CN114200062A - Method for detecting tetraethylene glycol dimethyl ether in leather - Google Patents
Method for detecting tetraethylene glycol dimethyl ether in leather Download PDFInfo
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- CN114200062A CN114200062A CN202111542484.9A CN202111542484A CN114200062A CN 114200062 A CN114200062 A CN 114200062A CN 202111542484 A CN202111542484 A CN 202111542484A CN 114200062 A CN114200062 A CN 114200062A
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 title claims abstract description 154
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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
- G01N30/02—Column chromatography
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to the technical field of chemical detection, in particular to a method for detecting tetraethylene glycol dimethyl ether in leather, which comprises the following steps: (1) preparing a standard solution; (2) sampling and ultrasonic extraction; (3) concentrating; (4) purifying by a solid phase extraction column; (5) concentrating and enriching; (6) and (4) gas chromatography-mass spectrometry detection. The method can simply, accurately and sensitively detect the tetraethylene glycol dimethyl ether in the leather, has the advantages of simplicity, convenience, sample impurity interference resistance, strong selectivity, high accuracy, strong sensitivity, good reproducibility, low detection limit and the like, has good recovery rate and precision, and can be widely applied to the detection of the content of the tetraethylene glycol dimethyl ether in the leather.
Description
Technical Field
The invention relates to the technical field of chemical detection, in particular to a method for detecting tetraethylene glycol dimethyl ether in leather.
Background
The tetraethylene glycol dimethyl ether is an organic non-protonic colorless solvent, can be used as an excellent solvent of alkali gold hydride, and can also be used in various chemical reaction processes such as alkylation condensation, reduction and the like. The compound has Lewis basicity, so that it can selectively absorb acid gas and can be used for purifying synthetic gas, natural gas and acetylene, etc. The tetraethylene glycol dimethyl ether coating can be used for a glucose sensor, so that the sensor has the anti-sticking characteristic and the connection between the biomimic molecule and the surface is enhanced; in promoting cell adhesion, tetraglyme contributes to the selective adsorption of proteins. In addition, the tetraethylene glycol dimethyl ether can be used as an inert additive for fixing the methylated methylol melamine resin in pressure-resistant cotton and fiber fabrics, is mainly used as a solvent in the textile industry, can be used as a solvent and a diluent for printing and dyeing, and is used as a textile auxiliary agent for synthesizing dyes and paint diluents; the leather leveling agent is mainly used for leather coloring agents, emulsifiers, emulsion stabilizers, ink solvents, leather and fiber leveling agents and the like.
Research shows that tetraethylene glycol dimethyl ether has reproductive toxicity, can cause central nervous system disorder and pathological changes of respiratory organs, kidneys and vascular systems, cause anemia and megalobemia, generate new granular white blood cells and seriously affect the fertility of people. On 19/1/2021, the european chemical administration (ECHA) member national committee (MSC) formally included tetraethylene glycol dimethylether into the SVHC list. This means that countries and regions such as the european union have begun to attach importance to the hazards of the tetraethylene glycol dimethylether material, i.e. relevant laws and regulations are about to be set out to limit its application to leather products and other products requiring the use of tetraethylene glycol dimethylether. The leather products produced in China need to be exported to European Union, and the requirements of European Union REACH regulations need to be met. In order to cope with the technical trade barriers which may appear in the future, enhance the export competitiveness of leather products in China, ensure the health and safety of people, further improve the detection capability of ecological leather products in China and have important practical significance in developing the detection method research of the tetraethylene glycol dimethyl ether in the leather.
At present, the domestic and foreign documents do not report the research on the detection method and the relevant standards of the tetraethylene glycol dimethyl ether in the leather. Because of the wide application of tetraethylene glycol dimethyl ether in leather products, a set of measuring method suitable for the tetraethylene glycol dimethyl ether in the leather is urgently needed to be established, so that the life and property safety of consumers can be guaranteed, and the capability of China in the aspect of leather detection can be improved.
Disclosure of Invention
Therefore, the method for detecting the tetraethylene glycol dimethyl ether in the leather needs to be provided, the tetraethylene glycol dimethyl ether in the leather sample is extracted, concentrated, purified, enriched and subjected to gas chromatography-mass spectrometry detection, and the method is simple, convenient, high in selectivity, high in accuracy, strong in sensitivity and low in detection limit, so that the defect that the method for detecting the tetraethylene glycol dimethyl ether in the leather is lacked in the prior art is overcome.
