AU2021105035A4 - High performance liquid chromatography tandem mass spectrometry method for determining quaternary ammonium salt in food packaging paper on the basis of dispersive solid phase extraction - Google Patents
High performance liquid chromatography tandem mass spectrometry method for determining quaternary ammonium salt in food packaging paper on the basis of dispersive solid phase extraction Download PDFInfo
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- 235000013305 food Nutrition 0.000 title claims abstract description 40
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 40
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 26
- 238000004885 tandem mass spectrometry Methods 0.000 title claims abstract description 19
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 14
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229960000228 cetalkonium chloride Drugs 0.000 claims abstract description 12
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims abstract description 11
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000006228 supernatant Substances 0.000 claims abstract description 11
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims abstract description 9
- 239000012629 purifying agent Substances 0.000 claims abstract description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 239000013076 target substance Substances 0.000 claims abstract description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 5
- -1 tetramethyl ammonium chloride benzyldodecyl dimethyl ammonium bromide Chemical compound 0.000 claims abstract description 5
- 238000003260 vortexing Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 44
- 239000000523 sample Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 10
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 10
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000004949 mass spectrometry Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 5
- 239000012488 sample solution Substances 0.000 claims description 5
- 239000010414 supernatant solution Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000004451 qualitative analysis Methods 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 claims 1
- 229940078672 didecyldimethylammonium Drugs 0.000 claims 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 4
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000013256 coordination polymer Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- 239000000022 bacteriostatic agent Substances 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- WNBGYVXHFTYOBY-UHFFFAOYSA-N benzyl-dimethyl-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WNBGYVXHFTYOBY-UHFFFAOYSA-N 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000004393 visual impairment Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0078—Testing material properties on manufactured objects
- G01N33/0081—Containers; Packages; Bottles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/34—Paper
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The disclosure provides a high performance liquid chromatography tandem mass
spectrometry method for determining a quaternary ammonium salt in food packaging paper on
the basis of dispersive solid-phase extraction. This method integrates purification and
extraction. First, an appropriate amount of an extractant is added to the sample, combined with
ultrasound-assisted technology, to quickly extract the target substance in the sample. Then the
sample is centrifuged and layered. A part of a supernatant liquid is collected and a purifying
agent PSA is added thereto. The purification process is accelerated by vortexing, and the
resulting product is centrifuged. The supernatant is filtered through an organic membrane. The
resulting solution is injected into a high performance liquid chromatography tandem mass
spectrometer for analysis. The dispersive solid-phase extraction technology is used, which
simplifies the pretreatment process, and saves the treatment time, and thus the method is
suitable for pretreatment of most of the food contact packaging paper on the market, has the
advantage of batch operation, could detect six kinds of quaternary ammonium salts of different
structure types at a time, which is simple, convenient and efficient.
1/17
7B7
tetramethyl ammonium chloride benzyldodecyl dimethyl ammonium
bromide
CI
dodecyl trimethyl chloride ammonium chloride
N*
ci-r
tetradecyl dimethyl benzyl ammonium chloride
N'
CI
benzyl dimethyl hexadecyl ammonium chloride
CP
didecyl dimethyl ammonium chloride
FIG.1
Description
1/17
7B7 ammonium bromide tetramethyl ammonium chloride benzyldodecyl dimethyl
CI dodecyl trimethyl chloride ammonium chloride
tetradecyl dimethyl benzyl ammonium chloride ci-r N'
CI benzyl dimethyl hexadecyl ammonium chloride
CP didecyl dimethyl ammonium chloride
FIG.1
[01] The disclosure relates to a method for analyzing quaternary ammonium salts in food packaging paper, in particular to a high performance liquid chromatography tandem mass
spectrometry method for determining quaternary ammonium salt bacteriostatic agents in
food antibacterial packaging paper on the basis of a dispersive solid phase extraction
technology.
[02] Food safety issues have been a major issue related to people's livelihood in recent
years. People's focus mainly lies in on substances that are directly added to foods and
harmful to the human body. However, in fact, packaging materials that directly contact food
are also closely related to our food safety issues. There are currently a large number of food
packaging materials of different types on the market, and manufacturers often add different
chemical additives during the production process to achieve certain special properties of the
materials. Paper packaging materials have characteristics of good performance and
recyclability, and have now become important packaging materials in the food packaging
industry at home and abroad. The safety of their use also needs our attentions.
