CN114965780B - Method for simultaneously measuring 30 mental active substances in environmental water body - Google Patents
Method for simultaneously measuring 30 mental active substances in environmental water body Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000007613 environmental effect Effects 0.000 title claims abstract description 18
- 239000013543 active substance Substances 0.000 title claims abstract description 10
- 230000003340 mental effect Effects 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 19
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 9
- 229930195729 fatty acid Natural products 0.000 claims abstract description 9
- 239000000194 fatty acid Substances 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
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- 239000012086 standard solution Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
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- 239000000523 sample Substances 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 26
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- 239000000126 substance Substances 0.000 claims description 16
- 239000012224 working solution Substances 0.000 claims description 15
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- UIKROCXWUNQSPJ-VIFPVBQESA-N (-)-cotinine Chemical compound C1CC(=O)N(C)[C@@H]1C1=CC=CN=C1 UIKROCXWUNQSPJ-VIFPVBQESA-N 0.000 claims description 6
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- 229950006073 cotinine Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- -1 mecalcanone Chemical compound 0.000 claims description 6
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
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- NGBBVGZWCFBOGO-UHFFFAOYSA-N 3,4-Methylenedioxyamphetamine Chemical compound CC(N)CC1=CC=C2OCOC2=C1 NGBBVGZWCFBOGO-UHFFFAOYSA-N 0.000 claims description 3
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- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 claims description 3
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- 238000010813 internal standard method Methods 0.000 claims description 3
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- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 claims description 3
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- KKIMDKMETPPURN-UHFFFAOYSA-N 1-(3-(trifluoromethyl)phenyl)piperazine Chemical compound FC(F)(F)C1=CC=CC(N2CCNCC2)=C1 KKIMDKMETPPURN-UHFFFAOYSA-N 0.000 claims description 2
- VHFVKMTVMIZMIK-UHFFFAOYSA-N 1-(3-chlorophenyl)piperazine Chemical compound ClC1=CC=CC(N2CCNCC2)=C1 VHFVKMTVMIZMIK-UHFFFAOYSA-N 0.000 claims description 2
- BEQZHFIKTBVCAU-UHFFFAOYSA-N 2-amino-2-(2-chlorophenyl)-1-cyclohexanone Chemical compound C=1C=CC=C(Cl)C=1C1(N)CCCCC1=O BEQZHFIKTBVCAU-UHFFFAOYSA-N 0.000 claims description 2
- PQHQBRJAAZQXHL-UHFFFAOYSA-N 2c-i Chemical compound COC1=CC(CCN)=C(OC)C=C1I PQHQBRJAAZQXHL-UHFFFAOYSA-N 0.000 claims description 2
- SHXWCVYOXRDMCX-UHFFFAOYSA-N 3,4-methylenedioxymethamphetamine Chemical compound CNC(C)CC1=CC=C2OCOC2=C1 SHXWCVYOXRDMCX-UHFFFAOYSA-N 0.000 claims description 2
- OLEWMKVPSUCNLG-UHFFFAOYSA-N 4-methylthioamphetamine Chemical compound CSC1=CC=C(CC(C)N)C=C1 OLEWMKVPSUCNLG-UHFFFAOYSA-N 0.000 claims description 2
- YQEZLKZALYSWHR-UHFFFAOYSA-N Ketamine Chemical compound C=1C=CC=C(Cl)C=1C1(NC)CCCCC1=O YQEZLKZALYSWHR-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- DUGOZIWVEXMGBE-UHFFFAOYSA-N Methylphenidate Chemical compound C=1C=CC=CC=1C(C(=O)OC)C1CCCCN1 DUGOZIWVEXMGBE-UHFFFAOYSA-N 0.000 claims description 2
- 238000011088 calibration curve Methods 0.000 claims description 2
- PJMPHNIQZUBGLI-UHFFFAOYSA-N fentanyl Chemical compound C=1C=CC=CC=1N(C(=O)CC)C(CC1)CCN1CCC1=CC=CC=C1 PJMPHNIQZUBGLI-UHFFFAOYSA-N 0.000 claims description 2
- 229960002428 fentanyl Drugs 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229960003299 ketamine Drugs 0.000 claims description 2
