CN111721881A - Trifluoroacetylation GC-MS (gas chromatography-mass spectrometry) detection method for banned azo dyes of textiles - Google Patents
Trifluoroacetylation GC-MS (gas chromatography-mass spectrometry) detection method for banned azo dyes of textiles Download PDFInfo
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- CN111721881A CN111721881A CN202010648214.5A CN202010648214A CN111721881A CN 111721881 A CN111721881 A CN 111721881A CN 202010648214 A CN202010648214 A CN 202010648214A CN 111721881 A CN111721881 A CN 111721881A
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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
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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
- G01N30/62—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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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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
- G01N2030/062—Preparation extracting sample from raw material
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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
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
Abstract
A trifluoroacetyl gas chromatography-mass spectrometry textile forbidden azo dye detection method comprises the following steps: s1-reduction and decomposition, cutting the textile sample to be detected into fragment samples, mixing uniformly, sampling, placing in a reactor, adding citric acid buffer solution, sealing and shaking; then placing the reactor in warm water for water bath and preserving heat for 30 min; then adding sodium hydrosulfite solution into the reactor, and immediately sealing and shaking; then placing the reactor in warm water again for water bath and heat preservation for 30 min; s2-extraction, namely adding 0.5mL of NaOH solution, 7g of NaCl and 5mL of tert-butyl methyl ether internal standard working solution into a reactor, sealing, placing the reactor in a mechanical oscillator, axially oscillating for 10min, and then standing until two phases are layered; s3-derivatization, wherein 1mL of supernatant is obtained from a reactor, 25 muL of trifluoroacetic anhydride solution and 3mLNaOH solution are added, and the mixture is sealed and vibrated for 10min to obtain a solution to be detected; s4-instrumental analysis, and performing azo-based detection analysis on the liquid to be detected by adopting a gas chromatograph-mass spectrometer. Convenient operation, shortened detection time, and avoided various false positive results.
Description
Technical Field
The invention relates to the technical field of textile detection, in particular to a trifluoroacetyl gas chromatography-mass spectrometry-based method for detecting azo dyes forbidden for textiles.
Background
The azo dye is an organic synthetic dye which contains azo groups (-N = N-) in the structure and is at least connected with one aromatic group, has the advantages of simple manufacturing process, various colors, wide applicability, excellent color, firm dyeing and the like, and is widely applied to textiles, leather products and some daily products needing coloring.
Some azo compounds have carcinogenic effects, such as "cream yellow" which has been used for coloring margarine, which can induce liver cancer, and methyl red used as an indicator can cause bladder and breast tumors. The reason is that the forbidden nitrogen dye can be absorbed by skin in the process of contacting with human body and is reduced and decomposed under the normal metabolism of human body, and some aromatic amine which has carcinogenic effect on human body or animal is released to become the inducing factor of human body pathological changes. Therefore, the industry has specifically limited this to prohibit the use of azo dyes that reduce carcinogenic aromatic amines.
Based on the above background, many detection methods for banning azo dyes have been proposed in the industry. At present, the main detection methods of carcinogenic aromatic amine are gas chromatography mass spectrometry (GC-MS), high performance liquid chromatography (HPLC/DAD) and the like. The detection principle is that a sample is reduced and decomposed by sodium hydrosulfite in a citric acid buffer solution medium to generate carcinogenic aromatic amine which may exist, the aromatic amine obtained by reduction is extracted and extracted by liquid-liquid extraction, and after concentration and volume fixing, different detection instruments are used for measurement. If necessary, the isomer is confirmed by one or more additional methods.
The gas chromatography-mass spectrometry has wide application due to the superiority in qualitative detection, most laboratories mainly adopt the method for detection at present, and the detection means of the method is as disclosed in the Chinese invention with the authorization publication number of CN102798677B, and discloses a rapid screening and detecting method for banned azo dyes in textiles, leather and dyes by using the gas chromatography-mass spectrometry. However, some carcinogenic aromatic amines present isomers that have not been banned. Isomers have the same relative molecular weight, similar polarity, close boiling point, and the same mass spectrum characteristic ions, and therefore have the same retention behavior in the separation column, and the mass spectra are also very similar, which can cause false qualitative results, i.e., false positive results. The occurrence of false positive problem can cause serious interference to the detection, influence the accuracy of qualitative result, bring certain difficulty to daily detection work, and can also cause detection dispute and economic loss when serious. Therefore, the Chinese invention with the authorization publication number of CN102798677B disclosed in the above-mentioned list discloses a rapid screening and detecting method for forbidden azo dyes in textiles, leather and dyes by using gas chromatography-mass spectrometry, and the suspected positive samples detected are screened, and the test is carried out again according to the standard method for detecting forbidden azo dyes
In actual detection, the aim of separating the carcinogenic aromatic amine and the isomers thereof can be achieved by changing a temperature raising program to prolong the detection time, but the method has the problems of long detection time, low efficiency and inapplicability of part of carcinogenic aromatic amine. Most laboratories currently adopt high performance liquid chromatography to further confirm suspected detection of aromatic amine by gas chromatography-mass spectrometry, and the method can separate and detect all carcinogenic aromatic amines, but has the problems of long detection time and low efficiency.
