CN111175396A - Method for rapidly detecting six additives in food contact material by supercritical fluid chromatography - Google Patents
Method for rapidly detecting six additives in food contact material by supercritical fluid chromatography Download PDFInfo
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- CN111175396A CN111175396A CN202010020113.3A CN202010020113A CN111175396A CN 111175396 A CN111175396 A CN 111175396A CN 202010020113 A CN202010020113 A CN 202010020113A CN 111175396 A CN111175396 A CN 111175396A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/26—Conditioning of the fluid carrier; Flow patterns
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
本发明公开了一种超临界流体色谱快速检测食品接触材料中六种添加剂的方法。包括超声波辅助萃取的前处理方法和超临界流体色谱系统，超声波辅助萃取过程中采用甲醇或乙腈或异丙醇作为提取溶剂，在设定温度和时间下对待测样品进行超声处理，萃取液经有机膜过滤后进行超临界流体色谱系统分析。本发明选取超声波萃取作为前处理方法，通过条件优化确定了最佳提取溶剂、温度和时间，消耗有机溶剂少，操作简单易行，可以为食品接触材料中添加剂的检测提供一定依据，为相关行业的产品监督管理提供技术支持，有助于超临界流体色谱的推广应用，并为该技术在塑料药物材料、迁移测试等中的应用做了铺垫。
The invention discloses a method for rapidly detecting six kinds of additives in food contact materials by supercritical fluid chromatography. Including the pretreatment method of ultrasonic-assisted extraction and supercritical fluid chromatography system, in the process of ultrasonic-assisted extraction, methanol or acetonitrile or isopropanol is used as the extraction solvent, and the sample to be tested is ultrasonically treated at the set temperature and time, and the extract is organically processed. Membrane filtration followed by supercritical fluid chromatography system analysis. The invention selects ultrasonic extraction as the pretreatment method, determines the optimal extraction solvent, temperature and time through the optimization of conditions, consumes less organic solvent, is simple and easy to operate, can provide a certain basis for the detection of additives in food contact materials, and can be used for related industries. The product supervision and management of the company provides technical support, which is helpful for the popularization and application of supercritical fluid chromatography, and lays the groundwork for the application of this technology in plastic pharmaceutical materials, migration testing, etc.
Description
Technical Field
The invention relates to the development of a method for rapidly detecting six additives in a food contact material by adopting a supercritical fluid chromatogram, in particular to a method for rapidly detecting six additives in a food contact material by adopting a supercritical fluid chromatogram.
Background
Photoinitiators and plasticizers are common additives in the manufacture of food contact materials. Many studies show that the additives can be in chemical or physical contact migration under certain conditions, so that certain pollution is caused to food in the package, and potential threats are caused to human health. For example, the photoinitiator 2-ITX can interfere with the human endocrine system by affecting the fluidity and rigidity of cell membranes; the photoinitiator Benzophenone (BP) has carcinogenicity, reproductive toxicity and sensitization; the plasticizer phthalic acid (2-ethylhexyl) Diester (DEHP) can enter a human body through respiratory tract, digestive tract, skin and the like and is not easy to be discharged out of the human body, and long-term contact with DEHP can cause endocrine dyscrasia, influence reproductive performance and even cause carcinogenesis and teratogenesis. Therefore, it is crucial to establish a simple, rapid and accurate method for detecting these additives. At present, the main detection methods include gas chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry and the like.
The ultrasonic-assisted extraction method utilizes strong vibration, high acceleration, disturbance effect and the like generated by ultrasonic waves to promote target substances to enter a solvent. Therefore, compared with the traditional liquid-liquid extraction method, the method has the advantages of rapidness, simplicity, practicability, solvent saving, high extraction efficiency and the like. Meanwhile, the dosage of the organic solvent related to the ultrasonic-assisted extraction is usually less, the scientific concept of environmental protection is met, and the method has considerable development prospect in the aspect of food contact materials.
