Method for detecting animal-derived natural dye cochineic acid in textile

Abstract

The invention provides a method for detecting animal-derived natural dye cochineic acid in textiles. The method comprises the following steps: sampling; adding a first volume of monitoring substance into the to-be-detected sample; adding a second volume of methanol solution and a third volume of formic acid solution into the to-be-detected sample, and carrying out ultrasonic treatment at a specified temperature for specified time to obtain extract liquor; diluting and filtering the extracting solution to obtain a loading test solution; and putting the loading test solution into a high performance liquid chromatography tandem mass spectrometer for qualitative and quantitative detection and analysis. According to the substance structure composition of the cochineal acid, a methanol-formic acid ultrasonic-assisted extraction method is adopted to carry out corresponding pretreatment on the cochineal acid, a high performance liquid chromatography tandem mass spectrometer multi-reaction monitoring MRM mode is adopted, exclusive recognition and qualitative and quantitative analysis are achieved through characteristic ion pairs of the cochineal acid, and by optimizing the conditions and parameters of the method, the cochineal acid can be accurately identified. The content of the animal-derived natural dye cochineic acid in the textile can be accurately determined.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical detection, in particular to a detection method of animal-derived natural dye carminic acid in textiles. BACKGROUND

[0002] Natural dyes (such as cochineal red, indigo, alizarin, etc.) have seen increasing demand in high-end textiles, food, cosmetics, and other fields in recent years due to their ecological friendliness and cultural value. Among them, the main component of animal-derived dyes (such as cochineal red) is carminic acid, and its detection is crucial for textile traceability, authenticity identification, and ecological certification.

[0003] However, natural dye detection faces the following challenges:

[0004] Complex composition: Textile substrates often contain synthetic dyes, additives, and other interferents, making it difficult for traditional methods to distinguish between natural and synthetic components.

[0005] Trace amounts: Ecological textiles require detection limits of μg / kg, and conventional techniques (such as ultraviolet spectrophotometry) lack sufficient sensitivity.

[0006] Standard absence: There is a lack of specialized detection standards for carminic acid in textiles both domestically and internationally, and companies rely on experiential judgment or high-cost outsourcing detection. SUMMARY

[0007] In view of the problems, the present application is proposed to provide a detection method of animal-derived natural dye carminic acid in textiles to overcome the problems or at least partially solve the problems.

[0008] A detection method of animal-derived natural dye carminic acid in textiles, comprising the following steps:

[0009] Sampling;

[0010] Adding a first volume of a monitoring substance to the sample to be tested;

[0011] Adding a second volume of methanol solution and a third volume of formic acid solution to the sample to be tested, and ultrasonically treating at a specified temperature for a specified time to obtain an extraction solution;

[0012] Diluting and filtering the extraction solution to obtain an on-machine test solution;

[0013] Placing the on-machine test solution in a high-performance liquid chromatograph tandem mass spectrometer for qualitative and quantitative detection analysis;

[0014] The chromatographic conditions of the high-performance liquid chromatograph tandem mass spectrometer include:

[0015] Chromatographic column: C18, 150 mm column length x 2.1 mm inner diameter, 3.5 μm particle size;

[0016] Column temperature: 40 °C; Injection volume: 20 μL; Flow rate: 0.3 mL / min;

[0017] Mobile phase: A: 0.1% formic acid, B: 0.1% formic acid acetonitrile;

[0018] Gradient elution program:

[0019] 0 min, 95% A, 5% B;

[0020] 3 min, 0% A, 100% B;

[0021] 16 min, 0% A, 100% B;

[0022] 16.1 min, 95% A, 5% B;

[0023] 20 min, 95% A, 5% B;

[0024] Parent ion: 328.94; Daughter ions: 285, 257;

[0025] Ion source temperature: 550 °C.

[0026] Further, the sampling step comprises:

[0027] Cut the sample to be tested into small pieces of 5 mm x 5 mm, and mix evenly;

[0028] Weigh 0.25 g ± 0.01 g of the cut sample to be tested in a test tube.

[0029] Further, the monitoring substance is 100 mg / L of Disperse Yellow 56.

[0030] Further, the first volume is 50 μL.

[0031] Further, the second volume is 4 mL and the third volume is 1 mL.

[0032] Further, the specified temperature is 70 ± 2 °C.

[0033] Further, the specified time is 60 min.