In order to achieve the purpose, the technical scheme of the invention provides a method for detecting tetraglyme in leather, which comprises the following steps:
step S1, preparing a standard solution: weighing a tetraethylene glycol dimethyl ether standard substance, and preparing to obtain a tetraethylene glycol dimethyl ether standard solution with various concentrations by using an extraction solvent as a solvent;
step S2, sampling and ultrasonic extraction: weighing a leather sample to be detected, putting the leather sample into an extraction bottle, adding an extraction solvent, adjusting the extraction temperature and the extraction time, and extracting by adopting an ultrasonic water bath extraction method to obtain a sample extract;
step S3, concentration: placing the sample extraction liquid in a concentration bottle, concentrating by using a rotary evaporator under the conditions that the vacuum degree is 150-550 mbar, the water bath temperature is 30-45 ℃ and the rotating speed is 10-50 rpm, blowing nitrogen to be dry, and adding 2-10 mL of dissolving solvent for dissolving to obtain a sample dissolving solution;
step S4, solid phase extraction column purification: transferring the sample solution into a solid phase extraction column, applying negative pressure to enable the sample solution to flow through the solid phase extraction column, blowing the solid phase extraction column with nitrogen, and eluting the solid phase extraction column with an elution solvent to obtain an elution solution;
step S5, concentration and enrichment: concentrating the elution solution to 2mL by a rotary evaporator or nitrogen purging, and filtering the solution through a filter to obtain a solution to be detected;
step S6, gas chromatography-mass spectrometry detection: and (4) respectively injecting the tetraethylene glycol dimethyl ether standard solution obtained in the step (S1) and the solution to be detected obtained in the step (S5), respectively detecting according to the set gas chromatography-mass spectrometry conditions, and obtaining the content of the tetraethylene glycol dimethyl ether in the leather sample to be detected through qualitative and quantitative analysis.
As a further embodiment of the present invention, in step S2, the extraction solvent is selected from one or more of methanol, ethyl acetate, dichloromethane, and acetone.
As a further embodiment of the present invention, in step S2, the extraction temperature is 20-50 ℃, the extraction time is 5-120 min, and the number of extraction times is 1-3.
In the extraction process of step S2, the sample extracts obtained from each extraction are combined for the subsequent concentration operation.
As a further embodiment of the present invention, in step S3, the dissolving solvent is selected from one or more of n-hexane, cyclohexane, carbon tetrachloride, toluene, and dichloromethane.
As a further embodiment of the present invention, in step S4, the solid phase extraction column is an unbound silica gel column, an alumina column, a florisil column, a cyano-bound silica gel column or an amino-bound silica gel column.
As a further embodiment of the present invention, in step S4, the elution solvent used in the elution step is a mixed solvent of one or more of methanol, isopropanol, acetonitrile, and acetone.
As a further embodiment of the present invention, in step S6, the chromatographic conditions for the gas chromatography-mass spectrometry detection include:
sample inlet temperature: 180-320 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 5-35 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 0.7-2.0 mL/min;
sample introduction volume: 1-3 mu L;
transmission line temperature: 250 to 320 ℃.
As a further embodiment of the invention, in step S6, the sample injection mode of the gas chromatograph adopts a split mode or a non-split mode, and the split ratio in the split mode ranges from 1:1 to 1: 50.
As a further embodiment of the present invention, in step S6, the gas chromatography column is one of DB-5MS, DB-624, DB-17MS, DB-1701, TG-35MS and TG-5MS, and has a column length of 30 to 60m, a film thickness of 0.25 μm and an inner diameter of 0.25 to 0.32 mm.
As a further embodiment of the present invention, in step S6, the mass spectrometric conditions of the gas chromatography-mass spectrometric detection include:
ion source temperature: 230-280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 0-5 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 35-350 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z.
Preferably, in step S6, the mass spectrometry analysis has a quantitative ion of 59m/z and a qualitative ion of 45, 59, 103, 220 m/z.
Different from the prior art, the technical scheme has the following beneficial effects:
aiming at the defect that the prior art lacks a method for detecting the tetraethylene glycol dimethyl ether in the leather, the invention provides a method for detecting the tetraethylene glycol dimethyl ether in the leather. The method can simply, accurately and sensitively detect the tetraethylene glycol dimethyl ether in the leather through extraction, concentration, purification, enrichment and gas chromatography-mass spectrometry detection, has the advantages of simplicity, convenience, sample impurity interference resistance, strong selectivity, high accuracy, strong sensitivity, good reproducibility, low detection limit and the like, has good recovery rate and precision, and can be widely applied to the detection of the content of the tetraethylene glycol dimethyl ether in the leather.
The above description of the present invention is only an overview of the technical solutions of the present application, and in order to make the technical solutions of the present application more clearly understood by those skilled in the art, the present invention may be further implemented according to the content described in the text and drawings of the present application, and in order to make the above objects, other objects, features, and advantages of the present application more easily understood, the following description is made in conjunction with the detailed description of the present application and the drawings.
Drawings
The drawings are only for purposes of illustrating the principles, implementations, applications, features, and effects of particular embodiments of the present application, as well as others related thereto, and are not to be construed as limiting the application.
