CN110988214A - Method for detecting chloropropanol in hydroxypropyl modified starch - Google Patents
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Abstract
The invention discloses a method for detecting chloropropanol in hydroxypropyl modified starch. The method comprises the following steps: s1, adding a solvent into a sample to be tested, carrying out ultrasonic extraction, and filtering to obtain a subsequent filtrate, namely a test sample solution; s2, taking a 1-chloro-2-propanol solution as a reference solution, diluting the reference solution with a solvent to obtain a sensitivity test solution, and diluting chloropropanol with the solvent to obtain a system applicability solution; and (4) respectively carrying out gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution, and judging whether the sample to be detected contains chloropropanol or not according to the determination result. The method is convenient to operate, good in specificity, high in accuracy and high in sensitivity, can realize qualitative and quantitative detection of chloropropanol in hydroxypropyl modified starch, and has wide popularization and application prospects.
Description
Technical Field
The invention belongs to the technical field of food and drug safety detection. More particularly, relates to a method for detecting chloropropanol in hydroxypropyl modified starch.
Background
The chloropropanol is an internationally recognized food pollutant and has genotoxicity, under the condition of no activation system, the mutagenicity dose of the chloropropanol is 5-10 mg/mL, and the oral dose of a rat is 10mg (kg · bw) after continuous 5 days-1·d-1、31mg·(kg·bw)-1·d-1、100mg mg·(kg·bw)-1·d-1Compared with a control group, the test group has a dose effect relationship on chromosome aberration, and the aberration is mainly dye monomer fracture when the chloropropanol mixed solution (comprising 75% by mass of 1-chloro-2-propanol and 25% by mass of 2-chloro-1-propanol) is used. Therefore, the chloropropanol content of the food needs to be strictly controlled.
Hydroxypropyl modified starch is prepared by reacting starch with propylene oxide, is often used as a thickening agent, a suspending agent and the like in the food industry, and can generate chloropropanol which is harmful to human bodies due to the use of chlorine-containing inorganic salt in the production process. The content of chloropropanol in hydroxypropyl modified starch is less than or equal to 1mg/kg as specified in the United states food additive Joint experts Committee and the United states food chemical Pharmacopeia, and the content of chloropropanol (1-chloro-2-propanol and 2-chloro-1-propanol) is less than or equal to 1mg/kg as also specified in the national standard.
At present, the existing method for detecting chloropropanol in hydroxypropyl modified starch mainly comprises a gas chromatography and solid phase extraction-gas chromatography-mass spectrometry combined method. When gas chromatography is used for detection, in the method, the pretreatment of a sample needs acid dissolution, then anhydrous ether extraction is carried out, ether layers are combined and then concentrated, sodium sulfate is easy to separate out and wrap chloropropanol in the extraction process, and chloropropanol can be dissolved in both ether and water, so that the recovery rate of chloropropanol is low; after sample injection according to the chromatographic conditions of the gas chromatography, the response value of chloropropanol is low, the limit of quantitation is only 0.5ppm, the sensitivity is low, the base line is not stable, the interference on the determination of chloropropanol is great, and the accuracy is poor.
When the solid phase extraction-gas chromatography-mass spectrometry combined method is used for detection, the solid phase extraction-gas chromatography-mass spectrometry combined method is used for detecting the content of chloropropanol in hydroxypropyl modified starch, but the pretreatment process of a sample to be detected is complicated, n-hexane ethyl acetate is required for elution, anhydrous sodium sulfate is used for removing water, heptafluorobutyrylimidazole is used for derivatization, n-butane is used for fixing the volume, chloropropanol loss is easily caused, and chloropropanol cannot be completely extracted by vortex extraction of the sample for 2 min.
Therefore, the existing method is difficult to meet the requirement of accurately, qualitatively and quantitatively detecting chloropropanol, and a method for detecting chloropropanol in hydroxypropyl modified starch, which is more convenient to operate, good in specificity, high in accuracy and high in sensitivity, needs to be researched urgently.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings of the existing method for detecting chloropropanol in hydroxypropyl modified starch and provides a method for detecting chloropropanol in hydroxypropyl modified starch.
