CN113189220A - Rapid detection method of azo dye product - Google Patents
Rapid detection method of azo dye product Download PDFInfo
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- CN113189220A CN113189220A CN202110433468.XA CN202110433468A CN113189220A CN 113189220 A CN113189220 A CN 113189220A CN 202110433468 A CN202110433468 A CN 202110433468A CN 113189220 A CN113189220 A CN 113189220A
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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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
The invention discloses a rapid detection method of an azo dye product, which comprises the steps of pretreatment and detection of the azo dye product, wherein the pretreatment comprises the steps of adding a citrate buffer solution and a sodium hydrosulfite aqueous solution, adopting a diatomite column for adsorption and the like; the detection is carried out by HPLC-DAD. By improving the existing standard sample pretreatment method and exploring and optimizing the detection parameters of the liquid chromatogram, the separation of the target aromatic amine component can be better realized, the forbidden azo dye can be rapidly identified, the detection efficiency and accuracy are improved, and the detection cost is reduced.
Description
Technical Field
The invention belongs to the technical field of detection of azo dye products, and particularly relates to a rapid detection method of an azo dye product.
Background
Azo dyes are artificially synthesized azo-group-containing dyes and are widely applied to dyeing and printing of various textiles and coloring of various paints, rubbers, plastics and the like. Under special conditions, some of these dyes decompose carcinogenic aromatic amine compounds (24 types in total), which, if absorbed by human body, will cause cytopathy and induce cancer, so that the use of these azo dyes which decompose to produce carcinogenic aromatic amine compounds is prohibited. In order to control the harmful substances from the source and avoid the harmful substances from being used in the downstream to harm the human health, the method has important significance for detecting the substances.
The national mandatory standard GB 19601-2013 Limit and determination of 23 harmful aromatic amines in dye products only relates to GC-MS qualitative and internal standard method quantitative detection of the 23 aromatic amines. The accuracy of GC-MS quantitative detection is greatly influenced by interference, the operation complexity of pretreatment increases the cost of experimental time, and the price of an internal standard substance is high, so that the detection cost is increased. In addition, the standard pretreatment method has the phenomena of poor solubility of the dye, precipitation in the extraction process and the like in the aqueous solution, so that the subsequent extraction effect is poor, and the loss of the target object is large; furthermore, the recovery obtained using this treatment method is low due to the poor stability of 2, 4-diaminotoluene and 2, 4-diaminoanisole. Meanwhile, other relevant standards at home and abroad, such as: the international standard ISO 14362-1:2017, the national recommended standard GB/T17592-2011 and the industry standard SN/T3786.1-2014 are all used for detecting azo dyes in textiles, and do not relate to the detection of azo dyes in azo dye products in other fields. Because azo dyes are various in product types, in order to improve the production efficiency and avoid banned azo dyes from flowing into the market, a detection method capable of quickly and accurately identifying the banned azo dyes is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a rapid detection method of azo dye products, which is characterized in that the detection parameters of liquid chromatogram are researched and optimized by improving the existing standard sample pretreatment method, and the high performance liquid chromatogram of 24 azo dye decomposition product aromatic amines with better separation degree is obtained, so that the detection efficiency and accuracy are improved, and the detection cost is reduced.
In order to realize the invention, the invention adopts the following technical scheme:
a rapid detection method of azo dye products comprises the pretreatment and detection of the azo dye products, wherein the pretreatment comprises the following steps:
step 1): accurately weighing 0.2g of representative negative sample into a 60mL glass reactor with a plug, weighing the sample to be accurate to 0.0001g, and adding 30 mu L of 24 aromatic amine standard solutions into the sample;
step 2): adding 12.0-17.0mL of 0.06mol/L citrate buffer solution with pH value of 6.0 preheated to 70 ℃ into the reactor, covering a stopper tightly, carrying out vortex mixing to wet a sample, placing the reactor into a water bath with constant temperature of 70 ℃ for standing extraction for 15min or ultrasonic extraction for 10min, wherein the ultrasonic frequency is 40KHz, and the power is 200W;
step 3): accurately adding 3.0mL of 200mg/mL sodium hydrosulfite aqueous solution after extraction is finished, shaking up, and reacting for 30min at constant temperature of 70 ℃;
step 4): taking out the reactor, placing the reactor in an ice water bath, and cooling the reactor to room temperature within 2 min;
step 5): transferring all reaction liquid in the reactor to a diatomite column, fully adsorbing for 15min, washing the reactor for 2 times by using 20mL of tert-butyl methyl ether or diethyl ether respectively, transferring all washing liquid to the diatomite packed column, adding 40mL of tert-butyl methyl ether or diethyl ether to the diatomite packed column, and collecting eluent to a 100mL round-bottom flask;
step 6): placing the eluent in a vacuum rotary evaporator in a water bath at 50 +/-2 ℃ for concentration to 1mL, and blowing the residual tert-butyl methyl ether or diethyl ether by slow nitrogen flow;
step 7): accurately adding 1.0mL of methanol into the round-bottom flask, quickly oscillating to fully dissolve residues, finally filtering the solution in the round-bottom flask by using a 0.45-micrometer PTFE microporous filter membrane, and taking the filtrate for analysis and detection;
the detection is HPLC-DAD detection, and the analysis conditions of the HPLC-DAD detection are as follows:
a chromatographic column: kromasil C18, 5 μm, 250 mm. times.4.6 mm;
sample introduction amount: 2 mu L of the solution;
flow rate: 0.8-1.2 mL/min;
column temperature: 30 ℃;
detection wavelength: 240nm, 280nm, 305 nm;
mobile phase A: 25mM potassium dihydrogen phosphate +25mM dipotassium hydrogen phosphate;
mobile phase B: 100% methanol;
the elution procedure is shown in table 1 below:
TABLE 1 elution procedure
As a further optimization of the method of the invention, the addition volume of the citrate buffer is 12.0mL, and better recovery rate can be obtained by adding the citrate buffer with the volume.
