CN112379013A - Method for detecting semi-volatile organic compounds in blood - Google Patents
Method for detecting semi-volatile organic compounds in blood Download PDFInfo
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- 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
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- G—PHYSICS
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
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- G—PHYSICS
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- 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
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Abstract
The invention belongs to the field of monitoring organic pollutants in a complex matrix biological sample, and discloses a method for detecting semi-volatile organic compounds in blood, which comprises the steps of firstly carrying out multistage extraction; then carrying out solid phase purification; then, carrying out gas chromatography-mass spectrometry analysis; and finally, calculating the concentration of each target semi-volatile organic compound to be detected. The method improves the design of the whole process flow of the method, firstly adopts specific pretreatment on a sample to be detected, then adopts a gas chromatography-mass spectrometry combined instrument multi-reaction monitoring mode to detect the pretreated sample, and detects various semi-volatile organic matters such as phthalic acid ester, polycyclic aromatic hydrocarbon, polybrominated diphenyl ether, polychlorinated biphenyl, pesticide and the like which are representative in blood; the detection method has the advantages of low detection limit, good recovery rate, high analysis efficiency and the like.
Description
Technical Field
The invention belongs to the field of monitoring of organic pollutants in a complex matrix biological sample, and particularly relates to a method for detecting semi-volatile organic compounds in blood, which is suitable for detecting 103 semi-volatile organic compounds.
Background
The semi-volatile organic compounds have boiling point of 170-350 deg.C and steam pressure of 1.3-10-2～10-8The organic matters between KPa comprise pesticides, polycyclic aromatic hydrocarbons, phthalate, flame retardants, polychlorinated biphenyl, polybrominated biphenyls and other compounds (Environ Res.2017; 158: 649-. Semi-volatile organic compounds are widely present in plastic products, finishing materials and household daily chemicals, and human activities are the main sources of the semi-volatile organic compounds in the environment. The semi-volatile organic compounds can be dissociated from the source by virtue of unique physical characteristics, are repeatedly desorbed and adsorbed on the surface of a contact carrier, and are permanently migrated in space multi-media, ubiquitous in the atmosphere, water and soil, and enter the body through the ways of body respiratory tracts, skin mucous membranes, food chains and the like (Environ int.2019; 127: 653-. Such as phthalate esters, are also a type of persistent organic contaminant, and as plasticizers, they are commonly used in everyday products such as food and medical packaging, toys, cleaners, personal care products, floors, and wallpaper, and even in processed foods by illegal vendors. The phthalate ester substances are combined with the products in a non-covalent bond form, are easy to release from the products, and can enter human bodies in a direct contact or indirect ingestion mode through environmental medium transmission (Sci Total environ.2018; 645: 1400-. 1409). Most of semi-volatile organic matters in the environment enter a human body in a mode of simultaneously exposing various substances, and a simple pretreatment and analysis method for synchronously detecting various semi-volatile organic matters in blood is established, so that the pretreatment and analysis time can be shortened, the labor intensity of experimenters is reduced, the cost benefit is improved, and the method has important significance for monitoring the human body exposure level of environmental pollutants.
Since there are many kinds of semi-volatile organic compounds and different physical and chemical properties, previous researches generally employ different pre-treatment and analysis methods for different kinds of compounds to detect in batches according to differences in polarity, volatility, stability and the like of the compounds. The sample matrix is also an important influencing factor. The components of a blood sample are complex, the contents of protein and phospholipid are high, and the interference on compound detection is large, so that in the existing analysis method aiming at semi-volatile organic compounds in the blood sample, the protein is inactivated mainly by adding substances such as formic acid, acetic acid, urea and the like, and a target compound is extracted by using organic solvents such as n-hexane, acetone, dichloromethane, methyl tert-butyl ether and the like through a liquid-liquid extraction or solid-phase extraction mode. However, most of the literatures carry out extraction detection on a certain single compound in a sample, and cannot simultaneously analyze the complex exposure level of multiple compounds. Or fractionating to extract various compounds in the sample, and detecting and analyzing by various instruments in batches. The pretreatment process is complex, the manpower consumption of reagents is large, the requirement on instruments is large, and the analysis time is long.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a method for detecting semi-volatile organic compounds in blood, wherein the design of the whole process flow of the method is improved, a sample to be detected is subjected to specific pretreatment, then the pretreated sample is detected in a gas chromatography-mass spectrometer multi-reaction monitoring mode, the detection conditions of the gas chromatography-mass spectrometer can be further optimized, particularly the concentration detection of the semi-volatile organic compounds such as phthalate, polycyclic aromatic hydrocarbon, polychlorinated biphenyl and pesticides which are representative in the blood can be carried out, the problems of pretreatment and detection of the sample which does not simultaneously contain phthalate, polycyclic aromatic hydrocarbon, polychlorinated biphenyl, polybrominated diphenyl ether and pesticide substances in the prior art are effectively solved, and the invention can simultaneously detect at least 2 semi-volatile organic compounds, and the detection method has the advantages of low detection limit, good recovery rate, high analysis efficiency and the like.