FIG. 1 is a graph showing the linear relationship between the concentration and the response signal of a tetraglyme series standard solution of example 1;
FIG. 2 is a full scan chromatogram of tetraethylene glycol dimethyl ether in a solution to be tested of a pig leather sample described in example 2;
FIG. 3 is a mass spectrum of tetraethylene glycol dimethyl ether obtained by full scanning of the solution to be tested of the pig leather sample described in example 2;
FIG. 4 is a signal comparison graph of tetraglyme obtained by continuously feeding 9 times the sample solution of the sheep leather sample described in example 4;
FIG. 5 is a total ion flow diagram of tetraethylene glycol dimethyl ether detected after unpurified and purified by a solid phase extraction column of the sheepskin sample ultrasonic extraction solution of example 5;
FIG. 6 is a selected ion flow diagram of tetraglyme obtained by detection of the sheepskin sample ultrasonic extraction solution of example 5 without purification and after purification treatment with a solid phase extraction column.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
The specific embodiment of the invention provides a method for detecting tetraglyme in leather, which comprises the following steps:
step S1, preparing a standard solution: weighing a tetraethylene glycol dimethyl ether standard substance, and preparing to obtain a tetraethylene glycol dimethyl ether standard solution with various concentrations by using an extraction solvent as a solvent;
step S2, sampling and ultrasonic extraction: weighing a leather sample to be detected, putting the leather sample into an extraction bottle, adding an extraction solvent, adjusting the extraction temperature and the extraction time, and extracting by adopting an ultrasonic water bath extraction method to obtain a sample extract;
step S3, concentration: placing the sample extraction liquid in a concentration bottle, concentrating by using a rotary evaporator under the conditions that the vacuum degree is 150-550 mbar, the water bath temperature is 30-45 ℃ and the rotating speed is 10-50 rpm, blowing nitrogen to be dry, and adding 2-10 mL of dissolving solvent for dissolving to obtain a sample dissolving solution;
step S4, solid phase extraction column purification: transferring the sample solution into a solid phase extraction column, applying negative pressure to enable the sample solution to flow through the solid phase extraction column, blowing the solid phase extraction column with nitrogen, and eluting the solid phase extraction column with an elution solvent to obtain an elution solution;
step S5, concentration and enrichment: concentrating the elution solution to 2mL by a rotary evaporator or nitrogen purging, and filtering the solution through a filter to obtain a solution to be detected;
step S6, gas chromatography-mass spectrometry detection: and (4) respectively injecting the tetraethylene glycol dimethyl ether standard solution obtained in the step (S1) and the solution to be detected obtained in the step (S5), respectively detecting according to the set gas chromatography-mass spectrometry conditions, and obtaining the content of the tetraethylene glycol dimethyl ether in the leather sample to be detected through qualitative and quantitative analysis.
The leather comprises different types of leather such as cow leather, sheep leather, pig leather and the like.
The technical scheme of the invention provides a method for detecting tetraglyme in leather, which has the following detection principle:
by analyzing a mass spectrogram obtained by detecting the tetraglyme standard substance in a gas chromatography-mass spectrometry, qualitative and quantitative characteristic fragment ions of the tetraglyme can be obtained, and the standard mass spectrogram of the tetraglyme is established. Performing spectrum library retrieval matching on a chromatographic peak of a total ion flow diagram of a sample to be detected to determine whether the tetraglyme exists in the sample to be detected, and determining whether the tetraglyme exists by combining retention time with the chromatographic peak with high matching degree; and quantitatively analyzing the tetraethylene glycol dimethyl ether in the sample to be detected by quantifying the characteristic ions. Quantitative analysis is carried out by an external standard method (standard curve equation), the concentration of the tetraethylene glycol dimethyl ether standard solution is taken as a horizontal coordinate, and the corresponding quantitative ion integral peak area is taken as a vertical coordinate, so that a standard curve is drawn. And comparing the peak area of the tetraethylene glycol dimethyl ether in the sample to be detected with a standard curve, and converting through a standard curve equation to obtain the content of the tetraethylene glycol dimethyl ether in the leather sample to be detected.
As a preferred embodiment, in step S2, the extraction solvent is selected from one or more of methanol, ethyl acetate, dichloromethane, and acetone.
In a preferred embodiment, in step S2, the extraction temperature is 20 to 50 ℃, the extraction time is 5 to 120min, and the number of times of extraction is 1 to 3.
As a preferred embodiment, in step S3, the dissolving solvent is selected from one or more of n-hexane, cyclohexane, carbon tetrachloride, toluene, and dichloromethane.
As a preferred embodiment, in step S4, the solid phase extraction column is an unbound silica gel column, an alumina column, a florisil column, a cyano-bound silica gel column or an amino-bound silica gel column.
In a preferred embodiment, in step S4, the elution solvent used in the elution step is a mixed solvent of one or more of methanol, isopropanol, acetonitrile, and acetone.
