CN113176365B - Colorant extraction column and detection method of artificially synthesized colorant in food - Google Patents
Colorant extraction column and detection method of artificially synthesized colorant in food Download PDFInfo
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Abstract
The application relates to the technical field of food colorant detection methods, and particularly discloses a colorant extraction column and a detection method for artificially synthesized colorants in food. The colorant extraction column comprises a tube body and an extraction column body fixed in the inner cavity of the tube body, wherein the extraction column body is prepared from the following raw materials, by weight, 8-15 parts of methyl acrylate organic matters, 40-50 parts of epoxy compounds, 3-8 parts of nano oxides, 10-20 parts of diallyl phthalate, 0.5-1 part of an initiator and 150-170 parts of a pore-foaming agent, and the detection method comprises the following steps: preparing a colorant extraction column, extracting a sample, purifying a colorant, and preparing a solution to be detected. The colorant extraction column of the present application can be used for the extraction of synthetic colorants, which improves the extraction efficiency of colorants. The detection method for artificially synthesizing the coloring agent in the food has higher detection accuracy.
Description
Technical Field
The application relates to the technical field of food colorant detection methods, in particular to a colorant extraction column and a detection method of artificially synthesized colorant in food.
Background
Colorants are a class of food additives, and are used primarily to color foods, enrich them with color, and improve their color. The colorant is divided into an artificial synthetic colorant and a natural colorant, the natural colorant is relatively unstable and is easily degraded in the food processing and storage processes, so that the food is poor in later-stage quality, and the stable performance of the artificial synthetic colorant makes up for the defects of the natural colorant and is widely used. However, food products contain excessive amounts of artificially synthesized colorants which are harmful to human health, and thus GB2760-2016 national food Standard additive for food safety sets forth maximum usage of artificially synthesized colorants.
The detection of the artificially synthesized colorant in China mainly adopts a high performance liquid chromatography, and the detection steps are as follows: adsorbing and extracting the colorant; removing impurities from the colorant; desorption of the colorant; and (4) measuring the sample. However, in the process of adsorption and extraction of the colorant in the related art, the artificially synthesized colorant with a sodium benzenesulfonate structure or a sodium benzoate structure is easily subjected to low extraction efficiency due to the influence of the matrix effect, and subsequent determination is influenced.
Disclosure of Invention
In order to improve the extraction efficiency of the colorant, the application provides a colorant extraction column.
The application provides a colorant extraction column adopts following technical scheme:
a colorant extraction column comprises a tube body and an extraction column body arranged in an inner cavity of the tube body, wherein the extraction column body is prepared from the following raw materials in parts by weight:
8-15 parts of methyl acrylate organic matter;
40-50 parts of an epoxy compound;
3-8 parts of a nano oxide;
10-20 parts of diallyl phthalate;
0.5-1 part of initiator;
150-170 parts of a pore-foaming agent;
the methyl acrylate organic matter is one or more of methyl methacrylate, methyl acrylate or hydroxymethyl methyl acrylate; the epoxy compound is glycidyl methacrylate; the nano oxide is nano silicon oxide or nano zirconium oxide; the pore-foaming agent is cetyl alcohol.
By adopting the technical scheme, the methyl propionate organic matter and the epoxy compound are polymerized in the presence of the initiator and the diallyl phthalate to form the extraction column body in the tube body, the pore-forming agent can enable the extraction column body in the tube to form a porous channel so as to facilitate the later extraction and synthesis of the colorant, the sample raw material can permeate into the porous channel, and after the methyl methacrylate, the methyl acrylate or the hydroxymethyl methacrylate reacts with the glycidyl methacrylate to generate the extraction column body, carboxyl can be generated in the extraction column body and can form hydrogen bonds with sulfonic acid groups or carboxyl groups in the colorant, so that the extraction capacity of the colorant is improved; and a large amount of hydroxyl on the surface of the nano oxide can form hydrogen bonds with the extraction column body, so that the nano oxide can be stably combined with the matrix, after the nano oxide is introduced into the extraction column body, the adsorption performance of the extraction column body on the colorant can be obviously improved by the nano oxide, and a large amount of hydroxyl on the surface of the nano oxide can form hydrogen bonds with synthetic colorants such as sodium benzenesulfonate and sodium benzoate, so that the extraction efficiency of the artificially synthesized colorant is obviously improved.