In order to achieve the above object, according to the present invention, there is provided a method for detecting semi-volatile organic compounds in blood, comprising the steps of:
(1) multi-stage extraction:
diluting 0.1-2mL of serum or plasma sample to be detected by 1-3 times with ultrapure water, adding 0.5-2mL of acetonitrile, carrying out closed ultrasonic treatment for 5-30 minutes, adding 1-5mL of first solvent, carrying out vibration extraction for more than 5 minutes, centrifuging, and taking supernatant, and recording as first supernatant; the first solvent includes but is not limited to any one of n-hexane, cyclohexane and isooctane;
then, adding 0.1-1mL of second solvent into the treated serum or plasma sample again, performing vibration extraction for more than 5 minutes, centrifuging, and taking the supernatant as a second supernatant; the second solvent includes but is not limited to any one of dichloromethane, methyl tert-butyl ether, chloroform, ethyl acetate and toluene;
combining the first supernatant and the second supernatant, drying by using nitrogen, and then re-dissolving by using at least 100 mu L of third solvent to obtain a re-dissolved sample to be loaded; the third solvent includes but is not limited to any one of n-hexane, dichloromethane, ethyl acetate and isooctane;
(2) impurity removal and activation of a solid phase extraction column:
rinsing the solid phase extraction column with 1-5mL of a fourth solvent, draining the solvent, and discarding the rinsing solution; then, rinsing the solid phase extraction column with 1-5mL of a fifth solvent, dripping the solvent, and removing the rinsing liquid; wherein the fourth solvent includes but is not limited to n-hexane, or a volume ratio of n-hexane to dichloromethane of 8:2, n-hexane/dichloromethane mixed solution; the fifth solvent includes but is not limited to dichloromethane, or a volume ratio of n-hexane to dichloromethane of 1:1 of n-hexane/dichloromethane mixed solution;
(3) loading:
adding the redissolved sample obtained in the step (1) into the solid phase extraction column obtained by the step (2), and collecting a dripping solution;
(4) and (3) elution:
after no solution is dripped in the step (3), adding 1-3mL of the fourth solvent into the solid phase extraction column, dripping the solvent, adding 1-3mL of the sixth solvent, dripping the solvent, adding 1-3mL of the fifth solvent, dripping the solvent, and collecting eluent; wherein the sixth solvent includes but is not limited to n-hexane/acetone mixed solution with volume ratio of 8:2, or n-hexane/ethyl acetate mixed solution with volume ratio of 8: 2;
(5) concentrating and fixing volume:
combining the solution collected in the step (3) and the eluent collected in the step (4), drying the mixture under the protection of nitrogen, re-dissolving the mixture with 0.05-1mL of the third solvent to obtain a concentrated solution, transferring the concentrated solution to a sample bottle, and performing on-machine analysis;
(6) analyzing the concentrated solution in the sample bottle obtained in the step (5) by using a gas chromatography-mass spectrometer, wherein the chromatographic conditions and the mass spectrum conditions of the gas chromatography-mass spectrometer are subjected to optimization treatment in a multi-reaction monitoring mode detection in advance; the optimization processing under the multi-reaction monitoring mode detection is realized by optimizing the detection sensitivity of each target semi-volatile organic compound to be detected in the chromatographic and mass spectrometric detection processes according to the type of the pre-selected target semi-volatile organic compound to be detected and based on a single standard substance solution of each target semi-volatile organic compound to be detected;
(7) calculating the concentration of each target semi-volatile organic compound to be detected in the serum or plasma sample to be detected according to the analysis result obtained in the step (6);
wherein, the preselected target semi-volatile organic compound to be tested is at least 2 semi-volatile organic compounds selected from: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, butylbenzyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate, PCB-28, PCB-52, PCB-101, PCB-118, PCB-138, PCB-153, PCB-180, naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene,
Benzo (b) fluoranthene, benzo [ k ]]Fluoranthene, benzo (a) pyrene, indeno [1,2,3-cd]Pyrene, diphenylanthracene, benzo (g, h, i) perylene, PBDE-28, PBDE-47, PBDE-99, PBDE-100, PBDE-153, dichlorvos, dimethos, anilazine, fenamiphos, trifluralin, phorate, alpha-hexahexa, hexachlorobenzene, atrazine, metamitron, beta-hexa, pentachloronitrobenzene, gamma-hexa, hexa,Pentyne, diazinon, etrimfos, delta-hexaxahexamine, clethodim, acetochlor, chlorpyrifos-methyl, methyl parathion, heptachlor, ametryn, prometryn, pirimiphos-methyl, fenitrothion, malathion, metolachlor, aldrin, cyanazine, isopulfosphos, isosulfocarb, oryzamutual, quinalphos, methidathion, o, p '-dichlorometai, chlorfenphos, paclobutrazol, butachlor, alpha-endosulfan, fenamiphos, profenofos, p' -dichlorometazin, oxadiazon, dieldrin, o, p '-dichlorodiphenyl, oxyfluorfen, aclonifen, isodieldrin, diflufenican, beta-thion, ethion, p' -dichlorodiphenyl, o, p '-dichlorodiphenyl, p' -dichlorodiphenyl thic, pyridaphenthrin, fenpropathrin, propathrin, Voriconophos, cyhalothrin, permethrin, coumaphos, cyfluthrin, cypermethrin, fenvalerate and deltamethrin.
As a further preferred aspect of the present invention, the preselected target semi-volatile organic compound to be detected simultaneously includes at least 2 types of semi-volatile organic compounds in phthalic acid esters, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers, and pesticides.
