CN119000960B - A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances - Google Patents
A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances Download PDFInfo
- Publication number
- CN119000960B CN119000960B CN202411455062.1A CN202411455062A CN119000960B CN 119000960 B CN119000960 B CN 119000960B CN 202411455062 A CN202411455062 A CN 202411455062A CN 119000960 B CN119000960 B CN 119000960B
- Authority
- CN
- China
- Prior art keywords
- orthodontic
- bisphenol
- sample
- cof
- perfluorinated compounds
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 32
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 title description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000001514 detection method Methods 0.000 claims abstract description 55
- 239000000523 sample Substances 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 47
- 239000012488 sample solution Substances 0.000 claims abstract description 29
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims abstract description 24
- 238000004458 analytical method Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000120 Artificial Saliva Substances 0.000 claims abstract description 15
- 239000003480 eluent Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000013310 covalent-organic framework Substances 0.000 claims description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- LVDGGZAZAYHXEY-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-pentacosafluorotridecanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVDGGZAZAYHXEY-UHFFFAOYSA-N 0.000 claims description 9
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 9
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 9
- PXUULQAPEKKVAH-UHFFFAOYSA-N perfluorohexanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PXUULQAPEKKVAH-UHFFFAOYSA-N 0.000 claims description 9
- CXZGQIAOTKWCDB-UHFFFAOYSA-N perfluoropentanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CXZGQIAOTKWCDB-UHFFFAOYSA-N 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 230000037427 ion transport Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 abstract description 18
- 239000007790 solid phase Substances 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000007781 pre-processing Methods 0.000 abstract 1
- -1 photoinitiators Substances 0.000 description 18
- 210000000214 mouth Anatomy 0.000 description 12
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 10
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IUUBODMNDCMSEU-UHFFFAOYSA-N 3-[6-amino-3-(3-hydroxypropyl)-2,4,5,9-tetrahydropurin-2-yl]propan-1-ol Chemical compound NC1=NC(CCCO)N(CCCO)C2N=CNC12 IUUBODMNDCMSEU-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 206010029350 Neurotoxicity Diseases 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 206010074268 Reproductive toxicity Diseases 0.000 description 2
- 206010044221 Toxic encephalopathy Diseases 0.000 description 2
- XEKVBIXIBCYLRT-RSAXXLAASA-N [4-[(2e)-2-[3-[(2s)-2-amino-2-carboxyethyl]-6-oxocyclohexa-2,4-dien-1-ylidene]hydrazinyl]phenyl]-trimethylazanium;chloride Chemical compound [Cl-].C1=CC([N+](C)(C)C)=CC=C1N\N=C/1C(=O)C=CC(C[C@H](N)C(O)=O)=C\1 XEKVBIXIBCYLRT-RSAXXLAASA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 231100000049 endocrine disruptor Toxicity 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 231100000025 genetic toxicology Toxicity 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 230000007135 neurotoxicity Effects 0.000 description 2
- 231100000228 neurotoxicity Toxicity 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000007696 reproductive toxicity Effects 0.000 description 2
- 231100000372 reproductive toxicity Toxicity 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 108020005497 Nuclear hormone receptor Proteins 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QPBQEXGQGCAOKS-UHFFFAOYSA-N cyclohexa-2,4-diene-1,1-diol Chemical compound OC1(O)CC=CC=C1 QPBQEXGQGCAOKS-UHFFFAOYSA-N 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000007674 genetic toxicity Effects 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 208000026278 immune system disease Diseases 0.000 description 1
- 230000007688 immunotoxicity Effects 0.000 description 1
- 231100000386 immunotoxicity Toxicity 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 102000006255 nuclear receptors Human genes 0.000 description 1
- 108020004017 nuclear receptors Proteins 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000581 reactive spray deposition Methods 0.000 description 1
- 208000017443 reproductive system disease Diseases 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000002137 ultrasound extraction Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- G01N30/08—Preparation using an enricher
-
- 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
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
-
- 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
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a detection method of bisphenol and perfluorinated compounds in an orthodontic transparent appliance, belonging to the technical field of detection. The method comprises the following steps of S1, adding an orthodontic transparent appliance sample into artificial saliva, incubating for 2 weeks in a rotary shaking table at 37 ℃ plus or minus 1 ℃, filtering to obtain a sample solution, S2, preprocessing the sample, adding a magnetic composite material Fe 3O4 @OH-COF into the sample solution, carrying out vortex processing, separating the magnetic composite material Fe 3O4 @OH-COF from the solution, eluting the separated magnetic composite material Fe 3O4 @OH-COF by using acetonitrile solution, separating to obtain eluent, and S3, detecting and analyzing the eluent by using a high performance liquid chromatography-tandem mass spectrometry detection method. The invention establishes a magnetic solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) method, can simultaneously detect the amounts of bisphenol compounds and perfluorinated compounds released by the orthodontic transparent appliance, and has high sensitivity, low detection limit and short analysis time.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance.
Background
Bisphenol compounds (Bisphenols, BPs) are important organic chemical raw materials, and are commonly used as modifiers, stabilizers, photoinitiators, rubber antioxidants and plasticizers for high molecular materials, reactive flame retardants for epoxy resins, polycarbonates and phenolic resins in printed circuit boards, and the like, because the heat resistance, moisture resistance and insulation properties of the materials can be remarkably improved. In recent years, there has been increasing concern about the safety of BPs, which are typical endocrine disruptors (Endocrine Disruptors, eds), which bind to a variety of nuclear receptors in the human body and interfere with the endocrine system of animals and humans even at low concentration levels. With the continuous development of scientific research, endocrine disrupting effects, cytotoxicity, reproductive toxicity, neurotoxicity, genotoxicity and other toxicological effects of BPs are continuously confirmed, and are related to the occurrence and development of diabetes, heart disease, obesity, immune system diseases and reproductive system diseases.
