CN108008041A - The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide - Google Patents
The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide Download PDFInfo
- Publication number
- CN108008041A CN108008041A CN201711275758.6A CN201711275758A CN108008041A CN 108008041 A CN108008041 A CN 108008041A CN 201711275758 A CN201711275758 A CN 201711275758A CN 108008041 A CN108008041 A CN 108008041A
- Authority
- CN
- China
- Prior art keywords
- level
- detection method
- ketjenblack
- trap
- acrylamide monomer
- 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
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
The invention discloses the detection method of residual quantity of acrylamide monomer in food grade polyacrylamide.The present invention monitors the residual quantity that (PRM) pattern measures food-grade PAM high molecular monomer AM by ketjenblack EC chromatography post separation, the parallel reaction of level Four bar electrostatic field orbit trap high resolution mass spectrum, on the one hand overcome existing assay method there are poor specificity, accuracy is low, interference is big the shortcomings that；On the other hand the application for solving Low Resolution Mass Spectra is difficult to differentiate between for this kind of small mass-to-charge ratio compounds of AM, its relevant interference thing, the problem of false positive results easily occurs.
Description
Technical field
The present invention relates to the detection method of residual quantity of acrylamide monomer, more particularly to propylene in food grade polyacrylamide
The detection method of amide monomer residual quantity.
Background technology
Polyacrylamide is the general designation of methacrylamide homopolymer, and as a kind of linear polymeric polymer, it is special to have
Physicochemical properties, and it is widely used in the industries such as oil exploitation, wastewater treatment, papermaking mineral products.In the food industry, polypropylene
Acid amides can be used as flocculant, filter aid in the processing technology of beverage (water process), sugar refining technology and zymotechnique, so
And it can slowly discharge acrylamide monomer during production, use.Acrylamide is by international cancer research institution (IARC)
It is classified as " may be to people's carcinogen ".Therefore, national food safety standard《GB 31629-2016》Clear stipulaties food-grade is gathered
The acrylamide monomer content of acrylamide must not exceed 0.025%, strictly meet standard requirement, it can just be used as food to add
Agent uses.
High performance liquid chromatography is used mostly in the measure of existing Acrylamide in Polyacrylamide level of residual monomers, it is high
Effect liquid phase chromatogram method there is the shortcomings that specificity is low, interference is big, and method sensitivity and dosing accuracy be difficult to meet it is actual
Demand, therefore it is badly in need of developing a kind of side of residual quantity of acrylamide monomer in accurate, easy measure food grade polyacrylamide
Method.
The content of the invention
In order to solve the above-mentioned problems in the prior art, technical purpose of the invention be can accurately, easy survey
The method of food grade polyacrylamide level of residual monomers is determined, as fast inspection and confirmation detection technique with the food of condensed food level PAM
Product security control.
The technical purpose of the present invention is to be achieved through the following technical solutions：
The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide of the present invention, including following step
Suddenly：
S1：The standard items of acrylamide monomer are configured to the standard solution of some concentration gradients；
S2：It is molten to standard obtained by step S1 with ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method
Liquid is measured, and calculates acrylamide monomer peak area, calibration model is established with least square method；
S3：Pre-treatment is carried out to polyacrylamide sample to be tested, obtains prepare liquid；
S4：With ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method to prepare liquid obtained by step S3
Acrylamide monomer content be measured, and be compared with the measurement result of standard solution.Preferably, the step
With the isotope of carbon -13 that AM is added before ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method in S2, S4
Internal standard.
Further, the content of acrylamide monomer standard solution is respectively 2 μ g/L, 5 μ g/ to the present invention in the step S1
L、10μg/L、20μg/L、50μg/L。
Further, calibration model is the present invention in the step S2：Acrylamide monomer concentration range is in 2~50 μ g/L
Interior equation of linear regression is y=-62618.4+484517x, wherein r2=0.9994, y-axis represents AM peak areas, and x represents AM
Concentration.