As a further preferred aspect of the present invention, the preselected target semi-volatile organic compounds to be detected are 103 semi-volatile organic compounds, wherein the target semi-volatile organic compounds include 7 phthalic acid esters, 7 polychlorinated biphenyls, 16 polycyclic aromatic hydrocarbons, 5 polybrominated diphenyl ethers, and 68 pesticides, and specifically include the following:
phthalates, including: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate;
polychlorinated biphenyls including: PCB-28, PCB-52, PCB-101, PCB-118, PCB-138, PCB-153, PCB-180;
polycyclic aromatic hydrocarbons, including: naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, anthracene,
Benzo (b) fluoranthene, benzo [ k ]]Fluoranthene and benzeneAnd (a) pyrene, indeno [1,2,3-cd]Pyrene, diphenylanthracene, benzo (g, h, i) perylene;
polybrominated diphenyl ethers, including: PBDE-28, PBDE-47, PBDE-99, PBDE-100, PBDE-153;
pesticides, including: dichlorvos, metoclopramide, anilide, diclofop, trifluralin, phorate, alpha-hexachlorobenzene, atrazine, metamitron, beta-hexachlorobenzene, pentachloronitrobenzene, gamma-hexachlorocyclohexane, propyzamide, diazinon, etrimfos, delta-hexachlorobenzene, clomazone, acetochlor, chlorpyrifos-methyl, parathion-methyl, heptachlor, ametryn, prometryn, pirimiphos, cartap, metolachlor, aldrin, cyanazine, pyrimidylphos, isoxathion, fenicol, oryzamine, quinalphos, methidathion, o, p ' -dichlorvos, paclobutrazol, butachlor, alpha-endosulfan, fenamiphos, profenofos, p ' -dichloros, oxadiazon, dieldrin, o, p ' -tricholorfen, oxyfen, isoflurane, isofluroxypyr, isofluridil, clodinium, clodinafzel, isofluridil, Fluazifop-butyl, beta-endosulfan, ethion, p ' -dichlorodiphenyl, o, p ' -dichlorodiphenyl, p ' -dichlorodiphenyl, pyridaphenthrin, fenpropathrin, fluvalinate, cyhalothrin, permethrin, coumaphos, cyfluthrin, cypermethrin, fenvalerate and deltamethrin.
As a further preferred aspect of the present invention, in the step (6), the chromatography conditions and mass spectrometry conditions of the gas chromatography-mass spectrometer are as follows:
(i) chromatographic conditions are as follows:
the sample inlet temperature is 300 ℃, helium is taken as carrier gas, the flow rate of the carrier gas is 1ml/min, the sample is injected without shunting, and the sample injection amount is 1 mu l; the chromatographic column is DB-5MS, the length is 30m, the inner diameter is 0.25mm, and the film thickness is 0.25 μm; adopting a temperature programming mode, wherein the temperature programming comprises the following steps: keeping at 45 deg.C for 1min, heating to 130 deg.C at a rate of 30 deg.C/min, keeping for 3min, heating to 180 deg.C at a rate of 12 deg.C/min, heating to 240 deg.C at a rate of 7 deg.C/min, keeping for 5min, heating to 325 deg.C at a rate of 12 deg.C/min, and keeping for 5 min;
(ii) mass spectrum conditions:
the ion source EI has the ion source temperature of 280-300 ℃, the transmission line temperature of 280-300 ℃, the ionization energy of 70eV, and the detection mode is a multi-reaction monitoring mode.
In a further preferred embodiment of the present invention, in the step (7), the calculation is a quantitative calculation based on an internal standard method peak area.
As a further preferred aspect of the present invention, in the step (1), the serum or plasma sample to be detected is processed in a glass tube;
in the step (1), the supernatant is taken by using a glass pipette.
In a further preferred embodiment of the present invention, the glass tube and the glass straw are both obtained by washing and then baking at 480 ℃ for 5 hours.
In a further preferred aspect of the present invention, in the step (5), the cap of the sample bottle is made of teflon;
and (5) specifically, transferring the concentrated solution into a 2mL sample bottle, covering the sample bottle with a bottle cap, refrigerating at 4 ℃ for storage, and waiting for analysis on a computer.
In a further preferred embodiment of the present invention, acetonitrile, n-hexane and dichloromethane are used, all of which are pesticide residue grades.
Through the technical scheme, compared with the prior art, the method can simultaneously carry out quantitative detection on various semi-volatile organic compounds, and particularly can simultaneously carry out quantitative detection on 103 typical semi-volatile organic compounds to obtain the concentrations of the semi-volatile organic compounds. Aiming at the physicochemical properties of 103 semi-volatile organic compounds (containing 7 items of phthalate, 7 items of polychlorinated biphenyl, 16 items of polycyclic aromatic hydrocarbon, 5 items of polybrominated diphenyl ether and 68 items of pesticide) in blood, the pretreatment method disclosed by the invention combines the extraction of mixed solutions with different polarities with the extraction of a Florisil solid phase extraction column, so that the interference of impurities and matrix is reduced, the treated sample can be subjected to qualitative and quantitative detection, the cost benefit is high, and the method is suitable for one-step treatment and simultaneous detection of multiple semi-volatile organic compounds in a blood sample complex matrix sample. The gas chromatography-mass spectrometer detection and analysis method established by the method adopts a multi-reaction monitoring mode, has the advantages of low detection limit, high sensitivity, good accuracy, high analysis efficiency and the like, particularly solves the problem that the existing method does not simultaneously contain phthalic acid ester, polycyclic aromatic hydrocarbon, polychlorinated biphenyl, polybrominated diphenyl ether, organochlorine insecticide, organophosphorus insecticide, herbicide, pyrethroid substance and other pesticides for treatment and detection, and provides a simple, convenient and efficient detection method for analyzing 103 semi-volatile organic compounds in blood.
For 103 semi-volatile organic compounds, the invention adopts a multi-reaction monitoring mode, optimizes the detection conditions of the gas chromatography-mass spectrometer, and has a detection limit range of 0.001-0.181 microgram mL when the characteristic ion pair is qualitative and the internal standard method is integrated and quantified-1The relative standard deviation of the parallel sample is 1.5-18.9%, and the secondary mass spectrum is adopted for qualitative analysis, so that the accuracy is good and the sensitivity is high.