The invention aims to provide a method for detecting chloropropanol in hydroxypropyl modified starch.
The invention also aims to provide application of the method in detecting chloropropanol in hydroxypropyl modified starch.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a method for detecting chloropropanol in hydroxypropyl modified starch, which comprises the following steps:
s1, adding a solvent into a sample to be tested, carrying out ultrasonic extraction, and filtering to obtain a subsequent filtrate, namely a test sample solution;
s2, taking a 1-chloro-2-propanol solution as a reference solution, diluting the reference solution with a solvent to obtain a sensitivity test solution, and diluting chloropropanol with the solvent to obtain a system applicability solution;
s3, performing gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution respectively, and judging whether the sample to be tested contains chloropropanol or not according to the determination result.
Preferably, the hydroxypropyl modified starch is any one or more of hydroxypropyl distarch phosphate, pregelatinized hydroxypropyl distarch phosphate, hydroxypropyl starch or pregelatinized hydroxypropyl starch.
Preferably, the chloropropanol is 1-chloro-2-propanol or 2-chloro-1-propanol.
Preferably, the method for judging whether the sample to be detected contains chloropropanol comprises the following steps: if peaks consistent with the chromatograms of the 1-chloro-2-propanol and the 2-chloro-1-propanol in the system applicability solution appear in the chromatogram of the test solution, the chloropropanol is contained in the sample to be detected.
Preferably, when the sample to be detected contains chloropropanol, the calculation formula of the content of chloropropanol is as follows:
preferably, the solvent in step S1 and step S2 is absolute ethanol.
Preferably, the temperature of the ultrasonic extraction in the step S1 is 25 ℃ to 60 ℃.
Preferably, the ultrasonic extraction time in the step S1 is 2.5-4.5 h.
Preferably, the concentration of the 1-chloro-2-propanol solution in the step S2 is 0.2-0.3. mu.g/mL.
More preferably, the concentration of the 1-chloro-2-propanol solution in the step S2 is 0.2104. mu.g/mL.
Preferably, the sensitivity test solution in the step S2 is a 1-chloro-2-propanol solution with a concentration of 0.09-0.11 μ g/mL.
More preferably, the sensitivity test solution of step S2 is a 1-chloro-2-propanol solution with a concentration of 0.1052. mu.g/mL.
Preferably, the chloropropanol in the step S2 is a mixture of 75 mass percent of 1-chloro-2-propanol and 25 mass percent of 2-chloro-1-propanol.
Preferably, the concentration of the 1-chloro-2-propanol solution in the system suitability solution in the step S2 is 0.18-0.22 μ g/mL.
More preferably, the concentration of the 1-chloro-2-propanol solution in the system suitability solution in step S2 is 0.2. mu.g/mL.
Preferably, the conditions of the GC-MS measurement in step S2 are as follows: using a capillary column with polyethylene glycol-20M as a stationary liquid, keeping the initial temperature at 70-90 ℃ for 8min, raising the temperature to 220 ℃ at the speed of 20-40 ℃/min, and keeping the temperature for 5 min; the temperature of a sample inlet is 150-250 ℃, and shunt sample injection is not performed; the detector is an electron impact source (EI) mass spectrum detector, the ionization energy is 70eV, the ion source temperature is 230 ℃, the carrier gas is helium, and the detection mode is SIM.
More preferably, the conditions of the GC assay in step S2 are: using a capillary column with polyethylene glycol-20M as stationary liquid, starting at 80 deg.C, maintaining for 8min, increasing to 220 deg.C at 35 deg.C/min, and maintaining for 5 min; the temperature of a sample inlet is 200 ℃, and the split-flow sample injection is not carried out; the detector is an electron impact source (EI) mass spectrum detector, the ionization energy is 70eV, the ion source temperature is 230 ℃, the carrier gas is helium, and the detection mode is SIM.
