CN107271578A - Method for amine substance content in determination sample - Google Patents
Method for amine substance content in determination sample Download PDFInfo
- Publication number
- CN107271578A CN107271578A CN201710177475.1A CN201710177475A CN107271578A CN 107271578 A CN107271578 A CN 107271578A CN 201710177475 A CN201710177475 A CN 201710177475A CN 107271578 A CN107271578 A CN 107271578A
- Authority
- CN
- China
- Prior art keywords
- extract
- sample
- amine substance
- liquid chromatogram
- substance content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
It is used for the method for amine substance content in determination sample the invention discloses a kind of, is related to material tests and analysis technical field.Comprise the following steps：1. the first pre-treatment step：Testing sample is extracted, extract is stand-by；2. the second pre-treatment step：Using extract described in flowing phase dilution and constant volume is carried out to it；3. sample separating step：Extract after constant volume is injected into liquid chromatogram, the mobile phase of liquid chromatogram and step 2. described in mobile phase it is identical, be the mixed liquor of aqueous formic acid and acetonitrile；4. detecting step：Extract imported into mass spectrum after liquid chromatogram post separation and detected, the mass spectrum uses electric spray ion source and cation multiple-reaction monitoring scan pattern, you can the concentration of amine substance in detection testing sample.The detection method is more sensitive, and detection limit is low, reachable 7 μ g/kg, and strong antijamming capability, and specificity is good.
Description
Technical field
The present invention relates to material tests and analysis technical field, it is used for amine substance in determination sample in particular to one kind and contains
The method of amount.
Background technology
China is DYE PRODUCTION big country, and textile dyestuff industry is fast-developing in recent years, according to incompletely statistics, the dyestuff of China
Yield, which has been accounted for, contains all kinds of complicated compounds, the reduction fracture of nitrogen-containing group therein in 60% of world wide production or so, dyestuff
Easily form the virose amine of tool in waste water, one of the important indicator of dye wastewater treatment is exactly that wherein amine substance contains
Amount.
Prior art generally carries out analysis detection using gas chromatography and chemical method to the amine substance in sample, and it is examined
Go out limit for height, respectively in 20mg/kg and 1000mg/kg or so, and anti-interference is poor, testing result is easily by the shadow of other impurities
Ring, the specificity of measurement result is low, as the parametric results for judging amine substance residual, there is larger defect, easily
By the big waste water from dyestuff of toxicity without being expelled directly out for discovering, harm ecological environment and health.
Not only in waste water from dyestuff field, the other field such as food security, environmental monitoring also all refers to the detection of amine substance,
Need low detection limits, the amine substance detection method of high specificity.
In fact, the detection limit in order to reduce testing result, it is thought that using more accurate detecting instrument such as mass spectrum come
Detected, specificity is detected in order to improve it, then need to carry out sample pre-treatment with so that testing sample is being detected
Try one's best and separate with impurity before, such as headspace sampling, using chromatographic column sample is separated.
Chinese invention patent if application publication number is the A of CN 102746187 discloses a kind of LC-MS LC-MS grades high
The preparation method of level acetonitrile reagent, is purified and is detected to acetonitrile reagent using LC-MS.
At present in the prior art, the elder generation being detected and analyzed using this method to the amine substance in sample is not yet found
Example.
The content of the invention
Present invention aim to provide a kind of detection method, for low detection limits, high specificity in sample
Amine substance is detected.
The LC-MS method that the present invention is designed be by separation means of high performance liquid chromatography, mass spectrum be one of detector
Comprehensive analysis technology, high separation capacity and mass spectrographic high sensitivity with liquid chromatogram, extremely strong qualitative exclusive specificity
The characteristics of.The LC-MS technology that the present invention is designed can not only carry out qualitative and quantitative analysis to the residual of amine extractant, also
Explore and obtained optimal liquid chromatogram measuring condition and Mass Spectrometry Conditions.
For the method for amine substance content in determination sample, comprise the following steps：
1. the first pre-treatment step：Testing sample is extracted, extract is stand-by；
2. the second pre-treatment step：Using extract described in flowing phase dilution and constant volume is carried out to it；
3. sample separating step：Extract after constant volume is injected into liquid chromatogram, the mobile phase and step of liquid chromatogram are 2.
Described in mobile phase it is identical, be the mixed liquor of aqueous formic acid and acetonitrile；
4. detecting step：Extract imported into mass spectrum after liquid chromatogram post separation and detected, the mass spectrum uses EFI
Mist ion gun and cation multiple-reaction monitoring scan pattern, you can the concentration of amine substance in detection testing sample.