Preferably, the raw material also comprises 10-18 parts of ethylenediamine and 8-15 parts of tetrahydrofuran.
By adopting the technical scheme, the ethylenediamine can be dissolved in the tetrahydrofuran, the larger polarity of the tetrahydrofuran can enable the ethylenediamine to be adsorbed as much as possible and to react with the extraction column body at high temperature, so that the reaction of the ethylenediamine and the matrix is relatively more complete, and the ring opening of the epoxy group at the end of the extraction column body can react with the ethylenediamine to introduce the ethylenediamine, thereby improving the hydrophilic performance of the extraction column body and enhancing the adsorption capacity of the water-soluble colorant with sulfonic group or carboxyl group.
Preferably, the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
By adopting the technical scheme, any one of the three initiators can play a good initiating role in the reaction of the matrix, and the reaction byproducts are relatively less.
Preferably, the weight ratio of the ethylenediamine to the tetrahydrofuran is 1: (0.8-1).
By adopting the technical scheme, under the condition of the proportion of the ethylenediamine and the tetrahydrofuran, the tetrahydrofuran has relatively small influence on the reaction of the ethylenediamine and the epoxy groups in the extraction column, and the tetrahydrofuran can play a better solvent role to promote the reaction of the ethylenediamine and the matrix.
Preferably, the metal oxide is nano silicon oxide, the particle size of the nano silicon oxide is 30-45nm, and the specific surface area is 250m 2 /g。
By adopting the technical scheme, the nano silicon oxide has larger specific surface area, and the number of the hydroxyl groups on the surface of the nano silicon oxide is more, so that the prepared extraction column has better colorant adsorption effect, and hydrogen bonds are more easily generated with the extraction column, thereby increasing the content of the nano oxide in the extraction column.
In a second aspect, the application provides a method for detecting a food artificially synthesized colorant, which adopts the following technical scheme: a detection method of artificially synthesized food colorant comprises the following steps:
preparation of a colorant extraction column: weighing the raw materials according to the raw material proportion of the colorant extraction column, uniformly mixing the raw materials to obtain a raw material mixture, adding the raw material mixture into an inner cavity of a tube body, sealing two ends of the tube body, standing at 60-75 ℃ for reacting for 18-20h to obtain the tube body with an extraction column body, opening two ends of the tube body, washing the tube body with methanol for 3-5min, and drying to obtain the extraction column;
and (3) extracting a sample: weighing a sample, adding an extracting agent, uniformly vortexing, performing ultrasonic treatment, performing centrifugal separation, extracting supernatant, and adjusting the pH to 5-7 to obtain a sample solution;
purification of the colorant: injecting methanol and phosphate solution into an extraction column to pretreat the extraction column, injecting a sample solution into the extraction column, eluting the extraction column by using an eluent after the elution by using the phosphate solution, and collecting the eluent, wherein the eluent adopts a mixed solution of ammonia water and methanol with a volume ratio of 1;
preparing a solution to be detected: and blowing the elution liquid nitrogen upwards until the elution liquid nitrogen is nearly dry, and fixing the volume by using methanol to obtain a sample to be detected.
By adopting the technical scheme, the preparation of the colorant extraction column is carried out at 60-75 ℃ for reaction, and two ends are sealed, so that the components can be more stably fixed in a tube body after the reaction is finished and are not easy to fall off, the reaction is insufficient when the temperature is lower than 60 ℃, the adsorption effect in the subsequent adsorption process is reduced, and the initiator is high in activity or decomposed easily when the temperature is higher than 75 ℃, and the reaction is difficult to carry out or does not carry out; the reaction is controlled within 18-20h, the reaction can be incomplete when the reaction time is less than 18h, and the energy waste can be caused when the reaction time is more than 20 h; the extraction column prepared by the method has higher stability and can be repeatedly used for detecting the coloring agent; after the sample is subjected to vortex, ultrasonic treatment and centrifugation in sequence, the extractant can be fully contacted with the sample, so that the extraction effect is improved; before the sample solution passes through the extraction column, the extraction column can be activated by using methanol and phosphate solution, the effect of the extraction column on the adsorption of a coloring agent is improved, and the coloring agent can be well eluted by using an ammonia-methanol solution; and the mixed solution of ammonia water and methanol with the volume ratio of 1.
