CN113504322A - Multi-component high-throughput analysis method for plastic additive - Google Patents
Multi-component high-throughput analysis method for plastic additive Download PDFInfo
- Publication number
- CN113504322A CN113504322A CN202110727339.1A CN202110727339A CN113504322A CN 113504322 A CN113504322 A CN 113504322A CN 202110727339 A CN202110727339 A CN 202110727339A CN 113504322 A CN113504322 A CN 113504322A
- Authority
- CN
- China
- Prior art keywords
- mobile phase
- percent
- volume percentage
- methanol
- volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—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
- G01N2030/042—Standards
- G01N2030/045—Standards internal
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention 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 with a recovery rate indicator; (2) adding a tetrahydrofuran solution containing ammonia water into the mixed solution obtained in the step (1), oscillating and mixing, and then carrying out ultrasonic treatment until the mixture 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 (4) carrying out quantitative analysis on the sample obtained in the step (4) by adopting an ultra performance liquid chromatography-tandem mass spectrometry. The method can realize the simultaneous detection of various plastic additives with different structures and purposes in the lipstick and the nail polish, and improve the analysis efficiency by shortening the analysis time and reducing the analysis cost.
Description
Technical Field
The invention relates to the field of analysis of plastic additives, in particular to a multi-component high-throughput analysis method for plastic additives.
Background
Plastic additives are a class of compounds that improve elasticity, durability, and extensibility, and are widely used in a variety of cosmetics, such as lipstick, nail polish, and the like. Common plastic additives include: plasticizers, flame retardants, UV stabilizers, antioxidants, etc., there are currently more emerging cosmetic additives that are gradually replacing traditional cosmetic additives. Human exposure to plastic additives, phthalates, parabens, and bisphenols has 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 consumer use in lipsticks and nail polishes that pose potential health risks. However, the existing research on plastic additives in lipstick and nail polish is usually only carried out on a single compound or a class of compounds for independent evaluation, and there is no concern about the possible composite effect of the simultaneous existence of multiple plastic additives, and most of the existing analysis methods are long in time consumption and high in cost, so that the development of a high-throughput and simple pretreatment analysis method capable of simultaneously detecting multiple plastic additives with different structures or purposes in lipstick and nail polish is urgently needed.
Disclosure of Invention
The invention aims to improve the existing analysis method of plastic additives in lipstick and nail polish, realize the simultaneous detection of various plastic additives with different structures and purposes in lipstick and nail polish, and improve the analysis efficiency by shortening the analysis time and reducing the analysis cost.
The purpose of the invention is realized by the following technical scheme:
a multi-component high throughput analysis method for plastic additives, comprising the steps of:
(1) uniformly mixing a sample to be detected with a recovery rate indicator;
(2) adding a tetrahydrofuran solution containing ammonia water into the mixed solution obtained in the step (1), oscillating and mixing, and then carrying out ultrasonic treatment until the mixture 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 (4) carrying out quantitative analysis on the sample obtained in the step (4) by adopting an ultra performance liquid chromatography-tandem mass spectrometry.
Preferably, in the step (2), the mixture obtained after adding the tetrahydrofuran solution containing ammonia is alkaline.
Further preferably, the tetrahydrofuran solution containing ammonia in step (2) contains 0.1 wt% of ammonia.
Preferably, the volume ratio of methanol to water in the methanol aqueous 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 4 mL.
Preferably, in step (3), the mixed solution obtained in step (2) is added with an aqueous methanol solution, and after shaking for homogenization, 2mL of the mixed solution is taken out of 10mL, centrifuged at 5000rpm for 5min, concentrated to 1mL under a nitrogen stream, and the solid particles are filtered through a 0.22 μm organic filter.
In step (3), 2mL of the 10mL mixed solution is used for diluting the sample injection, because the lipstick and the nail polish extracting solution are relatively thick, and the matrix effect of the instrumental analysis can be reduced by taking a part of the sample. Centrifugation was carried out at 5000rpm for 5min in order to precipitate impurities precipitated after addition of the aqueous methanol solution. The 0.22 μm organic filter was a commercial product from VWR corporation, usa, and was implemented as a 1.5mL centrifuge tube with a filter in the middle of the tube, which was less lossy than syringe-bound filters and did not introduce background contamination.