[03] Bacteriostatic agent is a kind of chemical agent that could effectively control or kill the
microorganisms in the system. According to its nature or structure, it could be classified into
active chlorides, inorganic compounds, organic acid salts, quaternary ammonium salts,
phenol, organic sulfur compounds, organic metals and other categories. Among them,
quaternary ammonium salt fungicides have good applicability and high sterilization ability,
and have been widely used. During the production of paper packaging paper, in order to achieve the purpose of better preservation of perishable foods, manufacturers would use related processes such as spraying, sizing, coating and dipping to add reagents with antibacterial properties to the sample paper, thereby endowing the paper with certain antibacterial properties, and then the antibacterial paper packaging materials are prepared. In addition, quaternary ammonium salt preservatives are also used in the process of wood preservation, and this part of the quaternary ammonium salt would also enter our food packaging paper, creating a potential risk of food contamination. As studies have shown, quaternary ammoniums are highly toxic to aquatic organisms and could cause human asthma, skin allergic reactions, vision loss, and other diseases. The European Food Safety Agency stipulates that the upper limit of quaternary ammonium salt residue in food is 0.1 mg/ kg. In view of the above situation, it is of great significance to provide a fast and effective detection method for accurate detection and risk assessment of quaternary ammonium salts in food packaging materials.
[04] At present, the detection methods for quaternary ammonium salt bacteriostatic agents mainly involve ultraviolet-visible spectrophotometry, capillary electrophoresis, liquid
chromatography and liquid chromatography-mass spectrometry/mass spectrometry, etc. The
involved research fields are mainly environmental water samples, soils and sediments, etc.;
however, there is little research on food packaging materials. In modem analytical work,
sample pretreatment plays a vital role, especially for complex matrices. Scientific
pretreatment methods could not only reduce the matrix effect and increase the enrichment
factor, even could greatly simplify the analysis process, which directly affects the advantages
and disadvantages of the analysis method. The dispersive solid phase extraction is easy to
operate and could effectively remove interference factors, thereby being a very effective
pretreatment technology. Mass spectrometry has a high selectivity, fast analysis speed, and
high sensitivity. In combination with high performance liquid chromatography, quaternary
ammonium salts could be detected and determined more accurately and quickly. Therefore,
in combination with the current effective pre-processing technology and cutting-edge mass
spectrometry technology, the present disclosure proposes a method for determining
quaternary ammonium salt bacteriostatic agents in food packaging paper. The method integrates extraction and purification, and could detect 6 kinds of quaternary ammonium salts of different structure types at one time, which is featured by simple and efficient.
[05] To overcome deficiencies in the prior art, the present disclosure aims to provide a high performance liquid chromatography tandem mass spectrometry method for determining a quaternary ammonium salt bacteriostatic agent in food antibacterial packaging paper on the basis of the dispersive solid phase extraction technology.
[06] This method integrates purification and extraction. First, an appropriate amount of extractant is added to the sample, combined with ultrasound-assisted technology, to quickly extract the target substance in the sample. Then the sample is centrifuged and layered. Apart of a supernatant liquid is collected and a purifying agent primary secondary amine (PSA) is added thereto. The purification process is accelerated by vortexing, and the resulting product is centrifuged; the supernatant is filtered through an organic membrane, and the resulting solution is injected into a high performance liquid chromatography tandem mass spectrometer for analysis.
[07] The pretreatment of the present disclosure requires simple equipment, is simple in operation and needs a short operation time, and thereby is suitable for the pretreatment of most of the packaging paper in contact with foods on the market, and has the advantage of batch operation. The quaternary ammonium salt in the food packaging paper to be determined in the present disclosure is at least one selected from the group consisting of tetramethyl ammonium chloride, benzyldodecyl dimethyl ammonium bromide, dodecyl trimethyl chloride ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, benzyl dimethyl hexadecyl ammonium chloride, and didecyl dimethyl ammonium chloride.
[08] The present disclosure provides the following technical solutions.
[09] The present disclosure provides a high performance liquid chromatography tandem mass spectrometry method for determining a quaternary ammonium salt in food packaging paper on the basis of dispersive solid phase extraction, comprising
[10] (1) pretreatment of a sample
[11] pulverizing dry food packaging paper, adding methanol to the pulverized food
packaging paper, sonicating the resulting mixture, and centrifuging (12000 rpm, 5 minutes),
and collecting a supernatant organic solution; mixing the supernatant organic solution with a
purifying agent PSA (N-propylethylenediamine), vortexing (2 minutes), centrifuging (8000
rpm, 3 minutes), collecting a supernatant solution, and filtering the supernatant solution through an organic membrane (with a pore size of 0.2 m) to obtain a sample solution to be
tested;
[12] (2) test
[13] injecting the sample solution to be tested obtained in step (1) into a high performance liquid chromatography tandem mass spectrometry system for analysis, adopting a mode of
partially injecting, gradient elution, and multi-reaction monitoring; obtaining a parent ion by
a first-level mass spectrometry scan and selecting two groups of target characteristic ion
pairs by a second-level mass spectrometry scan for qualitative and quantitative analysis, and
finally obtaining a total ion chromatogram and a selected ion chromatogram of the sample;
[14] (3) plotting a standard curve
[15] providing standard substances of tetramethylammonium chloride, benzyldodecyl dimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, tetradecyl dimethyl
benzyl ammonium chloride, benzyl dimethyl hexadecyl ammonium chloride and didecyl
dimethyl ammonium chloride, preparing a mixed standard stock solution by using
methanol-water (in a volume ratio of 1 : 1) as a solvent, diluting the mixed standard stock
solution to a series of concentrations, and coating negative food packaging paper with the
diluted mixed standard stock solution, respectively, after full adsorption for 24 hours
(already air-dried), pretreating the obtained paper sample to which the standard substance is
added according to the pretreatment in step (1), and subjecting the pretreated paper sample to
which the standard substance is added, to the test in step (2) to obtain an extracted ion
chromatogram of high performance liquid chromatography tandem mass spectrometry of the
standard substances, and plotting a standard curve of the peak area of quantitative ion pair in
the extracted ion chromatogram versus the concentration of the quaternary ammonium salt in
the paper sample;
[16] (4) acquisition of qualitative and quantitative results of the quaternary ammonium salt in the sample
[17] qualitatively determining the quaternary ammonium salt in the sample by comparing the qualitative ion pair of the target substance in the sample to be tested and that of the
standard substance;
[18] calculating the content of the quaternary ammonium salt in the sample by substituting the characteristic peak area of the quantitative ion pair of the target substance in the selected
ion chromatogram of high performance liquid chromatography tandem mass spectrometry of
the sample obtained in step (2) into the standard curve obtained in step (3).
[19] In some embodiments, a ratio of the pulverized food packaging paper sample (in g) to methanol (in mL) is 1 : 10.
[20] In some embodiments, a ratio of the purifying agent PSA (in g) to the supernatant organic solution (in mL) is 0.1 : 1.
[21] In some embodiments, the high performance liquid chromatography is performed under conditions of
a chromatography column of a C18 column (2.1 mmx50 mm, 1.7 m);
a gradient elution by using eluents of
30 vol% of A and 70 vol% of B, from minute 0.00 to minute 0.50;
30-10 vol% A and the balance of B, from minute 0.50 to minute 2.00;
10-2 vol% of A and the balance of B, from minute 2.00 to minute 4.00;
2-0 vol% of A and the balance of B, from minute 4.00 to minute 6.50;
0-30 vol% of A and the balance of B, from minute 6.50 to minute 6.60;
30 vol% of A and 70 vol% of B, from minute 6.6 to minute 7,
wherein A represents 5 mmol/L aqueous ammonium acetate solution, and B
represents a solution of 5 mmol/L ammonium acetate in methanol.
[22] In some embodiments, the mass spectrometry is performed under conditions of Perkin
Elmer Qsight series triple quadrupole mass spectrometer equipped with ESI ionization
source; a positive source mode; an ionization voltage of 4000 V; an ion source temperature
of 350 °C; a flow rate of backflush drying gas of 100 L/minute; a flow rate of atomizing gas of 180 L/minute; all gases used being high-purity nitrogen; an inlet voltage, collision energy, and characteristic ion pairs being shown in Table 1, where "a" represents the quantitative ion pair.