The testing sample can be the aqueous solution for being dissolved with organic amine；It is preferred that, also contain water in the testing sample
Soluble organic acid salt or inorganic salts.
The amine substance can be alkylamine；Preferably C21-C36 alkylamine；More preferably Alamine 304,
At least one of trioctylamine, TNA trinonylamine and tridecylamine.
The necessity that first pre-treatment step is present is：The testing sample is the most for the inorganic phase obtained after extraction
It is preferred that scheme.
As the preferred of above-mentioned technical proposal, step 1. in, the pH value of testing sample is adjusted to 2 ~ 5 first, then successively
Extract and salting-out agents are added, oscillation extraction is carried out, single extraction liquid is collected；At least extraction is repeated once, by the extraction being collected into
Liquid is taken to merge.
As the preferred of above-mentioned technical proposal, step 1. in, the extract be ether, the salting-out agents be sodium chloride.
Ether is as higher to the rate of recovery of amine substance during extractant, wherein reachable to the extraction recovery of trioctylamine
85%, as a comparison, methyl tertiary butyl ether(MTBE) is 82% to the extraction recovery of trioctylamine, and chloroform is to the extraction recovery of trioctylamine
83%。
Sodium chloride increases the polarity of aqueous phase as salting-out agents, beneficial to the separation of aqueous phase and organic phase, that is, saltouts, suppression
The formation of emulsion layer processed, beneficial to extraction；By adding sodium chloride, solubility of the amine substance in aqueous phase can also be reduced, is made
Distribution in organic phase is more, improves extraction yield.
As the preferred of above-mentioned technical proposal, step 2. with step 3. described in mobile phase use 0.1% aqueous formic acid
With acetonitrile using volume ratio as 4:6 ratio is mixed.
Mobile phase used has certain pH buffer capacities, therefore pH is difficult change, so as to ensure that the weight of analysis result
Renaturation and reappearance.
As the preferred of above-mentioned technical proposal, step 3. described in liquid chromatogram chromatographic column specification be 2.1mmx50mmx
1.7 μm, the flow velocity of mobile phase is 0.4ml/min, and sample size is 10 μ L, and column temperature is 10 ~ 30 DEG C.
As the preferred of above-mentioned technical proposal, step 4. in, mass spectrographic nebulizer pressure is 45psi, and drier flow velocity is
10L/min, scanning range is 50 ~ 360m/z, and heating-up temperature is 100 DEG C.
The present invention compared with prior art, with advantages below and beneficial effect：
（1）The detection method of amine substance content of the present invention is more sensitive, and detection limit is low, up to 7 μ g/kg；
（2）The characteristics of detection method of amine substance content of the present invention also has quick compared to conventional method；
（3）The detection method strong antijamming capability of amine substance content of the present invention, specificity is good；
（4）The detection method of amine substance content of the present invention has certain versatility, to be measured available for detection of complex
The content of amine substance in thing.
Brief description of the drawings
Fig. 1 is the reference colour spectrogram of trioctylamine；
Fig. 2 is the standard mass spectrogram of trioctylamine；
Fig. 3 is the chromatogram of the sample of addition concentration in embodiment 1；
Fig. 4 is the method standard working curve in embodiment 1；
Trioctylamine of the standard working curve by concentration in 0.1 ~ 1.0 μ g/mL described in Fig. 4 injects LC-MS instrument, with standard work
Make curve sample peak area for ordinate, standard concentration is abscissa, you can be made.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
Embodiment 1：A kind of method for determining trioctylamine content in dyeing waste water, in the present embodiment, laboratory apparatus are used：
The Agilent 1260-6460 high performance liquid chromatography GC-MSs and ZORBAX Eclipse Plus of Agilent company of the U.S.
C18 liquid-phase chromatographic analysis posts, and to rise 0.22 μm of syringe-type miillpore filter organic in Tianjin of Shanghai ANPEL Scientific Instrument Co., Ltd.
It is filter membrane.
In the present embodiment, grope using trioctylamine standard items first and determine optimal chromatographic condition and Mass Spectrometry Conditions.
1. the first pre-treatment step：Dyeing waste water sample 200mL accurately is measured in 500ml separatory funnels, is prepared above-mentioned
Totally 4 parts of sample, wherein it is 0.4 μ g/ml that 3 parts, which are separately added into concentration, 0.6 μ g/ml, 0.8 μ g/ml trioctylamine standard working solutions are adjusted
It is 5 to save pH value, first adds 45ml ether, adds 20g sodium chloride, and concussion extraction 15min is repeated 3 times, combining extraction liquid；
2. the second pre-treatment step：Extract is rotated to be concentrated by evaporation to 3mL, and mobile phase is settled to 10mL.
