CN118937546B - Method for measuring carbazole and 9 halogenated carbazole in sediment by internal standard method - Google Patents
Method for measuring carbazole and 9 halogenated carbazole in sediment by internal standard method Download PDFInfo
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000013049 sediment Substances 0.000 title claims abstract description 44
- 150000001716 carbazoles Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000010813 internal standard method Methods 0.000 title claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- CHEFFAKKAFRMHG-UHFFFAOYSA-N ethenyl-tris(trimethylsilyloxy)silane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C=C CHEFFAKKAFRMHG-UHFFFAOYSA-N 0.000 claims description 8
- DCMDRWCDFDTMLK-UHFFFAOYSA-N 2-(6,6-dimethylcyclohexa-2,4-dien-1-yl)-1-phenylethanone Chemical compound CC1(C)C=CC=CC1CC(=O)C1=CC=CC=C1 DCMDRWCDFDTMLK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 claims 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000004885 tandem mass spectrometry Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 35
- 239000001913 cellulose Substances 0.000 description 27
- 229920002678 cellulose Polymers 0.000 description 27
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 25
- 229910052710 silicon Inorganic materials 0.000 description 25
- 239000010703 silicon Substances 0.000 description 25
- 239000002114 nanocomposite Substances 0.000 description 23
- 239000012634 fragment Substances 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 150000001735 carboxylic acids Chemical class 0.000 description 19
- 159000000000 sodium salts Chemical class 0.000 description 19
- 238000011084 recovery Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 11
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 10
- -1 carbazole compound Chemical group 0.000 description 9
- AAXKJEWUYLSARD-UHFFFAOYSA-N 1-bromo-3,6-dichloro-9H-carbazole Chemical compound BrC1=CC(=CC=2C3=CC(=CC=C3NC1=2)Cl)Cl AAXKJEWUYLSARD-UHFFFAOYSA-N 0.000 description 8
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- BIMDTNQPZWJKPL-UHFFFAOYSA-N 3,6-dichloro-9h-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC=C3NC2=C1 BIMDTNQPZWJKPL-UHFFFAOYSA-N 0.000 description 4
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 4
- CABSFELLEWZIAK-UHFFFAOYSA-N 3-chloro-9h-carbazole Chemical compound C1=CC=C2C3=CC(Cl)=CC=C3NC2=C1 CABSFELLEWZIAK-UHFFFAOYSA-N 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FNHISDQCWYSMTO-UHFFFAOYSA-N 1,3,6,8-tetrabromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC(Br)=C3NC2=C1Br FNHISDQCWYSMTO-UHFFFAOYSA-N 0.000 description 3
- XEUQVTHGXKXLBB-UHFFFAOYSA-N 1,3,6,8-tetrachloro-9h-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC(Cl)=C3NC2=C1Cl XEUQVTHGXKXLBB-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000012224 working solution Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000185 dioxinlike effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001094 effect on targets Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for measuring carbazole and 9 halogenated carbazole in sediment by an internal standard method, belonging to the technical field of carbazole detection; the determination method comprises the steps of mixing sediment, an internal standard use solution, an extraction solvent, metal salt and a surfactant uniformly, carrying out ultrasonic extraction to obtain an extraction solution, adding a purification material into the extraction solution, carrying out purification treatment to obtain a liquid to be detected, and detecting carbazole and halogenated carbazole in the liquid to be detected by utilizing gas chromatography-tandem mass spectrometry. The invention provides a method for measuring carbazole and 9 halogenated carbazole in sediment by an internal standard method, which can not only effectively improve the extraction efficiency of target compounds and reduce the loss in the purification process, but also improve the test efficiency and accuracy.
Description
Technical Field
The invention relates to the technical field of carbazole detection, in particular to a method for measuring carbazole and 9 halogenated carbazole in sediment by an internal standard method.