In addition, the application of the method in the aspect of detecting chloropropanol in hydroxypropyl modified starch is also within the protection scope of the invention.
The invention has the following beneficial effects:
the invention provides a method for detecting chloropropanol in hydroxypropyl modified starch. The method established based on the gas chromatography-mass spectrometry can effectively detect chloropropanol in hydroxypropyl modified starch (especially hydroxypropyl distarch phosphate, pregelatinized hydroxypropyl distarch phosphate, hydroxypropyl starch or pregelatinized hydroxypropyl starch), and establishes a calculation formula for calculating chloropropanol content on the basis of qualitatively detecting chloropropanol, thereby realizing qualitative and quantitative detection of chloropropanol in hydroxypropyl modified starch;
the method has the advantages of simple pretreatment process of a sample to be detected, high chloropropanol recovery rate, convenient operation, good specificity, high accuracy and high sensitivity, greatly meets the actual requirement of detecting chloropropanol in hydroxypropyl modified starch, provides a detection means for timely and strictly controlling the content of chloropropanol in hydroxypropyl modified starch, and has wide popularization and application prospects.
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FIG. 1 is a chromatogram of 1-chloro-2-propanol and 2-chloro-1-propanol in a system suitability solution.
FIG. 2 is a chromatogram of a sensitivity test solution.
FIG. 3 is a chromatogram of a test solution of hydroxypropyl distarch phosphate.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
System applicability the chromatograms of 1-chloro-2-propanol and 2-chloro-1-propanol in solution are shown in fig. 1, and it can be seen that the chromatograms of 1-chloro-2-propanol and 2-chloro-1-propanol achieve baseline separation for locating and determining that baseline separation is achieved.
The chromatogram of the sensitivity test solution is shown in FIG. 2, and it can be seen that the 1-chloro-2-propanol chromatogram peak signal-to-noise ratio is 26.2.
Example 1 detection of chloropropanol in hydroxypropyl distarch phosphate
The chloropropanol in 9 batches of hydroxypropyl distarch phosphate is detected respectively as follows, and the batch numbers are respectively: FFS1070, LBG2301, 20171114, 20171115, 20180125, 20181023, 20181126, 20181219 and 20190504, and the specific experimental method and experimental result are as follows:
1. experimental methods
A method for detecting chloropropanol in hydroxypropyl distarch phosphate comprises the following steps:
s1, precisely weighing 2g of hydroxypropyl distarch phosphate, placing the hydroxypropyl distarch phosphate into a conical flask, precisely adding 10mL of absolute ethyl alcohol, ultrasonically extracting for 2.5h, cooling, precisely weighing, complementing the weight loss reduction amount with absolute ethyl alcohol, shaking up, filtering, and taking a subsequent filtrate as a test solution;
s2, precisely weighing 10.56mg of 1-chloro-2-propanol (content: 99.63%), placing the 1-chloro-2-propanol into a 100mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, shaking up, precisely transferring the 1mL into a 500mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 0.2104 mu g/mL as a reference solution; then, diluting the reference substance solution with absolute ethyl alcohol to obtain a 1-chloro-2-propanol solution with the concentration of 0.1052 mug/mL as a sensitivity test solution, and diluting chloropropanol (a mixture of 75% by mass of 1-chloro-2-propanol and 25% by mass of 2-chloro-1-propanol) with absolute ethyl alcohol to obtain a system applicability solution (the concentration of the 1-chloro-2-propanol solution in the solution is 0.2 mug/mL);
s3, respectively carrying out gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution, and judging whether the sample to be tested contains chloropropanol or not according to the determination result.
The method for judging whether the sample to be detected contains chloropropanol comprises the following steps: if peaks consistent with the chromatograms of the 1-chloro-2-propanol and the 2-chloro-1-propanol in the system applicability solution appear in the chromatogram of the test solution, the chloropropanol is contained in the sample to be detected.