Supercritical fluid chromatography is performed with a supercritical fluid (CO)2Etc.) as main mobile phase components, and has been receiving more and more attention in recent years due to its characteristics of low viscosity, good mass transfer performance, high separation efficiency, environmental protection, etc. In addition, because of the characteristics of the supercritical fluid, the method has certain advantages in separating and analyzing structural analogues, isomers, polar and nonpolar mixtures and other samples which are difficult to process by the conventional chromatographic technology at present. Eyes of a userPreviously, there has been no report on simultaneous detection of photoinitiators and plasticizers by supercritical fluid chromatography.
Disclosure of Invention
The invention provides a method for simultaneously measuring six additives in food contact materials by combining ultrasonic-assisted extraction with supercritical fluid chromatography. Through condition optimization, the chromatographic analysis process of the method can realize effective separation of target substances in only seven minutes, and the method has the advantages of low organic reagent consumption, time saving, environmental protection, good precision and accuracy and high reproducibility. The six additives included the plasticizer phthalic acid (2-ethylhexyl ester) (DEHP) and the following five photoinitiators: 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocure 1173); 2, 2-Diethoxybenzophenone (DEAP); 2-methylbenzophenone (2-MBP); 4-methylbenzophenone (4-MBP); methyl o-benzoylbenzoate (OMBB).
The invention is realized by the following technical scheme:
the invention discloses a separation and analysis method of six additives in a food contact material, which comprises a pretreatment method of ultrasonic-assisted extraction and a supercritical fluid chromatographic system, wherein methanol or acetonitrile or isopropanol is used as an extraction solvent in the ultrasonic-assisted extraction process, a sample to be detected is subjected to ultrasonic treatment at a set temperature and time, and extract liquid is subjected to supercritical fluid chromatographic system analysis after being filtered by an organic membrane.
As a further improvement, in the ultrasonic-assisted extraction process, acetonitrile is used as an extraction solvent. Methanol, acetonitrile and isopropanol are used as extraction solvents, experiments show that the extraction efficiency of acetonitrile and methanol on target substances is almost the same, but the acetonitrile is not easy to extract pigment, wax, fat and other nonpolar substances in a matrix, so the acetonitrile is finally selected as the extraction solvent.
As a further improvement, in the ultrasonic-assisted extraction process, the ultrasonic temperature is 20-50 ℃, and the ultrasonic time is 10-60 min.
As a further improvement, in the ultrasonic-assisted extraction process, the ultrasonic temperature is 40 ℃, and the ultrasonic time is 60 min. To achieve maximum extraction efficiency
As a further improvement, in the supercritical fluid chromatography of the invention, the modifier is 4% of methanol. The invention uses 4% methanol as the mobile phase modifier in the supercritical fluid chromatogram. Compared with methanol, acetonitrile cannot separate Darocure1173 and DEAP well, and isopropanol has high viscosity, so that the backpressure of the system is high. In the range of 2% to 8%, better peak shape and resolution were found at 4%.
As a further improvement, in the supercritical fluid chromatography, the temperature of a chromatographic column is 38-44 ℃, and the back pressure is 10-14 MPa.
As a further improvement, in the supercritical fluid chromatography, the temperature of the chromatographic column is 44 ℃, and the back pressure is 10 MPa. The backpressure condition of 10MPa was chosen to achieve better separation. Finally 44 ℃ was chosen as the final column temperature to achieve the best separation.
As a further improvement, in the supercritical fluid chromatography, the flow rate is 1.2-1.8 mL/min.
As a further improvement, in the supercritical fluid chromatography of the present invention, the detection wavelength was adjusted from 245nm to 224nm at the fifth minute, and the flow rate was 1.4 mL/min. Because the DEHP which comes out of the peak after the fifth minute has not strong absorption at 245nm, the absorption peak becomes strong after the adjustment to 224nm, which is helpful for improving the sensitivity of the method and facilitating quantitative analysis; the flow rate was finally set to 1.4mL/min, taking into account the analysis time, peak shape and separation effect.