The perfluoroalkyl compound (Perfluoroalkyl and polyfluoroalkyl substances, PFASs), also called perfluoro compound for short, is an artificially synthesized organic compound, and is widely applied to consumer products such as non-stick cookers, dirt-resistant textiles, food packaging materials and the like due to the advantages of high surface tension, excellent chemical and thermal stability and the like. However, these consumer products will constantly release PFASs into the environment during production and use. A large number of researches show that PFASs has various biotoxicity such as neurotoxicity, immunotoxicity, hepatotoxicity, reproductive toxicity, genetic toxicity and the like. At present PFASs has been detected in various environmental media and animals and plants.
The orthodontic transparent appliance is an instrument which is indispensable in orthodontic treatment, a user often needs to wear the orthodontic appliance in the oral cavity for 24 hours, the orthodontic treatment period is long, and in clinic, the orthodontic transparent appliance needs to be worn in the oral cavity of the user for 2 weeks, and then the orthodontic transparent appliance is replaced with a new orthodontic transparent appliance. The material base of the orthodontic appliances are polymers such as Polyethylene (PE), polyethylene terephthalate (PET), polyethylene terephthalate (PETG), polyurethane (PU) and polypropylene (PP). These polymers contain various additives to improve properties, stability, elasticity, etc. Bisphenol compounds (BPs) and perfluoro compounds (PFASs) are the largest content of these additives for hardening plastics and increasing their transparency.
The two types of additives in the orthodontic transparent appliance are easy to release into the oral cavity of a human body in the process of clinically wearing the orthodontic transparent appliance for 2 weeks, and when a certain concentration is accumulated in the human body, the two types of additives are easy to damage the human body, and due to the harm and the nondegradability of the two types of pollutants, the content measurement requirements on different BPs and different PFASs in the orthodontic transparent appliance are more and more urgent. In particular, when the patient wears the orthodontic appliance, it is necessary to know how much of the BPs and PFASs are released into the mouth of the person.
Because bisphenol compounds and perfluorinated compounds often exist in trace amounts in samples (orthodontic transparent appliances), accurate quantitative determination cannot be realized by a precise analytical instrument, the substrates of the samples (orthodontic transparent appliances) are complex, the substrate interference exists, the detection is difficult, and the pretreatment, enrichment and purification of the samples are required to be carried out, so that the detection can be carried out.
The existing method generally adopts liquid-liquid extraction, freeze drying and other modes to perform sample pretreatment aiming at bisphenol compounds or perfluorinated compounds, so that the operation is complicated, the time is long, and the rapid analysis requirement cannot be met. In addition, because bisphenol compounds (BPs) and perfluorinated compounds (PFASs) have large physical and chemical property differences, simultaneous extraction and enrichment cannot be realized, and the two pollutants are required to be extracted respectively, so that the workload and the analysis cost are increased. And simultaneously detect these two types of components, also put forward the challenge to optimizing instrument detection parameter. For rapid and accurate detection of BPs and PFASs in orthodontic appliances, simultaneous extraction and elution strategies are an effective approach. The strategy realizes simultaneous extraction of the two pollutants in the sample through one sample treatment process, so that the steps of sample pretreatment can be simplified, the analysis efficiency can be improved, the using amount of reagents can be reduced, and the analysis cost can be reduced.
At present, the detection of bisphenol compounds or perfluorinated compounds is mostly concentrated in surface water, sediment, sewage water and the like, but the research of orthodontic transparent appliance samples is very few mainly because the matrix of the orthodontic transparent appliance is complex, the interference is serious, the difficulty of analysis pretreatment is far greater than the detection of bisphenol compounds or perfluorinated compounds in water, and the prior art only aims at one type of components, and how to efficiently extract bisphenol compounds or perfluorinated compounds from the orthodontic transparent appliance samples becomes an analysis bottleneck of trace pollutants.
In the common extraction method of bisphenol compounds or perfluorinated compounds of the transparent appliance, a rapid solvent extraction method or an ultrasonic extraction method is adopted independently, so that the method has the advantages of short analysis time, small use amount of toxic solvents, high extraction efficiency and the like, but the background of an extract matrix is complex due to wide selectivity, so that the subsequent enrichment and purification difficulty is greatly increased. In the enrichment purification method, the solid phase extraction technology (SPE) is the most mature in development and wide in application, the operation is simple, the repeatability is good, the automation is easy to realize, and the like, but for an orthodontic transparent appliance sample with a complex matrix, the background interference is difficult to reduce to the greatest extent only through one-step purification, and the separation time is longer.
Magnetic solid-phase extraction (MSPE) combines the advantages of dispersion solid-phase extraction and Magnetic separation, and the adsorbent is separated from the solution by an external Magnetic field, so that complicated centrifugation steps are avoided, and the pretreatment time is shortened. At present, the adsorbent mainly used for enriching bisphenol compounds or perfluorinated compounds comprises polystyrene-divinylbenzene filler and silica gel, but the adsorbent has the defects of poor selectivity, low adsorption capacity and the like. The extraction efficiency of these adsorbents is limited when faced with complex substrates. Therefore, in order to extract bisphenol compounds and perfluorinated compounds in orthodontic appliances and reduce interference of matrix, it is important to develop a novel adsorbent with high selectivity and high adsorption capacity. The covalent organic frameworks (Covalent organicframeworks, COFs) have larger application potential in the fields of sample pretreatment and chromatographic separation due to the characteristics of large specific surface area, adjustable aperture, easiness in functionalization and the like.
In recent years, the instrument detection technology has been greatly improved, such as gas chromatography-mass spectrometry (GC/MS), gas chromatography-tandem mass spectrometry (GC-MS/MS), liquid chromatography-mass spectrometry (LC/MS), liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the like, and has higher sensitivity and accuracy, and quantitative determination is mainly performed by an external standard method. At present, the method has been widely applied to trace analysis of various complex matrixes such as foods, biological samples, inorganic samples, environment and the like. Therefore, establishing an analysis method for simultaneously detecting trace bisphenol compounds and perfluorinated compounds in an orthodontic transparent appliance with high recovery rate, good reproducibility, high accuracy and high precision becomes a key of research.
