CN115487791A - Amphiphilic magnetic solid-phase extraction material, preparation method thereof and application thereof in steroid hormone detection - Google Patents
Amphiphilic magnetic solid-phase extraction material, preparation method thereof and application thereof in steroid hormone detection Download PDFInfo
- Publication number
- CN115487791A CN115487791A CN202211012108.3A CN202211012108A CN115487791A CN 115487791 A CN115487791 A CN 115487791A CN 202211012108 A CN202211012108 A CN 202211012108A CN 115487791 A CN115487791 A CN 115487791A
- Authority
- CN
- China
- Prior art keywords
- phase extraction
- extraction material
- amphiphilic
- magnetic solid
- solid phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000003270 steroid hormone Substances 0.000 title claims abstract description 34
- 238000001514 detection method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005642 Oleic acid Substances 0.000 claims abstract description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000890 hydrocortisone Drugs 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001819 mass spectrum Methods 0.000 claims description 10
- 229960001048 fluorometholone Drugs 0.000 claims description 9
- FAOZLTXFLGPHNG-KNAQIMQKSA-N fluorometholone Chemical compound C([C@@]12C)=CC(=O)C=C1[C@@H](C)C[C@@H]1[C@]2(F)[C@@H](O)C[C@]2(C)[C@@](O)(C(C)=O)CC[C@H]21 FAOZLTXFLGPHNG-KNAQIMQKSA-N 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229960005205 prednisolone Drugs 0.000 claims description 8
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 claims description 8
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004807 desolvation Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000002352 surface water Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims description 2
- 239000013076 target substance Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000011324 bead Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 16
- 238000000132 electrospray ionisation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 206010049290 Feminisation acquired Diseases 0.000 description 1
- 208000034793 Feminization Diseases 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 108010090932 Vitellogenins Proteins 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- TZLFWVPLPHJLSE-UHFFFAOYSA-N cyclopentane phenanthrene Chemical group C1CCCC1.C1=CC=C2C3=CC=CC=C3C=CC2=C1 TZLFWVPLPHJLSE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 230000003832 immune regulation Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 238000001616 ion spectroscopy Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to the technical field of environmental functional materials and environmental detection, and discloses an amphiphilic magnetic solid phase extraction material, a preparation method thereof and application thereof in steroid hormone detection. The preparation method of the amphiphilic magnetic solid phase extraction material comprises the following steps: reducing ferric chloride and ferrous chloride by ammonia gas to prepare ferroferric oxide magnetic beads, and mixing and wrapping by using oleic acid to improve the oil solubility; and then polymerizing N-vinyl pyrrolidone and divinyl benzene serving as main raw materials and toluene serving as a solvent on the surface of the magnetic beads to obtain an amphiphilic HLB layer, thereby obtaining the amphiphilic magnetic solid-phase extraction material. The amphiphilic magnetic solid phase extraction material can be used for steroid hormones in a water body environment, such as steroid hormones containing carboxyl and hydroxyl, and the like, has simple extraction operation steps, is easy to separate an extraction phase from a sample, effectively avoids the consumption of an organic solvent, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and environmental detection, and particularly relates to an amphiphilic magnetic solid-phase extraction material, a preparation method thereof and application thereof in steroid hormone detection.
Background
Steroid hormones, also called steroid hormones, are lipid-soluble low-molecular compounds with a cyclopentane-phenanthrene structure as a core, and play a key role in regulating metabolism, treating related inflammation, maintaining water-salt balance, promoting sexual characteristic development and the like. As such, it is widely used in the fields of immune regulation, fertility regulation, etc., and this also results in its easy influx into the environment and its influence on the relevant organisms as the food chain is enriched. Studies prove that under the ng/L level, steroid estrogen can induce vitellogenin generation, so that some organisms have problems of feminization, reproductive disorder, immunity reduction and the like. In recent years, many relevant reports have also pointed out the detection of steroid hormones in environmental water samples. The enrichment in the environment inevitably brings serious harm to relevant aquatic organisms and ecosystems.
