CN113504322B - Multi-component high-throughput analysis method for plastic additive - Google Patents

Multi-component high-throughput analysis method for plastic additive Download PDF

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CN113504322B
CN113504322B CN202110727339.1A CN202110727339A CN113504322B CN 113504322 B CN113504322 B CN 113504322B CN 202110727339 A CN202110727339 A CN 202110727339A CN 113504322 B CN113504322 B CN 113504322B
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volume percentage
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CN113504322A (en
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陈达
虞飞翔
汤书琴
陈玉锟
刘晓途
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Jinan University
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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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/36—Control of physical parameters of the fluid carrier in high pressure liquid systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • 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
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Abstract

The invention discloses a multi-component high-throughput analysis method for a plastic additive. The method comprises the following steps: (1) uniformly mixing a sample to be detected and a recovery rate indicator; (2) Adding tetrahydrofuran solution containing ammonia water into the mixed solution obtained in the step (1), oscillating and mixing, and then performing ultrasonic treatment until the mixed solution is completely mixed; (3) Adding a methanol aqueous solution into the mixed solution obtained in the step (2), uniformly mixing, oscillating, centrifuging, concentrating, and filtering; (4) adding an internal standard into the filtrate obtained in the step (3); (5) And (3) quantitatively analyzing the sample obtained in the step (4) by adopting an ultra-high performance liquid chromatography-tandem mass spectrometer. The method can realize simultaneous detection of various plastic additives with different structures and purposes in lipstick and nail polish, and can reduce analysis cost and improve analysis efficiency by shortening analysis time.

Description

Multi-component high-throughput analysis method for plastic additive
Technical Field
The invention relates to the field of plastic additive analysis, in particular to a multi-component high-throughput analysis method for plastic additives.
Background
Plastic additives are a class of compounds that enhance elasticity, durability, and extensibility, and are widely used in various cosmetics, such as lipsticks, nail polish, and the like. Common plastic additives include: plasticizers, flame retardants, uv stabilizers, antioxidants, etc., there are now increasingly emerging cosmetic additives that are gradually replacing traditional cosmetic additives. Human exposure to plastic additives phthalate esters, parabens and bisphenols have been reported to cause adverse health effects including, for example, endocrine disorders, developmental or reproductive toxicity.
There may be a variety of plastic additives in lipsticks and nail polish used by consumers that pose potential health risks. However, the current research on plastic additives in lipsticks and nail polish is usually carried out on single compounds or single compounds, and the possible composite effect caused by the simultaneous existence of multiple plastic additives is not focused, and the existing analysis methods are mostly long in time consumption and high in cost, so that a high-throughput and simple pretreatment analysis method capable of simultaneously detecting multiple plastic additives with different structures or purposes in lipsticks and nail polish is needed to be developed.
Disclosure of Invention
The invention aims to perfect the existing analysis method of plastic additives in lipstick and nail polish, realize simultaneous detection of various plastic additives with different structures and purposes in lipstick and nail polish, and improve analysis efficiency by shortening analysis time, reducing analysis cost.
The aim of the invention is achieved by the following technical scheme:
a method for multi-component high throughput analysis of plastic additives comprising the steps of:
(1) Uniformly mixing a sample to be tested with a recovery rate indicator;
(2) Adding tetrahydrofuran solution containing ammonia water into the mixed solution obtained in the step (1), oscillating and mixing, and then performing ultrasonic treatment until the mixed solution is completely mixed;
(3) Adding a methanol aqueous solution into the mixed solution obtained in the step (2), uniformly mixing, oscillating, centrifuging, concentrating, and filtering;
(4) Adding an internal standard into the filtrate obtained in the step (3);
(5) And (3) quantitatively analyzing the sample obtained in the step (4) by adopting an ultra-high performance liquid chromatography-tandem mass spectrometer.
Preferably, in the step (2), the mixed solution obtained by adding the tetrahydrofuran solution containing ammonia water is alkaline.
It is further preferred that the aqueous ammonia-containing tetrahydrofuran solution of step (2) contains 0.1wt% aqueous ammonia.
Preferably, the volume ratio of methanol to water in the aqueous methanol solution in the step (3) is 3:1.