Further, ultra performance liquid chromatography condition is the present invention during step S2 ketjenblack ECs chromatography post separation：
A) chromatographic columns：Ketjenblack EC chromatographic column, 50mm × 2.1mm, 3 μm of particle diameter；
B) mobile phase As are water；Mobile phase B is methanol；Flow velocity is 0.2~0.5mL/min；Type of elution：Gradient elution；
Mass Spectrometer Method condition is：Using electric spray ion source, positive ion mode, electric spray ion source temperature is 300~500
℃；Spray voltage is：2500~4000V；First mass spectrometric full scan resolution ratio：17500~70000；C-trap maximum capacities：1
×105~3 × 106；C-trap maximum injection lengths：30~70ms；Parallel reaction monitors two level daughter ion full scan resolution ratio
17500~70000；Phase step type impact energy：10%~45%；Two level C-trap maximum capacities：1×105~3 × 106；Two level C-
Trap injection lengths：30~300ms.
The present invention further, in the step S3 pre-treatment include the following steps：With dilution by polyacrylamide sample
Product dilute, and stirring, constant volume, filtering, obtain prepare liquid.Preferably, the dilution is deionized water to the present invention, the polyacrylamide
The adding proportion g/ml of amine sample and dilution is 0.1:(50~1000).
Preferably, the speed of the stirring is 300rpm~500rpm to the present invention, and mixing time is 6h~8h；Filtration step
Using 0.22 μm of water phase membrane filtration；The water phase filter membrane used is filtered as polyether sulfone.
Further, ultra performance liquid chromatography condition is the present invention during step S4 ketjenblack ECs chromatography post separation：
A) chromatographic columns：Ketjenblack EC chromatographic column, 50mm × 2.1mm, 3 μm of particle diameter；
B) mobile phase As are water；Mobile phase B is methanol；Flow velocity is 0.2~0.5mL/min；Type of elution：Gradient elution；
Mass Spectrometer Method condition is：Using electric spray ion source, positive ion mode, electric spray ion source temperature is 300~500
℃；Spray voltage is：2500~4000V；First mass spectrometric full scan resolution ratio：17500~70000；C-trap maximum capacities：1
×105~3 × 106；C-trap maximum injection lengths：30~70ms；Parallel reaction monitors two level daughter ion full scan resolution ratio
17500~70000；Phase step type impact energy：10%~45%；Two level C-trap maximum capacities：1×105~3 × 106；Two level C-
Trap injection lengths：30~300ms.
Further, with volume percentage, the condition of gradient elution is the present invention：0~3min, 0%B；3~
5min, 0%~100%B；5~5.5min, 100%B；5.5~6,100%~0%B；6~7min, 0%B.
The present invention further, the analysis time of ultra performance liquid chromatography during the ketjenblack EC chromatography post separation
7min, wherein effluent switches to waste liquid during 3.5~6.5min.
Specifically, the level Four bar-electrostatic field Orbitrap mass method uses parallel reaction monitoring pattern, level-one matter to the present invention
Compose full scan resolution ratio (R)：70000, two level daughter ion full scan resolution ratio：17500；Phase step type impact energy：10%~40%.
The present invention passes through ketjenblack EC chromatography post separation, level Four bar-electrostatic field orbit trap high resolution mass spectrum parallel reaction
The residual quantity of the high molecular monomer AM of (PRM) pattern of monitoring measure food-grade PAM, on the one hand overcomes existing assay method and exists
The shortcomings that poor specificity, accuracy are low, interference is big；On the other hand the application of Low Resolution Mass Spectra is solved for this kind of small mass-to-charge ratioes of AM
Compound, its relevant interference thing are difficult to differentiate between, and the problem of false positive results easily occur.Under PRM patterns, to obvious fragment
Ion carries out molecule fitting, and carries out isotope matching, selects fragments characteristic, concludes molecular cleavage mode, further to grind
Offer theoretical foundation is provided.Pretreatment process, easy quick, direct dilution processing is realized environmental-friendly, can be used as fast inspection and confirmation
Detection technique uses, and technical support is provided for food additives quality monitoring.
Brief description of the drawings
Fig. 1 is chromatogram of the acrylamide monomer of the present invention under parallel reaction monitoring pattern；
Fig. 2 is the acrylamide monomer secondary fragment mass spectrum full figure of the present invention.