As a further improvement, the preparation method comprises the following specific preparation steps:
1) cleaning a food contact material sample by using deionized water, naturally drying the food contact material sample in the air, cutting the food contact material sample into uniform fragments with the size of about 5mm multiplied by 5mm, collecting the uniform fragments for later use, washing glass instruments by using the deionized water, and then leaching and drying by using ethanol;
2) accurately weighing 0.5g (accurate to 0.1mg) of the cut sample in a 10mL glass vial, adding 2mL acetonitrile solution (chromatographic purity), performing ultrasonic extraction at 40 ℃ for 60min, and filtering the extract with a 0.22 mu m organic filter membrane for SFC determination;
3) SFC testThe conditions were as follows: using Thermo ScientificTMAcclaimTMA 120C18(5 μm,4.6 mm. times.250 mm) chromatography column; the system backpressure is 10 MPa; the temperature of the chromatographic column is 44 ℃; the sample injection amount is 5 mu L; the mobile phase is (A) supercritical fluid CO2And (B) modifier methanol, with a volume ratio of 96: 4; the flow rate is 1.4 mL/min; setting ultraviolet gradient wavelength detection for 0-5min (245 nm); 5-7min (224 nm).
4) And (3) the liquid filtered by the membrane in the step 2) is subjected to supercritical fluid chromatography under the set conditions in the step 3) for detection, and qualitative and quantitative analysis, single-standard qualitative analysis and external standard quantitative analysis are performed according to the finally obtained chromatogram.
The invention has the following advantages and effects;
1) the simultaneous detection of the photoinitiator and the plasticizer by applying the supercritical fluid chromatography has not been studied so far;
2) the invention selects ultrasonic extraction as a pretreatment method, determines the best extraction solvent, temperature and time through condition optimization, consumes less organic solvent and has simple and easy operation;
3) the invention selects the supercritical fluid chromatogram which is a novel detection method, which is not completely popularized at present, and the mobile phase adopted by the technology is mainly CO2The method meets the requirements of green environmental protection analysis and detection, and has higher analysis efficiency compared with the common liquid chromatogram.
4) The effective separation of the six additives can be realized within 7min by optimizing the conditions of ultrasonic and supercritical fluid chromatography, and the method has the advantages of less time consumption, simplicity and easiness in operation, environmental friendliness, high accuracy and good repeatability;
5) the invention can provide a certain basis for the detection of the additive in the food contact material and provide technical support for the product supervision and management of related industries;
6) the invention is beneficial to the popularization and the application of the supercritical fluid chromatography, and lays a cushion for the application of the technology in plastic drug materials, migration tests and the like.
Drawings
FIG. 1 is an optimization of supercritical fluid chromatography-related conditions;
(a) selecting a modifier; (b) selecting the column temperature; (c) selecting back pressure; (d) selecting the proportion of modifier methanol; the corresponding substances of each peak number on all chromatograms are as follows:
(1)Darocure 1173,(2)DEAP,(3)OMBB,(4)2-MBP,(5)4-MBP,(6)DEHP
FIG. 2 is an optimized chart of the flow rate of supercritical fluid chromatography, with the peak numbers corresponding to species in FIG. 1;
FIG. 3 is a chromatogram of a blank sample and a blank sample with a standard (5ppm mixed standard solution) and the same substance as that in FIG. 1; (b is a chromatogram after a blank sample is labeled);
FIG. 4 is a chromatogram of an actual sample (canned potato chips) (b is a chromatogram after labeling);
fig. 5 shows a chromatogram of an actual sample (bubble bucket) (b is a chromatogram after labeling).
Detailed Description
The invention relates to the development of a method for rapidly detecting six additives in food contact materials by adopting supercritical fluid chromatography, in particular to the method for simply pre-treating the food contact materials by ultrasonic-assisted extraction, then separating and analyzing the six additives by utilizing Supercritical Fluid Chromatography (SFC) and quantifying by an external standard method.
The preparation method comprises the following specific steps:
1) and cleaning the food contact material sample by using deionized water, naturally drying, cutting the food contact material sample into uniform fragments with the size of about 5mm multiplied by 5mm, and collecting the fragments for later use. In addition, in order to reduce experimental errors and avoid the use of plastic product experimental tools as much as possible, all glass instruments are washed by deionized water and then are leached and dried by ethanol.
2) Accurately weighing 0.5g (accurate to 0.1mg) of the above cut-up sample into a 10mL glass vial, adding 2mL acetonitrile solution (chromatographic purity), performing ultrasonic extraction at 40 ℃ for 60min, and filtering the extract through a 0.22 mu m organic filter membrane for SFC determination.
3) The SFC measurement conditions were as follows: using Thermo ScientificTMAcclaimTMA 120C18(5 μm,4.6 mm. times.250 mm) chromatography column; the system backpressure is 10 MPa; the temperature of the chromatographic column is 44 ℃; the sample injection amount is 5 mu L; the mobile phase is (A) supercritical fluid CO2And (B) modifier methanol, with a volume ratio of 96: 4; the flow rate is 1.4 mL/min; setting ultraviolet gradient wavelength detection for 0-5min (245 nm); 5-7min (224 nm).
4) And (3) the liquid filtered by the membrane in the step 2) is subjected to supercritical fluid chromatography under the set conditions in the step 3) for detection, and qualitative and quantitative analysis, single-standard qualitative analysis and external standard quantitative analysis are performed according to the finally obtained chromatogram.
The technical scheme of the invention is further explained in detail by the following concrete implementation examples:
example 1: supercritical fluid chromatography condition optimization
The instrument comprises the following steps: nexera UC SFC system (Shimadzu, Japan)
A detector: SPD-20A UV detector detection wavelength: 245nm
A chromatographic column: thermo ScientificTMAcclaimTM120 C18
Sample preparation: 10ppm Mixed Standard solution
And (3) peak appearance sequence: (1) darocure1173, (2) DEAP, (3) OMBB, (4)2-MBP, (5)4-MBP, (6) DEHP
FIG. 1 is an optimization of supercritical fluid chromatography-related conditions;
(a) selecting a modifier; (b) selecting the column temperature; (c) selecting back pressure; (d) selecting the proportion of modifier methanol; the corresponding substances of each peak number on all chromatograms are as follows:
(1)Darocure 1173,(2)DEAP,(3)OMBB,(4)2-MBP,(5)4-MBP,(6)DEH。
FIG. 1(a) is a selection of modifiers
Column temperature: 44 ℃; back pressure: 10 MPa; flow rate: 1.2mL/min
It can be seen from the figure that only five peaks can be isolated when acetonitrile is used as modifier. When isopropanol is used as a modifier, although six target compounds can be separated, the peak shape is poor, and the viscosity of isopropanol is high, so that the system backpressure is easily too high. Therefore, combining the chromatogram and the physicochemical properties, methanol was finally selected as the modifier.
FIG. 1(b) shows the selection of the column temperature
Modifying agent: 8% CH3OH; back pressure: 10 MPa; flow rate:1.6mL/min
the change in temperature affects the supercritical fluid CO2In conjunction with fig. 1(b), it can be seen that the retention value of the target substance increases as the temperature increases. The optimum column temperature was 44 ℃ on the basis of the degree of separation and the analysis time.
FIG. 1(c) shows the selection of the back pressure
Modifying agent: 8% CH3OH; column temperature: 44 ℃; flow rate: 1.6mL/min
Back pressure can also affect supercritical fluid CO2The higher the back pressure, the shorter the retention value of each target substance, contrary to the temperature. Finally, 10MPa is selected as the optimal condition.
FIG. 1(d) shows the selection of the ratio of modifiers
Column temperature: 44 ℃; back pressure: 10 MPa; flow rate: 1.6mL/min
The modifier ratio represents the polarity of the mobile phase and therefore has some effect on the separation capacity. The larger the proportion of modifier, the shorter the retention time, but when the proportion of methanol exceeds 6%, the degree of separation of 2-MBP and 4-MBP decreases, so 4% CH is selected3OH as the final modifier.
FIG. 2 is an optimized chart of the flow rate of supercritical fluid chromatography, with the peak numbers corresponding to species in FIG. 1;
modifying agent: 4% CH3OH; column temperature: 44 ℃; back pressure: 10 MPa;
the larger the flow rate, the shorter the analysis time. After the optimization of the above conditions is completed, it can be found in conjunction with fig. 2 that the flow rate influence becomes small. In the case of ensuring baseline separation of all target substances, the analysis time is shortened as much as possible, so 1.4mL/min is selected as the optimum condition.
Example 2: blank sample standard (5ppm mixed standard solution) chromatogram
The instrument comprises the following steps: nexera UC SFC system (Shimadzu, Japan)
A detector: SPD-20A UV detector detection wavelength: 0-5min (245 nm); 5-7min (224nm)
A chromatographic column: thermo ScientificTMAcclaimTM120 C18；44℃
Back pressure: 10MPa
Mobile phase: (A) supercritical fluid CO2And (B) modifier methanol with the volume ratio of 96:4
Flow rate: 1.4mL/min
Sample preparation: adding 5ppm of mixed standard solution into a blank sample and then carrying out pretreatment
FIG. 3 is a chromatogram of a blank sample and a blank sample with a standard (5ppm mixed standard solution) and the same substance as that in FIG. 1; fig. 3 shows chromatograms obtained by processing (a) a blank sample and (b) a blank sample in a standard (5ppm mixed standard solution) under optimized ultrasonic extraction and supercritical fluid chromatography conditions, wherein the comparison of the two graphs (a and b) shows that no obvious impurity peak interference exists, six target substances can realize baseline separation, the peak shapes are good, and the method can be accurately determined and quantified, and is proved to have feasibility and accuracy.
Example 3: actual sample potato chip can test
The instrument comprises the following steps: nexera UC SFC system (Shimadzu, Japan)
A detector: SPD-20A UV detector detection wavelength: 0-5min (245 nm); 5-7min (224nm)
A chromatographic column: thermo ScientificTMAcclaimTM120 C18；44℃
Back pressure: 10MPa
Mobile phase: (A) supercritical fluid CO2And (B) modifier methanol with the volume ratio of 96:4
Flow rate: 1.4mL/min
Sample preparation: certain brand potato chip can randomly purchased by supermarket
FIG. 4(a) is a chromatogram obtained after the actual sample canned potato chips are processed according to the specific preparation steps; (b) and (4) adding a standard to the sample to obtain a chromatogram.
The peaks detected in the figure correspond to the OMBB, and no significant impurity peak interference exists. The method has high feasibility in the detection of actual samples and has great practical value. The OMBB content in this sample was finally obtained as 54.614. mu.g/g after quantification by external standard method.
Example 4: bucket test of actual sample instant noodles
The instrument comprises the following steps: nexera UC SFC system (Shimadzu, Japan)
A detector: SPD-20A UV detector detection wavelength: 0-5min (245 nm); 5-7min (224nm)
A chromatographic column: thermo ScientificTMAcclaimTM120 C18；44℃
Back pressure: 10MPa
Mobile phase: (A) supercritical fluid CO2And (B) modifier methanol with the volume ratio of 96:4
Flow rate: 1.4mL/min
Sample preparation: certain brand of bubble noodles randomly purchased by supermarket
FIG. 5(a) is a chromatogram obtained after the actual sample instant noodle barrel is processed according to the "concrete preparation step"; (b) and (4) adding a standard to the sample to obtain a chromatogram.
The peaks detected in the figure correspond to DEAP (former) and 2-MBP (latter), respectively, with no significant matrix interference and short analysis time. Although the peak is small, the method can still carry out qualitative and quantitative analysis, which shows that the method is also suitable for trace analysis of actual samples and has great practical value. After the quantification by an external standard method, the DEAP content of the sample is 1.612 mu g/g, and the 2-MBP content is 2.292 mu g/g.
Finally, it should be noted that the above list is only a few specific embodiments of the present invention. It is obvious that the invention is not limited to the above embodiment examples, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
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