CN112557542A - Method for rapidly detecting phosphorus flame retardant and degradation product thereof in blood plasma - Google Patents
Method for rapidly detecting phosphorus flame retardant and degradation product thereof in blood plasma Download PDFInfo
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- CN112557542A CN112557542A CN202011425857.XA CN202011425857A CN112557542A CN 112557542 A CN112557542 A CN 112557542A CN 202011425857 A CN202011425857 A CN 202011425857A CN 112557542 A CN112557542 A CN 112557542A
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Abstract
The invention discloses a method for rapidly detecting phosphorus flame retardants in plasma and degradation products thereof. In the invention, the phosphorus flame retardant and partial degradation products thereof in the plasma can be rapidly detected in two steps, the measurement is simple, and the requirement of rapid detection by taking the plasma as a sample is met.
Description
Technical Field
The invention relates to the field of detection methods of phosphorus flame retardants and degradation products thereof, in particular to a rapid detection method of phosphorus flame retardants and degradation products thereof in blood plasma.
Background
Organic Phosphorus Flame Retardants (OPFRs) are widely used in electronic products, foams, plastics and textiles due to their low smoke, low toxicity and high heat resistance. The organic phosphorus flame retardant is mainly added into the material in an adding mode rather than a chemical bond mode, so that the organic phosphorus flame retardant is easily leached from the treated material in modes of product abrasion, volatilization and permeation and is released into various environmental media, thereby affecting human beings and various organisms. Researchers have detected different concentrations of OPFRs in vivo and in various environmental media. Research shows that the organic phosphorus flame retardant can produce various toxic effects such as biological toxicity, potential carcinogenicity and neurotoxicity, and reduce the immunity of the organism. For example, TPHP inhibits monocyte carboxylase activity in human blood, which in turn has an adverse effect on the human immune system. TCP has potential biological toxicity and central nerve toxicity, and can be absorbed by human body and contact with skin to cause toxicity. TBOEP can have interfering effects on the endocrine system of the organism. Therefore, researches on the influence of OPFRs on the environment and human health gradually attract attention of students, but the current researches are only in the initial stage, the data in all aspects are not perfect, and the basic investigation needs to be carried out more deeply and more widely. Therefore, a set of complete detection method for the phosphorus flame retardant and the degradation product thereof in blood is established, and the method has important guiding significance for guaranteeing the physical health of residents and the safety of regional ecological environment, and making pollution control strategies and elimination measures of the organic phosphorus flame retardant according with national conditions and places.
14 kinds of human urinePhosphorus flame retardants and 3 kinds of metabolites, triethyl phosphate (TEP), diethyl phosphate (DEP), tripropyl phosphate (TPP), tributyl phosphate (TBP), tripentyl phosphate (TNP), trioctyl phosphate (TEHP), tri-m-tolyl phosphate (TMCP), diphenyl cresyl phosphate (CDP), tris (2-butoxyethyl) phosphate (TBOEP), triphenylphosphine oxide (TPPO) and 2-ethylhexyl diphenyl phosphate (EHDPP), triphenyl phosphate (TPHP), resorcinol tetraphenyl phosphate (RDP) and triisobutyl phosphate (TIBP)14 kinds of phosphorus flame retardants, bis (2-butoxyethyl) -2- (3-hydroxybutoxy) ethyl triester phosphate (BHEPT), bis (2-butoxyethyl) -2-hydroxyethyl triester phosphate (BHP), bis (butoxyethyl) phosphate (BBP), 3 kinds of tris (2-butoxyethyl) phosphate (TBOEP) phosphorus flame retardants Degradation products are obtained by using tri-n-butyl phosphate-d on the basis of analyzing the report of the content of phosphorus flame retardants in human urine in domestic literature27(TBP-d27) Tris (2-butoxyethyl) phosphate-d27(TBOEP-d27) As an indicator within standard substitutes.
At present, a few scholars have studied OPFRs in urine, and Chinese patent publication No. CN 105699527A discloses a method for detecting the content of bromine flame retardant and phosphorus flame retardant in serum, which includes a method for detecting the content of phosphorus flame retardant in serum, the method includes the following steps:
(1b) Mixing the serum to be detected with diatomite, adding an internal standard indicator, then adding a first organic solvent to extract a brominated flame retardant in the serum, and fully extracting to obtain an extracting solution;
(2b) Concentrating the extracting solution obtained in the step (1 b), transferring the extracting solution to a solid phase extraction column for purification, eluting the phosphorus flame retardant from the solid phase extraction column by using a second organic solvent, collecting the eluent, and concentrating; transferring the concentrated eluent to a composite alumina-silica gel column for further purification, eluting again by using a second organic solvent, and fixing the volume of the eluted eluent again;
(3b) Preparing a phosphorus flame retardant standard solution containing the internal standard indicator in the step (1 b), measuring the solution with the constant volume in the step (2 b) and the phosphorus flame retardant standard solution containing the internal standard indicator by using a gas chromatography-mass spectrometer, and performing data processing and quantitative analysis based on an internal standard method to obtain the content of the phosphorus flame retardant in serum.
