CN116338069A - Organic phosphate high-throughput suspected target analysis method - Google Patents
Organic phosphate high-throughput suspected target analysis method Download PDFInfo
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 92
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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
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Abstract
The method for analyzing the organic phosphate high-throughput suspected target comprises the steps of extracting and enriching organic phosphate contained in a sample to obtain a sample extracting solution; analyzing the sample extracting solution by using an ultra-high performance liquid chromatography-high resolution mass spectrometer to obtain high resolution mass spectrum data; and processing the acquired high-resolution mass spectrum data by combining a pre-established suspected target screening database of the organic phosphate and a set screening and filtering standard, and identifying and determining the specific type of the organic phosphate in the sample. According to the invention, a suspected target screening database containing at least 101 organic phosphates is established through a literature retrieval and prediction method, and the acquired high-resolution mass spectrum data is analyzed by combining a set screening and filtering standard, so that the high-throughput rapid identification of the at least 101 organic phosphates in a sample can be realized, and the technical defects in the prior art are overcome.
Description
Technical Field
The invention relates to the field of organic phosphate detection and analysis, in particular to an organic phosphate suspected target analysis and detection method, an organic phosphate suspected target analysis and detection system and application.
Background
Organic phosphate (Organophosphate esters, OPEs) is a class of artificially synthesized phosphoric acid derivatives, mainly used as flame retardants and plasticizers, and widely applied to industries such as electronic products, building materials, furniture, textiles, plastics, food packaging and the like. With the sequential supplementation of traditional brominated flame retardants such as polybrominated diphenyl ether and hexabromocyclododecane to the Stockholm convention, the production and use thereof are regulated, and the global yield and use amount of OPEs are rapidly increased. The global consumption of OPEs has risen from 18.6 ten thousand tons in 2001 to 100 ten thousand tons in 2018. China is one of the main countries for the production of organophosphorus flame retardants, and the 2014 annual yield is 14.2 ten thousand tons, 2020 increases to 29.4 ten thousand tons. OPEs are used as industrial additive type auxiliary agents, have no chemical bonding with high polymer materials, are easy to enter the environment through volatilization, abrasion and other modes, and are enriched in organisms. OPEs are widely present in all types of environmental media and organisms worldwide, and have become a new class of pollutants of global interest.
Currently, research directed to OPEs is focused primarily on target analysis. The disadvantage of target analysis is that a standard is required and fewer types and numbers of OPEs can be included. In addition, the target analysis method has the defects of poor aging, high cost and the like. In recent years, high Resolution mass spectrometry (High Resolution MassSpectrometers, HRMS) has been developed rapidly, and has a faster analysis speed (scanning frequency: 1: hz), a higher Resolution (: 20000), and a higher mass-to-charge ratio accuracy (deviation: 1 ppm). Therefore, HRMS-based suspected target (Non-target screening) and Non-target (Non-target screening) analysis methods are powerful tools for the discovery and screening of new pollutants in the environment. Therefore, there is a need to develop HRMS-based suspected target or non-target analysis methods to screen for contamination conditions that identify OPEs in a sample at high throughput.
Disclosure of Invention
Accordingly, the present invention is directed to a method, a system and an application for detecting suspected targets of organic phosphate esters, which aim to at least partially solve the above-mentioned problems.
In order to achieve the above object, as a first aspect of the present invention, a method for detecting a suspected target of an organic phosphate is provided, comprising the steps of:
extracting and enriching organic phosphate contained in a sample to obtain a sample extracting solution;
analyzing the sample extracting solution by using an ultra-high performance liquid chromatography-high resolution mass spectrometer to obtain high resolution mass spectrum data;
and carrying out data processing on the acquired high-resolution mass spectrum data by combining a pre-established suspected target screening database of the organic phosphate and a set screening and filtering standard, and identifying and determining the specific type of the organic phosphate in the sample.
As a second aspect of the present invention, there is also provided an organophosphate suspected target analysis detection system, comprising:
the storage unit is used for storing a pre-established suspected target screening database of the organic phosphate;
and the processing unit is used for carrying out data processing and analysis on the high-resolution mass spectrum data of the acquired sample by combining the set screening and filtering standard based on the suspected target screening database of the organic phosphate stored in the storage unit, so that the types of organic phosphate contained in the sample are detected and analyzed.
As a third aspect of the invention, the invention also provides an application of the method for detecting the suspected target analysis of the organic phosphate in the detection of the organic phosphate residue of the solid sample.