When the sample to be detected contains chloropropanol, the calculation formula of the content of chloropropanol is as follows:
the conditions for the gas chromatography-mass spectrometry of step S2 are:
using a capillary column with polyethylene glycol-20M as stationary liquid, starting at 80 deg.C, maintaining for 8min, increasing to 220 deg.C at 35 deg.C/min, and maintaining for 5 min; the temperature of a sample inlet is 200 ℃, and the split-flow sample injection is not carried out; the detector is an electron impact source (EI) mass spectrum detector, the ionization energy is 70eV, the ion source temperature is 230 ℃, the carrier gas is helium, and the detection mode is SIM.
2. Results of the experiment
The chromatogram of the hydroxypropyl distarch phosphate test solution is shown in fig. 3, and it can be seen that a chloropropanol chromatographic peak can be detected in the sample.
The detection results of chloropropanol in each batch of hydroxypropyl distarch phosphate are shown in table 1, and the data in the table show that when the method is used for detecting the content of chloropropanol in hydroxypropyl distarch phosphate, lower content can be effectively detected, which indicates that the detection sensitivity of the method is very high.
TABLE 1 detection results of chloropropanol in each lot of hydroxypropyl distarch phosphate
Example 2 detection of chloropropanol in pregelatinized hydroxypropyl distarch phosphate
The chloropropanol in 4 batches of pregelatinized hydroxypropyl distarch phosphate is respectively detected as follows, and the batch numbers are respectively: 170369K, 180089R, 180113R, MFC296, the specific experimental methods and experimental results are as follows:
1. experimental methods
A method for detecting chloropropanol in pregelatinized hydroxypropyl distarch phosphate comprises the following steps:
s1, precisely weighing 2g of pregelatinized hydroxypropyl distarch phosphate, placing the pregelatinized hydroxypropyl distarch phosphate in a conical flask, precisely adding 10mL of absolute ethyl alcohol, ultrasonically extracting for 4.5h at 60 ℃, cooling, precisely weighing, supplementing the weight loss by absolute ethyl alcohol, shaking up, filtering, and taking a subsequent filtrate as a sample solution;
s2, precisely weighing 10.56mg of 1-chloro-2-propanol (content: 99.63%), placing the 1-chloro-2-propanol into a 100mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, shaking up, precisely transferring the 1mL into a 500mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 0.2104 mu g/mL as a reference solution; then, diluting the reference substance solution with absolute ethyl alcohol to obtain a 1-chloro-2-propanol solution with the concentration of 0.1052 mug/mL as a sensitivity test solution, and diluting chloropropanol (a mixture of 75% by mass of 1-chloro-2-propanol and 25% by mass of 2-chloro-1-propanol) with absolute ethyl alcohol to obtain a system applicability solution (the concentration of the 1-chloro-2-propanol solution in the solution is 0.2 mug/mL);
s3, respectively carrying out gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution, and judging whether the sample to be tested contains chloropropanol or not according to the determination result.
The method for judging whether the sample to be detected contains chloropropanol is the same as that in the embodiment 1; when the sample to be detected contains chloropropanol, the calculation formula of the content of chloropropanol is the same as that in the embodiment 1; the conditions for the gas chromatography-mass spectrometry in step S2 were also the same as in example 1.
2. Results of the experiment
The detection results of chloropropanol in each batch of pregelatinized hydroxypropyl distarch phosphate are shown in table 2, and the data in the table show that the sensitivity is higher when the method is used for detecting the content of chloropropanol in pregelatinized hydroxypropyl distarch phosphate.
