WO2023005682A1 - Method for analyzing targeted exposure group of environmental pollutants in plasma, and use thereof - Google Patents

Method for analyzing targeted exposure group of environmental pollutants in plasma, and use thereof Download PDF

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Publication number
WO2023005682A1
WO2023005682A1 PCT/CN2022/105848 CN2022105848W WO2023005682A1 WO 2023005682 A1 WO2023005682 A1 WO 2023005682A1 CN 2022105848 W CN2022105848 W CN 2022105848W WO 2023005682 A1 WO2023005682 A1 WO 2023005682A1
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phosphate
acid
phthalate
mobile phase
bis
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PCT/CN2022/105848
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French (fr)
Chinese (zh)
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陈达
刘晓途
汤书琴
黄维
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暨南大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

Definitions

  • the invention relates to the technical fields of environmental science and organic matter analysis, in particular to a targeted exposure group analysis method for environmental pollutants in blood plasma and its application.
  • the human body is exposed to various chemical pollutants in daily life, such as plastic additives in plastic products, perfluorinated compounds in furniture products, pesticide residues in vegetables and fruits (organochlorine pesticides, organophosphorus pesticides), etc. These pollutants may enter the human body through ingestion, breathing, skin absorption, etc., and exposure of the human body to them will cause health hazards. Some pollutants have been shown to be neurotoxic, endocrine disrupting, and reproductively toxic.
  • the primary purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and provide a targeted exposure group analysis method for environmental pollutants in plasma.
  • Another object of the present invention is to provide the application of the targeted exposure group analysis method for environmental pollutants in plasma.
  • a method for analyzing targeted exposure groups of environmental pollutants in plasma comprising the steps of:
  • extraction solvent I is the mixed solvent that contains the ethyl acetate of formic acid and n-hexane; Described extraction solvent II is ethyl acetate;
  • step (3) Dry the extract obtained in step (2) with nitrogen, then add methanol to redissolve, freeze at -40 ⁇ 5°C, then freeze and centrifuge, and take the supernatant to obtain the pretreated sample;
  • step (2) Add an internal standard to the pretreated sample obtained in step (2), and then use liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and/or gas chromatography-tandem mass spectrometry (GC-MS /MS) for quantitative analysis of environmental pollutants.
  • UPLC-MS/MS liquid chromatography-tandem mass spectrometry
  • GC-MS /MS gas chromatography-tandem mass spectrometry
  • the dosage of the recovery rate indicators described in step (1) is calculated by adding 0.5-20 ng of each recovery rate indicator per 200 ⁇ L of plasma.
  • the recovery indicators described in step (1) include three 2-butoxy-[13C2]-ethyl) phosphate (Tris(2-butoxy-[13C2]-ethyl)phosphate), tri-n-butyl phosphate -d27(Tri-n-butyl phosphate-d27), Tris(2-chloroethyl)phosphate-d12(Tris(2-chloroethyl)phosphate-d12), Tris(1,3-dichloro-2-propyl ) phosphate-d15 (Tris(1,3-dichloro-2-propyl) phosphate-d15), triethyl phosphate-d15 (Triethylphosphate-d15), triphenyl phosphate-d15 (Triphenyl phosphate-d15), bis( Butoxyethyl) phosphate-d8(Bis(butoxyethyl)Phosphate-d8), bis(1,3-dichloro-2-propy
  • the plasma described in step (1) is human or animal plasma; preferably human or sheep blood plasma; more preferably human plasma.
  • the plasma described in step (1) is preferably obtained by centrifuging the collected blood, and taking the supernatant to obtain the required plasma.
  • the centrifugation condition is: centrifuge at 3000rpm for 3 minutes.
  • the added recovery indicator described in step (1) is the isotope-labeled compound of the measured target compound, which can effectively correct the loss of the compound in the pretreatment process; in the present invention, most of the target compounds have one-to-one correspondence
  • the recovery indicator if the compound cannot be one-to-one, use the isotope label corresponding to the same type of compound.
  • extraction solvent 1 described in step (2) is as follows: 298.2mL ethyl acetate, 198.8mL normal hexane and 3mL formic acid (ethyl acetate and normal hexane are by volume ratio 3:2, and formic acid accounts for 0.6 of extraction solvent 1 volume %).
  • step (2) requires 360-degree rotation and vibration to make the extraction more complete.
  • the number of repetitions described in step (2) is more than 2 times; preferably 2 times.
  • centrifugation conditions described in step (2) are: centrifugation at 3000-4000rpm for more than 3min; preferably: centrifugation at 3000rpm for 3min, the purpose of centrifugation is to precipitate suspended matter and help to transfer the extractant.
  • the freezing time described in step (3) is more than 12 hours.
  • the conditions for the refrigerated centrifugation in step (3) are: centrifuge at -10°C and 15000rpm for more than 5min.
  • step (3) the extract needs to be blown to near dryness and reconstituted with methanol for freezing.
  • the purpose is to precipitate lipids, and then it is necessary to keep low temperature in a refrigerated centrifuge for refrigerated centrifugation.
  • the purpose is to allow lipid precipitation to help The transfer of the supernatant, so as to achieve the purpose of removing lipids and reduce the matrix effect.
  • the amount of the internal standard described in step (4) is calculated by adding 1-20 ng of each internal standard per 50 ⁇ L of the pretreated sample.
  • the internal standard described in the step (4) includes internal standards of perfluorinated compounds, plasticizers (plastic additives), organochlorine pesticides, organophosphorus pesticides and liquid crystal monomers.
  • the internal standard of the perfluoro compound is perfluoro-n-[13C8]octanoic acid (Perfluoro-n-[13C8]octanoic acid; M8PFOA).
  • the positive mode internal standard of the plasticizer is coumaphos-d10 (coumaphos-d10), and the negative mode internal standard is bisphenol A-d16 (BisphenolA-d16; BPA-d16).
  • the internal standard of the organochlorine pesticide is decachlorodiphenyl ether (DCDE).
  • the positive mode internal standard of the organophosphorus pesticide is coumaphos-d10, and the negative mode internal standard is tert butyl paraben-d9.
  • the internal standard of the liquid crystal monomer is decachlorodiphenyl ether (DCDE).
  • step (4) The liquid chromatography-tandem mass spectrometry described in step (4) is carried out by using ultra-high performance liquid chromatography-tandem mass spectrometry.
  • Adopt liquid chromatography-tandem mass spectrometry described in step (4) to carry out the pollutant of quantitative analysis to environmental pollutant and comprise organophosphates (OPEs), phthalates (PAEs) ), personal care products (PCPs), phenolic compounds, ultraviolet stabilizers (UV), photoinitiators, antioxidants (AO), plasticizers, perfluorinated compounds (PFCs), organophosphorus pesticides (OPs), pyrethroids Esters, neonicotinoid pesticides, carbamate pesticides, acidic herbicides, azole pesticides, triadimefon pesticides, urea pesticides, amides pesticides, methoxyacrylate fungicides and other insecticides at least one of .
  • organophosphates OPEs
  • PAEs phthalates
  • PCPs personal care products
  • PFCs perfluorinated compounds
  • OPs organophosphorus pesticides
  • the organophosphates include at least one of organophosphate diesters and organophosphate triesters.
  • organophosphate diesters include bis-(1-chloro-2-propyl) phosphate (bis-(1-chloro-2-propyl) phosphate), diphenyl phosphate (Diphenyl phosphate) , dibutyl phosphate (Dibutyl phosphate), bis (1,3-dichloro-2-propyl) phosphate (Bis (1,3-dichloro-2-propyl) phosphate), two p-cresyl phosphate (di -p-tolyl-phosphate), bis(butoxyethyl)phosphate and bis(2-ethylhexyl)phosphate.
  • organophosphate triesters include triethyl phosphate (Triethyl phosphate), three (2-chloroethyl) phosphate (Tris (2-chloroethyl) phosphate), tripropyl phosphate (Tripropyl phosphate) , Tetrakis (2-Chloroethyl) dichloroisopentyl diphosphate, Triphenyl phosphate, Tris (2,3-dibromopropyl) phosphate (Tris(2,3-dibromopropyl)phosphate), Tributylphosphate, Cresyldiphenylphosphate, Tris(2-butoxyethyl)phosphate (Tris(2-butoxyethyl) phosphate), Tricresyl phosphate, Resorcinol bis(diphenyl phosphate), 2-Ethylhexyl-diphenyl phosphate (2-Ethylhexyl), 2-Ethylhexyl
  • the phthalic acid esters include at least one of phthalic acid monoesters and phthalic acid diesters.
  • the phthalate monoesters include monoethyl phthalate, monoisopropyl phthalate, monoisobutyl phthalate ), mono-n-pentyl phthalate, monocyclohexyl phthalate, monohexylphthalate, monobenzyl phthalate (monobenzyl phthalate), mono-2-heptyl phthalate (mono-2-heptyl phthalate), monooctyl phthalate (monoctyl phthalate), monoethylhexyl phthalate (monoethylhexyl phthalate), Monoisononyl phthalate (monoisononyl phthalate), mono(2-ethyl-5-oxohexyl) phthalate (mono(2-ethyl-5-oxohexyl) phthalate), mono(2-ethyl-5-oxohexyl) phthalate 2-Ethyl-5-hydroxyhexyl) este
  • the phthalate diesters include dimethyl isophthalate, dimethyl phthalate, diethyl phthalate , Diallyl phthalate, di-n-propyl phthalate, Diisopropyl phthalat, Diisobutyl phthalate Diisobutyl phthalate, dibutyl phthalate, isobutylcyclohexyl phthalate, diisopentyl phthalate, butyl phthalate Benzyl ester (butyl benzylphthalate), diphenyl isophthalate (diphenyl isophthalate), diphenyl phthalate (diphenylphthalate), dihexyl phthalate (dihexyl phthalate), diisohexyl phthalate ( diisohexylphthalate), bis(4-methyl-2-pentyl)phthalate, dibenzyl phthalate, diheptyl phthalate Diisoheptyl phthalate, dinonyl phthal
  • the personal care products include methyl paraben, butyl Paraben, benzyl Paraben, ethyl paraben Ethylparaben, Propylparaben, Heptylparaben and Triclosan.
  • the phenolic compound includes at least one of bisphenol analogues.
  • Described bisphenol analog includes bisphenol A (bisphenol A), bisphenol E (bisphenol E), bisphenol B (bisphenol B), bisphenol C (bisphenol C), bisphenol AF (bisphenol AF), bisphenol F (bisphenol F), bisphenol M (bisphenol M), bisphenol P (bisphenol P), bisphenol G (bisphenol G), bisphenol Z (bisphenol Z), bisphenol S (bisphenol S), bisphenol AP (bisphenol AP), bisphenol BP (bisphenol BP) and bisphenol PH (bisphenol PH).
  • the ultraviolet stabilizer includes at least one of benzophenones, benzothiazoles, benzotriazoles and other types of ultraviolet stabilizers.
  • Benzophenone UV stabilizers include 2,4-dihydroxybenzophenone (2,4-dihydroxybenzophenone), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'-tetrahydroxybenzophenone), 2-hydroxy-4-methoxybenzophenone (2-hydroxy-4-methoxybenzophenone), 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid benzophenone (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2'-dihydroxy-4 ,4'-dimethoxybenzophenone), 2,2'-hydroxy-4-methoxybenzophenone (2,2'-dihydroxy-4-methoxybenzophenone), 4-hydroxybenzophenone (4-hydroxybenzophenone) and 2 ,3,4-trihydroxybenzophenone (2,3,4-trihydroxybenzophenone (2,3,4-trihydroxy
  • Benzothiazoles UV stabilizers include 2-methylbenzothiazole (2-methylbenzothiazole), 2-benzothiazolyl-N-morpholinothioether (2-(morpholinothio)- benzothiazole), 2-(methylthio)benzothiazole), 2-aminobenzothiazole and 2-hydroxybenzothiazole.
  • Described benzotriazole UV stabilizers include 1-hydroxybenzotriazole (1-hydroxybenzotriazole), 5-methyl-1-hydrogenbenzotriazole (5-methyl-1-hydrogenbenzotriazole), 5-chlorobenzotriazole (5-chloro-1-hydrogenbenzotriazole), 4-methyl-1-hydrobenzotriazole (4-methyl-1H-benzotriazole), 2-(2'-hydroxyl-5 '-Methylphenyl)benzotriazole (2-(2-Hydroxy-5-methylphenyl)benzotriazole), 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole (2-(5 -tert-butyl-2-hydroxyphenyl)benzotriazole) and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole (2-(3,5-Di-tert-butyl-2-hydroxyphenyl-2-hydroxyphenyl)-
  • UV stabilizers include 4-tert-butyl-4'-methoxydibenzoylmethane (4-tert-butyl-4'-methoxydibenzoylmethane), 4-methylbenzylidene 4-methylbenzylidene camphor, isoamyl4-methoxycinnamate, isooctyl 2-cyano-3,3-diphenylacrylate (2-ethylhexyl2-cyano-3,3- diphenyl-2-propenoate(liquid)), octyl dimethyl-p-aminobenzoic acid, Ethylhexyl methoxycinnamate, 2-(2H-benzotriazole -2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl )phenol), 2,4-di
  • Described photoinitiator comprises benzophenone (benzophenone), 4-methylbenzophenone (4-methylbenzophenone), 1-hydroxycyclohexylphenyl ketone (1-hydroxycyclohexylphenyl ketone), 4-phenyl 4-phenylbenzophenone/4-benzoylbiphenyl, 1,2-diphenyl-1,2-ethanedione (1,2-diphenyl-1,2-ethanedione), 2-ethylanthraquinone (2-ethylanthraquinone), methyl-2-(benzoyl)benzoate (methyl-2-(benzoyl)benzoate), 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2- phenylacetophenone), p-dimethylaminobenzophenone (4-(dimethylamino)benzophenone), 4,4'-bis(dimethylamino)benzophen
  • the antioxidants include antioxidants detected in positive ion detection mode and negative ion detection mode.
  • the antioxidants detected under negative ion detection mode include 3-tert-butyl-4-hydroxyanisole (3-tert-butyl-4-hydroxyanisole), 3,5-di-tert-butyl-4-hydroxybenzene Formaldehyde (3,5-di-tert-butyl-4-hydroxybenzoic acid), 3,5-di-tert-butyl-4-hydroxybenzoic acid (3,5-di-tert-butyl-4-hydroxybenzoic acid), 2, 6-di-tert-butyl-4-(hydroxymethyl)phenol (2,6-di-tert-butyl-4-(hydroxymethyl)phenol), 2,4-di-tert-butylphenol (2,4-di- tert-butylphenol), 4,4'-butylene bis(6-tert-butyl-m-cresol) (4,4'-butylidenebis(6-tert-butyl-m-cresol)), 4-(1,1 ,3,3-tetramethylbuty
  • the antioxidants detected under the positive ion detection mode include 1,3-di-o-tolylguanidine (1,3-di-o-tolylguanidine), 1,3-diphenyl-2-thiourea (1, 3-diphenyl-2-thiourea), 2,2'-ethylene-bis(4,6-di-tert-butylphenol) (2,2'-ethylene-bis(4,6-di-tert-butylphenol) ), methyl-2-mercaptobenzimidazole (methyl-2-mercaptobenzimidazole), 11-methyldodecyl 3-[4-hydroxyl-3,5-bis(2-methyl-2-propanyl) Phenyl]propanoate (11-Methyldodecyl3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate), dibenzylhydroxylamine, tri(4-tert-butyl -3-hydroxy-2,6-dimethylbenzyl
  • plasticizers comprises diethyl succinate (diethyl succinate), dimethyl adipate (dimethyl adipate), diethyl adipate (diethyl adipate), dimethyl azelate ( dimethylazelate), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol-diisobutyrate), dibutyl fumarate ( dibutyl fumarate), dimethylsebacate, isopropyl myristate, triethyl citrate, diethylene glycol dibenzoate, decyl Dibutylsebacate, Isopropyl palmitate, Acetyl triethylcitrate, n-Propyl oleate, Di(2-ethyl maleate) Hexyl) ester (Di(2-ethylhexyl) maleate), di
  • the perfluorinated compounds include perfluoron-octanoic acid (Perfluoro-n-octanoic acid), perfluorooctane sulfonic acid (perfluorooctane sulfonic acid), perfluoron-butanoic acid (Perfluoro-n-butanoic acid), perfluoron-heptyl Perfluoro-n-heptanoic acid, Perfluoro-n-hexanoic acid, Perfluoro-n-decanoic acid, Perfluoro-n-dodecanoic acid ), Perfluoro-n-nonanoic acid, Perfluoro-n-undecanoic acid, Perfluoro-n-pentanoic acid, Perfluoro-n-decanoic acid Perfluoro-n-tetradecanoic acid, Perfluoro-n-tridecanoic acid, Potassium perfluoro-1-butanesul
  • the organophosphorus pesticides include chlorpyrifos (dursban/chlorpyrifos), diazinon (diazinon), methyl parathion (parathion-methyl), parathion (parathion), malathion (malathion), dimethoate ( dimethoate), dichlorvos (dichlorvos), 3-methyl-4-nitrophenol (3-methyl-4-nitrophenol), coumaphos, dioxabenzofos, edifenphos, 2-isopropyl-6-methyl-4-pyrimidinol (2-isopropyl-6-methyl-4-pyrimidinol), isofenphos-methyl, mecarbam, insecticides (methacrifos ), phosalone, pyrazophos and p-Nitrophenol.
  • Described pyrethroids include 3-phenoxybenzyl alcohol (3-PBA), 4-fluoro-3-phenoxybenzoic acid (4-fluoro-3-phenoxybenzoic acid), cis-3-(2- Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl-cyclopropanecarboxylic acid (cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl )-2,2-dimethyl-cyclopropanecarbox ylic acid) and Lambda-cyhalothrin.
  • 3-phenoxybenzyl alcohol (3-PBA)
  • 4-fluoro-3-phenoxybenzoic acid (4-fluoro-3-phenoxybenzoic acid)
  • Lambda-cyhalothrin Lambda-c
  • the neonicotinoid pesticides include Acetamiprid, Dinotefuran, Imidacloprid, Thiacloprid and Thiamethoxam.
  • the carbamate pesticides include Carbendazim, Carbofuran, Chlorpropham, Fenobucarb, Iprovalicarb, Methomyl, anti Pirimicarb and Propham.
  • the acidic herbicides include 2,4-dichlorophenoxybutyric acid (2,4-DB), 2,4,5-propionic acid (2,4,5-TP (Silvex)), 2,4 ,5-trichlorophenoxyacetic acid (2,4,5-trichlorophenoxyacetic acid), 2,4-dichlorprop, 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2-methyl- 4-chloropentyloxypropionic acid (Mecoprop) and 2-methyl-4-chlorophenoxybutyric acid (MCPB).
  • the azole pesticides include Bitertanol, Cyproconazole, Difenoconazole, Epoxiconazole, Fenbuconazole, Flusilazole (Flusilazole), Imazalil, Myclobutanil, Penconazole, Prochloraz, Tebuconazole, Tetraconazole, and Thiabendazole ).
  • the triadimefon pesticides include Chloridazon, Hexazinone, Metamitron, Metribuzin, Atryn, Atraton ), atrazine, prometon, prometryn, propazine, secbumeton, simazine, simetryn and Terbutryn/prenane.
  • the urea pesticides include Chloroxuron, Chlortoluron, 1-(3,4-dichlorophenyl)-3-methylurea (1-(3,4-dichlorophenyl)- 3-methylurea), 1-(3,5-dichlorophenyl)urea (DCPU), Methabenzthiazuron, Metobromuron, Metoxuron, Diuron ), 3-phenyl-1,1-dimethylurea (Fenuron), isoproturon (Isoproturon) and Linuron (Linuron).
  • the amide pesticides include Alachlor, Dimethachlor, N,N-dimethylamino-N-toluene (DMST) and Fenhexamid.
  • the methoxyacrylate fungicides include Azoxystrobin, Fluacrypyrim, Kresoxim-methyl, Pyraclostrobin and Trifloxystrobin .
  • insecticides mentioned include Flutolanil, Boscalid, Famoxadone, Metalaxyl, Nuarimol, and procarbal (Prosulfocarb).
  • step (4) The gas chromatography-tandem mass spectrometry described in step (4) is carried out by using gas chromatography-tandem mass spectrometry.
  • the pollutants for quantitative analysis of environmental pollutants by gas chromatography-tandem mass spectrometry (GC-MS/MS) described in step (4) include at least one of organochlorine pesticides and liquid crystal monomers.
  • the organochlorine pesticides include dichloropropionic acid (Aldrin), ALPHA-666 ( ⁇ -HCH), BETA-666 ( ⁇ -HCH), Lindane ( ⁇ -HCH (lindane)), ⁇ -6 66 ( ⁇ -HCH), ⁇ -666 ( ⁇ -HCH), cis-chlordane (cis-chlordane), trans-chlordane (trans-chlordane), oxy-chlordane (oxy-chlordane), 4,4-Didididi (p.p′-DDD), 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p.p′-DDE), 2,2-bis(p-chlorobenzene base)-1,1,1-trichloroethane (p.p′-DDT), 1-(2-chlorophenyl)-1-(4-chlorophenyl)-2,2-dichloroethane (o.p '-DDD), 3-o-chlor
  • the liquid crystal monomers include 4-vinyl-4'-propyl-1,1'-bicyclohexyl (1-(4-propylcyclohexyl)-4-vinylcyclohexane), 1-methoxy-4-( 4-propylcyclohexyl) cyclohexane (1-methoxy-4-(4-propylcyclohexyl)cyclohexane), 1-(prop-1-enyl)-4-(4-propylcyclohexyl)cyclohexane ( 1-(prop-l-enyl)-4-(4-propylcyclohexyl)cyclohexane), 1-ethoxy-2,3-difluoro-4-(4-propylcyclohexyl)benzene (1-ethoxy-2 ,3-difluoro-4-(4-propylcyclohexyl)benzene), 4-methyl-4'-pentyl biphenyl (4-methyl-4'-
  • Chromatographic conditions include:
  • Mobile phase A 0.1% formic acid aqueous solution by volume fraction
  • Chromatographic column C18 chromatographic column (preferably: Luna 2.5 ⁇ m C18(2)-HST 100 ⁇ 2.0mm);
  • the initial volume percentage of mobile phase B is 40%; 0 ⁇ 2min, the volume percentage of mobile phase B rises from 40% to 70%; 2 ⁇ 8min, the volume percentage of mobile phase B rises to 100%; Keep at 100% for 13 minutes, the volume percentage of mobile phase B drops to 40% at 13-13.1 minutes; keep at 40% for 13.1-17 minutes;
  • Mass spectrometry conditions include: electrospray ionization source, ion source temperature is 550°C; detection mode is positive ion detection mode;
  • Atomization pressure nitrogen, the pressure is 55psi;
  • Chromatographic conditions include:
  • Chromatographic column C18 chromatographic column (preferably: ZORBAX Extended-C18 3.5 ⁇ m 100 ⁇ 2.1mm);
  • the volume percentage of the initial mobile phase B is 10%; 0-0.5min keeps the number constant at 10%; 0.5-1min, the volume percentage of the mobile phase B rises from 10% to 50%; B volume fraction increased from 50% to 99%; 7-10min, kept at 99%; 10-10.1min, decreased from 99% to 10%, 10.1-12min, mobile phase B volume fraction remained at 10% ;
  • Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
  • 3Plasticizers plasticizers
  • benzothiazoles Benzothiazoles UV stabilizers
  • benzotriazoles benzotriazoles UV stabilizers
  • other UV stabilizers other UV stabilizers
  • Chromatographic conditions include:
  • Mobile phase A 0.1% formic acid aqueous solution by volume fraction
  • Chromatographic column C18 chromatographic column (preferably: Luna 2.5 ⁇ m C18(2)-HST 100 ⁇ 2.0mm);
  • initial mobile phase B volume percentage is 40%, 0-2min keeps 40% unchanged; 2-4min, mobile phase B volume percentage rises from 40% to 80%; 4-14min, mobile phase B volume percentage increases from 80% rises to 100%; 14-17min, the volume percentage of mobile phase B remains at 100%; 17-20min, the volume percentage of mobile phase B drops to 40%, 20-24min, the volume percentage of mobile phase B remains at 40% constant;
  • Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is positive ion detection mode; atomization pressure: nitrogen, pressure 55psi;
  • Chromatographic conditions include:
  • Mobile phase A a volume fraction of 0.1% formic acid in water
  • Chromatographic column RP18 chromatographic column (preferably: ACQUITY UPLC BEH Shield RP18, 1.7 ⁇ m, 100 ⁇ 2.1mm);
  • initial mobile phase B volume percentage is 5%, 0-1min maintains at 5%; 1-3min mobile phase B volume fraction rises from 5% to 40%; 3-12min rises from 40% to 100%; 12 From 15 minutes to 15 minutes, keep 100% unchanged; from 15 to 15.1 minutes, the volume percentage of mobile phase B decreases from 100% to 5%; from 15.1 to 18 minutes, the volume percentage of mobile phase B remains unchanged at 5%;
  • Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
  • Chromatographic conditions include:
  • Chromatographic column RP18 chromatographic column, preferably: ACQUITY UPLC BEH Shield RP18, 1.7 ⁇ m, 100 ⁇ 2.1mm);
  • initial mobile phase B volume percentage is 5%, 0 ⁇ 4min, rise from 5% to 35%; 4 ⁇ 7min, B phase volume fraction rises from 35% to 80%; 7 ⁇ 12min, rise from 80% to 100%; 12-14min keep 100% unchanged; 14-15min, mobile phase B volume percentage decreases from 100% to 5%; 15-20min, mobile phase B volume percentage remains unchanged at 5%;
  • Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
  • Chromatographic conditions include:
  • Mobile phase A 4mmol/L ammonium acetate aqueous solution
  • Chromatographic column C18 chromatographic column, preferably: Luna 2.5 ⁇ m C18(2)-HST 100 ⁇ 2.0mm;
  • the initial volume percentage of mobile phase B is 10%; 0-0.5min keeps 10% unchanged; 0.5-1min the volume percentage of mobile phase B increases from 10% to 50%, and 1-7min rises to 99%; From 7 to 10 minutes, it remained at 99%; from 10 to 10.1 minutes, the volume percentage of mobile phase B dropped rapidly to 10%; from 10.1 to 12 minutes, the volume percentage of mobile phase B remained unchanged at 10%;
  • Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
  • Chromatographic conditions include:
  • Chromatographic column RP18 chromatographic column, preferably: ACQUITY UPLC BEH Shield RP18, 1.7 ⁇ m; 100 ⁇ 2.1mm;
  • initial mobile phase B volume percentage is 40%; 40% remains unchanged within 0-2min, mobile phase B volume percentage rises to 66% in 2-3min; rises to 77% in 3-12min; mobile phase in 12-14min B volume fraction rises from 70% to 100%, and remains unchanged at 100% for 14-16 minutes; quickly drops to 40% for 16-16.1 minutes; 16.1-22 mobile phase B volume fraction remains unchanged at 40%;
  • Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
  • 8Organophosphorus pesticides Pyrethroids, Neonicotinoids, Carbamates, Acidherbicides, Azoles, Triazoles Ketone pesticides (Triazines/triazone), urea pesticides (Urea), amide pesticides (amide pesticides, Amide pesticides), methoxyacrylate fungicides (Strobilurins), other pesticides (Other Pesticides):
  • Chromatographic conditions include:
  • Chromatographic column C18 chromatographic column, preferably: Kinetex 2.6 ⁇ m C18 100*2.1mm; 00D4462-AN;
  • the volume percentage of the initial mobile phase B is 2%; the volume percentage of the mobile phase B increases from 2% to 30% in 0-4min; the volume percentage of the mobile phase increases from 30% to 68% in 4-22min; 22-22.1 Min mobile phase B increased from 68% to 99%; 22.1 ⁇ 23min, kept at 99%; 23 ⁇ 23.1min, mobile phase B volume percentage decreased from 99% to 2%; 23.1 ⁇ 26min, kept 2% unchanged ;
  • Mass spectrometry conditions electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi.
  • step (4) The detection condition of gas chromatography-tandem mass spectrometry described in step (4) is as follows:
  • Chromatographic conditions include:
  • Injection port temperature 260°C;
  • Heating program initial temperature is 60°C, keep for 1min; heat up to 300°C at a rate of 5°C/min, then keep for 9min;
  • Mass spectrometry conditions electron bombardment ion source, ion source temperature is 230°C, quadrupole temperature is 150°C, solvent delay is 3min;
  • Chromatographic conditions include:
  • Injection port temperature 260°C;
  • Heating program initial temperature 80°C, keep for 2.5min; then raise the temperature to 200°C at a rate of 25°C/min and keep for 1min; then rise to 250°C at a rate of 10°C/min and then rise to 285°C at a rate of 5°C/min , keep for 5min; finally rise to 300°C at the speed of 30°C/min, keep for 1min;
  • Mass spectrometry conditions electron bombardment ion source, ion source temperature 230°C, quadrupole temperature 150°C, solvent delay 6min.