Preferably, the dosage of the sample to be detected is 0.1g, the dosage of the tetrahydrofuran solution containing ammonia water is 6mL, and the dosage of the methanol aqueous solution is 4mL.
Preferably, in the step (3), the aqueous methanol solution is added to the mixed solution obtained in the step (2), and after mixing and shaking, 2mL of the mixed solution is taken out of 10mL of the mixed solution, centrifuged at 5000rpm for 5min, concentrated to 1mL under nitrogen flow, and the small solid particles are filtered through an organic filter membrane of 0.22 μm.
In the step (3), 2mL of mixed liquid is taken for dilution and sample injection, because lipstick and nail polish extracting liquid can be relatively thick, and taking part of samples can reduce the matrix effect of instrument analysis. Centrifugation is carried out at 5000rpm for 5min in order to precipitate impurities which are precipitated after the addition of the aqueous methanol solution. The 0.22 μm organic filter is a commercial product of VWR corporation in the united states, and is realized in the form of a 1.5mL centrifuge tube with a filter membrane in the middle, which is less lost than a syringe-combined filter membrane and does not introduce background contamination.
Preferably, the sample to be tested is one or more of lipstick and nail polish.
Preferably, the recovery rate indicator is an isotope-labeled chemical substance corresponding to the target object (plastic additive) and is used for correcting the loss in the pretreatment analysis process. When there are more compounds, if the isotope standards corresponding to all the compounds one by one cannot be satisfied, the compounds in the same class can be corrected by the corresponding isotope standards found in the class. All recovery indicators are part of table 1.
Preferably, the internal standard in step (4) is BPA-d16 (bisphenol A-deuterated d 16) and tert butyl paraben-d9 (tert-butyl paraben-deuterated d 9) in negative mode and coumaphos-d10 (coumaphos-deuterated d 10) in positive mode.
Preferably, in the tetrahydrofuran solution containing ammonia water, tetrahydrofuran and ammonia water need to adopt reagents with the grade not lower than LC-MS, and the solution needs to be prepared at present, for example, 500mL of tetrahydrofuran (containing 0.1% of ammonia water) is prepared, 499.5mL of tetrahydrofuran is firstly taken, and 0.5mL of ammonia water is added. The ultrasound step requires time adjustment according to the actual situation, as this step is affected by the sample consistency, viscosity.
Preferably, the methanol and the pure water in the aqueous methanol solution adopt reagents with the grade not lower than LC-MS, for example, 400mL of aqueous methanol solution (3:1, v/v) is prepared, and 300mL of methanol is taken and evenly mixed with 100mL of pure water.
Preferably, the different compounds of step (5) are detected using different instrumental methods, in particular as follows:
(1) The organic phosphotriester (Organophosphate triesters) chromatographic conditions include:
mobile phase A is formic acid aqueous solution with volume fraction of 0.1%;
mobile phase B, methanol;
chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm,100×2.1mm;
flow rate: 0.3mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 5%, and the volume percentage is kept at 5% for 0-1 min; 1-3min the volume fraction of mobile phase B increases from 5% to 40%;3-12min from 40% to 100%; keeping the state unchanged for 12-15 min; 15-15.1min, the volume percentage of the mobile phase B is reduced from 100% to 5%;15.1-18min, the volume fraction of mobile phase B is kept unchanged at 5%.
The mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen, pressure level 55psi.
(2) The organic phosphoric acid diester (Organophosphate diesters) chromatographic conditions include:
mobile phase a:0.2mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm,100×2.1mm;
flow rate: 0.3mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 5%,0-4min, and the volume percentage is increased from 5% to 35%;4-7min, and the volume fraction of the phase B is increased from 35% to 80%;7-12min from 80% to 100%; keeping the state unchanged for 12-14 min; 14-15min, the volume percentage of the mobile phase B is reduced from 100% to 5%;15-20min, the volume percentage of mobile phase B is kept at 5%.
The mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of negative ion; atomization air pressure: nitrogen, pressure level 55psi.