Preferably, the sample to be tested is one or more of lipstick and nail polish.
Preferably, the recovery indicator is an isotope-labeled chemical substance corresponding to the target analyte (plastic additive) and functions to correct the loss of the pretreatment analysis process. When there are many compounds, if all compounds cannot meet the one-to-one corresponding isotope standards, the compounds of the same class can be corrected by the corresponding isotope standards that can be found in the class. All recovery indicators are listed in table 1.
Preferably, the internal standard in step (4) is BPA-d16 (bisphenol A-deuterated d16) and tert-butyl paraben-d9 (tert-butyl paraben-deuterated d9) in the negative mode of an electrospray ion source and is coumaphos-d10 (coumaphos-deuterated d10) in the positive mode of the electrospray ion source.
Preferably, in the tetrahydrofuran solution containing ammonia water, reagents not lower than LC-MS grade are required to be adopted for tetrahydrofuran and ammonia water, and the solution is required to be prepared for use, for example, when 500mL of tetrahydrofuran (containing 0.1% of ammonia water) is prepared, 499.5mL of tetrahydrofuran is taken firstly, and 0.5mL of ammonia water is added. The ultrasound step requires time adjustment as the actual situation arises because this step is influenced by the consistency, viscosity of the sample.
Preferably, the methanol and pure water in the methanol aqueous solution adopt a reagent not lower than LC-MS grade, for example, 400mL of methanol aqueous solution (3:1, v/v) is prepared, and 300mL of methanol is uniformly mixed with 100mL of pure water.
Preferably, different compounds in the step (5) are detected by different instrumental methods, which specifically comprise the following steps:
(1) the chromatographic conditions for Organophosphate triesters (Organophosphate triesters) include:
the mobile phase A is 0.1 percent of formic acid aqueous solution by volume fraction;
the mobile phase B is methanol;
a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 5 percent, and the initial mobile phase B is kept at 5 percent in 0-1 min; 1-3min, the volume fraction of mobile phase B rises from 5% to 40%; 3-12min from 40% to 100%; keeping 100% unchanged for 12-15 min; 15-15.1min, the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent; the volume fraction of the mobile phase B is kept constant at 5% for 15.1-18 min.
The mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
(2) The chromatographic conditions for Organophosphate diesters (Organophosphate diesters) include:
mobile phase A: 0.2mmol/L aqueous ammonium acetate solution;
mobile phase B: methanol;
a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
elution procedure: initial mobile phase B volume percent 5%, 0-4min, rising from 5% to 35%; 4-7min, the volume fraction of the phase B is increased from 35% to 80%; 7-12min from 80% to 100%; keeping 100% unchanged for 12-14 min; 14-15min, the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent; the volume percentage of the mobile phase B is kept constant at 5 percent for 15-20 min.
The mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
(3) Organic phosphite (Organophosphite esters) chromatographic conditions included:
mobile phase A: 0.2mmol/L aqueous ammonium acetate solution;
mobile phase B: methanol;
a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm;
flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B was 40%; keeping the concentration unchanged at 40% in 0-3 min; increasing from 40% to 100% in 3-10 min; keeping constant at 100% for 10-15 min; the volume percentage content of the mobile phase B is reduced from 100 percent to 40 percent within 15-15.5 min; the volume fraction of the mobile phase B is kept unchanged at 40 percent for 15.5-18 min.
The mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
(4) The chromatographic conditions of Phthalate diesters (Phthalate esters) include:
mobile phase A: 0.1% by volume of aqueous formic acid;
mobile phase B: methanol;
a chromatographic column: luna 2.5. mu. m C18(2) -HST
100×2.0mm；
Flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage content of the initial mobile phase B is 40%; the volume percentage of the mobile phase B is increased from 40 percent to 70 percent in 0-2 min; 2-8min, the volume percentage of the mobile phase B is increased to 100%; keeping 100% unchanged for 8-13min, and reducing the volume percentage of mobile phase B to 40% in 13-13.1 min; 13.1-17min, and keeping the temperature constant at 40%.