Based on the above scheme, the analysis and detection method, system and application of the invention have at least one of the following advantages compared with the prior art:
the method of the invention uses an optimized dispersion solid-phase extraction method to pretreat OPEs in the sample. The method is characterized by simplicity, rapidness and high efficiency, and can keep original OPEs pollutants in the sample as much as possible on the premise of eliminating the interference of the environment matrix;
the invention carries out suspected target analysis on the high-resolution data collected by the ultra-high performance liquid chromatography-high resolution mass spectrometer under the full-scan and full-ion fragmentation scan modes based on the constructed suspected target screening database containing 101 organic phosphate, can realize high-throughput screening on 101 OPEs in a sample under the condition of no standard, greatly improves the detection speed and efficiency and reduces the detection cost;
the suspected target screening database of 101 organic phosphate constructed by the invention has the advantages that when the existing literature and the related mass spectrum database lack some OPEs fragment ions, the ion fragmentation software is utilized to predict and supplement the fragment ions, so that the confidence coefficient when the mass spectrum information of the actual sample is matched with the self-built spectrum library information is improved.
Drawings
FIG. 1 is a flow diagram of a method for the detection of organophosphate suspected target analysis according to the present invention;
FIG. 2 is a detailed flow chart of a method of the invention for suspected target analysis of organophosphates.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The suspected target analysis method is to construct a chemical list containing information such as accurate mass number, element composition, pre-ions, secondary fragments and the like of the compound based on prior information such as literature reports, public databases and the like, and identify suspected chemicals in a sample by using a software matching algorithm and screening and filtering criteria. The High Resolution mass spectrum (High Resolution MassSpectrometers, HRMS) has the advantages of higher analysis speed (scanning frequency is more than or equal to 1 Hz), higher Resolution (more than or equal to 20000), higher mass-to-charge ratio accuracy (deviation is less than or equal to 1 ppm) and the like. Therefore, HRMS-based suspected target (screening) analysis methods are powerful tools for the discovery and screening of new pollutants in the environment.
However, the target analysis method in the prior art has the defects of limited variety and quantity of OPEs, poor timeliness, high cost and the like, and the invention provides a suspected target analysis method for screening and identifying OPEs in a sample at high throughput. Where N varies by at least 101 according to the network gathering data and the original predictive data.
Compared with the pretreatment of OPEs target analysis, the pretreatment of OPEs high-throughput suspected target analysis is more important to the overall effective extraction of original OPEs pollutants in a sample on the premise of eliminating the interference of an environmental matrix. However, the discrete physicochemical properties of the mixed chemicals in the sample and the matrix effect of the sample itself present challenges to the overall efficient extraction and purification of OPEs based contaminants. Furthermore, the physicochemical properties of the OPEs of different structural types are greatly different, such as Trimethylphosphate (TMP) belonging to strongly polar and volatile OPE monomers (logkow= -0.65, vp=8×10 -1 torr), whereas TEHP is a non-polar and poorly volatile OPE monomer (log kow=9.5, vp=8×10) -8 torr) also presents difficulties in the overall efficient extraction and purification of the OPEs of different structural types in the sample. The QuEChERS method is used as a novel sample pretreatment technology, is applied to pretreatment of pesticide residues, medicines, personal care products, perfluorinated compounds and the like in complex sample matrixes, and can realize better extraction efficiency and purification effect. The pretreatment method for dispersion solid phase extraction, enrichment and purification of OPEs pollutants in complex samples is optimized based on the QuEChERS principle. And (3) performing marking recovery rate verification by using OPEs of the existing standard substances through an optimized pretreatment method. The sample labeling recovery rate range of 19 target OPEs (10 ng) of three structural types is 61-121%, and the requirement of effectively extracting OPEs in a complex sample is met.
