of variable concentrations all reaches more than 95%, and wherein the solution of 50ng/mL is almost degradable.Thereafter, the OTA aqueous solution degraded trend comparison of three kinds of concentration is steady.It is relevant that this mainly collides with the living radical that electron beam irradiation produces and OTA the probability combined.Electron beam intensity one timing, the living radical that water radiolysis produces is certain, and concentration is lower, and it is higher that OTA and free radical collide the probability combined, and degradation rate is higher.When the concentration is too high, living radical is not enough to all OTA molecules are all reacted, and therefore degradation rate declines.When the concentration in solution is too low, OTA molecule amount in unit volume solution is very few, to collide the probability combined very low with free radical, and just create from dieing out or reacting with other compounds in water, therefore the OTA aqueous solution degradation rate of three kinds of variable concentrations is more steady at high doses.Therefore suitably should reduce the initial concentration of the OTA aqueous solution.
Embodiment 4, pH value are tested the degradation effect of OTA in the aqueous solution
As shown in Figure 1, at ambient temperature,
The OTA aqueous solution of secure ph to be 4,7 and 10 initial concentrations be 50ng/mL respectively, adopts intensity to be that the electron beam of 0 ~ 10kGy carries out radiation treatment.
Structural analysis:
As shown in Figure 5, x-axis represents irradiation intensity, the ratio of the concentration after y-axis represents the initial concentration of the OTA aqueous solution and degrades, and ■ represents that pH value is the OTA aqueous solution of 4, ● represent that pH value is the OTA aqueous solution of 7, ▲ represent that pH value is the OTA aqueous solution of 10.
The degradation effect of initial pH value on OTA of the OTA aqueous solution has impact.Sour environment inhibits the degraded of OTA, and neutral and alkaline environment all can promote the degraded of OTA, and OTA degradation rate under alkaline environment is the highest.When 1kGy, under neutral and alkali condition, the degradation rate of middle OTA all reaches more than 98%, and under acid condition, degradation rate is 70.98%.In sour environment, H
+reproducibility can be consumed strong
thus in solution
concentration reduce, be unfavorable for the degraded of OTA; In alkaline environment, H free radical can become and OH
-reaction generates
and H
2o, now in solution
concentration raise, the degraded of OTA can be accelerated.Therefore the pH that the present invention adopts should more than 7.
Of the present inventionly devise a kind of method utilizing electron beam irradiation to improve ochratoxin A in degraded solutions.The present invention adopts electron beam irradiation to the OTA aqueous solution (the ochratoxin A aqueous solution), and the OTA aqueous solution is after irradiation, and aqueous solvent can produce the extremely strong OH of oxidisability, the aqueous electron that reproducibility is extremely strong by radiolysis
with H free radical, wherein OH free radical can with the phenyl ring of OTA and unsaturated bond generation addition reaction, aqueous electron
the Cl element of easy attack OTA, and make its dehalogenation; H free radical, after its dechlorination, adds to rapidly on group, causes OTA to degrade.Meanwhile, the present invention, by changing initial concentration and the initial pH value of the OTA aqueous solution, adopts electron beam to carry out irradiation-induced degradation to OTA, to improve its degradation effect further, under different initial concentrations and pH condition, and OH, aqueous electron in the OTA aqueous solution
with H free radical, corresponding change can occur, affect OTA degraded, in the basic conditions, the degradation effect of the OTA aqueous solution of low concentration is best.The present invention is easy and simple to handle, Be very effective, and the OTA during the OTA that can effectively degrade is water-soluble, OTA degradation rate is more than 98%.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (6)
1. utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution, it is characterized in that, comprising:
Step 1, preparation initial concentration are lower than the ochratoxin A solution of 200ng/mL;
Step 2, the pH value of ochratoxin A solution is adjusted to 7 ~ 10;
Step 3, the electron beam irradiation ochratoxin A solution produced with electron accelerator, ochratoxin A in degraded solutions.
2. utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution as claimed in claim 1, it is characterized in that, in described step 1, the initial concentration of ochratoxin A solution is 50ng/mL.
3. utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution as claimed in claim 2, it is characterized in that, in described step 1, the solvent of ochratoxin A solution is water.
4. utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution as claimed in claim 3, it is characterized in that, in described step 2, regulate the pH of ochratoxin A solution to 8 ~ 9.
5. utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution as claimed in claim 4, it is characterized in that, in described step 3, the intensity of the electron beam of irradiation ochratoxin A solution is 1 ~ 12kGy.
6. utilize electron beam irradiation to improve the method for ochratoxin A degradation effect in solution as claimed in any one of claims 1 to 5, wherein, it is characterized in that, in described step 3, the intensity of the electron beam of irradiation ochratoxin A solution is 10kGy.
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| CN105833459B (en) * | 2016-04-26 | 2019-01-11 | 中国农业科学院农产品加工研究所 | Application of the pseudomonas aeruginosa in degradation ochratoxin |
| CN106721926A (en) * | 2016-11-09 | 2017-05-31 | 中国农业科学院农产品加工研究所 | The method of irradiation-induced degradation ochratoxin |
| CN108225884B (en) * | 2017-12-15 | 2020-10-27 | 江南大学 | Combined degradation method of zearalenone and ochratoxin A in solution |
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| CN101485408A (en) * | 2009-03-02 | 2009-07-22 | 中国农业科学院农产品加工研究所 | Method for degrading aflatoxin |
| CN103039767A (en) * | 2013-01-22 | 2013-04-17 | 河南工业大学 | Method for improving use value of mildewed soybean by utilizing irradiation technique |
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| WO2002099142A2 (en) * | 2001-06-01 | 2002-12-12 | Wilhelm Holzapfel | Actinomycetes for breaking down aflatoxin b1, ochratoxin a and/or zearalenone |
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| KR101479526B1 (en) * | 2006-06-27 | 2015-01-26 | 더 텍사스 에이 앤드 엠 유니버시티 시스템 | Composition for the enterosoption and management of toxins comprising a calcium aluminosilicate clay |
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| CN1648056A (en) * | 2005-01-07 | 2005-08-03 | 南京大学 | Method for degradating microcystin RR in water using radiation |
| CN101485408A (en) * | 2009-03-02 | 2009-07-22 | 中国农业科学院农产品加工研究所 | Method for degrading aflatoxin |
| CN103039767A (en) * | 2013-01-22 | 2013-04-17 | 河南工业大学 | Method for improving use value of mildewed soybean by utilizing irradiation technique |
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