- UGFMBZYKVQSQFX-UHFFFAOYSA-N para-methoxy-n-methylamphetamine Chemical compound CNC(C)CC1=CC=C(OC)C=C1 UGFMBZYKVQSQFX-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- CWIBPAGDXLMLNI-UHFFFAOYSA-N 2,5-dimethoxy-4-methylaniline Chemical compound COC1=CC(N)=C(OC)C=C1C CWIBPAGDXLMLNI-UHFFFAOYSA-N 0.000 claims 1
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- 238000004853 microextraction Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- USSIQXCVUWKGNF-UHFFFAOYSA-N 6-(dimethylamino)-4,4-diphenylheptan-3-one Chemical compound C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 USSIQXCVUWKGNF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
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- KWTSXDURSIMDCE-OABOXVCPSA-N n,n,1,1,2-pentadeuterio-3-phenylpropan-2-amine Chemical compound [2H]C([2H])C([2H])(N([2H])[2H])CC1=CC=CC=C1 KWTSXDURSIMDCE-OABOXVCPSA-N 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical class CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 description 1
- GLUUGHFHXGJENI-SVYQBANQSA-N 2,2,3,3,5,5,6,6-octadeuteriopiperazine Chemical compound [2H]C1([2H])NC([2H])([2H])C([2H])([2H])NC1([2H])[2H] GLUUGHFHXGJENI-SVYQBANQSA-N 0.000 description 1
- UNQQFDCVEMVQHM-UHFFFAOYSA-N 2c-d Chemical compound COC1=CC(CCN)=C(OC)C=C1C UNQQFDCVEMVQHM-UHFFFAOYSA-N 0.000 description 1
- NGBBVGZWCFBOGO-MZAMZLCGSA-N 3-(1,3-benzodioxol-5-yl)-N,N,1,1,2-pentadeuteriopropan-2-amine Chemical compound C1OC=2C=C(CC(N([2H])[2H])(C([2H])[2H])[2H])C=CC=2O1 NGBBVGZWCFBOGO-MZAMZLCGSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- JJGYGPZNTOPXGV-FCKHSUDOSA-N C(C)(=O)O[C@@]1([C@]2([C@]34C=5C(=C(C=CC=5C[C@H]([C@@H]3C=C1[2H])N(C)CC4)O)O2)[2H])[2H] Chemical compound C(C)(=O)O[C@@]1([C@]2([C@]34C=5C(=C(C=CC=5C[C@H]([C@@H]3C=C1[2H])N(C)CC4)O)O2)[2H])[2H] JJGYGPZNTOPXGV-FCKHSUDOSA-N 0.000 description 1
- 241000202964 Mycoplasma mobile Species 0.000 description 1
- JJGYGPZNTOPXGV-VALGNVEGSA-N [(4r,4ar,7s,7ar,12bs)-9-hydroxy-3-(trideuteriomethyl)-2,4,4a,7,7a,13-hexahydro-1h-4,12-methanobenzofuro[3,2-e]isoquinoline-7-yl] acetate Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C([2H])([2H])[2H])[C@@H]3CC5=CC=C4O JJGYGPZNTOPXGV-VALGNVEGSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940025084 amphetamine Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AWZOLILCOUMRDG-UHFFFAOYSA-N edifenphos Chemical compound C=1C=CC=CC=1SP(=O)(OCC)SC1=CC=CC=C1 AWZOLILCOUMRDG-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- MKXKFYHWDHIYRV-UHFFFAOYSA-N flutamide Chemical compound CC(C)C(=O)NC1=CC=C([N+]([O-])=O)C(C(F)(F)F)=C1 MKXKFYHWDHIYRV-UHFFFAOYSA-N 0.000 description 1
- 229960002074 flutamide Drugs 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229960002525 mecamylamine Drugs 0.000 description 1
- IMYZQPCYWPFTAG-IQJOONFLSA-N mecamylamine Chemical compound C1C[C@@H]2C(C)(C)[C@@](NC)(C)[C@H]1C2 IMYZQPCYWPFTAG-IQJOONFLSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002351 wastewater Substances 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
-
- 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
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- 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)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to the field of analysis and test, and discloses a method for simultaneously measuring 30 mental active substances in environmental water. The method comprises the following steps: after a water sample is taken, adding an internal standard solution to obtain a mixed sample, adding ammonia water and an extracting solution containing an extracting agent into the mixed sample, vortex mixing, centrifuging, and taking a lower organic phase; and adding a mixed solution of fatty alcohol aqueous solution and fatty acid into the lower organic phase for back extraction, carrying out centrifugal layering after vortex mixing, and detecting the supernatant by using a high performance liquid chromatography-triple quadrupole mass spectrometer. The invention has the advantages of high analysis speed, low detection limit, simple pretreatment steps, and the sample can be analyzed without careful preparation of steps such as filtering, pH adjustment and the like. The method can provide data support for the formulation, examination and decision-making of the task of the forbidden task, thereby achieving the purpose of early warning the crime of the toxin-producing person and timely developing the action of drug-carrying.