In addition, how to pertinently build a suspected target screening database during the suspected target analysis is a technical difficulty in screening ops in a sample with high throughput. According to the invention, firstly, a suspected list of 101 OPEs is compiled according to the previous literature and pubchem, chemspider database in the Web of Science core collection, and the secondary fragment information of 49 OPEs is supplemented according to the literature, massBank, mzCloud, MS-Dial and other spectrogram databases. For 52 OPEs for which secondary fragment information is not available in spectrogram databases such as literature and MassBank, mzCloud, MS-Dial, for example, software (Mass front 8) can be used to predict their secondary fragments. After the Structure window of the Mass front 8 software Newfragments & Mechanisms module inputs the compound structural formula, the software predicts all secondary fragments that the compound may generate according to the built-in reaction mechanism library. Based on the structural characteristics of the OPEs using phosphoric acid as a core skeleton, the inventors innovatively selected phosphate ions (m/z= 98.98417) and dehydrated forms thereof (phosphite ions, m/z= 80.97361) as fragmentation endpoints, and filled all fragment ions generated in the fragmentation path that generated the phosphate ions and dehydrated forms thereof into the list, thereby realizing a new ion fragment prediction method. In order to ensure the accuracy of prediction, the method can be used for verifying the fragment ions obtained by the existing standard substance in a Full MS-DDA mode (three collision energies are set to be 20, 40 and 60ev respectively), and the prediction can be considered to be accurate when the number of the fragment ion matches is more than or equal to 3. The results show that the matching degree of the actual fragment ions generated by the standard substance under certain conditions by high-resolution Mass spectrum and the fragment ions obtained by Mass front 8 prediction is good (table 1). Finally, a screening database and screening filter criteria are established using data processing software (e.g., tracefilter 4.1) for high resolution mass spectrometry data resolution and screening matching, with better screening efficiency and better reproducibility than manual screening data.
According to the invention, ion fragmentation software is used for predicting the secondary mass spectrum fragment information of some OPEs, so that the defect that part of the secondary mass spectrum information of OPEs is lacking in the literature and public databases is overcome, and the screening and identification efficiency, accuracy and confidence are improved.
Table 1 shows the matching of the secondary fragments of 19 OPEs standards with the predicted fragment ions of Mass front
Specifically, the invention discloses a suspected target analysis and detection method of organic phosphate, which comprises the following steps:
extracting and enriching organic phosphate contained in a sample to obtain a sample extracting solution;
analyzing the sample extracting solution by using an ultra-high performance liquid chromatography-high resolution mass spectrometer to obtain high resolution mass spectrum data;
and carrying out data processing on the acquired high-resolution mass spectrum data by combining a pre-established suspected target screening database of the organic phosphate and a set screening and filtering standard, and identifying and determining the specific type of the organic phosphate in the sample.
Wherein the extraction and enrichment steps can be realized by a dispersion solid phase extraction method, for example.
In the extraction and enrichment step, acetonitrile/toluene (v: v=9:1) extracting solution containing 0.1% formic acid is used for extracting and enriching organic phosphate contained in a sample, and ethylenediamine-N-propyl silane is used for purifying and removing impurities from the sample extracting solution.
Wherein, when the ultra-high performance liquid chromatography-high resolution mass spectrometer is used for measuring the organic phosphate, the Acclaim ™ C18 chromatographic column (2.1 mm multiplied by 100 mm,2.2 μm) is used for chromatographic separation.
Wherein the chromatographic separation of the organic phosphate is carried out by gradient elution by using binary mobile phases of methanol and water (0.1% formic acid is added in each case in a volume ratio v/v).
When the ultra-high performance liquid chromatography-high resolution mass spectrometer is used for measuring organic phosphate, an electrospray ionization source (Electron Spray Ionization, ESI) is adopted to analyze the sample extracting solution in a full-scan and full-ion fragmentation scanning mode under the positive ion condition, so that high resolution mass spectrum data are obtained.
The organic phosphate suspected target screening database comprises information of chemical names, chemical formulas, precise mass numbers of primary parent ions, ionization modes and precise mass numbers of secondary fragment ions of organic phosphate.
And in the organic phosphate suspected target screening database, the types of the organic phosphate are at least 101 or more.
Wherein fragment ion information of the organic phosphate is obtained through the existing literature and a Pubchem, massBank, mzCloud, MS-Dial spectrogram database; for the organic phosphate secondary fragment information which cannot be obtained from the existing literature and spectrogram database, carrying out fragmentation prediction by using a prediction method; wherein, the prediction method comprises the following steps: cleavage rules in terms of mass spectrometry cleavage in mass spectrometry publications are collected and used in combination with the structure of the compound to predict the cleavage pathways and fragment ions of the compound.
The prediction method selects phosphate ions and phosphite ions in a dehydrated form thereof as fragmentation end points, and fills all fragment ions generated in a cleavage path for generating the phosphate ions and the phosphite ions in the dehydrated form thereof into the suspected target screening database of the organic phosphate as predicted fragment ion information of the corresponding organic phosphate.