Fig. 3 is equation of linear regression figure of the acrylamide monomer concentration range of the present invention in 2~50 μ g/L.
Embodiment
The present invention is described in further detail below by way of specific preferred embodiment, but the present invention be not limited in it is following
Embodiment.
Embodiment 1
Sample in the present embodiment 1 is food grade polyacrylamide, and detection method described in the present embodiment includes the following steps：
S1：The standard items of acrylamide monomer (AM) are diluted with deionized water, are configured to AM contents respectively as 2 μ g/L, 5
μ g/L, 10 μ g/L, 20 μ g/L, the standard solution of 50 μ g/L；
S2：It is molten to standard obtained by step S1 with ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method
Liquid is measured, and is calculated peak area, is carried out regression analysis with least square method, obtain the AM in 2~50 μ g/L ranges of linearity
Equation of linear regression is y=-62618.4+484517x r2=0.9994 (y:AM peak areas, x：AM concentration)
(r2=0.9990), shown in its Fig. 3.
Wherein, ultra performance liquid chromatography condition is during ketjenblack EC chromatography post separation：
A) chromatographic columns：Ketjenblack EC chromatographic column, 50mm × 2.1mm, 3 μm of particle diameter；
B) mobile phase As are water；Mobile phase B is methanol；Flow velocity is 0.3mL/min；Type of elution：Gradient elution, its condition
For：0~3min, 0%B；3~5min, 0%~100%B；5~5.5min, 100%B；5.5~6,100%~0%B；6~
7min, 0%B；
Mass Spectrometer Method condition is：Using electric spray ion source, positive ion mode, electric spray ion source temperature is 350 DEG C；Spray
Mist voltage is：3000V；First mass spectrometric full scan resolution ratio：70000；C-trap maximum capacities：2×105；The maximum notes of C-trap
The angle of incidence：50ms；Parallel reaction monitoring two level daughter ion full scan resolution ratio 17500；Phase step type impact energy：10%~45%；
Two level C-trap maximum capacities：2×105；Two level C-trap injection lengths：100ms；
Determine that detection limit (LOD) is 0.015 μ g/L using signal-to-noise ratio as 3, determine that quantitative limit (LOQ) is using signal-to-noise ratio as 10
0.05μg/L。
The preparation of S3, prepare liquid
A. determinand extracts
Food grade polyacrylamide sample 0.1g (being accurate to 0.1mg) is accurately weighed with assay balance to large capacity beaker,
Add 50ml deionized water preliminarily solubiliseds after, with numerical control blender with 300rpm high-speed stirreds 6 it is small when mix.
B.QuEChERS methods purify extracting solution
Extracting solution obtained by step a is transferred in 100mL volumetric flasks, is settled to scale, crosses 0.22 μm of water phase polyether sulfone filter
After film, prepare liquid measure is obtained.
The detection of S4, prepare liquid
With ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method to the acryloyl obtained by step S3
Amine monomers content is measured, and is compared with the measurement result of standard solution (by detecting acryloyl in prepare liquid
Amine monomers peak area, then calculates residual quantity of acrylamide monomer by equation of linear regression).
It is preferable that ketjenblack EC chromatographic column retains highly polar compound acrylamide monomer, and peak shape is symmetrical, such as the institute of attached drawing 1
Show.
Wherein the step S4 ketjenblack ECs chromatography post separation when ultra performance liquid chromatography condition be：
A) chromatographic columns：Ketjenblack EC chromatographic column, 50mm × 2.1mm, 3 μm of particle diameter；
B) mobile phase As are water；Mobile phase B is methanol；Flow velocity is 0.3mL/min；Type of elution：Gradient elution, it is eluted
Condition is：0~3min, 0%B；3~5min, 0%~100%B；5~5.5min, 100%B；5.5~6,100%~0%B；6
~7min, 0%B；
Mass Spectrometer Method condition is：Using electric spray ion source, positive ion mode, electric spray ion source temperature is 350 DEG C；Spray
Mist voltage is：3000V；First mass spectrometric full scan resolution ratio：70000；C-trap maximum capacities：2×105；The maximum notes of C-trap
The angle of incidence：50ms；Parallel reaction monitoring two level daughter ion full scan resolution ratio 17500；Phase step type impact energy：10%~45%；
Two level C-trap maximum capacities：2×105；Two level C-trap injection lengths：100ms.
Determine that detection limit (LOD) is 0.015 μ g/L using signal-to-noise ratio as 3, determine that quantitative limit (LOQ) is using signal-to-noise ratio as 10
0.05μg/L。
Compound molecular weight is less, chooses a feature daughter ion as qualitative and quota ion, its accurate mass number and
Retention time see the table below 1.
Level Four bar-electrostatic field Orbitrap mass can be accurately qualitative in parallel reaction monitoring pattern, and carries out high-throughout knot
Fruit is analyzed, and obtains compound secondary fragment full figure, as shown in Figure 2.[C can be confirmed3H3O]+(m/z 55.01786) is used as feature
Daughter ion is the qualitative and quota ion of acrylamide monomer.
Molecular formula, accurate mass number and the retention time of 1 AM of table
S5：Precision and the rate of recovery
Choose the less food-grade PAM mark-ons of one of background values, the horizontal mark-on selection 0.4mg/kg of low concentration, centre
Concentration level, high concentration difference mark-on 2mg/kg and 10mg/kg, concentrations above level by the experimental procedure and condition at
Reason measure, is repeated 6 times, the computational methods rate of recovery and relative standard deviation.The result is shown in table 2 below.
The measure relative standard deviation of AM and recovery of standard addition (n=6) in 2 PAM of table
S6 actual samples measure
PAM is formed by AM radical polymerizations, its polymerization is divided into polymerisation in bulk, polymerisation in solution, suspension polymerisation, lotion are gathered
Close etc., final product form is various, therefore the level of residual monomers of each PAM has bigger difference.To being produced from 6 kinds bought on the market are different
The PAM of producer is detected.Measurement result shows that the residual scope of AM is 0~0.43% in PAM, and portioned product exceedes state
Monomer residue limitation is marked, therefore there are certain security risk in food applications for Related product.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, therefore
It is every without departing from technical solution of the present invention content, what the technical spirit according to the present invention made above example any simply repaiies
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (10)
1. the detection method of residual quantity of acrylamide monomer in a kind of food grade polyacrylamide, it is characterised in that including following
Step：
S1：The standard items of acrylamide monomer are configured to the standard solution of some concentration gradients；
S2：With ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method to standard solution obtained by step S1 into
Row measure, calculates acrylamide monomer peak area, calibration model is established with least square method；
S3：Pre-treatment is carried out to polyacrylamide sample to be tested, obtains prepare liquid；
S4：With ketjenblack EC chromatography post separation, level Four bar-electrostatic field Orbitrap mass method to third of prepare liquid obtained by step S3
Acrylamide content of monomer is measured, and is compared with the measurement result of standard solution.
2. detection method according to claim 1, it is characterised in that acrylamide monomer standard solution in the step S1
Content be respectively 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L.
3. detection method according to claim 1, it is characterised in that calibration model is in the step S2：Acrylamide
Equation of linear regression of the monomer concentration scope in 2~50 μ g/L is y=-62618.4+484517x, wherein
r2=0.9994, y-axis represents AM peak areas, and x represents AM concentration.
4. detection method according to claim 1, it is characterised in that
Ultra performance liquid chromatography condition is during the step S2 ketjenblack ECs chromatography post separation：
A) chromatographic columns：Ketjenblack EC chromatographic column, 50mm × 2.1mm, 3 μm of particle diameter；
B) mobile phase As are water；Mobile phase B is methanol；Flow velocity is 0.2~0.5mL/min；Type of elution：Gradient elution；
Mass Spectrometer Method condition is：Using electric spray ion source, positive ion mode, electric spray ion source temperature is 300~500 DEG C；
Spray voltage is：2500~4000V；First mass spectrometric full scan resolution ratio：17500~70000；C-trap maximum capacities：1×
105~3 × 106；C-trap maximum injection lengths：30~70ms；Parallel reaction monitors two level daughter ion full scan resolution ratio
17500~70000；Phase step type impact energy：10%~45%；Two level C-trap maximum capacities：1×105~3 × 106；Two level C-
Trap injection lengths：30~300ms.