Preferably, in the step of preparing the colorant extraction column, before the step of extracting the sample, a mixed solution is added, wherein the mixed solution is a mixture of 10-18 parts of ethylenediamine and 8-15 parts of tetrahydrofuran, the two ends of a closed tube body are kept at a constant temperature of 70-80 ℃ for 3-5h, and the tube body is washed by water until the tube body is neutral and then dried.
By adopting the technical scheme, the reaction of the ethylenediamine and the matrix is relatively more sufficient within 70-80 ℃, the reaction of the ethylenediamine and the glycidyl methacrylate is possibly too violent above 80 ℃ and is not beneficial to the control of the reaction, and the tetrahydrofuran below 70 ℃ is possibly reacted with the extraction column to generate byproducts and influence the subsequent adsorption action of the extraction column.
Preferably, the phosphate solution used for pretreatment and rinsing in the colorant purification step has a pH of 4 to 6.
By adopting the technical scheme, the phosphate solution with the pH of 4-6 can play a good activating role on the extraction column, so that the extraction efficiency is relatively higher, and mainly because when the pH is maintained at 4-6, a static acting force and a hydrogen bond with higher acting force can be generated between the extraction column and the colorant.
In summary, the present application has the following beneficial effects:
1. the methyl propionate organic matter and the epoxy compound are crosslinked and polymerized to form a matrix composition in the tube body in the presence of an initiator and diallyl phthalate, the pore-forming agent can form a porous channel on the matrix in the tube so as to facilitate the later extraction and synthesis of the colorant, the sample raw material can permeate into the porous channel, and the carboxyl group in the methyl methacrylate, the methyl acrylate or the hydroxymethyl methacrylate can form a hydrogen bond with the sulfonic group or the carboxyl group in the colorant so as to facilitate the extraction of the colorant; hydroxyl on the surface of the nano oxide can form a hydrogen bond with glycidyl methacrylate, so that the nano oxide can be stably combined with a matrix, after the nano oxide is introduced into the extraction column, the adsorption performance of the extraction column to a colorant can be obviously improved by the nano oxide, and a large amount of hydroxyl on the surface of the nano oxide can form the hydrogen bond with synthetic colorants such as sodium benzenesulfonate and sodium benzoate, so that the extraction efficiency of the synthetic colorants is obviously improved;
2. the preparation of the colorant extraction column is carried out at 60-75 ℃ for reaction, and two ends are sealed, so that the components can be more stably fixed in a tube body after the reaction is finished and are not easy to fall off, the reaction is insufficient at the temperature lower than 60 ℃, the adsorption effect in the subsequent adsorption process is reduced, and the reaction is difficult to carry out or not carried out under the condition higher than 75 ℃, so that the activity of an initiator is high or the initiator is decomposed; after the sample is subjected to vortex, ultrasonic treatment and centrifugation in sequence, the extractant can be fully contacted with the sample, so that the extraction effect is improved; before the sample solution passes through the extraction column, the extraction column can be activated by using methanol and phosphate solution, the effect of the extraction column on the adsorption of a colorant is improved, and the colorant can be well eluted by using an ammonia-methanol solution;
3. the phosphate solution with the pH value of 4-6 can play a good activating role on the extraction column, so that the extraction efficiency is relatively higher, and mainly because when the pH value is maintained at 4-6, a static acting force and a hydrogen bond with higher acting force can be generated between the extraction column and the coloring agent; and the mixed solution of ammonia water and methanol with the volume ratio of 1.
Drawings
FIG. 1 is a chromatogram of a standard mixed solution of 9 synthetic colorants as provided herein;
FIG. 2 is a chromatogram of a sample tested according to the method of comparative example 1;
FIG. 3 is a chromatogram of a sample tested according to the method of example 1.