When the ultra-high performance liquid chromatography-high resolution mass spectrometer is used for measuring the organic phosphate, the high resolution mass spectrometer is used for analyzing the standard products of the known organic phosphate in a first-stage full-scanning mode and a second-stage data dependency scanning mode, the first-stage and second-stage mass spectrum information is obtained, the obtained second-stage fragment information is matched and compared with the second-stage fragments predicted by the prediction method, and when the matching number is more than or equal to 3, the prediction is considered to be accurate.
In the step of carrying out data processing on the obtained high-resolution mass spectrum data and identifying and determining the specific types of the organic phosphate in the sample, the data processing software compares and screens the obtained high-resolution mass spectrum data with a pre-established organic phosphate suspected target screening database, and the screening and filtering items are primary and secondary accurate mass numbers and isotope distribution modes; after deconvolution processing is carried out on the acquired high-resolution mass spectrum data, single compound spectrogram information is rapidly separated and extracted from a plurality of superimposed spectrograms, interference and background ions are removed, and therefore relatively pure compound mass spectrum and chromatographic information are obtained; and meanwhile, the data processing software also carries out retrieval comparison on the mass spectrum and chromatographic information of the compound obtained by deconvolution and a pre-established suspected target screening database of the organic phosphate, and carries out qualitative identification on the organic phosphate in the sample according to a screening filtering item.
The invention also discloses an organic phosphate suspected target analysis and detection system, which comprises:
the storage unit is used for storing a pre-established suspected target screening database of the organic phosphate;
and the processing unit is used for carrying out data processing and analysis on the high-resolution mass spectrum data of the acquired sample by combining the set screening and filtering standard based on the suspected target screening database of the organic phosphate stored in the storage unit, so that the types of organic phosphate contained in the sample are detected and analyzed.
The organic phosphate suspected target analysis and detection system is a desktop computer, a notebook computer, a server, a singlechip, a single-board computer, a Programmable Logic Controller (PLC), an FPGA and the like which can execute data operation processing.
The organic phosphate suspected target screening database comprises information of chemical names, chemical formulas, precise mass numbers of primary parent ions, ionization modes and precise mass numbers of secondary fragment ions of organic phosphate.
And in the organic phosphate suspected target screening database, the types of the organic phosphate are at least 101 or more.
The invention also discloses application of the organic phosphate suspected target analysis and detection method in detection of organic phosphate residues of solid samples.
In one embodiment, as shown in fig. 1, the invention discloses a suspected target analysis detection method for screening and identifying organic phosphate in a sample, which comprises the following steps:
(1) Extracting, enriching, purifying and concentrating OPEs contained in the sample to a constant volume by using dispersed solid phase extraction;
(2) And analyzing the sample extracting solution under the full-scanning and full-ion fragmentation scanning modes by using an ultra-high performance liquid chromatography-high resolution mass spectrometer to obtain high resolution mass spectrum data.
(3) Digging and analyzing the acquired high-resolution data by combining a set screening and filtering standard based on a pre-established suspected target screening database of N organic phosphate; the pre-established suspected target screening database of the N organic phosphate comprises information of compound names, chemical formulas, primary parent ion accurate mass numbers, addition modes and secondary fragment ion accurate mass numbers of OPEs; n is at least 101.
The samples in the step (1) can be sediment and soil in an environment medium, biological samples such as plants, animals and the like, and various food samples, wherein the food samples comprise solid or semisolid samples such as vegetables, fruits, meats, aquatic products and the like which can be eaten by human beings.
Among them, the dispersion solid phase extraction solvent used in the above step (1) may be, for example, acetonitrile/toluene (v: v=9:1) extract containing 0.1% formic acid. Since the differences of the physical and chemical characteristics such as octanol-water distribution coefficient (log Kow) and solubility of OPEs related to the invention are large, the inventor repeatedly tests that acetonitrile/toluene (v: v=9:1) containing 0.1% formic acid is an extract, the recovery rate of OPEs is high and is less influenced by a matrix, so that acetonitrile/toluene (v: v=9:1) containing 0.1% formic acid is selected as the extract.