The detection method can be used for judging whether the sample to be detected contains the target semi-volatile organic compounds (the type of the target semi-volatile organic compounds can be selected in advance) and the concentration of each target semi-volatile organic compound in the sample, and can be applied to scenes such as large environmental data of a collection area and the like to judge the exposure degree of each semi-volatile organic compound in human blood.
Drawings
FIG. 1 is a schematic flow chart of the method for detecting semi-volatile organic compounds in blood according to the present invention, which is suitable for detecting 103 semi-volatile organic compounds.
FIG. 2 is a gas chromatography-mass spectrometry chromatogram for the analysis and detection of 103 semi-volatile organic compounds in blood. The detection sample is added with 103 semi-volatile organic compounds into a certain blood sample, and the adding standard concentration of each semi-volatile organic compound is controlled to be 0.04 mg/L; the marks 1 to 103 shown in the figure correspond to 103 semi-volatile organic compounds, and the specific types of the semi-volatile organic compounds corresponding to the marks are consistent with the peak numbers of the chromatograms in table 2 and table 3.
FIG. 3 is a schematic diagram of the pretreatment process and the instrumental analysis of the detection of the semi-volatile organic compounds in blood according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the pretreatment and analysis method comprises the steps of subjecting a sample to ultrasonic extraction and vibration extraction in turn by using an organic mixed solvent with the polarity from small to large, enriching and loading the sample, purifying and separating by using a solid phase extraction small column, eluting organic matters enriched on the solid phase extraction small column in turn by using the organic mixed solvent with the polarity from small to large, and detecting by using a gas chromatography-mass spectrometer multi-reaction monitoring mode. Specifically, during pretreatment, ultrapure water is firstly used for dilution, acetonitrile, normal hexane and dichloromethane are sequentially added for extraction, extraction liquids are collected and combined, then nitrogen is blown dry, and normal hexane is used for redissolving. And (3) performing solid-phase extraction by using a solid-phase extraction small column, eluting the target by using mixed solution of n-hexane, n-hexane/ethyl acetate and n-hexane/dichloromethane in sequence, collecting eluent, drying by blowing nitrogen, and redissolving by using n-hexane for sample injection to detect the target. The detection and analysis are carried out by adopting a gas chromatography-mass spectrometer.
The detection method can be carried out according to the following steps:
(1) multi-stage extraction:
diluting 0.1-2mL of serum or plasma sample to be detected by adding ultrapure water by 1-3 times, adding 0.5-2mL of acetonitrile, carrying out closed ultrasonic treatment for 5-30 minutes, adding 1-5mL of a first solvent, carrying out vibration extraction for more than 5 minutes, centrifuging, and taking a supernatant, and marking as a first supernatant;
then, adding 0.1-1mL of a second solvent into the processed serum or plasma sample again, wherein the second solvent comprises but is not limited to dichloromethane, methyl tert-butyl ether, chloroform, ethyl acetate and toluene, performing vibration extraction for more than 5 minutes, and centrifuging to obtain a supernatant, and marking the supernatant as a second supernatant;
combining the first supernatant and the second supernatant, drying with nitrogen, and then re-dissolving with at least 100 μ L of a third solvent, wherein the third solvent comprises but is not limited to n-hexane, dichloromethane, ethyl acetate and isooctane, so as to obtain a re-dissolved sample to be loaded;
(2) impurity removal and activation of a solid phase extraction column:
rinsing the solid phase extraction column with 1-5mL of a fourth solvent including but not limited to a pure hexane solution, a mixed n-hexane/dichloromethane solution with n-hexane volume percentage not less than 80% (e.g., a mixed n-hexane/dichloromethane solution with a volume ratio of 9: 1, a mixed n-hexane/dichloromethane solution with a volume ratio of 8: 2), draining the solvent, and discarding the rinsing solution; then, rinsing the solid phase extraction column with 1-5mL of a fifth solvent, wherein the fifth solvent includes but is not limited to a pure dichloromethane solution and a mixed n-hexane/dichloromethane solution with dichloromethane volume percentage not less than 50% (e.g., a mixed n-hexane/dichloromethane solution with a volume ratio of 1:1 and a mixed n-hexane/dichloromethane solution with a volume ratio of 1: 9), draining the solvent, and discarding the rinsing solution;
(3) loading:
adding the redissolved sample obtained in the step (1) into the solid phase extraction column obtained by the step (2), and collecting a dripping solution;
(4) and (3) elution:
after no solution is dripped in the step (3), adding 1-3mL of a fourth solvent into the solid phase extraction column, dripping the solvent, then adding 1-3mL of a sixth solvent, dripping the solvent, and dripping the solvent, wherein the sixth solvent comprises but is not limited to a n-hexane/acetone mixed solution with a volume ratio of 8:2 and a n-hexane/ethyl acetate mixed solution with a volume ratio of 8:2, dripping the solvent, then adding 1-3mL of a fifth solvent, dripping the solvent, and collecting eluent;
(5) concentrating to constant volume
Drying the sample under the protection of pure nitrogen, redissolving 0.05-1mL of a third solvent (such as 0.1mL of n-hexane), transferring the concentrated solution into a 2mL sample bottle, covering the bottle cap, refrigerating at 4 ℃ and storing on a computer for analysis;
in the step (1), the glass tube and the glass suction tube are cleaned and then baked for 5 hours at 480 ℃, and the bottle cap is made of polytetrafluoroethylene material; the purity of the nitrogen in the steps (1) and (5) is more than 99.9 percent; the organic solvent in all the steps is pesticide residue grade solvent;
(6) analyzing the sample solution to be detected by a gas chromatography-mass spectrometer; the chromatographic conditions and mass spectrum conditions of the gas chromatography-mass spectrometer are subjected to optimization treatment in advance under the detection of a multi-reaction monitoring mode; the optimization processing under the multi-reaction monitoring mode detection is realized by optimizing the detection sensitivity of each target semi-volatile organic compound to be detected in the chromatographic and mass spectrometric detection processes according to the type of the pre-selected target semi-volatile organic compound to be detected and based on a single standard substance solution of each target semi-volatile organic compound to be detected;
(7) target compound concentration calculations (e.g., target concentration is calculated quantitatively from internal standard peak area).