  • the present invention has the following advantages and effects:
  • the present invention provides a high-throughput and convenient method for targeted exposure group analysis of environmental pollutants in human plasma. This method can simultaneously detect various types of environmental pollutants in plasma, and the pre-treatment is convenient.
  • the analysis time is short, the cost is low, the analysis efficiency can be improved to the greatest extent, and it can provide technical support for the follow-up observation and detection of the mixed effect of pollutants in the environment on human health.
  • the method of the present invention can simultaneously analyze hundreds of different kinds of environmental pollutants in blood plasma, and the processing method is simple, time-consuming and efficient.
  • the extract when the plasma sample is pretreated, the extract is blown to near dryness and redissolved with methanol for freezing to allow the lipid to separate out, and then it is necessary to keep the low temperature in a refrigerated centrifuge for refrigerated centrifugation to allow the lipid to precipitate It is helpful for the transfer of supernatant, so as to achieve the purpose of removing lipid, reduce matrix effect, and improve the recovery rate of standard addition.
  • Fig. 1 is the comparison result graph of the recovery rate of standard addition of the method of the present invention and comparative example 1.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • the test methods that do not indicate the specific experimental conditions in the following examples, usually follow the routine experimental conditions or the experimental conditions suggested by the manufacturer.
  • the reagents and raw materials used in the present invention can be obtained commercially.
  • the extraction solvent involved in the embodiment that is, the ethyl acetate and normal hexane in the mixed solvent containing 0.6% formic acid ethyl acetate and normal hexane are at least LC-MS level, and the volume ratio of ethyl acetate and normal hexane is 3: 2.
  • Example 1 Targeted exposome analysis of environmental pollutants in human plasma
  • a total of 377 standard compounds and 74 isotope-labeled chemical substances used as recovery indicators or internal standards were purchased from AccuStandard Company of the United States, Sigma-Aldrich Company of the United States, Wellington Laboratory of Canada and Toronto Research Chemicals of Canada; including 39 kinds Organophosphate esters (OPEs) (including organophosphate diesters and organophosphate triesters), 36 phthalates (PAEs) (including phthalate monoesters and phthalate diesters) , 7 kinds of personal care products (PCPs), 14 kinds of phenolic compounds (bisphenol analogues), 29 kinds of ultraviolet stabilizers (UV) (including benzophenones, benzothiazoles, benzotriazoles and other categories UV stabilizers), 15 photoinitiators, 34 antioxidants (AO) (including positive and negative ion detection modes), 31 plasticizers, 25 perfluorinated compounds (PFCs), 18 organophosphorus pesticides (OPs) , 24 kinds of organochlorine pesticides (
  • the target analytes were determined by ultra-high performance liquid chromatography-mass spectrometer (5500Q Trap triple quadrupole-linear ion Trap mass spectrometer) and gas chromatography-tandem mass spectrometer (7890B-5970A).
  • the instrument was purchased from AB Sciex Company in Toronto, Canada; the gas chromatography tandem mass spectrometer was purchased from Agilent Company in the United States; the nitrogen blowing instrument (12N-EvapTM) used in the experiment was purchased from Oganomation Company; the centrifuge was purchased from Hunan Xiangyi Company; the refrigerated centrifuge Purchased from Thermo Fisher Scientific; the oscillator was purchased from Kylin-Bell; the reagents used in the experiment were all LC-MS grade and purchased from Thermo Fisher Scientific.
  • Plasma samples were collected at the Third affiliated Hospital of Sun Yat-Sen University (Guangzhou, China) and collected with blood collection tubes (BD, USA). The collected plasma was centrifuged at 3000rpm for three minutes to separate plasma and blood cells, and the supernatant was transferred to a glass bottle and stored at -80°C before analysis. A total of 10 volunteer plasma samples were collected in this experiment.
  • organophosphate diester Phthalate recovery rate indicator 5ng organophosphate triesters recovery rate indicator 2ng, phthalic acid monoesters recovery rate indicator 2ng, phthalic acid diesters recovery rate indicator 1ng, personal care product recovery rate indicator Object 2ng, bisphenol analogue recovery indicator 2ng, benzophenone UV stabilizer recovery indicator 5ng, benzothiazole UV stabilizer recovery indicator 5ng, benzotriazole UV stabilizer recovery Indicator 5ng, other categories of UV stabilizer recovery indicator 5ng, photoinitiator recovery indicator 5ng, antioxidant recovery indicator 5ng, plasticizer recovery indicator 5ng, perfluorinated compound recovery indicator 0.5ng, organophosphorus pesticide Recovery rate indicator 5ng, organochlorine pesticide recovery rate indicator 20ng, pyrethroid recovery rate
  • BPA-d16 bisphenol A-d16
  • M8PFOA perfluorochemical internal standard perfluoro-n-[13C8]octanoic acid
  • M8PFOA perfluoro-n-[13C8]octanoic acid
  • DCDE Decachlorodiphenyl ether
  • the target compounds were quantitatively analyzed on ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), with a total of 8 analysis methods , the specific information is shown in Tables 2 and 3. in:
  • the mass spectrometry conditions in LC-MS/MS include: electrospray ion source, ion temperature is 550°C, detection mode is shown in Table 2; atomization pressure: nitrogen, pressure position 55psi;
  • the mass spectrometry conditions in GC-MS/MS include: electron bombardment ion source, ion source temperature of 230°C, quadrupole temperature of 150°C, solvent delay of 3min (organochlorine pesticide) or 6min (liquid crystal monomer).
  • the quality assurance and quality control procedures tested the recovery of the program blank and recovery indicators, while matrix-spiked samples were analyzed.
  • two laboratory program blanks were processed at the same time, and 200 ⁇ L of ultrapure water was used to replace the actual sample to prepare the program blank.
  • the processing process was the same as that of the actual sample, and was repeated three times.
  • the isotope standard recoveries of all samples were calculated by integrating with AB Sciex 5500 Q Trap triple quadrupole-linear ion trap mass spectrometer analysis software Analyst 1.6.3 software, ranging from 50% to 110%.
  • Each type of compound was quantified using a standard curve with more than five concentration levels, and the correlation coefficient of the standard curve was greater than 0.995.
  • the limit of quantification (LOQ) of the method is defined as the concentration of the compound corresponding to the response of 3 times or 10 times the standard deviation of the noise. If the calculated LOQ is lower than the background contamination value in the blank, use the highest blank Concentrations were used as LOQ.
  • the LOQs of all compounds are shown in Table 1.
  • the output rate is greater than 70%, of which perfluorooctanoic acid (PFOA), sodium perfluoro-1-heptane sulfonate (L-PFHxS), sodium perfluoro-1-hexanesulfonate (L-PFHpS), perfluoro-n-nonanoic acid (PFNA), perfluorooctanesulfonic acid (PFOS), perfluoron-decanoic acid (PFDA), perfluoron-undecanoic acid (PFUdA), 9-chlorohexadecafluoro-3-oxane-1 -Potassium sulfonate (9Cl-PF3ONS), 11-chloroeicosfluoro-3-oxetane-1-potassium sulfonate (11Cl-PF3OUdS) detection rate
  • Step (2) was repeated for the second extraction, and the extraction solvent was changed to ethyl acetate for the third extraction, and three extracts were combined;
  • the extract was blown to 1mL and then added with 3mL volume fraction of 0.6% aqueous formic acid for dilution, then concentrated to 3mL by nitrogen blowing, and the HLB column ( PRiME HLB 3cc (60mg) Extraction Cartridges) were placed on the SPE extraction device, and then the HLB column was pre-washed sequentially with 3mL methanol and 3mL water;
  • the recovery indicator and internal standard added by the above method are the same as those used in Example 1, only the pretreatment method is different.
  • Method 1 is the method used in Example 1, and Method 2 is the method used in Comparative Example 1.
  • the recovery rate of standard addition in method 1 is mostly around 70-100%, which is relatively stable and meets the standard.
  • the recovery rate of standard addition in method 2 is relatively scattered and unstable, and the recovery rate is relatively low compared to method 1. , and some compounds even had spiked recoveries of 0%. This result shows that method 2 has strong matrix interference, and overall, method 1 is significantly better than method 2.

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Abstract

Disclosed in the present invention are a method for analyzing a targeted exposure group of environmental pollutants in blood plasma, and the use thereof. The method comprises the following steps: (1) adding a recovery indicator to plasma to obtain a mixture of the plasma and the recovery indicator; (2) adding a mixed solvent of ethyl acetate and n-hexane that contains formic acid to perform extraction, then adding ethyl acetate to perform extraction, and combining extraction solutions; (3) performing blow-drying on the extraction solution using nitrogen, then adding methanol for redissolution, then freezing and centrifuging same, and taking a supernatant to obtain a pretreated sample; (4) adding an internal standard to the pretreated sample, and then performing quantitative analysis on environmental pollutants by means of using a liquid chromatography-tandem mass spectrometry and/or a gas chromatography-tandem mass spectrometry. The method in the present invention can realize the simultaneous detection of hundreds of different types of environmental pollutants in plasma, has a simple and convenient processing method, a short analysis time and is low cost, and can maximize analytical efficiency.

Description

一种血浆中环境污染物靶向暴露组分析方法及其应用A method for targeted exposure group analysis of environmental pollutants in plasma and its application
本申请要求于2021年07月27日提交中国专利局、申请号为202110849180.0、发明名称为“一种血浆中环境污染物靶向暴露组分析方法及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on July 27, 2021, with the application number 202110849180.0, and the title of the invention is "A Method for Targeting Exposureome Analysis of Environmental Pollutants in Plasma and Its Application". The entire contents are incorporated by reference in this application.
技术领域technical field
本发明涉及环境科学及有机物分析技术领域，特别涉及一种血浆中环境污染物靶向暴露组分析方法及其应用。The invention relates to the technical fields of environmental science and organic matter analysis, in particular to a targeted exposure group analysis method for environmental pollutants in blood plasma and its application.
背景技术Background technique
人体在日常生活中会接触到各种化学污染物，例如塑料用品中的塑料添加剂、家具用品中的全氟化合物、蔬菜水果中的残留的农药(有机氯农药、有机磷农药)等。而这些污染物可能通过摄食、呼吸、皮肤吸收等途径进入人体，人体暴露其中对健康产生危害。一些污染物已经被证实具有神经毒性，内分泌干扰性以及生殖毒性。The human body is exposed to various chemical pollutants in daily life, such as plastic additives in plastic products, perfluorinated compounds in furniture products, pesticide residues in vegetables and fruits (organochlorine pesticides, organophosphorus pesticides), etc. These pollutants may enter the human body through ingestion, breathing, skin absorption, etc., and exposure of the human body to them will cause health hazards. Some pollutants have been shown to be neurotoxic, endocrine disrupting, and reproductively toxic.
化学用品的使用促进了社会的发展，但同时也给环境造成了污染，以致对人体人健康产生危害。目前已有许多研究表明人体暴露于各种各样的环境污染物中，但人体血浆中的环境污染物的研究大多数都是关注单一或者一类的化合物，对于多种环境污染物的混合效应的研究比较缺乏，同时一些新型添加剂或环境污染物的暴露对人体产生的健康危害仍然未知，例如日常生活使用的手机和电脑等电子设备的屏幕中，一些液晶单体的释放也可能使人体暴露在其中产生危害。The use of chemicals promotes the development of society, but at the same time it also pollutes the environment, causing harm to human health. At present, many studies have shown that the human body is exposed to a variety of environmental pollutants, but most of the research on environmental pollutants in human plasma focuses on a single or a class of compounds, and the mixed effects of multiple environmental pollutants At the same time, the health hazards caused by the exposure of some new additives or environmental pollutants to the human body are still unknown. For example, the release of some liquid crystal monomers in the screens of electronic devices such as mobile phones and computers used in daily life may also expose the human body to harm in it.
要想实现研究多种化学污染物混合效应，前提是能同时检出血浆中的多种不同的环境污染物，因此亟需开发一种能快速检测到人体血液中不同的环境污染物的方法。由于当前一些检测方法前处理过程复杂、耗时久并且成本过高，检测化合物的种类单一，因此建立简便高效且成本低的人体血浆中环境污染物靶向暴露组分析方法很有必要，可以为后续评价各类环境污染物对人体的健康影响提供技术条件。In order to study the mixed effect of various chemical pollutants, the premise is that a variety of different environmental pollutants in plasma can be detected at the same time, so it is urgent to develop a method that can quickly detect different environmental pollutants in human blood. Due to the complex, time-consuming and high cost of the pretreatment process of some current detection methods, and the single type of detection compounds, it is necessary to establish a simple, efficient and low-cost targeted exposure group analysis method for environmental pollutants in human plasma. Provide technical conditions for follow-up evaluation of the impact of various environmental pollutants on human health.
发明内容Contents of the invention
本发明的首要目的在于克服现有技术的缺点与不足，提供一种血浆中环境污染物靶向暴露组分析方法。The primary purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and provide a targeted exposure group analysis method for environmental pollutants in plasma.
本发明的另一目的在于提供所述血浆中环境污染物靶向暴露组分析方法的应用。Another object of the present invention is to provide the application of the targeted exposure group analysis method for environmental pollutants in plasma.
本发明的目的通过下述技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种血浆中环境污染物靶向暴露组分析方法，包括如下步骤：A method for analyzing targeted exposure groups of environmental pollutants in plasma, comprising the steps of:
(1)将回收率指示物添加到血浆中，混合均匀，得到血浆和回收率指示物的混合物；(1) Add the recovery rate indicator to the plasma and mix evenly to obtain a mixture of the plasma and the recovery rate indicator;
(2)向步骤(1)中得到的血浆和回收率指示物的混合物中加入萃取溶剂I进行萃取，离心，取上清，重复此步骤1次以上；再加入萃取溶剂II进行萃取，得到萃取液；其中，所述萃取溶剂I为含有甲酸的乙酸乙酯和正己烷的混合溶剂；所述萃取溶剂II为乙酸乙酯；(2) Add extraction solvent I to the mixture of plasma and recovery indicator obtained in step (1) for extraction, centrifuge, take the supernatant, repeat this step more than 1 time; then add extraction solvent II for extraction to obtain the extracted Liquid; Wherein, described extraction solvent I is the mixed solvent that contains the ethyl acetate of formic acid and n-hexane; Described extraction solvent II is ethyl acetate;
(3)将步骤(2)中得到的萃取液用氮气吹干，然后加入甲醇复溶后，置于-40±5℃下进行冷冻，然后冷冻离心，取上清液，得到预处理后的样品；(3) Dry the extract obtained in step (2) with nitrogen, then add methanol to redissolve, freeze at -40±5°C, then freeze and centrifuge, and take the supernatant to obtain the pretreated sample;
(4)向步骤(2)中得到的预处理后的样品中加入内标，然后利用液相色谱-串联质谱法(UPLC-MS/MS)和/或气相色谱-串联质谱法(GC-MS/MS)对环境污染物进行定量分析。(4) Add an internal standard to the pretreated sample obtained in step (2), and then use liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and/or gas chromatography-tandem mass spectrometry (GC-MS /MS) for quantitative analysis of environmental pollutants.
步骤(1)中所述的回收率指示物的用量为按每200μL血浆加入每种回收率指示物0.5～20ng计算。The dosage of the recovery rate indicators described in step (1) is calculated by adding 0.5-20 ng of each recovery rate indicator per 200 μL of plasma.
步骤(1)中所述的回收率指示物包括三2-丁氧基-[13C2]-乙基)磷酸酯(Tris(2-butoxy-[13C2]-ethyl)phosphate)、磷酸三正丁酯-d27(Tri-n-butyl phosphate-d27)、三(2-氯乙基)磷酸酯-d12(Tris(2-chloroethyl)phosphate-d12)、三(1,3-二氯-2-丙基)磷酸酯-d15(Tris(1,3-dichloro-2-propyl)phosphate-d15)、磷酸三乙酯-d15(Triethylphosphate-d15)、磷酸三苯酯-d15(Triphenyl phosphate-d15)、双(丁氧基乙基)磷酸酯-d8(Bis(butoxyethyl)Phosphate-d8)、双(1,3-二氯-2-丙基)磷酸酯-d10(Bis(1,3-dichloro-2-propyl)phosphate-d10)、双(2-乙基己基)磷酸酯-d34(Bis(2-ethylhexyl)phosphate-d34)、磷酸二丁酯-d18(Dibutyl phosphate-d18)、磷酸二邻甲苯酯-d14(Di-o-cresyl Phosphate-d14)、二对甲苯基磷酸酯-d14(Di-p-tolyl-phosphate(Di-p-cresylphosphate)-d14)、磷酸二苯酯-d10(Diphenyl phosphate-d10)、邻苯二甲酸二苄酯-d4(Dibenzyl phthalate-d4)、邻苯二甲酸二正丁酯-d4(Di-n-butyl phthalate-d4)、邻苯二甲酸二异丁酯-3,4,5,6-d4(Di-iso-butyl phthalate-3,4,5,6-d4)、邻苯二甲酸二环己酯-3,4,5,6-d4(Dicyclohexyl phthalate-3,4,5,6-d4)、双(2-乙基己基)邻苯二甲酸酯-3,4,5,6-d4(Bis(2-ethylhexyl)phthalate-3,4,5,6-d4)、邻苯二甲酸二乙酯-3,4,5,6-d4(Diethyl phthalate-3,4,5,6-d4)、邻苯二甲酸二正己酯-3,4,5,6-d4(Di-n-hexylphthalate-3,4,5,6-d4)、邻苯二甲酸二甲酯-3,4,5,6-d4(Dimethyl phthalate-3,4,5,6-d4)、邻苯二甲酸二正戊酯-3,4,5,6-d4(Di-n-pentyl phthalate-3,4,5,6-d4)、邻苯二甲酸二正丙酯-3,4,5,6-d4(Di-n-propyl phthalate-3,4,5,6-d4)、邻苯二甲酸单苄酯-d4(Mono-benzyl phthalate-d4)、邻苯二甲酸单正丁酯-d4(Mono-n-butyl phthalate-d4)、双(2-乙基己基)己二酸酯-d8(Bis(2-ethylhexyl)adipate-d8)、O-乙酰柠檬酸三丁酯-d3(Tributyl O-acetylcitrate-d3)、双酚A-d6(Bisphenol A-d6)、双酚S-C12(Bisphenol S-C12)、三氯生-d3(Triclosan-d3)、2,4-二羟基二苯甲酮-13C6(2,4-dihydroxybenzophenone-13C6)、苯并噻唑-d4(benzothiazole-d4)、1H-苯并三唑-(环-d4)(1H-benzotriazole-(ring-d4))、5-甲基苯并三唑-d6(5-Methy-benzotriazole-d6)、二苯甲酮-d10(Benzophenone-d10)、2-羟基-4-甲氧基二苯甲酮-d5(2-Hydroxy-4-methoxybenzophenone-d5)、全氟-n-[(13)C4]丁酸(Perfluoro-n-[(13)C4]butanoicacid)、全氟-n-[1,2-(13)C2]己酸(Perfluoro-n-[1,2-(13)C2]hexanoic acid)、全氟-1-己烷[(18)O2]磺酸钠(Sodium perfluoro-1-hexane[(18)O2]sulfonate)、全氟-n-[1,2,3,4-(13)C4]辛酸(Perfluoro-n-[1,2,3,4-(13)C4]octanoic acid)、全氟-n-[1,2,3,4,5-(13)C5]壬酸(Perfluoro-n-[1,2,3,4,5-(13)C5]nonanoic acid)、全氟钠-1-[1,2,3,4-(13)C4]辛磺酸盐(Sodiumperfluoro-1-[1,2,3,4-(13)C4]octanesulfonate)、全氟-n-[1,2-(13)C2]癸酸(Perfluoro-n-[1,2-(13)C2]decanoic acid)、全氟-n-[1,2-(13)C2]十一烷酸(Perfluoro-n-[1,2-(13)C2]undecanoic acid)、全氟-n-[1,2-(13)C2]十二烷酸(Perfluoro-n-[1,2-(13)C2]dodecanoic acid)、全氟-1-[13C8]辛烷磺酰胺(Perfluoro-1-[13C8]octanesulfonamide)、N-甲基-d3-全氟-1-辛烷磺酰胺(N-methyl-d3-perfluoro-1-octanesulfonamide)、N-乙基-d5-全氟-1-辛烷磺酰胺(N-ethyl-d5-perfluoro-1-octanesulfonamide)、1H,1H,2H,2H-全氟-1-[1,2-13C2]-辛烷磺酸钠(Sodium1H,1H,2H,2H-perfluoro-1-[1,2-13C2]-octane sulfonate(6:2))、毒死蜱d10(chlorpyrifos d10)、γ-1,2,3,4,5,6-六氯环己烷-d6(gamma-1,2,3,4,5,6-Hexachlorocyclohexane-d6)、反式氯菊酯d6(trans-permethrin d6)、啶虫脒-d3(Acetamiprid-d3)、吡虫啉 -d4(Imidacloprid-d4)、噻虫啉-d4(Thiacloprid-d4)、噻虫嗪-d3(Thiamethoxam-d3)、多菌灵d3(Carbendazim d3)、呋喃丹d3(Carbofuran d3)、2,4-二氯苯氧基-3,5,6-d3-乙酸(2,4-Dd3)、2,4'-二氯二苯基三氯乙烷-d8(2,4'-Dichlorodiphenyltrichloroethane-d8)、2-(4-氯-2-甲基苯氧基)丙酸-D3(Mecoprop d3)、噻苯达唑d4(Thiabendazole d4)、十氘代西玛嗪(Simazined10)、特丁草净-D5(Terbutryn d5)、氘代敌草隆-D6(Diuron d6)、异丙隆d6(Isoproturon d6)、异丙甲草胺d6(Metolachlor d6)、嘧菌酯d4(Azoxystrobin d4)和啶酰菌胺d4(Boscalid d4)中的至少一种。The recovery indicators described in step (1) include three 2-butoxy-[13C2]-ethyl) phosphate (Tris(2-butoxy-[13C2]-ethyl)phosphate), tri-n-butyl phosphate -d27(Tri-n-butyl phosphate-d27), Tris(2-chloroethyl)phosphate-d12(Tris(2-chloroethyl)phosphate-d12), Tris(1,3-dichloro-2-propyl ) phosphate-d15 (Tris(1,3-dichloro-2-propyl) phosphate-d15), triethyl phosphate-d15 (Triethylphosphate-d15), triphenyl phosphate-d15 (Triphenyl phosphate-d15), bis( Butoxyethyl) phosphate-d8(Bis(butoxyethyl)Phosphate-d8), bis(1,3-dichloro-2-propyl)phosphate-d10(Bis(1,3-dichloro-2-propyl ) phosphate-d10), bis(2-ethylhexyl) phosphate-d34 (Bis(2-ethylhexyl) phosphate-d34), dibutyl phosphate-d18 (Dibutyl phosphate-d18), di-o-cresyl phosphate-d14 (Di-o-cresyl Phosphate-d14), Diphenyl phosphate-d14 (Di-p-tolyl-phosphate(Di-p-cresylphosphate)-d14), Diphenyl phosphate-d10 (Diphenyl phosphate-d10) , Dibenzyl phthalate-d4 (Dibenzyl phthalate-d4), Di-n-butyl phthalate-d4 (Di-n-butyl phthalate-d4), Diisobutyl phthalate-3,4 ,5,6-d4(Di-iso-butyl phthalate-3,4,5,6-d4), dicyclohexyl phthalate-3,4,5,6-d4(Dicyclohexyl phthalate-3,4 ,5,6-d4), bis(2-ethylhexyl)phthalate-3,4,5,6-d4 (Bis(2-ethylhexyl)phthalate-3,4,5,6-d4 ), Diethyl phthalate-3,4,5,6-d4 (Diethyl phthalate-3,4,5,6-d4), Di-n-hexyl phthalate-3,4,5,6- d4(Di-n-hexylphthalate-3,4,5,6-d4), dimethyl phthalate-3,4,5,6-d4(Dimeth yl phthalate-3,4,5,6-d4), di-n-pentyl phthalate-3,4,5,6-d4 (Di-n-pentyl phthalate-3,4,5,6-d4) , Di-n-propyl phthalate-3,4,5,6-d4 (Di-n-propyl phthalate-3,4,5,6-d4), Monobenzyl phthalate-d4 (Mono- benzyl phthalate-d4), mono-n-butyl phthalate-d4 (Mono-n-butyl phthalate-d4), bis(2-ethylhexyl) adipate-d8 (Bis(2-ethylhexyl) adipate- d8), O-acetyl tributyl citrate-d3 (Tributyl O-acetylcitrate-d3), bisphenol A-d6 (Bisphenol A-d6), bisphenol S-C12 (Bisphenol S-C12), triclosan- d3 (Triclosan-d3), 2,4-dihydroxybenzophenone-13C6 (2,4-dihydroxybenzophenone-13C6), benzothiazole-d4 (benzothiazole-d4), 1H-benzotriazole-(ring- d4)(1H-benzotriazole-(ring-d4)), 5-methylbenzotriazole-d6(5-Methy-benzotriazole-d6), benzophenone-d10(Benzophenone-d10), 2-hydroxy- 4-methoxybenzophenone-d5 (2-Hydroxy-4-methoxybenzophenone-d5), perfluoro-n-[(13)C4]butanoic acid (Perfluoro-n-[(13)C4]butanoic acid), Perfluoro-n-[1,2-(13)C2]hexanoic acid (Perfluoro-n-[1,2-(13)C2]hexanoic acid), perfluoro-1-hexane[(18)O2]sulfonic acid Sodium perfluoro-1-hexane[(18)O2]sulfonate, Perfluoro-n-[1,2,3,4-(13)C4]octanoic acid (Perfluoro-n-[1,2,3, 4-(13)C4]octanoic acid), perfluoro-n-[1,2,3,4,5-(13)C5]nonanoic acid (Perfluoro-n-[1,2,3,4,5- (13)C5]nonanoic acid), sodium perfluoro-1-[1,2,3,4-(13)C4] octanesulfonate (Sodium perfluoro-1-[1,2,3,4-(13) C4]octanesulfonate), perfluoro-n -[1,2-(13)C2]decanoic acid (Perfluoro-n-[1,2-(13)C2]decanoic acid), perfluoro-n-[1,2-(13)C2]undecane Perfluoro-n-[1,2-(13)C2]undecanoic acid, Perfluoro-n-[1,2-(13)C2]dodecanoic acid (Perfluoro-n-[1,2-( 13) C2]dodecanoic acid), perfluoro-1-[13C8]octanesulfonamide (Perfluoro-1-[13C8]octanesulfonamide), N-methyl-d3-perfluoro-1-octanesulfonamide (N- methyl-d3-perfluoro-1-octanesulfonamide), N-ethyl-d5-perfluoro-1-octanesulfonamide (N-ethyl-d5-perfluoro-1-octanesulfonamide), 1H,1H,2H,2H-all Fluoro-1-[1,2-13C2]-octane sulfonate (Sodium1H,1H,2H,2H-perfluoro-1-[1,2-13C2]-octane sulfonate(6:2)), chlorpyrifos d10( chlorpyrifos d10), gamma-1,2,3,4,5,6-hexachlorocyclohexane-d6 (gamma-1,2,3,4,5,6-Hexachlorocyclohexane-d6), trans-permethrin d6(trans-permethrin d6), acetamiprid-d3(Acetamiprid-d3), imidacloprid-d4(Imidacloprid-d4), thiacloprid-d4(Thiacloprid-d4), thiamethoxam-d3(Thiamethoxam-d3), Carbendazim d3 (Carbendazim d3), carbofuran d3 (Carbofuran d3), 2,4-dichlorophenoxy-3,5,6-d3-acetic acid (2,4-Dd3), 2,4'-di Chlorodiphenyltrichloroethane-d8(2,4'-Dichlorodiphenyltrichloroethane-d8), 2-(4-chloro-2-methylphenoxy)propionic acid-D3(Mecoprop d3), Thiabendazole d4 (Thiabendazole d4), decadeuterated simazine (Simazined10), terbutryn-D5 (Terbutryn d5), deuterated diuron-D6 (Diuron d6), isoproturon d6 (Isoproturon d6), isopropyl methyl Metolachlor d6, Azoxystrobin d4 and Boscalid d At least one of 4 (Boscalid d4).