Among them, the dispersed solid phase extraction adsorbent used in the step (1) may be ethylenediamine-N-propylsilane (primarysecondary amine, PSA), for example. PSA is a high purity silica gel matrix type polar adsorbent containing both primary and secondary amine groups, which has a polar effect and a weak anion exchange effect, and can effectively remove many polar matrix components, such as organic acids, some polar pigments and glycolipids, from a sample. The PSA can effectively separate the analyte (OPEs) from the interfering components, shortens the sample pretreatment process, and is convenient to operate, time-saving and labor-saving. Through repeated experiments of the inventor, the PSA purification is adopted, so that different impurities such as fatty acid, saccharide and the like in a sample can be removed, the adsorption effect on OPEs is small, the average recovery rate is high, and the purification effect is obvious.
Wherein, in the step (2), the ultra performance liquid chromatography-high resolution mass spectrometer is used for chromatographic separation, for example, by using an Acclaim ™ C18 chromatographic column (2.1 mm ×100 mm,2.2 μm) at a constant temperature of 40 ℃ when measuring OPEs. The Acclaim ™ C18 liquid chromatographic column has the advantages of excellent peak type to alkaline compounds under a formic acid system, and is particularly suitable for separating OPEs organic alkali compounds.
It is further preferred that the gradient elution is performed with a binary mobile phase of methanol and water added with 0.1% formic acid (v/v).
Further preferably, the sample extract is analyzed in Full scan (Full mass) and Full ion fragmentation scan modes under positive ion conditions of an electrospray Ionization source (ESI, electronSpray Ionization) to obtain high resolution mass spectrometry data. The full ion fragmentation scanning mode (All Ion Fragmentation, AIF) adopts a full spectrum fragmentation mode in the source so as to collect the fragment information of all compounds, thereby being beneficial to the comprehensive identification of OPEs.
When the suspected target screening database containing N organic phosphate esters is established in the step (3), a suspected list compound list of at least 101 OPEs is compiled, for example, according to the previous literature in the Web of Science core collection and pubchem, chemspider database, and compound names, chemical formulas, precise mass numbers, addition modes and polarity information of at least 101 OPEs are obtained.
Further preferably, the secondary fragmentation information of 49 OPEs is supplemented according to the spectrogram database of literature and MassBank, mzCloud, MS-Dial, etc.: for OPEs for which no secondary fragmentation information is available in the spectrogram databases of literature and MassBank, mzCloud, MS-Dial, their secondary fragments are predicted using Massfront 8 software (Thermo Fisher Scientific).
Further preferably, a suspected target screening database containing at least 101 organophosphates is built using the tracefilter version 4.1 software compundabase function, covering all information on compound name, chemical formula, exact mass, addition pattern, polarity and fragment ion of suspected OPEs.
Wherein, in the step (3), screening filtration criteria are set by using, for example, tracefilter version 4.1 software Method Development function, and screening filtration criteria are exact mass, isotope pattern and fragment ion. The TraceFinder4.1 software can automatically generate corresponding isotope pattern theoretical information according to the chemical formula of the compound, then compare the measured value with the isotope pattern theoretical information, and give corresponding scores according to the matching degree; the secondary mass spectrum of the sample can also be compared with fragment ions in a database. According to European Union standard 2002/657/EC, the high-resolution qualitative method can be characterized by matching only the parent ion with 1 child ion. If the deviation range set by the screening and filtering standard is met, determining that the sample contains the substance; if the set deviation range is not satisfied, the sample does not contain the substance; the setting of the magnitude of the deviation of each parameter in the screening filtration criteria directly affects the results of the qualitative analysis. If the deviation range is set too large, the false positive rate is high, and the data size is increased sharply; if the deviation range is set too small, the false negative rate is increased, and the detection is missed. After repeated optimization and summarization by the inventor, the final screening and filtering standard is set as follows: the mass deviation of both MS and MS/MS data was set to 5ppm; selecting a peak with a signal to noise ratio >5 and a peak intensity above 10,000; the allowable intensity deviation of the isotope mode is set to 25%, and the isotope mode comprehensive comparison scoring threshold is set to 75%; the number of the matched fragments is more than or equal to 1.
Further preferably, after the high-resolution data is automatically processed by using the traceFinder4.1 version of software to generate a screening result, the Chromatogram and Spectrum functions are selected in the traceFinder4.1 version of software to manually check the Chromatogram of each OPE, the isotope pattern matching result and the matching result of the secondary fragments, so that the accuracy is improved.
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited thereto. It will be apparent that the embodiments described hereinafter are only some, but not all, embodiments of the invention; all embodiments obtained by a person of ordinary skill in the art without making any inventive effort, based on the following embodiments of the present invention, are within the scope of the present invention.