As a preferred embodiment, in step S6, the chromatographic conditions for the gas chromatography-mass spectrometry detection include:
sample inlet temperature: 180-320 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 5-35 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 0.7-2.0 mL/min;
sample introduction volume: 1-3 mu L;
transmission line temperature: 250 to 320 ℃.
In a preferable embodiment, the sample injection mode of the gas chromatography adopts a split mode or a non-split mode, and the split ratio in the split mode ranges from 1:1 to 1: 50.
In a preferred embodiment, in step S6, the gas chromatography column is one of DB-5MS, DB-624, DB-17MS, DB-1701, TG-35MS and TG-5MS, and has a column length of 30 to 60m, a film thickness of 0.25 μm and an inner diameter of 0.25 to 0.32 mm.
As a preferred embodiment, in step S6, the mass spectrometric conditions of the gas chromatography-mass spectrometric detection include:
ion source temperature: 230-280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 0-5 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 35-350 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z.
Preferably, in step S6, the mass spectrometry analysis has a quantitative ion of 59m/z and a qualitative ion of 45, 59, 103, 220 m/z.
The above is the core technical solution of the present invention, and the following will explain each step in detail with reference to specific examples.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures in the following examples are conventional unless otherwise specified.
In the following examples, the equipment used was: ultrasonic extraction instrument, rotary evaporator, gas chromatography-mass spectrometer; the test materials used were: a pig leather sample, a sheep leather sample, a cow leather sample.
Example 1 measurement of tetraethylene glycol dimethyl ether in bovine leather sample
(1) Preparing a standard solution: using a liquid transfer gun to transfer 0.01013g of tetraethylene glycol dimethyl ether standard substance, using methanol as a solvent, and fixing the volume to 100mL to obtain 101.3mg/L tetraethylene glycol dimethyl ether standard stock solution, and diluting the tetraethylene glycol dimethyl ether standard stock solution into tetraethylene glycol dimethyl ether standard solutions with various concentrations, wherein the concentrations are 0.5, 1.0, 2.5, 5.0, 7.5 and 10.0mg/L respectively.
(2) Sampling and ultrasonic extraction: cutting a cattle leather sample without the tetraethylene glycol dimethyl ether into small samples with the size of 2mm multiplied by 2mm by using a scissors or a cloth chopper, accurately weighing 1.00g (+0.01g) of the samples, putting the samples into a glass bottle with a spiral cover (the volume is 40mL), adding 10mL of extraction solvent acetone and 0.2mL of 1.0mg/L tetraethylene glycol dimethyl ether standard solution, covering and screwing, and placing the mixture into an ultrasonic water bath at the temperature of 30 ℃ for ultrasonic treatment for 30min after vortex and uniform mixing. The supernatant was collected and the residue rinsed with 10mL acetone for another 5min extraction, and the sample extracts were combined in a concentration flask for subsequent concentration operations.
(3) Concentration: placing the concentration bottle on a rotary evaporator, evaporating and concentrating to be nearly dry under the conditions of a vacuum degree of 550mbar, a water bath temperature of 40 ℃ and a rotating speed of 20rpm, drying by using nitrogen, and adding 3.0mL of n-hexane for dissolving to obtain a sample dissolving solution;
(4) purifying by a solid phase extraction column: transferring the sample dissolved solution to a silica gel column which is activated by n-hexane and is not bonded, enabling the sample dissolved solution to flow through the silica gel column by applying negative pressure, blowing nitrogen to be dry, and eluting by using 5mL of an elution solvent acetone to obtain an elution solution.
(5) Concentration and enrichment: concentrating the elution solution to 2mL by a rotary evaporator or nitrogen purging, and filtering the concentrated solution by using an organic phase filter membrane with the aperture of 0.45 mu m to obtain the solution to be detected.
(6) Gas chromatography-mass spectrometry detection: and respectively injecting standard solutions of the tetraethylene glycol dimethyl ether standard solution and the blank cattle leather sample with different concentrations, and respectively detecting according to the set gas chromatography-mass spectrometry conditions.
The chromatographic conditions determined were as follows:
a chromatographic column: DB-5MS, specification 60m 0.25mm 0.25 μm;
sample inlet temperature: 280 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 1.0 mL/min;
sample introduction volume: 1.0 μ L;
sample introduction mode: no shunt sampling;
transmission line temperature: 280 ℃.
The mass spectral conditions determined were as follows:
ion source temperature: 280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 4 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 40 to 250 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z;
the quantitative ion was 59m/z, and the qualitative ion was 45, 59, 103, 220 m/z.