The mass spectrometry conditions include: 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 55 psi;
(5) chromatographic conditions of the phthalic acid monoesters (phthalates monoesters), benzophenones (benzophenones), phenols (biphenol analogues) and Parabens (Parabens) type include:
mobile phase A: 0.2mmol/L aqueous ammonium acetate solution;
mobile phase B: methanol;
a chromatographic column: ZORBAX Extended-C183.5 μm
100×2.1mm；
Flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping the 10% value unchanged for 0-0.5 min; the volume percentage of the mobile phase B is increased from 10 percent to 50 percent within 0.5-1 min; 1-7min, the volume fraction of the mobile phase B is increased from 50% to 99%; keeping the temperature constant at 99% for 7-10 min; 10-10.1min, from 99% to 10%, 10.1-12min, and the volume fraction of mobile phase B is kept constant at 10%.
The mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
(6) Non-phthalate plasticizers (Non-phthalate plasticizers), benzothiazoles (benzothiazoles), benzotriazoles (benzotriazoles), ultraviolet stabilizers (UV stabilizers), antioxidants (antioxidants) chromatographic conditions include:
mobile phase A: 0.1% by volume of aqueous formic acid;
mobile phase B: methanol;
a chromatographic column: luna 2.5. mu. m C18(2) -HST
100×2.0mm；
Flow rate: 0.3 mL/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 at 40% in 0-2 min; 2-4min, the volume percentage of the mobile phase B is increased from 40% to 80%; 4-14min, the volume percent of the mobile phase B is increased from 80% to 100%; 14-17min, keeping the volume percentage of the mobile phase B constant at 100%; the volume percentage of the mobile phase B is reduced to 40 percent in 17-20min, and the volume percentage of the mobile phase B is kept unchanged at 40 percent in 20-24 min;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
(7) Antioxidant (antioxidants) chromatographic conditions include:
mobile phase A: 4mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
a chromatographic column: luna 2.5. mu. m C18(2) -HST
100×2.0mm；
Flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping 10% unchanged at 0-0.5 min; the volume percentage of the mobile phase B is increased from 10% to 50% in 0.5-1min, and is increased to 99% in 1-7 min; keeping the temperature at 99% for 7-10 min; the volume percentage of the mobile phase B is rapidly reduced to 10 percent in 10-10.1 min; the volume fraction of mobile phase B is kept constant at 10.1-12 min.
The mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method of the invention can simultaneously analyze more than one hundred kinds of plastic additives;
(2) the method of the invention has simple operation, low cost and short time consumption.
Drawings
FIG. 1 is a graph of the results of the plastic additive concentration composition for the lipstick and nail polish samples of example 1.
FIG. 2 is a graph showing the results of the recovery of target compounds from different pretreatment processes.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1: multi-component analysis of Plastic additives in lipstick and nail enamel
(1) Reagents and materials
The target substance standard substance related in this example is 231 kinds of plastic additives, which are classified into seven major categories according to their molecular structure characteristics or uses: organophosphates (ops, n ═ 55) including organophosphate triesters (organophosphate triesters), organophosphate diesters (organophosphate diesters), and organophosphites (organophosphate esters); (ii) phthalates (PAEs; n ═ 41) including phthalates diesters (phthalates diesters) and phthalates monoesters (phthalates monoesters); (iii) non-phthalate plasticizers (non-PAE plasticizers, n-42); (iv) bisphenols and their analogues (BPs, n ═ 14); parabens (parabens, n is 6); sixty-violet stabilizers (UVs, n ═ 33) including benzotriazole (benzotriazoles), benzothiazole (benzothiazoles), benzophenones (benzophenones) and other uv stabilizers; seventhly, antioxidants (antioxidants, n is 40). There are 36 isotope standards for these targets, 33 of which serve as recovery indicators (recovery standards) and 3 of which serve as Internal standards (Internal standards), all purchased from the AccuStandard, usa or Wellington laboratories, canada. Details of the target compound and isotope standards are shown in table 1.