Description
Technical Field
The invention belongs to the field of analysis and test, and particularly relates to a method for simultaneously measuring 30 mental active substances in environmental water.
Background
The drugs not only have social and personal harmfulness, but also can be excreted into a sewage system in the form of original or metabolites through urine, excrement and the like through a sewer pipeline and finally enter water environments such as rivers, lakes and the like, so that the environmental problem is not negligible.
The existing pretreatment methods for detecting drugs in water in the environment mainly comprise two methods, namely solid-phase extraction and liquid-liquid extraction. The solid phase extraction method has the effects of purifying and enriching samples, can automatically treat the samples in batches, has the advantages of good reproducibility, environmental friendliness and the like, and is quite widely applied. However, the sample often has complicated preparation steps for filtration and pH adjustment prior to solid phase extraction, such as those required by Alvaro Lopes et al to adjust the pH of the sample during sample preparation, and the suspended materials in the sample are removed by passing the sample through a glass fiber filter (Analysis of cocaine and nicotine metabolites in wastewater by liquid chromatography–tandem mass spectrometry.Cross abuse index patterns on a major community.Science of the Total Environment 487(2014)673–680). and filtering. However, certain drugs such as methadone and its metabolite EDDP have some hydrophobicity and are more easily adsorbed onto solid matrices rich in organics. At present, studies have shown that cocaine is detected in suspended particulate matter of sludge. It is therefore desirable to create a comprehensive method for detecting psychoactive substances in an environmental body of water.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for simultaneously measuring 30 mental active substances in environmental water, which is a measuring extraction, purification and instrument analysis method and is used for qualitative and quantitative detection of 30 mental active substances in environmental water.
The invention aims at realizing the following technical scheme:
A method for simultaneously determining 30 psychoactive substances in an environmental water body, comprising the steps of:
(1) After a water sample is taken, adding an internal standard solution to obtain a mixed sample, adding ammonia water and an extracting solution containing an extracting agent into the mixed sample, vortex mixing, centrifuging, and taking a lower organic phase;
(2) And adding a mixed solution of fatty alcohol aqueous solution and fatty acid into the lower organic phase for back extraction, carrying out centrifugal layering after vortex mixing, and detecting the supernatant by using a high performance liquid chromatography-triple quadrupole mass spectrometer.
Preferably, the specific steps of the method are as follows:
(1) Taking 10-40 mL of water sample into a 50mL centrifuge tube, adding the mixed isotope internal standard solution, and uniformly mixing to obtain a mixed sample; adding ammonia water and 0.1-1 mL of extracting solution containing an extracting agent, carrying out vortex extraction, centrifuging and layering, and taking a lower organic phase in another centrifuge tube;
(2) Adding 0.1-1 mL of a mixed solution of fatty alcohol aqueous solution and fatty acid into the lower organic phase, carrying out vortex mixing extraction, centrifuging and layering, taking supernatant, and detecting by using a high performance liquid chromatography-triple quadrupole mass spectrometer.