In this example, a series of standard solutions of tetraglyme at different concentrations were determined by gas chromatography-mass spectrometry. The linear relation between the concentration and the response signal of the tetraglyme series standard solution is shown in figure 1, and it can be seen from the figure that the peak area of the characteristic ion of the tetraglyme in the concentration range of 0.1-10 mg/L has a good linear relation with the concentration, and the linear range comprises two orders of magnitude. Adding 0.2mg/kg of four ethylene glycol dimethyl ether compounds into a blank cow leather sample, and finding that the signal-to-noise ratio of the target component tetraethylene glycol dimethyl ether in the sample solution to be detected is 75, so that the sample can be ensured not to be detected under the quantitative limit. The lowest detection limit of the tetraglyme is 0.05mg/kg by the triple signal-to-noise ratio formula, and the linear equation, detection limit, quantitative limit and other information of the tetraglyme compound are shown in table 1. These data indicate that the method provided by the present invention has good linearity, wide linearity range, low detection limit, and high detection sensitivity.
TABLE 1 Linear equation, detection limits and quantitation limits for tetraethylene glycol dimethyl ether compounds
Example 2 measurement of tetraethylene glycol dimethyl ether in pig leather
(1) Sampling and ultrasonic extraction: cutting a pig leather sample into small samples with the size of less than 2mm multiplied by 2mm by using scissors or a cloth chopper, accurately weighing 1.00g of the samples, placing the samples into a glass bottle (the volume is 40mL) with a spiral cover, adding 10mL of extraction solvent acetone, covering and screwing, performing vortex mixing, and placing the mixture into an ultrasonic water bath at the temperature of 30 ℃ for ultrasonic treatment for 30 min. The supernatant was collected and the residue rinsed with 10mL acetone for another 5min extraction, and the sample extracts were combined in a concentration flask for subsequent concentration operations.
(3) Concentration: placing the concentration bottle on a rotary evaporator, evaporating and concentrating to be nearly dry under the conditions of a vacuum degree of 550mbar, a water bath temperature of 40 ℃ and a rotating speed of 20rpm, drying by using nitrogen, and adding 3.0mL of n-hexane for dissolving to obtain a sample dissolving solution;
(4) purifying by a solid phase extraction column: transferring the sample dissolving solution to an alumina column activated by n-hexane, enabling the sample dissolving solution to flow through the alumina column by applying negative pressure, blowing nitrogen to be dry, and eluting by using 5mL of elution solvent methanol to obtain an elution solution.
(5) Concentration and enrichment: concentrating the elution solution to 2mL by a rotary evaporator or nitrogen purging, and filtering the concentrated solution by a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu m to obtain the solution to be detected.
(6) Gas chromatography-mass spectrometry detection: and (3) injecting a solution to be detected of the pig leather sample, and detecting according to the set gas chromatography-mass spectrometry conditions.
The chromatographic conditions determined were as follows:
a chromatographic column: DB-5MS, specification 60m 0.25mm 0.25 μm;
sample inlet temperature: 280 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 1.0 mL/min;
sample introduction volume: 1.0 μ L;
sample introduction mode: split-flow sample injection is carried out, and the split-flow ratio is 1: 10;
transmission line temperature: 280 ℃.
The mass spectral conditions determined were as follows:
ion source temperature: 280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 4 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 40 to 250 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z;
the quantitative ion was 59m/z, and the qualitative ion was 45, 59, 103, 220 m/z.
Fig. 2 is a full scan chromatogram of tetraglyme in the solution to be tested of the pig leather sample in this embodiment. As can be seen from FIG. 2, the retention time of tetraglyme in the pig leather sample is 16.39min, and the obtained chromatographic peak is sharp, the column efficiency is high, and the accuracy is good.
Fig. 3 is a mass spectrum of tetraglyme obtained by full scanning of the solution to be tested of the pig leather sample in this embodiment, and the characteristic ion peaks m/z are 45, 59, 103, and 220, respectively. By performing spectrum library retrieval matching on the chromatographic peak of the total ion flow diagram of the sample to be detected, the matching degree reaches 82.66%, and the fact that the sample to be detected of the pig leather contains the tetraethylene glycol dimethyl ether can be determined. By checking the purity of characteristic ions of chromatographic peaks, the characteristic ions m/z 59 have the strongest signal and high sensitivity, so that the qualitative determination is carried out by adopting a selective ion detection (SIM) method, and the peak area of the extracted characteristic ions m/z 59 is quantitative, so that the content of the tetraglyme in the pig leather sample is 45.12 mg/kg.