[23] In some embodiments, the parent ion, qualitative ion pair and quantitative ion pair of the quaternary ammonium salt (parent ion/ qualitative ion/quantitative ion a) are as follows: tetramethylammonium chloride 74/42.1/58.la; benzyldodecyl dimethyl ammonium bromide 304/91.1/212.5a; dodecyl trimethyl ammonium chloride 228/57.1/60.2a; tetradecyl dimethyl benzyl ammonium chloride 332.4/240.5/91.la; benzyl dimethyl hexadecyl ammonium chloride 360.5/268.5/91.1a; didecyl dimethyl ammonium chloride 326.5/57.2/186.4.
[24] In some embodiments, the concentration ranges of the standard substances in the paper sample are as follows: 0.1-50 g/kg of tetramethyl ammonium chloride; 0.1-100 g/kg of benzyldodecyl dimethyl ammonium bromide; 0.1-50 g/kg of dodecyl trimethyl ammonium chloride; 0.1-50 g/kg of tetradecyl dimethyl benzyl ammonium chloride; 0.1-100 g/kg of benzyl dimethyl hexadecyl ammonium chloride; 0.1-50 g/kg of didecyl dimethyl ammonium chloride.
[25] In some embodiments, the characteristic peaks of the standard substances in the total ion chromatogram of high performance liquid chromatography tandem mass spectrometry are as follows: tetramethyl ammonium chloride at minute 0.74 ; benzyldodecyl dimethyl ammonium bromide at minute 2.71; dodecyl trimethyl ammonium chloride at minute 2.42; tetradecyl dimethyl benzyl ammonium chloride at minute 3.19; benzyl dimethyl hexadecyl ammonium chloride at minute 3.74; dicdecyl dimethyl ammonium chloride at minute 3.30.
[26] Compared with the prior art, the beneficial effects of the present disclosure are as follows:
[27] 1. The present disclosure provides an effective method for extracting the quaternary ammonium salt bacteriostatic agent from food packaging paper.
[28] 2. In the present disclosure, the dispersive solid phase extraction technology is used, which simplifies the pretreatment process and saves treatment time.
[29] FIG. 1 shows chemical structures of the quaternary ammonium salts in Example 1.
[301 FIG.2 shows the optimization of the type of the extractant in Example 1.
[311 FIG.3 shows the optimization of the volume of the extractant in Example 1.
[32] FIG.4 shows the optimization of the extraction time in Example 1.
[33] FIG.5 shows the optimization of the type of the purifying agent in Example 1.
[34] FIG.6 shows the optimization of the amount of the purifying agent in Example 1.
[351 FIGs.7A to 7L show extracted ion chromatograms of the quaternary ammonium salts in the food packaging paper to which the standard substance is added in Example 1, and the
concentration after adding standard substance is 10 pg/kg.
[36] The present disclosure will be further described with specific examples below, but the
scope of the present disclosure is not limited therein.
[371 The chemical information of the quaternary ammonium salts involved in the present
disclosure is as follows:
English name Abbreviation Molecular Formula CAS number
letramethyl ammonium chloride TAC C 4HI 2 ClN 75-57-0 benzyldodecyl dimchyl ammonium bromide BDAB C21Hl 3 hBrN 7281-04-1 dodecyl trimethyl ammonium chloride DTAC Cu13 IluClN 112-00-5 actradcyl dimethyl benzyl ammonium chloride TDBAC C2 3H4 CIN 139-08-2 benzyl dimethyl hexadecyl ammonium chloride BDIAC C 2 5 IH4ClN 122-18.9 didecyl dinetiyl ammonium chloride DDAC C2 IlaCN 7173-51-5
[381 Example 1: Test of the quaternary ammonium salts in food bacteriostatic packaging
paper
[39] (1) pretreatment of a sample
[40] The dry food packaging paper was cut into pieces with a size of smaller than 0.5
cmx0.5 cm, and 1.0 g of bacteriostatic paper sample was accurately weighed and placed into a 50 mL erlenmeyer flask. 10 mL of methanol was added with a pipette. The resulting mixture was sonicated for 3 minutes, and then centrifuged at 12000 r/min for 5 minutes. 1 mL of the supernatant organic solution was collected and transferred to a centrifuge tube pre-loaded with 100 mg of primary secondary amine (PSA) purifying agent. The resulting mixture was vortexed for 2 minutes, and centrifuged at 8000 r/min for 3 minutes. The supernatant solution was collected and filtered through an organic membrane, to obtain a sample solution for test.