Detailed Description
The following examples further illustrate the present application in detail.
All reagents used in the application are commercially available and are analytically pure; the tube body is a glass tube with the inner tube diameter of 4mm and the tube length of 50 mm; the methyl acrylate organic matter is selected from hydroxypropyl methyl acrylate and purchased from Shanghai Mierel chemical technology Co., ltd; the initiator is dimethyl azodiisobutyrate purchased from Michelin, and the pore-forming agent is hexadecanol.
The application mainly tests 9 artificially synthesized colorants such as lemon yellow, new red, amaranth, indigo, carmine, sunset yellow, allura red, brilliant blue, erythrosine and the like in chocolate (candies).
Preparing a standard solution: mixing 9 artificially synthesized colorants, preparing into 10mg/L mixed solution with pH 6 pure water, storing in 4 deg.C refrigerator, diluting with pH 6 pure water to obtain 0.20mg/L, 0.50mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L, 10mg/L standard solutions, filtering with 0.22 μm microporous membrane (purchased from Shanghai famous membrane Co., ltd.), and storing in 4 deg.C refrigerator
Examples
The components and the proportions of the extraction columns in the colorant extraction columns in each example are shown in Table 1:
table 1 shows the components and proportions of the extraction columns in the colorant extraction columns of the examples
The extraction method for extracting the sample to be detected in each embodiment is as follows:
examples 1 to 3
Preparation of a colorant extraction column: cleaning and pretreating the inner cavity of the tube body by using an acetone solution in advance, weighing raw material substances according to the proportion in table 2 after the tube body is dried, ultrasonically mixing for 10min under the ultrasonic power of 100W, filling the mixture into the inner cavity of the tube body, sealing two ends of the tube body by using a sealing film, standing at 67 ℃ for reacting for 20h, pouring out redundant liquid in the tube body, injecting a methanol solution into the tube body, and washing off the pore-forming agent which does not participate in the reaction to obtain the extraction column;
and (3) extracting a sample: randomly crushing a commercially available chocolate sample into sample powder by using a crusher, crushing the sample powder into 150 meshes, weighing 1.0g of the sample powder, placing the sample powder into a 50mL centrifugal tube, adding an ammonia water and methanol mixed solution with a volume ratio of 1; adding 5mL of extracting agent into the residual residues, repeating the extraction step, extracting the supernatant again, combining the supernatant obtained twice, and adjusting the pH value to 5 by using a citric acid solution with the mass fraction of 20% to obtain a sample solution;
purification of the colorant: 5mL of methanol and 5mL of pH 5 at a concentration of 20 mmol.L were injected into the extraction column at a rate of 0.5mL/min -1 Potassium phosphate buffer solution, pretreating and activating the extraction column, injecting the sample solution into the extraction column at a rate of 0.5mL/min, and using pH of 5 and a concentration of 20 mmol.L -1 Eluting the extraction column by 0.5mL/min potassium phosphate buffer solution, removing the solution, injecting 5mL of ammonia water and methanol mixed solution with the volume ratio of 1:99 by 0.2mL/min, carrying out resolution elution with the mass fraction of the ammonia water being 5% and the mass fraction of the methanol solution being 70%, and collecting eluent;
preparation of a solution to be tested: and (4) blowing the eluent to be nearly dry by using a nitrogen blower (the nitrogen blowing temperature is 45 ℃), and fixing the volume to be 1mL by using a methanol solution to prepare the sample to be detected.
Examples 4 to 6
The difference from example 2 is that: after the preparation of the colorant extraction column and before the extraction of a sample, ethylene diamine and tetrahydrofuran are weighed according to the proportion in table 1 and mixed and then injected into the prepared extraction column, two ends of the extraction column are sealed by a sealing film and placed at 75 ℃ for constant temperature reaction for 5 hours, pure water is injected into the extraction column for washing until the removed liquid is neutral, and then the extraction column is dried for later use.
Example 7
The difference from example 5 is that: the nano oxide is selected from nano zirconia.
Example 8
The difference from example 5 is that: a pH 6 potassium phosphate buffer was used for the purification of the colorant.
Example 9
The difference from example 5 is that: the purification of the colorant used was potassium phosphate buffer solution having a pH of 4.
Example 10
The difference from example 1 is that: methyl methylolacrylate was replaced with methyl methacrylate.
Example 11
The difference from example 1 is that: methyl methylolacrylate was replaced with methyl acrylate.
Comparative example 1
The difference from example 1 is that: dimethyl azodiisobutyrate was replaced with dicyclohexyl peroxydicarbonate.
Comparative example
Comparative example 1
The colorant extraction was carried out on the samples by the polyamide adsorption method in GB 5009.35-2016, determination of synthetic colorants in food.
Comparative example 2
The difference from comparative example 1 is that: the raw material of the extraction column does not contain nano silicon oxide.
Performance test
Detecting 9 artificially synthesized colorants by using a K2025 high performance liquid chromatograph, wherein a chromatographic column is a Thermo Hypersil GOLD C18 liquid chromatographic column (1.7 mu m multiplied by 2.1mm multiplied by 100 mm), a mobile phase is methanol and a 20mmol/L ammonium acetate solution for gradient elution, the flow rate is 0.2L/min, the sample introduction amount is 1 mu L, and the temperature of the chromatographic column is 35 ℃; the elution procedure, the wavelength of each target compound and the switching time are shown in tables 2 and 3, respectively.
TABLE 2 elution procedure
| Time(min) | Flow rate (mL/min) | Methanol solution (vol%) | Ammonium acetate solution (vol%) |
| 0 | 0.2 | 5 | 95 |
| 2 | 0.2 | 15 | 85 |
| 4.5 | 0.2 | 95 | 5 |
| 6.7 | 0.2 | 80 | 20 |
| 7.3 | 0.2 | 15 | 85 |
| 10.5 | 0.2 | 5 | 95 |
TABLE 3 wavelength of detection and switching time of target Compounds
| Time (min) | Detecting colorants | Detection wavelength (nm) |
| 0 | Lemon yellow | 428 |
| 3.1 | Amaranth | 518 |
| 3.8 | New red | 527 |
| 4.5 | Indigo blue | 608 |
| 5.1 | Carmine and allura red | 506 |
| 5.4 | Sunset yellow | 480 |
| 6.1 | Bright blue | 625 |
| 6.8 | Erythrosine | 532 |
And testing the prepared standard solution by using a high performance liquid chromatography, wherein the series concentration of the mixed standard solution of each target compound is as follows: 0.20mg/L, 0.50mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L and 10mg/L, automatically drawing a standard curve by an instrument, taking a peak area as a vertical coordinate, taking a target compound concentration as a horizontal coordinate, drawing the standard curve, quantifying by an external standard method, and showing retention time, a regression equation, a correlation coefficient and a method detection limit of each target compound in a table 4.
TABLE 4 Retention time, regression equation, correlation coefficient and method detection limits for each target Compound
Detection method
And (3) performing recovery rate calculation and relative standard deviation calculation on the sample by adopting a standard recovery test: the content of each additive in the sample to be tested in each example was first measured, and then 3 kinds of standard sample solutions (with concentrations of 0.20mg/kg,0.4mg/kg, and 2.0mg/kg, respectively) were added to the pulverized sample powder to be sufficiently absorbed, and then the procedure in each example was followed, and 5 experiments were performed for each group of samples, and the average recovery rate and the relative standard deviation of the 5 experiments were calculated and recorded in table 5.
Table 5 shows the normalized recovery and relative standard deviation of each example and comparative example
In the embodiment of the application, the recovery rate of the standard adding concentration of 0.20mg/kg is 92.7-99.6%, and the relative standard deviation is 1.06-4.52%; in the examples of the present application, the recovery rate of the added standard concentration of 0.40mg/kg is 90.4-99.2%, and the relative standard deviation is 1.35-4.92% (not shown in the tables); the recovery in the examples of this application was 90.9-105.2% at a loading of 2.0mg/kg, and a relative standard deviation of 2.15-7.92% (not shown in tables).
Combining comparative example 1 and table 5, it can be seen that the normalized recovery for example 1 ranges between 93.4-98.0% with a relative standard deviation between 2.29-3.94%; the range of the normalized recovery rate of the comparative example 1 is 88.9-97.5%, the relative standard deviation is 2.38-5.49%, and the normalized recovery rate of the example 1 is obviously higher than that of the comparative example 1, which shows that the accuracy of the detection method of the example 1 is higher than that of the comparative example 1; compared with the method of using the polyamide adsorption method to extract the coloring agent from the sample in the comparative example 1, the matrix effect is larger in the detection, especially the influence of erythrosine is larger, probably because erythrosine is not easily adsorbed by polyamide powder under the acidic condition in the polyamide adsorption method,
in addition, as can be seen by combining fig. 2 and fig. 3, in the sample solution subjected to adsorption treatment by the polyamide powder, the content of erythrosine is obviously less than that after extraction in the embodiment 1 of the present application, and in addition, the erythrosine to be detected has more peaks near the peak and has certain influence; and the content of erythrosine detected by adopting the sample extracted in the embodiment 1 is obviously higher than that of erythrosine detected in the comparative example 1, and the influence on the detection result is relatively small because the miscellaneous peak near the erythrosine wave peak is relatively weak.
As can be seen by combining example 1 and comparative example 2 and by combining Table 5, the normalized recovery rate measured subsequently after the colorant extraction column of comparative example 2 does not contain nano-oxide is lower than that of example 1, and the relative standard deviation is in the range of 3.27-8.22%, which is significantly higher than that of example 1, and it is possible that the content of the colorant in the extracted sample is relatively low due to the fact that the number of hydroxyl groups capable of forming hydrogen bonds with the water-soluble artificially synthesized colorant in the extraction column is significantly reduced after the nano-oxide is reduced, and thus the normalized recovery rate is relatively poor.
Combining example 1 with examples 10 and 11 and combining table 5, it can be seen that the change of the standard addition recovery rate and the relative standard deviation after the methyl acrylate organic substance is changed into methyl acrylate or methyl methacrylate is relatively small, mainly because the performances of methyl methacrylate, methyl acrylate and hydroxypropyl methyl acrylate are the same, the difference of the molecular weights is small, and the activities of the three in the reaction are not very different.
Combining example 2 and example 4 with table 5, it can be seen that the range of normalized recovery for the pigment extraction column containing ethylenediamine in example 4 is 97.3-99.4%, significantly better than 94.6-98.5% in example 2, and the range of relative standard deviation for example 4 is 1.26-2.37% better than the relative standard deviation for example 2; after the ethylenediamine reacts with the glycidyl methacrylate of the colorant extraction column, the ethylenediamine molecule can improve the hydrophilicity of the colorant extraction column, thereby obviously improving the adsorption capacity on the water-soluble target colorant.
Combining example 5 and example 7 with table 5, it can be seen that when example 7 replaces the added nano-oxide with nano-zirconia, the normalized recovery of example 7 ranges from 96.4 to 99.2%, the relative standard deviation ranges from 1.96 to 3.07%, comparative example 5 is relatively poor and the accuracy is relatively low; probably, the adsorption effect on the target colorant is poor because the number of hydroxyl groups carried on the surface of the nano zirconia is relatively small and hydrogen bonds formed between the nano zirconia and the target colorant are relatively small.
It can be seen by combining examples 5, 8 and 9 with table 5 that when the pH of the potassium phosphate buffer solution activating the colorant extraction column and rinsing the colorant extraction column was changed, the normalized recovery and relative standard deviation of examples 8 and 9 were inferior to those of example 5, mainly because the potassium phosphate buffer solution had a relatively better activating effect on the colorant extraction column at a pH of 5.0, so that the electrostatic and hydrogen bonding between the target colorant and the colorant extraction column was relatively higher, while the electrostatic and hydrogen bonding generated may be decreased at a pH higher or lower than 5.0, resulting in a decrease in extraction efficiency.