[0034] Further, the step of diluting and filtering the extract solution to obtain the test solution for the machine comprises:

[0035] After cooling the extract solution, take 1 mL of the supernatant, and dilute to 10 mL with 50% methanol water to obtain a dilute solution;

[0036] Filter the dilute solution with a 0.45 μm PTFE membrane, and obtain the test solution for the machine after filtration.

[0037] Further, the step of placing the machine test solution in a high performance liquid chromatography tandem mass spectrometer for qualitative and quantitative detection analysis, comprising:

[0038] establishing a standard curve containing the same monitoring substance;

[0039] qualitative analysis of the sample to be tested;

[0040] According to the standard curve and the chromatographic data, the content of the sample to be tested is calculated.

[0041] Further, the step of establishing a standard curve containing the same monitoring substance, comprising:

[0042] The rhodotonic acid standard substance is prepared into a standard stock solution with a concentration of 1000mg / L using a methanol solution;

[0043] The standard stock solution is diluted into standard working solutions with concentrations of 0.5mg / L, 1mg / L, 2mg / L and 5mg / L using a 50% methanol aqueous solution; wherein 0.05mL of 100mg / L monitoring substance is added to each standard working solution;

[0044] The standard working solution and the sample test solution are analyzed under the same conditions, and then the peak area corresponding to each concentration of the standard working solution is used to draw a standard curve.

[0045] The present application has the following advantages:

[0046] In the embodiments of the present application, a detection method of animal-derived natural dye carminic acid in textiles comprises the following steps: sampling; adding a first volume of a monitoring substance to the sample to be detected; adding a second volume of a methanol solution and a third volume of a formic acid solution to the sample to be detected, and ultrasonicating at a specified temperature for a specified time to obtain an extraction solution; diluting and filtering the extraction solution to obtain a test solution for machine; and placing the test solution for machine in a high performance liquid chromatograph tandem mass spectrometer for qualitative and quantitative detection analysis; wherein the chromatographic conditions of the high performance liquid chromatograph tandem mass spectrometer include: a chromatographic column: C18, 150 mm column length x 2.1 mm inner diameter x 3.5 μm particle size; column temperature: 40℃; sample size: 20 μL; flow rate: 0.3 mL / min; mobile phase: A: 0.1% formic acid, B: 0.1% formic acid acetonitrile; gradient elution program: 0 min, 95% A, 5% B; 3 min, 0% A, 100% B; 16 min, 0% A, 100% B; 16.1 min, 95% A, 5% B; 20 min, 95% A, 5% B; parent ion: 328.94; daughter ion: 285, 257; ion source temperature: 550℃. According to the material structure of carminic acid, the present application adopts methanol-formic acid ultrasonic assisted extraction method for corresponding pretreatment, shortens the extraction time to 60 minutes, reduces the solvent consumption by 40%, and does not need strong acid / strong base treatment, thereby preserving the integrity of the sample; adopts the multiple reaction monitoring (MRM) mode of the high performance liquid chromatograph tandem mass spectrometer, realizes exclusive recognition through the characteristic ion pair of carminic acid, performs qualitative and quantitative analysis, avoids the interference of synthetic dyes or plant pigments, and can accurately determine the content of animal-derived natural dye carminic acid in textiles by optimizing the conditions and parameters of the method. The present application provides a high specificity, high sensitivity, high efficiency, standardized and low cost solution for the accurate detection of carminic acid in textiles, and helps the green upgrading of the industry. BRIEF DESCRIPTION OF DRAWINGS

[0047] In order to more clearly illustrate the technical solutions of the present application, the following will briefly introduce the drawings needed to be used in the description of the present application. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0048] Figure 1 is a step flow chart of a detection method of animal-derived natural dye carminic acid in textiles provided by the embodiments of the present application;

[0049] Figure 2 is a chromatogram of a standard curve concentration point 0.5 mg / L carminic acid provided by the embodiments of the present application;

[0050] Figure 3is a chromatogram of a standard curve concentration point 1.0 mg / L bixin acid provided by the embodiment of the present application;

[0051] Figure 4 is a chromatogram of a standard curve concentration point 2.0 mg / L bixin acid provided by the embodiment of the present application;

[0052] Figure 5 is a chromatogram of a standard curve concentration point 5.0 mg / L bixin acid provided by the embodiment of the present application;

[0053] Figure 6 is a chromatogram of a sample spiked with bixin acid provided by the embodiment of the present application;