Because the method can bring influence to the environment at a low concentration scale, the key to monitoring the method is to find a proper pretreatment method such as enrichment, concentration, purification and the like. The current commonly used sample pretreatment technologies mainly comprise liquid-liquid extraction, dispersive extraction, solid-phase extraction and the like. The solid phase extraction has the advantages of simple operation, high enrichment factor and the like, and is mainly applied to enrichment and separation of detected substances in samples with complex composition, so that the detection sensitivity is improved. However, the traditional solid phase extraction method mainly depends on a solid phase extraction column for operation, and when a non-pure liquid environmental sample is faced, the extraction column may be blocked due to the existence of colloid or fine particles, thereby affecting enrichment; furthermore, in order to improve the efficiency of the pretreatment, pressurization is usually required to increase the flow rate of the sample, and the number of operation steps is increased.
Solid phase extraction with magnetic materials as adsorbents, known as magnetic solid phase extraction, has emerged to overcome the above-mentioned drawbacks of solid phase extraction. The magnetic solid phase extraction material is modified on the basis of the magnetic material to prepare the magnetic solid phase extraction material for specifically detecting the steroid hormone, and has wide application prospect and practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an amphiphilic magnetic solid-phase extraction material.
The invention also aims to provide the amphiphilic magnetic solid-phase extraction material prepared by the method.
The invention also aims to provide the application of the amphiphilic magnetic solid-phase extraction material in the detection of steroid hormones.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an amphiphilic magnetic solid phase extraction material comprises the following steps:
(1) Stirring and dissolving ferric chloride hexahydrate and ferrous chloride tetrahydrate in ultrapure water, and dropwise adding an acetone solution dissolved with oleic acid; after the dropwise addition is finished, stirring and uniformly mixing for 10-30 min, dropwise adding ammonia water into the mixed solution, and heating to 50-100 ℃ for reaction; cooling to room temperature after the reaction is finished, collecting the magnetic nanoparticles, washing with ethanol and ultrapure water respectively, and then carrying out vacuum drying to obtain oleic acid-coated magnetic nanoparticles;
(2) Dissolving sodium dodecyl sulfate, polyvinylpyrrolidone and hydroxyethyl cellulose in ultrapure water to obtain a water phase; dissolving the oleic acid-coated magnetic nanoparticles and azodiisobutyronitrile obtained in the step (1) in toluene to obtain an oil phase; equally dividing the oil phase into two parts, wherein one part is used for dissolving divinylbenzene to obtain an X solution, and the other part is used for dissolving vinyl pyrrolidone to obtain a Y solution;
stirring and heating the water phase to 20-40 ℃, dropwise adding the Y solution, continuously heating to 60-80 ℃ after dropwise adding, dropwise adding the X solution, finally reacting at 80 ℃ for 24-48 h at constant temperature, respectively washing with ethanol and acetonitrile, and then vacuum-drying the product at 30-50 ℃ for 6h to obtain the amphiphilic magnetic solid-phase extraction material.
The molar ratio of the ferric chloride hexahydrate to the ferrous chloride tetrahydrate in the step (1) is 1:1;
the mass ratio of the sodium dodecyl sulfate, the polyvinylpyrrolidone and the hydroxyethyl cellulose in the step (2) is 3;
the molar ratio of the divinylbenzene to the vinyl pyrrolidone in the step (2) is 1:1 to 1:2, preferably 2:3.
The mass concentration of the ammonia water in the step (1) is 25 percent;
the average molecular weight of the polyvinylpyrrolidone in the step (2) is 10000, K13-18;
the viscosity of the hydroxyethyl cellulose in the step (2) is 250-400mpa.s;
the stirring speed in the step (1) is 300-450 rpm, preferably 350rpm;
the reaction in the step (1) is carried out by heating to 80 ℃;
the stirring speed in the step (2) is 300 to 450rpm, preferably 400rpm.
The amphiphilic magnetic solid-phase extraction material prepared by the preparation method.
The amphiphilic magnetic solid phase extraction material is applied to enrichment, concentration and/or detection of steroid hormones.
The steroid hormone is steroid hormone containing hydroxyl and carboxyl in chemical structure, and comprises at least one of fluorometholone, hydrocortisone and prednisolone.
A method for enriching, concentrating and detecting steroid hormone by using the amphiphilic magnetic solid phase extraction material comprises the following steps:
(A) Sample preparation: adjusting the pH value of a sample to be extracted to 6.5-7.5;
(B) And (3) extraction: weighing an amphiphilic magnetic solid phase extraction material according to the amount of 100mg used by every 10mL of sample to be extracted, putting the amphiphilic magnetic solid phase extraction material into the sample to be extracted, shaking and uniformly mixing to enrich and concentrate a target substance, taking out the amphiphilic magnetic solid phase extraction material by using magnetic adsorption, and airing;
(C) And (3) elution: eluting and filtering the amphiphilic magnetic solid phase extraction material by using methanol to obtain an eluent;
(D) Detecting the eluent by using a liquid chromatography tandem mass spectrum; and converting according to a standard working curve drawn according to the concentration of the corresponding steroid hormone standard substance and the detection result of the liquid chromatogram tandem mass spectrum, and then according to the detection result of the liquid chromatogram tandem mass spectrum of the sample to be detected, so as to obtain the concentration or the content of the steroid hormone in the sample to be detected.