As further optimization of the method, the sample reactor is placed in a water bath at 70 ℃ for ultrasonic extraction, the ultrasonic frequency is 40KHz, the power is 200W, better extraction effect and higher extraction efficiency can be obtained, the extraction time is 10min, and the extraction efficiency can reach 90%.
As a further optimization of the method, 0.2mL of 20% sodium hydroxide aqueous solution is added into the extraction liquid which is cooled to room temperature after the reductive cracking, and the mixture is shaken up to keep the extraction liquid in an alkaline environment, so that the 2, 4-diaminotoluene and the 2, 4-diaminoanisole can obtain better stability to achieve the recovery rates of 20% and 50% required by the standard.
As the method is further optimized, tert-butyl methyl ether is adopted for extracting and enriching the reduction cracking solution, the mutual solubility of tert-butyl methyl ether and water is 1.5%, and the mutual solubility of diethyl ether and water is 7%.
Furthermore, when detecting azo dye products, weighing the azo dye products in the pretreatment step 1) into a glass reactor with a plug, and adding no aromatic amine standard solution; and comparing the high-performance liquid chromatogram obtained by detection with the high-performance liquid chromatogram obtained by the representative negative sample external standard method, and judging whether the product is a forbidden azo dye product.
Compared with the traditional detection technology, the method has the advantages that the azo dye product is detected by adopting HPLC-DAD, the detection time is greatly shortened, the detection efficiency of forbidden azo dyes is improved, 24 target substance chromatograms with better separation degree can be obtained by optimizing and selecting an HPLC-DAD elution program, and the detection accuracy is improved. The method can be widely used for detecting various azo dye products, is simple and quick, improves the efficiency, reduces the cost and has wide application field.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiments will be briefly described as follows:
FIG. 1 is a graph comparing the recovery rates of example 2 and example 5, and it can be seen that the recovery rate of the citrate buffer solution added in 12mL in example 2 is higher than the recovery rate of the citrate buffer solution added in 17mL in example 5.
FIG. 2 is a graph comparing the recovery rates of example 1 and example 4, and it is understood from the graph that the recovery rate of t-butyl methyl ether as an extraction washing solvent in example 1 is higher than the recovery rate of diethyl ether as an extraction washing agent in example 4.
FIG. 3 is a graph showing the comparison of the recovery rates of example 1 and example 3, and it can be seen that the recovery rate of the ultrasonic extraction treatment in example 1 is higher than that of the stationary water bath extraction in example 3.
FIG. 4 is a graph comparing the recovery rates of example 1 and example 2, and it can be seen from the graph that the recovery rate of 0.2mL of 20% NaOH added after cooling in the extraction of example 1 is higher than the recovery rate of NaOH not added after cooling in example 2.
In FIGS. 1 to 4, the reference numerals of the substances refer to the peak numbers of the substances in Table 2.
FIGS. 5 to 9 are high performance liquid chromatograms of examples 1 to 5 in this order.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention.