The specific method used in the following examples is a method for high-throughput suspected target analysis of organic phosphate, comprising the steps of:
extracting and enriching OPEs contained in the sample by using dispersion solid phase extraction, purifying and concentrating to fix the volume;
establishing a suspected target screening database containing 101 OPEs, and covering the information of the compound names, chemical formulas, accurate masses, addition modes, polarities and fragment ions of all the suspected OPEs;
and analyzing the sample extracting solution under the full-scanning and full-ion fragmentation scanning modes by using an ultra-high performance liquid chromatography-high resolution mass spectrometer to obtain high resolution mass spectrum data.
And mining and analyzing the acquired high-resolution data by combining the set screening and filtering standard based on the established suspected target screening database of 101 OPEs.
The extract of the dispersed solid phase extraction was acetonitrile/toluene of 0.1% formic acid (v: v=9:1), three times 0.1% formic acid acetonitrile/toluene (v: v=9:1), ultrasonic assisted extraction (twice, 15 min each) and centrifugation at 4000r/min for 5min with a centrifuge, and the supernatant was collected.
The enrichment and purification of the target by the dispersed solid phase extraction uses 100 mg PSA as an adsorbent to the pre-concentrated extract (about 2 mL), vortexed for 1min to mix well, centrifuged for 5min at 120000 r/min with a centrifuge, and the supernatant transferred to a clean corning centrifuge tube.
The purified supernatant is slowly blown to near dryness by using soft nitrogen flow after concentration and volume fixing, and is re-contained by using 1 mL methanol.
The partial information of the corresponding OPEs in the suspected target screening database of the 101 OPEs is shown in table 2.
Table 2 suspicious screening list of 101 OPEs
The conditions of the ultra-high performance liquid chromatography-high resolution mass spectrum are as follows:
ultra-high performance liquid chromatography-high resolution mass spectrometer: vanquish Flex UHPLC-Q-Orbitrap Exploris HRMS (ThermoFisher scientific).
OPEs chromatographic separation conditions are:
the column was an Acclaim ™ C18 column (2.1 mm. Times.100 mm,2.2 μm); column temperature: 40 ℃; mobile phase: a-ultrapure water containing 0.1% of formic acid, B-methanol containing 0.1%; flow rate: 0.4mL/min; the sample injection volume is 5 mu L; mobile phase gradient change: 10% B continues for 2min, increasing to 65% B at 5.5min, increasing to 80% B at 9.5 min, increasing to 100% B at 10.5min and holding for 7min, ending at 10% B to 21 min within 1 min.
Mass spectral parameters measured by OPEs:
ion source: ESI; ionization mode: a positive ion mode; sheath air pressure: 40 an arb; auxiliary air pressure: 25arb; the ion source temperature and the atomizer temperature are both 350 ℃; resolution ratio: fullMS and AIF are 60000FWHM; scanning range Full MS 100-1100 m/z, AIF100-1100 m/z; the acquisition mode is FullMass-AIF mode; the ion source is ESI; the ion spray voltage is 3500V; the collision energies were set at 20, 40 and 60ev.
The screening and filtering standard is as follows:
the mass deviation of both MS and MS/MS data was set to 5 ppm. Selecting a peak with a signal to noise ratio >5 and a peak intensity above 10,000; the allowable intensity deviation of the isotope mode is set to 25%, and the isotope mode comprehensive comparison scoring threshold is set to 75%; the number of the matched fragments is more than or equal to 1.
Example 1
The embodiment 1 of the invention provides a suspected target analysis method for screening and identifying organic phosphate in a sample by high throughput, which is used for screening suspected targets of OPEs in a mussel sample in Zhejiang and Xanthan city, and comprises the following steps:
(1) Sample pretreatment: accurately weighing 1 g mussel sample (dry weight) and adding the sample into a 15 mL centrifuge tube, then adding 5 mL acetonitrile/toluene (v: v=9:1) extract containing 0.1% formic acid, and swirling for 1min to allow complete mixing. After ultrasonic extraction for 15 min, the mixture was centrifuged at 4000r/min for 5min with a centrifuge, and the supernatant was collected. Repeating the above steps for three times, and mixing the extractive solutions. The combined extracts were concentrated to 2 mL with a nitrogen blower. To the sample concentrate was added 100 mg of PSA and vortexed for 1min to mix. After centrifugation at 120000 r/min for 5min with a centrifuge, the supernatant was transferred to a clean corning tube. The purified supernatant was slowly blown to near dryness with a nitrogen blower and the volume was fixed with 1 mL methanol. Prior to loading, samples were centrifuged at 120000 r/min for 5min with a high speed centrifuge and the supernatant was removed to about 0.5 mL for on-press analysis.