Disclosure of Invention
Based on the above, the invention aims to provide a method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance, which can simultaneously and qualitatively detect bisphenol compounds and perfluorinated compounds in the orthodontic transparent appliance by combining a specific sample pretreatment technology by using a high performance liquid chromatography-tandem mass spectrometry detection method, and determine the amount of released bisphenol compounds (BPs) and perfluorinated compounds (PFASs) in the orthodontic transparent appliance into the oral cavity of a human body after a user wears the orthodontic transparent appliance for 2 weeks.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
a method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance comprises the following steps:
S1, sample preparation:
adding an orthodontic transparent appliance sample into artificial saliva, incubating for 2 weeks in a rotary shaking table at 37 ℃ plus or minus 1 ℃, and filtering to obtain a sample solution;
s2, sample pretreatment:
adding a magnetic composite material Fe 3O4 @OH-COF into a sample solution, and carrying out vortex treatment; separating the magnetic composite material Fe 3O4 @OH-COF from the solution, eluting the separated magnetic composite material Fe 3O4 @OH-COF by using acetonitrile solution, and separating to obtain eluent;
s3, detection and analysis:
and detecting and analyzing the eluent by adopting a high performance liquid chromatography-tandem mass spectrometry detection method.
According to the detection method of the bisphenol and the perfluorinated compounds in the orthodontic transparent appliance, in the step S1, the orthodontic transparent appliance sample is placed with artificial saliva and incubated for 2 weeks in an environment of 37 ℃ plus or minus 1 ℃, so that the bisphenol compounds and the perfluorinated compounds in the orthodontic transparent appliance sample are released into a sample solution, the environment that a human body wears the orthodontic transparent appliance in an oral cavity is simulated through the step S1, and the bisphenol compounds and the perfluorinated compounds in the orthodontic transparent appliance sample are released into the oral cavity of the human body. Then, in the step S2, a magnetic composite material Fe 3O4 @OH-COF is used as a magnetic solid phase extraction adsorbent, bisphenol compounds and perfluorinated compounds in a sample solution are enriched efficiently, wherein the magnetic composite material Fe 3O4 @OH-COF is provided with triazine rings and OH, the acting force between the triazine rings in the magnetic composite material Fe 3O4 @OH-COF and the perfluorinated compounds is hydrophobic adsorption, and the acting force between the OH in the magnetic composite material Fe 3O4 @OH-COF and the bisphenol compounds is hydrogen bonding, so that the magnetic composite material Fe 3O4 @OH-COF can adsorb the bisphenol compounds and the perfluorinated compounds simultaneously, and then desorption treatment is carried out to elute the bisphenol compounds and the perfluorinated compounds adsorbed on the magnetic composite material Fe 3O4 @OH-COF, so that the bisphenol compounds and the perfluorinated compounds are transferred into an eluent. Finally, in step S3, the eluent is detected and analyzed by using a high performance liquid chromatography-tandem mass spectrometry detection method, and simultaneously, the bisphenol compound and the perfluorinated compound are detected qualitatively, and the contents of the bisphenol compound and the perfluorinated compound in the sample solution are determined, so that the amounts of the bisphenol compound and the perfluorinated compound released into the artificial saliva by the orthodontic transparent appliance sample are further obtained, and the amount released into the oral cavity of a human body after a user clinically wears the orthodontic transparent appliance for 2 weeks is simulated.
The invention establishes a method of magnetic solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) by combining a high performance liquid chromatography-tandem mass spectrometry detection method with a specific sample pretreatment technology, can detect bisphenol compounds and perfluorinated compounds existing in trace amounts in an orthodontic transparent appliance at the same time, and the established method has high sensitivity, low detection limit and short analysis time; the detection method of the bisphenol and the perfluorinated compounds in the orthodontic transparent appliance can solve the problems that the bisphenol compounds and the perfluorinated compounds exist in trace amounts in the orthodontic transparent appliance and cannot be detected simultaneously, so that the detection process is complicated and the time is long, and the quantity released to the oral cavity of a human body after a user clinically wears the orthodontic transparent appliance for 2 weeks cannot be judged.
Further, in step S1, the orthodontic appliance sample is preferably added in an amount of 0.1g of the orthodontic appliance sample per 1mL of artificial saliva. The mass-volume ratio of the orthodontic transparent appliance sample to the artificial saliva is set at a ratio of 0.1g/mL to simulate the oral cavity of a human body, so that bisphenol compounds and perfluorinated compounds existing in trace amounts in the orthodontic transparent appliance sample are released into a sample solution to be unsaturated after being incubated for 2 weeks in a rotary shaking table at 37 ℃ plus or minus 1 ℃ so as to improve the accuracy of subsequent detection.
Further, in the step S1, the orthodontic transparent appliance sample is obtained by cutting an orthodontic special punching clamp for the orthodontic transparent appliance into small discs, wherein the diameter of each small disc is preferably 5mm, the thickness of each small disc is preferably 0.75mm, and washing and sterilizing the small discs to obtain the orthodontic transparent appliance sample. The orthodontic transparent appliance is cut into small discs, so that the contact area between the orthodontic transparent appliance sample and the artificial saliva is enlarged, and bisphenol compounds and perfluorinated compounds in the orthodontic transparent appliance sample are conveniently transferred into the artificial saliva to form a sample solution.
Further, in step S2, the preparation method of the magnetic composite material Fe 3O4 @ OH-COF includes the following steps:
Preparing Fe 3O4 magnetic nano particles, namely adding ferric chloride hexahydrate, sodium acetate and ethylene glycol into a hydrothermal reaction kettle, stirring to obtain yellow suspension, and reacting for 6-10 hours at 180-220 ℃;
Dispersing the prepared Fe 3O4 magnetic nano particles in a mixed solution containing ethanol, water and ammonia water, dropwise adding tetraethoxysilane under a stirring state, reacting for 8-12 hours at room temperature, separating precipitate after the reaction is finished, cleaning and drying to obtain Fe 3O4@SiO2, dispersing Fe 3O4@SiO2 in anhydrous toluene by ultrasonic waves, dropwise adding 3-aminopropyl triethoxysilane, carrying out reflux reaction for 4-8 hours at 100-140 ℃, separating precipitate after the reaction is finished, cleaning and drying to obtain amino-modified Fe 3O4 magnetic nano particles, namely Fe 3O4@NH2;
Preparing a magnetic composite material Fe 3O4 @OH-COF, namely adding Fe 3O4@NH2, 2, 5-dihydroxyterephthalaldehyde, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, a1, 4-dioxane/toluene mixed solution and an acetic acid solution into a thick-wall reaction bottle, carrying out ultrasonic treatment for 4-6 minutes, reacting for 60-80 hours at 100-140 ℃, separating a precipitate after the reaction is finished, and washing and drying to obtain the magnetic composite material Fe 3O4 @OH-COF.
In the preparation method of the magnetic composite material Fe 3O4 @OH-COF, in the step of preparing the magnetic composite material Fe 3O4 @OH-COF, fe 3O4@NH2, 2, 5-dihydroxyterephthalaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine are reacted together (Schiff base reaction), so that the prepared magnetic composite material Fe 3O4 @OH-COF has triazine rings and OH, bisphenol compounds and perfluorinated compounds can be simultaneously adsorbed by utilizing the structural characteristics of the magnetic composite material Fe 3O4 @OH-COF, wherein the triazine rings in the magnetic composite material Fe 3O4 @OH-COF can form a hydrophobic adsorption effect with the perfluorinated compounds, and hydrogen bonding effect is formed between the OH and the bisphenol compounds in the magnetic composite material Fe 3O4 @OH-COF, and the magnetic composite material Fe 3O4 @OH-COF can simultaneously adsorb the bisphenol compounds and the perfluorinated compounds, and can simultaneously and efficiently enrich the bisphenol compounds and the perfluorinated compounds in the sample solution. The Fe 3O4 magnetic nano particles are introduced into the Fe 3O4 @OH-COF of the magnetic composite material, so that compared with the traditional dispersion extraction and solid phase extraction, the time is saved, the use of an organic solvent is reduced, and the economic efficiency is improved.
Further, in the step of preparing the Fe 3O4 magnetic nano-particles, the mass-volume ratio of ferric chloride hexahydrate, sodium acetate and ethylene glycol is 2-3:4-5:35-40, g/g/mL.
Further, in the step of amination modification of the Fe 3O4 magnetic nano-particles, the volume ratio of ethanol to water to ammonia water in a mixed solution of ethanol to water to ammonia water is 50:10:1.2, and in the step of preparing the magnetic composite material Fe 3O4 @OH-COF, the volume ratio of 1, 4-dioxane to toluene in a 1, 4-dioxane/toluene mixed solution is 4:1.
Further, in the step of preparing the Fe 3O4 magnetic nanoparticles and the step of amination modification of the Fe 3O4 magnetic nanoparticles, water and ethanol are used for cleaning alternately, drying is carried out at 80 ℃, and in the step of preparing the magnetic composite material Fe 3O4 @OH-COF, methanol and water are used for cleaning alternately. And removing unreacted reagent on the corresponding precipitate through the operations of cleaning and drying.
Further, in step S3, in the high performance liquid chromatography-tandem mass spectrometry detection method:
The chromatographic conditions are a Waters C18 chromatographic column with the specification of 50X 2.1 mm and 1.9 mu m, a mobile phase A of 0.1% formic acid aqueous solution and a mobile phase B of methanol solution, gradient elution of 0-1min,3% B, 1-3min,3-20% B, 3-5min,20-97% B, 5-5.5min,97% B, 5.5-9min,97-3% B, the flow rate of 0.2mL/min, the column temperature of 40 ℃ and the sample injection amount of 5 mu L. The mass spectrum conditions were ionization mode H-ESI+; spray voltage 3500V, ion source temperature 350 ℃, ion transport tube temperature 320 ℃, sheath gas 35Arb, assist gas 10Arb, purge gas 0Arb.
Further, the bisphenol compound comprises bisphenol A (BPA), bisphenol B (BPB) and bisphenol F (BPF), and the perfluoro compound comprises perfluoro butyric acid (PFBA), perfluoro valeric acid (PFPeA), perfluoro caproic acid (PFHxA), perfluoro heptanoic acid (PFHpA) and perfluoro tridecanoic acid (PFTriDA). The method of the invention can be used for simultaneously detecting BPA, BPB, BPF, PFBA, PFPeA, PFHxA, PFHpA, PFTriDA in an orthodontic appliance. It should be noted that the above listed components do not represent a limitation of the present method.
Further, in step S3, after the eluent is detected and analyzed by using a high performance liquid chromatography-tandem mass spectrometry detection method, the contents of bisphenol compounds and perfluorinated compounds in the sample solution are determined, so that the amounts of bisphenol compounds and perfluorinated compounds released by the orthodontic transparent appliance sample are determined. The method comprises the steps of determining the contents of bisphenol compounds and perfluorinated compounds in a sample solution, wherein a conventional analysis method can be adopted, for example, under the same conditions, a series of standard solutions of the bisphenol compounds and the perfluorinated compounds with concentration gradients are respectively prepared, the standard solutions are added into artificial saliva, the standard solutions are obtained by incubation for 2 weeks in a rotary shaking table with the temperature of 37 ℃ plus or minus 1 ℃, the same sample pretreatment and detection analysis steps are carried out, standard curves of the concentration-peak area of the standard solutions are drawn, corresponding linear regression equations are obtained, and the peak area values obtained by detection analysis of the samples are brought into the corresponding linear regression equations, so that the contents of the bisphenol compounds and the perfluorinated compounds in the sample solution can be obtained. The above are all possible to operate by a person skilled in the art and are not described in detail herein.