Disclosure of Invention
Aiming at the defects of the detection method of the forbidden azo dyes, the invention provides a method for detecting the forbidden azo dyes of the textile by using trifluoroacetyl gas chromatography and mass spectrometry, carcinogenic aromatic amine and trifluoroacetic anhydride are subjected to acetylation reaction and then are detected by using a gas chromatography and mass spectrometry instrument, the carcinogenic aromatic amine and the isomers thereof can be effectively separated in a short detection time, the probability of false positive problems is reduced, the probability of adopting high performance liquid chromatography for confirmation is reduced, the good detection accuracy is ensured, and meanwhile, the detection efficiency and the economic benefit are greatly improved.
In order to achieve the above object, the present invention adopts the following technical solutions.
A trifluoroacetyl gas chromatography-mass spectrometry textile forbidden azo dye detection method comprises the following steps:
s1-reductive decomposition
Shearing the textile sample to be detected into fragment samples, uniformly mixing, sampling, placing in a reactor, adding a citric acid buffer solution, and sealing and shaking;
then placing the reactor in warm water for water bath and preserving heat for 30 min;
then adding sodium hydrosulfite solution into the reactor, and immediately sealing and shaking;
then placing the reactor in warm water again for water bath and heat preservation for 30 min;
finally taking out the reactor and cooling to room temperature;
s2-extraction
Adding 0.5mL of NaOH solution, 7g of NaCl and 5mL of tert-butyl methyl ether internal standard working solution into a reactor, sealing, placing in a mechanical oscillator, axially oscillating for 10min, and then standing until two phases are layered;
s3-derivatization
Obtaining 1mL of supernatant from a reactor, adding 25 muL of trifluoroacetic anhydride solution and 3mLNaOH solution, and carrying out closed oscillation for 10min to obtain a solution to be detected;
s4-instrumental analysis
And (3) performing azo-based detection analysis on the solution to be detected by adopting a gas chromatograph-mass spectrometer.
Compared with the prior art, the invention has the beneficial effects that:
the method can effectively separate carcinogenic aromatic amine and isomers thereof in a short detection time, such as separation of o-toluidine, p-toluidine and m-toluidine and separation of 2, 4-xylidine and 2, 6-xylidine, and simultaneously the probability of detecting the 4, 4-diaminodiphenylmethane with 99 percent false positive is reduced, thereby reducing the condition that the 4, 4-diaminodiphenylmethane needs to be confirmed with high performance liquid chromatography for false positive. The whole process is convenient to operate, the detection time is shortened, various false positive results are avoided, the detection efficiency is improved, and the method is a systematic and effective solution.
The present invention will be further described with reference to specific embodiments.
Detailed Description
A trifluoroacetyl gas chromatography-mass spectrometry textile forbidden azo dye detection method comprises the following steps:
s1-reductive decomposition
Shearing the textile sample to be detected into fragment samples, uniformly mixing, sampling, placing in a reactor, adding a citric acid buffer solution, and sealing and shaking;
then placing the reactor in warm water for water bath and preserving heat for 30 min;
then adding sodium hydrosulfite solution into the reactor, and immediately sealing and shaking;
then placing the reactor in warm water again for water bath and heat preservation for 30 min;
finally taking out the reactor and cooling to room temperature;
s2-extraction
Adding 0.5mL of NaOH solution, 7g of NaCl and 5mL of tert-butyl methyl ether internal standard working solution into a reactor, sealing, placing in a mechanical oscillator, axially oscillating for 10min, and then standing until two phases are layered;
s3-derivatization
Obtaining 1mL of supernatant from a reactor, adding 25 muL of trifluoroacetic anhydride solution and 3mLNaOH solution, and carrying out closed oscillation for 10min to obtain a solution to be detected;
s4-instrumental analysis
And (3) performing azo-based detection analysis on the solution to be detected by adopting a gas chromatograph-mass spectrometer.
The method can effectively separate carcinogenic aromatic amine and isomers thereof, such as separation of o-toluidine, p-toluidine and m-toluidine and separation of 2, 4-xylidine and 2, 6-xylidine, in a short detection time, simultaneously reduces the probability of detecting the 4, 4-diaminodiphenylmethane with 99 percent false positive in the method, and reduces the condition of needing the high performance liquid chromatography to confirm the false positive of the 4, 4-diaminodiphenylmethane.
The method is convenient to operate, shortens the detection time, avoids various false positive results, improves the detection efficiency, and is a systematic and effective solution.
As an improvement of the above technical solution, preferably, the fragment sample in S1 is cut into 5 × 5mm fragments, and 1 ± 0.01g of the fragment sample is weighed after mixing.
Further, the citric acid buffer solution in S1 is 17mL of citric acid buffer solution preheated to 70 + -2 ℃, the added sodium dithionite solution is 3mL, and the water bath heat preservation system adopts warm water at 70 + -2 ℃.
Optionally, when the two phases are not separated obviously after standing in S2, the reactor is sealed and centrifuged for 3min at the rotating speed of 4000 r/min.