Example 3 measurement of tetraethylene glycol dimethyl ether in bovine leather sample
(1) Sampling and ultrasonic extraction: cutting a beef leather sample into small samples with the size of less than 2mm multiplied by 2mm by using scissors or a cloth cutter, accurately weighing 18 parts of 1.00g of the samples, respectively placing the samples into glass bottles with screw caps (the volume is 40mL), respectively adding 10mL of extraction solvent acetone, adding 0.1mL of 10mg/L tetraethylene glycol dimethyl ether standard solution into 6 of the glass bottles, capping and screwing, adding 0.2mL of 10mg/L tetraethylene glycol dimethyl ether standard solution into the other 6 of the glass bottles, capping and screwing, adding 0.1mL of 100mg/L tetraethylene glycol dimethyl ether standard solution into the rest 6 of the glass bottles, capping and screwing. Respectively vortexing and mixing uniformly, and then carrying out ultrasonic treatment in an ultrasonic water bath at 30 ℃ for 30 min. The supernatants were collected and the residue was rinsed with 10mL acetone and re-extracted for 5min, and the sample extracts were pooled in 18 concentration bottles for subsequent concentration operations.
(3) Concentration: respectively placing the concentration bottles on a rotary evaporator, evaporating and concentrating to be nearly dry under the conditions of a vacuum degree of 550mbar, a water bath temperature of 40 ℃ and a rotating speed of 35rpm, drying by using nitrogen, and adding 3.0mL of n-hexane for dissolving to obtain a sample solution;
(4) purifying by a solid phase extraction column: transferring the 18 sample solutions to 18 n-hexane-activated non-bonded silica gel columns, allowing the sample solutions to flow through the silica gel columns by applying negative pressure, blow-drying the silica gel columns with nitrogen, and eluting with 5mL of an elution solvent, namely acetone, to obtain elution solutions of 18 samples.
(5) Concentration and enrichment: concentrating the elution solutions of 18 samples to 2mL by a rotary evaporator or nitrogen purging, and filtering the concentrated solution by a polytetrafluoroethylene filter membrane with the aperture of 0.22 mu m to obtain 18 solutions to be detected.
(6) Gas chromatography-mass spectrometry detection: and respectively injecting 18 solutions to be detected, and determining 18 samples to be detected according to the set gas chromatography-mass spectrometry conditions.
The chromatographic conditions determined were as follows:
a chromatographic column: DB-5MS, specification 60m 0.25mm 0.25 μm;
sample inlet temperature: 280 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 1.0 mL/min;
sample introduction volume: 1.0 μ L;
sample introduction mode: no shunt sampling;
transmission line temperature: 280 ℃.
The mass spectral conditions determined were as follows:
ion source temperature: 280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 4 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 40 to 250 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z;
the quantitative ion was 59m/z, and the qualitative ion was 45, 59, 103, 220 m/z.
In this example, bovine leather commonly used in leather products was selected as a sample, and ethylene glycol dimethyl ether standard substances at three concentration levels of 1.0, 2.0 and 10.0mg/kg were added to perform the test. The spiked recovery data for the bovine leather samples are shown in table 2. The recovery rate of the tetraglycol dimethyl ether substance is between 82.3 and 103.6 percent, and the relative standard deviation is between 4.78 and 7.35 percent, which shows that the method provided by the invention has better precision and accuracy.
TABLE 2 recovery of bovine leather samples with standard addition
EXAMPLE 4 measurement of tetraethylene glycol dimethyl Ether in sheep leather samples
(1) Sampling and ultrasonic extraction: cutting a sheep leather sample into small samples with the size of less than 2mm multiplied by 2mm by using scissors or a cloth chopper, accurately weighing 1.00g of the samples, placing the samples into a glass bottle (the volume is 40mL) with a spiral cover, adding 10mL of extraction solvent acetone, covering and screwing, performing vortex mixing, and placing the mixture into an ultrasonic water bath at the temperature of 30 ℃ for ultrasonic treatment for 30 min. The supernatant was collected and the residue rinsed with 10mL acetone for another 5min extraction, and the sample extracts were combined in a concentration flask for subsequent concentration operations.
(3) Concentration: placing the concentration bottle on a rotary evaporator, evaporating and concentrating to be nearly dry under the conditions of a vacuum degree of 550mbar, a water bath temperature of 40 ℃ and a rotating speed of 20rpm, drying by using nitrogen, and adding 3.0mL of n-hexane for dissolving to obtain a sample dissolving solution;
(4) purifying by a solid phase extraction column: transferring the sample dissolving solution to an alumina column activated by n-hexane, enabling the sample dissolving solution to flow through the alumina column by applying negative pressure, blowing nitrogen to be dry, and eluting with 5mL of an elution solvent acetone to obtain an elution solution.
(5) Concentration and enrichment: concentrating the elution solution to 2mL by a rotary evaporator or nitrogen purging, and filtering the concentrated solution by a polytetrafluoroethylene filter membrane with the aperture of 0.22 mu m to obtain the solution to be detected.
(6) Gas chromatography-mass spectrometry detection: and (3) sampling the solution to be detected, and carrying out 9 continuous repeated determination tests on the solution to be detected according to the set gas chromatography-mass spectrometry conditions.