Example 1
A method for rapidly detecting azo dyes in textiles comprises pretreatment and detection of products, wherein the pretreatment comprises the following steps:
step 1): weighing 0.2g (accurate to 0.0001g) of dye negative sample into a glass reactor with a plug, and adding 30 μ L of 24 aromatic amine standard solutions;
step 2): adding 12.0mL of 0.06mol/L citrate buffer (pH 6.0) preheated to 70 ℃ into the reactor, covering the stopper tightly, performing vortex mixing to fully wet the sample, and performing ultrasonic extraction (frequency 40KHz and power 200W) in a 70 ℃ water bath for 10 min;
step 3): accurately adding 3.0mL of 200mg/mL sodium dithionite aqueous solution into the reactor after extraction is finished, shaking up, and reacting for 30min at the constant temperature of 70 ℃;
step 4): taking out the reactor, placing the reactor in an ice-water bath, cooling the reactor to room temperature within 2min, adding 0.2mL of 20% sodium hydroxide aqueous solution into the reaction solution, and shaking the mixture evenly;
step 5): transferring all reaction liquid to a diatomite column, enabling the diatomite column to be fully adsorbed for 15min, washing the reactor by using 20mL of multiplied by 2 tert-butyl methyl ether respectively, transferring all washing liquid to the diatomite packed column, adding 40mL of tert-butyl methyl ether into a purification column, and collecting eluent to a 100mL round-bottom flask;
step 6): placing the eluent in a vacuum rotary evaporator (50 +/-2) DEG C water bath for concentrating to 1mL, and blowing the residual tert-butyl methyl ether by slow nitrogen flow;
step 7): accurately adding 1.0mL of methanol into a round-bottom flask for quantification, quickly shaking to fully dissolve residues, filtering the solution by using a 0.45-micrometer PTFE microporous filter membrane, and taking the filtrate for analysis and detection.
Detection was performed using HPLC-DAD, with HPLC-DAD elution program parameters:
a chromatographic column is adopted: kromasil C18(5 μm, 250 mm. times.4.6 mm);
sample introduction amount: 2 mu L of the solution;
flow rate: 0.8-1.2 mL/min;
column temperature: 30 ℃;
detection wavelength: 240nm, 280nm, 305 nm;
mobile phase A: 25mM potassium dihydrogen phosphate +25mM dipotassium hydrogen phosphate;
mobile phase B: 100% methanol;
the elution procedure is shown in table 1 below:
TABLE 1 elution procedure
Example 2
The difference between this embodiment and embodiment 1 is:
pretreatment step 4): the reactor was taken out and placed in an ice-water bath, allowed to cool to room temperature over 2 min.
Example 3
The difference between this embodiment and embodiment 1 is:
pretreatment step 2): 12.0mL of 0.06mol/L citrate buffer (pH 6.0) preheated to 70 ℃ was added, the stopper was closed, vortex mixing was performed to wet the sample sufficiently, and the reactor was placed in a 70 ℃ water bath and extracted for 15 min.
Example 4
The difference between this embodiment and embodiment 1 is:
pretreatment step 5): the reaction solution was transferred to a celite column and allowed to adsorb well for 15min, the reactor was washed with 20mL of × 2 ether, respectively, and the wash solution was transferred to a celite packed column, 40mL of ether was added to a purification column, and the eluate was collected in a 100mL round-bottom flask.
Example 5
The difference between this embodiment and embodiment 2 is:
pretreatment step 2): 17.0mL of 0.06mol/L citrate buffer (pH 6.0) preheated to 70 ℃ was added, the stopper was closed and vortex-mixed to wet the sample thoroughly, and the reactor was subjected to ultrasonic extraction (frequency 40KHz, power 200W) in a 70 ℃ water bath for 10 min.
Examples 1 to 5 test data for the 24 aromatic amine components recovered are shown in Table 2.
TABLE 2 recovery of aromatic amine component from negative dye product by spiking
Note: the detection of the method shows that the o-aminoazotoluene (No.26) is decomposed into o-toluidine (No.8), and the 5-nitro-o-toluidine is decomposed into 2, 4-diaminotoluene (No. 3); 4-aminoazobenzene (No.24) is cleaved to aniline (No.4) or 1, 4-phenylenediamine (No. 1).
The high performance liquid chromatograms obtained in examples 1 to 5 are shown in fig. 5 to 9. As can be seen from the figure, 24 aromatic amine components, of which 3 have been decomposed during the pretreatment; including the decomposition products during pretreatment, 22 species in the spectrum had better resolution.
Example 6
The difference between this embodiment and embodiment 1 is:
in the pretreatment step 1), weighing azo dye products in the dye into a reactor with a plug without adding aromatic amine standard solution. And comparing the high-performance liquid chromatogram obtained by detection with the high-performance liquid chromatogram obtained by the representative negative sample external standard method, and obtaining a non-forbidden azo dye product if no peak appears in corresponding time.
The method of the invention can realize good separation of aromatic amine components, has good selectivity, meets the requirement of recovery rate, and can quickly detect whether forbidden azo dyes are contained, thereby improving the efficiency and reducing the cost.