TABLE 2 detection results of chloropropanol in pregelatinized hydroxypropyl distarch phosphate of each lot number
Example 3 detection of chloropropanol in hydroxypropyl starch
The chloropropanol in 20 batches of hydroxypropyl starch is detected respectively as follows, and the batch numbers are respectively: DGS1310, EG7527, 20170505, 20170506, 20170507, E005R, E006R, MGB5212, BGB2029, 20171019, 20171117, 20180113, 180301, 180302, 180303, 20180803, 20180608, 20181112, and the specific experimental methods and experimental results are as follows:
1. experimental methods
A method for detecting chloropropanol in hydroxypropyl starch comprises the following steps:
s1, precisely weighing 2g of hydroxypropyl starch, placing the hydroxypropyl starch in a conical flask, precisely adding 10mL of absolute ethyl alcohol, ultrasonically extracting for 2h, cooling, precisely weighing, complementing the weight loss reduction amount with diethyl ether, shaking up, filtering, and taking a subsequent filtrate as a test sample solution;
s2, precisely weighing 10.56mg of 1-chloro-2-propanol (content: 99.63%), placing the 1-chloro-2-propanol into a 100mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, shaking up, precisely transferring the 1mL into a 500mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 0.2104 mu g/mL as a reference solution; then, diluting the reference substance solution with absolute ethyl alcohol to obtain a 1-chloro-2-propanol solution with the concentration of 0.1052 mug/mL as a sensitivity test solution, and diluting chloropropanol (a mixture of 75% by mass of 1-chloro-2-propanol and 25% by mass of 2-chloro-1-propanol) with absolute ethyl alcohol to obtain a system applicability solution (the concentration of the 1-chloro-2-propanol solution in the solution is 0.2 mug/mL);
s3, respectively carrying out gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution, and judging whether the sample to be tested contains chloropropanol or not according to the determination result.
The method for judging whether the sample to be detected contains chloropropanol is the same as that in the embodiment 1; when the sample to be detected contains chloropropanol, the calculation formula of the content of chloropropanol is the same as that in the embodiment 1; the conditions for the gas chromatography-mass spectrometry in step S2 were also the same as in example 1.
2. Results of the experiment
The detection results of chloropropanol in each batch of hydroxypropyl starch are shown in table 3, and the data in the table show that when the method is used for detecting the content of chloropropanol in hydroxypropyl starch, lower content can be effectively detected, which indicates that the detection sensitivity of the method is very high.
TABLE 3 detection results of chloropropanol in hydroxypropyl starch of each lot number
Example 4 detection of chloropropanol in pregelatinized hydroxypropyl starch
The chloropropanol in 4 batches of pregelatinized hydroxypropyl starch was detected as follows: E006S, 20170830, 20171125, 20170927, the specific experimental methods and experimental results are as follows:
1. experimental methods
A method for detecting chloropropanol in pregelatinized hydroxypropyl starch comprises the following steps:
s1, precisely weighing 2g of pregelatinized hydroxypropyl starch, placing the pregelatinized hydroxypropyl starch in a conical flask, precisely adding 10mL of absolute ethyl alcohol, ultrasonically extracting for 3.5h, cooling, precisely weighing, supplementing the weight loss by absolute ethyl alcohol, shaking up, filtering, and taking a subsequent filtrate as a test sample solution;
s2, precisely weighing 10.56mg of 1-chloro-2-propanol (content: 99.63%), placing the 1-chloro-2-propanol into a 100mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, shaking up, precisely transferring the 1mL into a 500mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 0.2104 mu g/mL as a reference solution; then, diluting the reference substance solution with absolute ethyl alcohol to obtain a 1-chloro-2-propanol solution with the concentration of 0.1052 mug/mL as a sensitivity test solution, and diluting chloropropanol (a mixture of 75% by mass of 1-chloro-2-propanol and 25% by mass of 2-chloro-1-propanol) with absolute ethyl alcohol to obtain a system applicability solution (the concentration of the 1-chloro-2-propanol solution in the solution is 0.2 mug/mL);
s3, respectively carrying out gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution, and judging whether the sample to be tested contains chloropropanol or not according to the determination result.
The method for judging whether the sample to be detected contains chloropropanol is the same as that in the embodiment 1; when the sample to be detected contains chloropropanol, the calculation formula of the content of chloropropanol is the same as that in the embodiment 1;
the conditions for the gas chromatography-mass spectrometry in step S2 were also the same as in example 1.
2. Results of the experiment
The detection results of chloropropanol in each batch of pregelatinized hydroxypropyl starch are shown in table 4, and the data in the table show that when the method is used for detecting the content of chloropropanol in pregelatinized hydroxypropyl starch, lower content can be effectively detected, which indicates that the detection sensitivity of the method is very high.