[0054] Figure 7 is a chromatogram of a blank sample provided by the embodiment of the present application;

[0055] Figure 8 is a chromatogram of bixin acid in a sample provided by the embodiment of the present application;

[0056] Figure 9 is a chromatogram of a standard curve concentration point 0.5 mg / L monitor provided by the embodiment of the present application;

[0057] Figure 10 is a chromatogram of a standard curve concentration point 1.0 mg / L monitor provided by the embodiment of the present application;

[0058] Figure 11 is a chromatogram of a standard curve concentration point 2.0 mg / L monitor provided by the embodiment of the present application;

[0059] Figure 12 is a chromatogram of a standard curve concentration point 5.0 mg / L monitor provided by the embodiment of the present application;

[0060] Figure 13 is a chromatogram of a sample spiked with monitor provided by the embodiment of the present application;

[0061] Figure 14 is a chromatogram of a blank sample provided by the embodiment of the present application;

[0062] Figure 15 is a chromatogram of monitor in a sample provided by the embodiment of the present application. DETAILED DESCRIPTION

[0063] In order to make the purposes, features and advantages of the present application more obvious and easy to understand, the present application will be further described in detail below in combination with the drawings and specific embodiments. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0064] The inventors found through analysis of the prior art that:

[0065] Current natural dye detection mainly relies on the following technologies:

[0066] Spectrophotometry (UV-Vis): Based on the characteristic absorption peak of carminic acid at 494 nm, but cannot exclude the interference of similar structures (such as some synthetic red dyes) (Reference: Textile Research Journal, 2015, 85(3): 312-320).

[0067] High-performance liquid chromatography-diode array detector (HPLC-DAD): Can separate multiple dyes, but has insufficient sensitivity for trace carminic acid (<1 mg / kg) (Reference: Journal of Chromatography A, 2018, 1532: 208-215).

[0068] Liquid chromatography-mass spectrometry (LC-MS): Gradually becoming mainstream, but existing research focuses more on food / cosmetic fields (such as EU No 1333 / 2008 control of cochineal red), and the pretreatment method for textile substrates has not been optimized (Reference: Food Chemistry, 2020, 318: 126499).

[0069] The existing detection methods have obvious deficiencies in specificity, sensitivity, efficiency, standardization and cost, etc., which are specifically as follows:

[0070] (1) Poor specificity, unable to accurately distinguish target substances

[0071] Spectrophotometry (UV-Vis): Only relies on absorption spectrum (such as carminic acid characteristic peak at 494 nm), but synthetic dyes (such as azo) may produce overlapping absorption, leading to false positive results.

[0072] HPLC-DAD: Although it can separate multiple components, it cannot distinguish carminic acid from its structural analogues (such as some plant pigments), and needs to rely on retention time judgment, with high risk of misjudgment.

[0073] (2) Insufficient sensitivity, difficult to meet the needs of trace detection

[0074] The detection limit of existing methods (such as HPLC-DAD) is usually at the level of 1 mg / kg, while the ecological textile certification (such as OEKO- ) requires a detection limit at the level of μg / kg, which cannot be met by the existing technology (Food Chemistry, 2020).

[0075] The Soxhlet extraction method has a low recovery rate (<70%), which further reduces the actual detection sensitivity.

[0076] (3) Low pretreatment efficiency and strong destructiveness

[0077] Traditional extraction methods (such as Soxhlet extraction) require more than 6 hours and use a large amount of organic solvents (such as chloroform), which do not meet the green chemistry trend.

[0078] Strong acid / alkali hydrolysis (such as 6M hydrochloric acid) can destroy the sample structure and is not suitable for valuable cultural relics or high-value-added textiles (Heritage Science, 2021).

[0079] (4) Lack of standardized methods, poor data comparability

[0080] There is no detection standard for bixin acid in textiles at home and abroad at present, and each laboratory adopts self-built methods, resulting in large differences in data (such as recovery rate RSD> 15%).

[0081] (5) High cost, difficult to popularize

[0082] The existing LC-MS / MS method has not optimized the pretreatment process, the cost of single sample detection is high, and it needs to rely on imported equipment and consumables.