Background
Carbazole and its derivatives are a class of nitrogen-containing heterocyclic aromatic compounds, and are widely used in various fields such as photoelectric materials, dyes, medicines, supermolecular recognition, and the like. Halocarbazole is a carbazole compound substituted with one or more halogens, and 135 halocarbazole homologs have been found. Toxicology studies have shown that exposure to carbazole and halocarbazole has adverse effects on human health. The halogenated carbazole has cancerogenic and mutagenic dioxin-like toxicological effects, and can induce cancerogenesis, teratogenicity and mutagenesis of rodents, aquatic animals and humans.
The halogenated carbazole is continuously detected in different environmental media such as sediment, soil, natural water, drinking water, air dust and the like, and biological media such as animals, human bodies and the like. The halogenated carbazole has stable property in natural environment, can be remained in water, soil, sediment and air for a long time, and has potential durability and bioaccumulation. Therefore, it is important to develop a method for determining carbazole and halocarbazole in a deposit.
Disclosure of Invention
The invention aims to provide a method for measuring carbazole and 9 halogenated carbazole in sediment by an internal standard method, which not only can improve the recovery rate of a target compound, but also can improve the detection accuracy.
The technical scheme adopted by the invention for achieving the purpose is as follows:
In the preparation of the sodium salt of the silicon-based carboxylic acid, vinyl-tri (trimethylsiloxy) silane is firstly mixed with thioglycollic acid, reacted under the initiation condition of 2, 2-dimethyl-phenylacetophenone, and then salified with anhydrous sodium carbonate to obtain the sodium salt of the silicon-based carboxylic acid. The sodium salt of silicon-based carboxylic acid has strong surface activity and can obviously reduce the surface tension of liquid. The sodium salt of silicon-based carboxylic acid is used for assisting the ultrasonic extraction of the target compound, so that the interfacial tension and wetting angle between the sediment and the solvent can be reduced, the surface wettability of the sediment is promoted, and the extraction efficiency of the target compound is improved.
Preferably, the preparation method of the sodium salt of silicon-based carboxylic acid, specifically,
Mixing vinyl-tri (trimethylsiloxy) silane and thioglycollic acid, adding tetrahydrofuran, stirring uniformly, adding 2, 2-dimethyl-phenylacetophenone, performing reaction by ultraviolet irradiation, adding anhydrous sodium carbonate, performing reaction for 2-8 hours, removing solvent by rotary evaporation, repeatedly washing the precipitate with n-hexane for 3-5 times, and performing vacuum drying at 50-70 ℃ for 24-72 hours to obtain silicon-based carboxylic acid sodium salt.
More preferably, the weight ratio of vinyl-tris (trimethylsiloxy) silane to thioglycolic acid is 3-4:1.
More preferably, the liquid to solid ratio of thioglycollic acid to tetrahydrofuran is 1g:2-10mL.
More preferably, the weight ratio of thioglycollic acid to 2, 2-dimethyl-phenylacetophenone is 10-20:1.
More preferably, the ultraviolet light has an irradiation wavelength of 365nm and an irradiation time of 10 to 30 minutes.
More preferably, the weight ratio of vinyl-tris (trimethylsiloxy) silane to anhydrous sodium carbonate is 2-10:1.
A method for measuring carbazole and 9 halogenated carbazole in sediment by an internal standard method comprises the steps of mixing sediment, an internal standard use solution, an extraction solvent, metal salt and a surfactant uniformly, carrying out ultrasonic extraction to obtain an extraction solution, adding a purification material into the extraction solution, carrying out purification treatment to obtain a liquid to be measured, and detecting carbazole and halogenated carbazole in the liquid to be measured by utilizing gas chromatography tandem mass spectrometry.
Preferably, the internal standard use solution comprises a D8-carbazole standard, the mass concentration of the internal standard use solution is 0.1-0.5mg/mL, the extraction solvent comprises n-hexane and acetone, the volume ratio of the n-hexane to the acetone is 2-3:1, the metal salt comprises anhydrous magnesium sulfate and sodium chloride, and the weight ratio of the anhydrous magnesium sulfate to the sodium chloride is 3-5:1.