The pH value in the step (A) is adjusted to 7;
the samples to be extracted in the step (A) are surface water and waste water;
the rotation speed of the oscillating and uniform mixing in the step (B) is 1000-2500 rpm, and 1500rpm is preferred;
the oscillation time in the step (B) is 3-20 min, preferably 10min;
the ratio of the methanol dosage to the amphiphilic magnetic solid phase extraction material in the step (C) is 1mL/100mg, and the elution times are two times;
the conditions of the liquid chromatography tandem mass spectrometry described in the step (D) are as follows:
chromatographic conditions are as follows: the chromatographic column is a C18 column with the diameter of 1.9 μm and the size of 2.1 × 100mm, the mobile phase A is 0.1% formic acid water solution, the phase B is acetonitrile, the flow rate is 0.3mL/min, the column temperature is 40 ℃, and the sample injection amount is 10 μ L;
mass spectrum conditions: the ion source is an electrospray ion source (ESI); the detection mode and the scanning mode are respectively set to a multi-reaction detection (MRM) mode and a positive ion/negative ion mode; wherein the flow rate of the atomizing gas, the heating gas and the drying gas is respectively 3L/min, 10L/min and 10L/min; the interface temperature, the desolvation temperature, the DL temperature and the heating block temperature are 300 ℃, 526 ℃, 250 ℃ and 400 ℃ in sequence.
Compared with the prior art, the invention has the following advantages and effects:
(1) The invention provides an amphiphilic magnetic solid phase extraction material, which is prepared from magnetic cores (Fe) 3 O 4 ) And an amphiphilic adsorption layer (N-vinyl pyrrolidone and divinyl benzene polymer); the preparation method comprises the steps of dispersing magnetic cores in a solvent, and then polymerizing N-vinyl pyrrolidone and divinyl benzene to form an amphiphilic polymer on the surfaces of the magnetic cores, so as to obtain the solid phase extraction material capable of being applied to enrichment and extraction of steroid hormones.
(2) The amphiphilic magnetic solid phase extraction material has simple preparation process, and has excellent adsorption capacity and detection limit on steroid hormones; the material embodies better stability, still has higher recovery rate under repeated use for many times, has good economic benefit and is green and environment-friendly. The method can be widely applied to small-size rapid detection scenes.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of magnetic nanoparticles and an amphiphilic magnetic solid phase extraction material; wherein, (a) is a Fourier transform infrared spectrogram of the magnetic nanoparticles; (b) Is a Fourier transform infrared spectrogram of an amphiphilic magnetic solid phase extraction material.
Fig. 2 is a hysteresis curve graph of magnetic nanoparticles and an amphiphilic magnetic solid phase extraction material.
FIG. 3 is a diagram showing the adsorption of target compounds by the amphiphilic magnetic solid phase extraction material, wherein (a) is fluorometholone, (b) is hydrocortisone, and (c) is prednisolone.
FIG. 4 is a chromatogram of a steroid hormone wherein (a) is fluorometholone, (b) is hydrocortisone, and (c) is prednisolone.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The test methods in the following examples, in which specific experimental conditions are not specified, are generally performed according to conventional experimental conditions or according to the experimental conditions recommended by the manufacturer. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
Example 1
Preparing an amphiphilic magnetic solid phase extraction material:
(1) Respectively weighing 5.40g of ferric chloride hexahydrate and 1.99g of ferrous chloride tetrahydrate, stirring and dissolving in 150mL of ultrapure water to obtain a solution A; 2.00g of oleic acid was weighed out, dissolved well in 15mL of acetone and added slowly dropwise to solution A.