3. separating step：Extract after constant volume is injected into liquid chromatogram, the chromatographic column specification of liquid chromatogram is
2.1mmx50mmx1.8 μm, mobile phase is 0.1% aqueous formic acid-acetonitrile, and the volume ratio of aqueous formic acid-acetonitrile is 4:6, stream
Speed is 0.4ml/min, and sample size is 1 μ L, and column temperature is room temperature；
4. detecting step：Component after separation is detected with mass spectrum, mass spectrum uses electric spray ion source, reacted cation more
Monitoring scanning；Nebulizer pressure is 45psi；Drier flow velocity is 10L/min；Scanning range is 50 ~ 360m/z, and heating-up temperature is
100℃。
The rate of recovery and the precision test of embodiment 1：
The preparation of standard liquid：
Precision weighs 50mg trioctylamine standard items respectively, is dissolved with ethanol and is settled to 100ml, is made into concentration for 500 μ g/ml
Standard Stock solutions, then dilute 50 times be 10 μ g/ml standard working solutions, preserve at 4 DEG C.
The calibration curve equation and coefficient correlation of method：
It is respectively 0.1 μ g/ml, 0.2 μ g/ml, 0.4 μ g/ml, 0.6 μ g/ml, 0.8 μ g/ml, 1.0 μ g/ml injections to take six concentration
Liquid chromatography-mass spectrography/GC-MS, linear equation and coefficient correlation are shown in Table 1.
The calibration curve equation and coefficient correlation of trioctylamine described in the embodiment 1 of table 1
Y is chromatographic peak area in table 1；X is sample concentration；
To with the addition of 0.4 μ g/ml, 0.6 μ g/ml, 0.8 μ g/ml trioctylamines standard working solution carries out replica test.Each concentration
Divide and be repeated 7 times test in three days, the rate of recovery and precision are calculated according to measurement result, 4 are the results are shown in Table.
The rate of recovery and precision of trioctylamine described in the embodiment 1 of table 2
According to the ratio of instrumental response value and noise for 3 come computational methods detection limit, then the detection of trioctylamine is limited to 7 μ g/kg.
Embodiment 2：A kind of method for determining trioctylamine content in high salt extract waste water, laboratory apparatus be the same as Example
1。
1. the first pre-treatment step：High salt extract wastewater sample 200mL accurately is measured in 500ml separatory funnels, is made
Standby totally 4 parts of above-mentioned sample, wherein it is 0.4 μ g/ml, 0.6 μ g/ml, the work of 0.8 μ g/ml trioctylamines standard that 3 parts, which are separately added into concentration,
Liquid, regulation pH value is 2, first adds 20ml ether, adds 20g sodium chloride, and concussion extraction 15min is repeated 3 times, merges extraction
Liquid；
2. the second pre-treatment step：Extract is rotated to be concentrated by evaporation to 2mL, and mobile phase is settled to 10mL.
3. separating step：Extract after constant volume is injected into liquid chromatogram, the chromatographic column specification of liquid chromatogram is
2.1mmx50mmx1.8 μm, liquid chromatogram separation condition be the same as Example 1；
4. detecting step：Component after separation is detected with mass spectrum, Mass Spectrometer Method condition be the same as Example 1.
The rate of recovery and the precision test of embodiment 2：
The preparation of standard liquid：
Method be the same as Example 1, the calibration curve equation and coefficient correlation of trioctylamine are shown in Table 3.
The calibration curve equation and coefficient correlation of trioctylamine described in the embodiment 2 of table 3
To with the addition of 0.4 μ g/ml, 0.6 μ g/ml, 0.8 μ g/ml trioctylamines standard working solution carries out replica test.Each concentration
Divide and be repeated 7 times test in three days, the rate of recovery and precision are calculated according to measurement result, 4 are the results are shown in Table.
The rate of recovery and precision of trioctylamine described in the embodiment 2 of table 4
According to the ratio of instrumental response value and noise for 3 come computational methods detection limit, then the detection of trioctylamine is limited to 8 μ g/kg.
Embodiment 3：
A kind of method for determining TNA trinonylamine content in extract waste water, laboratory apparatus be the same as Example 1.