[41] (2) test The high performance liquid chromatography was performed under conditions of a chromatography column of a C18 column (2.1 mmx50 mm, 1.7 m), a gradient elution by using eluents of 30 vol% ofAand 70 vol% of B, from minute 0.00 to minute 0.50; 30-10 vol% of A and the balance of B, from minute 0.50 to minute 2.00; 10-2 vol% of A and the balance of B, from minute 2.00 to minute 4.00; 2-0 vol% of A and the balance of B, from minute 4.00 to minute 6.50; 0-30 vol% of A and the balance of B, from minute 6.50 to minute 6.60; 30 vol% of A and 70 vol% of B, from minute 6.6 to minute 7, wherein A represents 5 mmol/L aqueous ammonium acetate solution, and B represents a solution of 5 mmol/L ammonium acetate in methanol.
[42] The mass spectrometry was performed under conditions of Perkin Elmer Qsight series triple quadrupole mass spectrometer equipped with ESI ionization source; a positive source mode; an ionization voltage of 4000 V; an ion source temperature of 350 °C; a flow rate of backflush drying gas of 100 [L/min; a flow rate of atomizing gas of 180 [L/min; an inlet voltage, collision energy, and characteristic ion pairs being shown in Table 1 (where "a" represents the quantitative ion pair); all gases used being high-purity nitrogen.
[43] Table 1 Inlet voltage, collision energy, characteristic ion pairs of the quaternary ammonium salts Compound Inlet voltage (V) Collision energy (V) Residence time (ms) Characteristic ion pair (m/z) tetramethyl amm-oninun 25 -54 74>42.1 chloride 25 -29 100 74>58.13 benzyldodecl dinethyl 8 -21 304>91.1 aoride 10 -22 304>212.53 dodecyl trimethyl amnionium 11 -23 228>57.1 chloride 15 -28 228>60.2' tetradecyl dimethyl benzyl 5 -57 332.4>240.5 ammonum chloride 32 -31 332.4>91.1
' benzyl dinethyl hexadecyl 29 -33 360.5>268.5 ammoium chloride 27 -75 100 3605>91.1 didecyl dimethyl anunonium -28 16 326.5>57.2 chloride -30 14 326.5>186.43
[44] (3) plotting a standard curve
[45] The standard substances of tetramethyl ammonium chloride, benzyldodecyl dimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, benzyl dimethyl hexadecyl ammonium chloride, and didecyl dimethyl ammonium chloride were provided, and a mixed standard stock solution was prepared by using methanol-water (in a volume ratio of 1 : 1) as a solvent. The mixed standard stock solution was diluted to a series of concentrations, and negative food packaging paper was added therein. After adsorption for 24 hours, the obtained paper sample to which the standard substance is added was pretreated according to the pretreatment in step (1), and then the pretreated paper sample to which the standard substance is added was subjected to the test in step (2) to obtain an extracted ion chromatogram of high performance liquid chromatography tandem mass spectrometry of the standard substances. A standard curve of the peak area of a quantitative ion pair in the extracted ion chromatogram versus the concentration of the quaternary ammonium salt in the paper sample was plotted. The specific results are shown in Table 2.
[46] Table 2 Linear equation, linear range, linear correlation coefficient, detection limit, quantification limit and other indicators of the quaternary ammonium salts
Compound Linear equation Linear range Linear correlation coefficient Detection limit Quantification limit (pg-L~') (R') (pg-kg') (pg-kg~') tetramethyl ammonium y=I33562x-6515 0.1-50 0.9989 0.04 0.1 chloride benzyldodecyl dimethyl y=94051x+32566 0.1-100 0.9991 0.03 0.08 ammonium chloride
dodecyl trimethyl anmonium chloride y=63220x+41786 0.1-50 0.9993 0.03 0.1 tetradecyl dimethyl benzyl ammonium y=150536x+30581 0.1-50 0.9997 0.04 0.1 chloride benzyl dimethyl hexadecylammonium y=660631x+21206 0.1-100 0.9999 0.02 0.08 chloride
didecyl dimethyl 3 3 26 7 2 9 66 ammonium chloride y=1 x+ 0 0.1-50 0.9987 0.03 0.1
[47] (4) Method evaluation
[48] Under conditions of the above method, the spiked recovery, inter-day precision, and intra-day precision were investigated to evaluate the accuracy and reproducibility of the method. The results show that the recovery rate of each target substance is in the range of 79-113%, the intra-day precision is less than 8.9%, and the inter-day precision is less than 8.8%, showing good accuracy and reproducibility of the method. The specific results are shown in Table 3.