Stirring and mixing evenly for 30min, dropwise adding 15mL ammonia water into the mixed solution, stirring and mixing evenly for 1h at the temperature of 20-30 ℃, heating to 80 ℃, and reacting for 3h to obtain the magnetic nanoparticles. After cooling to room temperature, collecting black magnetic particles, washing with ethanol and ultrapure water for 4 times respectively, and then vacuum-drying the product at 45 ℃ for 12h to obtain magnetic nanoparticles MNP wrapped by oleic acid;
(2) Respectively weighing 0.30g of sodium dodecyl sulfate, 0.50g of polyvinylpyrrolidone and 0.30g of hydroxyethyl cellulose, and dissolving in 100mL of ultrapure water to obtain a water phase; respectively weighing 2.00g of oleic acid-coated magnetic nanoparticles MNP and 0.30g of azobisisobutyronitrile, and dissolving in 15mL of toluene to obtain an oil phase; weighing 1.56g of divinylbenzene, and dissolving the divinylbenzene in 7.50mL of oil phase solution to obtain an X solution; weighing 2.00g N-vinyl pyrrolidone, and dissolving in 7.50mL of oil phase solution to obtain Y solution;
stirring and heating the water phase to 40 ℃, and slowly dripping the Y solution; continuing to heat to 70 ℃, slowly dripping the X solution, finally reacting at 80 ℃ for 48h at constant temperature, respectively washing with ethanol and acetonitrile for 5 times, and then vacuum-drying the product at 45 ℃ for 6h to obtain the amphiphilic magnetic solid phase extraction material HLB-MNP;
it can be demonstrated by fourier transform infrared (FT-IR) maps: n-vinylpyrrolidone and divinylbenzene were successfully polymerized on the surface of the magnetic beads (FIG. 1). The material hysteresis loop is shown to be in an S-shaped curve passing through the magnetization zero point by a Vibration Sample Magnetometer (VSM). All VSM curves have little hysteresis, remanence and coercivity. With typical superparamagnetism (figure 2).
(3) Adsorption capacity of amphiphilic magnetic solid phase extraction material to steroid hormone
And (3) measuring the adsorption capacity of the amphiphilic magnetic solid phase extraction material (HLB-MNP) prepared in the step (2) on steroid hormones (fluorometholone, hydrocortisone and prednisolone), and specifically comprising the following steps:
preparing a steroid hormone mixed solution with the concentration of 400, 800, 1200, 1600 and 2000 mu g/L by using deionized water (the mass ratio of the fluorometholone to the hydrocortisone to the prednisolone is 1. Respectively measuring the initial concentration and the extracted solution concentration by LC-MS/MS, wherein the adsorption quantity = (initial concentration-extracted concentration) multiplied by the volume of the solution/the mass of the amphiphilic magnetic solid phase extraction material; the LC-MS/MS detection conditions were as follows:
liquid phase: a ShimadZU 20ADXR liquid chromatograph, a C18 column (2.1 multiplied by 100mm,1.9 mu m) is used as a chromatographic column, a phase A is 0.1% formic acid aqueous solution, a phase B is acetonitrile, the flow rate is 0.3mL/min, the column temperature is 40 ℃, and the sample injection amount is 10 mu L;
mass spectrum: SHIMADZU LCMS-8045 triple quadrupole LC MS, wherein the ion source is electrospray ionization (ESI); the detection mode and the scanning mode are respectively set to a multi-reaction detection (MRM) mode and a positive ion mode (hydrocortisone is in a negative ion mode); wherein the flow rate of the atomized gas, the flow rate of the heating gas and the flow rate of the drying gas are respectively 3L/min, 10L/min and 10L/min; the interface temperature, the desolvation temperature, the DL temperature and the heating block temperature are 300 ℃, 526 ℃, 250 ℃ and 400 ℃ in sequence.
The results of the adsorption amount of steroid hormones by the amphiphilic magnetic solid phase extraction material are shown in table 1.
TABLE 1 adsorption amount of steroid hormone by amphiphilic magnetic solid phase extraction material results (unit: ug/mg)
| Fluorometholone | Poison's nylon | Hydrocortisone | |
| HLB-MNP | 97.79 | 92.80 | 92.82 |
FIG. 3 is a graph for exploring the amount of steroid hormone adsorbed by the amphiphilic magnetic solid-phase extraction material. Experiments show that the adsorption rate of the amphiphilic magnetic solid phase extraction material to a target compound is higher than 90%, the adsorption amount of the material to the target compound is also explored, the adsorption amount is increased along with the increase of the standard concentration, and the standard concentration far exceeds the upper limit of the instrument. Table 1 gives the adsorption capacity of the material for several steroid hormones.