TABLE 4 detection results of chloropropanol in pregelatinized hydroxypropyl starch for each lot number
Example 5 verification of sensitivity of method for detecting chloropropanol in hydroxypropyl-based modified starch
1. Experimental methods
The sensitivity verification of the method for detecting chloropropanol in hydroxypropyl modified starch comprises the following steps:
s11, precisely weighing 10.56mg of 1-chloro-2-propanol (content: 99.63%), placing the 1-chloro-2-propanol into a 100mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, shaking up, precisely transferring the 1mL into a 500mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 0.2104 mu g/mL as a reference solution; placing 2mL of the reference solution into a 20mL measuring flask, diluting with absolute ethyl alcohol to obtain a 1-chloro-2-propanol solution with the concentration of 0.02104 mu g/mL as a detection limit solution, placing 5mL of the reference solution into the 20mL measuring flask, diluting with absolute ethyl alcohol to obtain a 1-chloro-2-propanol solution with the concentration of 0.05260 mu g/mL as a quantification limit solution;
s12, respectively carrying out gas chromatography-mass spectrometry on the detection limit solution and the quantitative limit test solution obtained in the step S11, and judging whether the concentration is a detection limit or a quantitative limit according to a measurement result;
the method for judging whether the concentration is a detection limit or a quantification limit comprises the following steps: if the s/n of the chromatographic peak of the 1-chloro-2-propanol is equal to 3, the detection limit is set; if the chromatographic peak s/n of the 1-chloro-2-propanol is equal to 10, the quantitative limit is determined;
the conditions for the gas chromatography-mass spectrometry of step S12 are: using a capillary column with polyethylene glycol-20M as stationary liquid, starting at 80 deg.C, maintaining for 8min, increasing to 220 deg.C at 35 deg.C/min, and maintaining for 5 min; the temperature of a sample inlet is 200 ℃, and the split-flow sample injection is not carried out; the detector is an electron impact source (EI) mass spectrum detector, the ionization energy is 70eV, the ion source temperature is 230 ℃, the carrier gas is helium, and the detection mode is SIM.
2. Results of the experiment
The s/n of the detection limiting solution is 3.4, and the s/n of the quantification limiting solution is 9.7; namely the detection limit of the 1-chloro-2-propanol is 0.02104 mug/mL, and the quantification limit is 0.05260 mug/mL; the method for detecting chloropropanol in hydroxypropyl modified starch has higher sensitivity than the national standard method (the limit of quantitation is 0.5 mu g/mL).
Example 6 verification of the accuracy of the method for detecting chloropropanol in hydroxypropyl-based modified starch
1. Experimental methods
The accuracy verification of the method for detecting chloropropanol in hydroxypropyl modified starch comprises the following steps:
s21, precisely weighing 10.56mg of 1-chloro-2-propanol (content: 99.63%), placing the 1-chloro-2-propanol into a 100mL measuring flask, diluting the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, shaking up, precisely transferring 2mL of the 1-chloro-2-propanol into the 100mL measuring flask, diluting the 2-mL of the 1-chloro-2-propanol to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 2.104 mu g/mL as a sample addition reference substance solution; precisely transferring 1mL of the solution into a 500mL measuring flask, diluting the solution to a scale with absolute ethyl alcohol, and shaking up to obtain a 1-chloro-2-propanol solution with the concentration of 0.2104 mu g/mL as a reference solution;
s22, precisely weighing 6 parts of 2g of hydroxypropyl distarch phosphate (lot number 180113R), placing the 6 parts in 6 conical flasks, precisely adding 1mL of sample adding reference substance solution and 9mL of absolute ethyl alcohol respectively, ultrasonically extracting for 2.5h, cooling, precisely weighing, supplementing the weight loss by using the absolute ethyl alcohol, shaking up, filtering, and taking the subsequent filtrate as a sample adding recovery solution;
s23, performing gas chromatography-mass spectrometry on the reference substance solution obtained in the step S21 and the sample adding and recovering solution obtained in the step S22 respectively, and verifying the accuracy of the method according to the determination results;
the method for judging the accuracy of the method comprises the following steps: calculating the content of chloropropanol in the sample-adding recovery solution and the sample-adding recovery rate, wherein the sample-adding recovery rate is 75-120%, and judging that the method has good accuracy;
the calculation formula of the chloropropanol content is as follows:
the calculation formula of the sample recovery rate is as follows:
the conditions for the gas chromatography-mass spectrometry of step S23 are: using a capillary column with polyethylene glycol-20M as stationary liquid, starting at 80 deg.C, maintaining for 8min, increasing to 220 deg.C at 35 deg.C/min, and maintaining for 5 min; the temperature of a sample inlet is 200 ℃, and the split-flow sample injection is not carried out; the detector is an electron impact source (EI) mass spectrum detector, the ionization energy is 70eV, the ion source temperature is 230 ℃, the carrier gas is helium, and the detection mode is SIM.