The chromatographic conditions determined were as follows:
a chromatographic column: DB-5MS, specification 60m 0.25mm 0.25 μm;
sample inlet temperature: 280 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 1.0 mL/min;
sample introduction volume: 1.0 μ L;
sample introduction mode: no shunt sampling;
transmission line temperature: 280 ℃.
The mass spectral conditions determined were as follows:
ion source temperature: 280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 4 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 40 to 250 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z;
the quantitative ion was 59m/z, and the qualitative ion was 45, 59, 103, 220 m/z.
Fig. 4 is a comparison graph of the signal of tetraglyme obtained in this example after 9 times of continuous sample injection of the solution to be measured, wherein the relative standard deviation is 2.27%, thus indicating that the method provided by the present invention has good stability.
EXAMPLE 5 measurement of tetraethylene glycol dimethyl Ether without and after purification treatment of a sample of sheep leather
(1) Sampling and ultrasonic extraction: cutting a sheep leather sample into small samples with the size of less than 2mm multiplied by 2mm by using scissors or a cloth chopper, accurately weighing two samples with the weight of 1.00g, placing the two samples into a glass bottle A and a glass bottle B with spiral covers, respectively adding 10mL of extraction solvent methanol, covering and screwing, respectively carrying out vortex mixing, and then placing the mixture into an ultrasonic water bath with the temperature of 30 ℃ for ultrasonic treatment for 30 min. And respectively collecting the supernatants in the glass bottle A and the glass bottle B, respectively rinsing the residues with 10mL of methanol, respectively extracting for 5min, and respectively combining the sample extracts in a concentration bottle C and a concentration bottle D for subsequent concentration operation.
(3) Concentration: and respectively placing the concentration bottles C and D on a rotary evaporator, evaporating and concentrating to be nearly dry under the conditions of a vacuum degree of 200mbar, a water bath temperature of 40 ℃ and a rotating speed of 35rpm, blow-drying by using nitrogen, and adding 2.0mL of dichloromethane for dissolving to obtain a sample dissolved solution E and a sample dissolved solution F. Wherein the sample dissolving solution F is filtered by a polytetrafluoroethylene filter membrane with the aperture of 0.22 mu m to obtain a solution G to be detected;
(4) solid phase extraction and purification: transferring the sample solution E to a silica gel column which is activated by normal hexane and is not bonded, enabling the sample solution to flow through the silica gel column by applying negative pressure, blowing the silica gel column by using nitrogen, and eluting by using 5mL of an elution solvent acetone to obtain an elution solution H.
(5) Concentration and enrichment: concentrating the elution solution H to 2mL by a rotary evaporator or nitrogen purging, and filtering the concentrated solution by a polytetrafluoroethylene filter membrane with the aperture of 0.22 mu m to obtain a solution I to be detected.
(6) Gas chromatography-mass spectrometry detection: and respectively injecting samples into the solution G to be detected and the solution I to be detected, and respectively detecting according to the set gas chromatography-mass spectrometry conditions.
The chromatographic conditions determined were as follows:
a chromatographic column: DB-5MS, specification 60m 0.25mm 0.25 μm;
sample inlet temperature: 280 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 1.0 mL/min;
sample introduction volume: 1.0 μ L;
sample introduction mode: no shunt sampling;
transmission line temperature: 280 ℃.
The mass spectral conditions determined were as follows:
ion source temperature: 280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 4 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 40 to 250 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z;
the quantitative ion was 59m/z, and the qualitative ion was 45, 59, 103, 220 m/z.
Fig. 5 is a total ion flow diagram of tetraglyme obtained by detecting the sheepskin sample ultrasonic extraction solution obtained in the present example after the solution is not purified and is purified by a solid phase extraction column; fig. 6 is a selected ion flow diagram of tetraglyme obtained by detecting the sheepskin sample ultrasonic extraction solution obtained in the present example without purification and after purification treatment by a solid phase extraction column.
As can be seen from FIGS. 5 and 6, after the purification treatment of the solid-phase extraction column, the gas chromatography-mass spectrometry detection is adopted, so that the sample has less impurity interference, strong selectivity and higher detection accuracy.
Aiming at the defect that the prior art lacks a method for detecting the tetraethylene glycol dimethyl ether in the leather, the invention provides a method for detecting the tetraethylene glycol dimethyl ether in the leather. The method can simply, accurately and sensitively detect the tetraethylene glycol dimethyl ether in the leather through extraction, concentration, purification, enrichment and gas chromatography-mass spectrometry detection, has the advantages of simplicity, convenience, sample impurity interference resistance, strong selectivity, high accuracy, strong sensitivity, good reproducibility, low detection limit and the like, has good recovery rate and precision, and can be widely applied to the detection of the content of the tetraethylene glycol dimethyl ether in the leather.
It should be understood that the technical solutions of the above embodiments, which are obtained by proportionally expanding or reducing the amounts of the raw materials or reagents used, are substantially the same as those of the above embodiments, and thus all belong to the protection scope of the present invention.