Example 2
The method for extracting and detecting steroid hormones in surface water by using the amphiphilic magnetic solid phase extraction material and liquid chromatography-mass spectrometry comprises the following steps:
(1) Preparing standard substance by using methanol (chromatographic purity) as solvent, preparing 40mg/L stock solution of fluorometholone, hydrocortisone and prednisolone, and storing at 4 deg.C; then preparing a mixed standard solution with the concentration of 10 mug/L, 20 mug/L, 40 mug/L, 100 mug/L, 200 mug/L, 400 mug/L and 1000 mug/L in sequence, and performing detection analysis by using LC-MS/MS, wherein the detection condition is consistent with the following sample to be detected; and performing unary linear regression fitting according to the response intensity and the concentration of the standard working curve (the curve model is y = Ax, wherein x is the concentration, y is the response intensity, and A is a correlation coefficient), wherein the standard working curve is specifically shown in Table 1.
(2) Solid phase extraction
(1) And (3) extraction: 100mg of the amphiphilic magnetic solid phase extraction material obtained in the embodiment is placed in 5mL of sample solution, and uniformly mixed by oscillation at constant temperature for 10min (the rotating speed is 1500 rpm); then taking the amphiphilic magnetic solid phase extraction material out of the sample solution through magnetic adsorption, washing with water and drying;
(2) and (3) elution: and (2) eluting the amphiphilic magnetic solid phase extraction material twice by using 1mL of methanol solution, shaking and eluting for 5min at the rotating speed of 1500rpm each time, filtering the obtained eluent by using a 0.22 mu m filter to remove fine particles in a sample, and detecting by using liquid mass tandem mass spectrometry (LC-MS/MS). Wherein, the LC-MS/MS detection conditions are as follows:
liquid phase: a Shimadzu 20ADXR liquid chromatograph, wherein the chromatographic column is a C18 column (2.1 × 100mm,1.9 μm), the mobile phase A is 0.1% formic acid aqueous solution, the mobile phase B is acetonitrile, the flow rate is 0.3mL/min, the column temperature is 40 ℃, and the sample injection amount is 10 μ L;
mass spectrum: SHIMADZU LCMS-8045 triple quadrupole LC MS, wherein the ion source is electrospray ionization (ESI); the detection mode and the scanning mode are respectively set to be a multi-reaction detection (MRM) mode and a positive ion mode (hydrocortisone is in a negative ion mode); wherein the flow rate of the atomized gas, the flow rate of the heating gas and the flow rate of the drying gas are respectively 3L/min, 10L/min and 10L/min; the interface temperature, the desolvation temperature, the DL temperature and the heating block temperature are 300 ℃, 526 ℃, 250 ℃ and 400 ℃ in sequence.
Other parameters are shown in Table 2, the gradient elution procedure is shown in Table 3, and the chromatogram of the target is shown in FIG. 4 ((a), (b), and (c) are fluorometholone, hydrocortisone, and prednisolone, respectively).
(3) As a result: the detection limit, linear range, and recovery rate of the target analyte (table 4) are shown in table 5 (recovery rate = (concentration after desorption × 2)/(sample concentration × 5) × 100%).
TABLE 2 qualitative, quantitative ion and Mass Spectrometry parameters of target analytes
TABLE 3 gradient elution schedule
TABLE 4 target analytes
TABLE 5 recovery of target in surface water
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the amphiphilic magnetic solid-phase extraction material is characterized by comprising the following steps:
(1) Stirring and dissolving ferric chloride hexahydrate and ferrous chloride tetrahydrate in ultrapure water, and dropwise adding an acetone solution dissolved with oleic acid; after the dropwise addition is finished, stirring and uniformly mixing for 10-30 min, dropwise adding ammonia water into the mixed solution, and heating to 50-100 ℃ for reaction; cooling to room temperature after the reaction is finished, collecting the magnetic nanoparticles, washing the magnetic nanoparticles with ethanol and ultrapure water respectively, and then drying in vacuum to obtain oleic acid-coated magnetic nanoparticles;
(2) Dissolving sodium dodecyl sulfate, polyvinylpyrrolidone and hydroxyethyl cellulose in ultrapure water to obtain a water phase; dissolving the oleic acid-coated magnetic nanoparticles and azodiisobutyronitrile obtained in the step (1) in toluene to obtain an oil phase; dividing the oil phase into two parts, wherein one part is used for dissolving divinylbenzene to obtain an X solution, and the other part is used for dissolving vinyl pyrrolidone to obtain a Y solution;
stirring and heating the water phase to 20-40 ℃, dropwise adding the Y solution, continuously heating to 60-80 ℃ after dropwise adding, dropwise adding the X solution, finally reacting at 80 ℃ for 24-48 h at constant temperature, respectively washing with ethanol and acetonitrile, and then vacuum-drying the product at 30-50 ℃ for 6h to obtain the amphiphilic magnetic solid-phase extraction material.