5. detection method according to claim 1, it is characterised in that pre-treatment includes the following steps in the step S3：
Laemmli sample is diluted with dilution, stirring, constant volume, filtering, obtain prepare liquid；The dilution is deionized water, institute
The adding proportion g/ml for stating Laemmli sample and dilution is 0.1:(50~1000).
6. detection method according to claim 5, it is characterised in that the speed of the stirring is 300rpm~500rpm, is stirred
It is 6h~8h to mix the time；Filtration step uses 0.22 μm of water phase membrane filtration；The water phase filter membrane used is filtered as polyether sulfone.
7. detection method according to claim 1, it is characterised in that surpass during the step S4 ketjenblack ECs chromatography post separation
High-efficient liquid phase chromatogram condition is：
A) chromatographic columns：Ketjenblack EC chromatographic column, 50mm × 2.1mm, 3 μm of particle diameter；
B) mobile phase As are water；Mobile phase B is methanol；Flow velocity is 0.2~0.5mL/min；Type of elution：Gradient elution；
Mass Spectrometer Method condition is：Using electric spray ion source, positive ion mode, electric spray ion source temperature is 300~500 DEG C；
Spray voltage is：2500~4000V；First mass spectrometric full scan resolution ratio：17500~70000；C-trap maximum capacities：1×
105~3 × 106；C-trap maximum injection lengths：30~70ms；Parallel reaction monitors two level daughter ion full scan resolution ratio
17500~70000；Phase step type impact energy：10%~45%；Two level C-trap maximum capacities：1×105~3 × 106；Two level C-
Trap injection lengths：30~300ms.
8. the detection method according to claim 4 or 7, it is characterised in that with volume percentage, the gradient elution
Condition is：0~3min, 0%B；3~5min, 0%~100%B；5~5.5min, 100%B；5.5~6,100%~0%B；6
~7min, 0%B.
9. detection method according to claim 1, it is characterised in that ultra high efficiency during the ketjenblack EC chromatography post separation
The analysis time 7min of liquid chromatogram, wherein effluent switches to waste liquid during 3.5~6.5min.
10. detection method according to claim 1, it is characterised in that the level Four bar-electrostatic field Orbitrap mass method is adopted
With parallel reaction monitoring pattern, first mass spectrometric full scan resolution ratio (R)：70000, two level daughter ion full scan resolution ratio：
17500；Phase step type impact energy：10%~40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711275758.6A CN108008041A (en) | 2017-12-06 | 2017-12-06 | The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711275758.6A CN108008041A (en) | 2017-12-06 | 2017-12-06 | The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108008041A true CN108008041A (en) | 2018-05-08 |
Family
ID=62056899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711275758.6A Pending CN108008041A (en) | 2017-12-06 | 2017-12-06 | The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108008041A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115078592A (en) * | 2022-07-15 | 2022-09-20 | 广东广纳安疗科技有限公司 | Detection method and application of acrylamide monomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290659A (en) * | 2016-10-28 | 2017-01-04 | 陕西科技大学 | Dispensed food for baby Pesticides and the Ultra Performance Liquid Chromatography level Four bar electrostatic field orbit ion trap mass spectrum screening method of veterinary drug |
| CN106526017A (en) * | 2016-10-28 | 2017-03-22 | 陕西科技大学 | Ultra-high performance liquid chromatography-quadrupole electrostatic field orbit ion trap mass spectrometry screening method for nutrition enhancer in milk and dairy product |
-
2017
- 2017-12-06 CN CN201711275758.6A patent/CN108008041A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290659A (en) * | 2016-10-28 | 2017-01-04 | 陕西科技大学 | Dispensed food for baby Pesticides and the Ultra Performance Liquid Chromatography level Four bar electrostatic field orbit ion trap mass spectrum screening method of veterinary drug |
| CN106526017A (en) * | 2016-10-28 | 2017-03-22 | 陕西科技大学 | Ultra-high performance liquid chromatography-quadrupole electrostatic field orbit ion trap mass spectrometry screening method for nutrition enhancer in milk and dairy product |
Non-Patent Citations (3)
| Title |
|---|
| 王仲来等: "基于石墨化炭黑预涂覆技术的色谱柱制备和性能评价", 《色谱》 * |
| 王成龙等: "超高效液相色谱－四级杆/静电场轨道阱高分辨质谱法对酒中氨基甲酸乙酯确认分析的研究", 《酿酒科技》 * |
| 简黎黎等: "HPLC-MS/MS法定量测定方便面中的丙烯酰胺", 《食品工业科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115078592A (en) * | 2022-07-15 | 2022-09-20 | 广东广纳安疗科技有限公司 | Detection method and application of acrylamide monomer |
| CN115078592B (en) * | 2022-07-15 | 2024-01-23 | 广东广纳安疗科技有限公司 | Detection method of acrylamide monomer and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2064312B1 (en) | Methods and devices for simultaneously monitoring the characteristics of microscopic particles in suspension and the characteristics of soluble components during reactions | |
| US20150004713A1 (en) | Methods and materials for the detection of melamine | |
| Mohammadi et al. | Applicability of cloud point extraction for the separation trace amount of lead ion in environmental and biological samples prior to determination by flame atomic absorption spectrometry | |
| CN108872448A (en) | A kind of method that ultra performance liquid chromatography-tandem mass spectrum detects 5 kinds of sweeteners in flavouring essence for tobacco | |
| CN108776187A (en) | A kind of method that ultra performance liquid chromatography-tandem mass spectrum detects 5 kinds of sweeteners in cigarette tipping paper | |
| Motomizu et al. | Spectrophotometric determination of anionic surfactants in water after solvent extraction coupled with flow injection | |
| CN102411035B (en) | New method for detecting trace amount bromate | |
| Rastegar et al. | Application of supramolecular solvent-based dispersive liquid–liquid microextraction for trace monitoring of lead in food samples | |
| Li et al. | Supramolecular solvent-based microextraction of copper and lead in water samples prior to reacting with synthesized Schiff base by flame atomic absorption spectrometry determination | |
| CN109374600A (en) | The rapid assay methods of 18 kinds of impurity elements in a kind of palladium ammonium salt calcined material | |
| CN108008041A (en) | The detection method of residual quantity of acrylamide monomer in food grade polyacrylamide | |
| Wang et al. | A novel polythiophene derivative as a sensitive colorimetric and fluorescent sensor for anionic surfactants in water | |
| Lei et al. | Preparation of gold nanoparticles using pyridine-formaldehyde as a reducing agent and its application in high sensitivity colorimetric detection of Pb 2+ | |
| Guan et al. | One-step enrichment and chemiluminescence detection of sodium dodecyl benzene sulfonate in river water using Mg–Al–carbonate layered double hydroxides | |
| CN111307963A (en) | Chromatographic detection method of nonionic surfactant | |
| Maldonado et al. | A multiparameter colloidal titrations for the determination of cationic polyelectrolytes | |
| CN105445208A (en) | Determination method for trace thallium in high-salt waste water | |
| CN108508110A (en) | The assay method of a variety of disperse dyes in a kind of edible packing material | |
| CN111413432A (en) | Method for detecting trace PFOA (perfluorooctanoic acid) in fluorine-containing polymer emulsion product | |
| CN104730013B (en) | A kind of method of graphite-pipe effective life in judgement graphite furnace atomic absorption spectrophotometer | |
| Khayatian et al. | Ion pair dispersive liquid-liquid microextraction for the determination of trace amounts of copper (II) in soil, multivitamin tablet, tea and water samples using flame atomic absorption spectrometry | |
| CN108918706B (en) | Method for detecting 2, 4-dichloro-1- (dichloromethyl) benzene in textile | |
| CN113984726B (en) | Method for detecting mercury ions by amino phenylboronic acid functionalized magnetic beads/glyoxal modified DNA | |
| CN104034822B (en) | A kind of method measuring glyoxal content in Food Contact paper products | |
| CN104297378A (en) | Sorbose fermentation process detection and fermentation end judgment method |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180508 |