When example 1 and comparative example 1 were combined and table 5 was used, it was found that when the initiator was changed to dicyclohexyl peroxydicarbonate, the recovery of the addition standard and the relative standard deviation were inferior to those of example 1, and the efficiency of the reaction initiated by the azo initiator was significantly higher than that of dicyclohexyl peroxydicarbonate; however, in the azo initiator, the azo diisobutyronitrile has relatively low activity, so that the preparation process is prolonged, the azo diisobutyronitrile has relatively high reactivity, the reaction process is not easy to control by workers, and the azo dimethyl diisobutyrate has moderate initiation activity and high conversion rate, so that the preparation of an extraction column is facilitated.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. A detection method for artificially synthesized food coloring agent is characterized by comprising the following steps:
preparation of a colorant extraction column:
comprises a tube body and an extraction column body arranged in the inner cavity of the tube body,
the extraction column body is prepared from the following raw materials in parts by weight:
8-15 parts of methyl acrylate organic matter,
40-50 parts of an epoxy compound,
3-8 parts of nano-oxide,
10-20 parts of diallyl phthalate,
0.5-1 part of azodiisobutyrate as an initiator,
150-170 parts of a pore-foaming agent;
the methyl acrylate organic matter is one or more of methyl methacrylate, methyl acrylate or hydroxymethyl methyl acrylate; the epoxy compound is glycidyl methacrylate; the nano oxide is nano silicon oxide or nano zirconium oxide; the pore-foaming agent is hexadecanol;
weighing the raw materials according to the raw material proportion of the colorant extraction column, uniformly mixing the raw materials to obtain a raw material mixture, adding the raw material mixture into an inner cavity of a tube body, sealing two ends of the tube body, standing at 60-75 ℃, reacting for 18-20h to obtain the tube body with an extraction column body, opening two ends of the tube body, washing the tube body with methanol for 3-5min, and drying to obtain the extraction column;
and (3) extracting a sample: weighing a sample, adding an extracting agent, uniformly vortexing, performing ultrasonic treatment, performing centrifugal separation, extracting supernatant, and adjusting the pH to 5-7 to obtain a sample solution;
purification of the colorant: injecting methanol and phosphate solution into an extraction column to pretreat the extraction column, injecting a sample solution into the extraction column, eluting the extraction column by using an eluent after the elution by using the phosphate solution, and collecting the eluent, wherein the eluent adopts a mixed solution of ammonia water and methanol with a volume ratio of 1;
preparing a solution to be detected: blowing the elution liquid nitrogen to be nearly dry, and performing constant volume by using methanol to prepare a sample to be detected;
in the preparation step of the colorant extraction column, before the extraction step of a sample, adding a mixed solution, wherein the mixed solution is a mixture of 10-18 parts of ethylenediamine and 8-15 parts of tetrahydrofuran, sealing two ends of a tube body, keeping the temperature at 70-80 ℃ for 3-5 hours, and washing the tube body to be neutral by water;
the detection method mainly tests 9 artificially synthesized colorants of lemon yellow, new red, amaranth, indigo, carmine, sunset yellow, allura red, brilliant blue and erythrosine; detecting 9 artificially synthesized colorants by adopting a K2025 high performance liquid chromatograph, wherein a chromatographic column is a Thermo Hypersil GOLD C18 liquid chromatographic column, a mobile phase is methanol and 20mmol/L ammonium acetate solution, and gradient elution is carried out according to the following elution procedures:
the wavelength and switching time of each target compound are as follows:
2. the method for detecting artificially synthesized food coloring agent according to claim 1, wherein: the weight ratio of the ethylenediamine to the tetrahydrofuran is 1:0.8-1.
3. The method for detecting artificially synthesized food coloring agent according to claim 1, wherein: the nano oxide is nano silicon oxide, the particle size of the nano silicon oxide is 30-45nm, and the specific surface area is 250m 2 /g。
4. The method for detecting artificially synthesized food coloring agent according to claim 1, wherein: in the step of clarifying the coloring agent, the phosphate solution used for the pretreatment and rinsing has a pH of 4 to 6.
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