1. the first pre-treatment step：Extract wastewater sample 200mL accurately is measured in 500ml separatory funnels, in preparation
Totally 4 parts of sample is stated, wherein it is 0.4 μ g/ml that 3 parts, which are separately added into concentration, 0.6 μ g/ml, 0.8 μ g/ml TNA trinonylamine standard working solutions,
It is 2 to adjust pH value, first adds 20ml ether, adds 20g sodium chloride, and concussion extraction 15min is repeated 3 times, combining extraction liquid；
2. the second pre-treatment step：Extract is rotated to be concentrated by evaporation to 2mL, and mobile phase is settled to 10mL.
3. separating step：Extract after constant volume is injected into liquid chromatogram, the chromatographic column specification of liquid chromatogram is
2.1mmx50mmx1.8 μm, liquid chromatogram separation condition be the same as Example 1；
4. detecting step：Component after separation is detected with mass spectrum, Mass Spectrometer Method condition be the same as Example 1.
The rate of recovery and the precision test of embodiment 3：
The preparation of standard liquid：
Method be the same as Example 1, the calibration curve equation and coefficient correlation of TNA trinonylamine are shown in Table 5.
The calibration curve equation and coefficient correlation of trioctylamine described in the embodiment 3 of table 5
To with the addition of 0.4 μ g/ml, 0.6 μ g/ml, 0.8 μ g/ml TNA trinonylamines standard working solution carries out replica test.Each concentration
Divide and be repeated 7 times test in three days, the rate of recovery and precision are calculated according to measurement result, 6 are the results are shown in Table.
The rate of recovery and precision of TNA trinonylamine described in the embodiment 3 of table 6
According to the ratio of instrumental response value and noise for 3 come computational methods detection limit, then the detection of TNA trinonylamine is limited to 7 μ g/kg.
Claims (6)
1. the method for amine substance content in determination sample, it is characterised in that comprise the following steps：
1. the first pre-treatment step：Testing sample is extracted, extract is stand-by；
2. the second pre-treatment step：Using extract described in flowing phase dilution and constant volume is carried out to it；
3. sample separating step：Extract after constant volume is injected into liquid chromatogram, the mobile phase and step of liquid chromatogram are 2.
Described in mobile phase it is identical, be the mixed liquor of aqueous formic acid and acetonitrile；
4. detecting step：Extract imported into mass spectrum after liquid chromatogram post separation and detected, the mass spectrum uses EFI
Mist ion gun and cation multiple-reaction monitoring scan pattern, you can the concentration of amine substance in detection testing sample.
2. according to claim 1 be used for the method for amine substance content in determination sample, it is characterised in that：Step is 1.
In, the pH value of testing sample is adjusted to 2 ~ 5 first, extract and salting-out agents is sequentially added, oscillation extraction is carried out, one is collected
Secondary extract；At least repeat extraction once, the extract being collected into is merged.
3. according to claim 2 be used for the method for amine substance content in determination sample, it is characterised in that：Step is 1.
In, the extract is ether, and the salting-out agents are sodium chloride.
4. according to claim 1 be used for the method for amine substance content in determination sample, it is characterised in that：Step 2. and
Step 3. described in mobile phase use 0.1% aqueous formic acid and acetonitrile using volume ratio as 4:6 ratio is mixed.
5. according to claim 4 be used for the method for amine substance content in determination sample, it is characterised in that：Step 3. in
The flow velocity of mobile phase is 0.4ml/min in the liquid chromatogram, and column temperature is 10 ~ 30 DEG C.
6. according to claim 1 be used for the method for amine substance content in determination sample, it is characterised in that：Step is 4.