(2) Instrument measurement and data screening:
mussel sample extracts were analyzed by injection in the mode of Full MS-AIF under a UHPLC-Orbitrap HRMS instrument.
And comparing the acquired high-resolution data with an established suspected target screening database containing 101 OPEs by using TraceFinder version 4.1 software, and screening the acquired high-resolution data by combining with a set screening filtration standard. And (3) establishing a sequence in the TraceFinder4.1 software, importing the original data of the analysis sample, and automatically identifying and generating a result by the software according to the established method principle after submitting the sequence to the analysis sample by choosing the analysis sample. The analysis result shows the matched material information, the matched fragment results meeting the screening conditions are all selected, the Chromatogram and Spectrum functions are selected in the traceFinder version 4.1 software to check the chromatographic and mass Spectrum information of each OPE, the secondary fragment matching condition is checked, the matched results are reserved, and finally the identification list of the OPEs is obtained. In example 1 of the present invention, 31 OPEs were identified, including 19 OPEs with standard and 12 OPEs without standard. The identification list includes the identified OPEs molecular formula, mass-to-charge ratio, retention time, ionization profile, adduction mode, and confidence level, as shown in Table 3, where 16 were confirmed with the standard (confidence level of 1) and 15 were confirmed by the characteristic ion, primary and secondary spectra (confidence level of 3).
Table 3 shows information on OPEs identified in mussel samples
Example 2
The embodiment 2 of the invention provides a suspected target analysis method for screening and identifying organic phosphate in a sample by high throughput, which is used for screening suspected targets of OPEs in a shrimp sample in a Longwan area of the city of Wittia in Zhejiang province.
The procedure is essentially the same as in example 1, and a total of 32 OPEs were identified in example 2 of the invention, including 16 OPEs with standard and 16 OPEs without standard. The identification list includes the identified OPEs molecular formula, mass-to-charge ratio, retention time, ionization profile, adduction mode, and confidence level, as shown in Table 4, where 16 were confirmed with the standard (confidence level of 1) and 16 were confirmed by the characteristic ion, primary and secondary spectra (confidence level of 3).
Table 4 shows the OPEs information identified in the shrimp sample
Example 3
The embodiment 3 of the invention provides a suspected target analysis method for screening and identifying organic phosphate in a sample by high throughput, which is used for screening suspected targets of OPEs in yellow croaker samples of Wen Lingshi Zhejiang province.
The procedure is essentially the same as in example 1, and a total of 28 OPEs were identified in example 3 of the invention, including 16 OPEs with standard and 12 OPEs without standard. The identification list includes the identified OPEs molecular formula, mass-to-charge ratio, retention time, ionization mode, adduction mode, confidence level, etc., as shown in Table 5, where 16 were confirmed with standard (confidence level of 1) and 12 were confirmed by characteristic ion, primary and secondary spectra (confidence level of 3).
Table 5 shows the OPEs information identified in yellow croaker samples
According to the embodiment, the method provided by the invention has the characteristics of rapidness and high flux, can realize the efficient identification of at least 101 organic phosphates, provides effective technical support for risk management, and has wide application prospects.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. A method for the suspected target analysis and detection of organic phosphate esters, comprising the steps of:
extracting and enriching organic phosphate contained in a sample to obtain a sample extracting solution;
analyzing the sample extracting solution by using an ultra-high performance liquid chromatography-high resolution mass spectrometer to obtain high resolution mass spectrum data;
carrying out data processing on the acquired high-resolution mass spectrum data by combining a pre-established suspected target screening database of the organic phosphate and a set screening and filtering standard, and identifying and determining the specific type of the organic phosphate in the sample; the organic phosphate suspected target screening database comprises information of chemical names, chemical formulas, precise mass numbers of primary parent ions, ionization modes and precise mass numbers of secondary fragment ions of organic phosphate; and fragment ion information of the organic phosphate is obtained through the existing literature and Pubchem, massBank, mzCloud, MS-Dial spectrogram database, and a prediction method is used for predicting fragmentation of the organic phosphate secondary fragment information which cannot be obtained from the existing literature and spectrogram database;
wherein, the prediction method comprises the following steps:
collecting cleavage rules in mass spectrum cleavage in mass spectrum publications, and predicting cleavage paths and fragment ions of the compounds by utilizing the rules in combination with the structure of the compounds; and
for organic phosphate, the prediction method selects phosphate ions and phosphite ions in dehydrated form thereof as fragmentation end points, and fills all fragment ions generated in the cleavage paths generating phosphate ions and phosphite ions in dehydrated form thereof into the organic phosphate suspected target screening database as predicted fragment ion information of the corresponding organic phosphate.