Preferably, the ratio of the amount of sediment to the amount of standard use solution is 1 g:2-5. Mu.L.
Preferably, the liquid to solid ratio of the sediment and the extraction solvent is 1g:2-4mL.
Preferably, the weight ratio of sediment to metal salt is 3-5:1.
Preferably, the weight ratio of metal salt to surfactant is 2-15:1.
Preferably, the ultrasonic extraction temperature is 20-60 ℃ and the ultrasonic extraction time is 10-30min.
Preferably, the purification material comprises the following components in parts by mass of 30 parts of ethylenediamine-N-propylsilane, 70 parts of octadecylsilane chemically bonded silica, 2 parts of graphitized carbon black and 50 parts of anhydrous magnesium sulfate.
Preferably, the weight ratio of sediment to purification material is 2-4:1.
Preferably, an internal standard method for determining carbazole and 9 halogenated carbazole in a deposit, specifically,
Adding D8-carbazole internal standard working solution with the mass concentration of 0.1-0.5mg/mL into the sediment, standing for 20-40min, adding n-hexane and acetone, vortex for 5min, adding anhydrous magnesium sulfate, sodium chloride and surfactant, immediately mixing the surfactant comprising at least one of silicon-based carboxylic acid sodium salt and ferroferric oxide/cellulose magnetic nanocomposite material for 20-60s, ultrasonically extracting for 10-30min at 20-60 ℃, centrifuging for 5-20min at 4000-8000rpm, taking supernatant, adding 1.0-3.0g of purifying material, vortex for 2-10min, centrifuging for 5-20min at 4000-8000rpm, blowing the supernatant to near dryness by liquid nitrogen, re-dissolving with 0.5-1.5mL of acetonitrile, filtering by using an organic film of 0.45 mu m, and detecting carbazole and halogenated carbazole in the solution to be detected by using gas chromatography tandem mass spectrometry. The ferroferric oxide/cellulose magnetic nanocomposite has larger specific surface area, porous structure and uniform pore size distribution, can improve the adsorption effect on target compounds and realize effective enrichment of the target compounds, and meanwhile, the ferroferric oxide/cellulose magnetic nanocomposite has extremely high surface energy and easy surface functionalization, and can fully approach particles and reduce balance time under the combination of the ferroferric oxide/cellulose magnetic nanocomposite and sodium salt of silicon-based carboxylic acid, thereby further improving the extraction efficiency of the target compounds.
More preferably, the surfactant comprises a sodium salt of a silicon-based carboxylic acid.
More preferably, the surfactant comprises a ferroferric oxide/cellulose magnetic nanocomposite.
More preferably, the surfactant comprises sodium salt of silicon-based carboxylic acid and ferroferric oxide/cellulose magnetic nanocomposite.
Still more preferably, the weight ratio of sodium salt of silicon-based carboxylic acid to ferroferric oxide/cellulose magnetic nanocomposite is 0.2-4:1.
More preferably, the preparation method of the ferroferric oxide/cellulose magnetic nanocomposite, in particular,
Soaking bamboo fiber in potassium hydroxide solution for 6-12h, filtering, washing until neutral, adding ammonium persulfate, oxidizing and degrading at 60-100 ℃ for 12-24h to prepare cellulose nano material, dispersing the cellulose nano material into water, adding ferroferric oxide and acetone in an inert environment, adding ammonia water under stirring, adjusting pH value to be alkaline, crystallizing at 40-80 ℃ for 0.5-2h, collecting the product by using a magnet, washing for 3-5 times by using ethanol, and drying to obtain the ferroferric oxide/cellulose magnetic nano composite material.
Still more preferably, the concentration of potassium hydroxide is 0.5 to 1.5mol/L.
Still more preferably, the weight ratio of the bamboo fiber to the ammonium persulfate is 1:1-3.
Still more preferably, the weight ratio of bamboo fibers to ferroferric oxide is 1:1-3.