(3) The organic phosphite (Organophosphite esters) chromatographic conditions include:
mobile phase a:0.2mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm,100×2.1mm;
flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percent of the initial mobile phase B is 40%; keeping 40% unchanged for 0-3 min; 3-10min from 40% to 100%; keeping the temperature at 100% unchanged for 10-15 min; 15-15.5min, the volume percentage of the mobile phase B is reduced from 100% to 40%;15.5-18min, the volume fraction of mobile phase B is kept unchanged at 40%.
The mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen, pressure level 55psi.
(4) The phthalate diester (Phthalate diesters) chromatographic conditions include:
mobile phase a: formic acid aqueous solution with volume fraction of 0.1%;
mobile phase B: methanol;
chromatographic column: luna 2.5 μm C18 (2) -HST
Figure BDA0003138001190000053
Figure BDA0003138001190000053
100×2.0mm；
Flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 40%;0-2min, the volume percentage of the mobile phase B is increased from 40% to 70%;2-8min, the volume percentage of the mobile phase B rises to 100%; maintaining the constant at 100% for 8-13min, and reducing the volume percentage of mobile phase B to 40% for 13-13.1 min; 13.1-17min, and is kept unchanged at 40%.
The mass spectrometry conditions included: an electrospray ion source, wherein the temperature of the ion source is 550 ℃; the detection mode is a positive ion detection mode; atomization air pressure: nitrogen at a pressure of 55psi;
(5) The phthalate monoester (Phthalate monoesters), benzophenone (benzophenones), phenol (Bisphenol analogues) and Parabens (para) chromatographic conditions include:
mobile phase a:0.2mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: ZORBAX Extended-C18.5 μm
Figure BDA0003138001190000054
Figure BDA0003138001190000054
100×2.1mm；
Flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percent of the initial mobile phase B is 10%; keeping the 10% constant for 0-0.5 min; 0.5-1min, the volume percentage of the mobile phase B is increased from 10% to 50%;1-7min, the volume fraction of the mobile phase B is increased from 50% to 99%;7-10min, keeping the temperature at 99% unchanged; the volume fraction of the mobile phase B is kept unchanged at 10% from 99% to 10% in 10-10.1min and 10.1-12 min.
The mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of negative ion; atomization air pressure: nitrogen, pressure level 55psi.
(6) Non-phthalate plasticizers (Non-phthalate plasticizers), benzothiazoles (benzotriazoles), benzotriazoles (benzotriazoles), ultraviolet stabilizers (UV stabilizers), antioxidants (anti-oxidants) chromatographic conditions include:
mobile phase a: formic acid aqueous solution with volume fraction of 0.1%;
mobile phase B: methanol;
chromatographic column: luna 2.5 μm C18 (2) -HST
Figure BDA0003138001190000063
Figure BDA0003138001190000063
100×2.0mm；
Flow rate: 0.3mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 40%, and the initial mobile phase B is kept unchanged for 0-2min by 40%; 2-4min, the volume percentage of the mobile phase B is increased from 40% to 80%;4-14min, the volume percentage of the mobile phase B is increased from 80% to 100%; the volume percentage of the mobile phase B is kept to be 100% after 14-17 min; 17-20min, the volume percentage of the mobile phase B is reduced to 40%, and 20-24min, the volume percentage of the mobile phase B is kept unchanged at 40%;
the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen, pressure level 55psi.
(7) Antioxidant (antioxidants) chromatographic conditions include:
mobile phase a:4mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: luna 2.5 μm C18 (2) -HST
Figure BDA0003138001190000064
Figure BDA0003138001190000064
100×2.0mm；
Flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percent of the initial mobile phase B is 10%; keeping 10% unchanged for 0-0.5 min; the volume percentage of the mobile phase B rises from 10% to 50% for 0.5-1min, and rises to 99% for 1-7 min; maintaining the temperature at 99% unchanged for 7-10 min; 10-10.1min, the volume percentage of the mobile phase B is rapidly reduced to 10%; the volume fraction of the mobile phase B is kept unchanged for 10.1-12 min.
The mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of negative ion; atomization air pressure: nitrogen, pressure level 55psi.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The method can analyze hundreds of plastic additives in various types simultaneously;
(2) The method has the advantages of simple and convenient operation, lower cost and shorter time consumption.