Optionally, centrifuging for 3min at a rotation speed of 4000r/min after shaking in S3, and taking supernatant as the liquid to be detected.
The gas chromatograph-mass spectrometer used in the above technical solution is an apparatus in which a gas chromatograph and a mass spectrometer are used in combination. Mass spectrometry can carry out effective qualitative analysis, but cannot analyze complex organic compounds; chromatography is an effective method for separating and analyzing organic compounds, and is particularly suitable for quantitative analysis of organic compounds, but qualitative analysis is difficult. Therefore, the effective combination of the two must provide a highly effective qualitative and quantitative analysis tool for chemists and biochemists to carry out complex organic compounds.
Preferably, model 7890B-5977B GC is used in S4.
Wherein, the analysis conditions of the gas chromatograph-mass spectrometer are as follows:
capillary column: DB-35MS column, 30m × 0.25mm × 0.25 μm;
temperature programming: initial temperature: maintaining at 100 deg.C for 0.5 min;
the first stage is as follows: 30 ℃/min to 280 ℃ and keeping for 2 minutes;
and a second stage: keeping the temperature at 20 ℃/min to 300 ℃ for 1.5 min;
final stabilization time: 0.5 min;
carrier gas: helium gas;
flow rate: 1 mL/min;
sample inlet temperature: 250 ℃;
sample introduction amount: 2 muL;
the sample feeding mode is divided, and the division ratio is 5: 1;
scanning range: 50-400 amu.
It will be clear to a person skilled in the art that the scope of protection of the present invention is not limited to details of the foregoing illustrative embodiments, and that all changes which come within the meaning and range of equivalency of the claims are intended to be embraced therein by the appended claims without departing from the spirit or essential characteristics thereof.
Claims (7)
1. A trifluoroacetyl gas chromatography-mass spectrometry-based detection method for banned azo dyes of textiles is characterized by comprising the following steps:
s1-reductive decomposition
Shearing the textile sample to be detected into fragment samples, uniformly mixing, sampling, placing in a reactor, adding a citric acid buffer solution, and sealing and shaking;
then placing the reactor in warm water for water bath and preserving heat for 30 min;
then adding sodium hydrosulfite solution into the reactor, and immediately sealing and shaking;
then placing the reactor in warm water again for water bath and heat preservation for 30 min;
finally taking out the reactor and cooling to room temperature;
s2-extraction
Adding 0.5mL of NaOH solution, 7g of NaCl and 5mL of tert-butyl methyl ether internal standard working solution into a reactor, sealing, placing in a mechanical oscillator, axially oscillating for 10min, and then standing until two phases are layered;
s3-derivatization
Obtaining 1mL of supernatant from a reactor, adding 25 muL of trifluoroacetic anhydride solution and 3mLNaOH solution, and carrying out closed oscillation for 10min to obtain a solution to be detected;
s4-instrumental analysis
And (3) performing azo-based detection analysis on the solution to be detected by adopting a gas chromatograph-mass spectrometer.
2. The method for detecting trifluoroacetyl gas chromatography-mass spectrometry forbidden azo dyes of claim 1, wherein the fragment sample in S1 is cut into 5x5mm fragments, and the sample of the uniformly mixed fragments is weighed to be 1 +/-0.01 g.
3. The method for detecting the trifluoroacetyl gas chromatography-mass spectrometry forbidden azo dye of the textile according to claim 2, wherein the citric acid buffer solution in S1 is 17mL of citric acid buffer solution preheated to 70 +/-2 ℃, the sodium hydrosulfite solution is 3mL, and the water bath heat preservation system adopts warm water at 70 +/-2 ℃.
4. The method for detecting the trifluoroacetyl gas chromatography-mass spectrometry forbidden azo dye for the textile according to claim 1, wherein when the two phases are not separated obviously after standing in S2, the reactor is sealed and centrifuged at 4000r/min for 3 min.
5. The method for detecting the azo dye forbidden for the textile by using the combination of trifluoroacetyl gas and mass spectrometry as claimed in claim 1, wherein the centrifugation is carried out for 3min at the rotation speed of 4000r/min after the oscillation in S3, and supernatant is taken as the liquid to be detected.
6. The method for detecting trifluoroacetylated GC-MS forbidden azo dye of textile according to claim 1, wherein S4 is a GC model number of 7890B-5977B.
7. The method for detecting the azo dye banned on textile by using the trifluoroacetylation gas chromatography-mass spectrometry as claimed in claim 6, wherein the analysis conditions of the gas chromatography-mass spectrometry are as follows:
capillary column: DB-35MS column, 30m × 0.25mm × 0.25 μm;
temperature programming: initial temperature: maintaining at 100 deg.C for 0.5 min;
the first stage is as follows: 30 ℃/min to 280 ℃ and keeping for 2 minutes;
and a second stage: keeping the temperature at 20 ℃/min to 300 ℃ for 1.5 min;
final stabilization time: 0.5 min;
carrier gas: helium gas;
flow rate: 1 mL/min;
sample inlet temperature: 250 ℃;
sample introduction amount: 2 muL;
the sample feeding mode is divided, and the division ratio is 5: 1;
scanning range: 50-400 amu.
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