Although embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (6)
1. A rapid detection method of azo dye products comprises the pretreatment and detection of the azo dye products, and is characterized in that: the pretreatment comprises the following steps:
step 1): accurately weighing 0.2g of representative negative sample into a 60mL glass reactor with a plug, weighing the sample to be accurate to 0.0001g, and adding 30 mu L of 24 aromatic amine standard solutions into the sample;
step 2): adding 12.0-17.0mL of 0.06mol/L citrate buffer solution with pH value of 6.0 preheated to 70 ℃ into the reactor, covering a stopper tightly, carrying out vortex mixing to wet a sample, placing the reactor into a water bath with constant temperature of 70 ℃ for standing extraction for 15min or ultrasonic extraction for 10min, wherein the ultrasonic frequency is 40KHz, and the power is 200W;
step 3): accurately adding 3.0mL of 200mg/mL sodium hydrosulfite aqueous solution after extraction is finished, shaking up, and reacting for 30min at constant temperature of 70 ℃;
step 4): taking out the reactor, placing the reactor in an ice water bath, and cooling the reactor to room temperature within 2 min;
step 5): transferring all reaction liquid in the reactor to a diatomite column, fully adsorbing for 15min, washing the reactor for 2 times by using 20mL of tert-butyl methyl ether or diethyl ether respectively, transferring all washing liquid to the diatomite packed column, adding 40mL of tert-butyl methyl ether or diethyl ether to the diatomite packed column, and collecting eluent to a 100mL round-bottom flask;
step 6): placing the eluent in a vacuum rotary evaporator in a water bath at 50 +/-2 ℃ for concentration to 1mL, and blowing the residual tert-butyl methyl ether or diethyl ether by slow nitrogen flow;
step 7): accurately adding 1.0mL of methanol into the round-bottom flask, quickly oscillating to fully dissolve residues, finally filtering the solution in the round-bottom flask by using a 0.45-micrometer PTFE microporous filter membrane, and taking the filtrate for analysis and detection;
the detection is HPLC-DAD detection, and the analysis conditions of the HPLC-DAD detection are as follows:
a chromatographic column: kromasil C18, 5 μm, 250 mm. times.4.6 mm;
sample introduction amount: 2 mu L of the solution;
flow rate: 0.8-1.2 mL/min;
column temperature: 30 ℃;
detection wavelength: 240nm, 280nm, 305 nm;
mobile phase A: 25mM potassium dihydrogen phosphate +25mM dipotassium hydrogen phosphate;
mobile phase B: 100% methanol;
the elution procedure is shown in table 1 below:
TABLE 1 elution procedure
2. The method for rapidly detecting azo dye products according to claim 1, wherein the volume of citrate buffer added in the pretreatment step 2) is 12.0 mL.
3. The method for rapidly detecting the azo dye product according to claim 1, wherein the pretreatment step 2) comprises the step of placing the reactor in a water bath which is kept at a constant temperature of 70 ℃ for ultrasonic extraction for 10min, wherein the ultrasonic frequency is 40KHz, and the power is 200W.
4. The method for rapidly detecting azo dye products according to claim 1, wherein the pretreatment step 4) further comprises cooling to room temperature, adding 0.2mL of 20% sodium hydroxide aqueous solution into the reaction solution, and shaking up.
5. The method for rapidly detecting azo dye products according to claim 1, wherein the pretreatment step 5) employs tert-butyl methyl ether as an extraction washing solvent.
6. The method for rapidly detecting azo dye products according to any one of claims 1 to 5, wherein when detecting azo dye products, the azo dye products are weighed in a reactor with a stopper in the pretreatment step 1), and the aromatic amine standard solution is not added; and comparing the high-performance liquid chromatogram obtained by detection with the high-performance liquid chromatogram obtained by the representative negative sample external standard method, and judging whether the product is a forbidden azo dye product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104697835A (en) * | 2015-03-24 | 2015-06-10 | 李乐 | Mixed standard solution for detection of aromatic amine in textiles and preparing method and application of mixed standard solution |
| CN107045036A (en) * | 2017-06-16 | 2017-08-15 | 云南中烟工业有限责任公司 | The detection method of fragrant amine content in a kind of azo dyes |
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- 2021-04-16 CN CN202110433468.XA patent/CN113189220A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104697835A (en) * | 2015-03-24 | 2015-06-10 | 李乐 | Mixed standard solution for detection of aromatic amine in textiles and preparing method and application of mixed standard solution |
| CN107045036A (en) * | 2017-06-16 | 2017-08-15 | 云南中烟工业有限责任公司 | The detection method of fragrant amine content in a kind of azo dyes |
Non-Patent Citations (4)
| Title |
|---|
| LU YANG 等: "Determination of aromatic amines from textiles using dispersive liquid-liquid microextraction", 《J. SEP. SCI.》 * |
| 李巧 等: "高效液相色谱法测定纺织品中22种致癌芳香胺", 《印染助剂》 * |
| 王立群 等: "禁用偶氮染料测试萃取过程最佳条件的选择", 《纺织报告》 * |
| 钱微君 等: "染色纺织品中禁用偶氮染料的高效液相色谱-电喷雾电离质谱联用法测定", 《纺织学报》 * |
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Application publication date: 20210730 |