Drawings
FIG. 1 is a graph showing the results of the concentration of plastic additives in lipstick and nail polish samples of example 1.
FIG. 2 is a graph showing the results of labeled recovery of target compounds after treatment by different pretreatment methods.
Detailed Description
The following describes the embodiments of the present invention further with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1: multi-component analysis of plastic additives in lipsticks and nail polish
(1) Reagents and materials
The target standard substance related to the embodiment totally comprises 231 plastic additives, and the plastic additives are classified into seven categories according to the molecular structural characteristics or the application of the plastic additives: (1) organophosphates (OPEs, n=55), including organophosphate triesters (organophosphate triesters), organophosphate diesters (organophosphate diesters), and organophosphites (organophosphite esters); (2) phthalate esters (PAEs; n=41), including phthalate diesters (phthalates diesters) and phthalate monoesters (phthalates monoesters); (3) non-phthalate plasticizers (non-PAE displacers, n=42); (4) bisphenols and analogues thereof (BPs, n=14); (5) parabens (parabens, n=6); (6) uv stabilizers (UVs, n=33) including benzotriazoles (benzotriazoles), benzothiazoles (benzotriazoles), benzophenones (benzophenones), and other uv stabilizers; (7) antioxidants (antioxidants, n=40). The corresponding isotope standards for these targets were 36 in total, 33 as recovery indicators (surrogate standards), 3 as internal standards (Internal standards), all purchased from AccuStandard or wellngton laboratories, canada. Details of the target compounds and isotope standards are shown in table 1.
The instruments used in this example are mainly: liquid chromatograph tandem mass spectrometer (model 5500Q-Trap, AB Sciex, canada), nitrogen blower (model 12N-EvapTM, orgnomonation, U.S.A.), centrifuge (model L600, hunan Xiang instruments, U.S.A.), vortex oscillator (model MX-S). Tetrahydrofuran, ammonia, methanol, water, formic acid, and ammonium acetate used in the experiments were Optima grade, all purchased from Fisher Scientific company in the United states.
(2) Sample collection
34 lipstick and 15 nail polish samples analyzed in this example were purchased from a network brand name, and all samples were kept dry and protected from light until analysis.
(3) Sample pretreatment and instrument analysis
Taking 0.1g of nail polish or lipstick preserved at normal temperature, placing the nail polish or lipstick into a 15mL glass centrifuge tube, adding a recovery rate indicator, and uniformly mixing; adding 6mL tetrahydrofuran (containing 0.1wt% ammonia water), shaking and mixing, and performing ultrasonic treatment in a water bath until the mixture is completely mixed (10 min); then adding 4mL of methanol aqueous solution (3:1, v/v), uniformly mixing and oscillating for 10min; taking 2mL from 10mL of the mixed solution, and centrifuging for 5min at 5000 revolutions; concentrating to 1mL under a gentle nitrogen flow, filtering small solid particles by using an organic filter membrane with the thickness of 0.22 mu m, transferring to a 1.5mL sample bottle, adding an internal standard, and detecting under a high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with 8 detection methods, wherein the instrument method information is shown in tables 2 and 3.
(4) Quality assurance and quality control
This example employs a series of quality assurance and control procedures to evaluate process contamination and matrix effects. During sample pretreatment, at least one process blank was set for process contamination evaluation for each 7 samples. The plastic additive content in the process blank (n=8) was low and the concentration was much lower than for lipsticks and nail polish, the final concentration would subtract the blank contamination. In the labeled sample analysis, the recovery rate of phthalate and non-phthalate plasticizers was 26-181%, the organic phosphate was 39-172%, the bisphenol and p-hydroxybenzoate were 90-148%, and the ultraviolet stabilizer and antioxidant were 31-155%. The recovery of lipstick and nail polish indicators was 61-188%. The limit of quantification (LOQ) of each target compound is initially set to 3 times its signal-to-noise ratio (SNR), then adjusted according to LC-MS/MS analysis and quality assurance and control results, and if the calculated LOQ is below the background contamination value in the blank, the highest blank concentration is used as the LOQ. The detection limit of all final plastic additives is 0.53-1590 ng/g (see Table 1).