2. The method for preparing the amphiphilic magnetic solid-phase extraction material according to claim 1, wherein:
the molar ratio of the ferric chloride hexahydrate to the ferrous chloride tetrahydrate in the step (1) is 1:1;
the mass ratio of the sodium dodecyl sulfate, the polyvinylpyrrolidone and the hydroxyethyl cellulose in the step (2) is 3;
the molar ratio of the divinyl benzene to the vinyl pyrrolidone in the step (2) is 1:1-1:2.
3. The method for preparing the amphiphilic magnetic solid-phase extraction material according to claim 1, wherein:
the mass concentration of the ammonia water in the step (1) is 25 percent;
the polyvinyl pyrrolidone in the step (2) has the average molecular weight of 10000, K13-18;
the viscosity of the hydroxyethyl cellulose in the step (2) is 250-400mpa.s;
the stirring speed in the step (1) is 300-450 rpm;
the reaction in the step (1) is carried out by heating to 80 ℃;
the stirring speed in the step (2) is 300-450 rpm.
4. The method for preparing the amphiphilic magnetic solid-phase extraction material according to claim 1, wherein: the molar ratio of the divinyl benzene to the vinyl pyrrolidone in the step (2) is 2:3;
the stirring speed in the step (1) is 350rpm;
the stirring speed in the step (2) is 400rpm.
5. An amphiphilic magnetic solid-phase extraction material prepared by the preparation method of any one of claims 1 to 4.
6. Use of the amphiphilic magnetic solid phase extraction material according to claim 5 for enrichment, concentration and/or detection of steroid hormones.
7. Use according to claim 6, characterized in that: the steroid hormone is steroid hormone containing hydroxyl and carboxyl in chemical structure, and comprises at least one of fluorometholone, hydrocortisone and prednisolone.
8. A method for enriching, concentrating and detecting steroid hormones by using the amphiphilic magnetic solid phase extraction material according to claim 5, comprising the steps of:
(A) Sample preparation: adjusting the pH value of a sample to be extracted to 6.5-7.5;
(B) And (3) extraction: weighing an amphiphilic magnetic solid phase extraction material according to the amount of 100mg used by every 10mL of sample to be extracted, putting the amphiphilic magnetic solid phase extraction material into the sample to be extracted, shaking and uniformly mixing to enrich and concentrate a target substance, taking out the amphiphilic magnetic solid phase extraction material by using magnetic adsorption, and airing;
(C) And (3) elution: eluting and filtering the amphiphilic magnetic solid phase extraction material by using methanol to obtain an eluent;
(D) Detecting the eluent by using a liquid chromatography tandem mass spectrum; and converting according to a standard working curve drawn according to the concentration of the corresponding steroid hormone standard substance and the detection result of the liquid chromatogram tandem mass spectrum, and then according to the detection result of the liquid chromatogram tandem mass spectrum of the sample to be detected, so as to obtain the concentration or the content of the steroid hormone in the sample to be detected.
9. The method of claim 8, wherein:
the pH value in the step (A) is adjusted to 7;
the samples to be extracted in the step (A) are surface water and waste water;
the rotating speed of the oscillating and mixing in the step (B) is 1000-2500 rpm;
the oscillation time in the step (B) is 3-20 min;
the ratio of the methanol dosage to the amphiphilic magnetic solid phase extraction material in the step (C) is 1mL/100mg, and the elution times are two times;
the conditions of the liquid chromatography tandem mass spectrometry described in the step (D) are as follows:
chromatographic conditions are as follows: the chromatographic column is a C18 column with the diameter of 1.9 μm and the size of 2.1 × 100mm, the mobile phase A is 0.1% formic acid water solution, the phase B is acetonitrile, the flow rate is 0.3mL/min, the column temperature is 40 ℃, and the sample injection amount is 10 μ L;
mass spectrum conditions: the ion source is an electrospray ion source (ESI); the detection mode and the scanning mode are respectively set to a multi-reaction detection (MRM) mode and a positive ion/negative ion mode; wherein the flow rate of the atomized gas, the flow rate of the heating gas and the flow rate of the drying gas are respectively 3L/min, 10L/min and 10L/min; the interface temperature, the desolvation temperature, the DL temperature and the heating block temperature are 300 ℃, 526 ℃, 250 ℃ and 400 ℃ in sequence.