2. The method of claim 1, wherein the extracting and enriching steps are accomplished using a dispersed solid phase extraction method; and/or
In the extracting and enriching step, acetonitrile/toluene extracting solution containing 0.1% formic acid is used for extracting and enriching organic phosphate contained in a sample, and ethylenediamine-N-propyl silane is used for purifying and removing impurities from the sample extracting solution; wherein, the volume ratio of acetonitrile to toluene in the acetonitrile/toluene extracting solution is 9:1.
3. The method according to claim 1, wherein the ultra performance liquid chromatography-high resolution mass spectrometer is used for chromatographic separation using an Acclaim ™ c18 chromatographic column, the Acclaim ™ c18 chromatographic column having a specification of 2.1mm x 100 mm,2.2 μm, when measuring the organophosphate.
4. A method according to claim 3, characterized in that the chromatographic separation of the organic phosphate is carried out using a binary mobile phase of methanol and water, both of which are added with 0.1% by volume of formic acid, for gradient elution.
5. The method according to claim 1, wherein the ultra-high performance liquid chromatography-high resolution mass spectrometer is used for analyzing the sample extract by using an electrospray ionization source ESI in a full-scan and full-ion fragmentation scanning mode under positive ion conditions to obtain high resolution mass spectrum data when measuring organic phosphate; and/or
And in the organic phosphate suspected target screening database, the types of the organic phosphate are at least more than or equal to 101.
6. The method according to claim 5, wherein the ultra-high performance liquid chromatography-high resolution mass spectrometer is used for analyzing standard substances of known organic phosphate esters in a first-stage full-scan mode and a second-stage data-dependent scan mode by using the high resolution mass spectrometer when measuring the organic phosphate esters, obtaining first-stage and second-stage mass spectrum information, and carrying out matching comparison on the obtained second-stage fragment information and the second-stage fragment predicted by the prediction method, wherein the prediction is considered to be accurate when the number of matches is more than or equal to 3.
7. The method according to claim 1, wherein in the step of performing data processing on the acquired high-resolution mass spectrum data to identify and determine specific types of organic phosphate in the sample, the data processing software performs comparison screening on the acquired high-resolution mass spectrum data with a pre-established suspected target screening database of organic phosphate, and screening filtering terms are primary and secondary accurate mass numbers and isotope distribution patterns; after deconvolution processing is carried out on the acquired high-resolution mass spectrum data, single compound spectrogram information is rapidly separated and extracted from a plurality of superimposed spectrograms, interference and background ions are removed, and therefore relatively pure compound mass spectrum and chromatographic information are obtained; and meanwhile, the data processing software also carries out retrieval comparison on the mass spectrum and chromatographic information of the compound obtained by deconvolution and a pre-established suspected target screening database of the organic phosphate, and carries out qualitative identification on the organic phosphate in the sample according to a screening filtering item.
8. Use of the method for the suspected target assay detection of an organophosphate according to any one of claims 1-7, for the detection of organophosphate residues in a solid sample.
9. An organophosphate suspected target assay detection system, comprising:
the storage unit is used for storing a pre-established suspected target screening database of the organic phosphate;
and the processing unit is used for carrying out data processing and analysis on the high-resolution mass spectrum data of the acquired sample by combining the set screening and filtering standard based on the suspected target screening database of the organic phosphate stored in the storage unit, so that the types of organic phosphate contained in the sample are detected and analyzed.
10. The system for analyzing and detecting the suspected target of the organic phosphate according to claim 9, wherein the suspected target screening database of the organic phosphate comprises information of chemical names, chemical formulas, precise mass numbers of primary parent ions, ionization modes and precise mass numbers of secondary fragment ions of the organic phosphate; and/or
And in the organic phosphate suspected target screening database, the types of the organic phosphate are at least more than or equal to 101.
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