Preferably, the volume fraction of the ammonia water in the step (1) is 20-25%, the volume ratio of the water sample to the ammonia water is 100:1-200:1, the volume ratio of the water sample to the internal standard solution is 100:1-200:1, and the internal standard mass is 10ng calculated by cotinine-d 3.
Preferably, the extracting solution in the step (1) is a mixed solution of methanol and an extracting agent, the volume ratio of the methanol to the extracting agent is 3:1-5:1, and the extracting agent is a mixed solvent of dichloromethane and ethyl acetate;
The fatty alcohol in the step (2) is methanol, ethanol or propanol, and the fatty acid is formic acid.
Preferably, the volume ratio of the methanol to the extractant in the step (1) is 5:1, and the volume ratio of the dichloromethane to the ethyl acetate in the extractant is 1:1.
Preferably, the volume fraction of the aqueous solution of the fatty alcohol in the step (2) is 10-30%, and the volume ratio of the aqueous solution of the fatty alcohol to the fatty acid is 15:1-30:1.
Preferably, the vortex mixing conditions of step (1) are: mixing at 2500-3500 rpm for 1-3 min, wherein the centrifugation conditions are as follows: centrifuging at 6000-8000 rpm for 5-10 min;
the vortex mixing conditions of step (2) are: mixing at 2500-3500 rpm for 3-5 min, wherein the centrifugation conditions are as follows: centrifugal force of 10000-12000 rpm for 5-10 min.
Preferably, the high performance liquid chromatography-triple quadrupole mass spectrometer detection comprises the following steps:
(1) Preparation of standard working solution
Measuring 30 standard substances and 23 internal standard substances by a micropipette respectively to prepare a stock solution and a working solution, and finally preparing a standard working solution with gradient concentration;
(2) High performance liquid chromatography-mass spectrometer detection
Measuring the standard working solution of each concentration gradient in the step (1) in a high performance liquid chromatography-mass spectrometer, taking the concentration of a target object as an abscissa, taking the ratio of the product of the peak area of the target object and the concentration of the corresponding internal standard object to the peak area of the corresponding internal standard object as an ordinate, and establishing a calibration curve; under the same condition, injecting a sample solution to be detected into a high performance liquid chromatography-mass spectrometer for measurement, calculating the concentration of a target compound in the solution through a standard working curve, and then calculating according to the volume of the sample to obtain the content of the target compound in the sample; the concentration of the target substance in the sample solution is in the linear range of the standard working curve, and if the measured concentration exceeds the linear range of the standard working curve, the sample amount can be reduced and then re-extracted and measured.
Preferably, the liquid chromatography conditions are as follows:
chromatographic column: the Shim-pack GIST-HP C18 has an inner diameter of 2.1mm, a column length of 100mm and a filler particle size of 1.9 μm;
column temperature is 35 ℃; the flow rate is 0.3mL/min; the sample injection amount is 1-10 mu L;
mobile phase a:0.1% formic acid water; mobile phase B: acetonitrile;
mobile phase gradient elution: 0-6 min 20% mobile phase B, 6-10 min 20-58% mobile phase B, 10-11 min 58-100% mobile phase B, 11-14 min 100% mobile phase B, 14-14.1 min 100-5% mobile phase B, 14.1-21 min 5% mobile phase B;
The mass spectrometry conditions were as follows:
The detection mode is a multi-reaction monitoring mode MRM and a negative ion mode;
atomizing air flow rate: 3L/min; heating air flow: 10L/min;
Interface temperature: 300 ℃; DL temperature: 250 ℃; heating block temperature: 400 ℃; dry air flow: 10L/min;
mass spectrometry conditions for the target compounds under the above conditions are shown in table 1:
table 1 mass spectral parameters of 30 targets and internal standards
The method is applied to the determination of the active substance residues in the environmental water body.