The method takes serum as a sample, has more complicated steps, and cannot meet the requirement of rapid detection by taking plasma as the sample.
Disclosure of Invention
The invention aims to establish a method for rapidly detecting phosphorus flame retardants in blood plasma and partial degradation products thereof by taking human blood plasma as a sample.
The technical scheme adopted by the invention for realizing the purpose is as follows: a method for rapidly detecting phosphorus flame retardants and degradation products thereof in blood plasma comprises the following steps:
step S1, sample preprocessing step; this step removes lipid materials from the plasma;
step S2, performing liquid chromatography detection on the pretreated sample; the method comprises the following steps: the detection is carried out by adopting a triple quadrupole liquid mass spectrometer, and the specific conditions of the apparatus are as follows:
the triple quadrupole rod LC-MS is Agilent 1260-;
the chromatographic column is; the column temperature is 35 ℃; the sample amount is 10 mu L, the mobile phase is methanol and 0.005mol/L ammonium acetate solution, and the flow rate of the mobile phase is 250 mu L/min; the gradient is as follows:
mass spectrum conditions: an electrospray ionization source; a multiple reaction monitoring mode; the ion source temperature is 550 ℃; ion source ionization mode: except DEPHA is Negative, the other objects are Positive;
the capillary voltage is 3500V, the atomizer pressure is 45psi, the carrier gas is high-purity nitrogen, the carrier gas temperature is 330 ℃, the flow rate is 9.5L/min, the concentration of the analytes is 500 mug/L by detecting with a multi-reaction monitoring mode (MRM);
determining parent ions and ionic ions of each compound through a total ion flow diagram and a corresponding mass spectrogram result, and optimizing collision energy and declustering voltage according to response conditions.
Further, in the method for rapidly detecting the phosphorus flame retardant and the degradation product thereof in the blood plasma, the following steps are carried out: in step S1, lipid substances in plasma are removed by the following method:
taking a mixture of acetonitrile and formic acid with the volume of 4 times of the volume of the blood plasma to be detected, and adding the mixture into a 1mLPRiME HLB column, wherein: the content of the mixed solution of acetonitrile and formic acid is 1 percent;
adding blood plasma to be detected;
performing 1ml of mixed RiME HLB column;
naturally dripping under the action of gravity, and collecting filtrate.
In the invention, the phosphorus flame retardant and partial degradation products thereof in the plasma can be rapidly detected in two steps, the measurement is simple, and the requirement of rapid detection by taking the plasma as a sample is met.
The present invention will be described in more detail with reference to the following examples.
Detailed Description
Example 1, this example is a method for rapidly detecting phosphorus flame retardants and their degradation products in plasma, and after removing lipid substances in plasma, the method employs a triple quadrupole liquid chromatography-mass spectrometer for detection, which is fast and has few steps.
The method comprises the following specific steps:
1) sample pretreatment:
adding 800 μ L acetonitrile (containing 1% formic acid (volume ratio)) into 1ml PLPIME HLB column, adding 200 μ L blood plasma to be detected, mixing completely in the column, allowing it to drip naturally under the action of gravity, collecting filtrate, and directly introducing the filtrate into triple quadrupole rod liquid mass spectrometer (LC-MS/MS) system;
2) detecting by using a liquid chromatogram-triple quadrupole liquid chromatograph-mass spectrometer: the specific conditions of the apparatus are as follows:
the instrument model is as follows: -Agilent 1260-; the column temperature is 35 ℃; the sample amount was 10. mu.L, the mobile phase was methanol (A) and 0.005mol/L ammonium acetate solution (B), and the flow rate of the mobile phase was 250. mu.L/min. The gradients are shown in Table 1.
TABLE 1 gradient elution of mobile phase
Mass spectrum conditions:
electrospray ionization source (ESI); multiple reaction monitoring mode (MRM); the ion source temperature is 550 ℃; ion source ionization mode: except DEPHA is Negative, the other objects are Positive;
capillary voltage is 3500V, atomizer pressure is 45psi, carrier gas is high-purity nitrogen, carrier gas temperature is 330 deg.C, flow rate is 9.5L/min, and concentration of analyte is 500 μ g/L by multi-reaction monitoring mode (MRM). The parent and daughter ions for each compound were determined from the total ion flow plot and corresponding mass spectrogram results, and the Collision Energy (CE) and declustering voltage (DP) were optimized for the response, with each analyte ion and collision being shown in table 2.
TABLE 2 ESI-MS/MS time, monitoring ions, input voltage, Collision energy
3) Drawing a standard curve: the target sample used for the instrumental analysis in the experiment contained 21 phosphorus-based flame retardants and 3 metabolites, trimethyl phosphate (TMP), di-n-butyl phosphate (DBP), triethyl phosphate (TEP), diethyl phosphate (DEP), tris (2-chloroethyl) phosphate (TCEP), tripropyl phosphate (TPP), tris (1, 3-dichloroisopropyl) phosphate (TDCPP), triisopropyl phosphate (TrP), triphenylphosphine oxide (TPPO), tris- (2-chloroisopropyl) phosphate (TCIPP), bis (2-ethylhexyl) phosphate (DEPHA), triphenyl phosphate (TPHP), tributyl phosphate (TPP), diphenylcresyl phosphate (TBP), triisobutyl phosphate (TIBP), tris (2-butoxyethyl) phosphate (OEP), tri-m-cresyl phosphate (TMCP), 2-ethylhexyl diphenyl phosphate (DPP), Tri-n-pentyl phosphoric acid (TPeP), trioctyl phosphate (TEHP), resorcinol tetraphenyl phosphate(RDP) 21 phosphorus flame retardants, bis (2-butoxyethyl) -2- (3-hydroxybutoxy) ethyl phosphotriester (BHEPT), bis (2-butoxyethyl) -2-hydroxyethyl phosphotriester (BHP), bis (butoxyethyl) phosphate (BBP)3 tris (2-butoxyethyl) phosphate (TBOEP) phosphorus flame retardant degradation products, Using Tri-n-butyl phosphate-d27(TBP-d27) Tris (2-butoxyethyl) phosphate-d27(TBOEP-d27) Trimethyl phosphate-C as an indicator for internal standards for standard substitutes13（TMP- C13) As an internal standard, standard curves of the target were prepared at concentrations of 2, 5, 10, 50, 100, 500. mu.g/L.
TABLE 3 target retention time, working curve equation, correlation coefficient for the method of the invention
4) The method is blank: when samples are processed, a blank sample is inserted into each batch of experiments, ultrapure water is used for replacing the samples, the same processing steps as the samples are carried out, and computer measurement is carried out, so that the interference of components to be measured in the experimental process environment is avoided.
5) The method has the advantages of simple operation, reduced interference of protein and lipid, simple process, shortened experimental period, reduced workload of experimenters, optimal extraction effect while saving reagent as much as possible, and high recovery rate and data accuracy.
The principal features, principles and advantages of the invention have been shown and described above. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The appended claims and their equivalents define the scope of the invention which is claimed.
Claims (2)
1. A method for rapidly detecting phosphorus flame retardants and degradation products thereof in blood plasma is characterized by comprising the following steps: the method comprises the following steps:
step S1, sample preprocessing step; this step removes lipid materials from the plasma;
step S2, performing liquid chromatography detection on the pretreated sample; the method comprises the following steps:
the chromatographic column is; the column temperature is 35 ℃; the sample amount is 10 mu L, the mobile phase is methanol and 0.005mol/L ammonium acetate solution, and the flow rate of the mobile phase is 250 mu L/min; the gradient is as follows:
mass spectrum conditions: an electrospray ionization source; a multiple reaction monitoring mode; the ion source temperature is 550 ℃; ion source ionization mode: except DEPHA is Negative, the other objects are Positive;
the capillary voltage is 3500V, the atomizer pressure is 45psi, the carrier gas is high-purity nitrogen, the carrier gas temperature is 330 ℃, the flow rate is 9.5L/min, the concentration of the analytes is 500 mug/L by detecting with a multi-reaction monitoring mode (MRM);
determining parent ions and ionic ions of each compound through a total ion flow diagram and a corresponding mass spectrogram result, and optimizing collision energy and declustering voltage according to response conditions.
2. The method for rapidly detecting the phosphorus flame retardant and the degradation products thereof in the plasma according to claim 1, wherein the method comprises the following steps: in step S1, lipid substances in plasma are removed by the following method:
taking a mixture of acetonitrile and formic acid with the volume of 4 times of the volume of the blood plasma to be detected, and adding the mixture into a 1mLPRiME HLB column, wherein: the content of the mixed solution of acetonitrile and formic acid is 1 percent;
adding blood plasma to be detected;
performing 1ml of mixed RiME HLB column;
naturally dripping under the action of gravity, and collecting filtrate.
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Cited By (1)
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Inventor after: Zhu Tingting Inventor after: Dai Zhiguang Inventor after: Jin Xingliang Inventor after: Deng Chen Inventor after: Xie Linshen Inventor after: Hu Rong Inventor after: Wang Jinling Inventor after: Qi Xiujuan Inventor after: Chen Jianyi Inventor after: Shen Zhizhi Inventor after: Li Wei Inventor before: Deng Chen Inventor before: Dai Zhiguang Inventor before: Jin Xingliang Inventor before: Zhu Tingting Inventor before: Xie Linshen Inventor before: Hu Rong Inventor before: Wang Jinling Inventor before: Qi Xiujuan Inventor before: Chen Jianyi Inventor before: Shen Zhizhi Inventor before: Li Wei |
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Application publication date: 20210326 |