(5) Analysis results
As shown in fig. 1, of the 231 plastic additives, 44 compounds were detected at a rate higher than 50% in the lipstick and nail polish samples, 47 in the lipstick and 57 in the nail polish. Among all plastic additives with detection rates higher than 70%, the concentration of Parabens (Parabens) was the greatest (33.3%) and higher than Non-phthalate plasticizers (Non-PAE plasticizers, 26.2%), phthalates (PAEs, 17.9%), bisphenols and their analogues (BPs, 7.1%), organic phosphates (OPEs, 5.6%), antioxidants (Antioxidants, 2.5%) and ultraviolet stabilizers (UVs, 0%).
Comparative example 1
Different pretreatment methods are selected for comparison in matrix labeling experiments:
the method I is the method of the invention, and is specifically as follows: taking 0.1g of two parts of nail polish and lipstick preserved at normal temperature, placing the two parts into a 15mL glass centrifuge tube, adding a target object and a recovery rate indicator into one part of the nail polish and the lipstick simultaneously, adding only the recovery rate indicator into the other part of the nail polish and the lipstick, uniformly mixing, adding 6mL of tetrahydrofuran (containing 0.1% ammonia water) respectively, oscillating, mixing, and performing ultrasonic treatment in a water bath until the mixture is completely mixed uniformly (about 10 min); then adding 4mL of methanol aqueous solution (3:1, v/v), uniformly mixing and oscillating for 10min; taking 2mL from 10mL of the mixed solution, and centrifuging for 5min at 5000 revolutions; concentrating to 1mL under a gentle nitrogen flow, filtering small solid particles by using an organic filter membrane with the thickness of 0.22 mu m, transferring to a 1.5mL sample bottle, adding an internal standard, and quantitatively analyzing by an instrument;
the second method is as follows: taking 0.1g of nail polish and lipstick stored at normal temperature, placing the two parts into a 15mL glass centrifuge tube, adding a target object and a recovery rate indicator into one part of nail polish and lipstick at the same time, adding the recovery rate indicator into the other part of nail polish and lipstick, adding 1mL of methanol into the other part of nail polish and lipstick at the same time, balancing for 30min at room temperature, adding 3mL of mixed solvent with the volume ratio of 3:1 of dichloromethane to n-hexane, oscillating for 20min, centrifuging for 5min at 5000rpm, taking supernatant, transferring to another 15mL glass centrifuge tube, adding 3mL of mixed solvent with the volume ratio of 3:1 of dichloromethane to n-hexane, repeating the above processes, oscillating for 20min in the water bath, centrifuging for 5min at 5000rpm, transferring supernatant, merging, concentrating 10mL of supernatant to 1mL under a light nitrogen flow, filtering solid small particles by using an organic filter membrane of 0.22 mu m, transferring to a 1.5mL sample bottle, adding an internal standard, and waiting for quantitative analysis;
the analysis results are shown in fig. 2, the labeled recovery rate of the first target compounds is concentrated between 75% and 120%, the recovery rate of the second target compounds is more dispersed between 25% and 200%, the time consumption of the first target compounds is shorter than that of the second target compounds, and the first target compounds are better than the second target compounds on the premise of meeting the standard.
Table 1 quantitative analysis of plastic additive targets and corresponding isotopic chemical information
Figure BDA0003138001190000101
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Figure BDA0003138001190000111
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Figure BDA0003138001190000121
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Figure BDA0003138001190000131
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Figure BDA0003138001190000141
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Figure BDA0003138001190000151
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Figure BDA0003138001190000161
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Figure BDA0003138001190000171
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Figure BDA0003138001190000181
Table 2 chromatographic information
Figure BDA0003138001190000182
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Figure BDA0003138001190000191
TABLE 3 Instrument information for each compound
Figure BDA0003138001190000192
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Figure BDA0003138001190000201
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Figure BDA0003138001190000211
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Figure BDA0003138001190000221
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Figure BDA0003138001190000231
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Figure BDA0003138001190000241
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Figure BDA0003138001190000251
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Claims (9)

1. A method for multi-component high throughput analysis of plastic additives, comprising the steps of:
(1) Uniformly mixing a sample to be tested with a recovery rate indicator;
(2) Adding tetrahydrofuran solution containing ammonia water into the mixed solution obtained in the step (1), oscillating and mixing, and then performing ultrasonic treatment until the mixed solution is completely mixed;
(3) Adding a methanol aqueous solution into the mixed solution obtained in the step (2), uniformly mixing, oscillating, centrifuging, concentrating, and filtering;
(4) Adding an internal standard into the filtrate obtained in the step (3);
(5) Quantitatively analyzing the sample obtained in the step (4) by adopting an ultra-high performance liquid chromatography-tandem mass spectrometer;
the plastic additives are (1) organic phosphotriesters, (2) organic phosphodiesters, (3) organic phosphites, (4) phthalic diesters, (5) phthalic monoesters, benzophenones, bisphenols and their analogs, and parabens, (6) non-phthalate plasticizers, benzothiazoles, benzotriazoles, uv stabilizers, a first antioxidant, and (7) a second antioxidant;
(1) The organic phosphotriester chromatography conditions include:
mobile phase A is formic acid aqueous solution with volume fraction of 0.1%;
mobile phase B, methanol;
chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm,100×2.1mm;
flow rate: 0.3mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 5%, and the volume percentage is kept at 5% for 0-1 min; 1-3min the volume fraction of mobile phase B increases from 5% to 40%;3-12min from 40% to 100%; keeping the state unchanged for 12-15 min; 15-15.1min, the volume percentage of the mobile phase B is reduced from 100% to 5%;15.1-18min, the volume fraction of the mobile phase B is kept unchanged at 5%;
the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen, pressure level 55psi;
(2) The organic phosphoric acid diester chromatography conditions include:
mobile phase a:0.2mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm,100×2.1mm;
flow rate: 0.3mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 5%,0-4min, and the volume percentage is increased from 5% to 35%;4-7min, and the volume fraction of the phase B is increased from 35% to 80%;7-12min from 80% to 100%; keeping the state unchanged for 12-14 min; 14-15min, the volume percentage of the mobile phase B is reduced from 100% to 5%;15-20min, the volume percentage of the mobile phase B is kept unchanged at 5%;
the mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of negative ion; atomization air pressure: nitrogen, pressure level 55psi;
(3) The organophosphite chromatographic conditions include:
mobile phase a:0.2mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm,100×2.1mm;
flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percent of the initial mobile phase B is 40%; keeping 40% unchanged for 0-3 min; 3-10min from 40% to 100%; keeping the temperature at 100% unchanged for 10-15 min; 15-15.5min, the volume percentage of the mobile phase B is reduced from 100% to 40%;15.5-18min, the volume fraction of the mobile phase B is kept unchanged at 40%;
the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen, pressure level 55psi;
(4) The phthalate diester chromatographic conditions include:
mobile phase a: formic acid aqueous solution with volume fraction of 0.1%;
mobile phase B: methanol;
chromatographic column: luna 2.5 μm C18 (2) -HST
Figure FDA0004111656070000032
100×2.0mm；
Flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 40%;0-2min, the volume percentage of the mobile phase B is increased from 40% to 70%;2-8min, the volume percentage of the mobile phase B rises to 100%; maintaining the constant at 100% for 8-13min, and reducing the volume percentage of mobile phase B to 40% for 13-13.1 min; 13.1-17min, keeping the temperature at 40%;