[0083] Reference Figure 1 , a step flow chart of a detection method for animal-derived natural dye bixin acid in textiles according to an embodiment of the present application is shown;

[0084] The detection method comprises:

[0085] S110, sampling;

[0086] S120, adding a first volume of a monitoring substance to the sample to be tested;

[0087] S130, adding a second volume of a methanol solution and a third volume of a formic acid solution to the sample to be tested, and ultrasonicating at a specified temperature for a specified time to obtain an extraction solution;

[0088] S140, diluting and filtering the extraction solution to obtain an on-machine test solution;

[0089] S150, placing the on-machine test solution in a high-performance liquid chromatograph mass spectrometer for qualitative and quantitative detection analysis;

[0090] The chromatographic conditions of the high performance liquid chromatograph coupled with mass spectrometer include:

[0091] Chromatographic column: C18, 150 mm column length x 2.1 mm inner diameter, 3.5 μm particle size;

[0092] Column temperature: 40℃; injection volume: 20 μL; flow rate: 0.3 mL / min;

[0093] Mobile phase: A: 0.1% formic acid, B: 0.1% formic acid acetonitrile;

[0094] Gradient elution program:

[0095] 0 min, 95% A, 5% B;

[0096] 3 min, 0% A, 100% B;

[0097] 16 min, 0% A, 100% B;

[0098] 16.1 min, 95% A, 5% B;

[0099] 20 min, 95% A, 5% B;

[0100] Parent ion: 328.94; daughter ion: 285, 257;

[0101] Ion source temperature: 550℃.

[0102] In the embodiment of the present application, a method for detecting animal-derived natural dye carminic acid in textiles comprises the following steps: sampling; adding a first volume of a monitoring substance to the sample to be tested; adding a second volume of a methanol solution and a third volume of a formic acid solution to the sample to be tested, and ultrasonicating at a specified temperature for a specified time to obtain an extract; diluting and filtering the extract to obtain a test solution for the machine; and placing the test solution for the machine in a high-performance liquid chromatograph tandem mass spectrometer for qualitative and quantitative detection analysis; wherein the chromatographic conditions of the high-performance liquid chromatograph tandem mass spectrometer include: a chromatographic column: C18, 150 mm column length x 2.1 mm inner diameter x 3.5 μm particle size; column temperature: 40°C; sample size: 20 μL; flow rate: 0.3 mL / min; mobile phase: A: 0.1% formic acid, B: 0.1% formic acid acetonitrile; gradient elution program: 0 min, 95% A, 5% B; 3 min, 0% A, 100% B; 16 min, 0% A, 100% B; 16.1 min, 95% A, 5% B; 20 min, 95% A, 5% B; parent ion: 328.94; daughter ion: 285, 257; ion source temperature: 550°C. According to the material structure of carminic acid, the present application uses methanol-formic acid ultrasonic-assisted extraction method for corresponding pretreatment, shortens the extraction time to 60 minutes, reduces the solvent usage by 40%, and does not require strong acid / strong base treatment, thereby preserving the integrity of the sample; uses a high-performance liquid chromatograph tandem mass spectrometer in a multiple reaction monitoring (MRM) mode, realizes exclusive recognition through characteristic ion pairs of carminic acid, performs qualitative and quantitative analysis, avoids interference from synthetic dyes or plant pigments, and accurately determines the content of animal-derived natural dye carminic acid in textiles by optimizing the conditions and parameters of the method. The present application provides a high-specificity, high-sensitivity, high-efficiency, standardized, and low-cost solution for precise detection of carminic acid in textiles, and helps the green upgrade of the industry.

[0103] In the following, a method for detecting animal-derived natural dye carminic acid in textiles in the present exemplary embodiment will be further described.

[0104] As described in step S110, sampling is one of the important steps for extracting a small amount of target substance from the target object for detection, which is one of the effective ways to obtain the target object for testing to obtain various data without affecting the main properties of the target object. The amount of measured substance extracted should be sufficient for 3-5 tests, and the sampling area selection process of the measured substance requires randomness.

[0105] As an example, the sample to be tested is cut into small pieces of 5 mm x 5 mm and mixed uniformly; and 0.25 g ± 0.01 g of the cut sample is weighed in a test tube.

[0106] As described in the step S120, a first volume of monitor is added to the sample to be measured to correct the pre-treatment deviation. The pre-treatment deviation mainly includes human deviation (sample handling, pipetting method, etc.), equipment deviation (pipette, ultrasonic frequency, etc.).

[0107] By adding the monitor (internal standard), a standard solution with a known concentration is added, and the sample recovery of the whole pre-treatment can be understood through the final instrument reading, so that the final concentration of the sample can be better analyzed. At the same time, the retention time and response value of the internal standard also help to understand the instrument stability and sensitivity.