The apparatus used in this example mainly includes: liquid chromatography tandem mass spectrometer (AB Sciex, Canada, model 5500Q-Trap), nitrogen blower (Orgnation, USA, model 12N-Evap), centrifuge (Hunan instrument, model L600), vortex shaker (Scilogex, USA, model MX-S). Tetrahydrofuran, ammonia, methanol, water, formic acid, ammonium acetate used in the experiments were Optima grade and were purchased from Fisher Scientific, usa.
(2) Sample collection
The 34 lipstick and 15 nail polish samples analyzed in this example were purchased from network brand, all kept in dry, dark conditions and waiting for analysis.
(3) Sample pretreatment and instrumental analysis
Putting 0.1g of nail polish or lipstick stored at normal temperature into a 15mL glass centrifuge tube, adding a recovery rate indicator, and uniformly mixing; adding 6mL of tetrahydrofuran (containing 0.1 wt% of ammonia water), oscillating, mixing, and performing ultrasonic treatment in a water bath until the mixture is completely mixed (10 min); then adding 4mL of methanol water solution (3:1, v/v), mixing uniformly and oscillating for 10 min; taking 2mL of the mixed solution from 10mL, and centrifuging for 5min at 5000 r; concentrating to 1mL under gentle nitrogen flow, filtering solid small particles through a 0.22-micron organic filter membrane, transferring to a 1.5-mL sample bottle, adding an internal standard, and detecting under a high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) instrument with 8 detection methods, wherein the information of the instrument and the method 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 substrate effects. In the sample pretreatment process, at least one process blank is set for each 7 samples for process pollution evaluation. The process blank (n-8) has a lower plastic additive content and a much lower concentration than lipstick and nail polish, the final concentration would subtract out the blank contamination. In the analysis of the spiked samples, the recovery of phthalate and non-phthalate plasticizers ranged from 26 to 181%, the organic phosphate ranged from 39 to 172%, the bisphenol and parabens ranged from 90 to 148%, and the UV stabilizer and antioxidant ranged from 31 to 155%. Recovery indicators for lipstick and nail polish were 61-188% recovery. The limit of quantitation (LOQ) for each target compound was initially set at 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 lower than the background contamination value in the blank, the highest blank concentration was used as the LOQ. Finally, the detection limit of all plastic additives is 0.53-1590 ng/g (see Table 1).
(5) Analysis results
As shown in FIG. 1, of the 231 plastics additives, there were 44 compounds with a detection rate of greater than 50% in both the lipstick and nail polish samples, 47 in the lipstick and 57 in the nail polish. Of all plastics additives with detectable rates above 70%, the Parabens (Parabens) concentration (33.3%) is the greatest by weight, above the Non-phthalate plasticizers (Non-PAE plasticizers, 26.2%), the phthalates (PAEs, 17.9%), the bisphenols and their analogs (BPs, 7.1%), the organophosphates (ops, 5.6%), the Antioxidants (Antioxidants, 2.5%) and the uv stabilizers (UVs, 0%).
Comparative example 1
Different pretreatment methods are selected as matrix standard addition experiments for comparison:
the first method is the method of the invention, and comprises the following specific steps: taking 0.1g of nail polish and lipstick which are stored at normal temperature, placing the two parts in a 15mL glass centrifuge tube, adding a target object and a recovery rate indicator into one part of the nail polish and the lipstick at the same time, adding the recovery rate indicator into the other part of the nail polish and the lipstick, uniformly mixing, adding 6mL of tetrahydrofuran (containing 0.1% of ammonia water) into the mixture, oscillating and mixing, and performing ultrasonic treatment in a water bath until the mixture is completely mixed (about 10 min); then adding 4mL of methanol water solution (3:1, v/v), mixing uniformly and oscillating for 10 min; taking 2mL of the mixed solution from 10mL, and centrifuging for 5min at 5000 r; concentrating to 1mL under a gentle nitrogen flow, filtering solid small particles through a 0.22-micron organic filter membrane, transferring to a 1.5-mL sample bottle, adding an internal standard, and waiting for quantitative analysis by an instrument;