Still more preferably, the liquid to solid ratio of ferroferric oxide to acetone is 1g:2-3mL.
The silicon-based sodium carboxylate prepared by the method has the advantages of remarkably reducing the surface tension of liquid, reducing the interfacial tension and wetting angle between sediment and a solvent, promoting the surface wettability of the sediment, and improving the extraction effect of target compounds. The ferroferric oxide/cellulose magnetic nanocomposite prepared by the method has the advantages of larger specific surface area, porous structure, uniform pore size distribution, capability of improving the adsorption effect on the target compound and realizing the effective enrichment of the target compound, extremely high surface energy, easy surface functionalization, capability of enabling particles to be sufficiently close to each other and reducing the balance time under the combination with the sodium salt of silicon-based carboxylic acid, and further improvement of the extraction efficiency on the target compound. Therefore, the invention provides a method for measuring carbazole and halogenated carbazole in sediment by an internal standard method, which is efficient, simple and convenient and has good recovery rate and precision.
Drawings
FIG. 1 is a total ion flow diagram of carbazole, D8-carbazole, and 9 halogenated carbazole.
FIG. 2 is a carbazole quantitative ion chromatogram and a characteristic fragment mass spectrum.
FIG. 3 is a quantitative ion chromatogram of D8-carbazole and a characteristic fragment mass spectrum.
FIG. 4 is a quantitative ion chromatogram of 3-chlorocarbazole and a characteristic fragment mass spectrum.
FIG. 5 is a quantitative ion chromatogram of 3-bromocarbazole and a characteristic fragment mass spectrum.
FIG. 6 is a quantitative ion chromatogram and a characteristic fragment mass chromatogram of 3, 6-dichlorocarbazole.
FIG. 7 is a quantitative ion chromatogram and a characteristic fragment mass spectrum of 1,3,6, 8-tetrachlorocarbazole.
FIG. 8 is a quantitative ion chromatogram and a characteristic fragment mass spectrum of 1-bromo-3, 6-bischlorocarbazole.
FIG. 9 is a quantitative ion chromatogram and a characteristic fragment mass chromatogram of 3, 6-dibromocarbazole.
FIG. 10 is a quantitative ion chromatogram and a characteristic fragment mass chromatogram of 2, 7-dibromocarbazole.
FIG. 11 is a quantitative ion chromatogram and a characteristic fragment mass spectrum of 1, 8-bromo-3, 6-bischlorocarbazole.
FIG. 12 is a quantitative ion chromatogram and a characteristic fragment mass spectrum of 1,3,6, 8-tetrabromocarbazole.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1:
s1, preparing a standard solution, which comprises the following steps of,
Accurately weighing or absorbing carbazole, D8-carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 2, 7-dibromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-bromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole standard substances, adding acetonitrile to dissolve and fix the standard graduation lines to prepare a mixed standard stock solution with the mass concentration of 100mg/L, accurately absorbing 50 mu L of standard stock solution, adding acetonitrile to fix the standard graduation lines to prepare a standard intermediate solution with the mass concentration of 500ng/mL, preserving the standard intermediate solution at 20 ℃, accurately weighing D8-carbazole standard substances, adding acetonitrile to dissolve and fix the standard graduation lines to prepare an internal standard graduation line with the mass concentration of 100mg/L, preserving the standard stock solution at 20 ℃, accurately absorbing the internal standard graduation solution at 100 mu L, adding acetonitrile to fix the standard graduation lines to prepare the standard stock solution with the mass concentration of 1mg/L, preserving the standard intermediate solution at 20 DEG, and diluting the standard stock solution with the mass concentration of 10ng to prepare the standard stock solution with the mass concentration of 10ng to the standard graduation line at the 10ng/mL, and the mass concentration of the standard stock solution at the 10ng/mL, and the working standard stock solution with the mass concentration of 10ng to be measured is prepared at the intermediate solution at the 10 ng/mL.