[49] Table 3 Methodological indicators of the quaternary ammonium salts
Compound Concentration after adding Recovery Inter-day precision Intra-day precision standard substance (pg.kg-) (%,n=6) (%,n=6) (%,n=5) tetranethyl amnmonimun 1,5,10 90,103,105 4.5, 1.9, 3.6 7.1 chloride benzyldodecyl diinethyl 1,5,10 87,79,95 2.6, 7.7, 8.9 8.8 ammoniui chloride dodecyl trimethyl 1,5,10 98,104,113 2.5, 3.4,4.9 3.9 aimmonum chloride tetradecyl dimethyl 1,5, 10 95,97,100 7.8, 6.6, 3.9 4.1 benzyl annoniun chloride benzyl dimethyl hexadecyl ammonium l1,5, 10 88,89,95 2.0, 1.8,4.3 2.7 chloride didecyl dimethyl arninonlium chloride 1,5, 10 97,101,110 3.3,4.6, 6.9 3.7
Claims (5)
1. A high performance liquid chromatography tandem mass spectrometry method for
determining a quaternary ammonium salt in food packaging paper on the basis of dispersive
solid phase extraction, comprising
(1) pretreatment of a sample
pulverizing dry food packaging paper, adding methanol to the pulverized food
packaging paper, sonicating the resulting mixture, centrifuging, and collecting a supernatant
organic solution; mixing the supernatant organic solution with a purifying agent primary
secondary amine, vortexing, centrifuging, collecting a supernatant solution, and filtering the
supernatant solution through an organic membrane, to obtain a sample solution to be tested;
(2) test
injecting the sample solution to be tested obtained in step (1) into the high performance
liquid chromatography tandem mass spectrometry system for analysis, adopting a mode of
partially injecting, gradient elution, and multi-reaction monitoring; obtaining a parent ion by
a first-level mass spectrometry scan and selecting two groups of target characteristic ion
pairs by a second-level mass spectrometry scan for qualitative and quantitative analysis, and
finally obtaining a total ion chromatogram and a selected ion chromatogram of the sample;
(3) plotting a standard curve
providing standard substances of tetramethyl ammonium chloride, benzyldodecyl
dimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, tetradecyl dimethyl
benzyl ammonium chloride, benzyl dimethyl hexadecyl ammonium chloride, and didecyl
dimethyl ammonium chloride, preparing a mixed standard stock solution by using
methanol-water as a solvent, diluting the mixed standard stock solution to a series of
concentrations, and coating negative food packaging paper with the diluted mixed standard
stock solution, respectively, after full adsorption for 24 hours, pretreating the obtained paper
sample to which the standard substance is added according to the pretreatment in step (1),
and subjecting the pretreated paper sample to which the standard substance is added to the
test in step (2) to obtain an extracted ion chromatogram of high performance liquid chromatography tandem mass spectrometry of the standard substances, and plotting a standard curve of the peak area of a quantitative ion pair in the extracted ion chromatogram versus the concentration of the quaternary ammonium salt in the paper sample;
(4) acquisition of qualitative and quantitative results of the quaternary ammonium salt
in the sample
qualitatively determining the quaternary ammonium salt in the sample by comparing a
qualitative ion pair of the target substance in the sample to be tested and that of the standard
substance;
calculating the content of the quaternary ammonium salt in the sample by substituting
the characteristic peak area of the quantitative ion pair of the target substance in the selected
ion chromatogram of high performance liquid chromatography tandem mass spectrometry of
the sample obtained in step (2) into the standard curve obtained in step (3).
2. The high performance liquid chromatography tandem mass spectrometry method for
determining a quaternary ammonium salt in food packaging paper on the basis of dispersive
solid phase extraction as claimed in claim 1, wherein in step (1), a ratio of the pulverized
food packaging paper sample to methanol is 1 : 10.
3. The high performance liquid chromatography tandem mass spectrometry method for
determining a quaternary ammonium salt in food packaging paper on the basis of dispersive
solid phase extraction as claimed in claim 1, wherein in step (1), a ratio of the purifying
agent PSA to the supernatant organic solution is 0.1 : 1.
4. The high performance liquid chromatography tandem mass spectrometry method for
determining a quaternary ammonium salt in food packaging paper on the basis of dispersive
solid phase extraction as claimed in claim 1, wherein in step (2), the high performance liquid
chromatography is performed under conditions of
a chromatography column of a C18 column; and
a gradient elution by using eluents of
30 vol% of A and 70 vol% of B, from minute 0.00 to minute 0.50 ; 30-10 vol% of A and the balance of B, from minute 0.50 to minute 2.00; 10-2 vol% of A and the balance of B, from minute 2.00 to minute 4.00; 2-0 vol% of A and the balance of B, from minute 4.00 to minute 6.50; 0-30 vol% of A and the balance of B, from minute 6.50 to minute 6.60; 30 vol% of A and 70 vol% of B, from minute 6.6 to minute 7, wherein A represents 5 mmol/L aqueous ammonium acetate solution, and B represents a solution of 5 mmol/L ammonium acetate in methanol; and wherein the mass spectrometry is performed under conditions of Perkin Elmer Qsight series triple quadrupole mass spectrometer equipped with ESI ionization source; a positive source mode; an ionization voltage of 4000 V; an ion source
temperature of 350 °C; a flow rate of backflush drying gas of 100 tL/minute; a flow rate of atomizing gas of 180 p/minute; all gases used being high-purity nitrogen; an inlet voltage, collision energy, and characteristic ion pairs being shown in the table below, where "a" represents the quantitative ion pair, Compound Inlet voltage (V) Collision energy (V) Residence time (ms) Characteristic ion pair (m/z) tetranethyl ammonium 25 -54 100 74>42.1 chloride 25 -29 74>58.13 benzyldodecyl diniethyl 8 -21 304>91.1 ammomum enloride 10 -22 too 304>212.53 dodecyl tritmethyl ammoniuim 11 -23 228>57.1 chloride 15 -28 228>60.2' tetradecyl dirmethyl benzyl 5 -57 332.4>240.5 ammornum chloride 32 -31 332.4>91.1 '
benzyl dirnethyl hexadecyl 29 -33 360.5>268.5 ammouin chloride 27 -75 100 360.5>91.1 didecyl dimethyl ammonium -28 16 326.5>57.2 chloride -30 14 100 326.5>186.4'
5. The high performance liquid chromatography tandem mass spectrometry method for determining a quaternary ammonium salt in food packaging paper on the basis of dispersive solid phase extraction as claimed in claim 1, wherein in step (3), the concentration ranges of the standard substances in the paper sample are as follows: 0.1-50 pg/kg of tetramethyl ammonium chloride; 0.1-100 pg/kg of benzyldodecyl dimethyl ammonium bromide; 0.1-50 jtg/kg of dodecyl trimethyl ammonium chloride;
0.1-50 g/kg of tetradecyl dimethyl benzyl ammonium chloride; 0.1-100 g/kg of benzyl
dimethyl hexadecyl ammonium chloride; 0.1-50 g/kg of didecyl dimethyl ammonium
chloride,
and wherein in step (3), the characteristic peaks of the standard substances in the total
ion chromatogram of high performance liquid chromatography tandem mass spectrometry
are as follows:
tetramethyl ammonium chloride at minute 0.74; benzyldodecyl dimethyl
ammonium bromide at minute 2.71; dodecyl trimethyl ammonium chloride at minute 2.42;
tetradecyl dimethyl benzyl ammonium chloride at minute 3.19; benzyl dimethyl hexadecyl
ammonium chloride at minute 3.74; didecyl dimethyl ammonium chloride at minute 3.30.
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| CN115184497A (en) * | 2022-07-18 | 2022-10-14 | 浙江省农业科学院 | Method for measuring content of 2, 4-epibrassinolide in dendrobium officinale |
| CN117990839A (en) * | 2024-02-07 | 2024-05-07 | 华南农业大学 | Method for simultaneously measuring dodecyl dimethyl benzyl ammonium chloride and hydroxylation metabolite thereof in plants |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115184497A (en) * | 2022-07-18 | 2022-10-14 | 浙江省农业科学院 | Method for measuring content of 2, 4-epibrassinolide in dendrobium officinale |
| CN117990839A (en) * | 2024-02-07 | 2024-05-07 | 华南农业大学 | Method for simultaneously measuring dodecyl dimethyl benzyl ammonium chloride and hydroxylation metabolite thereof in plants |
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