In, mass spectrographic nebulizer pressure is 45psi, and drier flow velocity is 10L/min, and scanning range is 50 ~ 360m/z, and heating-up temperature is
100℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710177475.1A CN107271578A (en) | 2017-03-23 | 2017-03-23 | Method for amine substance content in determination sample |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710177475.1A CN107271578A (en) | 2017-03-23 | 2017-03-23 | Method for amine substance content in determination sample |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107271578A true CN107271578A (en) | 2017-10-20 |
Family
ID=60073709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710177475.1A Pending CN107271578A (en) | 2017-03-23 | 2017-03-23 | Method for amine substance content in determination sample |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107271578A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1750126A1 (en) * | 2004-05-26 | 2007-02-07 | Ajinomoto Co., Inc. | Method and apparatus for analyzing aminofunctional compound |
| CN102680590A (en) * | 2011-08-15 | 2012-09-19 | 宁波市环境监测中心 | Two-dimensional liquid chromatogram (LC)-tandem mass spectrometry method for detecting four amine substances in water |
| CN103760261A (en) * | 2014-01-07 | 2014-04-30 | 深圳市谱尼测试科技有限公司 | Method for measuring ethanolamine substance residual quantity in cosmetics |
| CN105486794A (en) * | 2015-12-25 | 2016-04-13 | 广州广电计量检测股份有限公司 | Method for detecting banned dye in printing ink |
-
2017
- 2017-03-23 CN CN201710177475.1A patent/CN107271578A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1750126A1 (en) * | 2004-05-26 | 2007-02-07 | Ajinomoto Co., Inc. | Method and apparatus for analyzing aminofunctional compound |
| CN102680590A (en) * | 2011-08-15 | 2012-09-19 | 宁波市环境监测中心 | Two-dimensional liquid chromatogram (LC)-tandem mass spectrometry method for detecting four amine substances in water |
| CN103760261A (en) * | 2014-01-07 | 2014-04-30 | 深圳市谱尼测试科技有限公司 | Method for measuring ethanolamine substance residual quantity in cosmetics |
| CN105486794A (en) * | 2015-12-25 | 2016-04-13 | 广州广电计量检测股份有限公司 | Method for detecting banned dye in printing ink |
Non-Patent Citations (4)
| Title |
|---|
| JAMES M. ROBERTS 等: "Influence of the Hofmeister Series on the Retention of Amines in Reversed-Phase Liquid Chromatography", 《ANAL.CHEM.》 * |
| 朱丽波 等: "双柱串联-超高效液相色谱-质谱法检测水中的4种胺类物质", 《分析化学》 * |
| 王朝虹 等: "超高效液相色谱-MS/MS 法测定血中11种苯丙胺类物质", 《中国法医杂志》 * |
| 金薇 等: "液相色谱-串联质谱法测定化妆品中丙烯酰胺单体残留量", 《药物分析杂志》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103257198B (en) | GC-MS/MS (Gas Chromatography-Mass Spectrometer) method for analyzing organo-chlorine pesticide residues in tobacco and tobacco products | |
| CN109696499B (en) | High-sensitivity determination method for nitrosamine in water based on high-resolution mass spectrum | |
| CN103728398B (en) | A kind of Ion-pair Liquid Chromatography measures the method for dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate | |
| CN110174470A (en) | The high-flux detection method of marine biotoxins in a kind of aquatic products | |
| CN104297399B (en) | By-product 4-methylimidazole and the detection method of 2-acetyl group-4-hydroxy-butyl imidazoles in caramel color | |
| CN103512983B (en) | The high-performance liquid chromatogram determination method of caffeine in a kind of coffee and goods | |
| CN106950317A (en) | A kind of method for closing the specific aromatic amine that azo dyes discharges in phase chromatographic tandem mass spectrometric determination Cigarette paper | |
| CN112505190B (en) | Method for detecting acrylic acid in soil | |
| CN105628837A (en) | Detecting method for mesotrione and metabolite thereof in soil | |
| CN110887913B (en) | HPLC detection method of biotin intermediate diamino substance | |
| CN102998396B (en) | Method for determining epoxy chloropropane in water | |
| CN108760920A (en) | A method of cyazofamid and its metabolite residue amount are measured based on HPLC-MSMS methods | |
| CN107271578A (en) | Method for amine substance content in determination sample | |
| CN104713954B (en) | Method for detecting content of haloacetonitrile substances in water sample through dispersive liquid-liquid microextraction programmed temperature gas chromatography-mass spectrometry | |
| CN105158372A (en) | Method for determining urocanic acid and ethyl ester thereof in cosmetics | |
| CN114166974B (en) | Method for detecting triethylamine in soil and sediment by gas chromatography-mass spectrometry | |
| CN113759068B (en) | Method for detecting demulsifier in oilfield sewage | |
| CN104849383A (en) | Method for determining nitroimidazole drug in bee pollen powder through combination of rapid solvent extraction-gel chromatography purification-LC/MS/MS | |
| CN109633071B (en) | Method for detecting Saisentong copper in water by using UPLC-MS/MS method | |
| Gyllenhaal et al. | Electron-capture gas chromatography of sulphonamides after extractive alkylation | |
| CN106324169A (en) | Solid phase extraction-gas chromatography-tandem mass spectrum detection method for amide fungicides in wine | |
| CN113607852A (en) | Method for measuring turpentine in soil | |
| CN109030683B (en) | A method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid | |
| CN106442786A (en) | High performance liquid chromatography-tandem mass spectrometry detection method for paralytic shellfish poisoning toxins | |
| CN113049701A (en) | Method for detecting formaldehyde content in water-based paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |
|
| RJ01 | Rejection of invention patent application after publication |