2. Results of the experiment
The results of the 6 times of sample adding and recovery detection are shown in table 5, and the data in the table show that the sample adding and recovery rate of the method for detecting chloropropanol in hydroxypropyl modified starch established by the invention is 100.6-106.4%, the average sample adding and recovery rate is 102.3%, the relative standard deviation is only 2.2%, and the detection accuracy is high.
TABLE 5 sample recovery test results
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for detecting chloropropanol in hydroxypropyl modified starch is characterized by comprising the following steps:
s1, adding a solvent into a sample to be tested, carrying out ultrasonic extraction, and filtering to obtain a subsequent filtrate, namely a test sample solution;
s2, taking a 1-chloro-2-propanol solution as a reference solution, diluting the reference solution with a solvent to obtain a sensitivity test solution, and diluting chloropropanol with the solvent to obtain a system applicability solution;
s3, performing gas chromatography-mass spectrometry on the test solution obtained in the step S1, the reference solution obtained in the step S2, the sensitivity test solution and the system applicability solution respectively, and judging whether the sample to be tested contains chloropropanol or not according to the determination result.
2. The method according to claim 1, wherein the hydroxypropyl modified starch is any one or more of hydroxypropyl distarch phosphate, pregelatinized hydroxypropyl distarch phosphate, hydroxypropyl starch, or pregelatinized hydroxypropyl starch.
3. The process according to claim 1, characterized in that the chloropropanol is 1-chloro-2-propanol or 2-chloro-1-propanol.
4. The method according to claim 1, wherein the method for judging whether the sample to be tested contains chloropropanol comprises the following steps: if peaks consistent with the chromatograms of the 1-chloro-2-propanol and the 2-chloro-1-propanol in the system applicability solution appear in the chromatogram of the test solution, the chloropropanol is contained in the sample to be detected.
5. The method according to claim 4, wherein when the sample to be tested contains chloropropanol, the calculation formula of the content of chloropropanol is as follows:
6. the method of claim 1, wherein the solvent in steps S1 and S2 is absolute ethanol.
7. The method according to claim 1, wherein the temperature of the ultrasonic extraction of step S1 is 25-60 ℃; the ultrasonic extraction time of the step S1 is 2.5-4.5 h.
8. The method according to claim 1, wherein the concentration of the 1-chloro-2-propanol solution in the step S2 is 0.2-0.3 μ g/mL; the sensitivity test solution in the step S2 is a 1-chloro-2-propanol solution with the concentration of 0.09-0.11 mu g/mL.
9. The method according to claim 1, characterized in that the chloropropanol of step S2 is a mixture of 75% by mass of 1-chloro-2-propanol and 25% by mass of 2-chloro-1-propanol; the concentration of the 1-chloro-2-propanol solution in the system suitability solution in the step S2 is 0.18-0.22 mu g/mL.
10. The method of any one of claims 1 to 9, which is applied to the detection of chloropropanol in hydroxypropyl modified starch.
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