the second method comprises the following steps: taking 0.1g of nail polish and lipstick which are stored at normal temperature, placing the nail polish and lipstick into a 15mL glass centrifuge tube, adding a target object and a recovery rate indicator into one part of the nail polish and lipstick at the same time, adding the recovery rate indicator into the other part of the nail polish and lipstick respectively, adding 1mL of methanol respectively, balancing for 30min at room temperature, adding a mixed solvent of 3mL of dichloromethane and n-hexane with a volume ratio of 3:1, oscillating for 20min, carrying out ultrasonic treatment in a water bath for 20min, centrifuging for 5min at 5000r, taking supernatant, transferring to another 15mL glass centrifuge tube, adding a mixed solvent of 3mL of dichloromethane and n-hexane with a volume ratio of 3:1, repeating the above processes, adding 3mL of n-hexane for the third time, oscillating for 20min, carrying out ultrasonic treatment in a water bath for 20min, centrifuging for 5min at 5000r, transferring the supernatant, combining, concentrating 10mL of supernatant to 1mL in a gentle nitrogen flow, filtering solid small particles through an organic filter membrane with the thickness of 0.22 μm, transferring the sample into a 1.5mL sample bottle, adding an internal standard, and waiting for quantitative analysis of an instrument;
the results after the analysis treatment are shown in fig. 2, the recovery rates of the target compounds by the first method are concentrated between 75% and 120%, the recovery rates by the second method are more dispersed between 25% and 200%, and the time consumption of the first method is shorter than that of the second method.
TABLE 1 quantitative analysis of Plastic additive targets and corresponding isotopic chemical information
TABLE 2 chromatographic information
TABLE 3 Instrument information for each Compound
Claims (10)
1. A multi-component high-throughput analysis method for a plastic additive is characterized by comprising the following steps:
(1) uniformly mixing a sample to be detected with a recovery rate indicator;
(2) adding a tetrahydrofuran solution containing ammonia water into the mixed solution obtained in the step (1), oscillating and mixing, and then carrying out ultrasonic treatment until the mixture 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 (4) carrying out quantitative analysis on the sample obtained in the step (4) by adopting an ultra performance liquid chromatography-tandem mass spectrometry.
2. The method for multi-component high-throughput analysis of plastic additives of claim 1, wherein in the step (2), the mixed solution obtained after adding the tetrahydrofuran solution containing ammonia is alkaline.
3. The method for multi-component high-throughput analysis of plastic additives of claim 2, wherein the aqueous solution of tetrahydrofuran containing ammonia in step (2) contains 0.1 wt% of ammonia.
4. A plastic additive multi-component high throughput analysis method according to any one of claims 1-3, wherein the volume ratio of methanol to water in said methanol aqueous solution of step (3) is 3: 1.
5. The multi-component high-throughput analysis method for the plastic additive according to any one of claims 1 to 3, wherein the amount of the sample to be tested is 0.1g, the amount of the tetrahydrofuran solution containing ammonia water is 6mL, and the amount of the methanol aqueous solution is 4 mL.
6. The method for multi-component high-throughput analysis of a plastic additive according to any one of claims 1 to 3, wherein in the step (3), the mixed solution obtained in the step (2) is added with methanol aqueous solution, after shaking for uniform mixing, 2mL of the 10mL mixed solution is centrifuged at 5000rpm for 5min, then concentrated to 1mL under nitrogen flow, and the solid particles are filtered through a 0.22 μm organic filter.
7. A plastic additive multi-component high throughput analysis method according to any one 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 analyte.