the mass spectrometry conditions included: an electrospray ion source, wherein the temperature of the ion source is 550 ℃; the detection mode is a positive ion detection mode; atomization air pressure: nitrogen at a pressure of 55psi;
(5) The phthalate monoester, benzophenone, phenol and paraben chromatographic conditions include:
mobile phase a:0.2mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: ZORBAX Extended-C18.5 μm
Figure FDA0004111656070000031
100×2.1mm；
Flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percent of the initial mobile phase B is 10%; keeping the 10% constant for 0-0.5 min; 0.5-1min, the volume percentage of the mobile phase B is increased from 10% to 50%;1-7min, the volume fraction of the mobile phase B is increased from 50% to 99%;7-10min, keeping the temperature at 99% unchanged; 10-10.1min, decreasing from 99% to 10%,10.1-12min, and keeping the volume fraction of mobile phase B at 10%;
the mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of negative ion; atomization air pressure: nitrogen, pressure level 55psi;
(6) Non-phthalate plasticizers, benzothiazoles, benzotriazoles, uv stabilizers, first antioxidant chromatographic conditions include:
mobile phase a: formic acid aqueous solution with volume fraction of 0.1%;
mobile phase B: methanol;
chromatographic column: luna 2.5 μm C18 (2) -HST
Figure FDA0004111656070000041
100×2.0mm；
Flow rate: 0.3mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 40%, and the initial mobile phase B is kept unchanged for 0-2min by 40%; 2-4min, the volume percentage of the mobile phase B is increased from 40% to 80%;4-14min, the volume percentage of the mobile phase B is increased from 80% to 100%; the volume percentage of the mobile phase B is kept to be 100% after 14-17 min; 17-20min, the volume percentage of the mobile phase B is reduced to 40%, and 20-24min, the volume percentage of the mobile phase B is kept unchanged at 40%;
the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen, pressure level 55psi;
(7) The second antioxidant chromatographic conditions include:
mobile phase a:4mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
chromatographic column: luna 2.5 μm C18 (2) -HST
Figure FDA0004111656070000042
100×2.0mm；
Flow rate: 0.2mL/min;
column temperature: 40 ℃;
elution procedure: the volume percent of the initial mobile phase B is 10%; keeping 10% unchanged for 0-0.5 min; the volume percentage of the mobile phase B rises from 10% to 50% for 0.5-1min, and rises to 99% for 1-7 min; maintaining the temperature at 99% unchanged for 7-10 min; 10-10.1min, the volume percentage of the mobile phase B is rapidly reduced to 10%; the volume fraction of the mobile phase B is kept unchanged for 10.1-12 min;
the mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of negative ion; atomization air pressure: nitrogen, pressure level 55psi;
the instrument information for each compound in the plastic additive is shown in the following table:
Figure FDA0004111656070000051
/>
Figure FDA0004111656070000061
/>
Figure FDA0004111656070000071
/>
Figure FDA0004111656070000081
/>
Figure FDA0004111656070000091
2. the method of claim 1, wherein in step (2), the mixed solution obtained by adding a tetrahydrofuran solution containing ammonia water is alkaline.
3. The method of claim 2, wherein the aqueous tetrahydrofuran solution containing ammonia in step (2) contains 0.1wt% aqueous ammonia.
4. A plastics additive multicomponent high throughput analysis method according to any one of claims 1-3, wherein the volume ratio of methanol to water in said aqueous methanol solution of step (3) is 3:1.
5. A method of multi-component high throughput analysis of plastic additives according to any of claims 1-3, wherein the sample to be tested is used in an amount of 0.1g, the aqueous tetrahydrofuran solution containing ammonia is used in an amount of 6mL, and the aqueous methanol solution is used in an amount of 4mL.
6. A method according to any one of claims 1 to 3, wherein in step (3), an aqueous methanol solution is added to the mixture obtained in step (2), and after shaking, 2mL of the mixture is taken out of 10mL of the mixture, centrifuged at 5000rpm for 5min, concentrated to 1mL under nitrogen flow, and small solid particles are filtered through a 0.22 μm organic filter.
7. A method of multi-component high throughput analysis of plastic additives according to any of claims 1-3, wherein the sample to be tested is one or more of lipstick and nail polish; the recovery rate indicator is an isotope labeled chemical substance corresponding to the target object to be detected.
8. A method of multi-component high throughput analysis of plastic additives according to any of claims 1-3, wherein the internal standard of step (4) is bisphenol a-deuterated d16 and tert-butyl paraben-deuterated d9 in negative mode and coumaphos-deuterated d10 in positive mode of electrospray ion source.
9. A method of multi-component high throughput analysis of plastic additives according to any of claims 1-3, wherein said aqueous ammonia-containing tetrahydrofuran solution is ready for use, and wherein said tetrahydrofuran and aqueous ammonia are employed with a reagent not lower than LC-MS grade; the methanol and the pure water in the methanol aqueous solution adopt reagents not lower than LC-MS grade.
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