[0108] In the embodiment, the monitor is 100 mg / L Disperse Yellow 56; and the first volume is 50 μL.

[0109] As an example, 50 μL of 100 mg / L Disperse Yellow 56 is added to the test tube containing the sample to be measured.

[0110] As described in the step S130, a second volume of methanol solution and a third volume of formic acid solution are added to the sample to be measured, and the sample is ultrasonically treated at a specified temperature for a specified time to obtain an extraction solution. That is, the sample to be measured is pre-treated, and the pre-treatment is generally a step of purifying the target before the effective process, and in some special experiments, the pre-treatment step also includes changing the properties of the substance, etc. In the embodiment, the sample is preferably pre-treated by ultrasonic wave.

[0111] In the embodiment, the second volume is 4 mL, and the third volume is 1 mL; the specified temperature is 70±2℃, and the specified time is 60 min.

[0112] As an example, 4 mL of methanol and 1 mL of formic acid are added to the test tube, and ultrasonic treatment is performed at 70℃±2℃ for 60 min to obtain an extraction solution. In the embodiment, the formic acid is added to stabilize the target, prevent oxidation, and facilitate ionization.

[0113] As described in the step S140, the extraction solution is diluted and filtered to obtain a test solution for instrument.

[0114] As an example, after the extraction solution is cooled, 1 mL of clear liquid is taken, and the volume is made to 10 mL with 50% methanol water to obtain a diluted solution; the diluted solution is filtered with a 0.45 μm PTFE membrane to prevent adsorption of the target, and the filtered solution is obtained as the test solution for instrument.

[0115] Due to the risk of formic acid in the extract liquid to damage the instrument equipment, shorten the service life of the chromatographic column, by diluting the extract liquid can reduce the concentration of formic acid. At the same time, 50% methanol can better separate ions and improve the accuracy of instrument analysis.

[0116] As described in step S150, the test solution is placed in a high performance liquid chromatography tandem mass spectrometer for qualitative and quantitative detection analysis;

[0117] The chromatographic conditions of the high performance liquid chromatography tandem mass spectrometer include:

[0118] Chromatographic column: C18, 150mm column length x 2.1mm inner diameter, 3.5μm particle size;

[0119] Column temperature: 40℃;

[0120] Injection volume: 20μL;

[0121] Flow rate: 0.3mL / min;

[0122] Mobile phase: A: 0.1% formic acid, B: 0.1% formic acid acetonitrile;

[0123] The gradient elution program is shown in Table 1:

[0124] Time Proportion of mobile phase (A) Proportion of mobile phase (B) 0 min 95％ 5％ 3 min 0％ 100％ 16 min 0％ 100％ 16.1 min 95％ 5％ 20 min 95％ 5％

[0125] Target: Buxbaumionate parent ion: 328.94; daughter ion: 285, 257;

[0126] Ion source temperature: 550℃.

[0127] As an example, the step of placing the test solution in a high performance liquid chromatography tandem mass spectrometer for qualitative and quantitative detection analysis includes: establishing a standard curve containing the same monitoring substance; qualitative analysis of the sample to be tested; calculating the content of buxbaumionate in the sample to be tested according to the standard curve and chromatographic data.

[0128] The step of establishing a standard curve containing the same monitoring substance includes:

[0129] 1. The buxbaumionate standard substance is prepared into a standard stock solution with a concentration of 1000mg / L using methanol solution; specifically:

[0130] Prepare 1000mg / L stock solution (primary stock solution): weigh 10.0mg of buxbaumionate standard (accurate to 0.1mg), dissolve in tetrahydrofuran and dilute to 10mL capacity bottle;

[0131] Preparation of 100 mg / L intermediate solution (secondary stock solution): 1.0 mL of the primary stock solution (1000 mg / L) was taken; 50% methanol water was used to make up to 10 mL volumetric flask

[0132] Preparation of 10 mg / L working solution (tertiary stock solution): 1.0 mL of the secondary stock solution (100 mg / L) was taken; 50% methanol water was used to make up to 10 mL volumetric flask.

[0133] It should be noted that tetrahydrofuran is a polar ether solvent, which can well dissolve standard substances such as bixin acid; methanol water is used subsequently to keep the same proportion as the final solvent in the pretreatment process; at the same time, it is convenient for the standard curve and the sample to be analyzed in the same solvent environment.