8. A plastic additive multi-component high throughput analysis method according to any one of claims 1 to 3, wherein in step (5), different instrumental methods are used for detecting different compounds, specifically as follows:
(1) the chromatographic conditions for the organophosphate triesters include:
the mobile phase A is 0.1 percent of formic acid aqueous solution by volume fraction;
the mobile phase B is methanol;
a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B is 5 percent, and the initial mobile phase B is kept at 5 percent in 0-1 min; 1-3min, the volume fraction of mobile phase B rises from 5% to 40%; 3-12min from 40% to 100%; keeping 100% unchanged for 12-15 min; 15-15.1min, the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent; the volume fraction of the mobile phase B is kept unchanged at 5 percent for 15.1-18 min;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen at 55 psi;
(2) the chromatographic conditions for the organophosphate diesters comprise:
mobile phase A: 0.2mmol/L aqueous ammonium acetate solution;
mobile phase B: methanol;
a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
elution procedure: initial mobile phase B volume percent 5%, 0-4min, rising from 5% to 35%; 4-7min, the volume fraction of the phase B is increased from 35% to 80%; 7-12min from 80% to 100%; keeping 100% unchanged for 12-14 min; 14-15min, the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent; the volume percentage of the mobile phase B is kept unchanged at 5 percent for 15-20 min;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen at 55 psi;
(3) the organophosphite ester chromatographic conditions comprise:
mobile phase A: 0.2mmol/L aqueous ammonium acetate solution;
mobile phase B: methanol;
a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm;
flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B was 40%; keeping the concentration unchanged at 40% in 0-3 min; increasing from 40% to 100% in 3-10 min; keeping constant at 100% for 10-15 min; the volume percentage content of the mobile phase B is reduced from 100 percent to 40 percent within 15-15.5 min; the volume fraction of the mobile phase B is kept unchanged at 40 percent for 15.5-18 min;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen at 55 psi;
(4) the chromatographic conditions of the phthalate diester comprise:
mobile phase A: 0.1% by volume of aqueous formic acid;
mobile phase B: methanol;
a chromatographic column: luna 2.5. mu. m C18(2) -HST
100×2.0mm；
Flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage content of the initial mobile phase B is 40%; the volume percentage of the mobile phase B is increased from 40 percent to 70 percent in 0-2 min; 2-8min, the volume percentage of the mobile phase B is increased to 100%; keeping 100% unchanged for 8-13min, and reducing the volume percentage of mobile phase B to 40% in 13-13.1 min; 13.1-17min, keeping constant at 40%;
the mass spectrometry conditions include: 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 55 psi;
(5) the chromatographic conditions of the phthalic acid monoester, the benzophenone, the phenol and the p-hydroxybenzoic acid ester comprise:
mobile phase A: 0.2mmol/L aqueous ammonium acetate solution;
mobile phase B: methanol;
a chromatographic column: ZORBAX Extended-C183.5 μm
100×2.1mm；
Flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping the 10% value unchanged for 0-0.5 min; the volume percentage of the mobile phase B is increased from 10 percent to 50 percent within 0.5-1 min; 1-7min, the volume fraction of the mobile phase B is increased from 50% to 99%; keeping the temperature constant at 99% for 7-10 min; 10-10.1min, from 99% to 10%, 10.1-12min, keeping the volume fraction of mobile phase B at 10%;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen at 55 psi;
(6) non-phthalate plasticizers, benzothiazole, benzotriazole, uv stabilizers, antioxidant chromatography conditions included:
mobile phase A: 0.1% by volume of aqueous formic acid;
mobile phase B: methanol;
a chromatographic column: luna 2.5. mu. m C18(2) -HST
100×2.0mm；
Flow rate: 0.3 mL/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 at 40% in 0-2 min; 2-4min, the volume percentage of the mobile phase B is increased from 40% to 80%; 4-14min, the volume percent of the mobile phase B is increased from 80% to 100%; 14-17min, keeping the volume percentage of the mobile phase B constant at 100%; the volume percentage of the mobile phase B is reduced to 40 percent in 17-20min, and the volume percentage of the mobile phase B is kept unchanged at 40 percent in 20-24 min;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen at 55 psi;
(7) the antioxidant chromatographic conditions included:
mobile phase A: 4mmol/L ammonium acetate aqueous solution;
mobile phase B: methanol;
a chromatographic column: luna 2.5. mu. m C18(2) -HST
100×2.0mm；
Flow rate: 0.2 mL/min;
column temperature: 40 ℃;
elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping 10% unchanged at 0-0.5 min; the volume percentage of the mobile phase B is increased from 10% to 50% in 0.5-1min, and is increased to 99% in 1-7 min; keeping the temperature at 99% for 7-10 min; the volume percentage of the mobile phase B is rapidly reduced to 10 percent in 10-10.1 min; the volume fraction of the mobile phase B is kept constant at 10.1-12 min;
the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen, at a pressure of 55 psi.
9. A multi-component high throughput analysis method for plastics additives according to any of claims 1-3, wherein said internal standard of step (4) is bisphenol a-deuterated d16 and tert-butyl paraben-deuterated d9 in negative mode of electrospray ion source and coumaphos-deuterated d10 in positive mode of electrospray ion source.
10. The method for multi-component high-throughput analysis of plastic additives according to any one of claims 1 to 3, wherein the tetrahydrofuran solution containing ammonia is prepared as it is, and the tetrahydrofuran and ammonia are used in a reagent not lower than LC-MS grade; and in the methanol aqueous solution, a reagent not lower than LC-MS grade is adopted for methanol and pure water.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110727339.1A CN113504322B (en) | 2021-06-29 | 2021-06-29 | Multi-component high-throughput analysis method for plastic additive |
| PCT/CN2022/102262 WO2023274288A1 (en) | 2021-06-29 | 2022-06-29 | Multi-component and high-throughput analysis method for plastic additives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110727339.1A CN113504322B (en) | 2021-06-29 | 2021-06-29 | Multi-component high-throughput analysis method for plastic additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113504322A true CN113504322A (en) | 2021-10-15 |
| CN113504322B CN113504322B (en) | 2023-04-28 |
Family
ID=78010900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110727339.1A Active CN113504322B (en) | 2021-06-29 | 2021-06-29 | Multi-component high-throughput analysis method for plastic additive |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113504322B (en) |
| WO (1) | WO2023274288A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023274288A1 (en) * | 2021-06-29 | 2023-01-05 | 暨南大学 | Multi-component and high-throughput analysis method for plastic additives |
| CN115656393A (en) * | 2022-12-27 | 2023-01-31 | 安徽医科大学 | Method for simultaneously detecting contents of multiple plastic additives in vegetables |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116087374B (en) * | 2023-04-11 | 2023-06-27 | 农业农村部环境保护科研监测所 | Detection method for trace bisphenol compounds in agricultural products |
| CN116550006B (en) * | 2023-07-07 | 2023-11-10 | 上海奥浦迈生物科技股份有限公司 | Formula, preparation method and application of chromatographic combination liquid |
| CN117665173B (en) * | 2024-02-01 | 2024-04-30 | 深圳天祥质量技术服务有限公司 | Method for determining tetrahydrofurfuryl alcohol in consumer goods |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981239A (en) * | 1997-09-24 | 1999-11-09 | Great Lakes Chemical Corp. | Synthesis of optically active phenylalanine analogs using Rhodotorula graminis |
| CN112986416A (en) * | 2021-02-03 | 2021-06-18 | 暨南大学 | Multi-component large-flux detection method for plastic additive in atmospheric particulates |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102062766B (en) * | 2010-12-07 | 2014-01-08 | 中国检验检疫科学研究院 | Method for measuring nonyl phenol in cosmetic |
| US9715998B2 (en) * | 2014-01-09 | 2017-07-25 | Kaohsuing Medical University | Method for monitoring level of paraben in cosmetics |
| CN105891398A (en) * | 2014-12-15 | 2016-08-24 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | Technology for detecting multiple benzophenone ultraviolet light absorbers in cosmetics and application thereof |
| CN105891344A (en) * | 2014-12-15 | 2016-08-24 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | Technology for rapidly detecting and confirming multiple ultraviolet light absorbers in cosmetics |
| CN108709947B (en) * | 2018-07-10 | 2021-01-12 | 中国检验检疫科学研究院 | Method for measuring transfer volume of phthalate plasticizer in food contact material |
| CN111912930B (en) * | 2020-07-10 | 2021-05-25 | 甘肃省药品检验研究院 | Method for simultaneously determining 10 phthalic acid esters in aromatic cosmetics |
| CN112229936B (en) * | 2020-12-14 | 2021-03-19 | 南京市产品质量监督检验院 | Method for simultaneously detecting 33 plastic additives in food contact material |
| CN113504322B (en) * | 2021-06-29 | 2023-04-28 | 暨南大学 | Multi-component high-throughput analysis method for plastic additive |
-
2021
- 2021-06-29 CN CN202110727339.1A patent/CN113504322B/en active Active