The method of the present invention will be described in detail below by taking the example of detecting 103 pre-selected semi-volatile organic compounds (the 103 semi-volatile organic compounds are phthalate 7, polychlorinated biphenyl 7, polycyclic aromatic hydrocarbon 16, polybromodiphenyl ether 5, and pesticide 68).
Example 1
(1) Preparation of standard solution of semi-volatile organic compound to be measured
Taking a proper amount of each high-concentration single standard solution, preparing the single standard solution with the concentration of 10 mu g/mL (7 items of phthalate, 7 items of polychlorinated biphenyl, 16 items of polycyclic aromatic hydrocarbon and 5 items of polybrominated diphenyl ether) by using n-hexane, and preparing the single standard solution with the concentration of 10 mu g/mL (68 items of pesticide) by using methanol.
(2) Optimization of chromatography/mass spectrometry conditions
Taking chromatographic column DB-5MS (30 × m × 0.25mm × 0.25 μm) as an example, 10 μ g/mL of single standard solution is directly injected, full scan is performed to find a molecular ion peak with strong response to high specificity as a parent ion (i.e., a molecular ion), different collision energies are set according to different pre-selected collision energy requirements to bombard the parent ion (collision energy requirements are pre-selected, for example, refer to the prior art document Jia, Xiaoqian, et al. environmental polarization 251.AUG. (2019): 400:406.), secondary ions (i.e., a daughter ion) are generated, the molecular ion and 2-3 daughter ions with high specificity to signal intensity are combined into a monitoring ion pair (in an extreme case, only 1 daughter ion with high specificity to signal intensity can be taken, the molecular ion and the daughter ion are combined into 1 monitoring ion pair, the highest energy response (highest collision characteristic), i.e. highest response peak), so that the selected parent ion and daughter ion pairs have the best sensitivity, and the compound is qualitatively and quantitatively determined (the qualitative corresponds to the determination of the compound type, and the quantitative corresponds to the determination of the compound content; different characteristic peaks can be selected qualitatively and quantitatively; of course, in extreme cases, the same characteristic peak can be selected), thereby completing the optimization of the conditions under the detection of the multi-reaction monitoring mode.
Then, different injection port temperatures, ion source temperatures and transmission line temperatures are set respectively, and the injection port temperatures, the ion source temperatures and the transmission line temperatures are selected optimally according to the comprehensive response of various compounds (the optimal comprehensive response can be the optimal response with the highest peak height according to the weight corresponding to 103 compounds in advance). Different temperature raising programs and carrier gas flow rates are set, and the temperature raising programs and the carrier gas flow rates are selected when the response effect of the 103 semi-volatile organic compounds is optimal (the response effect and the separation effect among the compounds are considered at the time).
(3) Setting of chromatographic/mass spectrometric conditions
A triple quadrupole gas chromatography mass spectrometer (bruker GC-MS/MS) can be used, with the parameter conditions set as follows:
an ion source: electron bombardment ion source EI;
the detection mode is as follows: a multiple reaction monitoring mode;
ionization energy: 70 eV;
a chromatographic column: DB-5MS, 30 × m 0.25mm × 0.25 μm;
sample inlet temperature: 300 ℃;
ion source temperature: 280 ℃;
transmission line temperature: 280 ℃;
carrier gas flow: 1 mL/min;
temperature rising procedure: keeping at 45 ℃ for 1min, then heating to 130 ℃ at a heating rate of 30 ℃/min, keeping for 3min, then heating to 180 ℃ at a heating rate of 12 ℃/min, then heating to 240 ℃ at a heating rate of 7 ℃/min, keeping for 5min, then heating to 325 ℃ at a heating rate of 12 ℃/min, and keeping for 5 min; the carrier gas flow is 1 mL/min;
specific conditions for Multiple Reaction Monitoring (MRM) are shown in table 1.
Table 1103 multi-ion reaction detection conditions for semi-volatile organic compounds
(4) Determination of laboratory detection limits
Similar to conventional processing, the detection limit may be set at the spiked concentration at which the experimental blank spiked sample instrument response is three times the baseline noise ratio
C is the spiked concentration, S is the peak height, and N is the baseline noise.