[0134] 2, Preparation of standard working solution, (50 mL constant volume system), as shown in Table Two:

[0135]

[0136] Finally, the instrument analysis was carried out under the same conditions for each standard working solution and sample test solution, and then the standard curve was drawn with the peak area corresponding to each concentration of the standard working solution. The bixin acid content in the sample to be tested was calculated according to the detection peak of the standard curve and the sample to be tested, and the data reliability was verified by monitoring the recovery rate.

[0137] The application has the characteristics of high sensitivity (low detection limit), short analysis time and high accuracy through the synergistic innovation of methanol-formic acid ultrasonic extraction and LC-MS / MS detection method; the pretreatment process of the liquid chromatography-mass spectrometry analysis sample is simple, so that the sample analysis is more simple and saves labor cost.

[0138] The application will be further described in detail in combination with specific implementation cases, but the application will not be limited in the scope of the implementation cases.

[0139] Example: Detection of bixin acid in red textile cloth sample and standard addition recovery test.

[0140] 1, Preparation of standard solution with target concentration of 0.5 mg / L, 1.0 mg / L, 2.0 mg / L and 5.0 mg / L.

[0141] 2. Red textile fabric was cut into 5x5 mm pieces, and 0.251 g of sample and 0.250 g of sample (spiked) were accurately weighed separately (allowing ± 0.01 g error); 50 μL of Disperse Yellow 56 (100 μg / mL) was added; 250 μL of 1000 mg / L standard solution of carminic acid was added to the sample spike (the final concentration of the spike was 5.0 mg / L); 4 mL of methanol + 1 mL of formic acid was added, and ultrasonic treatment was performed at 70 °C for 60 min; then 1 mL of supernatant was taken, and diluted with 50% methanol water to 10 mL; after passing through a 0.45 μm PTFE membrane, it was analyzed on the machine.

[0142] The standard curve linear equation was y = 533.39026x + 1.16188e5 (R = 0.99827), and the detection data are shown in Table Three below:

[0143] Sample name Test substance Peak area Retention time (min) Concentration (pg / L) Standard curve 1 - 0.5 mg / L Kathon CG 4.598e5 8.95 644.17 Standard curve 2 - 1.0 mg / L Kathon CG 6.102e5 9.00 926.14 Standard curve 3 - 2.0 mg / L Kathon CG 1.120e6 9.00 1882.22 Standard curve 4 - 5.0 mg / L Kathon CG 2.808e6 8.99 5047.47 Sample spiked Kathon CG 2.753e6 9.00 4943.02 Blank Kathon CG N / A N / A N / A Sample Kathon CG 3.704e5 9.02 476.67

[0144] The chromatogram is shown in Figure 2 - Figure 8 As can be seen from the figure, the detected chromatographic peak retention time is consistent with the standard substance, and the multiple reaction monitoring ion pairs of the target compound all appear, and the abundance ratio of the multiple reaction monitoring ion pairs is consistent with that of the standard substance, indicating that the sample contains the target compound. The retention time of the detected target compound carminic acid was 9.02 min, and the retention time and abundance of all the analyzed samples were within the allowable deviation range.

[0145] The recovery rate of the monitor substance is shown in Table Four below:

[0146]

[0147]

[0148] The chromatogram is shown in Figure 9 - Figure 15 .

[0149] The sample spike recovery rate was calculated as follows:

[0150] The sample spike peak area was 2.753e6 (corresponding to a concentration of 4943.02 μg / L);

[0151] The sample peak area was 3.704e5 (corresponding to a concentration of 476.67 μg / L);

[0152] The theoretical concentration of the spike was 5.0 mg / L, i.e. 5000 μg / L;

[0153] The calculation formula was (4943.02-476.67) / 5000*100% = 89.3%.

[0154] Conclusion: By adding standard recovery test to the textile product, the animal source dye amur ketone acid can reach 80%-120% recovery rate by using the method provided by the application, which meets the technical requirements of conventional detection, and the recovery rate reaches the expected effect, which shows that the test result has high feasibility.

[0155] The application embodiment has low detection limit, high sensitivity, short analysis time and high accuracy; the pretreatment process of the sample analyzed by the liquid chromatography-mass spectrometry is simple, so that the sample analysis is more simple and saves labor cost.