The invention establishes a rapid and efficient extraction method by utilizing a liquid-liquid microextraction technology, and after extraction, the extraction liquid is back-extracted to achieve the effect of purifying a sample, and finally, the detection is carried out by utilizing a high performance liquid chromatography-triple quadrupole mass spectrometer, so that the qualitative and quantitative analysis of 30 mental active substances in an environmental water body is effectively determined.
Compared with the prior art, the invention has the following advantages:
(1) Compared with the traditional liquid-liquid extraction technology, the method has the characteristics of simplicity in operation, time and labor saving and high recovery rate. In addition, the method does not need to concentrate the extraction solvent, so that the loss of the compound to be tested caused by the concentration process can be reduced.
(2) Compared with the complex steps of filtering the sample, accurately adjusting the pH value, controlling the flow rate of solid phase extraction and the like, the liquid-liquid microextraction method has the advantages that the pretreatment steps are fewer, and the sample treatment efficiency is higher. In addition, compared with solid phase extraction, liquid-liquid microextraction does not need consumable materials such as a solid phase extraction column, and has low cost and wide applicability. The extraction solution is purified by combining the back extraction technology, so that the effects of reducing matrix interference and protecting instruments are achieved.
(3) The invention has accurate quantification, the correlation linear coefficient R 2 of 30 compounds to be detected is more than or equal to 0.995, the recovery rate of 30 compounds to be detected at the concentration level of 5 ng/L-20 ng/L is 67.8-114.4%, the standard deviation is less than 1.5%, the detection limit range is 0.03 ng/L-1.42 ng/L, and the detection method is sensitive and has high stability.
Drawings
FIG. 1 is a total ion flow diagram of a test compound and an internal standard.
FIG. 2 is a graph showing the effect of centrifugal delamination after liquid-liquid microextraction extraction.
FIG. 3 is a graph showing the effect of centrifugal delamination after back extraction.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters that are not specifically noted.
Instruments and reagents used in the examples
1. Target substance
Cotinine, morphine, 6-acetylmorphine, mecamylamine, methamphetamine, p-methoxymethamphetamine, 3, 4-methylenedioxymethamphetamine, 3, 4-methylenedioxyamphetamine, 4-methylthioamphetamine, 2-methylamino-1- (3, 4-methylenedioxyphenyl) -1-propanone, 3, 4-methylenedioxymexisone, ketamine, norketamine, flutamide, 1- (3-chlorophenyl) piperazine, 1- (3-trifluoromethylphenyl) piperazine, methylenedioxypyrrole pentanone, cocaine, codeine, heroin, fentanyl, acetenib, acrylofentanyl, 2, 5-dimethoxy-4-iodophenethylamine, 2, 5-dimethoxy-4-methylphenylethylamine, ritaline, 2-ethylene-1, 5-dimethyl-3, 3-diphenylpyrazine, methadone, and methadone, all available from CERILLIANT.
2. Internal standard substance
Cotinine-D3, morphine-D3, 6-acetylmorphine-D3, mecamylamine-D3, methamphetamine-D3, amphetamine-D5, methamphetamine-D5, 3, 4-methylenedioxymethamphetamine-D3, 4-methylenedioxyamphetamine-D5, ketamine-D4, norketamine-D4, 1- (3-chlorophenyl) piperazine-D8, 1- (3-trifluoromethylphenyl) piperazine-D4, cocaine-D3, codeine-D6, heroin-D9, fentanyl-D5, acefentanyl 13C-6, acrylofentanyl-D5, ritaline-D9, 2-ethylene-1, 5-dimethyl-3, 3-diphenylpiperaziridine-D3, methadone-D3, are all available from CERILLIANT.
3. Experimental reagent and material
Acetonitrile, HPLC grade, MERCK company;
Methanol, HPLC grade, MERCK company;
Dichloromethane, HPLC grade, MERCK company;
Ethyl acetate, HPLC grade, CNW company;
Formic acid, LCMS grade, CNW company;
Ammonia, AR grade, guangzhou chemical reagent plant.