步骤(1)中所述的血浆为人或动物的血浆；优选为人或绵羊血血浆；更优选为人体血浆。The plasma described in step (1) is human or animal plasma; preferably human or sheep blood plasma; more preferably human plasma.
步骤(1)中所述的血浆优选通过如下方式获得：将采集的血液离心分离，取上清液，获得所需要的血浆。The plasma described in step (1) is preferably obtained by centrifuging the collected blood, and taking the supernatant to obtain the required plasma.
所述的离心的条件为：3000rpm下离心3分钟。The centrifugation condition is: centrifuge at 3000rpm for 3 minutes.
步骤(1)中所述的添加的回收率指示物为所测目标化合物的同位素标记的化合物，能有效的校正前处理过程中化合物的损失；本发明中，大部分目标化合物都具有一一对应的回收率指示物，无法一一对应的化合物则使用同类别化合物对应的同位素标。The added recovery indicator described in step (1) is the isotope-labeled compound of the measured target compound, which can effectively correct the loss of the compound in the pretreatment process; in the present invention, most of the target compounds have one-to-one correspondence For the recovery indicator, if the compound cannot be one-to-one, use the isotope label corresponding to the same type of compound.
步骤(2)中所述的萃取溶剂I的配方如下：298.2mL乙酸乙酯、198.8mL正己烷和3mL甲酸(乙酸乙酯和正己烷按体积比3:2，甲酸占萃取溶剂I体积的0.6％)。The formula of extraction solvent 1 described in step (2) is as follows: 298.2mL ethyl acetate, 198.8mL normal hexane and 3mL formic acid (ethyl acetate and normal hexane are by volume ratio 3:2, and formic acid accounts for 0.6 of extraction solvent 1 volume %).
步骤(2)中所述的萃取需要360度旋转震荡使得萃取更加充分。The extraction described in step (2) requires 360-degree rotation and vibration to make the extraction more complete.
步骤(2)中所述的重复的次数为2次以上；优选为2次。The number of repetitions described in step (2) is more than 2 times; preferably 2 times.
步骤(2)中所述的离心的条件为：3000～4000rpm下离心3min以上；优选为：3000rpm下离心3min，离心目的是沉淀悬浮物，有助于转移萃取剂。The centrifugation conditions described in step (2) are: centrifugation at 3000-4000rpm for more than 3min; preferably: centrifugation at 3000rpm for 3min, the purpose of centrifugation is to precipitate suspended matter and help to transfer the extractant.
步骤(3)中所述的冷冻的时间为12小时以上。The freezing time described in step (3) is more than 12 hours.
步骤(3)中所述的冷冻离心的条件为：-10℃、15000rpm条件下离心5min以上。The conditions for the refrigerated centrifugation in step (3) are: centrifuge at -10°C and 15000rpm for more than 5min.
步骤(3)中，需要将萃取液吹至近干用甲醇复溶后进行冷冻，目的是让脂质析出，然后需要在冷冻离心机中保持低温进行冷冻离心，目的是让脂质沉淀有助于上清液的转移，从而达到去除脂质的目的，减少基质效应。In step (3), the extract needs to be blown to near dryness and reconstituted with methanol for freezing. The purpose is to precipitate lipids, and then it is necessary to keep low temperature in a refrigerated centrifuge for refrigerated centrifugation. The purpose is to allow lipid precipitation to help The transfer of the supernatant, so as to achieve the purpose of removing lipids and reduce the matrix effect.
步骤(4)中所述的内标的用量为按每50μL预处理后的样品加入每种内标1～20ng计算。The amount of the internal standard described in step (4) is calculated by adding 1-20 ng of each internal standard per 50 μL of the pretreated sample.
步骤(4)中所述的内标包括全氟化合物，增塑剂(塑料添加剂)，有机氯农药，有机磷农药和液晶单体的内标。The internal standard described in the step (4) includes internal standards of perfluorinated compounds, plasticizers (plastic additives), organochlorine pesticides, organophosphorus pesticides and liquid crystal monomers.
所述的全氟化合物的内标为全氟-n-[13C8]辛酸(Perfluoro-n-[13C8]octanoicacid；M8PFOA)。The internal standard of the perfluoro compound is perfluoro-n-[13C8]octanoic acid (Perfluoro-n-[13C8]octanoic acid; M8PFOA).
所述的增塑剂的正模式的内标为蝇毒磷-d10(coumaphos-d10)，负模式的内标为双酚A-d16(BisphenolA-d16；BPA-d16)。The positive mode internal standard of the plasticizer is coumaphos-d10 (coumaphos-d10), and the negative mode internal standard is bisphenol A-d16 (BisphenolA-d16; BPA-d16).
所述的有机氯农药的内标为十氯二苯醚(Decachlorodiphenyl ether；DCDE)。The internal standard of the organochlorine pesticide is decachlorodiphenyl ether (DCDE).
所述的有机磷农药的正模式的内标为蝇毒磷-d10(coumaphos-d10)，负模式的内标为对羟基苯甲酸叔丁酯-d9(tert butyl paraben-d9)。The positive mode internal standard of the organophosphorus pesticide is coumaphos-d10, and the negative mode internal standard is tert butyl paraben-d9.
所述的液晶单体的内标为十氯二苯醚(Decachlorodiphenyl ether；DCDE)。The internal standard of the liquid crystal monomer is decachlorodiphenyl ether (DCDE).
步骤(4)中所述的液相色谱-串联质谱法为采用超高效液相色谱-串联质谱联用仪进行。The liquid chromatography-tandem mass spectrometry described in step (4) is carried out by using ultra-high performance liquid chromatography-tandem mass spectrometry.
步骤(4)中所述的采用液相色谱-串联质谱法(UPLC-MS/MS)对环境污染物进行定量分析的污染物包括有机磷酸酯类(OPEs)，邻苯二甲酸酯类 (PAEs)，个人护理产品(PCPs)，苯酚类化合物，紫外稳定剂(UV)，光引发剂，抗氧化剂(AO)，增塑剂，全氟化合物(PFCs)，有机磷农药(OPs)，拟除虫菊酯，新烟碱类农药，氨基甲酸酯类农药，酸性除草剂，唑类农药，三唑酮类农药，尿素类农药，酰胺类农药，甲氧基丙烯酸酯类杀菌剂和其他杀虫剂中的至少一种。Adopt liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) described in step (4) to carry out the pollutant of quantitative analysis to environmental pollutant and comprise organophosphates (OPEs), phthalates (PAEs) ), personal care products (PCPs), phenolic compounds, ultraviolet stabilizers (UV), photoinitiators, antioxidants (AO), plasticizers, perfluorinated compounds (PFCs), organophosphorus pesticides (OPs), pyrethroids Esters, neonicotinoid pesticides, carbamate pesticides, acidic herbicides, azole pesticides, triadimefon pesticides, urea pesticides, amides pesticides, methoxyacrylate fungicides and other insecticides at least one of .
所述的有机磷酸酯类(OPEs)包括有机磷酸二酯类和有机磷酸三酯类中的至少一种。The organophosphates (OPEs) include at least one of organophosphate diesters and organophosphate triesters.
所述的有机磷酸二酯类(Organophosphate diesters)包括双-(1-氯-2-丙基)磷酸酯(bis-(1-chloro-2-propyl)phosphate)、磷酸二苯酯(Diphenyl phosphate)、磷酸二丁酯(Dibutyl phosphate)、双(1,3-二氯-2-丙基)磷酸酯(Bis(1,3-dichloro-2-propyl)phosphate)、二对甲苯基磷酸酯(di-p-tolyl-phosphate)、双(丁氧基乙基)磷酸酯(bis(butoxyethyl)phosphate)和双(2-乙基己基)磷酸酯(bis(2-ethylhexyl)phosphate)。Described organophosphate diesters (Organophosphate diesters) include bis-(1-chloro-2-propyl) phosphate (bis-(1-chloro-2-propyl) phosphate), diphenyl phosphate (Diphenyl phosphate) , dibutyl phosphate (Dibutyl phosphate), bis (1,3-dichloro-2-propyl) phosphate (Bis (1,3-dichloro-2-propyl) phosphate), two p-cresyl phosphate (di -p-tolyl-phosphate), bis(butoxyethyl)phosphate and bis(2-ethylhexyl)phosphate.
所述的有机磷酸三酯类(Organophosphate triesters)包括磷酸三乙酯(Triethyl phosphate)、三(2-氯乙基)磷酸酯(Tris(2-chloroethyl)phosphate)、磷酸三丙酯(Tripropyl phosphate)、四(2-氯乙基)二氯异戊基二磷酸酯(Tetrakis(2-Chloroethyl)dichloroisopentyl diphosphate)、磷酸三苯酯(Triphenyl phosphate)、三(2,3-二溴丙基)磷酸酯(Tris(2,3-dibromopropyl)phosphate)、磷酸三丁酯(Tributylphosphate)、磷酸甲酚二苯酯(Cresyldiphenyl phosphate)、三(2-丁氧基乙基)磷酸酯(Tris(2-butoxyethyl)phosphate)、磷酸三甲苯酯(Tricresyl phosphate)、间苯二酚双(磷酸二苯酯)(Resorcinol bis(diphenyl phosphate))、2-乙基己基-二苯基磷酸酯(2-Ethylhexyl-diphenyl phosphate)、磷酸异癸基二苯酯(Isodecyl diphenyl phosphate)、三(3,5-二甲基苯基)磷酸酯(Tris(3,5-dimethylphenyl)phosphate)、双酚A双(磷酸二苯酯)(Bisphenol A bis(diphenyl phosphate))、三(2-异丙基苯基)磷酸酯(Tris(2-isopropylphenyl)phosphate)、三(2-乙基己基)磷酸酯(Tris(2-ethylhexyl)phosphate)、叔丁基苯基二苯基磷酸酯(t-butylphenyl diphenyl phosphate)、2-异丙基苯基二苯基磷酸酯(2-Isopropylphenyl diphenyl phosphate)、4-异丙基苯基二苯基磷酸酯(4-Isopropylphenyl diphenyl phosphate)、双(2-异丙基苯基)苯基磷酸酯(Bis(2-isopropylphenyl)phenyl phosphate)、2,4-二异丙基苯基二苯基磷酸酯(2,4-Diisopropylphenyl diphenyl phosphate)、双(4-异丙基苯基)苯基磷酸酯(Bis(4-isopropylphenyl)phenyl phosphate)、三(3,4-二甲基苯基)磷酸酯(Trsi(3,4-dimethyphenyl)phosphate)、三(4-叔丁基苯基)磷酸酯(Tris(4-tert-butylphenyl)phosphate)、双(2,4-二异丙基苯基)苯基磷酸酯(Bis(2,4-diisopropylphenyl)phenylphosphate)、三(3-异丙基苯基)磷酸酯(Tris(3-isopropylphenyl)phosphate)、三(4-异丙基苯基)磷酸酯(Tris(4-isopropylphenyl)phosphate)、2-叔丁基苯基二苯基磷酸酯(2-tert-Butylphenyl diphenyl phosphate)、4-叔丁基苯基二苯基磷酸酯(4-tert-Butylphenyl diphenyl phosphate)、双(2-叔丁基苯基)苯基磷酸酯(Bis(2-tert-butylphenyl)phenyl phosphate)和双(4-叔丁基苯基)苯基磷酸酯(Bis(4-tert-butylphenyl)phenyl phosphate)。Described organophosphate triesters (Organophosphate triesters) include triethyl phosphate (Triethyl phosphate), three (2-chloroethyl) phosphate (Tris (2-chloroethyl) phosphate), tripropyl phosphate (Tripropyl phosphate) , Tetrakis (2-Chloroethyl) dichloroisopentyl diphosphate, Triphenyl phosphate, Tris (2,3-dibromopropyl) phosphate (Tris(2,3-dibromopropyl)phosphate), Tributylphosphate, Cresyldiphenylphosphate, Tris(2-butoxyethyl)phosphate (Tris(2-butoxyethyl) phosphate), Tricresyl phosphate, Resorcinol bis(diphenyl phosphate), 2-Ethylhexyl-diphenyl phosphate (2-Ethylhexyl-diphenyl phosphate ), Isodecyl diphenyl phosphate (Isodecyl diphenyl phosphate), three (3,5-dimethylphenyl) phosphate (Tris (3,5-dimethylphenyl) phosphate), bisphenol A bis (diphenyl phosphate ) (Bisphenol A bis (diphenyl phosphate)), three (2-isopropylphenyl) phosphate (Tris (2-isopropylphenyl) phosphate), three (2-ethylhexyl) phosphate (Tris (2-ethylhexyl) phosphate), t-butylphenyl diphenyl phosphate (t-butylphenyl diphenyl phosphate), 2-isopropylphenyl diphenyl phosphate (2-Isopropylphenyl diphenyl phosphate), 4-isopropylphenyl diphenyl 4-Isopropylphenyl diphenyl phosphate, bis(2-isopropylphenyl)phenyl phosphate (Bis(2-isopropylphenyl)phenyl phosphate), 2,4-diisopropylphenyl diphenyl phosphate Esters (2,4-Diisopropylphenyl diphenyl phosphate ), bis(4-isopropylphenyl)phenyl phosphate (Bis(4-isopropylphenyl)phenyl phosphate), tris(3,4-dimethylphenyl)phosphate (Trsi(3,4-dimethylphenyl) phosphate), three (4-tert-butylphenyl) phosphate (Tris (4-tert-butylphenyl) phosphate), bis (2,4-diisopropylphenyl) phenyl phosphate (Bis (2,4 -diisopropylphenyl)phenylphosphate), Tris(3-isopropylphenyl)phosphate (Tris(3-isopropylphenyl)phosphate), Tris(4-isopropylphenyl)phosphate (Tris(4-isopropylphenyl)phosphate), 2-tert-butylphenyl diphenyl phosphate (2-tert-Butylphenyl diphenyl phosphate), 4-tert-butylphenyl diphenyl phosphate (4-tert-Butylphenyl diphenyl phosphate), bis(2-tert-butyl Bis(2-tert-butylphenyl)phenyl phosphate and Bis(4-tert-butylphenyl)phenyl phosphate.
所述的邻苯二甲酸酯类(PAEs)包括邻苯二甲酸单酯类和邻苯二甲酸二酯类中的至少一种。The phthalic acid esters (PAEs) include at least one of phthalic acid monoesters and phthalic acid diesters.
所述的邻苯二甲酸单酯类(Phthalate monoesters)包括邻苯二甲酸单乙酯(monoethyl phthalate)、邻苯二甲酸单异丙酯(monoisopropyl phthalate)、邻苯二甲酸单丁酯(monoisobutyl phthalate)、邻苯二甲酸单正戊酯(mono-n-pentyl phthalate)、邻苯二甲酸单环己酯(monocyclohexyl  phthalate)、邻苯二甲酸单己基酯(monohexylphthalate)、邻苯二甲酸单苄酯(monobenzyl phthalate)、邻苯二甲酸单-2-庚酯(mono-2-heptyl phthalate)、邻苯二甲酸单辛酯(monooctyl phthalate)、邻苯二甲酸单乙基己基酯(monoethylhexyl phthalate)、邻苯二甲酸单异壬酯(monoisononyl phthalate)、邻苯二甲酸单(2-乙基-5-氧己基)酯(mono(2-ethyl-5-oxohexyl)phthalate)、邻苯二甲酸单(2-乙基-5-羟基己基)酯(mono(2-ethyl-5-hydroxyhexyl)phthalate)和单(2-乙基-5-羧基戊基)邻苯二甲酸酯(mono(2-ethyl-5carboxypentyl)phthalate)。The phthalate monoesters include monoethyl phthalate, monoisopropyl phthalate, monoisobutyl phthalate ), mono-n-pentyl phthalate, monocyclohexyl phthalate, monohexylphthalate, monobenzyl phthalate (monobenzyl phthalate), mono-2-heptyl phthalate (mono-2-heptyl phthalate), monooctyl phthalate (monoctyl phthalate), monoethylhexyl phthalate (monoethylhexyl phthalate), Monoisononyl phthalate (monoisononyl phthalate), mono(2-ethyl-5-oxohexyl) phthalate (mono(2-ethyl-5-oxohexyl) phthalate), mono(2-ethyl-5-oxohexyl) phthalate 2-Ethyl-5-hydroxyhexyl) ester (mono(2-ethyl-5-hydroxyhexyl) phthalate) and mono(2-ethyl-5-carboxypentyl) phthalate (mono(2-ethyl -5carboxypentyl)phthalate).
所述的邻苯二甲酸二酯类(Phthalate diesters)包括间苯二甲酸二甲酯(dimethyl isophthalate)、邻苯二甲酸二甲酯(dimethyl phthalate)、邻苯二甲酸二乙酯(diethyl phthalate)、邻苯二甲酸二烯丙酯(diallyl phthalate)、邻苯二甲酸二丙酯(di-n-propyl phthalate)、邻苯二甲酸二异丙酯(Diisopropyl phthalat)、邻苯二甲酸二异丁酯(diisobutyl phthalate)、邻苯二甲酸二丁酯(dibutyl phthalate)、邻苯二甲酸异丁环己酯(isobutylcyclohexyl phthalate)、邻苯二甲酸二异戊酯(diisopentyl phthalate)、邻苯二甲酸丁苄酯(butyl benzylphthalate)、间苯二甲酸二苯酯(diphenyl isophthalate)、邻苯二甲酸二苯酯(diphenylphthalate)、邻苯二甲酸二己酯(dihexyl phthalate)、邻苯二甲酸二异己酯(diisohexylphthalate)、邻苯二甲酸双-4-甲基-2-戊酯(bis(4-methyl-2-pentyl)phthalate)、邻苯二甲酸二苄酯(dibenzyl phthalate)、邻苯二甲酸二庚酯(diisoheptyl phthalate)、邻苯二甲酸二壬酯(dinonyl phthalate)、邻苯二甲酸二十二烷基酯(diundecyl phthalate)和己二酸二(2-乙基己基)酯(bis(2-ethylhexyl)adipate)。The phthalate diesters include dimethyl isophthalate, dimethyl phthalate, diethyl phthalate , Diallyl phthalate, di-n-propyl phthalate, Diisopropyl phthalat, Diisobutyl phthalate Diisobutyl phthalate, dibutyl phthalate, isobutylcyclohexyl phthalate, diisopentyl phthalate, butyl phthalate Benzyl ester (butyl benzylphthalate), diphenyl isophthalate (diphenyl isophthalate), diphenyl phthalate (diphenylphthalate), dihexyl phthalate (dihexyl phthalate), diisohexyl phthalate ( diisohexylphthalate), bis(4-methyl-2-pentyl)phthalate, dibenzyl phthalate, diheptyl phthalate Diisoheptyl phthalate, dinonyl phthalate, diundecyl phthalate and bis(2-ethylhexyl) adipate (bis(2-ethylhexyl) ) adipate).
所述的个人护理产品(Personal Care Products)类包括对羟基苯甲酸甲酯(methyl paraben)、对羟基苯甲酸丁酯(butyl Paraben)、对羟基苯甲酸苄酯(benzylParaben)、对羟基苯甲酸乙酯(ethylparaben)、对羟基苯甲酸丙酯(propylparaben)、正庚基对羟基苯甲酸酯(heptyl paraben)和三氯生(Triclosan)。The personal care products (Personal Care Products) include methyl paraben, butyl Paraben, benzyl Paraben, ethyl paraben Ethylparaben, Propylparaben, Heptylparaben and Triclosan.
所述的苯酚类化合物包括双酚类似物中的至少一种。The phenolic compound includes at least one of bisphenol analogues.
所述的双酚类似物包括双酚A(bisphenolA)、双酚E(bisphenol E)、双酚B(bisphenol B)、双酚C(bisphenol C)、双酚AF(bisphenol AF)、双酚F(bisphenol F)、双酚M(bisphenol M)、双酚P(bisphenol P)、双酚G(bisphenol G)、双酚Z(bisphenol Z)、双酚S(bisphenol S)、双酚AP(bisphenol AP)、双酚BP(bisphenol BP)和双酚PH(bisphenol PH)。Described bisphenol analog includes bisphenol A (bisphenol A), bisphenol E (bisphenol E), bisphenol B (bisphenol B), bisphenol C (bisphenol C), bisphenol AF (bisphenol AF), bisphenol F (bisphenol F), bisphenol M (bisphenol M), bisphenol P (bisphenol P), bisphenol G (bisphenol G), bisphenol Z (bisphenol Z), bisphenol S (bisphenol S), bisphenol AP (bisphenol AP), bisphenol BP (bisphenol BP) and bisphenol PH (bisphenol PH).
所述的紫外稳定剂(UV)包括苯甲酮类、苯并噻唑类、苯并三唑类以及其他类别的紫外稳定剂中的至少一种。The ultraviolet stabilizer (UV) includes at least one of benzophenones, benzothiazoles, benzotriazoles and other types of ultraviolet stabilizers.
所述的苯甲酮类紫外稳定剂(Benzophenone UV stabilizers)包括2,4-二羟基二苯甲酮(2,4-dihydroxybenzophenone)、2,2',4,4'-四羟基二苯甲酮(2,2',4,4'-tetrahydroxybenzophenone)、2-羟基-4-甲氧基苯并苯酮(2-hydroxy-4-methoxybenzophenone)、2-羟基-4-甲氧基-5-磺酸二苯甲酮(2-hydroxy-4-methoxybenzophenone-5-sulfonicacid hydrate)、2,2'-二羟基-4,4'-二甲氧基二苯甲酮(2,2'-dihydroxy-4,4'-dimethoxybenzophenone)、2,2'-羟基-4-甲氧基二苯甲酮(2,2’-dihydroxy-4-methoxybenzophenone)、4-羟基二苯甲酮(4-hydroxybenzophenone)和2,3,4-三羟基二苯甲酮(2,3,4-trihydroxybenzophenone)。Described benzophenone UV stabilizers (Benzophenone UV stabilizers) include 2,4-dihydroxybenzophenone (2,4-dihydroxybenzophenone), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'-tetrahydroxybenzophenone), 2-hydroxy-4-methoxybenzophenone (2-hydroxy-4-methoxybenzophenone), 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid benzophenone (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2'-dihydroxy-4 ,4'-dimethoxybenzophenone), 2,2'-hydroxy-4-methoxybenzophenone (2,2'-dihydroxy-4-methoxybenzophenone), 4-hydroxybenzophenone (4-hydroxybenzophenone) and 2 ,3,4-trihydroxybenzophenone (2,3,4-trihydroxybenzophenone).
所述的苯并噻唑类紫外稳定剂(Benzothiazoles UV stabilizers)包括2-甲基苯并噻唑(2-methylbenzothiazole)、2-苯并噻唑基-N-吗啉基硫醚(2-(morpholinothio)-benzothiazole)、2-甲硫基苯并噻唑(2-(methylthio)benzothiazole)、2-氨基苯并噻唑(2-aminobenzothiazole)和2-羟基苯并噻唑(2-hydroxybenzothiazole)。Described benzothiazole UV stabilizers (Benzothiazoles UV stabilizers) include 2-methylbenzothiazole (2-methylbenzothiazole), 2-benzothiazolyl-N-morpholinothioether (2-(morpholinothio)- benzothiazole), 2-(methylthio)benzothiazole), 2-aminobenzothiazole and 2-hydroxybenzothiazole.
所述的苯并三唑类紫外稳定剂(benzotriazoles UV stabilizers)包括1-羟基苯并三唑(1-hydroxy benzotriazole)、5-甲基苯并三氮唑(5-methyl-1-hydrogenbenzotriazole)、5-氯代苯并三氮唑(5-chloro-1-hydrogenbenzotriazole)、4-甲基-1-氢苯并三唑(4-methyl-1H-benzotriazole)、2-(2'-羟基-5'-甲基苯基)苯并三唑(2-(2-Hydroxy-5-methylphenyl)benzotriazole)、2-(5-叔丁基-2-羟苯基)苯并三唑(2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole)和2-(2'-羟基-3',5'-二叔丁基苯基)-苯并三唑(2-(3,5-Di-tert-butyl-2-hydroxyphenyl)2H-benzotriazole)。Described benzotriazole UV stabilizers (benzotriazoles UV stabilizers) include 1-hydroxybenzotriazole (1-hydroxybenzotriazole), 5-methyl-1-hydrogenbenzotriazole (5-methyl-1-hydrogenbenzotriazole), 5-chlorobenzotriazole (5-chloro-1-hydrogenbenzotriazole), 4-methyl-1-hydrobenzotriazole (4-methyl-1H-benzotriazole), 2-(2'-hydroxyl-5 '-Methylphenyl)benzotriazole (2-(2-Hydroxy-5-methylphenyl)benzotriazole), 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole (2-(5 -tert-butyl-2-hydroxyphenyl)benzotriazole) and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole (2-(3,5-Di-tert- butyl-2-hydroxyphenyl) 2H-benzotriazole).
所述的其他类别紫外稳定剂(other UV stabilizers)包括4-叔丁基-4'-甲氧基二苯甲酰甲烷(4-tert-butyl-4’-methoxydibenzoylmethane)、4-甲基苄亚基樟脑(4-methylbenzylidene camphor)、甲氧基肉桂酸异戊酯(isoamyl4-methoxycinnamate)、2-氰基-3,3-二苯基丙烯酸异辛酯(2-ethylhexyl2-cyano-3,3-diphenyl-2-propenoate(liquid))、对二甲氨基苯甲酸异辛酯(octyl dimethyl-p-aminobenzoic acid)、对甲氧基肉桂酸辛酯(Ethylhexyl methoxycinnamate)、2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯乙基)苯酚(2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol)、2,4-二叔丁基-6-(5-氯-2H-苯并三唑-2-基)苯酚(2,4-Di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol)和2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚(2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol)。The other UV stabilizers (other UV stabilizers) include 4-tert-butyl-4'-methoxydibenzoylmethane (4-tert-butyl-4'-methoxydibenzoylmethane), 4-methylbenzylidene 4-methylbenzylidene camphor, isoamyl4-methoxycinnamate, isooctyl 2-cyano-3,3-diphenylacrylate (2-ethylhexyl2-cyano-3,3- diphenyl-2-propenoate(liquid)), octyl dimethyl-p-aminobenzoic acid, Ethylhexyl methoxycinnamate, 2-(2H-benzotriazole -2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl )phenol), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol (2,4-Di-tert-butyl-6-(5-chloro- 2H-benzotriazol-2-yl)phenol) and 2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol (2-(2H-benzotriazol-2-yl)-4, 6-di-tert-pentylphenol).
所述的光引发剂(photoinitiatorAdditives)包括苯甲酮(benzophenone)、4-甲基二苯甲酮(4-methylbenzophenone)、1-羟基环己基苯基甲酮(1-hydroxycyclohexylphenyl ketone)、4-苯基二苯甲酮(4-phenylbenzophenone/4-benzoylbiphenyl)、1,2-二苯基-1,2-乙二酮(1,2-diphenyl-1,2-ethanedione)、2-乙基蒽醌(2-ethylanthraquinone)、邻苯甲酰苯甲酸甲酯(methyl-2-(benzoyl)benzoate)、2，2-二甲氧基-2-苯基苯乙酮(2,2-dimethoxy-2-phenylacetophenone)、对二甲氨基二苯甲酮(4-(dimethylamino)benzophenone)、4,4'-双(二甲氨基)二苯甲酮(4,4'-bis(dimethylamino)benzophenone)、4,4'-双(二乙氨基)二苯甲酮(4,4'-bis(diethylamino)benzophenone)、4-氨基苯甲酸乙酯(ethyl-4-aminobenzoate)、4-二甲氨基苯甲酸乙酯(ethyl-4-dimethylaminobenzoate)、2-异丙基噻吨酮(2-isopropylthioxanthone)和2,4-二乙基噻吨酮(2,4-diethylthioxanthone/2,4-diethyl-9H-thioxanthen-9-one)。Described photoinitiator (photoinitiatorAdditives) comprises benzophenone (benzophenone), 4-methylbenzophenone (4-methylbenzophenone), 1-hydroxycyclohexylphenyl ketone (1-hydroxycyclohexylphenyl ketone), 4-phenyl 4-phenylbenzophenone/4-benzoylbiphenyl, 1,2-diphenyl-1,2-ethanedione (1,2-diphenyl-1,2-ethanedione), 2-ethylanthraquinone (2-ethylanthraquinone), methyl-2-(benzoyl)benzoate (methyl-2-(benzoyl)benzoate), 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2- phenylacetophenone), p-dimethylaminobenzophenone (4-(dimethylamino)benzophenone), 4,4'-bis(dimethylamino)benzophenone (4,4'-bis(dimethylamino)benzophenone), 4, 4'-bis(diethylamino)benzophenone (4,4'-bis(diethylamino)benzophenone), 4-aminobenzoic acid ethyl ester (ethyl-4-aminobenzoate), 4-dimethylaminobenzoic acid ethyl ester (ethyl-4-dimethylaminobenzoate), 2-isopropylthioxanthone (2-isopropylthioxanthone) and 2,4-diethylthioxanthone (2,4-diethylthioxanthone/2,4-diethyl-9H-thioxanthen-9 -one).