[0156] Although the preferred embodiments of the application have been described, those skilled in the art can make further changes and modifications to the embodiments once they know the basic inventive concept. Therefore, the appended claims are intended to cover all changes and modifications falling within the scope of the application.

[0157] Finally, it should also be noted that in this paper, relational terms such as first and second are used merely to distinguish one entity or action from another entity or action, and do not necessarily require or imply that there is any such actual relationship or order between these entities or actions. Moreover, the terms "include", "contain" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or terminal device including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such process, method, article or terminal device. Without more limitations, the element defined by the statement "including a" does not exclude the presence of other identical elements in the process, method, article or terminal device including the element.

[0158] The above provides a detailed introduction to the detection method of animal source natural dye amur ketone acid in the textile product provided by the application, and the principle and implementation mode of the application are described in this paper. The above embodiment description is only used to help understand the method and core idea of the application; at the same time, for those skilled in the art, according to the idea of the application, the specific implementation mode and application range will be changed; in view of the above, the content of the specification should not be understood as a limitation of the application.

Claims

1. A method for detecting animal-derived natural dye, kermesic acid, in a textile, characterized by, The method comprises the following steps: sampling; adding a first volume of a monitoring substance to a sample to be tested; adding a second volume of a methanol solution and a third volume of a formic acid solution to the sample to be tested, and ultrasonically treating at a specified temperature for a specified time to obtain an extract solution; diluting and filtering the extract solution to obtain a test solution for instrument analysis; qualitatively and quantitatively detecting and analyzing the test solution for instrument analysis by using a high-performance liquid chromatograph-mass spectrometer; The chromatographic conditions of the high-performance liquid chromatograph-mass spectrometer comprise: a chromatographic column: C18, 150 mm in length, 2.1 mm in inner diameter, and 3.5 μm in particle size; a column temperature: 40 ℃; a sample injection amount: 20 μL; and a flow rate: 0.3 mL / min; mobile phases: A: 0.1% formic acid, and B: 0.1% formic acid acetonitrile; a gradient elution program: 0 min, 95% A, 5% B; 3 min, 0% A, 100% B; 16 min, 0% A, 100% B; 16.1 min, 95% A, 5% B; 20 min, 95% A, 5% B; a parent ion: 328.94; and daughter ions: 285, 257; an ion source temperature: 550 ℃.

2. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 1, characterized by, The sampling step comprises: cutting the sample to be tested into small pieces of 5 mm x 5 mm, and mixing the sample; weighing 0.25 g ± 0.01 g of the cut sample in a test tube.

3. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 1, characterized by, The monitoring substance is Disperse Yellow 56 at a concentration of 100 mg / L.

4. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 3, characterized by, The first volume is 50 μL.

5. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 4, characterized by, The second volume is 4 mL, and the third volume is 1 mL.

6. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 5, characterized by, The specified temperature is 70 ± 2 ℃.

7. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 6, characterized by, The specified time is 60 min.

8. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 7, characterized by, The step of diluting and filtering the extract solution to obtain a test solution for instrument analysis comprises: after cooling the extract solution, taking 1 mL of the supernatant, and diluting the supernatant to 10 mL with 50% methanol water to obtain a diluted solution; filtering the diluted solution by using a 0.45 μm PTFE membrane to obtain a test solution for instrument analysis.

9. The method for detection of animal-derived natural dye Bixin in textile according to claim 1, characterized in that, The step of qualitatively and quantitatively detecting and analyzing the test solution for instrument analysis by using a high-performance liquid chromatograph-mass spectrometer comprises: establishing a standard curve containing the same monitoring substance; qualitatively analyzing the sample to be tested; calculating the content of kermesic acid in the sample to be tested according to the standard curve and chromatographic data.

10. The method for detecting animal-derived natural dye carminic acid in a textile according to claim 9, characterized in that, The step of establishing a standard curve containing the same monitoring substance comprises: preparing a standard stock solution of kermesic acid standard substance by using a methanol solution, and the concentration of the standard stock solution is 1000 mg / L; diluting the standard stock solution into standard working solutions of 0.5 mg / L, 1 mg / L, 2 mg / L, and 5 mg / L by using a 50% methanol water solution; wherein 0.05 mL of the monitoring substance at a concentration of 100 mg / L is added to each standard working solution; taking the standard working solutions and the sample test solution to perform instrument analysis under the same conditions, and then plotting a standard curve by using the peak areas corresponding to the concentrations of the standard working solutions.

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