The water used is water prepared by an ultrapure water machine.
The detection instrument is a high performance liquid chromatography-mass spectrometer (LC-MS/MS) Shimadzu LC-20XR/Shimadzu LCMS-8045.
The domestic sewage used in the examples was obtained from a sewage treatment plant in Guangzhou chemical Co., ltd.
Example 1
(1) Sample pretreatment
Taking 20mL of domestic sewage sample, adding 100 mu L of mixed internal standard working solution with the concentration of 100 mu g/L (calculated by cotinine) into a 50mL centrifuge tube, obtaining a mixed sample, adding 100 mu L of aqueous ammonia solution with the volume fraction of 25% into the mixed sample, uniformly mixing, adding 200 mu L of mixed solvent of dichloromethane and ethyl acetate (V: V=1:1) into 1mL of methanol, adding the extracted solution into the mixed sample, carrying out vortex mixing and extraction for 3min at the rotating speed of 2500rpm, centrifuging for 5min at the rotating speed of 8000rpm, taking out the whole lower organic phase into a 2mL centrifuge tube, adding 200 mu L of mixed solution containing 190 mu L of aqueous solution with the volume fraction of 20% of methanol and 10 mu L of formic acid, carrying out vortex mixing and extraction for 1min at the rotating speed of 2500rpm, centrifuging for 5min at the rotating speed of 12000rpm by using a centrifuge, taking the supernatant, and waiting for instrument analysis and test in a sample injection vial.
(2) Preparation of standard working solution
Accurately transferring the target compound by using a micropipette, diluting the target compound to a constant volume of 10mL by using acetonitrile, so that substances such as cotinine, morphine, amphetamine, mecalcidone, codeine, 3, 4-methylenedioxyamphetamine, O6-monoacetylmorphine, heroin and the like are prepared into mixed standard stock solution with the concentration of 1mg/L, and the concentration of the rest substances is 1 mug/L. And accurately transferring the internal standard compound by using a micropipette, diluting the internal standard compound to a constant volume of 10mL by using acetonitrile, so that substances such as cotinine-d 3, morphine-d 3, amphetamine-d 5, mecalcanone-d 3, codeine-d 6, 3, 4-methylenedioxyamphetamine-d 5, O6-monoacetylmorphine-d 3, heroin-d 9 and the like are prepared into a mixed internal standard stock solution with the concentration of 1mg/L, and the concentration of the rest substances is 1 mug/L.
The mixed standard stock solution was diluted with acetonitrile to 100. Mu.g/L (calculated as cotinine) of mixed standard working solution and 1. Mu.g/L (calculated as cotinine-d 3) of mixed internal standard working solution, and finally 2. Mu.g/L, 5. Mu.g/L, 10. Mu.g/L, 20. Mu.g/L, 50. Mu.g/L of standard working solution was prepared, wherein the concentration of the internal standard compound was 10. Mu.g/L (calculated as cotinine-d 3), and the standard working curve was established using the internal standard method.
(3) High performance liquid chromatography-mass spectrometer detection
Liquid chromatography conditions: chromatographic column: the Shim-pack GIST-HP C18 had an inner diameter of 2.1mm, a column length of 100mm and a packing particle size of 1.9. Mu.m. Mobile phase: a:0.1% formic acid water; mobile phase B: acetonitrile. Gradient elution: 0-6 min 20% mobile phase B, 6-10 min 20-58% mobile phase B, 10-11 min 58% -100% mobile phase B, 11-14 min 100% mobile phase B14-14.1 min 100-5% mobile phase B, 14.1-21 min 5% mobile phase B. Column temperature: 35 ℃; the flow rate is 0.3mL/min; the sample injection amount was 5. Mu.L.
Mass spectrometry conditions: the detection mode is a multi-reaction monitoring mode (MRM), an anion mode and an atomized air flow rate: 3L/min; heating air flow: 10L/min; interface temperature: 300 ℃; DL temperature: 250 ℃; heating block temperature: 400 ℃; dry air flow: 10L/min.
Under the above conditions, mass spectrometry conditions for 30 targets and internal standards are shown in table 1.
The qualitative and quantitative analysis method comprises the following steps: taking the retention time of the target compound and the abundance ratio of qualitative and quantitative ion pairs as qualitative judgment basis, and quantifying by an internal standard method;
Adding standard recovery rate and precision:
The recovery rate adopts 6 times of parallel marking, and the marking method comprises the following steps: 50 mu L, 100 mu L, 200 mu L and 100 mu g/L (calculated as cotinine) of mixed standard working solution are respectively added into 20mL of water sample, and after the mixed standard working solution is uniformly mixed, the extraction and the measurement are carried out according to the steps (1) and (3). And subtracting the blank sample concentration from the standard adding concentration, and comparing the standard adding concentration with the theoretical adding concentration to obtain the recovery rate of the target compound, wherein the precision of the method is expressed by the standard deviation of 6 parallel standard adding results.
Detection limit and quantification limit:
the detection limit and the quantification limit of the result are calculated according to the requirements in annex A of HJ 168-2020. The detection limit and the quantitative limit of the final product are shown in Table 2.
TABLE 2 method recovery, detection limit and quantification limit
A mean ± standard deviation (%) (n=6)
The invention has accurate quantification, the correlation linear coefficient R 2 of 30 compounds to be detected is more than or equal to 0.995, the recovery rate of 30 compounds to be detected at the concentration level of 5 ng/L-20 ng/L is 67.8-114.4%, the standard deviation is less than 1.5%, the detection limit range is 0.03 ng/L-1.42 ng/L, and the detection method is sensitive and has high stability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A method for simultaneously determining 30 psychoactive substances in an environmental water body, comprising the steps of:
(1) Taking 10-40 mL of water sample, adding an internal standard solution to obtain a mixed sample, adding ammonia water and 0.1-1 mL of extracting solution containing an extracting agent into the mixed sample, vortex mixing, centrifuging, and taking a lower organic phase;
(2) Adding 0.1-1 mL of a mixed solution of fatty alcohol aqueous solution and fatty acid into the lower organic phase for back extraction, carrying out centrifugal layering after vortex mixing, and detecting supernatant by using a high performance liquid chromatography-triple quadrupole mass spectrometer;
the extracting solution in the step (1) is a mixed solution of methanol and an extracting agent, the volume ratio of the methanol to the extracting agent is 3:1-5:1, and the extracting agent is a mixed solvent of dichloromethane and ethyl acetate;
The volume fraction of the ammonia water in the step (1) is 20-25%, the volume ratio of the water sample to the ammonia water is 100:1-200:1, and the volume ratio of the dichloromethane to the ethyl acetate in the extractant is 1:1;
The fatty alcohol in the step (2) is methanol, ethanol or propanol, the fatty acid is formic acid, and the volume ratio of the fatty alcohol aqueous solution to the fatty acid is 15:1-30:1;
The volume fraction of fatty alcohol in the fatty alcohol aqueous solution in the step (2) is 10-30%;
the 30 mental active substances are cotinine, morphine, 6-acetylmorphine, mecalcanone, methamphetamine, p-methoxymethamphetamine, 3, 4-methylenedioxymethamphetamine, 3, 4-methylenedioxyamphetamine, 4-methylthioamphetamine, 2-methylamino-1- (3, 4-methylenedioxyphenyl) -1-propanone, 3, 4-methylenedioxymexicadone, ketamine, norketamine, fluoraminoketone, 1- (3-chlorophenyl) piperazine, 1- (3-trifluoromethylphenyl) piperazine, methylenedioxypyrrole pentanone, cocaine, codeine, heroin, fentanyl, acefenatinib, acrylofentanyl, 2, 5-dimethoxy-4-iodophenethylamine, 2, 5-dimethoxy-4-methylphenylamine, ritaline, 2-ethylene-1, 5-dimethyl-3, 3-diphenylpyrrolidine, methamphetamine;
the liquid chromatography conditions were as follows:
chromatographic column: the Shim-pack GIST-HP C18 has an inner diameter of 2.1mm, a column length of 100mm and a filler particle size of 1.9 μm;
column temperature is 35 ℃; the flow rate is 0.3mL/min; the sample injection amount is 1-10 mu L;
mobile phase a:0.1% formic acid water; mobile phase B: acetonitrile;
Mobile phase gradient elution: 0-6 min 20% mobile phase B, 6-10 min 20-58% mobile phase B, 10-11 min 58-100% mobile phase B, 11-14 min 100% mobile phase B, 14-14.1 min 100-5% mobile phase B, 14.1-21 min 5% mobile phase B;
The mass spectrometry conditions were as follows:
The detection mode is a multi-reaction monitoring mode MRM and a negative ion mode;
atomizing air flow rate: 3L/min; heating air flow: 10L/min;
Interface temperature: 300 ℃; DL temperature: 250 ℃; heating block temperature: 400 ℃; dry air flow: 10L/min.
2. A method for simultaneous determination of 30 psychoactive substances in an environmental body of water according to claim 1, wherein the method comprises the specific steps of:
(1) Taking 10-40 mL of water sample into a 50mL centrifuge tube, adding the mixed isotope internal standard solution, and uniformly mixing to obtain a mixed sample; adding ammonia water and 0.1-1 mL of extracting solution containing an extracting agent, carrying out vortex extraction, centrifuging and layering, and taking a lower organic phase in another centrifuge tube;
(2) Adding 0.1-1 mL of a mixed solution of fatty alcohol aqueous solution and fatty acid into the lower organic phase, carrying out vortex mixing extraction, centrifuging and layering, taking supernatant, and detecting by using a high performance liquid chromatography-triple quadrupole mass spectrometer.
3. The method for simultaneously determining 30 mental active substances in an environmental water body according to claim 1 or 2, wherein the volumes of the water sample and the internal standard solution in the step (1) are 100:1-200:1, and the internal standard mass is 10ng calculated by cotinine-d 3.
4. A method according to claim 3, wherein the volume ratio of methanol to extractant in step (1) is 5:1.
5. A method for simultaneous determination of 30 psychoactive substances in an environmental body of water according to claim 1 or 2, wherein the vortex mixing conditions of step (1) are: mixing at 2500-3500 rpm for 1-3 min, wherein the centrifugation conditions are as follows: centrifuging at 6000-8000 rpm for 5-10 min;
The vortex mixing conditions in the step (2) are as follows: mixing at 2500-3500 rpm for 3-5 min, wherein the centrifugation conditions are as follows: centrifugal force of 10000-12000 rpm for 5-10min.
6. The method for simultaneous determination of 30 psychoactive substances in an environmental water body according to claim 1, wherein mass spectrum parameters of each target compound are shown in table 1:
table 1 mass spectral parameters of 30 targets and internal standards
7. The method of claim 6, wherein the high performance liquid chromatography-triple quadrupole mass spectrometer detection comprises the steps of:
(1) Preparation of standard working solution
Measuring 30 standard substances and 23 internal standard substances by a micropipette respectively to prepare a stock solution and a working solution, and finally preparing a standard working solution with gradient concentration;
(2) High performance liquid chromatography-mass spectrometer detection
Measuring standard working solutions of all concentration gradients in a high performance liquid chromatography-mass spectrometer, and establishing a calibration curve by using an internal standard method; under the same condition, injecting a sample solution to be detected into a high performance liquid chromatography-mass spectrometer for measurement, calculating the concentration of a target compound in the solution through a standard working curve, and then calculating according to the volume of the sample to obtain the content of the target compound in the sample; the concentration of the target compound in the sample solution is in the linear range of the standard working curve, and if the measured concentration exceeds the linear range of the standard working curve, the sample amount is reduced and then the sample is extracted and measured again.
8. Use of the method of any one of claims 1 to 7 for determining the psychotropic substance residue in an environmental body of water.
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