10. The method of claim 8, wherein: the rotating speed of the oscillating and uniform mixing is 1500rpm; the oscillation time is 10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211012108.3A CN115487791A (en) | 2022-08-23 | 2022-08-23 | Amphiphilic magnetic solid-phase extraction material, preparation method thereof and application thereof in steroid hormone detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211012108.3A CN115487791A (en) | 2022-08-23 | 2022-08-23 | Amphiphilic magnetic solid-phase extraction material, preparation method thereof and application thereof in steroid hormone detection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115487791A true CN115487791A (en) | 2022-12-20 |
Family
ID=84466905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211012108.3A Pending CN115487791A (en) | 2022-08-23 | 2022-08-23 | Amphiphilic magnetic solid-phase extraction material, preparation method thereof and application thereof in steroid hormone detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115487791A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117368380A (en) * | 2023-12-08 | 2024-01-09 | 北京梅斯质谱生物科技有限责任公司 | Kit and method for detecting steroid hormone |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106458644A (en) * | 2014-05-20 | 2017-02-22 | 米兰理工大学 | Amphiphilic magnetic nanoparticles and aggregates to remove hydrocarbons and metal ions and synthesis thereof |
| CN107999037A (en) * | 2017-12-18 | 2018-05-08 | 南京大学 | A kind of magnetic high-molecular sorbing material, preparation method and application |
| CN109001335A (en) * | 2018-09-13 | 2018-12-14 | 山东师范大学 | Method for measuring 17 steroids hormones in krill |
| CN109682897A (en) * | 2019-01-17 | 2019-04-26 | 南京大学 | A kind of method of a variety of incretion interferents in while determination of the environment water sample |
| CN110658280A (en) * | 2019-10-21 | 2020-01-07 | 天津师范大学 | Method for detecting bisphenol compounds based on magnetic metal organic framework composite material |
| CN114324643A (en) * | 2021-12-24 | 2022-04-12 | 浙江树人学院（浙江树人大学） | Method for detecting macrolide antibiotics in organic fertilizer and sample treatment method thereof |
-
2022
- 2022-08-23 CN CN202211012108.3A patent/CN115487791A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106458644A (en) * | 2014-05-20 | 2017-02-22 | 米兰理工大学 | Amphiphilic magnetic nanoparticles and aggregates to remove hydrocarbons and metal ions and synthesis thereof |
| CN107999037A (en) * | 2017-12-18 | 2018-05-08 | 南京大学 | A kind of magnetic high-molecular sorbing material, preparation method and application |
| WO2019119568A1 (en) * | 2017-12-18 | 2019-06-27 | 南京大学 | Magnetic polymer adsorption material, preparation method therefor and application thereof |
| CN109001335A (en) * | 2018-09-13 | 2018-12-14 | 山东师范大学 | Method for measuring 17 steroids hormones in krill |
| CN109682897A (en) * | 2019-01-17 | 2019-04-26 | 南京大学 | A kind of method of a variety of incretion interferents in while determination of the environment water sample |
| CN110658280A (en) * | 2019-10-21 | 2020-01-07 | 天津师范大学 | Method for detecting bisphenol compounds based on magnetic metal organic framework composite material |
| CN114324643A (en) * | 2021-12-24 | 2022-04-12 | 浙江树人学院（浙江树人大学） | Method for detecting macrolide antibiotics in organic fertilizer and sample treatment method thereof |
Non-Patent Citations (3)
| Title |
|---|
| VAROON SINGH ET AL.: ""Magnetic hydrophilic–lipophilic balance sorbent for efficientextraction of chemical warfare agents from water samples"", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 1434, pages 39 - 49, XP029405773, DOI: 10.1016/j.chroma.2016.01.028 * |
| ZEYING HE ET AL.: ""Hydrophilic–lipophilic balanced magnetic nanoparticles: Preparation and application in magnetic solid-phase extraction of organochlorine pesticides and triazine herbicides in environmental water samples"", 《TALANTA》, vol. 127, pages 1 - 8, XP028850717, DOI: 10.1016/j.talanta.2014.03.074 * |
| ZHIJIAN YAO ET AL.: ""Fabrication and characterization of amphiphilic magnetic water purification materials for efficient PPCPs removal"", 《CHEMICAL ENGINEERING JOURNAL》, vol. 360, pages 511 - 518 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117368380A (en) * | 2023-12-08 | 2024-01-09 | 北京梅斯质谱生物科技有限责任公司 | Kit and method for detecting steroid hormone |
| CN117368380B (en) * | 2023-12-08 | 2024-03-01 | 北京梅斯质谱生物科技有限责任公司 | Kit and method for detecting steroid hormone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Adsorption of aflatoxins and ochratoxins in edible vegetable oils with dopamine-coated magnetic multi-walled carbon nanotubes | |
| Huang et al. | Magnetic immobilization of amine-functionalized magnetite microspheres in a knotted reactor for on-line solid-phase extraction coupled with ICP-MS for speciation analysis of trace chromium | |
| Du et al. | Novel magnetic SPE method based on carbon nanotubes filled with cobalt ferrite for the analysis of organochlorine pesticides in honey and tea | |
| Razmkhah et al. | Extraction and determination of three steroid molecules in milk using functionalized magnetic carbon nanotube-based solid phase extraction coupled with HPLC | |
| CN110841612A (en) | Magnetic NH2Preparation and application of-MOFs nano material | |
| Yan et al. | Synthesis of 3-fluorobenzoyl chloride functionalized magnetic sorbent for highly efficient enrichment of perfluorinated compounds from river water samples | |
| Liu et al. | Facile synthesis of boric acid-functionalized magnetic covalent organic frameworks and application to magnetic solid-phase extraction of trace endocrine disrupting compounds from meat samples | |
| Xu et al. | Simultaneous determination of sulfonamides and fluoroquinolones from environmental water based on magnetic double-template molecularly imprinting technique | |
| CN113295795B (en) | Method and kit for detecting zearalenone mycotoxins and application thereof | |
| Amiri et al. | Preparation and characterization of magnetic Wells–Dawson heteropoly acid nanoparticles for magnetic solid-phase extraction of aromatic amines in water samples | |
| Fei et al. | In-tube solid-phase microextraction with a hybrid monolithic column for the preconcentration of ultra-trace metals prior to simultaneous determination by ICP-MS | |
| CN115487791A (en) | Amphiphilic magnetic solid-phase extraction material, preparation method thereof and application thereof in steroid hormone detection | |
| Wang et al. | Determination of estrogens in milk samples by magnetic‐solid‐phase extraction technique coupled with high‐performance liquid chromatography | |
| Ding et al. | Determination of roxithromycin from human plasma samples based on magnetic surface molecularly imprinted polymers followed by liquid chromatography-tandem mass spectromer. | |
| Cao et al. | Preparation of magnetic dummy template molecularly imprinted polymers for the determination of aminoglycosides antibiotics in milk | |
| Chen et al. | Magnetic solid‐phase extraction based on a triethylenetetramine‐functionalized magnetic graphene oxide composite for the detection of ten trace phenolic environmental estrogens in environmental water | |
| CN106770730A (en) | Method for measuring methyl mercury and ethyl mercury | |
| CN101274154A (en) | Impregnating resin with ionic liquid film containing extractive agent on surface, producing method and application thereof | |
| CN111495332A (en) | Magnetic adsorption material and application thereof in benzoyl urea pesticide detection | |
| Yang et al. | Porous capillary monolithic column coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry for fast and effective separation and determination of estrogens | |
| Wang et al. | Effective extraction of the metabolites of toluene and xylene based on a postsynthetic-modified magnetic covalent organic polymer | |
| CN116459797A (en) | Composite magnetic solid phase extraction material, preparation method thereof and application thereof in steroid hormone extraction | |
| Pourreza et al. | Vortex-assisted dispersive solid-phase extraction using schiff-base ligand anchored nanomagnetic iron oxide for preconcentration of phthalate esters and determination by gas chromatography and flame ionization detector | |
| Fan et al. | Application of core–satellite polydopamine-coated Fe 3 O 4 nanoparticles–hollow porous molecularly imprinted polymer combined with HPLC-MS/MS for the quantification of macrolide antibiotics | |
| Wan et al. | Extraction of ochratoxin A in red wine with dopamine‐coated magnetic multi‐walled carbon nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |