CN119000958B - Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance - Google Patents
Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance Download PDFInfo
- Publication number
- CN119000958B CN119000958B CN202411455059.XA CN202411455059A CN119000958B CN 119000958 B CN119000958 B CN 119000958B CN 202411455059 A CN202411455059 A CN 202411455059A CN 119000958 B CN119000958 B CN 119000958B
- Authority
- CN
- China
- Prior art keywords
- orthodontic
- sample
- perfluorinated compounds
- transparent
- hexachloroprene
- 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 89
- 238000001514 detection method Methods 0.000 title claims abstract description 81
- 239000000523 sample Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000012488 sample solution Substances 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004458 analytical method Methods 0.000 claims abstract description 24
- 238000004885 tandem mass spectrometry Methods 0.000 claims abstract description 23
- 239000003480 eluent Substances 0.000 claims abstract description 19
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims abstract description 18
- 239000000120 Artificial Saliva Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 30
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=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)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000004949 mass spectrometry Methods 0.000 claims description 8
- 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
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XBCGIUJJUZHWMC-UHFFFAOYSA-N 2,5-dichloroterephthalaldehyde Chemical compound ClC1=CC(C=O)=C(Cl)C=C1C=O XBCGIUJJUZHWMC-UHFFFAOYSA-N 0.000 claims description 4
- JGUVAGVIFMBVCK-UHFFFAOYSA-N 4-[1,2,2-tris(4-aminophenyl)ethenyl]aniline Chemical group C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 JGUVAGVIFMBVCK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005576 amination reaction Methods 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
- HYWZIAVPBSTISZ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecane-1-sulfonic acid Chemical compound OS(=O)(=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)F HYWZIAVPBSTISZ-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
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 9
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- LQSJUQMCZHVKES-UHFFFAOYSA-N 6-iodopyrimidin-4-amine Chemical compound NC1=CC(I)=NC=N1 LQSJUQMCZHVKES-UHFFFAOYSA-N 0.000 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000013310 covalent-organic framework Substances 0.000 description 31
- -1 polypropylene Polymers 0.000 description 16
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 12
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- 210000000214 mouth Anatomy 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 8
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 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 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 206010074268 Reproductive toxicity Diseases 0.000 description 2
- 238000011960 computer-aided design Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 231100000372 reproductive toxicity Toxicity 0.000 description 2
- 230000007696 reproductive toxicity Effects 0.000 description 2
- 210000002345 respiratory system Anatomy 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
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 206010011703 Cyanosis Diseases 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 208000001953 Hypotension Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 231100000005 chromosome aberration Toxicity 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate 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
- 235000013305 food Nutrition 0.000 description 1
- 230000037406 food intake Effects 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
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 210000004251 human milk Anatomy 0.000 description 1
- 235000020256 human milk Nutrition 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
- 230000004941 influx Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 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
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000581 reactive spray deposition Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000013049 sediment Substances 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
- 241000894007 species Species 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 238000003260 vortexing 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 hexachloroprene and perfluorinated compounds in an orthodontic transparent appliance, and belongs 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 @Cl-COF into the sample solution, carrying out vortex processing, separating the magnetic composite material Fe 3O4 @Cl-COF from the solution, eluting the separated magnetic composite material Fe 3O4 @Cl-COF by using a methanol solution, separating to obtain an eluent, and S3, detecting and analyzing the eluent by adopting a high performance liquid chromatography-tandem mass spectrometry detection method and a high performance gas chromatography-tandem mass spectrometry detection method. The detection method can simultaneously detect the amounts of hexachloroprene and perfluorinated compounds released by the orthodontic transparent appliance, and has the advantages of 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 detection method of hexachloroprene and perfluorinated compounds in an orthodontic transparent appliance.
Background
With rapid advances in biological materials, computer Aided Design (CAD), and manufacturing (CAM) technology, transparent appliance therapy has become a promising alternative to traditional fixed appliances in the orthodontic field. The global orthodontic transparent appliance market size is expected to increase from $31 billion in 2021 to $116 billion in 2027 with a Composite Annual Growth Rate (CAGR) of 13%. Orthodontic appliances are typically composed of a series of transparent plastic trays that closely fit over the teeth, which are used by the patient at any time except for eating and brushing, and are typically replaced every one to two weeks to complete the planned orthodontic tooth movement. Although there are a variety of commercially available orthodontic appliances systems worldwide today, the use of clear thermoformed plastic materials to make the appliances is still a common feature. The most common polymers (alone or in combination) used to make orthodontic clear plastic orthodontic appliances for use in the industry include polyesters, polyurethanes or copolyesters, polypropylene, polycarbonate, ethylene vinyl acetate, polyvinyl chloride, and the like. As an intraoral appliance material, although orthodontic transparent appliance materials are promoted to be free of harmful substances, are expected not to exude any potential toxins that may cause adverse local or systemic reactions, are not carcinogenic, and do not cause any developmental defects, these polymers contain various additives that may improve specific properties such as performance, stability, elasticity, etc., but these additives may be toxic to the human body. Furthermore, since there are few control trials on orthodontic appliances and the results mentioned in published literature contradict each other, a lack of evidence-based literature results, which continues to exacerbate the debate about the potential for toxic effects that may result from using an invisible appliance. In addition, with the continued influx of a variety of commercial appliance systems, there is a need to continue testing the toxicity of orthodontic appliances produced by different manufacturers.
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.
Hexachloroprene (Hexachlorobutadiene, HCBD), an aliphatic halogenated hydrocarbon, was added to the stockholm convention regulatory list in 2017, and is a new class of Persistent Organic Pollutants (POPs). HCBD has low boiling point, is volatile and stable in chemical property, and is commonly used for solvents of rubber and other polymers. HCBD have three toxicogenicity and potential reproductive toxicity, and are classified as human carcinogens group C. HCBD is a novel persistent organic pollutant which is difficult to degrade, has bioaccumulation and can be absorbed by organisms through respiration, ingestion, skin contact and other ways. HCBD has strong stimulation to eyes, skin and respiratory tract of human, inhalation can cause respiratory system injury, arterial hypotension, etc., long-term exposure can cause liver and kidney lesions, central nervous system inhibition, cyanosis, chromosomal aberration, etc., and can be transmitted to infants through breast milk. At present, the domestic research on HCBD is very limited, the occurrence of the HCBD in orthodontic transparent appliance materials and the influence on human bodies are still unclear, and the pollution control of the POPs is not facilitated.
The orthodontic transparent appliance is an indispensable device 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 clinically, 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). PFASs and HCBD may be one of these additives for enhancing the overall properties of the material. The two additives in the orthodontic transparent appliance are easy to release into the oral cavity of a human body in the process of being clinically worn by a user for 2 weeks, and when a certain concentration is accumulated in the human body, the two additives are easy to cause harm to the human body. Due to the hazards and difficult degradability of these two types of contaminants, the need for content measurement of different PFASs and HCBD in orthodontic appliances is becoming more and more urgent. In particular, when the orthodontic appliance is worn by a patient, it is necessary to know how much of PFASs and HCBD are released into the mouth of the person.
Because hexachloroprene 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, substrate interference exists, the detection is difficult, and the samples are required to be pretreated, enriched and purified, so that the detection can be realized. Sample pretreatment (including pretreatment) not only extracts and enriches the target and removes the interfering substances, but also converts the sample into a state suitable for storage or a form suitable for instrumental analysis. These processes can directly affect the reliability and sensitivity of the overall assay, and are an indispensable important link, especially for the detection of trace species PFASs and HCBD. The existing method generally aims at PFASs and HCBD, adopts liquid-liquid extraction, freeze drying and other modes to perform sample pretreatment, has complex operation and long time consumption, and cannot meet the requirement of rapid analysis. In addition, as Hexachloroprene (HCBD) and perfluoro 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 PFASs and HCBD 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 hexachloroprene and perfluorinated compounds is mostly concentrated in surface water, sediment, sewage water and the like, but the research on orthodontic transparent appliance samples is very few, mainly because the orthodontic transparent appliance has complex matrix and serious interference, the difficulty in analysis pretreatment is far greater than the detection of hexachloroprene or perfluorinated compounds in water, and the technology at present only aims at one type of components, and how to efficiently extract hexachloroprene and perfluorinated compounds from orthodontic transparent appliance samples becomes an analysis bottleneck of trace pollutants. In the common extraction method of hexachloroprene or perfluorinated compounds of the orthodontic transparent appliance, the rapid solvent extraction method or the 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 adsorbents mainly used for enriching perfluorinated compounds or hexachloroprene comprise polystyrene-divinylbenzene filler and silica gel, but the adsorbents have 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 hexachloroprene or perfluorinated compounds in orthodontic appliances and reduce interference with the matrix, it is important to develop new adsorbents 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 detection methods of 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 detecting trace hexachloroprene 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 detection method of hexachloroprene and perfluorinated compounds in an orthodontic transparent appliance, which can qualitatively detect the hexachloroprene and perfluorinated compounds in the orthodontic transparent appliance by combining a high performance liquid chromatography-tandem mass spectrometry detection method and a gas chromatography-tandem mass spectrometry detection method with a specific sample pretreatment technology, and determine the release amount of the Hexachloroprene (HCBD) 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 detection method of hexachloroprene 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 @Cl-COF into a sample solution, and carrying out vortex treatment; separating the magnetic composite material Fe 3O4 @Cl-COF from the solution, eluting the separated magnetic composite material Fe 3O4 @Cl-COF by using a methanol solution, and separating to obtain an eluent;
s3, detection and analysis:
And respectively detecting and analyzing the eluent by adopting a high performance liquid chromatography-tandem mass spectrometry detection method and a gas chromatography-tandem mass spectrometry detection method.
According to the detection method of hexachloroprene and perfluorinated compounds in the orthodontic transparent appliance, in the step S1, artificial saliva is placed on an orthodontic transparent appliance sample, the orthodontic transparent appliance sample is incubated for 2 weeks in an environment of 37 ℃ plus or minus 1 ℃, so that the hexachloroprene and perfluorinated compounds in the orthodontic transparent appliance sample are released into a sample solution, the environment of wearing the orthodontic transparent appliance in a human oral cavity is simulated through the step S1, and the hexachloroprene and perfluorinated compounds in the orthodontic transparent appliance sample are released into the oral cavity of the human body. Then, in the step S2, hexachloroprene and perfluorinated compounds in a sample solution are efficiently enriched by using a magnetic composite material Fe 3O4 @Cl-COF as a magnetic solid-phase extraction adsorbent, wherein the magnetic composite material Fe 3O4 @Cl-COF is provided with benzene rings and Cl, the acting force of the Cl in the magnetic composite material Fe 3O4 @Cl-COF and the hexachloroprene is Cl-Cl interaction adsorption, and the acting force of the benzene rings in the magnetic composite material Fe 3O4 @Cl-COF and the perfluorinated compounds is hydrophobic adsorption, so that the magnetic composite material Fe 3O4 @Cl-COF can adsorb the hexachloroprene and the perfluorinated compounds simultaneously, and then desorption treatment is carried out to elute the hexachloroprene and the perfluorinated compounds adsorbed on the magnetic composite material Fe 3O4 @Cl-COF so as to transfer the hexachloroprene and the perfluorinated compounds into an eluent. Finally, in step S3, the eluent is respectively detected and analyzed by a high performance liquid chromatography-tandem mass spectrometry detection method and a gas chromatography-tandem mass spectrometry detection method, hexachloroprene and perfluorinated compounds are qualitatively detected, and the content of the hexachloroprene and perfluorinated compounds in a sample solution is determined, so that the content of the hexachloroprene and perfluorinated compounds released into artificial saliva by an orthodontic transparent appliance sample is further obtained, and the content of the hexachloroprene and perfluorinated compounds 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/gas chromatography-tandem mass spectrometry (MSPE-HPLC/GC-MS/MS) by combining a high performance liquid chromatography-tandem mass spectrometry detection method and a gas chromatography-tandem mass spectrometry detection method with a specific sample pretreatment technology, can detect hexachloroprene and perfluorinated compounds existing in trace amounts in an orthodontic transparent appliance, and has high sensitivity, low detection limit and short analysis time; the detection method of hexachloroprene and perfluorinated compounds in the orthodontic transparent appliance can solve the problems that in the existing detection method, the hexachloroprene and perfluorinated compounds exist in trace amounts in the orthodontic transparent appliance and cannot be detected at the same time, 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, and the orthodontic transparent appliance sample simulates the oral cavity of a human body, so that hexachloroprene 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 hexachloroprene 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 @ Cl-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, ultrapure water and ammonia water, dropwise adding tetraethoxysilane under stirring, 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, 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 @Cl-COF, namely adding Fe 3O4@NH2, 2, 5-dichloro terephthalaldehyde, tetra (4-aminophenyl) ethylene, acetonitrile and acetic acid solution into a reaction bottle, carrying out ultrasonic treatment for 10-15 minutes, reacting at room temperature for 65-80 hours, separating a precipitate after the reaction is finished, cleaning and drying to obtain the magnetic composite material Fe 3O4 @Cl-COF.
In the preparation method of the magnetic composite material Fe 3O4 @Cl-COF, fe 3O4@NH2, 2, 5-dichloro terephthalaldehyde and tetra (4-aminophenyl) ethylene are reacted together (Schiff base reaction), so that benzene rings and Cl are arranged in the prepared magnetic composite material Fe 3O4 @F-COF, hexachloroprene and perfluorinated compounds can be adsorbed simultaneously by utilizing the structural characteristics of the benzene rings and the Cl, the benzene ring in the magnetic composite material Fe 3O4 @Cl-COF can form a hydrophobic adsorption effect with the perfluorinated compounds, and the Cl-Cl interaction adsorption effect is formed between the Cl and the hexachloroprene in the magnetic composite material Fe 3O4 @Cl-COF, so that the magnetic composite material Fe 3O4 @Cl-COF can adsorb the hexachloroprene and the perfluorinated compounds simultaneously, and can efficiently enrich the hexachloroprene and the perfluorinated compounds in the sample solution simultaneously. The Fe 3O4 magnetic nano particles are introduced into the Fe 3O4 @Cl-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 nanoparticles, 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.
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 @Cl-COF, acetonitrile and water are used for cleaning alternately. And removing unreacted reagent on the corresponding precipitate through the operations of cleaning and drying.
Further, in the step S3, the chromatographic conditions of the HPLC-MS detection method are that the chromatographic conditions are a Hypersil GOLD C18 chromatographic column with the specification of 50 multiplied by 2.1 mm and 1.8 mu m, the mobile phase is that A is 5mmol of ammonium acetate aqueous solution, B is methanol solution, gradient elution is that 0-1min,3% B, 1-3min,3-15% B, 3-5min,15-90% B, 5-5.5min,90% B, 5.5-10min,90-3% B, the flow rate is 0.3mL/min, the column temperature is 35 ℃, the sample injection amount is 5 mu L, the mass spectrometry conditions are that the ionization mode H-ESI-, the spray voltage is 3500V, the ion source temperature is 380 ℃, the ion transmission tube temperature is 330 ℃, the sheath gas is 40Arb, the auxiliary gas is 20Arb, and the purge gas is 0Arb.
Further, in the step S3, the chromatographic conditions in the gas chromatography-tandem mass spectrometry detection method are Agilent gas chromatography column with the specification of 30 m ×0.25 mm and 0.25 μm, sample inlet temperature of 280 ℃ and column temperature of 130 ℃ and 1 min respectively, temperature rise from 15 ℃ to 220 ℃ and 2 min respectively, high purity helium gas (99.999%) as carrier gas, flow rate of 0.8 ml/min, mass spectrometry conditions of ion source, electron bombardment energy of 80 eV, mass scanning range of 40-500 amu, ion source temperature of 220 ℃ and solvent delay time of 8 min.
Further, the perfluorinated compounds include perfluorobutyric acid (PFBA), perfluorovaleric acid (PFPe A), perfluorobutyl sulfonic acid (PFBS), perfluorooctyl sulfonic acid (PFOS), perfluorodecyl sulfonic acid (PFDS). The method of the present invention can be used to detect HCBD in orthodontic appliances and PFBA, PFPe A, PFBS, PFOS, PFDS, HCBD as listed above. It should be noted that the above listed components do not represent a limitation of the present method.
Further, in the step S3, after the eluent is detected and analyzed by adopting a high performance liquid chromatography-tandem mass spectrometry detection method, the content of the perfluorinated compounds in the sample solution is determined, after the eluent is detected and analyzed by adopting a gas chromatography-tandem mass spectrometry detection method, the content of the hexachloroprene in the sample solution is determined, and thus the amounts of the hexachloroprene and the perfluorinated compounds released by the orthodontic transparent appliance sample are determined. The method comprises the steps of determining the content of hexachloroprene and perfluorinated compounds in a sample solution, wherein a conventional analysis method can be adopted, for example, a series of standard solutions of hexachloroprene or perfluorinated compounds with concentration gradients are respectively prepared under the same conditions, 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 content of hexachloroprene and 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:
According to the detection method of the hexachloroprene and the perfluorinated compounds in the orthodontic transparent appliance, the oral environment of a human body is simulated, the hexachloroprene and the perfluorinated compounds in the orthodontic transparent appliance are released into a sample solution, the characteristics of magnetic composite material Fe 3O4 @Cl-COF can be utilized to absorb the hexachloroprene and the perfluorinated compounds simultaneously, meanwhile, the hexachloroprene and the perfluorinated compounds in the sample solution are enriched efficiently, a method of magnetic solid phase extraction-high performance liquid chromatography/gas chromatography-tandem mass spectrometry (MSPE-HPLC/GC-MS) is established, the hexachloroprene and the perfluorinated compounds in the orthodontic transparent appliance can be detected qualitatively and simultaneously, and the content of the hexachloroprene and the perfluorinated compounds in the sample solution is determined, so that the quantity of the hexachloroprene and the perfluorinated compounds released into the artificial saliva by the orthodontic transparent appliance sample is further obtained, and the quantity of the hexachloroprene and the perfluorinated compounds released into the oral cavity of the human body after a user wears the orthodontic transparent appliance for 2 weeks in clinic is simulated and judged. The detection method of hexachloroprene 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 PFBA obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 2 is a correlation spectrum of PFPe A obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 3 is a correlation spectrum of PFBS obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 4 is a correlation spectrum of PFOS obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 5 is a correlation spectrum of PFDS obtained by HPLC-MS/MS detection of four different samples in example 1 of the present invention;
FIG. 6 is a correlation spectrum of HCBD obtained after GC-MS detection of each of the 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 hexachloroprene and perfluorinated compounds are present in trace amounts in orthodontic appliances, detection is also difficult to achieve with sensitive analytical instruments, and thus a combination of sample pretreatment techniques is required.
The embodiment provides a detection method of Hexachloroprene (HCBD) 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 @Cl-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 @Cl-COF:
Fe 3O4@NH2 (50 mg), 2, 5-dichloro-terephthalaldehyde (38.7 mg) and tetrakis (4-aminophenyl) ethylene (43.6 mg), acetonitrile 12mL and acetic acid solution (0.6 mL,12 mol/L) were added to a reaction flask, sonicated for 15 minutes, reacted at room temperature for 65 hours, after the reaction was completed, the product was collected with a magnet and washed alternately with acetonitrile and ultrapure water, and dried in vacuo for 12 hours to obtain a magnetic composite Fe 3O4 @Cl-COF.
S2 magnetic solid phase extraction:
10mg of the magnetic composite Fe 3O4 @ Cl-COF was added to the 10 mL sample solution, and after vortexing for 5 minutes, the magnetic composite Fe 3O4 @ Cl-COF was collected from the solution with a magnet and the supernatant was removed. Then, 3.0 mL methanol solution was added to the centrifuge tube and vortexed for 1 minute to elute hexachloroprene and perfluoro-based compounds adsorbed on the magnetic composite Fe 3O4 @ Cl-COF. Finally, the magnetic composite material Fe 3O4 @Cl-COF obtained by filtration is alternately cleaned with 2 mL methanol solution and ultrapure water respectively and dried for the next use.
S3, detection and analysis:
And (3) establishing high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS) detection and analysis methods, and respectively carrying out instrument analysis on the eluents. The method comprises the steps of detecting and analyzing eluent by adopting a high performance liquid chromatography-tandem mass spectrometry detection method, determining the content of perfluorinated compounds in a sample solution, detecting and analyzing the eluent by adopting a gas chromatography-tandem mass spectrometry detection method, determining the content of hexachloroprene in the sample solution, determining the amounts of hexachloroprene and perfluorinated compounds released by an orthodontic transparent appliance sample, and determining the amounts of Hexachloroprene (HCBD) and perfluorinated compounds released by the orthodontic transparent appliance sample.
Since the apparatus used in the high performance liquid chromatography-tandem mass spectrometry detection method and the gas chromatography-tandem mass spectrometry detection method can be selected from the existing conventional high performance liquid chromatography and gas chromatography equipment, the operation methods of analysis of the high performance liquid chromatography-tandem mass spectrometry detection method and the gas chromatography-tandem mass spectrometry detection method are conventional methods, and therefore, in this embodiment, except for the corresponding chromatographic conditions and mass spectrometry conditions, the description of the present invention will not be repeated.
The liquid chromatography-tandem mass spectrometry detection method comprises the following steps:
Chromatographic conditions:
chromatographic column Hypersil GOLD C18 (50X 2.1 mm,1.8 μm)
The mobile phase composition and gradient elution conditions are shown in Table 1
TABLE 1 Mobile phase composition and gradient elution Table
Mass spectrum parameters are shown in Table 2
Table 2 mass spectrometry parameter settings
The gas chromatography-tandem mass spectrometry detection method comprises the following steps:
the chromatographic conditions were an Agilent gas chromatographic column (30 m X0.25 mm,0.25 μm), an inlet temperature of 280℃and a column temperature of 130℃were maintained at 1min, and a temperature rise at 15℃/min to 220℃was maintained at 2 min. The carrier gas was high purity helium (99.999%) at a flow rate of 0.8 ml/min.
The mass spectrum conditions are ion source, electron bombardment energy 80 eV, mass scanning range 40-500 amu, ion source temperature 220 deg.C and solvent delay time 8 min.
In the method for detecting Hexachloroprene (HCBD) and perfluoro compounds in the orthodontic transparent appliance of the embodiment, the perfluoro compounds detected include perfluorobutyric acid (PFBA), perfluorovaleric acid (PFPe A), perfluorobutyl sulfonic acid (PFBS), perfluorooctyl sulfonic acid (PFOS) and perfluorodecyl sulfonic acid (PFDS).
In this example, the detection methods for Hexachloroprene (HCBD) and 5 perfluorinated compounds (PFBA, PFPe A, PFBS, PFOS, PFDS) were established using the methods described above. FIGS. 1 to 5 show the spectra of four different samples, namely, 2ng/g of each standard substance added to the sample solution, then pretreatment, eluent obtained after step S2 (actual sample after pretreatment), and sample solution obtained after step S1 (actual sample before pretreatment), respectively, for 5 perfluorinated compounds (PFBA, PFPe A, PFBS, PFOS, PFDS), respectively, by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) under the above-mentioned chromatographic conditions and mass spectrometry conditions. FIG. 6 shows graphs related to hexachloroprene obtained by gas chromatography-tandem mass spectrometry (GC-MS/MS) detection of four different samples, namely, hexachloroprene standard 2ng/g, eluent obtained by pretreatment after addition of hexachloroprene standard 2ng/g to a sample solution, eluent obtained after step S2 (actual sample after pretreatment), and sample solution obtained after step S1 (actual sample before pretreatment), under the above-mentioned chromatographic conditions and mass spectrometry conditions, respectively. As can be seen from FIGS. 1-6, the hexachloroprene and 5 perfluorinated compounds have good chromatographic peak shapes, and can be well separated under the current chromatographic conditions and mass spectrum conditions.
Example 2
Methodology evaluation:
In order to evaluate the analysis performance of the magnetic solid phase extraction-high performance liquid chromatography/gas chromatography-tandem mass spectrometry (MSPE-HPLC/GC-MS/MS) method established by the invention, the embodiment also respectively prepares mother solutions with the concentration of 20ng/g for the 5 perfluorinated compounds (PFBA, PFPeA, PFBS, PFOS, PFDS) and Hexachloroprene (HCBD), respectively, gradually dilutes the mother solutions into series standard working concentrations of 0.1ng/g, 0.5ng/g, 1ng/g, 2ng/g, 5ng/g, 10ng/g and 20ng/g by methanol, performs the same sample pretreatment method by referring to the method of the embodiment 1, performs magnetic solid phase extraction by using the same detection analysis method, and respectively detects the corresponding eluents by adopting a high performance liquid chromatography-tandem mass spectrometry detection method (MSPE-HPLC-MS) and a gas chromatography-tandem mass spectrometry detection method (MSPE-GC-MS) under the same chromatographic conditions, and respectively inspects the linear range, the detection limit, the quantitative limit and the relative deviation of the method, wherein the linear range, the detection limit and the relative deviation of the standard table show that the concentration of the sample represents the sample to be detected as shown by 4 x-area, and the sample concentration represents the sample to be detected by the same area. The result shows that the method has good linearity within the range of 0.10-20 ng/g (R 2 is more than or equal to 0.9982), the LODs and LOQs of the perfluorinated compounds are respectively between 0.011-0.023 and ng/g and 0.043-0.076 and ng/g, and the LODs and LOQs of the hexachloroprene are respectively 0.065ng/g and 0.216ng/g. The intra-day precision and the inter-day precision are less than 10%, which indicates that the method has lower detection limit.
TABLE 3 MSPE-HPLC-MS/MS methodological parameters
TABLE 4 MSPE GC-MS recipe parameters
Example 3
Accuracy of the method:
Target (5 perfluorinated compounds and hexachloroprene) was added to a blank sample (untreated sample solution) at three concentration levels (0.2, 2.0, 10.0 ng/g), and the standard recovery rates were measured, respectively, and the results are shown in Table 5. The standard recovery rate of the perfluorinated compounds and hexachloroprene in the sample is 82.7-104.5%, and the RSDs are less than or equal to 9.2%. The method can accurately measure the perfluorinated compounds and hexachloroprene in the sample solution of the orthodontic transparent appliance, and further accurately measure the amount of the perfluorinated compounds and hexachloroprene released by the orthodontic transparent appliance sample.
TABLE 5 MSPE-HPLC/GC-MS/MS addition recovery experiments
Example 4
And (3) detecting an actual sample:
The results of the actual sample test of example 1 are shown in table 6, and these results indicate that the established magnetic solid phase extraction-high performance liquid chromatography/gas chromatography-tandem mass spectrometry (MSPE-HPLC/GC-MS/MS) method can be used to detect hexachloroprene and perfluorinated compounds in an orthodontic appliance, and the actual results are the content of the perfluorinated compounds and the hexachloroprene released into the artificial saliva per 1g of the actual sample of the orthodontic appliance.
TABLE 6 detection results of actual samples
According to the detection method of the perfluorinated compounds and the hexachloroprene in the orthodontic transparent appliance, the perfluorinated compounds and the hexachloroprene in the orthodontic transparent appliance are released into a sample solution by simulating the oral environment of a human body, and the perfluorinated compounds and the hexachloroprene in the orthodontic transparent appliance can be simultaneously adsorbed by utilizing the characteristic that a magnetic composite material Fe 3O4 @Cl-COF can be used for simultaneously enriching the perfluorinated compounds and the hexachloroprene in the sample solution, so that a method of magnetic solid phase extraction-high performance liquid chromatography/gas chromatography-tandem mass spectrometry (MSPE-HPLC/GC-MS) is established, the perfluorinated compounds and the hexachloroprene in the orthodontic transparent appliance can be simultaneously detected qualitatively, and the content of the hexachloroprene and the perfluorinated compounds in the sample solution is determined, so that the quantity of the hexachloroprene and the perfluorinated compounds released into the artificial saliva by a sample of the orthodontic transparent appliance is further obtained, and the quantity released into the oral cavity of the human body after a user wears the orthodontic transparent appliance for 2 weeks in clinic is simulated and judged. The detection method of the perfluorochloroprene and the 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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411455059.XA CN119000958B (en) | 2024-10-18 | 2024-10-18 | Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411455059.XA CN119000958B (en) | 2024-10-18 | 2024-10-18 | Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN119000958A CN119000958A (en) | 2024-11-22 |
| CN119000958B true CN119000958B (en) | 2025-01-17 |
Family
ID=93482969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411455059.XA Active CN119000958B (en) | 2024-10-18 | 2024-10-18 | Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119000958B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102740836A (en) * | 2009-04-24 | 2012-10-17 | 伊休蒂卡有限公司 | Method for the production of commercial nanoparticle and microparticle powders |
| WO2023078376A1 (en) * | 2021-11-04 | 2023-05-11 | 华南理工大学 | Application of carboxylated covalent organic magnetic framework material as magnetic solid-phase extraction adsorbent |
-
2024
- 2024-10-18 CN CN202411455059.XA patent/CN119000958B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102740836A (en) * | 2009-04-24 | 2012-10-17 | 伊休蒂卡有限公司 | Method for the production of commercial nanoparticle and microparticle powders |
| WO2023078376A1 (en) * | 2021-11-04 | 2023-05-11 | 华南理工大学 | Application of carboxylated covalent organic magnetic framework material as magnetic solid-phase extraction adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN119000958A (en) | 2024-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Speciation analysis of inorganic arsenic in water samples by immobilized nanometer titanium dioxide separation and graphite furnace atomic absorption spectrometric determination | |
| Bakkaus et al. | Anion exchange liquid chromatography–inductively coupled plasma-mass spectrometry detection of the Co2+, Cu2+, Fe3+ and Ni2+ complexes of mugineic and deoxymugineic acid | |
| Draffan et al. | Quantitative determination of the herbicide paraquat in human plasma by gas chromatographic and mass spectrometric methods | |
| CN108276584A (en) | The detection method of aromatic amine compound in a kind of human urine | |
| CN103105437B (en) | Method for simultaneous determination of residual quantity of 8 ester allergenic aromatics in toys | |
| CN103134781B (en) | Method for determination of antimony in water sample | |
| CN112505223B (en) | Method for simultaneously detecting content of toxoflavin and content of mirostrobin in food | |
| CN119000958B (en) | Detection method of hexachloroprene and perfluorinated compounds in orthodontic transparent appliance | |
| CN102225247B (en) | Method for processing solution containing trace silver ions and adopted solid-phase extraction adsorbent | |
| Karlıdağ et al. | Determination of cobalt in chamomile tea samples at trace levels by flame atomic absorption spectrophotometry after poly (vinyl alcohol)-magnetic hydrogel based dispersive solid phase extraction | |
| Chang et al. | Synthesis and efficiency of a polyacrylacylisothiourea chelating fibre for the preconcentration and separation of trace amounts of gold, palladium and ruthenium from solution samples | |
| CN119000959B (en) | A method for detecting perfluorinated and hexabromocyclododecane compounds in orthodontic transparent appliances | |
| CN105842351B (en) | Method for rapidly detecting isothiazolinone compounds in water-based adhesive for cigarettes | |
| CN119000960B (en) | A method for detecting bisphenols and perfluorinated compounds in orthodontic transparent appliances | |
| CN105699574A (en) | Method for detecting content of cyanide in milk and milk powder | |
| CN107688073B (en) | Method for detecting content of phosphatidylserine | |
| CN105548381A (en) | Method for detecting tributyltin in marine fishes and shellfishes | |
| CN104950051B (en) | Method for detecting isothiazolinone compounds in water-based adhesive for cigarettes | |
| CN111024846B (en) | Method for measuring bisphenol A in water body | |
| CN111992184A (en) | Magnetic metal organic framework material and preparation method thereof | |
| CN102944635A (en) | Method for determining tris (2,3-dibromopropyl) phosphate content of water | |
| CN116381093A (en) | Analysis method for phthalate migration amount in enrichment sample based on magnetic MOF material | |
| CN111474279B (en) | Methods and kits for the detection of macrolide antibiotic compounds | |
| CN104297387B (en) | A kind of method detecting 4,5-bis-chloro-Kathons in seawater | |
| CN114034799A (en) | Method for detecting fluxapyroxad residual quantity in grapes |
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 |