-
2022
- 2022-06-29 WO PCT/CN2022/102262 patent/WO2023274288A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981239A (en) * | 1997-09-24 | 1999-11-09 | Great Lakes Chemical Corp. | Synthesis of optically active phenylalanine analogs using Rhodotorula graminis |
| CN112986416A (en) * | 2021-02-03 | 2021-06-18 | 暨南大学 | Multi-component large-flux detection method for plastic additive in atmospheric particulates |
Non-Patent Citations (4)
| Title |
|---|
| RUNZENG LIU等: "Organophosphite Antioxidants in Indoor Dust Represent an Indirect Source of Organophosphate Esters", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| RUNZENG LIU等: "Unexpectedly High Concentrations of a Newly Identified Organophosphate Ester, Tris(2,4-di-tert-butylphenyl) Phosphate, in Indoor Dust from Canada", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| 张晓利等: "纺织品中磷酸三酯类化合物的超声提取-GC/MS检测", 《印染》 * |
| 边海涛等: "高效液相色谱-串联质谱法测定化妆品中13种紫外线吸收剂", 《日用化学工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023274288A1 (en) * | 2021-06-29 | 2023-01-05 | 暨南大学 | Multi-component and high-throughput analysis method for plastic additives |
| CN115656393A (en) * | 2022-12-27 | 2023-01-31 | 安徽医科大学 | Method for simultaneously detecting contents of multiple plastic additives in vegetables |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113504322B (en) | 2023-04-28 |
| WO2023274288A1 (en) | 2023-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113504322B (en) | Multi-component high-throughput analysis method for plastic additive | |
| US8409865B2 (en) | Methods and kits for the determination of the presence and quantity of vitamin D analogs in samples | |
| CN111044643B (en) | Detection method of organic phosphate | |
| CN113125601B (en) | Method for simultaneously detecting concentrations of 4 fat-soluble vitamins in serum | |
| CN112684030A (en) | Method for detecting perfluoroalkanoic acid compound in aquatic product by enrichment purification-liquid chromatography tandem mass spectrometry and application | |
| CN113176364A (en) | Method for simultaneously detecting trimethylamine oxide and phenylacetylglutamine, detection kit and application thereof | |
| CN113791146B (en) | Method for detecting organic phosphate pollutants in food and sample treatment method thereof | |
| CN112858499A (en) | Method for simultaneously determining modified nucleoside and creatinine in urine | |
| US20130186186A1 (en) | Methods and kits for the determination of the presence and quantity of vitamin d analogs in samples | |
| CN115932095A (en) | Method for detecting fat-soluble vitamins in serum | |
| CN112946153B (en) | Method for simultaneously determining multiple pollutants in plastic barreled vegetable oil | |
| CN113267589B (en) | Analysis method of 16 synthetic cannabinoids and metabolites thereof in hair | |
| CN112362796A (en) | Method for detecting biotoxin in bee pollen and application thereof | |
| KR20210117268A (en) | High-Speed Sample Workflow for LC-MS-Based HBA1C Instrumentation | |
| CN113640401B (en) | Method for detecting aristolochic acid in soil | |
| CN110609097A (en) | Method for screening phosphatidylserine compounds | |
| CN115144494B (en) | Method for detecting oligosaccharide in mammal milk | |
| CN113376292B (en) | Method for simultaneously determining residues of 3 veterinary drugs in honeyed pills or water-honeyed pills | |
| CN115112810B (en) | Sample pretreatment method for 25-hydroxy vitamin D detection and application | |
| CN115290778B (en) | Analysis and identification method for trace glucocorticoid in environmental water body | |
| CN113092627B (en) | Method for detecting cannabinoid component in cosmetics | |
| CN107085063A (en) | A kind of analysis method of mycotoxin in medicine-food two-purpose kind subclass Chinese medicine | |
| CN115078559A (en) | Rapid vitamin D detection method based on single quadrupole mass spectrometry, kit and application | |
| CN118169278A (en) | Method for detecting organic phosphate pollutants and diester compounds in infant formula milk powder | |
| CN115541788A (en) | Method for rapidly detecting four perfluorinated compounds in dairy product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |