CN113670904A - Application of acidic electrolyzed water in preparation of preparation for removing residual antibiotic norfloxacin in food - Google Patents
Application of acidic electrolyzed water in preparation of preparation for removing residual antibiotic norfloxacin in food Download PDFInfo
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- 230000002378 acidificating effect Effects 0.000 title claims abstract description 109
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229960001180 norfloxacin Drugs 0.000 title claims abstract description 97
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
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- G—PHYSICS
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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Abstract
The invention relates to the technical field of acidic electrolyzed water, in particular to application of acidic electrolyzed water in preparation of a preparation for removing residual antibiotic norfloxacin in food. The invention creatively discovers that the acidic electrolyzed water has a new application of degrading the antibiotic norfloxacin, and verifies the influence of different proportions of acidic electrolyzed water content, different pH values and different soaking times on the degradation rate of norfloxacin solution through three methods. The invention points out a new development direction for exploring green and high-efficiency removal of antibiotic residues in food, and has wide industrial application prospect.
Description
Technical Field
The invention relates to the technical field of acidic electrolyzed water, in particular to application of acidic electrolyzed water in preparation of a preparation for removing residual antibiotic norfloxacin in food.
Background
Since the advent of penicillin, antibiotics have been widely used in various fields due to their excellent bacteriostatic ability, and have been widely used in the medical field. Meanwhile, the antibiotics also have important effects in the fields of animal husbandry, aquaculture, animal growth acceleration, animal disease prevention and treatment and the like, and the scale of animal and aquatic product cultivation is greatly improved. However, the unrestricted use of antibiotics by humans results in strong resistance of new bacteria, and now it is found that "super bacteria" which are not affected by antibiotics exist, and the animals and plants using antibiotics have the residual antibiotics used before in their excretions, and the excretions carry the residual antibiotics into the food chain through the natural circulation action such as water circulation, and the accumulation of the antibiotics in the food chain is further advanced, so that the ecological environment is greatly polluted and the health of human beings is seriously injured.
The antibiotics commonly used are of various types, such as quinolone antibiotics, which are widely distributed in domestic sewage and drinking water and are difficult to completely degrade in natural environments, and even if some of the quinolone antibiotics are photolyzed under natural conditions, the degree of photolysis is very low. In recent years, antibiotics in many foods exceed the standard, such as meat products, egg products, milk products and the like. Antibiotics accumulate in human bodies, so that the human bodies generate resistance to the antibiotics, and various tissue and organ diseases are caused. Therefore, to ensure food safety, antibiotic residues have been included in the regulatory detection range of food.
At present, a plurality of methods for degrading antibiotics comprise a physical degradation method, a chemical degradation method, a biological degradation method and the like, but most of the methods are applied to the environmental field, and reports on how to remove antibiotic residues in specific research foods at home are few. In particular, how to remove residual antibiotics without affecting the quality of food, and products produced by the reaction of newly added reactants and antibiotics do not affect the eating, and the research and reports related to the removal of residual antibiotics are few, so more attention is needed to the problem of removal of residual antibiotics in the field of food.
The acidic electrolyzed water is a colorless, transparent and safe disinfectant without obvious pungent smell. Compared with the traditional bactericide, the acidic electrolyzed water has the advantages of low cost, environmental friendliness, safety, simple and convenient preparation, easy removal from food and the like, and is widely applied to the fields of food, agriculture, medical treatment, livestock production, aquatic products and the like. However, at present, the acidic electrolyzed water is mainly used for sterilization and disinfection, and has not been reported in the aspect of antibiotic degradation.
Disclosure of Invention
The invention aims to provide application of acidic electrolyzed water in preparation of a preparation for removing residual antibiotic norfloxacin in food aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
application of acidic electrolyzed water in preparation of preparation for removing residual antibiotic norfloxacin in food.
In the technical scheme, the pH value of the acidic electrolyzed water is 3-6.
In the technical scheme, the volume ratio of the acidic electrolyzed water to the norfloxacin solution of 2mg/L is 1: 20-1: 1.
In the technical scheme, the volume ratio of the acidic electrolyzed water to the norfloxacin solution of 2mg/L is 1: 10.
In the technical scheme, the preparation containing the acidic electrolyzed water is used for soaking food in the form of aqueous solution, and the soaking time is not less than 10 min.
The invention has the beneficial effects that:
the invention discovers for the first time that the acidic electrolyzed water has a new purpose of degrading antibiotic norfloxacin, and the experiment verifies the clearance rate of the acidic electrolyzed water on norfloxacin solution through three methods, namely the influence of different proportions of acidic electrolyzed water content, different pH values of acidic electrolyzed water and different soaking times on the degradation rate of norfloxacin solution, and the result proves that: when the volume ratio of the acidic electrolyzed water to the norfloxacin is 1:10, the degradation rate can reach more than 80 percent, and the residual acidic electrolyzed water is not required to be removed from the food by spending too much time; when the pH value of the acidic electrolyzed water is 6, the norfloxacin degradation rate is the highest and reaches 73.91 percent, and the optimal pH value which can improve the degradation rate and is close to that of food is selected; when the acidic electrolyzed water is soaked in norfloxacin for 10 minutes, the highest degradation rate of 77.20 percent can be achieved. As shown above, the acidic electrolyzed water has the known sterilization and disinfection effects and also has the effect of degrading antibiotics such as norfloxacin. Therefore, the acidic electrolyzed water can be used for preparing a preparation for removing residual antibiotics in food, and the acidic electrolyzed water has the advantages of low cost, environmental friendliness, safety, easiness in preparation, easiness in removal from food and the like, so that the preparation can remove the residual antibiotics without influencing the quality of the food, and a product generated by the reaction of a newly added reactant and the antibiotics does not influence the eating. Therefore, the invention points out a new development direction for exploring green and high-efficiency removal of antibiotic residues in food, and has wide industrial application prospect.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a standard curve of the antibiotic norfloxacin of this example.
Detailed Description
The invention is further described with reference to the following examples.
The first experiment method comprises the following steps:
1. preparation of acidic electrolyzed water
The preparation of the acidic electrolyzed water needs to use sodium chloride, and the acidic electrolyzed water with the pH value of 3 can be produced only when the concentration of a sodium chloride solution reaches 18g/L through a plurality of experiments.
Weighing 18g of sodium chloride solid, pouring the sodium chloride solid into a beaker, dissolving the sodium chloride solid with tap water, using a glass rod to drain the sodium chloride solid, pouring the sodium chloride solid into a volumetric flask of 1L, using the tap water to fix the volume to 1L, uniformly shaking, pouring the mixture into an acidic electrolyzed water level generator, keeping the water levels on two sides consistent, adjusting the water production time to 15min, placing the beaker for receiving water, and waiting for 15min to obtain the acidic electrolyzed water.
2. Determination of norfloxacin standard curve
Norfloxacin is a medicine which is insoluble in water, but is easily dissolved in acetic acid, hydrochloric acid and sodium hydroxide solution, in the embodiment, hydrochloric acid solution with the concentration of 0.1mol/L is selected as a solvent, 0.2000g of norfloxacin reference substance is accurately weighed by an analytical balance, the norfloxacin reference substance is added into a 100.0mL volumetric flask, the volume is fixed to a scale by using 0.1mol/L hydrochloric acid solution, the norfloxacin reference substance is shaken up, 1.00mL of the norfloxacin reference substance is taken out, the norfloxacin reference substance is added into another 100.0mL volumetric flask, and the norfloxacin reference substance is added into the volumetric flask to be measured and used as the liquid to be measured.
Norfloxacin is a compound with a benzene ring and conjugated double bonds, has characteristic absorption in an ultraviolet region, and refers to data to know that a liquid sample to be detected has a maximum absorption peak at 277nm and auxiliary materials do not interfere at 277nm, so that 277nm is used as a measurement wavelength.
To 8 25mL cuvettes, 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, and 3.5mL of each of the solutions to be measured was added, diluted to 10.0mL with 0.1mol/L hydrochloric acid, and the absorbance of each sample was measured at a wavelength of 277nm using a 1cm quartz cuvette using 0.1mol/L hydrochloric acid solution as a reference solution, and a standard curve was drawn after the measurement.
A standard curve was plotted with norfloxacin concentration (mg/L) as the abscissa and absorbance as the ordinate, and the results are shown in FIG. 1. As can be seen from fig. 1, the linear fitting equation and the correlation coefficient are respectively: y is 0.1339x-0.0037, R2 is 0.9991, which shows that the absorption value and the concentration of norfloxacin standard have good linear relation in the range of 1-7 mg/L.
3. Influence of acidic electrolyzed water content with different proportions on norfloxacin degradation rate
As can be seen from the absorbance values of the standard curve, the absorbance value measured by the norfloxacin solution of 2mg/L is within a relatively suitable measurement range, so that the norfloxacin solution of 2mg/L is selected as the blank control in this example.
In the process of preliminary experiments, the fact that the acidic electrolyzed water can degrade antibiotics is found, and the influence of different proportions of the acidic electrolyzed water and the norfloxacin solution on the norfloxacin degradation rate is firstly researched. The higher the adding proportion of the acidic electrolyzed water is, the higher the norfloxacin degradation rate is, but the more the acidic electrolyzed water is added, the larger the workload of removing the acidic electrolyzed water in the later period is, so that a proper proportion that the acidic electrolyzed water is less in adding amount and can degrade norfloxacin in a large amount needs to be found.
In this example, different volumes of acidic electrolyzed water are added to 2mg/L of norfloxacin solution respectively, as shown in table 1, the volume ratios of the 2mg/L norfloxacin solution to the acidic electrolyzed water are respectively adjusted to 100:1, 80:1, 60:1, 50:1, 40:1, 20:1, 10:1, 1:5, 1:10, 1:20, 1:30 and 1:40, shaking is performed after each addition of the acidic electrolyzed water, the absorbance is immediately measured by using 0.1mol/L hydrochloric acid solution as a reference solution until the values of different concentrations do not change greatly, the absorbance of the 2mg/L norfloxacin solution and the acidic electrolyzed water at 277nm is measured at the same time, and the degradation rate of the acidic electrolyzed water to norfloxacin is calculated, wherein the calculation formula of the degradation rate is as follows:
TABLE 1 influence of acidic electrolyzed water on norfloxacin degradation rate
As can be seen from table 1, when the acidic electrolyzed water: when the volume ratio of norfloxacin is increased from 1:100 to 1:1, the degradation rate of norfloxacin is increased sharply, and the degradation rate is increased from 25.19% to 87.22%; continuously increasing the acid electrolyzed water: the norfloxacin degradation rate has little change according to the norfloxacin proportion, and when the norfloxacin proportion of the acidic electrolyzed water to the norfloxacin is 10:1, the norfloxacin degradation rate of the acidic electrolyzed water reaches the maximum value of 87.97%; further increasing the ratio of the acid electrolyzed water to the norfloxacin, and basically keeping the degradation rate of the norfloxacin unchanged. Although the degradation rate is highest when the ratio of the acidic electrolyzed water to the norfloxacin solution is 10:1, the difference between the acidic electrolyzed water and the norfloxacin solution is small and 1:1 is a very proper ratio. In addition, when the ratio of the acidic electrolyzed water to the norfloxacin solution is 1:10, the degradation rate can also reach more than 80%, but the addition amount of the acidic electrolyzed water is reduced by 90% compared with that of the acidic electrolyzed water with the ratio of 1: 1.
Therefore, the degradation rate of norfloxacin is not remarkably improved by adding excessive acidic electrolyzed water, and the separation of the acidic electrolyzed water from the product is increased. Considering the factors of cost and the like, the proportion of 1:10 is better to be selected in practical application, the degradation rate can reach more than 80%, and the residual acidic electrolyzed water does not need to be removed from the food by spending too much time.
4. Influence of acidic electrolyzed water with different pH values on degradation rate of norfloxacin solution
The acidic electrolyzed water is divided into three types, the pH value is below 3, and the acidic electrolyzed water is the strongly acidic electrolyzed water; the pH value is 5.0-6.5, and the water is weakly acidic electrolyzed water; the pH value is 5.0-6.5, and the water is subacid electrolyzed water. Strongly acidic electrolyzed water is mainly used for sterilization and disinfection in medical treatment, and weakly acidic electrolyzed water and slightly acidic electrolyzed water are more applied to foods and have been approved as food additives in japan because they are not harmful to human health.
According to the results of the proportion experiment, the ratio of the acidic electrolyzed water to norfloxacin is 1:50, so that the influence of the pH value on the degradation rate can be more visually seen, and a 0.1mol/L hydrochloric acid solution is used as a reference solution. Firstly, measuring the light absorption values of freshly prepared acidic electrolyzed water and norfloxacin solution, then measuring the pH value of the freshly prepared acidic electrolyzed water by using a pH meter, wherein the pH value of the freshly prepared acidic electrolyzed water is about 3, subpackaging the freshly prepared acidic electrolyzed water into four beakers, respectively adding 0.1mol/L sodium hydroxide solution, respectively adjusting the freshly prepared acidic electrolyzed water to four gradients of pH 3, pH 4, pH 5 and pH 6, respectively absorbing 10mL of norfloxacin solution, adding the norfloxacin solution into 25mL of colorimetric tubes, then adding 0.2mL of the acidic electrolyzed water with different gradients which are just prepared, shaking up, immediately adding the acidic electrolyzed water into a cuvette, placing the cuvette into an ultraviolet visible spectrophotometer to measure the light absorption value, and repeating the operation for four times. The influence of acidic electrolyzed water with different pH values on the degradation rate of the norfloxacin solution is measured, and the result is shown in Table 2.
TABLE 2 influence of pH of acidic electrolyzed water on degradation rate of norfloxacin solution
As can be seen from Table 2, when the pH of the acidic electrolyzed water is increased from 3 to 4, the degradation rate of the acidic electrolyzed water on the norfloxacin solution is not obviously increased; when the pH value of the acidic electrolyzed water is increased from 4 to 6, the degradation rate of the acidic electrolyzed water on the norfloxacin solution is continuously increased, but the amplification is strengthened; when the pH value is 6, the degradation rate of the norfloxacin solution by the acidic electrolyzed water reaches the maximum value of 73.91%.
In actual production, the pH value of the food is high or low, and from experimental results, the increase of the pH value is not obvious although the degradation rate is improved. Therefore, the pH value should be selected in consideration of the influence of the pH value on the state or sense of the food, taking into consideration the pH of the food actually used, and selecting a result that can increase the degradation rate and approach the pH value of the food to be optimal.
5. Influence of different soaking times on degradation rate of norfloxacin solution
In this example, a ratio of norfloxacin solution concentration of 2mg/L to 50:1 (norfloxacin: electrolyzed acidic water) was selected for the experiment, and 0.1mol/L hydrochloric acid solution was used as a reference solution. Firstly, measuring the light absorption values of freshly prepared acidic electrolyzed water and norfloxacin solution, preparing 8 colorimetric tubes with the volume of 25mL, respectively adding 10mL of norfloxacin solution into eight colorimetric tubes, simultaneously adding 0.2mL of freshly prepared acidic electrolyzed water after the norfloxacin solution is added, starting timing, and measuring the light absorption value of the solution to be measured in one colorimetric tube every five minutes until the data is not changed greatly stably. Since there was no change in absorbance data after 10min, data were measured for 0, 5, 10, 15, and 20min, respectively. The effect of acidic electrolyzed water on norfloxacin degradation rate is shown in table 3.
TABLE 3 influence of soaking time on degradation rate of norfloxacin solution
As can be seen from table 3, the soaking time is in a proportional linear relationship with respect to the degradation rate of the norfloxacin solution, but at the same time, the degradation rate of the norfloxacin solution by the acidic electrolyzed water tends to be unchanged with the contact of the acidic electrolyzed water with light and air, and when the soaking time lasts from 0 to 5 minutes, the degradation rate of the norfloxacin solution by the acidic electrolyzed water is obviously increased; when the soaking time is continued from 5 to 10 minutes, the degradation rate of the norfloxacin solution by the acidic electrolyzed water is continuously increased, but the amplification degree is reduced; and the degradation rate of the acidic electrolyzed water reaches a maximum value after the soaking time reaches 10min, the degradation rate tends to be stable, and the degradation rate is 77.2 percent, so that the acidic electrolyzed water can be removed from the food after being soaked for ten minutes when norfloxacin is degraded by the acidic electrolyzed water.
II, experimental results and analysis:
in this example, a standard curve of norfloxacin was determined, and three methods were used to verify the clearance of acidic electrolyzed water on norfloxacin solution, that is, the influence of acidic electrolyzed water content with different proportions on norfloxacin degradation rate, the influence of acidic electrolyzed water with different pH values on norfloxacin degradation rate, and the influence of different soaking times on norfloxacin degradation rate, and the experimental results are as follows:
(1) standard curve of norfloxacin (see fig. 1) the results show that norfloxacin solutions have a good linear relationship of absorbance to concentration in the range of 1-7 mg/L. The linear fitting equation and the correlation coefficient are 0.1339x-0.0037 for y and 0.9991 for R2, respectively.
(2) The influence of the acidic electrolyzed water content in different proportions on the norfloxacin degradation rate: when the ratio of the acidic electrolyzed water to norfloxacin is 1:10(V/V), the degradation rate can reach more than 80 percent, and the residual acidic electrolyzed water does not need to be removed from the food by spending too much time.
(3) Influence of acidic electrolyzed water with different pH values on degradation rate of norfloxacin solution: when the pH value of the acidic electrolyzed water is 6, the norfloxacin degradation rate is the highest, and the degradation rate reaches 73.91%. The increase in pH, while an increase in degradation rate, is not significant. The pH should be selected in consideration of the pH of the food product actually used, and a pH which can increase the degradation rate and is close to that of the food product is selected as an optimum.
(4) Effect of different soaking times on norfloxacin solution degradation rate: the highest degradation rate of 77.20% can be achieved after the acidic electrolyzed water is soaked in norfloxacin for 10 minutes.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. Application of acidic electrolyzed water in preparation of preparation for removing residual antibiotic norfloxacin in food.
2. The use of the acidic electrolyzed water according to claim 1 for preparing a preparation for removing residual antibiotic norfloxacin in food, characterized in that: the pH value of the acidic electrolyzed water is 3-6.
3. The use of the acidic electrolyzed water according to claim 1 for preparing a preparation for removing residual antibiotic norfloxacin in food, characterized in that: the volume ratio of the acidic electrolyzed water to the norfloxacin solution of 2mg/L is 1: 20-1: 1.
4. Use of acidic electrolyzed water according to claim 3 for preparing a preparation for removing residual antibiotic norfloxacin in food, characterized in that: the volume ratio of the acidic electrolyzed water to the norfloxacin solution of 2mg/L is 1: 10.
5. The use of the acidic electrolyzed water according to claim 1 for preparing a preparation for removing residual antibiotic norfloxacin in food, characterized in that: the preparation containing acidic electrolyzed water is used for soaking food in the form of aqueous solution for not less than 10 min.
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Citations (9)
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