According to the above-mentioned detection limit calculation mode, it is goodThe detection limit range of the method for detecting 103 semi-volatile organic compounds is 0.001-0.181 mu g L-1。
Example 2
According to the detection detail parameter condition setting of the triple quadrupole gas chromatography-mass spectrometer determined in the embodiment 1, collecting whole blood of a volunteer, and centrifuging to obtain serum; the serum was divided equally into 7 aliquots as replicates and the experiments were performed. The method comprises the following specific steps:
(1) multi-stage liquid-liquid extraction:
diluting 0.1mL of a serum sample to be detected by 2 times with ultrapure water, adding 0.5mL of acetonitrile, carrying out closed ultrasonic treatment for 5 minutes, adding 1mL of n-hexane, carrying out vibration extraction for 5 minutes, centrifuging, and taking a supernatant, wherein the supernatant is marked as a first supernatant;
then, adding 0.1mL of dichloromethane into the treated serum sample again, performing vibration extraction for 5 minutes, centrifuging, and taking the supernatant as a second supernatant;
combining the first supernatant and the second supernatant, drying the combined supernatant by using pure nitrogen with the purity of not less than 99.9%, and then re-dissolving the combined supernatant by using 100 mu L of n-hexane to obtain a re-dissolved sample to be loaded;
(2) impurity removal and activation of the solid phase extraction column:
rinsing the Florisil solid phase extraction column by using 1mL of n-hexane/dichloromethane mixed solution with the volume ratio of 8:2, dripping the solvent, and discarding the rinsing liquid; then, rinsing the Florisil solid phase extraction column by using 1mL of normal hexane/dichloromethane mixed solution with the volume ratio of 1:1, dripping the solvent, and discarding the rinsing liquid;
(3) loading:
adding the redissolved sample obtained in the step (1) into the solid phase extraction column obtained by the treatment in the step (2), rinsing a container filled with the first supernatant and the second supernatant by using 0.5mL of n-hexane, adding the containers into the solid phase extraction column together, and collecting a dripping solution;
(4) and (3) elution:
after no solution is dripped in the step (3), adding 1mL of n-hexane/dichloromethane mixed solution with the volume ratio of 8:2 into the solid phase extraction column, dripping the solvent, adding 1mL of n-hexane/ethyl acetate mixed solution with the volume ratio of 8:2, dripping the solvent, adding 1mL of n-hexane/dichloromethane mixed solution with the volume ratio of 1:1, dripping the solvent, and collecting eluent;
(5) concentrating and fixing volume:
combining the solution collected in the step (3) and the eluent collected in the step (4), drying the mixture under the protection of pure nitrogen with the purity of not less than 99.9%, re-dissolving the mixture with 0.1mL of n-hexane to obtain a concentrated solution, transferring the concentrated solution into a sample bottle, and performing on-machine analysis;
(6) analyzing the concentrated solution in the sample bottle obtained in the step (5) by using a triple quadrupole gas chromatograph-mass spectrometer, wherein the chromatographic conditions and the mass spectrum conditions of the triple quadrupole gas chromatograph-mass spectrometer are optimized in advance under the detection of a multiple reaction monitoring mode; the optimization processing under the multi-reaction monitoring mode detection is realized by optimizing the detection sensitivity of each target semi-volatile organic compound to be detected in the chromatographic and mass spectrometric detection processes according to the type of the pre-selected target semi-volatile organic compound to be detected and based on a single standard substance solution of each target semi-volatile organic compound to be detected;
(7) calculating the concentration of each target semi-volatile organic compound to be detected in the serum sample to be detected by using the analysis result obtained in the step (6);
the recovery rate of the 103 semi-volatile organic matrixes is shown in table 2 in detail, and the recovery rate ranges from 74.25% to 111.87%.
The relative standard deviation of the duplicate determinations of the 7 groups of the parallel samples is 3.95-16.97%.
TABLE 2103 Standard recovery of semi-volatile organic substrate
Example 3
According to the detection detail parameter condition setting of the triple quadrupole gas chromatography-mass spectrometer determined in the embodiment 1, collecting whole blood of another volunteer, and centrifuging to obtain serum; the serum was divided equally into 7 aliquots as replicates and the experiments were performed. The method comprises the following specific steps:
(1) multi-stage liquid-liquid extraction:
diluting 2mL of a serum sample to be detected by 3 times by adding ultrapure water, adding 2mL of acetonitrile, carrying out closed ultrasonic treatment for 20 minutes, adding 5mL of n-hexane, carrying out vibration extraction for 5 minutes, centrifuging, and taking a supernatant, wherein the supernatant is marked as a first supernatant;
then, adding 1mL of dichloromethane into the treated serum sample again, performing vibration extraction for 5 minutes, centrifuging, and taking a supernatant as a second supernatant;
combining the first supernatant and the second supernatant, drying the combined supernatant by using pure nitrogen with the purity of not less than 99.9%, and then re-dissolving the combined supernatant by using 100 mu L of n-hexane to obtain a re-dissolved sample to be loaded;
(2) impurity removal and activation of the solid phase extraction column:
rinsing the Florisil solid phase extraction column by using 5mL of n-hexane/dichloromethane mixed solution with the volume ratio of 8:2, dripping the solvent, and discarding the rinsing liquid; then, rinsing the Florisil solid phase extraction column by using 5mL of a mixed solution of n-hexane and dichloromethane with the volume ratio of 1:1, dripping the solvent, and discarding the rinsing liquid;
(3) loading:
adding the redissolved sample obtained in the step (1) into the solid phase extraction column obtained by the treatment in the step (2), rinsing a container filled with the first supernatant and the second supernatant by using 2mL of n-hexane, adding the containers into the solid phase extraction column together, and collecting a dripping solution;
(4) and (3) elution:
after no solution is dripped in the step (3), adding 3mL of n-hexane/dichloromethane mixed solution with the volume ratio of 8:2 into the solid phase extraction column, dripping the solvent, adding 3mL of n-hexane/ethyl acetate mixed solution with the volume ratio of 8:2, dripping the solvent, adding 3mL of n-hexane/dichloromethane mixed solution with the volume ratio of 1:1, dripping the solvent, and collecting eluent;
(5) concentrating and fixing volume:
combining the solution collected in the step (3) and the eluent collected in the step (4), drying the mixture under the protection of pure nitrogen with the purity of not less than 99.9%, re-dissolving the mixture with 0.1mL of n-hexane to obtain a concentrated solution, transferring the concentrated solution into a sample bottle, and performing on-machine analysis;
(6) analyzing the concentrated solution in the sample bottle obtained in the step (5) by using a triple quadrupole gas chromatograph-mass spectrometer, wherein the chromatographic conditions and the mass spectrum conditions of the triple quadrupole gas chromatograph-mass spectrometer are optimized in advance under the detection of a multiple reaction monitoring mode; the optimization processing under the multi-reaction monitoring mode detection is realized by optimizing the detection sensitivity of each target semi-volatile organic compound to be detected in the chromatographic and mass spectrometric detection processes according to the type of the pre-selected target semi-volatile organic compound to be detected and based on a single standard substance solution of each target semi-volatile organic compound to be detected;
(7) calculating the concentration of each target semi-volatile organic compound to be detected in the serum sample to be detected by using the analysis result obtained in the step (6);
the recovery rate of the 103 semi-volatile organic matrixes is detailed in table 3, and the recovery rate ranges from 75.24% to 114.84%.
The relative standard deviation of the double-sample determination of 7 groups of parallel samples is 4.95-14.85%.
TABLE 3103 Standard recovery of semi-volatile organic substrates
In the above embodiments, the sample pretreatment and analysis methods and results of 103 semi-volatile organic compounds such as phthalic acid ester, polycyclic aromatic hydrocarbon, polychlorinated biphenyl, pesticide and the like which are representative in blood are summarized and summarized, and can be flexibly adjusted according to actual requirements.
The various organic solvents used in the invention are pesticide residue grade solvents, and the purity of nitrogen and helium is not lower than 99.9%.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1.A method for detecting semi-volatile organic compounds in blood is characterized by comprising the following steps:
(1) multi-stage extraction:
diluting 0.1-2mL of serum or plasma sample to be detected by 1-3 times with ultrapure water, adding 0.5-2mL of acetonitrile, carrying out closed ultrasonic treatment for 5-30 minutes, adding 1-5mL of first solvent, carrying out vibration extraction for more than 5 minutes, centrifuging, and taking supernatant, and recording as first supernatant; the first solvent includes but is not limited to any one of n-hexane, cyclohexane and isooctane;
then, adding 0.1-1mL of second solvent into the treated serum or plasma sample again, performing vibration extraction for more than 5 minutes, centrifuging, and taking the supernatant as a second supernatant; the second solvent includes but is not limited to any one of dichloromethane, methyl tert-butyl ether, chloroform, ethyl acetate and toluene;
combining the first supernatant and the second supernatant, drying by using nitrogen, and then re-dissolving by using at least 100 mu L of third solvent to obtain a re-dissolved sample to be loaded; the third solvent includes but is not limited to any one of n-hexane, dichloromethane, ethyl acetate and isooctane;
(2) impurity removal and activation of a solid phase extraction column:
rinsing the solid phase extraction column with 1-5mL of a fourth solvent, draining the solvent, and discarding the rinsing solution; then, rinsing the solid phase extraction column with 1-5mL of a fifth solvent, dripping the solvent, and removing the rinsing liquid; wherein the fourth solvent includes but is not limited to n-hexane, or a volume ratio of n-hexane to dichloromethane of 8:2, n-hexane/dichloromethane mixed solution; the fifth solvent includes but is not limited to dichloromethane, or a volume ratio of n-hexane to dichloromethane of 1:1 of n-hexane/dichloromethane mixed solution;
(3) loading:
adding the redissolved sample obtained in the step (1) into the solid phase extraction column obtained by the step (2), and collecting a dripping solution;
(4) and (3) elution:
after no solution is dripped in the step (3), adding 1-3mL of the fourth solvent into the solid phase extraction column, dripping the solvent, adding 1-3mL of the sixth solvent, dripping the solvent, adding 1-3mL of the fifth solvent, dripping the solvent, and collecting eluent; wherein the sixth solvent includes but is not limited to n-hexane/acetone mixed solution with volume ratio of 8:2, or n-hexane/ethyl acetate mixed solution with volume ratio of 8: 2;
(5) concentrating and fixing volume:
combining the solution collected in the step (3) and the eluent collected in the step (4), drying the mixture under the protection of nitrogen, re-dissolving the mixture with 0.05-1mL of the third solvent to obtain a concentrated solution, transferring the concentrated solution to a sample bottle, and performing on-machine analysis;
(6) analyzing the concentrated solution in the sample bottle obtained in the step (5) by using a gas chromatography-mass spectrometer, wherein the chromatographic conditions and the mass spectrum conditions of the gas chromatography-mass spectrometer are subjected to optimization treatment in a multi-reaction monitoring mode detection in advance; the optimization processing under the multi-reaction monitoring mode detection is realized by optimizing the detection sensitivity of each target semi-volatile organic compound to be detected in the chromatographic and mass spectrometric detection processes according to the type of the pre-selected target semi-volatile organic compound to be detected and based on a single standard substance solution of each target semi-volatile organic compound to be detected;
(7) calculating the concentration of each target semi-volatile organic compound to be detected in the serum or plasma sample to be detected according to the analysis result obtained in the step (6);
wherein, the preselected target semi-volatile organic compound to be tested is at least 2 semi-volatile organic compounds selected from: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, butylbenzyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate, PCB-28, PCB-52, PCB-101, PCB-118, PCB-138, PCB-153, PCB-180, naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene,
Benzo (b) fluoranthene, benzo [ k ]]Fluoranthene, benzo (a) pyrene, indeno [1,2,3-cd]Pyrene, dianthracene, benzo (g, h, i) perylene, PBDE-28, PBDE-47, PBDE-99, PBDE-100, PBDE-153, dichlorvos, dimethos, anilazine, fenamiphos, trifluralin, phorate, alpha-hexahexa, hexachlorobenzene, atrazine, metamitron, beta-hexahexa, pentachloronitrobenzene, gamma-hexa, pentyne, diazinon, etrimfos, delta-hexahexa, clomazone, acetochlor, chlorpyrifos-methyl, methyl parathion, heptachlor, ametryn, prometryn, pirimiphos-methyl, fenitrothion, malathion, metolachlor, aldrin, cyanazine, phos-ethyl, isoxathion, fenitrocarb, phenthoate, quinalphos, methidathion, o, p' -dichlorvos, dicarb, paclobutrazol, butachlor, alpha-thion, fenamiphos, naprophos, propaquizam, prophos, Profenofos, p ' -diedifen, oxadiazon, dieldrin, o, p ' -diedifen, oxyfluorfen, aclonifen, endrin, fluazifop-butyl, beta-endosulfan, ethion, p ' -diedifen, o, p ' -diutan, p ' -diutan, pyridaphenthrin, fenpropathrin, fluvaliphos,Cyhalothrin, permethrin, coumaphos, cyfluthrin, cypermethrin, fenvalerate and deltamethrin.
2. The method according to claim 1, wherein the pre-selected target semi-volatile organic compounds to be detected include at least 2 semi-volatile organic compounds selected from the group consisting of phthalic acid esters, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers, and pesticides.
3. The method according to claim 1, wherein the pre-selected target semi-volatile organic compounds are 103 semi-volatile organic compounds, including 7 phthalic acid esters, 7 polychlorinated biphenyls, 16 polycyclic aromatic hydrocarbons, 5 polybrominated diphenyl ethers, and 68 pesticides, and specifically comprises the following steps:
phthalates, including: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate;
polychlorinated biphenyls including: PCB-28, PCB-52, PCB-101, PCB-118, PCB-138, PCB-153, PCB-180;
polycyclic aromatic hydrocarbons, including: naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, anthracene,
Benzo (b) fluoranthene, benzo [ k ]]Fluoranthene, benzo (a) pyrene, indeno [1,2,3-cd]Pyrene, diphenylanthracene, benzo (g, h, i) perylene;
polybrominated diphenyl ethers, including: PBDE-28, PBDE-47, PBDE-99, PBDE-100, PBDE-153;
pesticides, including: dichlorvos, metoclopramide, anilide, diclofop, trifluralin, phorate, alpha-hexachlorobenzene, atrazine, metamitron, beta-hexachlorobenzene, pentachloronitrobenzene, gamma-hexachlorocyclohexane, propyzamide, diazinon, etrimfos, delta-hexachlorobenzene, clomazone, acetochlor, chlorpyrifos-methyl, parathion-methyl, heptachlor, ametryn, prometryn, pirimiphos, cartap, metolachlor, aldrin, cyanazine, pyrimidylphos, isoxathion, fenicol, oryzamine, quinalphos, methidathion, o, p ' -dichlorvos, paclobutrazol, butachlor, alpha-endosulfan, fenamiphos, profenofos, p ' -dichloros, oxadiazon, dieldrin, o, p ' -tricholorfen, oxyfen, isoflurane, isofluroxypyr, isofluridil, clodinium, clodinafzel, isofluridil, Fluazifop-butyl, beta-endosulfan, ethion, p ' -dichlorodiphenyl, o, p ' -dichlorodiphenyl, p ' -dichlorodiphenyl, pyridaphenthrin, fenpropathrin, fluvalinate, cyhalothrin, permethrin, coumaphos, cyfluthrin, cypermethrin, fenvalerate and deltamethrin.
4. The method for detecting semi-volatile organic compounds in blood according to claim 3, wherein in the step (6), the chromatographic conditions and mass spectrometric conditions of the GC-MS are as follows:
(i) chromatographic conditions are as follows:
the sample inlet temperature is 300 ℃, helium is taken as carrier gas, the flow rate of the carrier gas is 1ml/min, the sample is injected without shunting, and the sample injection amount is 1 mu l; the chromatographic column is DB-5MS, the length is 30m, the inner diameter is 0.25mm, and the film thickness is 0.25 μm; adopting a temperature programming mode, wherein the temperature programming comprises the following steps: keeping at 45 deg.C for 1min, heating to 130 deg.C at a rate of 30 deg.C/min, keeping for 3min, heating to 180 deg.C at a rate of 12 deg.C/min, heating to 240 deg.C at a rate of 7 deg.C/min, keeping for 5min, heating to 325 deg.C at a rate of 12 deg.C/min, and keeping for 5 min;
(ii) mass spectrum conditions:
the ion source EI has the ion source temperature of 280-300 ℃, the transmission line temperature of 280-300 ℃, the ionization energy of 70eV, and the detection mode is a multi-reaction monitoring mode.
5. The method for detecting semi-volatile organic compounds in blood according to claim 1, wherein in the step (7), the calculation is carried out quantitatively according to the peak area of an internal standard method.
6. The method for detecting semi-volatile organic compounds in blood according to claim 1, wherein in step (1), the serum or plasma sample to be detected is treated in a glass tube;
in the step (1), the supernatant is taken by using a glass pipette.
7. The method according to claim 6, wherein the glass tube and the glass pipette are cleaned and then baked at 480 ℃ for 5 hours.
8. The method for detecting semi-volatile organic compounds in blood according to any one of claims 1 to 7, wherein in the step (5), the cap of the sample bottle is made of polytetrafluoroethylene;
and (5) specifically, transferring the concentrated solution into a 2mL sample bottle, covering the sample bottle with a bottle cap, refrigerating at 4 ℃ for storage, and waiting for analysis on a computer.
9. The method for detecting semi-volatile organic compounds in blood as claimed in any one of claims 1 to 8, wherein acetonitrile, n-hexane and dichloromethane are used as pesticide residue.
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