所述的抗氧化剂(antioxidants)包括在正离子检测模式和负离子检测模式下进行检测的抗氧化剂。The antioxidants (antioxidants) include antioxidants detected in positive ion detection mode and negative ion detection mode.
所述的在负离子检测模式下进行检测的抗氧化剂包括3-叔丁基-4-羟基茴香醚(3-tert-butyl-4-hydroxyanisole)、3,5-二叔丁基-4-羟基苯甲醛(3,5-di-tert-butyl-4-hydroxybenzaldehyde)、3,5-二叔丁基-4-羟基苯甲酸(3,5-di-tert-butyl-4-hydroxybenzoic acid)、2,6-二叔丁基-4-(羟甲基)苯酚(2,6-di-tert-butyl-4-(hydroxymethyl)phenol)、2,4-二叔丁基苯酚(2,4-di-tert-butylphenol)、4,4'-亚丁基双(6-叔丁基-间甲酚)(4,4'-butylidenebis(6-tert-butyl-m-cresol))、4-(1,1,3,3-四甲基丁基)苯酚(4-(1,1,3,3-tetra-methylbutyl)phenol)、2,2'-亚甲基双(4-乙基-6-叔丁基苯酚)(2,2'-methylenebis(4-ethyl-6-tert-butylphenol))、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)(2,2'-methylenebis(6-tert-butyl-4-methylphenol))、二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯(diethyl-3,5-Di-tert-butyl-4-hydroxybenzylphosphonate)、2,2'-硫代双(6-叔丁 基-对甲酚)(2,2'-thiobis(6-tert-butyl-p-cresol))、1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼(1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine)和4,4'-硫代双(6-叔丁基-间甲酚)(4,4'-thiobis(6-tert-butyl-m-cresol))。The antioxidants detected under negative ion detection mode include 3-tert-butyl-4-hydroxyanisole (3-tert-butyl-4-hydroxyanisole), 3,5-di-tert-butyl-4-hydroxybenzene Formaldehyde (3,5-di-tert-butyl-4-hydroxybenzoic acid), 3,5-di-tert-butyl-4-hydroxybenzoic acid (3,5-di-tert-butyl-4-hydroxybenzoic acid), 2, 6-di-tert-butyl-4-(hydroxymethyl)phenol (2,6-di-tert-butyl-4-(hydroxymethyl)phenol), 2,4-di-tert-butylphenol (2,4-di- tert-butylphenol), 4,4'-butylene bis(6-tert-butyl-m-cresol) (4,4'-butylidenebis(6-tert-butyl-m-cresol)), 4-(1,1 ,3,3-tetramethylbutyl)phenol (4-(1,1,3,3-tetra-methylbutyl)phenol), 2,2'-methylenebis(4-ethyl-6-tert-butyl phenylphenol) (2,2'-methylenebis(4-ethyl-6-tert-butylphenol)), 2,2'-methylene bis(6-tert-butyl-4-methylphenol) (2,2' -methylenebis(6-tert-butyl-4-methylphenol)), diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate (diethyl-3,5-Di-tert-butyl-4 -hydroxybenzylphosphonate), 2,2'-thiobis(6-tert-butyl-p-cresol) (2,2'-thiobis(6-tert-butyl-p-cresol)), 1,2-bis(3 ,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine) and 4,4'-thiobis(6 -tert-butyl-m-cresol) (4,4'-thiobis(6-tert-butyl-m-cresol)).
所述的在正离子检测模式下进行检测的抗氧化剂包括1,3-二邻甲苯胍(1,3-di-o-tolylguanidine)、1,3-二苯基-2-硫脲(1,3-diphenyl-2-thiourea)、2,2'-亚乙基-双(4,6-二叔丁基苯酚)(2,2'-ethylidene-bis(4,6-di-tert-butylphenol))、甲基-2-巯基苯并咪唑(methyl-2-mercaptobenzimidazole)、11-甲基十二烷基3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酸酯(11-Methyldodecyl3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate)、二苄基羟胺(dibenzylhydroxylamine)、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯(Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate)、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯(1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene)、2,6-二叔丁基-4-(二甲氨基-甲基)苯酚(2,6-Di-tert-butyl-4-(dimethylamino-methyl)phenol)、三(2,4-二叔丁基苯基)亚磷酸酯(tris(2,4-ditert-butylphenyl)phosphite)、磺基二基二-2,1-乙二基双[3-(4-羟基-3,5-双(2-甲基-2-丙烷基)苯基)丙酸酯](Sulfanediyldi-2,1-ethanediylbis[3-(4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl)propanoate])、2,2'-硫代双(6-叔丁基-对甲酚)、N,N'-1,6-己二基双[3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酰胺](N,N'-1,6-Hexanediylbis[3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanamide])、1,2-乙二基双(氧-2,1-乙二基)双[3-[4-羟基-3-甲基-5-(2-甲基-2-丙烷基)苯基]丙酸酯](1,2-Ethanediylbis(oxy-2,1-ethanediyl)bis[3-[4-hydroxy-3-methyl-5-(2-methyl-2-propanyl)phenyl]propanoate])、1,6-己二基双[3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酸酯](1,6-Hexanediylbis[3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate])、4-[[4,6-双(辛基硫烷基)-1,3,5-三嗪-2-基]氨基]-2,6-二叔丁基苯酚(4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-ditert-butylphenol)、n-苯基-1-萘胺(n-phenyl-1-naphthylamine)、双[4-(2-苯基-2-丙基)苯基]胺(bis[4-(2-phenyl-2-propyl)phenyl]amine)、N,N'-二苯基-1,4-苯二胺(N,N'-Diphenyl-1,4-benzenediamine)、(1,2-二氧代-1,2-乙二基)双(亚氨基-2,1-乙二基)双[3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酸酯]((1,2-Dioxo-1,2-ethanediyl)bis(imino-2,1-ethanediyl)bis[3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate])、N，N'-二乙基硫脲(N,N'-diethylthiourea)和1,3-二苯基胍(1,3-Diphenylguanidine)。The antioxidants detected under the positive ion detection mode include 1,3-di-o-tolylguanidine (1,3-di-o-tolylguanidine), 1,3-diphenyl-2-thiourea (1, 3-diphenyl-2-thiourea), 2,2'-ethylene-bis(4,6-di-tert-butylphenol) (2,2'-ethylene-bis(4,6-di-tert-butylphenol) ), methyl-2-mercaptobenzimidazole (methyl-2-mercaptobenzimidazole), 11-methyldodecyl 3-[4-hydroxyl-3,5-bis(2-methyl-2-propanyl) Phenyl]propanoate (11-Methyldodecyl3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate), dibenzylhydroxylamine, tri(4-tert-butyl -3-hydroxy-2,6-dimethylbenzyl)isocyanurate (Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate), 1,3,5-trimethyl Base-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (1,3,5-trimethyl-2,4,6-tris(3,5-di-tert -butyl-4-hydroxybenzyl)benzene), 2,6-di-tert-butyl-4-(dimethylamino-methyl)phenol (2,6-Di-tert-butyl-4-(dimethylamino-methyl)phenol) , Tris (2,4-ditert-butylphenyl) phosphite (tris (2,4-ditert-butylphenyl) phosphite), sulfodi-2,1-ethylenediylbis[3-(4 -Hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl)propionate](Sulfanediyldi-2,1-ethanediylbis[3-(4-hydroxy-3,5-bis(2- methyl-2-propanyl)phenyl)propanoate]), 2,2'-thiobis(6-tert-butyl-p-cresol), N,N'-1,6-hexanediylbis[3-[4 -Hexanediylbis[3-[4-hydroxy-3,5-bis( 2-methyl-2-propanyl)phenyl]propanamide]), 1,2-ethanediylbis(oxygen-2,1-ethanediyl)bis[3-[4- Hydroxy-3-methyl-5-(2-methyl-2-propanyl)phenyl]propionate](1,2-Ethanediylbis(oxy-2,1-ethanediyl)bis[3-[4-hydroxy -3-methyl-5-(2-methyl-2-propanyl)phenyl]propanoate]), 1,6-hexanediylbis[3-[4-hydroxy-3,5-bis(2-methyl-2 -Propanyl)phenyl]propanoate](1,6-Hexanediylbis[3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate]), 4-[[4 ,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol (4-[[4,6-bis(octylsulfanyl) -1,3,5-triazin-2-yl]amino]-2,6-ditert-butylphenol), n-phenyl-1-naphthylamine (n-phenyl-1-naphthylamine), bis[4-(2 -Phenyl-2-propyl)phenyl]amine (bis[4-(2-phenyl-2-propyl)phenyl]amine), N,N'-diphenyl-1,4-phenylenediamine (N ,N'-Diphenyl-1,4-benzenediamine), (1,2-dioxo-1,2-ethanediyl)bis(imino-2,1-ethanediamine)bis[3-[4- Hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propionate]((1,2-Dioxo-1,2-ethanediyl)bis(imino-2,1-ethanediyl)bis [3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl)phenyl]propanoate]), N,N'-diethylthiourea (N,N'-diethylthiourea) and 1,3 - Diphenylguanidine (1,3-Diphenylguanidine).
所述的增塑剂(plasticizers)包括丁二酸二乙酯(diethyl succinate)、己二酸二甲酯(dimethyl adipate)、己二酸二乙酯(diethyl adipate)、壬二酸二甲酯(dimethylazelate)、2,2,4-三甲基-1,3-戊二醇二异丁酸酯(2,2,4-trimethyl-1,3-pentanediol-diisobutyrate)、富马酸二丁酯(dibutyl fumarate)、癸二酸二甲酯(dimethylsebacate)、肉豆蔻酸异丙酯(isopropyl myristate)、柠檬酸三乙酯(Triethyl citrate)、二甘醇二苯甲酸酯(Diethylene glycol dibenzoate)、癸二酸二丁酯(dibutylsebacate)、棕榈酸异丙酯(Isopropyl palmitate)、乙酰柠檬酸三乙酯(Acetyl triethylcitrate)、油酸丙酯(n-Propyl oleate)、马来酸二(2-乙基己基)酯(Di(2-ethylhexyl)maleate)、二苯甲酸二聚丙二醇酯(Oxydipropyl dibenzoate)、甘油单油酸酯(Glycerolmonooleate)、 壬二酸二己酯(Di-n-hexyl azelate)、硬脂酸甘油酯(Glycerolmonostearate)、柠檬酸三丁酯(Tributyl citrate)、(Z)-油酸-2-四氢呋喃甲酯(Tetrahydrofurfuryl oleate)、12-乙酰氧基-[R-(Z)]-9-烯-十八酸丁酯(n-Butylacetyl ricinoleate)、壬二酸二异辛酯(Diisooctyl azelate)、乙酰柠檬酸三正丁酯(acetyl tri-n-butyl citrate)、癸二酸二异辛酯(2-Ethylhexyl sebacate)、丁酰柠檬酸三正己酯(n-Butyryltri-n-hexyl citrate)、己二酸庚基壬基酯(di(n-heptyl,n-nonyl)adipate)、己二酸二丁酯(dibutyl adipate)、己二酸二异癸烷基酯(diisodecyladipate)、环己烷1，2-二甲酸二异壬基酯(di-isononyl cyclohexane-1,2-dicarboxylate)和偏苯三酸三辛酯(trioctyl trimellitate)。Described plasticizer (plasticizers) comprises diethyl succinate (diethyl succinate), dimethyl adipate (dimethyl adipate), diethyl adipate (diethyl adipate), dimethyl azelate ( dimethylazelate), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol-diisobutyrate), dibutyl fumarate ( dibutyl fumarate), dimethylsebacate, isopropyl myristate, triethyl citrate, diethylene glycol dibenzoate, decyl Dibutylsebacate, Isopropyl palmitate, Acetyl triethylcitrate, n-Propyl oleate, Di(2-ethyl maleate) Hexyl) ester (Di(2-ethylhexyl) maleate), dipropylene glycol dibenzoate (Oxydipropyl dibenzoate), glycerol monooleate (Glycerolmonooleate), di-n-hexyl azelate (Di-n-hexyl azelate), hard Glycerolmonostearate, Tributyl citrate, (Z)-oleic acid-2-tetrahydrofurfuryl oleate, 12-acetoxy-[R-(Z)]-9 -ene-butyl octadecanoate (n-Butylacetyl ricinoleate), diisooctyl azelate (Diisooctyl azelate), acetyl tri-n-butyl citrate (acetyl tri-n-butyl citrate), diisooctyl sebacate 2-Ethylhexyl sebacate, n-Butyryltri-n-hexyl citrate, di(n-heptyl,n-nonyl) adipate, di(n-heptyl,n-nonyl) adipate dibutyl adipate, diisodecyl adipate, di-isononyl cyclohexane-1,2-dicarbox ylate) and trioctyl trimellitate.
所述的全氟化合物包括全氟正辛酸(Perfluoro-n-octanoic acid)、全氟辛烷磺酸(perfluorooctane sulfonic acid)、全氟正丁酸(Perfluoro-n-butanoic acid)、全氟正庚酸(Perfluoro-n-heptanoic acid)、全氟正己酸(Perfluoro-n-hexanoic acid)、全氟正癸酸(Perfluoro-n-decanoic acid)、全氟正十二烷酸(Perfluoro-n-dodecanoicacid)、全氟正壬酸(Perfluoro-n-nonanoic acid)、全氟正十一烷酸(Perfluoro-n-undecanoic acid)、全氟正戊酸(Perfluoro-n-pentanoic acid)、全氟正十四烷酸(Perfluoro-n-tetradecanoic acid)、全氟正十三烷酸(Perfluoro-n-tridecanoicacid)、全氟-1-丁烷磺酸钾(Potassium perfluoro-1-butanesulfonate)、全氟-1-癸烷磺酸钠(Sodium perfluoro-1-decanesulfonate)、全氟-1-庚烷磺酸钠(Sodium perfluoro-1-heptanesulfonate)、全氟-1-己磺酸钠(Sodium perfluoro-1-hexanesulfonate)、全氟-1-辛烷磺酰胺(Perfluoro-1-octanesulfonamide)、N-甲基全氟-1-辛磺酰胺(N-methylperfluoro-1-octansulfonamide)、N-乙基全氟-1-辛烷磺酰胺(N-ethylperfluoro-1-octanesulfonamide)、1H,1H,2H,2H-全氟己烷磺酸钠(4:2)(Sodium1H,1H,2H,2H-perfluorohexane sulfonate(4:2))、1H,1H,2H,2H-全氟辛烷磺酸钠(6:2)(Sodium1H,1H,2H,2H-perfluorooctane sulfonate(6:2))、1H,1H,2H,2H-全氟癸烷磺酸钠(8:2)(Sodium1H,1H,2H,2H-perfluorodecane sulfonate(8:2))、氯十六烷-氟-3-氧杂戊烷-1-磺酸钾(Potassium9-chlorohexadeca-fluoro-3-oxanonane-1-sulfonate)、11-氯二十碳氟-3-氧十一烷-1-磺酸钾(Potassium11-chloroeicosafluoro-3-oxaundecane-1-sulfonate)和全氟-2,5-二甲基-3,6-二恶烷酸(perfluoro-2,5-dimethyl-3,6-dioxanonanoic acid)。The perfluorinated compounds include perfluoron-octanoic acid (Perfluoro-n-octanoic acid), perfluorooctane sulfonic acid (perfluorooctane sulfonic acid), perfluoron-butanoic acid (Perfluoro-n-butanoic acid), perfluoron-heptyl Perfluoro-n-heptanoic acid, Perfluoro-n-hexanoic acid, Perfluoro-n-decanoic acid, Perfluoro-n-dodecanoic acid ), Perfluoro-n-nonanoic acid, Perfluoro-n-undecanoic acid, Perfluoro-n-pentanoic acid, Perfluoro-n-decanoic acid Perfluoro-n-tetradecanoic acid, Perfluoro-n-tridecanoic acid, Potassium perfluoro-1-butanesulfonate, Perfluoro-1 -Sodium perfluoro-1-decanesulfonate, Sodium perfluoro-1-heptanesulfonate, Sodium perfluoro-1-hexanesulfonate ), Perfluoro-1-octanesulfonamide, N-methylperfluoro-1-octansulfonamide, N-ethyl perfluoro-1- Octanesulfonamide (N-ethylperfluoro-1-octanesulfonamide), 1H,1H,2H,2H-perfluorohexane sulfonate (4:2) (Sodium1H,1H,2H,2H-perfluorohexane sulfonate(4:2) ), 1H,1H,2H,2H-sodium perfluorooctane sulfonate (6:2) (Sodium1H,1H,2H,2H-perfluorooctane sulfonate(6:2)), 1H,1H,2H,2H-perfluorooctane Sodium decane sulfonate (8:2) (Sodium1H,1H,2H,2H-perfluorodecane sulfonate(8:2)), chlorohexadecane-fluoro -3-oxapentane-1-sulfonate potassium (Potassium9-chlorohexadeca-fluoro-3-oxanonane-1-sulfonate), 11-chloroeicosane-3-oxoundecane-1-sulfonate potassium ( Potassium11-chloroeicosafluoro-3-oxaundecane-1-sulfonate) and perfluoro-2,5-dimethyl-3,6-dioxane acid (perfluoro-2,5-dimethyl-3,6-dioxanonanoic acid).
所述的有机磷农药包括毒死蜱(dursban/chlorpyrifos)、二嗪农(diazinon)、甲基对硫磷(parathion-methyl)、对硫磷(parathion)、马拉硫磷(malathion)、乐果(dimethoate)、敌敌畏(dichlorvos)、3-甲基-4-硝基苯酚(3-methyl-4-nitrophenol)、香豆磷(coumaphos)、二恶唑磷(dioxabenzofos)、杀灭磷(edifenphos)、2-异丙基-6-甲基-4-嘧啶醇(2-isopropyl-6-methyl-4-pyrimidinol)、异灭磷(isofenphos-methyl)、美卡巴姆(mecarbam)、杀虫剂(methacrifos)、磷酮(phosalone)、吡唑磷(pyrazophos)和对硝基苯酚(p-Nitrophenol)。The organophosphorus pesticides include chlorpyrifos (dursban/chlorpyrifos), diazinon (diazinon), methyl parathion (parathion-methyl), parathion (parathion), malathion (malathion), dimethoate ( dimethoate), dichlorvos (dichlorvos), 3-methyl-4-nitrophenol (3-methyl-4-nitrophenol), coumaphos, dioxabenzofos, edifenphos, 2-isopropyl-6-methyl-4-pyrimidinol (2-isopropyl-6-methyl-4-pyrimidinol), isofenphos-methyl, mecarbam, insecticides (methacrifos ), phosalone, pyrazophos and p-Nitrophenol.
所述的拟除虫菊酯包括3-苯氧基苄醇(3-PBA)、4-氟-3-苯氧基苯甲酸(4-fluoro-3-phenoxy benzoic acid)、顺-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基-环丙烷羧酸(cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl-cyclopropanecarbox ylic acid)和高效氯氟氰菊酯(Lambda-cyhalothrin)。Described pyrethroids include 3-phenoxybenzyl alcohol (3-PBA), 4-fluoro-3-phenoxybenzoic acid (4-fluoro-3-phenoxybenzoic acid), cis-3-(2- Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl-cyclopropanecarboxylic acid (cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl )-2,2-dimethyl-cyclopropanecarbox ylic acid) and Lambda-cyhalothrin.
所述的新烟碱类农药包括啶虫脒(Acetamiprid)、呋虫胺(Dinotefuran)、吡虫啉(Imidacloprid)、噻虫啉(Thiacloprid)和噻虫嗪(Thiamethoxam)。The neonicotinoid pesticides include Acetamiprid, Dinotefuran, Imidacloprid, Thiacloprid and Thiamethoxam.
所述的氨基甲酸酯类农药包括多菌灵(Carbendazim)、呋喃丹 (Carbofuran)、氯丙胺(Chlorpropham)、非诺威(Fenobucarb)、异威威(Iprovalicarb)、灭多威(Methomyl)、抗蚜威(Pirimicarb)和苯胺灵(Propham)。The carbamate pesticides include Carbendazim, Carbofuran, Chlorpropham, Fenobucarb, Iprovalicarb, Methomyl, anti Pirimicarb and Propham.
所述的酸性除草剂包括2,4-二氯苯氧丁酸(2,4-DB)、2,4,5-涕丙酸(2,4,5-TP(Silvex))、2,4,5-三氯苯氧乙酸(2,4,5-trichlorophenoxyacetic acid)、2,4-滴丙酸(Dichlorprop)、2-甲基-4-氯苯氧乙酸(MCPA)、2-甲基-4-氯戊氧基丙酸(Mecoprop)和2-甲基-4-氯苯氧基丁酸(MCPB)。The acidic herbicides include 2,4-dichlorophenoxybutyric acid (2,4-DB), 2,4,5-propionic acid (2,4,5-TP (Silvex)), 2,4 ,5-trichlorophenoxyacetic acid (2,4,5-trichlorophenoxyacetic acid), 2,4-dichlorprop, 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2-methyl- 4-chloropentyloxypropionic acid (Mecoprop) and 2-methyl-4-chlorophenoxybutyric acid (MCPB).
所述的唑类农药包括联苯三唑醇(Bitertanol)、环唑醇(Cyproconazole)、苯醚甲环唑(Difenoconazole)、氟环唑(Epoxiconazole)、芬布康唑(Fenbuconazole)、氟硅唑(Flusilazole)、抑菌灵(Imazalil)、丁苯胺(Myclobutanil)、戊康唑(Penconazole)、丙氯灵(Prochloraz)、戊唑醇(Tebuconazole)、四康唑(Tetraconazole)和噻菌灵(Thiabendazole)。The azole pesticides include Bitertanol, Cyproconazole, Difenoconazole, Epoxiconazole, Fenbuconazole, Flusilazole (Flusilazole), Imazalil, Myclobutanil, Penconazole, Prochloraz, Tebuconazole, Tetraconazole, and Thiabendazole ).
所述的三唑酮类农药包括氯唑草酮(Chloridazon)、己嗪酮(Hexazinone)、苯嗪草酮(Metamitron)、嗪草酮(Metribuzin)、苯胺(ametryn)、阿特拉顿(atraton)、阿特拉津(atrazine)、扑灭通(prometon)、扑草净(prometryn)、扑灭津(propazine)、仲丁通(secbumeton)、西玛津(simazine)、西草净(simetryn)和特丁净(terbutryn/prenane)。The triadimefon pesticides include Chloridazon, Hexazinone, Metamitron, Metribuzin, Atryn, Atraton ), atrazine, prometon, prometryn, propazine, secbumeton, simazine, simetryn and Terbutryn/prenane.
所述的尿素类农药包括氯磺隆(Chloroxuron)、氯脲酮(Chlortoluron)、1-(3,4-二氯苯基)-3-甲基脲(1-(3,4-dichlorophenyl)-3-methylurea)、1-(3,5-二氯苯基)脲(DCPU)、甲基苯噻隆(Methabenzthiazuron)、溴谷隆(Metobromuron)、甲氧隆(Metoxuron)、敌草隆(Diuron)、3-苯基-1,1-二甲基脲(Fenuron)、异丙隆(Isoproturon)和利谷隆(Linuron)。The urea pesticides include Chloroxuron, Chlortoluron, 1-(3,4-dichlorophenyl)-3-methylurea (1-(3,4-dichlorophenyl)- 3-methylurea), 1-(3,5-dichlorophenyl)urea (DCPU), Methabenzthiazuron, Metobromuron, Metoxuron, Diuron ), 3-phenyl-1,1-dimethylurea (Fenuron), isoproturon (Isoproturon) and Linuron (Linuron).
所述的酰胺类农药包括甲草胺(Alachlor)、二甲草胺(Dimethachlor)、N,N-二甲基氨基-N-甲苯(DMST)和环酰菌胺(Fenhexamid)。The amide pesticides include Alachlor, Dimethachlor, N,N-dimethylamino-N-toluene (DMST) and Fenhexamid.
所述的甲氧基丙烯酸酯类杀菌剂包括嘧菌酯(Azoxystrobin)、嘧螨酯(Fluacrypyrim)、醚菌酯(Kresoxim-methyl)、吡唑醚菌酯(Pyraclostrobin)和肟菌酯(Trifloxystrobin)。The methoxyacrylate fungicides include Azoxystrobin, Fluacrypyrim, Kresoxim-methyl, Pyraclostrobin and Trifloxystrobin .
所述的其他杀虫剂包括氟担菌宁(Flutolanil)、啶酰菌胺(Boscalid)、恶唑菌酮(Famoxadone)、甲霜灵(Metalaxyl)、氟苯嘧啶醇(Nuarimol)和苄草丹(Prosulfocarb)。Other insecticides mentioned include Flutolanil, Boscalid, Famoxadone, Metalaxyl, Nuarimol, and procarbal (Prosulfocarb).
步骤(4)中所述的气相色谱-串联质谱法为采用气相色谱-串联质谱联用仪进行。The gas chromatography-tandem mass spectrometry described in step (4) is carried out by using gas chromatography-tandem mass spectrometry.
步骤(4)中所述的采用气相色谱-串联质谱法(GC-MS/MS)对环境污染物进行定量分析的污染物包括有机氯农药和液晶单体中的至少一种。The pollutants for quantitative analysis of environmental pollutants by gas chromatography-tandem mass spectrometry (GC-MS/MS) described in step (4) include at least one of organochlorine pesticides and liquid crystal monomers.
所述的有机氯农药包括二氯丙酸(Aldrin)、ALPHA-六六六(α-HCH)、BETA-六六六(β-HCH)、林丹(γ-HCH(lindane))、δ-六六六(δ-HCH)、Ε-六六六(ε-HCH)、顺式A-氯丹(cis-chlordane)、反式氯丹(trans-chlordane)、氧氯丹(oxy-chlordane)、4,4-滴滴滴(p.p′-DDD)、2,2-双(4-氯苯基)-1,1-二氯乙烯(p.p′-DDE)、2,2-双(对氯苯基)-1,1,1-三氯乙烷(p.p′-DDT)、1-(2-氯苯基)-1-(4-氯苯基)-2,2-二氯乙烷(o.p′-DDD)、3-邻氯苯基-2-对氯苯基-1,1-二氯乙烯溶液(o.p′-DDE)、1,1,1-三氯-2-(2-氯苯基)-2-(4-氯苯基)乙烷(o.p′-DDT)、狄氏剂(Dieldrin)、alpha-硫丹(α-Endosulfan)、BETA-硫丹(β-Endosulfan)、安特灵(Endrin)、异狄氏剂酮(Endrin ketone)、七氯(Heptachlor)、内环氧七氯(Heptachlor-exo-epoxide)、六氯苯(Hexachlorobenzene)和吡唑草胺(Metazachlor)。The organochlorine pesticides include dichloropropionic acid (Aldrin), ALPHA-666 (α-HCH), BETA-666 (β-HCH), Lindane (γ-HCH (lindane)), δ-6 66 (δ-HCH), Ε-666 (ε-HCH), cis-chlordane (cis-chlordane), trans-chlordane (trans-chlordane), oxy-chlordane (oxy-chlordane), 4,4-Didididi (p.p′-DDD), 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p.p′-DDE), 2,2-bis(p-chlorobenzene base)-1,1,1-trichloroethane (p.p′-DDT), 1-(2-chlorophenyl)-1-(4-chlorophenyl)-2,2-dichloroethane (o.p '-DDD), 3-o-chlorophenyl-2-p-chlorophenyl-1,1-dichloroethylene solution (o.p'-DDE), 1,1,1-trichloro-2-(2-chlorobenzene base)-2-(4-chlorophenyl)ethane (o.p′-DDT), Dieldrin, alpha-Endosulfan (α-Endosulfan), BETA-Endosulfan (β-Endosulfan), Antetra Endrin, Endrin ketone, Heptachlor, Heptachlor-exo-epoxide, Hexachlorobenzene and Metazachlor.