Furthermore, it should be noted that, although the above embodiments have been described herein, the scope of the present invention is not limited thereby. The technical parameters which are not described in detail herein can still obtain the same or similar technical effects as the above embodiments when they are changed within the range of the parameters recited in the present invention, and still belong to the protection scope of the present invention. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (10)
1. A method for detecting tetraethylene glycol dimethyl ether in leather is characterized by comprising the following steps:
step S1, preparing a standard solution: weighing a tetraethylene glycol dimethyl ether standard substance, and preparing to obtain a tetraethylene glycol dimethyl ether standard solution with various concentrations by using an extraction solvent as a solvent;
step S2, sampling and ultrasonic extraction: weighing a leather sample to be detected, putting the leather sample into an extraction bottle, adding an extraction solvent, adjusting the extraction temperature and the extraction time, and extracting by adopting an ultrasonic water bath extraction method to obtain a sample extract;
step S3, concentration: placing the sample extraction liquid in a concentration bottle, concentrating by using a rotary evaporator under the conditions that the vacuum degree is 150-550 mbar, the water bath temperature is 30-45 ℃ and the rotating speed is 10-50 rpm, blowing nitrogen to be dry, and adding 2-10 mL of dissolving solvent for dissolving to obtain a sample dissolving solution;
step S4, solid phase extraction column purification: transferring the sample solution into a solid phase extraction column, applying negative pressure to enable the sample solution to flow through the solid phase extraction column, blowing the solid phase extraction column with nitrogen, and eluting the solid phase extraction column with an elution solvent to obtain an elution solution;
step S5, concentration and enrichment: concentrating the elution solution to 2mL by a rotary evaporator or nitrogen purging, and filtering the solution through a filter to obtain a solution to be detected;
step S6, gas chromatography-mass spectrometry detection: and (4) respectively injecting the tetraethylene glycol dimethyl ether standard solution obtained in the step (S1) and the solution to be detected obtained in the step (S5), respectively detecting according to the set gas chromatography-mass spectrometry conditions, and obtaining the content of the tetraethylene glycol dimethyl ether in the leather sample to be detected through qualitative and quantitative analysis.
2. The detection method according to claim 1, wherein in step S2, the extraction solvent is selected from one or more of methanol, ethyl acetate, dichloromethane, and acetone.
3. The detection method according to claim 1, wherein in step S2, the extraction temperature is 20-50 ℃, the extraction time is 5-120 min, and the number of extraction times is 1-3.
4. The detection method according to claim 1, wherein in step S3, the dissolution solvent is selected from one or more of n-hexane, cyclohexane, carbon tetrachloride, toluene, and dichloromethane.
5. The detection method according to claim 1, wherein in step S4, the solid phase extraction column is an unbound silica gel column, an alumina column, a Flori silica column, a cyano-bound silica gel column or an amino-bound silica gel column.
6. The detection method according to claim 1, wherein in step S4, the elution solvent used in the elution step is a mixed solvent of one or more of methanol, isopropanol, acetonitrile, and acetone.
7. The detection method according to claim 1, wherein in step S6, the chromatographic conditions of the gas chromatography-mass spectrometry detection include:
sample inlet temperature: 180-320 ℃;
temperature rising procedure: the initial temperature is 35 ℃, the temperature is kept for 5min, then the temperature is raised to 280 ℃ at the speed of 5-35 ℃/min, and the temperature is kept for 2 min;
carrier gas: high-purity helium with the volume content of 99.999 percent, and the flow rate is 0.7-2.0 mL/min;
sample introduction volume: 1-3 mu L;
transmission line temperature: 250 to 320 ℃.
8. The detection method according to claim 1, wherein in step S6, the sample injection mode of the gas chromatograph adopts a split mode or a non-split mode, and the split ratio in the split mode ranges from 1:1 to 1: 50.
9. The detection method according to claim 1, wherein in step S6, the gas chromatography column is one of DB-5MS, DB-624, DB-17MS, DB-1701, TG-35MS and TG-5MS, and has a column length of 30-60 m, a film thickness of 0.25 μm and an inner diameter of 0.25-0.32 mm.
10. The detection method according to claim 1, wherein in step S6, the mass spectrometric conditions of the gas chromatography-mass spectrometric detection comprise:
ion source temperature: 230-280 ℃;
an ionization mode: electron Ionization (EI);
ionization capacity: 70 eV;
solvent delay time: 0-5 min;
an acquisition mode: SCAN + SIM;
SCAN mass SCAN range: 35-350 m/z;
SIM quality scanning: 45, 59, 103, 220 m/z;
preferably, in step S6, the mass spectrometry analysis has a quantitative ion of 59m/z and a qualitative ion of 45, 59, 103, 220 m/z.
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