Compared with the prior art, the invention has the following beneficial effects:
The method for detecting the bisphenol and the perfluorinated compounds in the orthodontic transparent appliance comprises the steps of simulating the oral environment of a human body, enabling the bisphenol compounds and the perfluorinated compounds in the orthodontic transparent appliance to be released into a sample solution, utilizing the characteristic that a magnetic composite material Fe 3O4 @OH-COF can simultaneously adsorb the bisphenol compounds and the perfluorinated compounds, simultaneously efficiently enriching the bisphenol compounds and the perfluorinated compounds in the sample solution, establishing a magnetic solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) method, simultaneously qualitatively detecting the bisphenol compounds and the perfluorinated compounds in the orthodontic transparent appliance, determining the content of the bisphenol compounds and the perfluorinated compounds in the sample solution, and further obtaining the quantity of the bisphenol compounds and the perfluorinated compounds released into the artificial saliva by the orthodontic transparent appliance sample, so that the quantity released into the oral cavity of the human body after a user clinically wears the orthodontic transparent appliance is simulated and judged. The detection method of bisphenol and perfluorinated compounds in the orthodontic transparent appliance has the advantages of high sensitivity, low detection limit and short analysis time.
For a better understanding and implementation, the present invention is described in detail below with reference to the drawings.
Drawings
FIG. 1 is a correlation spectrum of BPA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 2 is a correlation spectrum of BPB obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 3 is a correlation spectrum of BPF obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 4 is a correlation spectrum of PFBA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 5 is a correlation spectrum of PFPeA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 6 is a correlation spectrum of PFHxA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 7 is a correlation spectrum of PFHpA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 8 is a correlation spectrum of PFTriDA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention.
Detailed Description
The invention is described in detail below with reference to specific embodiments and accompanying drawings. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated. Further, the embodiments should be construed as illustrative, and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention.
Example 1
Since bisphenol compounds and perfluorinated compounds exist in trace amounts in orthodontic transparent appliances, detection is difficult to achieve with sensitive analytical instruments, and thus, a sample pretreatment technique needs to be combined.
The embodiment provides a method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance, which specifically comprises the following steps:
S1, sample preparation:
(1) Cutting the special perforating pliers for orthodontics into small discs for standby, wherein the diameter of the small discs is 5mm and the thickness of the small discs is 0.75mm;
(2) Weighing 1g of small discs, washing with ultrapure water, and sterilizing with 115V ultraviolet rays in a biosafety cabinet for 15min;
(3) Then turning over the small discs by using sterile forceps, and sterilizing for 15min in a container to obtain an orthodontic transparent appliance sample;
(4) Placing an orthodontic transparent appliance sample weighing 1g into 10mL of artificial saliva, namely placing the orthodontic transparent appliance sample in a proportion of 0.1g/mL, incubating the orthodontic transparent appliance sample in a rotary shaking table (230 rpm) at 37 ℃ for 2 weeks, and filtering to obtain a sample solution;
S2, pretreatment of a sample:
S21, preparing a magnetic composite material Fe 3O4 @OH-COF:
① Preparation of Fe 3O4 magnetic nanoparticles (Magnetic nanoparticles, MNPs):
Ferric chloride hexahydrate (2.8 g), sodium acetate (4.9 g) and ethylene glycol (40 mL) were added to a hydrothermal reaction kettle, and a yellow suspension was obtained by stirring, and reacted at 200 ℃ for 8 hours. After the reaction, collecting the precipitate by a magnet, alternately cleaning the precipitate by ultrapure water and ethanol to remove unreacted reagents, and vacuum drying the cleaned precipitate at 80 ℃ to obtain Fe 3O4 Magnetic Nanoparticles (MNPs).
②Fe3O4 Amination modification of Magnetic Nanoparticles (MNPs):
The prepared Fe 3O4 Magnetic Nanoparticles (MNPs) were dispersed in a mixed solution of 50mL of ethanol, 10 mL ultrapure water and 1.2 mL ammonia water, 0.4 mL tetraethyl orthosilicate was slowly added dropwise under mechanical stirring, and reacted at room temperature for 8 hours. After the reaction is finished, filtering or collecting the precipitate by using a magnet, alternately cleaning the precipitate by using ultrapure water and ethanol to remove unreacted reagent, and vacuum drying the cleaned precipitate at 80 ℃ to obtain Fe 3O4@SiO2. Then, 0.2 g Fe 3O4@SiO2 was ultrasonically dispersed in 130: 130 mL anhydrous toluene, 17 mL of 3-aminopropyl triethoxysilane was added dropwise, and the mixture was reacted at 120℃under reflux for 6 hours. After the reaction, the precipitate was collected with a magnet, washed alternately with ultrapure water and ethanol to remove unreacted reagents, and dried in vacuo at 80 ℃.
③ Preparing a magnetic composite material Fe 3O4 @OH-COF:
Fe 3O4@NH2 (50 mg), 2,5-dihydroxyterephthalaldehyde (2, 5-Dihydroxyterephthalaldehyde, DHPA) (18.9 mg), 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (4, 4'' - (1, 3,5-Triazine-2,4, 6-triyl) trianiline, TAPT) (26.4 mg) 1, 4-dioxane/toluene mixed solution (6 mL,4:1, v/v) and acetic acid solution (0.6 mL,3 mol/L) were added to a thick-walled reaction flask, sonicated for 5 minutes, and reacted at 120℃for 60 hours. After the reaction, the product was collected with a magnet and washed alternately with methanol and ultrapure water, and vacuum-dried for 12 hours to obtain a magnetic composite material Fe 3O4 @ OH-COF.
(Before preparing magnetic composite material Fe 3O4 @OH-COF, in order to facilitate the preparation of magnetic composite material Fe 3O4 @OH-COF by using optimized synthesizing conditions of OH-COF, the present example also selects synthesizing conditions of optimized OH-COF by adding 2,5-dihydroxyterephthalaldehyde (2, 5-Dihydroxyterephthalaldehyde, DHPA) (18.9 mg), 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (4, 4'' - (1, 3,5-Triazine-2,4, 6-triyl) trianiline, TAPT) (26.4 mg), an absolute ethanol/1, 2-dichlorobenzene mixed solution (2 mL,1:1, v/v) and acetic acid solution (0.2 mL,12 mol/L), conducting ultrasonic treatment for 10 minutes, then after the reaction for 72 hours at 125 ℃, centrifuging the precipitate, alternately removing the precipitate by using 1, 2-dichlorobenzene and methanol, conducting the reaction alternately, and conducting the vacuum synthesis of the solution under the conditions of Fe-1, 2-dichlorobenzene, 3-5-COF, 6-COF, and the magnetic composite material under the conditions of 35, 3, 6-COF, which are prepared by using the optimized synthesizing conditions of Fe-6-COF under the conditions of 35, 6-COF, 6-5-COF, 6-5-3, 5-COF, and 3, 3-COF, 3, 5-COF, and 3, 3-dihydroxybenzene mixed solution (2-COF, 3, 35) are used as basic materials, obtaining the magnetic composite material Fe 3O4 @OH-COF. )
S22 magnetic solid phase extraction:
10mg of the magnetic composite Fe 3O4 @ OH-COF was added to the 15 mL sample solution, vortexed for 5 minutes, and the magnetic composite Fe 3O4 @ OH-COF was collected from the solution with a magnet and the supernatant was removed. Then, 1.0 mL acetonitrile solution was added to the centrifuge tube and vortexed for 1 minute to elute the bisphenol compound and the perfluoro compound adsorbed on the magnetic composite Fe 3O4 @ OH-COF. And finally, alternately cleaning and filtering the obtained magnetic composite material Fe 3O4 @OH-COF by using 2 mL acetonitrile solution and ultrapure water respectively, and drying the magnetic composite material Fe 3O4 @OH-COF for the next use.
S3, detection and analysis:
and (3) establishing a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) detection analysis method, performing instrument analysis on the eluent, detecting bisphenol compounds and perfluorinated compounds at the same time, determining the contents of the bisphenol compounds and the perfluorinated compounds in a sample solution, and determining the amounts of the bisphenol compounds and the perfluorinated compounds released by the orthodontic transparent appliance sample.
Since the apparatus used in the combined high performance liquid chromatography-tandem mass spectrometry method can be selected from the existing conventional high performance liquid chromatography equipment, the operation method of high performance liquid chromatography-tandem mass spectrometry is a conventional method, and therefore, in this embodiment, except for the chromatographic conditions and the mass spectrometry conditions, the description of the present invention will not be repeated.
Chromatographic conditions:
Chromatographic column Waters C18 (50X 2.1 mm,1.9 μm)
The mobile phase composition and gradient elution conditions are shown in Table 1
TABLE 1 Mobile phase composition and gradient elution Table
Mass spectrometry conditions:
Mass spectrum parameters are shown in Table 2
Table 2 mass spectrometry parameter settings
The method for detecting bisphenol and perfluorinated compounds in the orthodontic transparent appliance comprises bisphenol A (BPA), bisphenol B (BPB) and bisphenol F (BPF), wherein the detected perfluorinated compounds comprise perfluorobutyric acid (PFBA), perfluorovaleric acid (PFPeA), perfluorocaproic acid (PFHxA), perfluoroheptanoic acid (PFHpA) and perfluorotridecanoic acid (PFTriDA).
In this example, the above method was used to establish detection methods for 3 bisphenol compounds (BPA, BPB, BPF) and 5 perfluorinated compounds (PFBA, PFPeA, PFHxA, PFHpA, PFTriDA). FIGS. 1 to 8 show spectra related to each substance obtained by performing high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) detection under the above-described chromatographic conditions and mass spectrometry conditions on four different samples, respectively, namely, an eluent obtained by adding 2ng/g of each substance standard to a sample solution and then performing pretreatment, an eluent obtained after the step S2 (actual sample after pretreatment), and a sample solution obtained after the step S1 (actual sample before pretreatment). As can be seen from fig. 1 to 8, the 3 bisphenol compounds and the 5 perfluorinated compounds have good chromatographic peak shapes, and under the current chromatographic conditions and mass spectrum conditions, the 3 bisphenol compounds and the 5 perfluorinated compounds are well separated.
Example 2
Methodology evaluation:
In order to evaluate the analysis performance of the magnetic solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) method established by the invention, the embodiment also respectively prepares mother solutions with the concentration of 20ng/g for the 3 bisphenol compounds (BPA, BPB, BPF) and the 5 perfluorinated compounds (PFBA, PFPeA, PFHxA, PFHpA, PFTriDA), respectively, and respectively dilutes the mother solutions with methanol into series standard working concentrations of 0.1ng/g, 0.6ng/g, 0.8ng/g, 2ng/g, 5ng/g and 10ng/g step by step, and performs the same sample pretreatment method by referring to the method of the embodiment 1 to perform magnetic solid phase extraction, and performs high performance liquid chromatography-tandem mass spectrometry system detection on corresponding eluents under the same chromatographic conditions and mass spectrometry conditions, respectively, so as to inspect the linear range, detection limit, quantitative limit and relative standard deviation of the method, and the result is shown in a table 3, wherein x represents the concentration of the object to be detected, and y represents the peak area of the object to be detected. The result shows that the method has good linearity (R 2 is more than or equal to 0.9982) within the range of 0.10-20 ng/g, LODs and LOQs are respectively between 0.009-0.025 ng/g and 0.032-0.085 ng/g, and the daily precision and the daytime precision are less than 10%, which indicates that the method has lower detection limit.