所述的液晶单体包括4-乙烯基-4'-丙基-1,1'-联环己烷(1-(4-propylcyclohexyl)-4-vinylcyclohexane)、1-甲氧基-4-(4-丙基环己基)环己烷(1-methoxy-4-(4-propylcyclohexy1)cyclohexane)、1-(丙-1-烯基)-4-(4-丙基环己基)环己烷(1-(prop-l-enyl)-4-(4-propylcyclohexyl)cyclohexane)、1-乙氧基-2,3-二氟-4-(4-丙基环己基)苯 (1-ethoxy-2,3-difluoro-4-(4-propylcyclohexyl)benzene)、4-甲基-4'-戊基联苯(4-methyl-4'-pentylbiphenyl)、1-乙氧基-2,3-二氟-4-(4-丙基苯基)苯(1-ethoxy-2,3-difluoro-4-(4-propylphenyl)benzene)、4-(4-乙基环己基)-4'-(三氟甲氧基)联苯(4-(4-ethylcyclohexyl)-4'-(tnfluoromethoxy)biphenyl)、4-(4-甲基苯基)-4'-乙烯基-1,1'-双(环己基)(4-(4-methylphenyl)-4'-vinyl-1,1'-bi(cyclohexyl))、4-[二氟(3,4,5-三氟苯氧基)甲基]-3,5-二氟-4'-丙基联苯(4-[difluoro(3,4,5-trifluorophenoxy)methyl]-3,5-difluoro-4'-propylbiphenyl)、1-甲基-4-(4-(4-丙基环己基)环己基)苯(1-methyl-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene)、4-[二氟(2-甲基-3,4,5-三氟苯氧基)甲基]-3,5-二氟-4'-丙基联苯(4-[difluoro(2-methyl-3,4,5-trifluorophenoxy)methyl]-3,5-difluoro-4'-propylbi phenyl)、2,3-二氟-1-甲氧基-4-(4-(4-丙基环己基)环己基)苯(2,3-difluoro-l-methoxy-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene)、l-乙基-4-(4-(4丙基环己基)苯基)苯(l-ethyl-4-(4-(4propylcyclohexyl)phenyl)benzene)、2，3-二氟-1-乙氧基-4-(4-(4-乙基环己基)苯基)苯(2,3-difluoro-1-ethoxy-4-(4-(4-ethylcyclohexyl)phenyl)benzene)、4"-乙基-2'-氟-4-丙基-l,l':4',1"-三联苯(4"-ethyl-2'-fluoro-4-propyl-l,l':4',1"-terphenyl)、(4-乙氧基-2,3-二氟-4'-(4-丙基环己基)联苯)(4-ethoxy-2,3-difluoro-4'-(4-propylcyclohexyl)biphenyl)、2,3-二氟-1-丙氧基-4-(4-(4-丙基环己基)环己基)苯(2,3-difluoro-l-propoxy-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene)、1-(4-(4-丁基环己基)环己基)-4-乙氧基-2,3-二氟苯(1-(4-(4-butylcyclohexyl)cyclohexyl)-4-ethoxy-2,3-difluorobenzene)、4-丁基-4"-乙基-2'-氟-l,l':4',1"-三联苯(4-butyl-4"-ethyl-2'-fluoro-l,l':4',1"-terphenyl)、3,4-二氟-4'-[4'-乙基-1,1'-双(环己基)-4-基]联苯(3,4-difluoro-4'-[4'-ethyl-1,1'-bi(cyclohexyl)-4-yl]biphenyl)、3,4-二氟-4'-丙基-l,l'-联苯(3,4-difluoro-4'-propyl-l,l'-Biphenyl)、4'-乙基联苯-4-甲腈(4'-ethylbiphenyl-4-carbonitril)、4'-丙氧基-4-联苯甲腈(4'-propoxy-4-biphenylcarbonitrfle)、4-丙基1-4'-[4-(三氟甲氧基)苯基]-1,1'-双环己基(4-propy1-4'-[4-(trifluoromethoxy)phenyl]-1,1'-bicyclohexyl)、4"-乙基-2',3,4,5-四氟-1,1':4',1"-三联苯(4"-ethyl-2',3,4,5-tetrafluoro-1,1':4',1"-terphenyl)、4-氰基-4'-戊氧基联苯(4-cyano-4'-pentyloxybiphenyl)、4-己氧基-4-联苯甲腈(4-hexyloxy-4-biphenylcarbonitrile)和4'-(辛氧基)-4-联苯甲腈(4'-(octyloxy)-4-biphenylcarbonitrile)。The liquid crystal monomers include 4-vinyl-4'-propyl-1,1'-bicyclohexyl (1-(4-propylcyclohexyl)-4-vinylcyclohexane), 1-methoxy-4-( 4-propylcyclohexyl) cyclohexane (1-methoxy-4-(4-propylcyclohexyl)cyclohexane), 1-(prop-1-enyl)-4-(4-propylcyclohexyl)cyclohexane ( 1-(prop-l-enyl)-4-(4-propylcyclohexyl)cyclohexane), 1-ethoxy-2,3-difluoro-4-(4-propylcyclohexyl)benzene (1-ethoxy-2 ,3-difluoro-4-(4-propylcyclohexyl)benzene), 4-methyl-4'-pentyl biphenyl (4-methyl-4'-pentylbiphenyl), 1-ethoxy-2,3-difluoro -4-(4-propylphenyl)benzene (1-ethoxy-2,3-difluoro-4-(4-propylphenyl)benzene), 4-(4-ethylcyclohexyl)-4'-(trifluoro Methoxy)biphenyl (4-(4-ethylcyclohexyl)-4'-(tnfluoromethoxy)biphenyl), 4-(4-methylphenyl)-4'-vinyl-1,1'-bis(cyclohexyl )(4-(4-methylphenyl)-4'-vinyl-1,1'-bi(cyclohexyl)), 4-[difluoro(3,4,5-trifluorophenoxy)methyl]-3, 5-difluoro-4'-propylbiphenyl (4-[difluoro(3,4,5-trifluorophenoxy)methyl]-3,5-difluoro-4'-propylbiphenyl), 1-methyl-4-(4 -(4-propylcyclohexyl)cyclohexyl)benzene (1-methyl-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene), 4-[difluoro(2-methyl-3,4,5- Trifluorophenoxy)methyl]-3,5-difluoro-4'-propylbiphenyl (4-[difluoro(2-methyl-3,4,5-trifluorophenoxy)methyl]-3,5-difluoro -4'-propylbi phenyl), 2,3-difluoro-1-methoxy-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene (2,3-difluoro-l-methoxy-4 -(4-(4-propylcyclohexyl)cyclohexyl)benzene), l-ethyl-4-(4-(4propane ylcyclohexyl)phenyl)benzene (l-ethyl-4-(4-(4propylcyclohexyl)phenyl)benzene), 2,3-difluoro-1-ethoxy-4-(4-(4-ethylcyclo Hexyl)phenyl)benzene (2,3-difluoro-1-ethoxy-4-(4-(4-ethylcyclohexyl)phenyl)benzene), 4"-ethyl-2'-fluoro-4-propyl-l, l':4',1"-terphenyl (4"-ethyl-2'-fluoro-4-propyl-l,l':4',1"-terphenyl), (4-ethoxy-2,3 -Difluoro-4'-(4-propylcyclohexyl)biphenyl)(4-ethoxy-2,3-difluoro-4'-(4-propylcyclohexyl)biphenyl), 2,3-difluoro-1-propane Oxygen-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene (2,3-difluoro-l-propoxy-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene), 1-(4 -(4-butylcyclohexyl)cyclohexyl)-4-ethoxy-2,3-difluorobenzene (1-(4-(4-butylcyclohexyl)cyclohexyl)-4-ethoxy-2,3-difluorobenzene), 4 -Butyl-4"-ethyl-2'-fluoro-l,l':4',1"-terphenyl (4-butyl-4"-ethyl-2'-fluoro-l,l':4' ,1"-terphenyl), 3,4-difluoro-4'-[4'-ethyl-1,1'-bis(cyclohexyl)-4-yl]biphenyl (3,4-difluoro-4' -[4'-ethyl-1,1'-bi(cyclohexyl)-4-yl]biphenyl), 3,4-difluoro-4'-propyl-l,l'-biphenyl (3,4-difluoro -4'-propyl-l, l'-Biphenyl), 4'-ethylbiphenyl-4-carbonitrile (4'-ethylbiphenyl-4-carbonitril), 4'-propoxy-4-biphenylcarbonitrile (4'-propoxy-4-biphenylcarbonitrfle), 4-propyl 1-4'-[4-(trifluoromethoxy)phenyl]-1,1'-bicyclohexyl (4-propy1-4'-[ 4-(trifluoromethoxy)phenyl]-1,1'-bicyclohexyl), 4"-ethyl-2',3,4,5-tetrafluoro-1,1':4',1"-terphenyl (4" -ethyl-2',3,4,5-tetraflu oro-1,1':4',1"-terphenyl), 4-cyano-4'-pentyloxybiphenyl (4-cyano-4'-pentyloxybiphenyl), 4-hexyloxy-4-biphenyl Carbonitrile (4-hexyloxy-4-biphenylcarbonitrile) and 4'-(octyloxy)-4-biphenylcarbonitrile (4'-(octyloxy)-4-biphenylcarbonitrile).
步骤(4)中所述的液相色谱-串联质谱法的检测条件如下：The detection condition of the liquid chromatography-tandem mass spectrometry described in step (4) is as follows:
①邻苯二甲酸二酯类(Phthalate diesters)：① Phthalate diesters:
色谱条件包括：Chromatographic conditions include:
流动相A：体积分数为0.1％的甲酸水溶液；Mobile phase A: 0.1% formic acid aqueous solution by volume fraction;
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：C18色谱柱(优选为：Luna 2.5μm C18(2)-HST 100×2.0mm)；Chromatographic column: C18 chromatographic column (preferably: Luna 2.5μm C18(2)-HST 100×2.0mm);
流速：0.2mL/min；Flow rate: 0.2mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B的体积百分含量为40％；0～2min，流动相B体积百分数从40％上升至70％；2～8min，流动相B体积百分数上升至100％；8～13min保持在100％不变，13～13.1min流动相B体积百分数降 至40％；13.1～17min，保持在40％不变；Elution procedure: the initial volume percentage of mobile phase B is 40%; 0~2min, the volume percentage of mobile phase B rises from 40% to 70%; 2~8min, the volume percentage of mobile phase B rises to 100%; Keep at 100% for 13 minutes, the volume percentage of mobile phase B drops to 40% at 13-13.1 minutes; keep at 40% for 13.1-17 minutes;
质谱条件包括：电喷雾离子源，离子源温度为550℃；检测模式为正离子检测模式；Mass spectrometry conditions include: electrospray ionization source, ion source temperature is 550°C; detection mode is positive ion detection mode;
雾化气压：氮气，压力为55psi；Atomization pressure: nitrogen, the pressure is 55psi;
②邻苯二甲酸单酯类(Phthalate monoesters)，苯甲酮类紫外线稳定剂(Benzophenone UV stabilizers)，双酚类似物(Bisphenol analogues)以及个人护理产品(Personal Care Products)：② Phthalate monoesters, Benzophenone UV stabilizers, Bisphenol analogues and Personal Care Products:
色谱条件包括：Chromatographic conditions include:
流动相A：0.2mmol/L乙酸铵水溶液；Mobile phase A: 0.2mmol/L ammonium acetate aqueous solution;
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：C18色谱柱(优选为：ZORBAX Extended-C18 3.5μm 100×2.1mm)；Chromatographic column: C18 chromatographic column (preferably: ZORBAX Extended-C18 3.5μm 100×2.1mm);
流速：0.2mL/min；Flow rate: 0.2mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B的体积百分数为10％；0～0.5min保持在10％数不变；0.5～1min，流动相B体积百分数从10％上升至50％；1～7min，流动相B体积分数从50％上升至99％；7～10min，保持在99％不变；10～10.1min，从99％下降到10％，10.1～12min，流动相B体积分数保持在10％不变；Elution procedure: the volume percentage of the initial mobile phase B is 10%; 0-0.5min keeps the number constant at 10%; 0.5-1min, the volume percentage of the mobile phase B rises from 10% to 50%; B volume fraction increased from 50% to 99%; 7-10min, kept at 99%; 10-10.1min, decreased from 99% to 10%, 10.1-12min, mobile phase B volume fraction remained at 10% ;
质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
③增塑剂(plasticizers)，苯并噻唑类(Benzothiazoles UV stabilizers)、苯并三唑(benzotriazoles UV stabilizers)类和其他类别紫外稳定剂(other UVstabilizers)，光引发剂(photoinitiatorAdditives)以及在正离子检测模式下进行检测的抗氧化剂：③Plasticizers (plasticizers), benzothiazoles (Benzothiazoles UV stabilizers), benzotriazoles (benzotriazoles UV stabilizers) and other UV stabilizers (other UVstabilizers), photoinitiatorAdditives and positive ion detection Antioxidants detected in the mode:
色谱条件包括：Chromatographic conditions include:
流动相A：体积分数为0.1％的甲酸水溶液；Mobile phase A: 0.1% formic acid aqueous solution by volume fraction;
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：C18色谱柱(优选为：Luna 2.5μm C18(2)-HST 100×2.0mm)；Chromatographic column: C18 chromatographic column (preferably: Luna 2.5μm C18(2)-HST 100×2.0mm);
流速：0.3mL/min；Flow rate: 0.3mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B体积百分数为40％，0～2min保持40％不变；2～4min，流动相B体积百分数由40％上升至80％；4～14min，流动相B体积百分数从80％上升至100％；14～17min，流动相B体积百分数保持在100％不变；17～20min，流动相B体积百分数下降至40％，20～24min，流动相B体积百分数保持在40％不变；Elution procedure: initial mobile phase B volume percentage is 40%, 0-2min keeps 40% unchanged; 2-4min, mobile phase B volume percentage rises from 40% to 80%; 4-14min, mobile phase B volume percentage increases from 80% rises to 100%; 14-17min, the volume percentage of mobile phase B remains at 100%; 17-20min, the volume percentage of mobile phase B drops to 40%, 20-24min, the volume percentage of mobile phase B remains at 40% constant;
质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为正离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is positive ion detection mode; atomization pressure: nitrogen, pressure 55psi;
④有机磷酸三酯类(Organophosphate triesters)：④Organophosphate triesters:
色谱条件包括：Chromatographic conditions include:
流动相A：体积分数为0.1％甲酸水溶液；Mobile phase A: a volume fraction of 0.1% formic acid in water;
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：RP18色谱柱(优选为：ACQUITY UPLC BEH Shield RP18,1.7μm,100×2.1mm)；Chromatographic column: RP18 chromatographic column (preferably: ACQUITY UPLC BEH Shield RP18, 1.7μm, 100×2.1mm);
流速：0.3mL/min；Flow rate: 0.3mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B体积百分数为5％，0～1min保持在5％；1～3min流动相B体积分数从5％上升至40％；3～12min从40％上升至100％；12～15min保持100％不变；15～15.1min，流动相B体积百分数从 100％降至5％；15.1～18min，流动相B体积分数保持在5％不变；Elution procedure: initial mobile phase B volume percentage is 5%, 0-1min maintains at 5%; 1-3min mobile phase B volume fraction rises from 5% to 40%; 3-12min rises from 40% to 100%; 12 From 15 minutes to 15 minutes, keep 100% unchanged; from 15 to 15.1 minutes, the volume percentage of mobile phase B decreases from 100% to 5%; from 15.1 to 18 minutes, the volume percentage of mobile phase B remains unchanged at 5%;
质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
⑤有机磷酸二酯类(Organophosphate diesters)：⑤Organophosphate diesters:
色谱条件包括：Chromatographic conditions include:
流动相A：0.2mmol/L乙酸铵水溶液；Mobile phase A: 0.2mmol/L ammonium acetate aqueous solution;
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：RP18色谱柱，优选为：ACQUITY UPLC BEH Shield RP18,1.7μm,100×2.1mm)；Chromatographic column: RP18 chromatographic column, preferably: ACQUITY UPLC BEH Shield RP18, 1.7μm, 100×2.1mm);
流速：0.3mL/min；Flow rate: 0.3mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B体积百分数为5％，0～4min，从5％上升至35％；4～7min，B相体积分数从35％上升至80％；7～12min从80％升至100％；12～14min保持100％不变；14～15min，流动相B体积百分数从100％降至5％；15～20min，流动相B体积百分数保持在5％不变；Elution procedure: initial mobile phase B volume percentage is 5%, 0~4min, rise from 5% to 35%; 4~7min, B phase volume fraction rises from 35% to 80%; 7~12min, rise from 80% to 100%; 12-14min keep 100% unchanged; 14-15min, mobile phase B volume percentage decreases from 100% to 5%; 15-20min, mobile phase B volume percentage remains unchanged at 5%;
质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
⑥在负离子检测模式下进行检测的抗氧化剂：⑥Antioxidants detected in negative ion detection mode:
色谱条件包括：Chromatographic conditions include:
流动相A：4mmol/L乙酸铵水溶液；Mobile phase A: 4mmol/L ammonium acetate aqueous solution;
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：C18色谱柱，优选为：Luna 2.5μm C18(2)-HST 100×2.0mm；Chromatographic column: C18 chromatographic column, preferably: Luna 2.5μm C18(2)-HST 100×2.0mm;
流速：0.2mL/min；Flow rate: 0.2mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B的体积百分数为10％；0～0.5min保持10％不变；0.5～1min流动相B的体积百分数从10％上升至50％，1～7min上升至99％；7～10min保持在99％不变；10～10.1min，流动相B体积百分数迅速下降至10％；10.1～12min流动相B体积分数保持10％不变；Elution procedure: the initial volume percentage of mobile phase B is 10%; 0-0.5min keeps 10% unchanged; 0.5-1min the volume percentage of mobile phase B increases from 10% to 50%, and 1-7min rises to 99%; From 7 to 10 minutes, it remained at 99%; from 10 to 10.1 minutes, the volume percentage of mobile phase B dropped rapidly to 10%; from 10.1 to 12 minutes, the volume percentage of mobile phase B remained unchanged at 10%;
质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
⑦全氟化合物：⑦ Perfluorinated compounds:
色谱条件包括：Chromatographic conditions include:
流动相A：0.2mmol/L甲酸铵(pH＝4)；Mobile phase A: 0.2mmol/L ammonium formate (pH=4);
流动相B：甲醇；Mobile phase B: Methanol;
色谱柱：RP18色谱柱，优选为：ACQUITY UPLC BEH Shield RP18,1.7μm；100×2.1mm；Chromatographic column: RP18 chromatographic column, preferably: ACQUITY UPLC BEH Shield RP18, 1.7μm; 100×2.1mm;
流速：0.3mL/min；Flow rate: 0.3mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B体积百分数为40％；0～2min内保持40％不变，2～3min流动相B体积百分数上升至66％；3～12min上升至77％；12～14min流动相B体积分数由70％上升至100％，14～16min保持在100％不变；16～16.1min迅速降至40％；16.1～22流动相B体积分数保持在40％不变；Elution procedure: initial mobile phase B volume percentage is 40%; 40% remains unchanged within 0-2min, mobile phase B volume percentage rises to 66% in 2-3min; rises to 77% in 3-12min; mobile phase in 12-14min B volume fraction rises from 70% to 100%, and remains unchanged at 100% for 14-16 minutes; quickly drops to 40% for 16-16.1 minutes; 16.1-22 mobile phase B volume fraction remains unchanged at 40%;
质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
⑧有机磷农药(organophosphorus pesticide)，拟除虫菊酯(Pyrethroids)，新烟碱类农药(Neonicotinoids)，氨基甲酸酯类农药(Carbamates)，酸性除草剂(Acidherbicides)，唑类农药(Azoles)，三唑酮类农药(Triazines/triazone)，尿素类农药(Urea)，酰胺类农药(酰胺杀虫剂，Amide  pesticides)，甲氧基丙烯酸酯类杀菌剂(Strobilurins)，其他杀虫剂(Other Pesticides)：⑧Organophosphorus pesticides, Pyrethroids, Neonicotinoids, Carbamates, Acidherbicides, Azoles, Triazoles Ketone pesticides (Triazines/triazone), urea pesticides (Urea), amide pesticides (amide pesticides, Amide pesticides), methoxyacrylate fungicides (Strobilurins), other pesticides (Other Pesticides):
色谱条件包括：Chromatographic conditions include:
流动相A：5mmol/L的乙酸铵溶液；Mobile phase A: 5mmol/L ammonium acetate solution;
流动相B：乙腈；Mobile phase B: acetonitrile;
色谱柱：C18色谱柱，优选为：Kinetex 2.6μm C18 100*2.1mm；00D4462-AN；Chromatographic column: C18 chromatographic column, preferably: Kinetex 2.6μm C18 100*2.1mm; 00D4462-AN;
流速：0.4mL/min；Flow rate: 0.4mL/min;
柱温：40℃；Column temperature: 40°C;
洗脱程序：初始流动相B的体积百分数为2％；0～4min流动相B体积百分数从宏观2％上升至30％；4～22min流动相体积百分数从30％上升至68％；22～22.1min流动相B从68％上升至99％；22.1～23min，保持在99％不变；23～23.1min，流动相B体积百分数从99％降至2％；23.1～26min，保持2％不变；Elution procedure: the volume percentage of the initial mobile phase B is 2%; the volume percentage of the mobile phase B increases from 2% to 30% in 0-4min; the volume percentage of the mobile phase increases from 30% to 68% in 4-22min; 22-22.1 Min mobile phase B increased from 68% to 99%; 22.1~23min, kept at 99%; 23~23.1min, mobile phase B volume percentage decreased from 99% to 2%; 23.1~26min, kept 2% unchanged ;
质谱条件：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi。Mass spectrometry conditions: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi.
步骤(4)中所述的气相色谱-串联质谱法的的检测条件如下：The detection condition of gas chromatography-tandem mass spectrometry described in step (4) is as follows:
⑨有机氯农药：⑨Organochlorine pesticides:
色谱条件包括：Chromatographic conditions include:
色谱柱：安捷伦HP-5MS色谱柱19091S-433(Agilent 19091S-433，HP-5MS，30m×0.250mm×0.25μm)；Chromatographic column: Agilent HP-5MS chromatographic column 19091S-433 (Agilent 19091S-433, HP-5MS, 30m×0.250mm×0.25μm);
进样口温度：260℃；Injection port temperature: 260°C;
升温程序：起始温度60℃，保持1min；以5℃/min的速度升温至300℃后保持9min；Heating program: initial temperature is 60°C, keep for 1min; heat up to 300°C at a rate of 5°C/min, then keep for 9min;
质谱条件：电子轰击离子源，离子源温度为230℃，四极杆温度为150℃，溶剂延时3min；Mass spectrometry conditions: electron bombardment ion source, ion source temperature is 230°C, quadrupole temperature is 150°C, solvent delay is 3min;
⑩液晶单体：⑩Liquid crystal monomer:
色谱条件包括：Chromatographic conditions include:
色谱柱：安捷伦HP-5MS色谱柱19091S-433(Agilent 19091S-433，HP-5MS，30m×0.250mm×0.25μm)；Chromatographic column: Agilent HP-5MS chromatographic column 19091S-433 (Agilent 19091S-433, HP-5MS, 30m×0.250mm×0.25μm);
进样口温度：260℃；Injection port temperature: 260°C;
升温程序：起始温度80℃，保持2.5min；然后以25℃/min的速度升温至200℃后保持1min；再以10℃/min速度升至250℃后以5℃/min升至285℃，保持5min；最后以30℃/min的速度升至300℃，保持1min；Heating program: initial temperature 80°C, keep for 2.5min; then raise the temperature to 200°C at a rate of 25°C/min and keep for 1min; then rise to 250°C at a rate of 10°C/min and then rise to 285°C at a rate of 5°C/min , keep for 5min; finally rise to 300℃ at the speed of 30℃/min, keep for 1min;
质谱条件：电子轰击离子源，离子源温度230℃，四极杆温度为150℃，溶剂延时6min。Mass spectrometry conditions: electron bombardment ion source, ion source temperature 230°C, quadrupole temperature 150°C, solvent delay 6min.
所述的血浆中环境污染物靶向暴露组分析方法在非疾病诊断治疗目的的分析血浆中环境污染物中的应用。The application of the targeted exposure group analysis method for environmental pollutants in plasma to the analysis of environmental pollutants in plasma for non-disease diagnosis and treatment purposes.
本发明相对于现有技术具有如下的优点及效果：Compared with the prior art, the present invention has the following advantages and effects:
(1)本发明提供了一种高通量且便捷的人体血浆中环境污染物靶向暴露组分析方法，该方法能实现同时检测血浆中多种类型各异的环境污染物，前处理方便，分析时间短，成本低，能够最大程度提高分析效率，可为后续观察和检测环境中的污染物的混合效应对人体健康的影响提供技术支持。(1) The present invention provides a high-throughput and convenient method for targeted exposure group analysis of environmental pollutants in human plasma. This method can simultaneously detect various types of environmental pollutants in plasma, and the pre-treatment is convenient. The analysis time is short, the cost is low, the analysis efficiency can be improved to the greatest extent, and it can provide technical support for the follow-up observation and detection of the mixed effect of pollutants in the environment on human health.
(2)本发明方法能够同时分析血浆中不同种类数百种环境污染物，处理方法简便，耗时短，效率高。(2) The method of the present invention can simultaneously analyze hundreds of different kinds of environmental pollutants in blood plasma, and the processing method is simple, time-consuming and efficient.
(3)本发明中对血浆样品进行预处理时，将萃取液吹至近干用甲醇复溶后进行冷冻，让脂质析出，然后需要在冷冻离心机中保持低温进行冷冻离心，让脂质沉淀有助于上清液的转移，从而达到去除脂质的目的，减少 基质效应，进而提高加标回收率。(3) In the present invention, when the plasma sample is pretreated, the extract is blown to near dryness and redissolved with methanol for freezing to allow the lipid to separate out, and then it is necessary to keep the low temperature in a refrigerated centrifuge for refrigerated centrifugation to allow the lipid to precipitate It is helpful for the transfer of supernatant, so as to achieve the purpose of removing lipid, reduce matrix effect, and improve the recovery rate of standard addition.
附图说明Description of drawings
图1是本发明与对比例1的方法加标回收率对比结果图。Fig. 1 is the comparison result graph of the recovery rate of standard addition of the method of the present invention and comparative example 1.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。下列实施例中未注明具体实验条件的试验方法，通常按照常规实验条件或按照制造厂所建议的实验条件。除非特别说明，本发明所用试剂和原材料均可通过市售获得。Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field. For the test methods that do not indicate the specific experimental conditions in the following examples, usually follow the routine experimental conditions or the experimental conditions suggested by the manufacturer. Unless otherwise specified, the reagents and raw materials used in the present invention can be obtained commercially.
实施例中所涉及的萃取溶剂，即含0.6％甲酸的乙酸乙酯和正己烷的混合溶剂中的乙酸乙酯和正己烷至少为LC-MS级别，乙酸乙酯和正己烷体积比为3:2，用甲酸调节酸碱度(甲酸含量为0.6％)；例如配置500mL萃取剂，乙酸乙酯用量为298.2mL，正己烷用量为198.8mL，甲酸用量为3mL。The extraction solvent involved in the embodiment, that is, the ethyl acetate and normal hexane in the mixed solvent containing 0.6% formic acid ethyl acetate and normal hexane are at least LC-MS level, and the volume ratio of ethyl acetate and normal hexane is 3: 2. Use formic acid to adjust the pH (formic acid content is 0.6%); for example, configure 500mL extractant, the amount of ethyl acetate is 298.2mL, the amount of n-hexane is 198.8mL, and the amount of formic acid is 3mL.
实施例1：人体血浆中环境污染物靶向暴露组分析Example 1: Targeted exposome analysis of environmental pollutants in human plasma
(1)试剂与材料(1) Reagents and materials
从美国AccuStandard公司、美国Sigma-Aldrich公司、加拿大惠灵顿实验室以及加拿大Toronto Research Chemicals公司购买共377种化合物的标准品、74种作为回收率指示物或者内标的同位素标记的化学物质；其中包括39种有机磷酸酯(OPEs)(包括有机磷酸二酯类和有机磷酸三酯类)，36种邻苯二甲酸酯(PAEs)(包括邻苯二甲酸单酯类和邻苯二甲酸二酯类)，7种个人护理产品(PCPs)，14种苯酚类化合物(双酚类似物)，29种紫外稳定剂(UV)(包括苯甲酮类、苯并噻唑类、苯并三唑类以及其他类别紫外稳定剂)，15种光引发剂，34种抗氧化剂(AO)(包括正、负离子检测模式)，31种增塑剂，25种全氟化合物(PFCs)，18种有机磷农药(OPs)，24种有机氯农药(OCPs)，4种拟除虫菊酯，5种新烟碱类农药，8种氨基甲酸酯类农药，7种酸性除草剂，13种唑类农药，14种三唑酮类农药，11种尿素类农药，4种酰胺类农药(酰胺杀虫剂)，5种甲氧基丙烯酸酯类杀菌剂，6种其他类型农药(其他杀虫剂)，28种液晶单体(LCMs)。具体化合物的详细信息见表1。A total of 377 standard compounds and 74 isotope-labeled chemical substances used as recovery indicators or internal standards were purchased from AccuStandard Company of the United States, Sigma-Aldrich Company of the United States, Wellington Laboratory of Canada and Toronto Research Chemicals of Canada; including 39 kinds Organophosphate esters (OPEs) (including organophosphate diesters and organophosphate triesters), 36 phthalates (PAEs) (including phthalate monoesters and phthalate diesters) , 7 kinds of personal care products (PCPs), 14 kinds of phenolic compounds (bisphenol analogues), 29 kinds of ultraviolet stabilizers (UV) (including benzophenones, benzothiazoles, benzotriazoles and other categories UV stabilizers), 15 photoinitiators, 34 antioxidants (AO) (including positive and negative ion detection modes), 31 plasticizers, 25 perfluorinated compounds (PFCs), 18 organophosphorus pesticides (OPs) , 24 kinds of organochlorine pesticides (OCPs), 4 kinds of pyrethroids, 5 kinds of neonicotinoid pesticides, 8 kinds of carbamate pesticides, 7 kinds of acid herbicides, 13 kinds of azole pesticides, 14 kinds of triadimefon Pesticides, 11 kinds of urea pesticides, 4 kinds of amide pesticides (amide insecticides), 5 kinds of methoxyacrylate fungicides, 6 kinds of other types of pesticides (other insecticides), 28 kinds of liquid crystal monomers (LCMs ). Details of the specific compounds are listed in Table 1.
用超高效液相色谱质谱联用仪(5500Q Trap triple quadrupole-linear ion Trap mass spectrometer)和气相色谱串联质谱联用仪(7890B-5970A)对目标分析物进行测定，超高效液相色谱串联质谱联用仪器购置于加拿大多伦多AB Sciex公司；气相色谱串联质谱联用仪购置于美国安捷伦公司；实验所用氮吹仪(12N-EvapTM)购置于Oganomation公司；离心机购置于湖南湘仪公司；冷冻离心机购置于赛默飞世尔科技公司(ThermoFisher Scientific)；振荡仪购置与Kylin-Bell公司；实验所用试剂均为LC-MS级别，购买于Thermo Fisher Scientific公司。The target analytes were determined by ultra-high performance liquid chromatography-mass spectrometer (5500Q Trap triple quadrupole-linear ion Trap mass spectrometer) and gas chromatography-tandem mass spectrometer (7890B-5970A). The instrument was purchased from AB Sciex Company in Toronto, Canada; the gas chromatography tandem mass spectrometer was purchased from Agilent Company in the United States; the nitrogen blowing instrument (12N-EvapTM) used in the experiment was purchased from Oganomation Company; the centrifuge was purchased from Hunan Xiangyi Company; the refrigerated centrifuge Purchased from Thermo Fisher Scientific; the oscillator was purchased from Kylin-Bell; the reagents used in the experiment were all LC-MS grade and purchased from Thermo Fisher Scientific.
表1定量检测的化合物Table 1 Quantitatively detected compounds
Figure PCTCN2022105848-appb-000001
Figure PCTCN2022105848-appb-000001
Figure PCTCN2022105848-appb-000002
Figure PCTCN2022105848-appb-000002
Figure PCTCN2022105848-appb-000003
Figure PCTCN2022105848-appb-000003
Figure PCTCN2022105848-appb-000004
Figure PCTCN2022105848-appb-000004
Figure PCTCN2022105848-appb-000005
Figure PCTCN2022105848-appb-000005
Figure PCTCN2022105848-appb-000006
Figure PCTCN2022105848-appb-000006
Figure PCTCN2022105848-appb-000007
Figure PCTCN2022105848-appb-000007
Figure PCTCN2022105848-appb-000008
Figure PCTCN2022105848-appb-000008
Figure PCTCN2022105848-appb-000009
Figure PCTCN2022105848-appb-000009
Figure PCTCN2022105848-appb-000010
Figure PCTCN2022105848-appb-000010
Figure PCTCN2022105848-appb-000011
Figure PCTCN2022105848-appb-000011
Figure PCTCN2022105848-appb-000012
Figure PCTCN2022105848-appb-000012
Figure PCTCN2022105848-appb-000013
Figure PCTCN2022105848-appb-000013
Figure PCTCN2022105848-appb-000014
Figure PCTCN2022105848-appb-000014
(2)样品采集(2) Sample collection
血浆样品采集于中山大学第三附属医院(中国广州)，用采血管(美国BD公司)进行收集。收集后的血浆在3000rpm下离心三分钟将血浆和血细胞进行分离，取上清液即转移至玻璃瓶中，并在分析之前储存在-80℃下。本实验共采集10个志愿者的血浆样品。Plasma samples were collected at the Third Affiliated Hospital of Sun Yat-Sen University (Guangzhou, China) and collected with blood collection tubes (BD, USA). The collected plasma was centrifuged at 3000rpm for three minutes to separate plasma and blood cells, and the supernatant was transferred to a glass bottle and stored at -80°C before analysis. A total of 10 volunteer plasma samples were collected in this experiment.
(3)样品前处理与仪器分析(3) Sample pretreatment and instrumental analysis
①取200μL样品于15mL玻璃离心管中，加入回收率指示物(200μL血浆中每种回收率指示物的加入量为0.5～20ng，本实验具体加入回收率指示物的用量如下：有机磷酸二酯类回收率指示物5ng、有机磷酸三酯类回收率指示物2ng、邻苯二甲酸单酯类回收率指示物2ng、邻苯二甲酸二酯类回收率指示物1ng、个人护理产品回收率指示物2ng、双酚类似物回收率指示物2ng、苯甲酮类紫外线稳定剂类回收率指示5ng、苯并噻唑类紫外线稳定剂类回收率指示5ng、苯并三唑类紫外稳定剂类回收率指示5ng、其他类别紫外稳定剂类回收率指示5ng、光引发剂回收率指示5ng、抗氧化剂回收率指示5ng、增塑剂回收率指示5ng、全氟化合物回收率指示物0.5ng、有机磷农药回收率指示物5ng、有机氯农药回收率指示物20ng、拟除虫菊酯回收率指示物5ng、新烟碱类农药回收率指示物5ng、氨基甲酸酯类农药回收率指示物5ng、酸性除草剂回收率指示物5ng、唑类农药回收率指示物5ng、三唑酮类回收率指示物5ng、尿素类农药回收 率指示物5ng、酰胺杀虫剂回收率指示物5ng、甲氧基丙烯酸酯类杀菌剂回收率指示物5ng、其他杀虫剂回收率指示物5ng、液晶单体回收率指示物20ng)，混匀后在离心管内加入3mL萃取溶剂，然后将混合物旋转震荡5min后再在3000rpm下离心3min，取上清液转移至另一个玻璃离心管中，再重复上述步骤两次；其中，前两次萃取溶剂为含0.6％(v/v)甲酸的乙酸乙酯和正己烷的混合溶剂(乙酸乙酯：正己烷＝3：2，体积比)，第三次萃取剂为乙酸乙酯(3mL)；①Take 200 μL of the sample into a 15 mL glass centrifuge tube, and add the recovery indicator (the amount of each recovery indicator in 200 μL plasma is 0.5-20 ng, and the specific amount of the recovery indicator added in this experiment is as follows: organophosphate diester Phthalate recovery rate indicator 5ng, organophosphate triesters recovery rate indicator 2ng, phthalic acid monoesters recovery rate indicator 2ng, phthalic acid diesters recovery rate indicator 1ng, personal care product recovery rate indicator Object 2ng, bisphenol analogue recovery indicator 2ng, benzophenone UV stabilizer recovery indicator 5ng, benzothiazole UV stabilizer recovery indicator 5ng, benzotriazole UV stabilizer recovery Indicator 5ng, other categories of UV stabilizer recovery indicator 5ng, photoinitiator recovery indicator 5ng, antioxidant recovery indicator 5ng, plasticizer recovery indicator 5ng, perfluorinated compound recovery indicator 0.5ng, organophosphorus pesticide Recovery rate indicator 5ng, organochlorine pesticide recovery rate indicator 20ng, pyrethroid recovery rate indicator 5ng, neonicotinoid pesticide recovery rate indicator 5ng, carbamate pesticide recovery rate indicator 5ng, acid herbicide recovery Rate indicator 5ng, azole pesticide recovery rate indicator 5ng, triadimefolone recovery rate indicator 5ng, urea pesticide recovery rate indicator 5ng, amide insecticide recovery rate indicator 5ng, methoxyacrylate bactericidal Insecticide recovery indicator 5ng, other insecticide recovery indicator 5ng, liquid crystal monomer recovery indicator 20ng), after mixing, add 3mL extraction solvent into the centrifuge tube, then rotate the mixture for 5min and then centrifuge at 3000rpm 3min, the supernatant was transferred to another glass centrifuge tube, and the above steps were repeated twice; wherein, the first two extraction solvents were a mixed solvent of ethyl acetate containing 0.6% (v/v) formic acid and normal hexane ( Ethyl acetate:n-hexane=3:2, volume ratio), the third extractant is ethyl acetate (3mL);
②合并后的萃取液氮吹至近干后再加入50μL甲醇复溶，然后转移到1.5mL离心管中，-40℃下冷冻一晚后在冷冻离心机-10℃、15000rpm条件下离心5min，转移上清液至1.5mL进样瓶，加入内标(每种内标的用量为1～20ng，本实验中的内标用量如下：正模式内标蝇毒磷(coumaphos-d10)用量1ng、负模式内标双酚A-d16(BPA-d16)用量5ng、全氟化合物内标全氟-n-[13C8]辛酸(Perfluoro-n-[13C8]octanoic acid(M8PFOA))用量1ng、内标十氯二苯醚(Decachlorodiphenyl ether(DCDE))用量为20ng)(内标见表1)待进样分析。②The combined extracts were blown to nearly dry, then added 50 μL of methanol to redissolve, then transferred to a 1.5 mL centrifuge tube, frozen overnight at -40°C, centrifuged at -10°C, 15,000 rpm for 5 min in a refrigerated centrifuge, transferred Add the supernatant to a 1.5mL injection bottle, add internal standard (the amount of each internal standard is 1~20ng, the amount of internal standard in this experiment is as follows: the amount of internal standard coumaphos-d10 in positive mode is 1ng, and the amount of internal standard in negative mode is 1ng. The amount of internal standard bisphenol A-d16 (BPA-d16) is 5ng, the amount of perfluorochemical internal standard perfluoro-n-[13C8]octanoic acid (Perfluoro-n-[13C8]octanoic acid (M8PFOA)) is 1ng, the internal standard of decachloro The amount of diphenyl ether (Decachlorodiphenyl ether (DCDE)) is 20ng) (internal standard see Table 1) to be injected and analyzed.
目标化合物均在超高效液相色谱-串联质谱联用仪(UPLC-MS/MS)和气相色谱-串联质谱联用仪(GC-MS/MS)上对样品进行定量分析，共8种分析方法，具体信息如表2和3所示。其中：The target compounds were quantitatively analyzed on ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), with a total of 8 analysis methods , the specific information is shown in Tables 2 and 3. in:
LC-MS/MS中的质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式见表2；雾化气压：氮气，压力位55psi；The mass spectrometry conditions in LC-MS/MS include: electrospray ion source, ion temperature is 550°C, detection mode is shown in Table 2; atomization pressure: nitrogen, pressure position 55psi;
GC-MS/MS中的质谱条件包括：电子轰击离子源，离子源温度为230℃，四极杆温度为150℃，溶剂延时3min(有机氯农药)或6min(液晶单体)。The mass spectrometry conditions in GC-MS/MS include: electron bombardment ion source, ion source temperature of 230°C, quadrupole temperature of 150°C, solvent delay of 3min (organochlorine pesticide) or 6min (liquid crystal monomer).
表2化合物LC-MS/MS信息(柱温：40℃)Table 2 Compound LC-MS/MS information (column temperature: 40°C)
Figure PCTCN2022105848-appb-000015
Figure PCTCN2022105848-appb-000015
Figure PCTCN2022105848-appb-000016
Figure PCTCN2022105848-appb-000016
Figure PCTCN2022105848-appb-000017
Figure PCTCN2022105848-appb-000017
表3化合物GC-MS/MS信息(进样口温度：260℃)Table 3 Compound GC-MS/MS information (injection port temperature: 260°C)
Figure PCTCN2022105848-appb-000018
Figure PCTCN2022105848-appb-000018
(4)质量保证和质量控制(4) Quality assurance and quality control
质量保证和质量控制程序检测了程序空白和回收率指示物的回收率，同时对基质加标样品进行了分析。每处理10个不同血浆样品时同时处理两个实验室程序空白，用200μL超纯水替代实际样品来制备程序空白，处理过程与实际样品相同，三次重复。用AB Sciex 5500 Q Trap triple quadrupole-linear ion trap mass spectrometer分析软件Analyst 1.6.3软件积分计算所有样品的同位素标回收率为50～110％。The quality assurance and quality control procedures tested the recovery of the program blank and recovery indicators, while matrix-spiked samples were analyzed. When processing 10 different plasma samples, two laboratory program blanks were processed at the same time, and 200 μL of ultrapure water was used to replace the actual sample to prepare the program blank. The processing process was the same as that of the actual sample, and was repeated three times. The isotope standard recoveries of all samples were calculated by integrating with AB Sciex 5500 Q Trap triple quadrupole-linear ion trap mass spectrometer analysis software Analyst 1.6.3 software, ranging from 50% to 110%.
将标准品加入五份绵羊血血浆中(中国广州未来生物技术有限公司)，每种标准品加入量为1～10ng，本实验中的标准品的具体加入量如下：有机磷酸二酯类5ng、有机磷酸三酯类2ng、邻苯二甲酸单酯类2ng、邻苯二甲酸二酯类1ng、个人护理产品2ng、双酚类似物2.5ng、苯甲酮类紫外线稳定剂5ng、苯并噻唑类紫外稳定剂5ng、苯并三唑类紫外稳定剂5ng、其他类别紫外稳定剂2ng、光引发剂5ng、抗氧化剂5ng、增塑剂5ng、全氟化合物2ng、有机磷农药2ng、有机氯农药3.5ng、拟除虫菊酯2ng、新烟碱类2ng、氨基甲酸酯类农药2ng、酸性除草剂2ng、唑类农药2ng、三唑酮类农药2ng、尿素类农药2ng、酰胺杀虫剂2ng、甲氧基丙烯酸酯类农药2ng、其他杀虫剂2ng、液晶单体10ng，用上述步骤(3)相同的前处理方法处理(三次重复)，用AB Sciex 5500 Q Trap triple quadrupole-linear ion trap mass spectrometer分析软件Analyst 1.6.3软件积分计算获得目标化合物的平均回收率和基质效应：所有目标化合物的平均回收率范围在71～98％，基质效应在96～120％范围内。Add the standard product into five parts of sheep blood plasma (China Guangzhou Future Biotechnology Co., Ltd.), the amount of each standard product added is 1-10 ng, the specific added amount of the standard product in this experiment is as follows: Organophosphate triesters 2ng, phthalic acid monoesters 2ng, phthalic acid diesters 1ng, personal care products 2ng, bisphenol analogs 2.5ng, benzophenone UV stabilizers 5ng, benzothiazoles UV stabilizer 5ng, benzotriazole UV stabilizer 5ng, other types of UV stabilizer 2ng, photoinitiator 5ng, antioxidant 5ng, plasticizer 5ng, perfluorinated compound 2ng, organophosphorus pesticide 2ng, organochlorine pesticide 3.5 ng, pyrethroids 2ng, neonicotinoids 2ng, carbamate pesticides 2ng, acidic herbicides 2ng, azole pesticides 2ng, triadimefon pesticides 2ng, urea pesticides 2ng, amide insecticides 2ng, methoxy 2ng of acrylate pesticides, 2ng of other insecticides, and 10ng of liquid crystal monomers were treated with the same pretreatment method as in step (3) above (three repetitions), and analyzed by AB Sciex 5500 Q Trap triple quadrupole-linear ion trap mass spectrometer The average recovery rate and matrix effect of the target compound were calculated by software Analyst 1.6.3 software integration: the average recovery rate of all target compounds was in the range of 71-98%, and the matrix effect was in the range of 96-120%.
每类化合物用五个以上浓度水平的标准曲线进行定量，标准曲线的相关系数大于0.995。方法定量限(limit of quantification，LOQ)即检出限定义为3倍或10倍于噪声标准方差的响应所对应的化合物浓度，若计算得出LOQ低于空白中的背景污染值，使用最高空白浓度作为LOQ。具体所有化合物的LOQ如表1所示。Each type of compound was quantified using a standard curve with more than five concentration levels, and the correlation coefficient of the standard curve was greater than 0.995. The limit of quantification (LOQ) of the method is defined as the concentration of the compound corresponding to the response of 3 times or 10 times the standard deviation of the noise. If the calculated LOQ is lower than the background contamination value in the blank, use the highest blank Concentrations were used as LOQ. The LOQs of all compounds are shown in Table 1.
(5)分析结果(5) Analysis results
总共所测化合物为377种，共有40种化合物检出率大于50％，其中有32种化合物的检出率大于70％；全氟化合物检测出种类最多，25种全氟化合物中，13种检出率大于70％，其中全氟辛酸(PFOA)、全氟-1-庚烷磺酸钠(L-PFHxS)、全氟-1-己烷磺酸钠(L-PFHpS)、全氟正壬烷酸(PFNA)、全氟辛烷磺酸(PFOS)、全氟正癸酸(PFDA)、全氟正十一烷酸(PFUdA)、9-氯十六氟-3-氧杂环己烷-1-磺酸钾(9Cl-PF3ONS)、11-氯二十氟-3-氧杂环丁烷-1-磺酸钾(11Cl-PF3OUdS)检出率为100％；塑料添加剂中邻苯二甲酸酯检出种类最多，但检出浓度最高的是增塑剂类中的甘油单油酸(GMO)，浓度范围为127～10914ng/mL；农药类别只有有机氯农药检出，其中α-六氯环己烷(α-HCH)和4,4'-滴滴涕(p,p′-DDE)检出率为100％。具体化合物检出信息如表4所示。A total of 377 compounds were detected, and the detection rate of 40 compounds was greater than 50%, of which 32 compounds were more than 70%. The output rate is greater than 70%, of which perfluorooctanoic acid (PFOA), sodium perfluoro-1-heptane sulfonate (L-PFHxS), sodium perfluoro-1-hexanesulfonate (L-PFHpS), perfluoro-n-nonanoic acid (PFNA), perfluorooctanesulfonic acid (PFOS), perfluoron-decanoic acid (PFDA), perfluoron-undecanoic acid (PFUdA), 9-chlorohexadecafluoro-3-oxane-1 -Potassium sulfonate (9Cl-PF3ONS), 11-chloroeicosfluoro-3-oxetane-1-potassium sulfonate (11Cl-PF3OUdS) detection rate is 100%; phthalic acid in plastic additives The most types of esters were detected, but the highest detection concentration was glycerol monooleic acid (GMO) in the plasticizer category, with a concentration range of 127-10914ng/mL; only organochlorine pesticides were detected in the pesticide category, of which α-hexachloro The detection rate of cyclohexane (α-HCH) and 4,4'-DDT (p,p'-DDE) was 100%. The specific compound detection information is shown in Table 4.
表4化合物检出信息Table 4 Compound detection information
Figure PCTCN2022105848-appb-000019
Figure PCTCN2022105848-appb-000019
Figure PCTCN2022105848-appb-000020
Figure PCTCN2022105848-appb-000020
对比例1Comparative example 1
按照实施例1步骤(2)中的方法采集样品，然后按如下方法进行检测：Collect samples according to the method in embodiment 1 step (2), then detect as follows:
(1)取200μL血浆，置于15mL玻璃离心管中，加入回收率指示物混合均匀；(1) Take 200 μL of plasma, put it in a 15mL glass centrifuge tube, add recovery indicator and mix well;
(2)向离心管中加入3mL体积比为3:2的乙酸乙酯和正己烷的萃取溶剂(含0.6％(v/v)甲酸)，旋转震荡5min后，在3000rpm下离心3min，取上清液转移至另一个玻璃离心管内；(2) Add 3 mL of ethyl acetate and n-hexane extraction solvent (containing 0.6% (v/v) formic acid) with a volume ratio of 3:2 to the centrifuge tube, rotate and shake for 5 min, centrifuge at 3000 rpm for 3 min, and take the Transfer the supernatant to another glass centrifuge tube;
(3)第二次萃取重复步骤(2)，第三次萃取将萃取溶剂换成乙酸乙酯，合并三次萃取液；(3) Step (2) was repeated for the second extraction, and the extraction solvent was changed to ethyl acetate for the third extraction, and three extracts were combined;
(4)在缓慢的氮气流下将萃取液吹至1mL后加入3mL体积分数为0.6％的甲酸水溶液稀释，然后氮吹浓缩至3mL，把HLB柱(
Figure PCTCN2022105848-appb-000021
PRiME HLB 3cc(60mg)Extraction Cartridges)放置在SPE萃取装置上，然后用3mL甲醇、3mL水依次预洗HLB柱； (4) Under the slow nitrogen flow, the extract was blown to 1mL and then added with 3mL volume fraction of 0.6% aqueous formic acid for dilution, then concentrated to 3mL by nitrogen blowing, and the HLB column (
Figure PCTCN2022105848-appb-000021
PRiME HLB 3cc (60mg) Extraction Cartridges) were placed on the SPE extraction device, and then the HLB column was pre-washed sequentially with 3mL methanol and 3mL water;
(5)然后转移稀释液到HLB柱，再用3mL体积分数为2％的甲酸水溶液去除干扰，等溶剂流完后，再加入3mL甲醇水洗脱，用玻璃管接住洗脱液氮吹至50μL转移至进样瓶，加入内标待上样；(5) Then transfer the diluent to the HLB column, and then use 3mL of formic acid aqueous solution with a volume fraction of 2% to remove the interference. After the solvent flows out, add 3mL of methanol water to elute, and use a glass tube to catch the eluent and blow it with nitrogen. Transfer 50 μL to the injection bottle, add internal standard and wait for sample loading;
(6)在超高效液相色谱-串联质谱联用仪(UPLC-MS/MS)和气相色谱-串联质谱联用仪(GC-MS/MS)下对样品进行定量分析，方法如实施例1步骤(3)(表2、表3)。(6) Quantitatively analyze the sample under ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), the method is as in Example 1 Step (3) (Table 2, Table 3).
上述方法所加的回收率指示物以及内标与实施例1所用相同，只有前处理的方法不同。The recovery indicator and internal standard added by the above method are the same as those used in Example 1, only the pretreatment method is different.
用上述前处理方法进行基质加标实验，取6份绵羊血血浆(中国广州未来生物技术有限公司)，置于15mL玻璃离心管，其中5份中，每种目标化合物的加入量为2～10ng，具体加入量如下：有机磷酸二酯类5ng、有机磷酸三酯类2ng、邻苯二甲酸单酯类2ng、邻苯二甲酸二酯类1ng、个人护理产品2ng、双酚类似物2.5ng、苯甲酮类紫外线稳定剂5ng、苯并噻唑类紫外稳定剂5ng、苯并三唑类紫外稳定剂5ng、其他类型紫外稳定剂2ng、光引发剂5ng、抗氧化剂5ng、增塑剂5ng、全氟化合物2ng、有机磷农药2ng、有机氯农药3.5ng、拟除虫菊酯2ng、新烟碱类农药2ng、氨基甲酸酯类农药2ng、酸性除草剂2ng、唑类农药2ng、三唑酮类农药2ng、尿素类农药2ng、酰胺杀虫剂2ng、甲氧基丙烯酸酯类农药2ng、其他杀虫剂2ng、液晶单体10ng，另一份作为空白对照，然后全部加入回收率指示物混匀，后续按上述步骤进行前处理和进样分析(三次重复)。Use the above pretreatment method to carry out the matrix spike experiment, take 6 parts of sheep blood plasma (Guangzhou Future Biotechnology Co., Ltd., China), and put them in 15mL glass centrifuge tubes, and in 5 parts, the amount of each target compound added is 2-10ng , the specific dosage is as follows: 5 ng of organic phosphate diesters, 2 ng of organic phosphate triesters, 2 ng of phthalic acid monoesters, 1 ng of phthalic acid diesters, 2 ng of personal care products, 2.5 ng of bisphenol analogues, Benzophenone UV stabilizer 5ng, benzothiazole UV stabilizer 5ng, benzotriazole UV stabilizer 5ng, other types of UV stabilizer 2ng, photoinitiator 5ng, antioxidant 5ng, plasticizer 5ng, all Fluorine compound 2ng, organophosphorus pesticide 2ng, organochlorine pesticide 3.5ng, pyrethroid 2ng, neonicotinoid pesticide 2ng, carbamate pesticide 2ng, acid herbicide 2ng, azole pesticide 2ng, triadimefon pesticide 2ng , urea pesticides 2ng, amide pesticides 2ng, methoxyacrylate pesticides 2ng, other pesticides 2ng, liquid crystal monomer 10ng, the other part was used as a blank control, and then all were added to the recovery indicator and mixed evenly. Pretreatment and injection analysis were performed according to the above steps (three repetitions).
结果如图1所示：方法一为实施例1所用方法，方法二为对比例1所用方法。如图所示，方法一的加标回收率大部分在70～100％左右，比较稳定且符合标准，方法二的加标回收率则比较分散不稳定，且回收率相对方法一来说比较低，有些化合物甚至加标回收率为0％。此结果说明方法二的基质干扰较强，综合来看，方法一明显优于方法二。The results are shown in Figure 1: Method 1 is the method used in Example 1, and Method 2 is the method used in Comparative Example 1. As shown in the figure, the recovery rate of standard addition in method 1 is mostly around 70-100%, which is relatively stable and meets the standard. The recovery rate of standard addition in method 2 is relatively scattered and unstable, and the recovery rate is relatively low compared to method 1. , and some compounds even had spiked recoveries of 0%. This result shows that method 2 has strong matrix interference, and overall, method 1 is significantly better than method 2.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (11)

  1. 一种血浆中环境污染物靶向暴露组分析方法，其特征在于，包括如下步骤：A targeted exposure group analysis method for environmental pollutants in plasma, characterized in that it comprises the following steps:
    (1)将回收率指示物添加到血浆中，混合均匀，得到血浆和回收率指示物的混合物；(1) Add the recovery rate indicator to the plasma and mix evenly to obtain a mixture of the plasma and the recovery rate indicator;
    (2)向步骤(1)中得到的血浆和回收率指示物的混合物中加入萃取溶剂I进行萃取，离心，取上清，重复此步骤1次以上；再加入萃取溶剂II进行萃取，得到萃取液；其中，所述萃取溶剂I为含有甲酸的乙酸乙酯和正己烷的混合溶剂；所述萃取溶剂II为乙酸乙酯；(2) Add extraction solvent I to the mixture of plasma and recovery indicator obtained in step (1) for extraction, centrifuge, take the supernatant, repeat this step more than 1 time; then add extraction solvent II for extraction to obtain the extracted Liquid; Wherein, described extraction solvent I is the mixed solvent that contains the ethyl acetate of formic acid and n-hexane; Described extraction solvent II is ethyl acetate;
    (3)将步骤(2)中得到的萃取液用氮气吹干，然后加入甲醇复溶后，置于-40±5℃下进行冷冻，然后冷冻离心，取上清液，得到预处理后的样品；(3) Dry the extract obtained in step (2) with nitrogen, then add methanol to redissolve, freeze at -40±5°C, then freeze and centrifuge, and take the supernatant to obtain the pretreated sample;
    (4)向步骤(3)中得到的预处理后的样品中加入内标，然后利用液相色谱-串联质谱法和/或气相色谱-串联质谱法对环境污染物进行定量分析。(4) adding an internal standard to the pretreated sample obtained in step (3), and then quantitatively analyzing the environmental pollutants by using liquid chromatography-tandem mass spectrometry and/or gas chromatography-tandem mass spectrometry.
  2. 根据权利要求1所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：步骤(1)中所述的回收率指示物的用量为按每200μL血浆加入每种回收率指示物0.5～20ng计算；The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1, characterized in that: the amount of the recovery rate indicator described in step (1) is to add 0.5% of each recovery rate indicator per 200 μL of plasma. ~20ng calculation;
    步骤(2)中所述的萃取溶剂I的配方如下：298.2mL乙酸乙酯、198.8mL正己烷和3mL甲酸；The formula of extraction solvent I described in step (2) is as follows: 298.2mL ethyl acetate, 198.8mL n-hexane and 3mL formic acid;
    步骤(4)中所述的内标的用量为按每50μL预处理后的样品加入每种内标1～20ng计算。The amount of the internal standard described in step (4) is calculated by adding 1-20 ng of each internal standard per 50 μL of the pretreated sample.
  3. 根据权利要求1所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1, characterized in that:
    步骤(3)中所述的冷冻的时间为12小时以上；The freezing time described in step (3) is more than 12 hours;
    步骤(3)中所述的冷冻离心的条件为：-10℃、15000rpm条件下离心5min以上。The conditions for the refrigerated centrifugation in step (3) are: centrifuge at -10°C and 15000rpm for more than 5min.
  4. 根据权利要求1所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1, characterized in that:
    步骤(4)中所述的利用液相色谱-串联质谱法对环境污染物进行定量分析的污染物包括有机磷酸酯类，邻苯二甲酸酯类，个人护理产品，苯酚类化合物，紫外稳定剂，光引发剂，抗氧化剂，增塑剂，全氟化合物，有机磷农药，拟除虫菊酯，新烟碱类农药，氨基甲酸酯类农药，酸性除草剂，唑类农药，三唑酮类农药，尿素类农药，酰胺类农药，甲氧基丙烯酸酯类杀菌剂和其他杀虫剂中的至少一种；The pollutants that utilize liquid chromatography-tandem mass spectrometry described in step (4) to quantitatively analyze environmental pollutants include organophosphates, phthalates, personal care products, phenolic compounds, UV stabilizers , photoinitiators, antioxidants, plasticizers, perfluorinated compounds, organophosphorus pesticides, pyrethroids, neonicotinoid pesticides, carbamate pesticides, acidic herbicides, azole pesticides, triadimefon pesticides, At least one of urea pesticides, amide pesticides, methoxyacrylate fungicides and other insecticides;
    步骤(4)中所述的利用气相色谱-串联质谱法对环境污染物进行定量分析的污染物包括有机氯农药和液晶单体中的至少一种。The pollutants that are quantitatively analyzed by gas chromatography-tandem mass spectrometry in the step (4) include at least one of organochlorine pesticides and liquid crystal monomers.
  5. 根据权利要求4所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 4, characterized in that:
    所述的有机磷酸酯类包括有机磷酸二酯类和有机磷酸三酯类中的至少一种；The organophosphates include at least one of organophosphate diesters and organophosphate triesters;
    所述的有机磷酸二酯类包括双-(1-氯-2-丙基)磷酸酯、磷酸二苯酯、磷酸二丁酯、双(1,3-二氯-2-丙基)磷酸酯、二对甲苯基磷酸酯、双(丁氧基乙基)磷酸酯和双(2-乙基己基)磷酸酯；The organic phosphoric acid diesters include bis-(1-chloro-2-propyl) phosphate, diphenyl phosphate, dibutyl phosphate, bis(1,3-dichloro-2-propyl) phosphate , di-p-cresyl phosphate, bis(butoxyethyl) phosphate and bis(2-ethylhexyl) phosphate;
    所述的有机磷酸三酯类包括磷酸三乙酯、三(2-氯乙基)磷酸酯、磷酸三丙酯、四(2-氯乙基)二氯异戊基二磷酸酯、磷酸三苯酯、三(2,3-二溴丙基)磷酸酯、磷酸三丁酯、磷酸甲酚二苯酯、三(2-丁氧基乙基)磷酸酯、磷 酸三甲苯酯、间苯二酚双(磷酸二苯酯)、2-乙基己基-二苯基磷酸酯、磷酸异癸基二苯酯、三(3,5-二甲基苯基)磷酸酯、双酚A双(磷酸二苯酯)、三(2-异丙基苯基)磷酸酯、三(2-乙基己基)磷酸酯、叔丁基苯基二苯基磷酸酯、2-异丙基苯基二苯基磷酸酯、4-异丙基苯基二苯基磷酸酯、双(2-异丙基苯基)苯基磷酸酯、2,4-二异丙基苯基二苯基磷酸酯、双(4-异丙基苯基)苯基磷酸酯、三(3,4-二甲基苯基)磷酸酯、三(4-叔丁基苯基)磷酸酯、双(2,4-二异丙基苯基)苯基磷酸酯、三(3-异丙基苯基)磷酸酯、三(4-异丙基苯基)磷酸酯、2-叔丁基苯基二苯基磷酸酯、4-叔丁基苯基二苯基磷酸酯、双(2-叔丁基苯基)苯基磷酸酯和双(4-叔丁基苯基)苯基磷酸酯；Described organophosphate triesters include triethyl phosphate, tri(2-chloroethyl) phosphate, tripropyl phosphate, tetrakis(2-chloroethyl) dichloroisoamyl diphosphate, triphenyl phosphate ester, tris(2,3-dibromopropyl) phosphate, tributyl phosphate, cresol diphenyl phosphate, tris(2-butoxyethyl) phosphate, tricresyl phosphate, resorcinol Bis(diphenyl phosphate), 2-ethylhexyl-diphenyl phosphate, isodecyl diphenyl phosphate, tris(3,5-dimethylphenyl) phosphate, bisphenol A bis(diphenyl phosphate phenyl ester), tris(2-isopropylphenyl) phosphate, tris(2-ethylhexyl) phosphate, tert-butylphenyl diphenyl phosphate, 2-isopropylphenyl diphenyl phosphate ester, 4-isopropylphenyl diphenyl phosphate, bis(2-isopropylphenyl)phenyl phosphate, 2,4-diisopropylphenyl diphenyl phosphate, bis(4- Isopropylphenyl) phenyl phosphate, tris(3,4-dimethylphenyl) phosphate, tris(4-tert-butylphenyl) phosphate, bis(2,4-diisopropylphenyl) Base) phenyl phosphate, tris (3-isopropylphenyl) phosphate, tris (4-isopropylphenyl) phosphate, 2-tert-butylphenyl diphenyl phosphate, 4-tert-butyl phenyl diphenyl phosphate, bis(2-tert-butylphenyl)phenyl phosphate and bis(4-tert-butylphenyl)phenyl phosphate;
    所述的邻苯二甲酸酯类包括邻苯二甲酸单酯类和邻苯二甲酸二酯类中的至少一种；The phthalic acid esters include at least one of phthalic acid monoesters and phthalic acid diesters;
    所述的邻苯二甲酸单酯类包括邻苯二甲酸单乙酯、邻苯二甲酸单异丙酯、邻苯二甲酸单丁酯、邻苯二甲酸单正戊酯、邻苯二甲酸单环己酯、邻苯二甲酸单己基酯、邻苯二甲酸单苄酯、邻苯二甲酸单-2-庚酯、邻苯二甲酸单辛酯、邻苯二甲酸单乙基己基酯、邻苯二甲酸单异壬酯、邻苯二甲酸单(2-乙基-5-氧己基)酯、邻苯二甲酸单(2-乙基-5-羟基己基)酯和单(2-乙基-5-羧基戊基)邻苯二甲酸酯；The phthalic acid monoesters include monoethyl phthalate, monoisopropyl phthalate, monobutyl phthalate, mono-n-pentyl phthalate, mono-phthalate Cyclohexyl phthalate, monohexyl phthalate, monobenzyl phthalate, mono-2-heptyl phthalate, monooctyl phthalate, monoethylhexyl phthalate, ortho Mono-isononyl phthalate, mono(2-ethyl-5-oxohexyl) phthalate, mono(2-ethyl-5-hydroxyhexyl) phthalate and mono(2-ethyl-5-hydroxyhexyl) phthalate -5-carboxypentyl)phthalate;
    所述的邻苯二甲酸二酯类包括邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二烯丙酯、邻苯二甲酸二丙酯、邻苯二甲酸二异丙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸异丁环己酯、邻苯二甲酸二异戊酯、邻苯二甲酸丁苄酯、邻苯二甲酸二苯酯、邻苯二甲酸二己酯、邻苯二甲酸二异己酯、邻苯二甲酸双-4-甲基-2-戊酯、邻苯二甲酸二苄酯、邻苯二甲酸二庚酯、邻苯二甲酸二壬酯和邻苯二甲酸二十二烷基酯；The phthalic acid diesters include dimethyl phthalate, diethyl phthalate, diallyl phthalate, dipropyl phthalate, diisophthalate Propyl ester, diisobutyl phthalate, dibutyl phthalate, isobutylcyclohexyl phthalate, diisoamyl phthalate, butyl benzyl phthalate, phthalate Diphenyl formate, dihexyl phthalate, diisohexyl phthalate, bis-4-methyl-2-pentyl phthalate, dibenzyl phthalate, di-phthalate Heptyl, dinonyl phthalate and behenyl phthalate;
    所述的个人护理产品包括对羟基苯甲酸甲酯、对羟基苯甲酸丁酯、对羟基苯甲酸苄酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、正庚基对羟基苯甲酸酯和三氯生；Said personal care products include methylparaben, butylparaben, benzylparaben, ethylparaben, propylparaben, n-heptylparaben esters and triclosan;
    所述的苯酚类化合物包括双酚类似物中的至少一种；The phenolic compound includes at least one of bisphenol analogues;
    所述的双酚类似物包括双酚A、双酚E、双酚B、双酚C、双酚AF、双酚F、双酚M、双酚P、双酚G、双酚Z、双酚S、双酚AP、双酚BP和双酚PH；The bisphenol analogs include bisphenol A, bisphenol E, bisphenol B, bisphenol C, bisphenol AF, bisphenol F, bisphenol M, bisphenol P, bisphenol G, bisphenol Z, bisphenol S, bisphenol AP, bisphenol BP and bisphenol PH;
    所述的紫外稳定剂包括苯甲酮类、苯并噻唑类、苯并三唑类以及其他类别的紫外稳定剂中的至少一种；The ultraviolet stabilizer includes at least one of benzophenones, benzothiazoles, benzotriazoles and other types of ultraviolet stabilizers;
    所述的苯甲酮类紫外稳定剂包括2,4-二羟基二苯甲酮、2,2',4,4'-四羟基二苯甲酮、2-羟基-4-甲氧基苯并苯酮、2-羟基-4-甲氧基-5-磺酸二苯甲酮、2,2'-二羟基-4,4'-二甲氧基二苯甲酮、2,2'-羟基-4-甲氧基二苯甲酮、4-羟基二苯甲酮和2,3,4-三羟基二苯甲酮；Described benzophenone UV stabilizer includes 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzo Benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-hydroxy - 4-methoxybenzophenone, 4-hydroxybenzophenone and 2,3,4-trihydroxybenzophenone;
    所述的苯并噻唑类紫外稳定剂包括2-甲基苯并噻唑、2-苯并噻唑基-N-吗啉基硫醚、2-甲硫基苯并噻唑、2-氨基苯并噻唑和2-羟基苯并噻唑；Described benzothiazole UV stabilizer includes 2-methylbenzothiazole, 2-benzothiazolyl-N-morpholinyl sulfide, 2-methylthiobenzothiazole, 2-aminobenzothiazole and 2-Hydroxybenzothiazole;
    所述的苯并三唑类紫外稳定剂包括1-羟基苯并三唑、5-甲基苯并三氮唑、5-氯代苯并三氮唑、4-甲基-1-氢苯并三唑、2-(2'-羟基-5'-甲基苯基)苯并三唑、2-(5-叔丁基-2-羟苯基)苯并三唑和2-(2'-羟基-3',5'-二叔丁基苯基)-苯并三唑；Described benzotriazole UV stabilizer includes 1-hydroxybenzotriazole, 5-methylbenzotriazole, 5-chlorobenzotriazole, 4-methyl-1-hydrobenzotriazole Triazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole and 2-(2'- Hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole;
    所述的其他类别紫外稳定剂包括4-叔丁基-4'-甲氧基二苯甲酰甲烷、4-甲基苄亚基樟脑、甲氧基肉桂酸异戊酯、2-氰基-3,3-二苯基丙烯酸异辛酯、对二甲氨基苯甲酸异辛酯、对甲氧基肉桂酸辛酯、2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯乙基)苯酚、2,4-二叔丁基-6-(5-氯-2H-苯并三唑-2-基)苯酚和2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚；Other classes of UV stabilizers mentioned include 4-tert-butyl-4'-methoxydibenzoylmethane, 4-methylbenzylidene camphor, isoamyl methoxycinnamate, 2-cyano- 3,3-Diphenylisooctyl acrylate, isooctyl p-dimethylaminobenzoate, octyl p-methoxycinnamate, 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenethyl)phenol, 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol and 2-(2H-benzo Triazol-2-yl)-4,6-di-tert-amylphenol;
    所述的光引发剂包括苯甲酮、4-甲基二苯甲酮、1-羟基环己基苯基甲酮、4-苯基二苯甲酮、1,2-二苯基-1,2-乙二酮、2-乙基蒽醌、邻苯甲酰苯 甲酸甲酯、2,2-二甲氧基-2-苯基苯乙酮、对二甲氨基二苯甲酮、4,4'-双(二甲氨基)二苯甲酮、4,4'-双(二乙氨基)二苯甲酮、4-氨基苯甲酸乙酯、4-二甲氨基苯甲酸乙酯、2-异丙基噻吨酮和2,4-二乙基噻吨酮；Described photoinitiator comprises benzophenone, 4-methyl benzophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenyl benzophenone, 1,2-diphenyl-1,2 -Ethylenedione, 2-ethylanthraquinone, methyl phthaloylbenzoate, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminobenzophenone, 4,4 '-Bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, ethyl 4-aminobenzoate, ethyl 4-dimethylaminobenzoate, 2-iso Propylthioxanthone and 2,4-diethylthioxanthone;
    所述的抗氧化剂包括在正离子检测模式和负离子检测模式下进行检测的抗氧化剂；The antioxidants include antioxidants detected in positive ion detection mode and negative ion detection mode;
    所述的在负离子检测模式下进行检测的抗氧化剂包括3-叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基苯甲醛、3,5-二叔丁基-4-羟基苯甲酸、2,6-二叔丁基-4-(羟甲基)苯酚、2,4-二叔丁基苯酚、4,4'-亚丁基双(6-叔丁基-间甲酚)、4-(1,1,3,3-四甲基丁基)苯酚、2,2'-亚甲基双(4-乙基-6-叔丁基苯酚)、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)、二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯、2,2'-硫代双(6-叔丁基-对甲酚)、1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼和4,4'-硫代双(6-叔丁基-间甲酚)；The antioxidants detected under negative ion detection mode include 3-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl- 4-Hydroxybenzoic acid, 2,6-di-tert-butyl-4-(hydroxymethyl)phenol, 2,4-di-tert-butylphenol, 4,4'-butylenebis(6-tert-butyl-m- cresol), 4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2' -Methylenebis(6-tert-butyl-4-methylphenol), diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,2'-thiobis( 6-tert-butyl-p-cresol), 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine and 4,4'-thiobis(6-tert-butyl- m-cresol);
    所述的在正离子检测模式下进行检测的抗氧化剂包括1,3-二邻甲苯胍、1,3-二苯基-2-硫脲、2,2'-亚乙基-双(4,6-二叔丁基苯酚)、甲基-2-巯基苯并咪唑、11-甲基十二烷基3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酸酯、二苄基羟胺、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、2,6-二叔丁基-4-(二甲氨基-甲基)苯酚、三(2,4-二叔丁基苯基)亚磷酸酯、磺基二基二-2,1-乙二基双[3-(4-羟基-3,5-双(2-甲基-2-丙烷基)苯基)丙酸酯]、2,2'-硫代双(6-叔丁基-对甲酚)、N,N'-1,6-己二基双[3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酰胺]、1,2-乙二基双(氧-2,1-乙二基)双[3-[4-羟基-3-甲基-5-(2-甲基-2-丙烷基)苯基]丙酸酯]、1,6-己二基双[3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酸酯]、4-[[4,6-双(辛基硫烷基)-1,3,5-三嗪-2-基]氨基]-2,6-二叔丁基苯酚、n-苯基-1-萘胺、双[4-(2-苯基-2-丙基)苯基]胺、N,N'-二苯基-1,4-苯二胺、(1,2-二氧代-1,2-乙二基)双(亚氨基-2,1-乙二基)双[3-[4-羟基-3,5-双(2-甲基-2-丙烷基)苯基]丙酸酯]、N,N'-二乙基硫脲和1,3-二苯基胍；The antioxidants detected in the positive ion detection mode include 1,3-di-o-tolylguanidine, 1,3-diphenyl-2-thiourea, 2,2'-ethylene-bis(4, 6-di-tert-butylphenol), methyl-2-mercaptobenzimidazole, 11-methyldodecyl 3-[4-hydroxy-3,5-bis(2-methyl-2-propanyl) Phenyl]propionate, dibenzylhydroxylamine, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-(dimethylamino-methyl)phenol, tris(2, 4-di-tert-butylphenyl)phosphite, sulfodiyldi-2,1-ethanediylbis[3-(4-hydroxy-3,5-bis(2-methyl-2-propanyl) )phenyl)propionate], 2,2'-thiobis(6-tert-butyl-p-cresol), N,N'-1,6-hexanediylbis[3-[4-hydroxy- 3,5-bis(2-methyl-2-propanyl)phenyl]propionamide], 1,2-ethanediylbis(oxy-2,1-ethanediyl)bis[3-[4-hydroxy -3-methyl-5-(2-methyl-2-propanyl)phenyl]propionate], 1,6-hexanediylbis[3-[4-hydroxy-3,5-bis(2 -methyl-2-propanyl)phenyl]propionate], 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]- 2,6-di-tert-butylphenol, n-phenyl-1-naphthylamine, bis[4-(2-phenyl-2-propyl)phenyl]amine, N,N'-diphenyl-1 ,4-Phenylenediamine, (1,2-dioxo-1,2-ethanediyl)bis(imino-2,1-ethanediyl)bis[3-[4-hydroxyl-3,5- Bis(2-methyl-2-propanyl)phenyl]propionate], N,N'-diethylthiourea and 1,3-diphenylguanidine;
    所述的增塑剂包括丁二酸二乙酯、己二酸二甲酯、己二酸二乙酯、壬二酸二甲酯、2,2,4-三甲基-1,3-戊二醇二异丁酸酯、富马酸二丁酯、癸二酸二甲酯、肉豆蔻酸异丙酯、柠檬酸三乙酯、二甘醇二苯甲酸酯、癸二酸二丁酯、棕榈酸异丙酯、乙酰柠檬酸三乙酯、油酸丙酯、马来酸二(2-乙基己基)酯、二苯甲酸二聚丙二醇酯、甘油单油酸酯、壬二酸二己酯、硬脂酸甘油酯、柠檬酸三丁酯、(Z)-油酸-2-四氢呋喃甲酯、12-乙酰氧基-[R-(Z)]-9-烯-十八酸丁酯、壬二酸二异辛酯、乙酰柠檬酸三正丁酯、癸二酸二异辛酯、丁酰柠檬酸三正己酯、己二酸庚基壬基酯、己二酸二丁酯、己二酸二异癸烷基酯、环己烷1，2-二甲酸二异壬基酯和偏苯三酸三辛酯；The plasticizer includes diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl azelate, 2,2,4-trimethyl-1,3-pentane Glycol Diisobutyrate, Dibutyl Fumarate, Dimethyl Sebacate, Isopropyl Myristate, Triethyl Citrate, Diethylene Glycol Dibenzoate, Dibutyl Sebacate , Isopropyl Palmitate, Acetyl Triethyl Citrate, Propyl Oleate, Di(2-Ethylhexyl) Maleate, Dipropylene Glycol Dibenzoate, Glyceryl Monooleate, Azelaic Acid Di Hexyl ester, glyceryl stearate, tributyl citrate, (Z)-oleic acid-2-tetrahydrofuryl methyl ester, 12-acetoxy-[R-(Z)]-9-ene-octadecanoic acid butyl Esters, di-isooctyl azelate, tri-n-butyl acetyl citrate, di-iso-octyl sebacate, tri-n-hexyl butyryl citrate, heptylnonyl adipate, dibutyl adipate, Diisodecyl adipate, diisononyl cyclohexane 1,2-dicarboxylate and trioctyl trimellitate;
    所述的全氟化合物包括全氟正辛酸、全氟辛烷磺酸、全氟正丁酸、全氟正庚酸、全氟正己酸、全氟正癸酸、全氟正十二烷酸、全氟正壬酸、全氟正十一烷酸、全氟正戊酸、全氟正十四烷酸、全氟正十三烷酸、全氟-1-丁烷磺酸钾、全氟-1-癸烷磺酸钠、全氟-1-庚烷磺酸钠、全氟-1-己磺酸钠、全氟-1-辛烷磺酰胺、N-甲基全氟-1-辛磺酰胺、N-乙基全氟-1-辛烷磺酰胺、1H,1H,2H,2H-全氟己烷磺酸钠(4:2)、1H,1H,2H,2H-全氟辛烷磺酸钠(6:2)、1H,1H,2H,2H-全氟癸烷磺酸钠(8:2)、氯十六烷-氟-3-氧杂戊烷-1-磺酸钾、11-氯二十碳氟-3-氧十一烷-1-磺酸钾和全氟-2,5-二甲基-3,6-二恶烷酸；The perfluorinated compounds include perfluoron-octanoic acid, perfluorooctanesulfonic acid, perfluoron-butyric acid, perfluoron-heptanoic acid, perfluoron-hexanoic acid, perfluoron-decanoic acid, perfluoron-dodecanoic acid, Perfluoro-n-nonanoic acid, perfluoro-n-undecanoic acid, perfluoro-n-valeric acid, perfluoro-n-tetradecanoic acid, perfluoro-n-tridecanoic acid, perfluoro-1-butanesulfonic acid potassium, perfluoro- Sodium 1-decanesulfonate, sodium perfluoro-1-heptanesulfonate, sodium perfluoro-1-hexanesulfonate, perfluoro-1-octanesulfonamide, N-methylperfluoro-1-octanesulfonate Amide, N-ethylperfluoro-1-octanesulfonamide, 1H,1H,2H,2H-sodium perfluorohexanesulfonate (4:2), 1H,1H,2H,2H-perfluorooctanesulfonate sodium perfluorodecane sulfonate (6:2), sodium 1H,1H,2H,2H-perfluorodecanesulfonate (8:2), potassium chlorohexadecane-fluoro-3-oxopentane-1-sulfonate, 11 - Potassium chloroeicosafluoro-3-oxoundecane-1-sulfonate and perfluoro-2,5-dimethyl-3,6-dioxane acid;
    所述的有机磷农药包括毒死蜱、二嗪农、甲基对硫磷、对硫磷、马拉硫磷、乐果、敌敌畏、3-甲基-4-硝基苯酚、香豆磷、二恶唑磷、杀灭磷、2-异丙基-6-甲基-4-嘧啶醇、异灭磷、美卡巴姆、杀虫剂、磷酮、吡唑磷和对硝基苯酚；The organophosphorus pesticides include chlorpyrifos, diazinon, methyl parathion, parathion, malathion, dimethoate, dichlorvos, 3-methyl-4-nitrophenol, coumarin, dioxin Azophos, methazol, 2-isopropyl-6-methyl-4-pyrimidinol, isofenfos, mecarbam, insecticides, phosphonone, pyrazophos, and p-nitrophenol;
    所述的拟除虫菊酯包括3-苯氧基苄醇、4-氟-3-苯氧基苯甲酸、顺-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基-环丙烷羧酸和高效氯氟氰菊酯；The pyrethroids include 3-phenoxybenzyl alcohol, 4-fluoro-3-phenoxybenzoic acid, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl) - 2,2-Dimethyl-cyclopropanecarboxylic acid and lambda-cyhalothrin;
    所述的新烟碱类农药包括啶虫脒、呋虫胺、吡虫啉、噻虫啉和噻虫嗪；The neonicotinoid pesticides include acetamiprid, dinotefuran, imidacloprid, thiacloprid and thiamethoxam;
    所述的氨基甲酸酯类农药包括多菌灵、呋喃丹、氯丙胺、非诺威、异威威、灭多威、抗蚜威和苯胺灵；The carbamate pesticides include carbendazim, carbofuran, chlorpromine, fenovir, isocarb, methomyl, pirimicarb and phenhydramine;
    所述的酸性除草剂包括2,4-二氯苯氧丁酸、2,4,5-涕丙酸、2,4,5-三氯苯氧乙酸、2,4-滴丙酸、2-甲基-4-氯苯氧乙酸、2-甲基-4-氯戊氧基丙酸和2-甲基-4-氯苯氧基丁酸；Described acidic herbicide comprises 2,4-dichlorophenoxybutyric acid, 2,4,5-nylpropionic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dipropionic acid, 2- Methyl-4-chlorophenoxyacetic acid, 2-methyl-4-chloropentyloxypropionic acid and 2-methyl-4-chlorophenoxybutyric acid;
    所述的唑类农药包括联苯三唑醇、环唑醇、苯醚甲环唑、氟环唑、芬布康唑、氟硅唑、抑菌灵、丁苯胺、戊康唑、丙氯灵、戊唑醇、四康唑和噻菌灵；The azole pesticides include bifendazole, cyproconazole, difenoconazole, econazole, fenbuconazole, flusilazole, fenzazolin, butylaniline, penconazole, prochloraz , tebuconazole, tetraconazole and thiabendazole;
    所述的三唑酮类农药包括氯唑草酮、己嗪酮、苯嗪草酮、嗪草酮、苯胺、阿特拉顿、阿特拉津、扑灭通、扑草净、扑灭津、仲丁通、西玛津、西草净和特丁净；The triadimefon pesticides include chlorfentrazone, hexazone, fenmetrione, metrizone, aniline, atrazine, atrazine, prometon, promethazine, propazine, Dingtong, Simazine, Xicaojing and Terdingjing;
    所述的尿素类农药包括氯磺隆、氯脲酮、1-(3,4-二氯苯基)-3-甲基脲、1-(3,5-二氯苯基)脲、甲基苯噻隆、溴谷隆、甲氧隆、敌草隆、3-苯基-1,1-二甲基脲、异丙隆和利谷隆；The urea pesticides include chlorsulfuron, chlorourea, 1-(3,4-dichlorophenyl)-3-methylurea, 1-(3,5-dichlorophenyl)urea, methyl Benzhiuron, Broglucuron, Methoxyuron, Diuron, 3-Phenyl-1,1-Dimethylurea, Isoproturon, and Riguron;
    所述的酰胺类农药包括甲草胺、二甲草胺、N,N-二甲基氨基-N-甲苯和环酰菌胺；The amide pesticides include alachlor, dimethachlor, N,N-dimethylamino-N-toluene and fenhexamid;
    所述的甲氧基丙烯酸酯类杀菌剂包括嘧菌酯、嘧螨酯、醚菌酯、吡唑醚菌酯和肟菌酯；The methoxyacrylate fungicides include azoxystrobin, pyrimaben, kysstrobin, pyraclostrobin and trifloxystrobin;
    所述的其他杀虫剂包括氟担菌宁、啶酰菌胺、恶唑菌酮、甲霜灵、氟苯嘧啶醇和苄草丹；The other insecticides mentioned include flunobendonin, boscalid, oxaflucondone, metalaxyl, pyrimidol and procarbal;
    所述的有机氯农药包括二氯丙酸、ALPHA-六六六、BETA-六六六、林丹、δ-六六六、Ε-六六六、顺式A-氯丹、反式氯丹、氧氯丹、4,4-滴滴滴、2,2-双(4-氯苯基)-1,1-二氯乙烯、2,2-双(对氯苯基)-1,1,1-三氯乙烷、1-(2-氯苯基)-1-(4-氯苯基)-2,2-二氯乙烷、3-邻氯苯基-2-对氯苯基-1,1-二氯乙烯溶液、1,1,1-三氯-2-(2-氯苯基)-2-(4-氯苯基)乙烷、狄氏剂、alpha-硫丹、BETA-硫丹、安特灵、异狄氏剂酮、七氯、内环氧七氯、六氯苯和吡唑草胺；The organochlorine pesticides include dichloropropionic acid, ALPHA-666, BETA-666, lindane, δ-666, Ε-666, cis-A-chlordane, trans-chlordane, Oxychlordane, 4,4-Dididi, 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene, 2,2-bis(p-chlorophenyl)-1,1,1 -Trichloroethane, 1-(2-chlorophenyl)-1-(4-chlorophenyl)-2,2-dichloroethane, 3-o-chlorophenyl-2-p-chlorophenyl-1 , 1-dichloroethylene solution, 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl)ethane, dieldrin, alpha-endosulfan, BETA- Endosulfan, Antralin, Endrinone, Heptachlor, Endoepoxide, Hexachlorobenzene, and Metafenac;
    所述的液晶单体包括4-乙烯基-4'-丙基-1,1'-联环己烷、1-甲氧基-4-(4-丙基环己基)环己烷、1-(丙-1-烯基)-4-(4-丙基环己基)环己烷、1-乙氧基-2,3-二氟-4-(4-丙基环己基)苯、4-甲基-4'-戊基联苯、1-乙氧基-2,3-二氟-4-(4-丙基苯基)苯、4-(4-乙基环己基)-4'-(三氟甲氧基)联苯、4-(4-甲基苯基)-4'-乙烯基-1,1'-双(环己基)、4-[二氟(3,4,5-三氟苯氧基)甲基]-3,5-二氟-4'-丙基联苯、1-甲基-4-(4-(4-丙基环己基)环己基)苯、4-[二氟(2-甲基-3,4,5-三氟苯氧基)甲基]-3,5-二氟-4'-丙基联苯、2,3-二氟-1-甲氧基-4-(4-(4-丙基环己基)环己基)苯、l-乙基-4-(4-(4丙基环己基)苯基)苯、2,3-二氟-1-乙氧基-4-(4-(4-乙基环己基)苯基)苯、4"-乙基-2'-氟-4-丙基-l,l':4',1"-三联苯、(4-乙氧基-2,3-二氟-4'-(4-丙基环己基)联苯)、2,3-二氟-1-丙氧基-4-(4-(4-丙基环己基)环己基)苯、1-(4-(4-丁基环己基)环己基)-4-乙氧基-2,3-二氟苯、4-丁基-4"-乙基-2'-氟-l,l':4',1"-三联苯、3,4-二氟-4'-[4'-乙基-1,1'-双(环己基)-4-基]联苯、3,4-二氟-4'-丙基-l,l'-联苯、4'-乙基联苯-4-甲腈、4'-丙氧基-4-联苯甲腈、4-丙基1-4'-[4-(三氟甲氧基)苯基]-1,1'-双环己基、4"-乙基-2',3,4,5-四氟-1,1':4',1"-三联苯、4-氰基-4'-戊氧基联苯、4-己氧基-4-联苯甲腈和4'-(辛氧基)-4-联苯甲腈。The liquid crystal monomers include 4-vinyl-4'-propyl-1,1'-bicyclohexane, 1-methoxy-4-(4-propylcyclohexyl)cyclohexane, 1- (Prop-1-enyl)-4-(4-propylcyclohexyl)cyclohexane, 1-ethoxy-2,3-difluoro-4-(4-propylcyclohexyl)benzene, 4- Methyl-4'-pentylbiphenyl, 1-ethoxy-2,3-difluoro-4-(4-propylphenyl)benzene, 4-(4-ethylcyclohexyl)-4'- (Trifluoromethoxy)biphenyl, 4-(4-methylphenyl)-4'-vinyl-1,1'-bis(cyclohexyl), 4-[difluoro(3,4,5- Trifluorophenoxy)methyl]-3,5-difluoro-4'-propylbiphenyl, 1-methyl-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene, 4- [Difluoro(2-methyl-3,4,5-trifluorophenoxy)methyl]-3,5-difluoro-4'-propylbiphenyl, 2,3-difluoro-1-methyl Oxy-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene, l-ethyl-4-(4-(4-propylcyclohexyl)phenyl)benzene, 2,3-difluoro- 1-ethoxy-4-(4-(4-ethylcyclohexyl)phenyl)benzene, 4"-ethyl-2'-fluoro-4-propyl-l,l':4',1" -Terphenyl, (4-ethoxy-2,3-difluoro-4'-(4-propylcyclohexyl)biphenyl), 2,3-difluoro-1-propoxy-4-(4 -(4-Propylcyclohexyl)cyclohexyl)benzene, 1-(4-(4-butylcyclohexyl)cyclohexyl)-4-ethoxy-2,3-difluorobenzene, 4-butyl-4" -Ethyl-2'-fluoro-l,l':4',1"-terphenyl, 3,4-difluoro-4'-[4'-ethyl-1,1'-bis(cyclohexyl) -4-yl]biphenyl, 3,4-difluoro-4'-propyl-l,l'-biphenyl, 4'-ethylbiphenyl-4-carbonitrile, 4'-propoxy-4 -Biphenylcarbonitrile, 4-propyl 1-4'-[4-(trifluoromethoxy)phenyl]-1,1'-bicyclohexyl, 4"-ethyl-2',3,4, 5-tetrafluoro-1,1':4',1"-terphenyl, 4-cyano-4'-pentyloxybiphenyl, 4-hexyloxy-4-biphenylcarbonitrile and 4'-( octyloxy)-4-biphenylcarbonitrile.
  6. 根据权利要求4或5所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：所述邻苯二甲酸酯类替换为间苯二甲酸二甲酯、间苯二甲酸二苯酯和己二酸二(2-乙基己基)酯。The targeted exposure group analysis method for environmental pollutants in plasma according to claim 4 or 5, characterized in that: the phthalates are replaced by dimethyl isophthalate and diphenyl isophthalate and bis(2-ethylhexyl) adipate.
  7. 根据权利要求1或2所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1 or 2, characterized in that:
    步骤(1)中所述的回收率指示物包括三2-丁氧基-[13C2]-乙基)磷酸酯、磷酸三正丁酯-d27、三(2-氯乙基)磷酸酯-d12、三(1，3-二氯-2-丙基)磷酸酯-d15、磷酸三乙酯-d15、磷酸三苯酯-d15、双(丁氧基乙基)磷酸酯-d8、双(1，3-二氯-2-丙基)磷酸酯-d10、双(2-乙基己基)磷酸酯-d34、磷酸二丁酯-d18、磷酸二邻甲苯酯-d14、二对甲苯基磷酸酯-d14、磷酸二苯酯-d10、邻苯二甲酸二苄酯-d4、邻苯二甲酸二正丁酯-d4、邻苯二甲酸二异丁酯-3，4，5，6-d4、邻苯二甲酸二环己酯-3，4，5，6-d4、双(2-乙基己基)邻苯二甲酸酯-3，4，5，6-d4、邻苯二甲酸二乙酯-3，4，5，6-d4、邻苯二甲酸二正己酯-3，4，5，6-d4、邻苯二甲酸二甲酯-3，4，5，6-d4、邻苯二甲酸二正戊酯-3，4，5，6-d4、邻苯二甲酸二正丙酯-3，4，5，6-d4、邻苯二甲酸单苄酯-d4、邻苯二甲酸单正丁酯-d4、双(2-乙基己基)己二酸酯-d8、O-乙酰柠檬酸三丁酯-d3、双酚A-d6、双酚S-C12、三氯生-d3、2，4-二羟基二苯甲酮-13C6、苯并噻唑-d4、1H-苯并三唑-(环-d4)、5-甲基苯并三唑-d6、二苯甲酮-d10、2-羟基-4-甲氧基二苯甲酮-d5、全氟-n-[(13)C4]丁酸、全氟-n-[1，2-(13)C2]己酸、全氟-1-己烷[(18)O2]磺酸钠、全氟-n-[1，2，3，4-(13)C4]辛酸、全氟-n-[1，2，3，4，5-(13)C5]壬酸、全氟钠-1-[1，2，3，4-(13)C4]辛磺酸盐、全氟-n-[1，2-(13)C2]癸酸、全氟-n-[1，2-(13)C2]十一烷酸、全氟-n-[1，2-(13)C2]十二烷酸、全氟-1-[13C8]辛烷磺酰胺、N-甲基-d3-全氟-1-辛烷磺酰胺、N-乙基-d5-全氟-1-辛烷磺酰胺、1H，1H，2H，2H-全氟-1-[1，2-13C2]-辛烷磺酸钠、毒死蜱d10、γ-1，2，3，4，5，6-六氯环己烷-d6、反式氯菊酯d6、啶虫脒-d3、吡虫啉-d4、噻虫啉-d4、噻虫嗪-d3、多菌灵d3、呋喃丹d3、2，4-二氯苯氧基-3，5，6-d3-乙酸、2，4′-二氯二苯基三氯乙烷-d8、2-(4-氯-2-甲基苯氧基)丙酸-D3、噻苯达唑d4、十氚代西玛嗪、特丁草净-D5、氚代敌草隆-D6、异丙隆d6、异丙甲草胺d6、嘧菌酯d4和啶酰菌胺d4中的至少一种。The recovery indicators described in step (1) include three 2-butoxy-[13C2]-ethyl) phosphate, tri-n-butyl phosphate-d27, three (2-chloroethyl) phosphate-d12 , Tris(1,3-dichloro-2-propyl) phosphate-d15, triethyl phosphate-d15, triphenyl phosphate-d15, bis(butoxyethyl) phosphate-d8, bis(1 , 3-dichloro-2-propyl) phosphate-d10, bis(2-ethylhexyl) phosphate-d34, dibutyl phosphate-d18, di-o-cresyl phosphate-d14, 2-p-cresyl phosphate -d14, diphenyl phosphate-d10, dibenzyl phthalate-d4, di-n-butyl phthalate-d4, diisobutyl phthalate-3,4,5,6-d4, Dicyclohexyl phthalate-3,4,5,6-d4, bis(2-ethylhexyl)phthalate-3,4,5,6-d4, diethyl phthalate Ester-3,4,5,6-d4, di-n-hexyl phthalate-3,4,5,6-d4, dimethyl phthalate-3,4,5,6-d4, o-phthalate Di-n-pentyl dicarboxylate-3,4,5,6-d4, di-n-propyl phthalate-3,4,5,6-d4, monobenzyl phthalate-d4, phthalic acid Mono-n-butyl ester-d4, bis(2-ethylhexyl)adipate-d8, O-acetyl tributyl citrate-d3, bisphenol A-d6, bisphenol S-C12, triclosan-d3 , 2,4-dihydroxybenzophenone-13C6, benzothiazole-d4, 1H-benzotriazole-(ring-d4), 5-methylbenzotriazole-d6, benzophenone-d10 , 2-hydroxy-4-methoxybenzophenone-d5, perfluoro-n-[(13)C4]butanoic acid, perfluoro-n-[1,2-(13)C2]hexanoic acid, perfluoro-n-[1,2-(13)C2]hexanoic acid, Fluoro-1-hexane[(18)O2]sodium sulfonate, perfluoro-n-[1,2,3,4-(13)C4]octanoic acid, perfluoro-n-[1,2,3,4 , 5-(13)C5]nonanoic acid, perfluorosodium-1-[1,2,3,4-(13)C4]octylsulfonate, perfluoro-n-[1,2-(13)C2 ]decanoic acid, perfluoro-n-[1,2-(13)C2]undecanoic acid, perfluoro-n-[1,2-(13)C2]dodecanoic acid, perfluoro-1-[ 13C8] Octanesulfonamide, N-methyl-d3-perfluoro-1-octanesulfonamide, N-ethyl-d5-perfluoro-1-octanesulfonamide, 1H, 1H, 2H, 2H-perfluoro Fluoro-1-[1,2-13C2]-octane sulfonate sodium, chlorpyrifos d10, γ-1,2,3,4,5,6-hexachlorocyclohexane-d6, trans-permethrin d6, Acetamiprid-d3, imidacloprid-d4, thiacloprid-d4, thiamethoxam-d3, carbendazim d3, carbofuran d3, 2,4-dichlorophenoxy-3,5,6-d3-acetic acid , 2,4'-dichlorodiphenyltrichloroethane-d8, 2-(4-chloro-2-methylphenoxy)propionic acid-D3, thiabendazole d4, decatritium simazine Terding At least one of turfone-D5, diuron-D6 tritiated, isoproturon d6, metolachlor d6, azoxystrobin d4 and boscalid d4.
  8. 根据权利要求1或4所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1 or 4, characterized in that:
    步骤(4)中所述的内标包括全氟化合物、增塑剂、有机氯农药、有机磷农药和液晶单体的内标；The internal standard described in step (4) comprises the internal standard of perfluorinated compound, plasticizer, organochlorine pesticide, organophosphorus pesticide and liquid crystal monomer;
    所述的全氟化合物的内标为全氟-n-[13C8]辛酸；The internal standard of the perfluorinated compound is perfluoro-n-[13C8] octanoic acid;
    所述的增塑剂的正模式的内标为蝇毒磷-d10，负模式的内标为双酚A-d16；The internal standard of the positive mode of the plasticizer is musphos-d10, and the internal standard of the negative mode is bisphenol A-d16;
    所述的有机氯农药的内标为十氯二苯醚；The internal standard of the organochlorine pesticide is decachlorodiphenyl ether;
    所述的有机磷农药的正模式的内标为蝇毒磷-d10，负模式的内标为对羟基苯甲酸叔丁酯-d9；The internal standard of the positive mode of the organophosphorus pesticide is muscarin-d10, and the internal standard of the negative mode is tert-butyl p-hydroxybenzoate-d9;
    所述的液晶单体的内标为十氯二苯醚。The internal standard of the liquid crystal monomer is decachlorodiphenyl ether.
  9. 根据权利要求1或4所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1 or 4, characterized in that:
    步骤(4)中所述的液相色谱-串联质谱法的检测条件如下：The detection condition of the liquid chromatography-tandem mass spectrometry described in step (4) is as follows:
    ①邻苯二甲酸二酯类：① Phthalic acid diesters:
    色谱条件包括：Chromatographic conditions include:
    流动相A：体积分数为0.1％的甲酸水溶液；Mobile phase A: 0.1% formic acid aqueous solution by volume fraction;
    流动相B：甲醇；Mobile phase B: Methanol;
    色谱柱：C18色谱柱；Chromatographic column: C18 chromatographic column;
    流速：0.2mL/min；Flow rate: 0.2mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B的体积百分含量为40％；0～2min，流动相B体积百分数从40％上升至70％；2～8min，流动相B体积百分数上升至100％；8～13min保持在100％不变，13～13.1min流动相B体积百分数降至40％；13.1～17min，保持在40％不变；Elution procedure: the initial volume percentage of mobile phase B is 40%; 0~2min, the volume percentage of mobile phase B rises from 40% to 70%; 2~8min, the volume percentage of mobile phase B rises to 100%; Keep at 100% for 13 minutes, the volume percentage of mobile phase B drops to 40% at 13-13.1 minutes; keep at 40% for 13.1-17 minutes;
    质谱条件包括：电喷雾离子源，离子源温度为550℃；检测模式为正离子检测模式；雾化气压；氮气，压力为55psi；The mass spectrometry conditions include: electrospray ion source, the ion source temperature is 550°C; the detection mode is positive ion detection mode; atomization air pressure; nitrogen, the pressure is 55psi;
    ②邻苯二甲酸单酯类，苯甲酮类紫外线稳定剂，双酚类似物以及个人护理产品：② Phthalic acid monoesters, benzophenone UV stabilizers, bisphenol analogues and personal care products:
    色谱条件包括：Chromatographic conditions include:
    流动相A：0.2mmol/L乙酸铵水溶液；Mobile phase A: 0.2mmol/L ammonium acetate aqueous solution;
    流动相B：甲醇；Mobile phase B: Methanol;
    色谱柱：C18色谱柱；Chromatographic column: C18 chromatographic column;
    流速：0.2mL/min；Flow rate: 0.2mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B的体积百分数为10％；0～0.5min保持在10％数不变；0.5～1min，流动相B体积百分数从10％上升至50％；1～7min，流动相B体积分数从50％上升至99％；7～10min，保持在99％不变；10～10.1min，从99％下降到10％，10.1～12min，流动相B体积分数保持在10％不变；Elution procedure: the volume percentage of the initial mobile phase B is 10%; 0-0.5min keeps the number constant at 10%; 0.5-1min, the volume percentage of the mobile phase B rises from 10% to 50%; B volume fraction increased from 50% to 99%; 7-10min, kept at 99%; 10-10.1min, decreased from 99% to 10%, 10.1-12min, mobile phase B volume fraction remained at 10% ;
    质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
    ③增塑剂，苯并噻唑类、苯并三唑类和其他类别紫外稳定剂，光引发剂以及在正离子检测模式下进行检测的抗氧化剂：③Plasticizers, benzothiazoles, benzotriazoles and other UV stabilizers, photoinitiators and antioxidants detected in positive ion detection mode:
    色谱条件包括：Chromatographic conditions include:
    流动相A：体积分数为0.1％的甲酸水溶液；Mobile phase A: 0.1% formic acid aqueous solution by volume fraction;
    流动相B：甲醇；Mobile phase B: Methanol;
    色谱柱：C18色谱柱；Chromatographic column: C18 chromatographic column;
    流速：0.3mL/min；Flow rate: 0.3mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B体积百分数为40％，0～2min保持40％不变；2～4min，流动相B体积百分数由40％上升至80％；4～14min，流动相B体积百分数从80％上升至100％；14～17min，流动相B体积百分数保持在100％不变；17～20min，流动相B体积百分数下降至40％，20～24min，流动相B体积百分数保持在40％不变；Elution procedure: initial mobile phase B volume percentage is 40%, 0-2min keeps 40% unchanged; 2-4min, mobile phase B volume percentage rises from 40% to 80%; 4-14min, mobile phase B volume percentage increases from 80% rises to 100%; 14-17min, the volume percentage of mobile phase B remains at 100%; 17-20min, the volume percentage of mobile phase B drops to 40%, 20-24min, the volume percentage of mobile phase B remains at 40% constant;
    质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为正离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is positive ion detection mode; atomization pressure: nitrogen, pressure 55psi;
    ④有机磷酸三酯类：④Organophosphate triesters:
    色谱条件包括：Chromatographic conditions include:
    流动相A：体积分数为0.1％甲酸水溶液；Mobile phase A: a volume fraction of 0.1% formic acid in water;
    流动相B：甲醇；Mobile phase B: Methanol;
    色谱柱：RP18色谱柱；Chromatographic column: RP18 chromatographic column;
    流速：0.3mL/min；Flow rate: 0.3mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B体积百分数为5％，0～1min保持在5％；1～3min流动相B体积分数从5％上升至40％；3～12min从40％上升至100％；12～15min保持100％不变；15～15.1min，流动相B体积百分数从100％降至5％；15.1～18min，流动相B体积分数保持在5％不变；Elution procedure: initial mobile phase B volume percentage is 5%, 0-1min maintains at 5%; 1-3min mobile phase B volume fraction rises from 5% to 40%; 3-12min rises from 40% to 100%; 12 From 15 minutes to 15 minutes, keep 100% unchanged; from 15 to 15.1 minutes, the volume percentage of mobile phase B decreases from 100% to 5%; from 15.1 to 18 minutes, the volume percentage of mobile phase B remains unchanged at 5%;
    质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
    ⑤有机磷酸二酯类：⑤Organophosphate diesters:
    色谱条件包括：Chromatographic conditions include:
    流动相A：0.2mmol/L乙酸铵水溶液；Mobile phase A: 0.2mmol/L ammonium acetate aqueous solution;
    流动相B：甲醇；Mobile phase B: Methanol;
    A子检测模式；雾化气压：氮气，压力位55psi：A sub-detection mode; atomization pressure: nitrogen, pressure 55psi:
    色谱柱：RP18色谱柱；Chromatographic column: RP18 chromatographic column;
    流速：0.3mL/min；Flow rate: 0.3mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B体积百分数为5％，0～4min，从5％上升至35％；4～7min，B相体积分数从35％上升至80％；7～12min从80％升至100％；12～14min保持100％不变；14～15min，流动相B体积百分数从100％降至5％；15～20min，流动相B体积百分数保持在5％不变；Elution procedure: initial mobile phase B volume percentage is 5%, 0~4min, rise from 5% to 35%; 4~7min, B phase volume fraction rises from 35% to 80%; 7~12min, rise from 80% to 100%; 12-14min keep 100% unchanged; 14-15min, mobile phase B volume percentage decreases from 100% to 5%; 15-20min, mobile phase B volume percentage remains unchanged at 5%;
    质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi：Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure position 55psi:
    ⑥在负离子检测模式下进行检测的抗氧化剂：⑥Antioxidants detected in negative ion detection mode:
    色谱条件包括：Chromatographic conditions include:
    流动相A：4mmol/L乙酸铵水溶液；Mobile phase A: 4mmol/L ammonium acetate aqueous solution;
    流动相B：甲醇；Mobile phase B: Methanol;
    色谱柱：C18色谱柱；Chromatographic column: C18 chromatographic column;
    流速：0.2mL/min；Flow rate: 0.2mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B的体积百分数为10％；0～0.5min保持10％不变；0.5～1min流动相B的体积百分数从10％上升至50％，1～7min上升至99％；7～10min保持在99％不变；10～10.1min，流动相B体积百分数迅速下降至10％；10.1～12min流动相B体积分数保持10％不变；Elution procedure: the initial volume percentage of mobile phase B is 10%; 0-0.5min keeps 10% unchanged; 0.5-1min the volume percentage of mobile phase B increases from 10% to 50%, and 1-7min rises to 99%; From 7 to 10 minutes, it remained at 99%; from 10 to 10.1 minutes, the volume percentage of mobile phase B dropped rapidly to 10%; from 10.1 to 12 minutes, the volume percentage of mobile phase B remained unchanged at 10%;
    质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；⑦全氟化合物：Mass spectrometry conditions include: electrospray ion source, ion temperature of 550°C, detection mode of negative ion detection mode; atomization pressure: nitrogen, pressure position 55psi; ⑦ perfluorinated compounds:
    色谱条件包括：Chromatographic conditions include:
    流动相A：0.2mmol/L甲酸铵；Mobile phase A: 0.2mmol/L ammonium formate;
    流动相B：甲醇；Mobile phase B: Methanol;
    色谱柱：RP18色谱柱；Chromatographic column: RP18 chromatographic column;
    流速：0.3mL/min；Flow rate: 0.3mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B体积百分数为40％；0～2min内保持40％不变，2～3min流动相B体积百分数上升至66％；3～12min上升至77％；12～14min流动相B体积分数由70％上升至100％，14～16min保持在100％不变；16～16.1min迅速降至40％；16.1～22流动相B体积分数保持在40％不变；Elution procedure: initial mobile phase B volume percentage is 40%; 40% remains unchanged within 0-2min, mobile phase B volume percentage rises to 66% in 2-3min; rises to 77% in 3-12min; mobile phase in 12-14min B volume fraction rises from 70% to 100%, and remains unchanged at 100% for 14-16 minutes; quickly drops to 40% for 16-16.1 minutes; 16.1-22 mobile phase B volume fraction remains unchanged at 40%;
    质谱条件包括：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions include: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
    ⑧有机磷农药，拟除虫菊酯，新烟碱类农药，氨基甲酸酯类农药，酸性除草剂，唑类农药，三唑酮类农药，尿素类农药，酰胺类农药，甲氧基丙烯酸酯类杀菌剂，其他杀虫剂：⑧Organophosphorus pesticides, pyrethroids, neonicotinoid pesticides, carbamate pesticides, acidic herbicides, azole pesticides, triadimefon pesticides, urea pesticides, amide pesticides, methoxyacrylate fungicides pesticides, other insecticides:
    流动相A：5mmol/L的乙酸铵溶液；Mobile phase A: 5mmol/L ammonium acetate solution;
    流动相B：乙腈；Mobile phase B: acetonitrile;
    色谱柱：C18色谱柱；Chromatographic column: C18 chromatographic column;
    流速：0.4mL/min；Flow rate: 0.4mL/min;
    柱温：40℃；Column temperature: 40°C;
    洗脱程序：初始流动相B的体积百分数为2％；0～4min流动相B体积百分数从宏观2％上升至30％；4～22min流动相体积百分数从30％上升至68％；22～22.1min流动相B从68％上升至99％；22.1～23min，保持在99％不变；23～23.1min，流动相B体积百分数从99％降至2％；23.1～26min，保持2％不变；Elution procedure: the volume percentage of the initial mobile phase B is 2%; the volume percentage of the mobile phase B increases from 2% to 30% in 0-4min; the volume percentage of the mobile phase increases from 30% to 68% in 4-22min; 22-22.1 Min mobile phase B increased from 68% to 99%; 22.1~23min, kept at 99%; 23~23.1min, mobile phase B volume percentage decreased from 99% to 2%; 23.1~26min, kept 2% unchanged ;
    质谱条件：电喷雾离子源，离子温度为550℃，检测模式为负离子检测模式；雾化气压：氮气，压力位55psi；Mass spectrometry conditions: electrospray ion source, ion temperature is 550°C, detection mode is negative ion detection mode; atomization pressure: nitrogen, pressure 55psi;
    步骤(4)中所述的气相色谱-串联质谱法的的检测条件如下：The detection condition of gas chromatography-tandem mass spectrometry described in step (4) is as follows:
    ⑨有机氯农药：⑨Organochlorine pesticides:
    色谱条件包括：Chromatographic conditions include:
    色谱柱：安捷伦HP-5MS色谱柱19091S-433；Chromatographic column: Agilent HP-5MS chromatographic column 19091S-433;
    进样口温度：260℃；Injection port temperature: 260°C;
    升温程序：起始温度60℃，保持1min；以5℃/min的速度升温至300℃后保持9min；Heating program: initial temperature is 60°C, keep for 1min; heat up to 300°C at a rate of 5°C/min, then keep for 9min;
    质谱条件：电子轰击离子源，离子源温度为230℃，四极杆温度为150℃，溶剂延时3min；Mass spectrometry conditions: electron bombardment ion source, ion source temperature is 230°C, quadrupole temperature is 150°C, solvent delay is 3min;
    ⑩液晶单体：⑩Liquid crystal monomer:
    色谱条件包括：Chromatographic conditions include:
    色谱柱：安捷伦HP-5MS色谱柱19091S-433；Chromatographic column: Agilent HP-5MS chromatographic column 19091S-433;
    进样口温度：260℃；Injection port temperature: 260°C;
    升温程序：起始温度80℃，保持2.5min；然后以25℃/min的速度升温至200℃后保持1min；再以10℃/min速度升至250℃后以5℃/min升至285℃，保持5min；最后以30℃/min的速度升至300℃，保持1minHeating program: initial temperature 80°C, keep for 2.5min; then raise the temperature to 200°C at a rate of 25°C/min and keep for 1min; then rise to 250°C at a rate of 10°C/min and then rise to 285°C at a rate of 5°C/min , hold for 5min; finally rise to 300°C at a speed of 30°C/min, hold for 1min
    质谱条件：电子轰击离子源，离子源温度230℃，四极杆温度为150℃，溶剂延时6min。Mass spectrometry conditions: electron bombardment ion source, ion source temperature 230°C, quadrupole temperature 150°C, solvent delay 6min.
  10. 根据权利要求1所述的血浆中环境污染物靶向暴露组分析方法，其特征在于：The targeted exposure group analysis method for environmental pollutants in plasma according to claim 1, characterized in that:
    步骤(1)中所述的血浆为人的血浆或动物的血浆；The plasma described in step (1) is human plasma or animal plasma;
    步骤(1)中所述的血浆通过如下方式获得：将采集的血液离心分离，取上清液，获得所需要的血浆；The plasma described in step (1) is obtained by centrifuging the collected blood, and taking the supernatant to obtain the required plasma;
    所述的离心的条件为：3000rpm下离心3分钟；The centrifugation condition is: centrifugation at 3000rpm for 3 minutes;
    步骤(2)中所述的重复的次数为2次以上；The number of repetitions described in step (2) is more than 2 times;
    步骤(2)中所述的离心的条件为：3000～4000rpm下离心3min以上；The centrifugation conditions described in step (2) are: centrifugation at 3000-4000rpm for more than 3min;
    步骤(4)中所述的液相色谱-串联质谱法为采用超高效液相色谱-串联质谱联用仪进行；The liquid chromatography-tandem mass spectrometry described in the step (4) is carried out by adopting ultra-high performance liquid chromatography-tandem mass spectrometry;
    步骤(4)中所述的气相色谱-串联质谱法为采用气相色谱-串联质谱联用仪进行。The gas chromatography-tandem mass spectrometry described in step (4) is carried out by using gas chromatography-tandem mass spectrometry.
  11. 权利要求1～10任一项所述的血浆中环境污染物靶向暴露组分析方法在非疾病诊断治疗目的的分析血浆中环境污染物中的应用。Application of the targeted exposome analysis method for environmental pollutants in plasma according to any one of claims 1 to 10 in the analysis of environmental pollutants in plasma for non-disease diagnosis and treatment purposes.
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