S2, preparing silicon-based carboxylic acid sodium salt, which comprises,
3.22G of vinyl-tris (trimethylsiloxy) silane and 1.01g of thioglycollic acid are mixed, 5mL of tetrahydrofuran is added, stirring is uniform, 0.0698g of 2, 2-dimethyl-phenylacetophenone is added, 365nm ultraviolet light is used for irradiation reaction for 15min, 0.53g of anhydrous sodium carbonate is added, after reaction for 5h, solvent is removed by rotary evaporation, precipitate is repeatedly washed 3 times with n-hexane, and vacuum drying is carried out for 48h at 60 ℃ to obtain sodium silicate-based carboxylate.
S3, preparing the ferroferric oxide/cellulose magnetic nanocomposite, which comprises,
1G of bamboo fiber is placed in 1mol/L potassium hydroxide solution for 8 hours, filtered and washed until neutral, 2.28g of ammonium persulfate is added for oxidative degradation at 80 ℃ for 16 hours to prepare a cellulose nano material, the cellulose nano material is dispersed in water, 2g of ferroferric oxide is added in an inert environment, 5mL of acetone is added, ammonia water is added under stirring, the pH value is adjusted to 10, after crystallization at 60 ℃ for 1 hour, a magnet is used for collecting the product, and the product is washed for 4 times by ethanol and dried to obtain the ferroferric oxide/cellulose magnetic nano composite material.
S4, sample pretreatment, which comprises,
5.00G of sediment is weighed, 15 mu L of D8-carbazole with the mass concentration of 0.1mg/L is added, standing is carried out for 30min, 10.5mL of normal hexane and 4.5mL of acetone are added and vortex is carried out for 5min, 1g of anhydrous magnesium sulfate, 0.25g of sodium chloride and surfactant are added, the surfactant comprises 0.3g of sodium salt of silicon-based carboxylic acid and 0.2g of ferroferric oxide/cellulose magnetic nanocomposite, the mixture is immediately mixed by hand for 30s, ultrasonic extraction is carried out for 15min at 30 ℃, centrifugation is carried out for 10min at 6000rpm, the supernatant is taken, 300mg of ethylenediamine-N-propyl silane, 700mg of octadecylsilane bonded silica gel, 20mg of graphitized carbon black and 500mg of anhydrous magnesium sulfate are added, vortex is carried out for 5min, the supernatant is blown to be dried by liquid nitrogen, the supernatant is dissolved by 1.0mL of acetonitrile in a redissolved mode through 0.45 mu m organic film filtration, and the measurement is carried out.
S5, chromatographic conditions, including,
Agilgent DB-5MS, 30m×250 μm×0.25 μm, heating to 50deg.C for 3min, heating to 300deg.C at 10 deg.C/min for 10min, helium as carrier gas, flow rate of 1.0mL/min, constant pressure of 8.4679psi, sample inlet temperature of 280 deg.C, sample injection amount of 1 μl, and sample injection mode of no-split sample injection.
S6, mass spectrum conditions, including,
The electron bombards the ion source, the electron energy is 70eV, the collision gas is nitrogen, the data acquisition mode is a multi-reaction monitoring mode, the ion source temperature is 280 ℃, the quadrupole temperature is 280 ℃, and the solvent delay time is 5min. Mass spectrum parameters of each carbazole and halogenated carbazole compound are shown in table 1.
Table 1 mass spectral parameters of carbazole, D8-carbazole and 9 halocarbazoles
S7, linear relationship and sensitivity, including,
And (3) sucking a proper amount of mixed standard stock solution, adding an internal standard working solution, gradually diluting the mixed standard stock solution into a mixed series of standard working solutions with required concentration by acetonitrile, and carrying out analysis and detection under the instrument conditions of the steps S5 and S6. The detection limit was calculated with a 3-fold signal-to-noise ratio (S/N), the quantification limit was calculated with a 10-fold signal-to-noise ratio (S/N), and the measurement results are shown in Table 2.
As shown in Table 2, the linear range of carbazole and 9 halogenated carbazole compounds is 0.2-20.0 mug/kg, and the detection limit and the quantitative limit are 0.10 mug/kg and 0.20 mug/kg respectively, which indicates that the detection method established in the study can meet the quantitative requirement.
TABLE 2 Linear ranges, detection limits and quantification limits for carbazole and 9 halocarbazole compounds
Example 2:
The conditions were the same as in example 1 except that the components of the surfactant were changed in the sample pretreatment in step S4. The surfactant in this example included 0.1g sodium salt of a silicon-based carboxylic acid and 0.2g of a ferroferric oxide/cellulose magnetic nanocomposite.
Example 3:
The conditions were the same as in example 1 except that the components of the surfactant were changed in the sample pretreatment in step S4. The surfactant in this example included 0.3g sodium salt of a silicon-based carboxylic acid and 0.1g of a ferroferric oxide/cellulose magnetic nanocomposite.
Example 4:
The conditions were the same as in example 1 except that the components of the surfactant were changed in the sample pretreatment in step S4. The surfactant in this example comprises 0.3g sodium salt of a silicon-based carboxylic acid.
Example 5:
The conditions were the same as in example 1 except that the components of the surfactant were changed in the sample pretreatment in step S4. The surfactant in this example comprises 0.1g of sodium salt of a silicon-based carboxylic acid.
Example 6:
The conditions were the same as in example 1 except that the components of the surfactant were changed in the sample pretreatment in step S4. The surfactant in this example comprises 0.2g of ferroferric oxide/cellulose magnetic nanocomposite.
Example 7:
The conditions were the same as in example 1 except that the components of the surfactant were changed in the sample pretreatment in step S4. The surfactant in this example comprises 0.1g of ferroferric oxide/cellulose magnetic nanocomposite.
Comparative example 1:
the conditions were the same as in example 1 except that no surfactant was added in the pretreatment of the sample in step S4.
Experimental example:
1. Detection of carbazole and 9 halogenated carbazole.
Detection of carbazole and 9 halocarbazoles was performed as in comparative example 1.
FIG. 1 is a total ion flow diagram of carbazole, D8-carbazole and 9 halocarbazoles, wherein a is the ion peak of D8-carbazole and carbazole, b is the ion peak of 3-chlorocarbazole, c is the ion peak of 3-bromocarbazole, D is the ion peak of 3, 6-dichlorocarbazole, e is the ion peak of 1,3,6, 8-tetrachlorocarbazole, f is the ion peak of 1-bromo-3, 6-dichlorocarbazole, g is the ion peak of 3, 6-dibromocarbazole, h is the ion peak of 2, 7-dibromocarbazole and 1, 8-bromo-3, 6-dichlorocarbazole, i is the ion peak of 1,3,6, 8-tetrabromocarbazole; FIG. 2 is a carbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram with a retention time of 20.739min and a mass to charge ratio of from 167.1amu to 115.1amu; FIG. 3 is a quantitative ion chromatogram of D8-carbazole and a characteristic fragment mass spectrum with a retention time of 20.703min and a mass to charge ratio of from 175.1amu to 122.1amu; FIG. 4 is a 3-chlorocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, a retention time of 23.533min, a mass-to-charge ratio of 201.0amu to 140.1amu, FIG. 5 is a 3-bromocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, a retention time of 24.672min, a mass-to-charge ratio of 244.9amu to 139.1amu, FIG. 6 is a 3, 6-dichlorocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, a retention time of 26.031min, a mass-to-charge ratio of 234.9amu to 164.1amu, FIG. 7 is a1, 3,6, 8-tetrachlorocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, a retention time of 26.350min, a mass-to-charge ratio of 304.8amu to 232.0amu, FIG. 8 is a 1-bromo-3, 6-dichlorocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, a retention time of 27.116min, a mass-to a mass-charge ratio of 314.8amu to 164.0amu, FIG. 9 is a 3, 6-dibromocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, a retention time of 76, mass to charge ratio from 324.9amu to 165.1amu, fig. 10 is a2, 7-dibromocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, retention time is 28.173min, mass to charge ratio from 324.9amu to 165.1amu, fig. 11 is a1, 8-bromo-3, 6-dichlorocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, retention time is 28.182min, mass to charge ratio from 392.8amu to 198.1amu, fig. 12 is a1, 3,6, 8-tetrabromocarbazole quantitative ion chromatogram and a characteristic fragment mass chromatogram, retention time is 30.576min, mass to charge ratio from 482.7amu to 322.9amu. This demonstrates that the method can be used to accurately detect both carbazole and 9 halocarbazoles in a deposit.
2. Average recovery and relative standard deviation of carbazole and 9 halocarbazoles at different labelling concentrations
The carbazole and 9 kinds of halogenated carbazole were detected according to the method of comparative example 1, the standard addition levels were 1-fold, 3-fold and 10-fold quantitative limits of carbazole and 9 kinds of halogenated carbazole, respectively, and 6 parts of solutions to be measured were prepared in parallel at each concentration level, and the measurement results are shown in table 3.
As is clear from Table 3, the average recovery rates of carbazole and 9 halogenated carbazole compounds detected in comparative example 1 were 85.67% to 103.90%, and the relative standard deviation was 2.72% to 8.17%. The method is stable and reliable, has good accuracy and precision, and can meet the requirement of simultaneously detecting carbazole and 9 halogenated carbazole compounds in a sediment sample.
TABLE 3 average recovery and relative standard deviation of carbazole and 9 halocarbazoles of comparative example 1
3. Average recovery and relative standard deviation of different treatment groups carbazole and 9 halogenated carbazole
Carbazole was detected in the same manner as in examples 1 to 7 and comparative example 1, respectively, at a standard level of 0.20. Mu.g/kg, to prepare 6 sets of parallel test solutions, and the measurement results are shown in tables 4 to 5.
Table 4 average recovery of carbazole and 9 halocarbazoles (%)
TABLE 5 relative standard deviation of carbazole and 9 halocarbazoles (%)
As can be seen from tables 4 to 5, the average recovery rate and the relative standard deviation of carbazole and 9 kinds of halogenated carbazole of example 1 of the present invention are superior to those of comparative example 1, because the surfactant including sodium salt of silicon-based carboxylic acid and ferroferric oxide/cellulose magnetic nanocomposite is added to assist ultrasonic extraction in the pretreatment of the sediment sample of example 1 of the present invention, whereas the surfactant is not added to assist ultrasonic extraction in comparative example 1, which illustrates that the method provided in example 1 of the present invention can improve the average recovery rate of carbazole and 9 kinds of halogenated carbazole, and the accuracy of detection thereof.
The average recovery rate and the relative standard deviation of carbazole and 9 halogenated carbazole of example 1 of the present invention are superior to those of examples 2-3, because the use amount of the silicon-based carboxylic acid sodium salt and the ferroferric oxide/cellulose magnetic nanocomposite added in the pretreatment of the sediment sample of example 1 is different from that of example 2-3, which indicates that the addition of a proper amount of the silicon-based carboxylic acid sodium salt and the ferroferric oxide/cellulose magnetic nanocomposite helps to improve the average recovery rate of carbazole and 9 halogenated carbazole in the sediment and the accuracy of detection thereof.
The average recovery rate and the relative standard deviation of carbazole and 9 halogenated carbazole of the embodiment 1 are better than those of the embodiment 4-7, because the embodiment 1 uses sodium salt of silicon-based carboxylic acid and ferroferric oxide/cellulose magnetic nanocomposite material to assist ultrasonic extraction in the pretreatment of sediment samples in a synergic manner, while the embodiment 4-5 only adds sodium salt of silicon-based carboxylic acid to assist ultrasonic extraction in the pretreatment of sediment samples, the embodiment 6-7 only adds ferroferric oxide/cellulose magnetic nanocomposite material to assist ultrasonic extraction in the pretreatment of sediment samples, and the embodiment 4-5 obtains carbazole and 9 halogenated carbazole, and the average recovery rate and the relative standard deviation of carbazole are better than those of the embodiment 6-7, which indicates that the further addition of ferroferric oxide/cellulose magnetic nanocomposite material on the basis of using sodium salt of silicon-based carboxylic acid as surfactant to assist ultrasonic extraction, so that the average recovery rate of carbazole and 9 halogenated carbazole in sediment is improved, and the accuracy effect of detection is best.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art, and are not described herein.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The method for measuring carbazole and 9 halogenated carbazole in sediment by using an internal standard method comprises the steps of uniformly mixing sediment, an internal standard use solution, an extraction solvent, metal salt and a surfactant, performing ultrasonic extraction to obtain an extraction solution, adding a purification material into the extraction solution, and performing purification treatment to obtain a liquid to be measured;
The surfactant comprises sodium silicon-based carboxylate, sulfur-containing elements and silicon oxygen groups, wherein in the preparation of the sodium silicon-based carboxylate, vinyl-tri (trimethylsiloxy) silane is firstly mixed with mercaptoacetic acid, the mixture reacts under the initiation condition of 2, 2-dimethyl-phenylacetophenone and then salified with anhydrous sodium carbonate to obtain the sodium silicon-based carboxylate, the weight ratio of vinyl-tri (trimethylsiloxy) silane to mercaptoacetic acid is 3-4:1, the liquid-solid ratio of mercaptoacetic acid to tetrahydrofuran is 1g:2-10mL, the weight ratio of mercaptoacetic acid to 2, 2-dimethyl-phenylacetophenone is 10-20:1, the ultraviolet irradiation wavelength is 365nm, the irradiation time is 10-30min, and the weight ratio of vinyl-tri (trimethylsiloxy) silane to anhydrous sodium carbonate is 2-10:1.
2. The method for determining carbazole and 9 halogenated carbazole in sediment according to claim 1, wherein the internal standard use solution comprises a D8-carbazole standard, the mass concentration of the internal standard use solution is 0.1-0.5mg/mL, the extraction solvent comprises n-hexane and acetone, the volume ratio of n-hexane to acetone is 2-3:1, the metal salt comprises anhydrous magnesium sulfate and sodium chloride, and the weight ratio of anhydrous magnesium sulfate to sodium chloride is 3-5:1.
3. The method for determining carbazole and 9 halogenated carbazole in a sediment according to claim 1, wherein the usage ratio of the sediment to the internal standard usage liquid is 1g:2-5 μl.
4. The method for determining carbazole and 9 halogenated carbazole in a sediment according to claim 1, wherein the liquid-solid ratio of the sediment and the extraction solvent is 1g:2-4mL.
5. The method for determining carbazole and 9 halogenated carbazole in a sediment according to claim 1, wherein the weight ratio of the sediment to metal salt is 3-5:1.
6. The method for determining carbazole and 9 halogenated carbazole in a sediment according to claim 1, wherein the weight ratio of the metal salt to the surfactant is 2-15:1.
7. The method for measuring carbazole and 9 halogenated carbazole in sediment according to claim 1, wherein the ultrasonic extraction temperature is 20-60 ℃ and the ultrasonic extraction time is 10-30min.
8. The method for measuring carbazole and 9 halogenated carbazole in sediment according to claim 1, wherein the purifying material comprises the following components in parts by mass of 30 parts of ethylenediamine-N-propyl silane, 70 parts of octadecylsilane chemically bonded silica, 2 parts of graphitized carbon black and 50 parts of anhydrous magnesium sulfate.
9. The method for determining carbazole and 9 halogenated carbazole in a sediment according to claim 1, wherein the weight ratio of the sediment to the purification material is 2-4:1.
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