TABLE 3 MSPE-HPLC-MS/MS methodological parameters
Example 3
Accuracy of the method:
Three concentration levels (0.5, 2.0, 10.0 ng/g) of the target (3 bisphenol compounds and 5 perfluoro compounds) were added to the blank samples (untreated sample solutions), and the standard recovery rates were measured, respectively, and the results are shown in Table 4. The standard recovery rate of bisphenol compounds and perfluorinated compounds in the sample is 87.6-103.2%, and RSDs are less than or equal to 6.3%. The method can accurately measure the bisphenol compound and the perfluorinated compound in the sample solution of the orthodontic transparent appliance, and further accurately measure the amounts of the bisphenol compound and the perfluorinated compound released by the orthodontic transparent appliance sample.
TABLE 4 MSPE-HPLC-MS/MS labeled recovery experiment
Example 4
Actual sample detection results:
The results of the actual sample testing of example 1 are shown in table 5, and demonstrate that the established magnetic solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) method can be used to test bisphenol compounds and perfluorinated compounds in an orthodontic appliance, where the actual results are the amount of bisphenol compounds and perfluorinated compounds released into artificial saliva per 1g of actual sample of an orthodontic appliance.
TABLE 5 detection results of actual samples
The method for detecting the bisphenol and the perfluorinated compounds in the orthodontic transparent appliance comprises the steps of simulating the oral environment of a human body, enabling the bisphenol compounds and the perfluorinated compounds in the orthodontic transparent appliance to be released into a sample solution, utilizing the characteristic that a magnetic composite material Fe 3O4 @OH-COF can simultaneously adsorb the bisphenol compounds and the perfluorinated compounds, simultaneously efficiently enriching the bisphenol compounds and the perfluorinated compounds in the sample solution, establishing a magnetic solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) method, simultaneously qualitatively detecting the bisphenol compounds and the perfluorinated compounds in the orthodontic transparent appliance, determining the content of the bisphenol compounds and the perfluorinated compounds in the sample solution, further obtaining the content of the orthodontic transparent appliance sample released into artificial saliva, and simulating and judging the content of the orthodontic transparent appliance released into the oral cavity after a user wears the orthodontic transparent appliance clinically for 2 weeks. The detection method of bisphenol and perfluorinated compounds in the orthodontic transparent appliance has the advantages of high sensitivity, low detection limit and short analysis time.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.
Claims (8)
1. A detection method of bisphenol and perfluorinated compounds in an orthodontic transparent appliance is characterized in that the bisphenol compounds comprise bisphenol A, bisphenol B and bisphenol F, the perfluorinated compounds comprise perfluorobutyric acid, perfluorovaleric acid, perfluorocaproic acid, perfluorocaprylic acid and perfluorotridecanoic acid, and the detection method comprises the following steps:
S1, sample preparation:
adding an orthodontic transparent appliance sample into artificial saliva, incubating for 2 weeks in a rotary shaking table at 37 ℃ plus or minus 1 ℃, and filtering to obtain a sample solution;
s2, sample pretreatment:
adding a magnetic composite material Fe 3O4 @OH-COF into a sample solution, and carrying out vortex treatment; separating the magnetic composite material Fe 3O4 @OH-COF from the solution, eluting the separated magnetic composite material Fe 3O4 @OH-COF by using acetonitrile solution, and separating to obtain eluent;
In the step S2, the preparation method of the magnetic composite material Fe 3O4 @OH-COF comprises the following steps:
Preparing Fe 3O4 magnetic nano particles, namely adding ferric chloride hexahydrate, sodium acetate and ethylene glycol into a hydrothermal reaction kettle, stirring to obtain yellow suspension, and reacting for 6-10 hours at 180-220 ℃;
Dispersing the prepared Fe 3O4 magnetic nano particles in a mixed solution containing ethanol, water and ammonia water, dropwise adding tetraethoxysilane under a stirring state, reacting for 8-12 hours at room temperature, separating precipitate after the reaction is finished, cleaning and drying to obtain Fe 3O4@SiO2, dispersing Fe 3O4@SiO2 in anhydrous toluene by ultrasonic waves, dropwise adding 3-aminopropyl triethoxysilane, carrying out reflux reaction for 4-8 hours at 100-140 ℃, separating precipitate after the reaction is finished, cleaning and drying to obtain amino-modified Fe 3O4 magnetic nano particles, namely Fe 3O4@NH2;
Preparing a magnetic composite material Fe 3O4 @OH-COF, namely adding Fe 3O4@NH2, 2, 5-dihydroxyterephthalaldehyde, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 1, 4-dioxane/toluene mixed solution and acetic acid solution into a thick-wall reaction bottle, carrying out ultrasonic treatment for 4-6 minutes, and reacting for 60-80 hours at 100-140 ℃, separating precipitate after the reaction is finished, and washing and drying to obtain the magnetic composite material Fe 3O4 @OH-COF;
s3, detection and analysis:
Detecting and analyzing the eluent by adopting a high performance liquid chromatography-tandem mass spectrometry detection method;
in step S3, in the high performance liquid chromatography-tandem mass spectrometry detection method:
The chromatographic conditions are a Waters C18 chromatographic column with the specification of 50X 2.1 mm and 1.9 mu m, a mobile phase A of 0.1% formic acid aqueous solution and a mobile phase B of methanol solution, gradient elution of 0-1min,3% B, 1-3min,3-20% B, 3-5min,20-97% B, 5-5.5min,97% B, 5.5-9min,97-3% B, the flow rate of 0.2mL/min, the column temperature of 40 ℃ and the sample injection amount of 5 mu L.
2. The method for detecting bisphenol and perfluorinated compounds in an orthodontic appliance according to claim 1, wherein in the step S1, the orthodontic appliance sample is added in an amount of 0.1g of the orthodontic appliance sample per 1mL of artificial saliva.
3. The method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance according to claim 1, wherein in the step S1, the orthodontic transparent appliance sample is obtained by cutting an orthodontic special punching clamp for an orthodontic transparent appliance into small discs with the diameter of 5mm and the thickness of 0.75mm, and washing and sterilizing the small discs to obtain the orthodontic transparent appliance sample.
4. The method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance according to claim 1, wherein in the step of preparing Fe 3O4 magnetic nanoparticles, the mass-volume ratio of ferric chloride hexahydrate, sodium acetate and ethylene glycol is 2-3:4-5:35-40, g/g/mL.
5. The method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance according to claim 1, wherein in the step of amination modification of Fe 3O4 magnetic nanoparticles, the volume ratio of ethanol to water to ammonia water in a mixed solution of ethanol, water and ammonia water is 50:10:1.2, and in the step of preparing a magnetic composite material Fe 3O4 @OH-COF, the volume ratio of 1, 4-dioxane to toluene in a1, 4-dioxane/toluene mixed solution is 4:1.
6. The method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance according to claim 1, wherein in the step of preparing Fe 3O4 magnetic nanoparticles and the step of amination modification of Fe 3O4 magnetic nanoparticles, water and ethanol are used for cleaning alternately, drying is carried out at 80 ℃, and in the step of preparing the magnetic composite material Fe 3O4 @OH-COF, methanol and water are used for cleaning alternately.
7. The method for detecting bisphenol and perfluorinated compounds in an orthodontic transparent appliance according to claim 1, wherein in the step S3, the high performance liquid chromatography-tandem mass spectrometry detection method comprises the following steps:
the mass spectrum conditions were ionization mode H-ESI+; spray voltage 3500V, ion source temperature 350 ℃, ion transport tube temperature 320 ℃, sheath gas 35Arb, assist gas 10Arb, purge gas 0Arb.
8. The method for detecting bisphenol and perfluorinated compounds in an orthodontic appliance according to claim 1, wherein in the step S3, after the eluent is detected and analyzed by a high performance liquid chromatography-tandem mass spectrometry detection method, the contents of bisphenol and perfluorinated compounds in a sample solution are determined, so that the amounts of bisphenol and perfluorinated compounds released by a sample of the orthodontic appliance are determined.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411455062.1A CN119000960B (en) | 2024-10-18 | 2024-10-18 | A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411455062.1A CN119000960B (en) | 2024-10-18 | 2024-10-18 | A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN119000960A CN119000960A (en) | 2024-11-22 |
| CN119000960B true CN119000960B (en) | 2025-01-17 |
Family
ID=93487981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411455062.1A Active CN119000960B (en) | 2024-10-18 | 2024-10-18 | A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119000960B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113671068B (en) * | 2021-07-27 | 2023-01-24 | 暨南大学 | A method for targeted exposure group analysis of environmental pollutants in plasma and its application |
| CN117665180A (en) * | 2023-10-20 | 2024-03-08 | 中山大学 | Method for synchronously extracting and detecting 62 typical environmental endocrine disruptors in serum |
-
2024
- 2024-10-18 CN CN202411455062.1A patent/CN119000960B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Determination of perfluorooctane sulfonate and perfluorooctanoic acid in food packaging using liquid chromatography coupled with tandem mass spectrometry;Somrutai Poothong等;Journal of Hazardous Materials;20150109;139-143页 * |
| 液相色谱－串联质谱法同时测定婴幼儿配方乳粉中全氟辛酸、全氟辛烷磺酸、双酚Ａ 和壬基酚残留;王浩等;色谱;20181231;第36卷(第12期);1279-1283 * |
| 磁性氧化石墨烯分散固相萃取/液相色谱－串联质谱法测定PVC儿童用品中内分泌干扰物迁移量;曹慧等;分析测试学报;20220831;第41卷(第8期);1207-1213 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN119000960A (en) | 2024-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108262019B (en) | Magnetic sulfonic group functionalized COFs material and preparation method and application thereof | |
| CN108276584A (en) | The detection method of aromatic amine compound in a kind of human urine | |
| CN103285840A (en) | Embedded triazine ring amide silica gel stationary phase for liquid chromatograph and preparation method thereof | |
| CN119000960B (en) | A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances | |
| KR20040076387A (en) | Improved solid phase microextraction fiber, preparation method thereof and determination method of alkylphenols and bisphenol-a in water samples with the spme fiber | |
| CN109725095A (en) | A kind of method that adopts HPLC to simultaneously detect the content of various biogenic amines in soy sauce | |
| CN107389811A (en) | The assay method of diisopropyl naphthalene in cigarette tipping paper | |
| CN107991277B (en) | Serotonin-magnetic particle composite and method for enriching sialylated glycoprotein | |
| CN111024846B (en) | Method for measuring bisphenol A in water body | |
| CN119000959B (en) | A method for detecting perfluorinated and hexabromocyclododecane compounds in orthodontic transparent appliances | |
| CN119000958B (en) | Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance | |
| CN103285814B (en) | Fixed metal affinity chromatographic stationary phase based on strong chelating ligand and preparation method of stationary phase | |
| CN105891387B (en) | A kind of enrichment method for being used to detect hydrophilic amino acid | |
| CN107831259A (en) | The assay method of free amino acid in a kind of spleen aminopeptide | |
| CN104950051B (en) | Method for detecting isothiazolinone compounds in water-based adhesive for cigarettes | |
| CN108434783B (en) | Solid phase extraction column, method for manufacturing solid phase extraction column filler and method for detecting aflatoxin by using solid phase extraction column | |
| CN207913283U (en) | Phenyl bonded silica solid-phase extraction column | |
| CN111921509B (en) | Solid phase extraction column and preparation method thereof and detection method of lactoferrin | |
| CN105413663B (en) | The sorbing material and preparation method and applications of a kind of bisphenol-A | |
| CN108828101B (en) | Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline | |
| CN110596269B (en) | Content determination method for simultaneously detecting multiple components in creatine powder | |
| CN110824089B (en) | Method for rapidly detecting cartap residue in vegetables | |
| Chang et al. | Silica gel-immobilized-vanillin derivatives as selective solid-phase extractants for determination of chromium (III) in environmental samples by ICP-OES | |
| CN114034799A (en) | Method for detecting fluxapyroxad residual quantity in grapes | |
| CN108426971B (en) | Method for rapidly detecting microcystin in water |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |